TW200535221A - Systems, methods, and catalysts for producing a crude product - Google Patents

Abstract

Contact of a crude feed with one or more catalysts produces a total product that include a crude product. The crude product is a liquid mixture at 25 DEG C and 0.101 Mpa. One or more other properties of the crude product may be changed by at least 10% relative to the respective properties of the crude feed.

Description

200535221 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates generally to systems, methods, and catalysts for processing crude oil feeds' and to compositions that can be produced using such systems, methods, and catalysts. More specifically, the specific examples described herein relate to systems, methods, and catalysts used to convert crude oil feeds to a total product, where the total product contains a crude product that is at 25 ° C and MPa It is a liquid mixture and has one or more changed properties compared to the individual properties of the crude feed. [Prior art] One type of crude oil with inappropriate properties that cannot allow crude oil to be economically rotated or processed using conventional equipment is often referred to as "inferior crude oil." Inferior crude oil may contain a sieve component that contributes to the total acid number ("TAN") of the crude feed. Poor crude oils with fairly high TANs during transportation and / or force: during the processing of such poor crude oils may cause corrosion of metal components. Removal of acidic components from inferior crudes may involve neutralizing the acidic components with various alkali chemistry. Alternatively, the 'to # metal can be used in carousel and / or processing equipment. The use of resistant metals usually involves considerable costs, so the use of resistant metals in existing equipment may not be what we would expect. Another method of inhibiting rot # may involve adding rotten preparations to inferior raw A before transporting and / or defending inferior crude. The use of rot button inhibitors may have a negative impact on the quality of the equipment used in Jiayu crude oil and / or the products made from crude oil. Inferior crude oils generally contain considerable residues. Such large amounts of residues can be difficult to transport and / or process using expensive equipment and / or costly. 200535221 Poor crude oils often contain organically bound heteroatoms (eg nitrogen). Organically bound heteroatoms can cause lice and ring in several cases. Bad effects on catalysts Inferior crude oil may contain a significant amount of metal contaminants such as brocade, vanadium, and / or iron. During the processing of this type of crude oil, the chemical compounds of the genus Coca-Cola and / or gold may be deposited on the surface of the catalyst or in the volume of the catalyst. Such deposits may cause a decrease in catalyst activity. , ′, During contact: force :: 1, coke may be formed and / or deposited sharply on a surface during crude oil. The cost of catalysts contaminated with coke can be expensive. The high temperatures used during regeneration may also reduce activity and / or cause degradation. h make the catalyst potassium, = metal that may contain organic acid metal salt forms (such as Mai, from the conventional formula = ⑹ organic acid metal salt form metal can not typically be borrowed from a row such as desalination and / or pickling from inferior quality Separation in crude oil. When ::: Metals in the form of organic acid metal salt, the conventional method and metal deposited in the form of organic acid metal salt on the surface of the catalyst may be preferentially combined. In the volume, in particular, β is in the form of a metal salt in the form of pores that accumulate between catalyst particles: "on top of: pollutants, such as organic acid beds, increase in pressure drop and actually clog the catalyst == metal Metals in the form of salts may cause rapid deactivation of the catalyst. Deficiency per gram = oil may contain organic oxygen compounds. Processing crude oil with oxygen content of at least the mother gram inferior shellfish is at least available during processing. The treatment of poor-quality crude oil with oxygen can be a problem. Organic oxygen compounds may generate higher-level oxides (such as ketones and / or alcohols to form acids, and / or ethers) when heated during processing. Generate acid), which is difficult to Removal of processed crude oil and / or corrosion / contamination of equipment during processing and blockage of pipelines. Inferior crude oil may contain unsaturated smoke. When processing unsaturated smoke, especially if it is produced by cracking, If the unsaturated segment is from a natural source, the average amount of hydrogen must usually be increased. Hydrogenation during processing, which typically involves the use of active hydrogenation catalysts, may require the inhibition of unsaturated segment formation of coke. Hydrogen is expensive to produce and / or transport Costly to processing equipment. Inferior crude oil also tends to show instability during processing with conventional equipment. Crude instability can cause component phase separation and / or formation of non-ideal by-products (such as hydrogen sulfide) during processing , Water, and carbon dioxide) methods generally lack the ability to change selected properties of inferior crude oil without significantly altering other properties of inferior crude oil. ”Methods often lack significant reduction of tan in inferior crude oil and change specific components in inferior crude oil. (Such as sulfur or metallic forces. For example, the TAN is known while only contaminating the desired amount of pollutants) Content capacity.

No. 6,547,957; awarded 200535221

6,277,269 by Meyers et al .; "M Plus" awarded by Grande et al. 5,928,502 awarded to Bearden et al .; 5々, 914,033 awarded to Kudah et al .; awarded to Trachte et al. "Π ;; Luzhou Grab to Hew et al .; and 5,851,381 to Tanaka #" describe various methods, systems, and catalysts for processing crude oil. However, the methods and systems described in these patents And catalysts have limited applicability due to the many technical issues raised above. In short, inferior crude oils often have non-ideal, properties (e.g., a relatively high TAN, a tendency to become unstable during processing, and / or a tendency to consume a significant amount of hydrogen during processing). Other non-ideal properties include considerable amounts of non-ideal ingredients (e.g. residues, organically bound heterogen +, metal contaminants, metals in the form of organic acid metal salts, and / or organic oxygen compounds). Such properties tend to cause problems with conventional conveying and / or processing equipment, including increased corrosion during processing, reduced catalyst life, blocked processes, and / or increased use of chlorine. So, what about converting inferior crudes into crude products with more desirable properties? Wenliang Department 'System, method, and / or catalyst still have significant economic = technical needs. There is also a significant economic and technical need for systems, methods, and / or catalysts that can change the selected properties of inferior crudes and / or remotely change other properties of inferior crudes. [Summary of the Invention] This Maoming is generally related to the system, method, and catalyst used to convert crude oil feed to a total product containing crude oil and non-condensable gas in the right dry example. The present invention also relates generally to compositions containing novel amidine combinations of the ingredients therein. Such compositions can be obtained using the system and 200535221 method described herein. The present invention provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product is a liquid mixture at G.1G1 MPaT and the crude oil The feed has a TAN of at least 0 3, the at least one catalyst has a pore size distribution with a median pore size in the range of 90 A to 180 A, and the total number of pores in the pore size distribution to v 60 / 〇 has among 45 people Pore size within the pore size range, where the pore size distribution is determined by ASTM method D4282; and the contact conditions are controlled so that the crude oil product has a TAN of the crude oil feed with a TAN of 90% at most, where tan is by ASTM method D664 Determination. The present invention also provides a method for producing a crude oil product, which comprises: contacting a crude oil feed or a catalyst to produce a total product containing a crude oil product, wherein the crude oil product is a liquid mixture at 25 t: and 0 · 101 MPa The crude oil feed has a TAN of at least 0.3, the at least one catalyst has a pore size distribution with a median pore I of at least 90A, which is determined by ASTM method D4282, " Hai catalyst in each gram of catalyst, Contains 0.0001 grams to 0.08 grams of glutamate, one or more molybdenum compounds, or mixtures thereof, based on the weight of molybdenum; and controlling the contact conditions so that the crude oil product has a TAN of tan up to 90% of the crude feed , Where TAN is determined by ASTM method D664. The present invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product is at 25. It is a liquid mixture at 0 and 0 · 101 MPa. The crude oil feed has a TAN of at least 0 · 3, which is determined by ASTM D664. "At least one catalyst has a pore size distribution with a median pore size of at least 1 80 A, 200535221. It is determined by ASTM method D4282, the catalyst has a pore size distribution containing one or more metals of the sixth table of the Periodic Table, one or more metals of the sixth table of the Periodic Table-or a compound thereof, or a mixture thereof; and control The contact conditions were such that the crude product had a TAN of the crude feed of up to 90%, where TAN was determined by ASTM method D664.

The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feedstock or a catalyst to produce a total product containing a crude oil product, wherein the crude oil product is at 25. (: And 0.101 MPaT is a liquid mixture, the crude oil feed has a TAN of at least 0.3, determined by ASTM method D664, the at least one catalyst comprises: (a) one or more metals in column 6 of the periodic table, the periodic table One or more compounds of one or more metals in column 6, or mixtures thereof; and (b) one or more metals in block 10 of the periodic table, one or more compounds of one or more metals in block 10 of the periodic table, Or its mixture 'whose molar ratio of total HM free metal to total M free metal is in the range of 1 to 10, and the contact conditions are controlled so that the crude oil product

The tan has a tan of 90% of the crude oil feed, where TAN is determined by ASTM method D664. The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with-or a plurality of catalysts to produce a total product containing a crude oil product, wherein the crude oil product is liquid at a pressure of 0.1 MPa Mixture, the crude oil feed has a TAN of up to 3, and the catalyst or catalysts include: the first catalyst, which is per gram of the first catalyst, based on the weight of the metal, contains 0 to 1 0.06 g of column 6 of the periodic table—or more than one metal, column 6 of the periodic table—or one or more compounds of the metals, or a mixture thereof 10 200535221 :; and ⑻ second catalyst, the second catalyst In: Contains at least based on metal weight. -Grams of the metal of the periodic table, or column 6 of the periodic table-or a combination of metals or a mixture thereof; and controlling the contact conditions so that the crude oil has a TAN of at most 90% of the crude oil feed TAN, where M is determined by ASTM method D664. The invention also provides a catalyst composition comprising: ⑷ of the periodic table 5-or more metals, periodic ... one or more of the metals-or multiple compounds' or mixtures thereof; ⑻ carrier, which has Θ oxidation Shao content content = at least ° in the body, 1 gram of θ oxide, which is measured by X-ray diffraction. The catalyst has a pore size distribution with a median pore size of at least 23〇A, which is determined by ASTM method D4282. Determination.

The present invention also provides a catalyst composition, which includes: (6) of the periodic table (6) one or more metals' of the periodic table '(6)-or a plurality of metals-or a plurality of compounds, or a mixture thereof; (b) a carrier' which has Θ alumina contains denier of at least G1 grams per gram of carrier towel, which is diffracted by X-rays = Ding Er, where the catalyst has a pore size distribution with a median pore size of at least 23A, which is determined by ASTM method D4282 Determination. The invention also provides a catalyst composition, which includes one or more metals of the periodic table 5 =, one or more metals of column 5 of the periodic table—or evening compounds, one or more of the sixth column of the periodic table Metal, one or more compounds of one or more metals of the Periodic Table, or a mixture thereof; (b) a support having a θ alumina content of at least 0.01 g of rhenium alumina per gram of support by X-ray diffraction measurement; wherein the catalyst has a pore size distribution with a median pore diameter of 11 200535221) of 23 0A, which is measured by ASTM method D4282. The present invention also provides a method for producing a catalyst, which comprises: combining a support with one or more metals to form a support / metal mixture, wherein the support comprises Θ alumina and the one or more metals include a Or more metals' one or more compounds of one or more metals in column 5 of the Periodic Table, or a mixture thereof; heat-treating the alumina carrier / metal mixture at a temperature of at least 40 hrs; and forming a catalyst, wherein the catalyst It has a pore size distribution with a median pore size of at least 230 A, as determined by ASTM method d4282.

The present invention also provides a method for producing a catalyst, which comprises: combining a support with one or more metals to form a support / metal mixture, wherein the support comprises Θ alumina, and the one or more metals include one in column 6 of the periodic table. Or more metals, one or more compounds of one or more metals in column 6 of the Periodic Table, or / and the mouthpiece, heat-treated the alumina carrier / metal mixture at a temperature of at least 400 C; and forming a catalyst, wherein the The catalyst has a pore size distribution with a median pore size of at least 230 A, which is determined by ASTM method D4282.

The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product is liquid at 25t and 0.1 (1) MPa Mixture, the crude oil feed has at least Q 3 # TAN, the at least one catalyst has a median: pore size distribution with an L diameter of at least 180 °, which is determined by the astm method d gamma 'the catalyst has The _ or more genus in the 6th periodic table of God, the _ or more metals _ or more compounds in column 6 of the periodic table, 2 the pore size distribution of the mixture; and the contact conditions are controlled so that the crude oil has a TAN of 9 at most 0% of the tan of the crude oil feed, of which ⑽ 12 200535221 was determined by ASTM method D664. The present invention also provides a method for producing a crude oil product, which includes ... contacting a crude oil feed with one or more catalysts in the presence of a hydrogen source to produce crude oil containing

The total product of the product, wherein the crude oil product is a liquid mixture at 25 MPa and 0.001 MPa, the crude oil feed has a TAN of at least 0.3, and the crude oil feed has at least 0.3 gram of crude oil feed to the parent gram crude oil. With 0.1 g of oxygen, the at least one catalyst has a pore size distribution with a median pore size of at least 90 A, as determined by ASTM method D42 82; and controlling the contact conditions to reduce the TAN so that the crude product has a TAN of at most 90% of the tan of the crude oil feed, and reducing the content of organic oxygen compounds so that the crude oil product has the oxygen content of the crude oil feed with a maximum oxygen content of 90%, where TAN is determined by ASTM method D664 The oxygen content was determined by the ASTM method £ 385. The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and G.HH MPaT , The

The crude oil feed has at least (M @ TAN, the at least _ catalyst in each gram of catalyst, based on the weight of metal, contains at least 0 001 grams of the sixth table of the periodic table-or more metals, the sixth table of the periodic table One or more compounds of one or more metals, or mixtures thereof; and controlling the contact conditions so that in the contact zone: the liquid space velocity exceeds 10 h 'and the crude product has a TAN of 90% of the crude feed of the crude oil, beans

Assay D664. "The TAN system is also provided by ASTM Siemin for the production of crude oil products, which includes: contacting a crude oil feed with-or a plurality of catalysts under a hydrogen source to produce a total product containing crude oil 13 200535221 product, wherein the crude oil The product is a liquid compound at 25 ° C and 0. 101 MPa. The crude feed has a tan of at least 0.001 and the crude feed has a sulfur content of at least 0.0000 per gram of crude feed. 1 gram of sulfur, the catalyst includes one or more metals of the sixth table of the periodic table, one or more compounds of one or more metals of the sixth table of the periodic table, or a mixture thereof; The raw material feed absorbs knife hydrogen at a fixed rate during the contact period to suppress the phase separation of the crude oil feed material during the contact period, so that the liquid space velocity in one or more contact zones exceeds 10 hi, so that the crude oil product has The tan is at most 90% of the TAN of the crude oil feed, and the crude oil product has a sulfur content of 70 to 130% of the crude oil feed, where TAN is determined by ASTM method 0664 and Sulfur content is measured by ASTM method D4294. ^ 本 发A method of producing a crude oil product is also provided which includes: contacting a crude oil feed with one or more catalysts in the presence of a gaseous hydrogen source to produce a total product containing a crude oil product, wherein the crude oil product pit and 〇i〇i Mb The following is a liquid mixture; and controlling the contact conditions so that the crude oil feed absorbs hydrogen at a selected rate during the contact to suppress phase separation of the crude feed during the contact. The present invention also provides a method for producing a crude oil product, including: 'Contacting a crude oil feed with hydrogen to produce a total product containing a crude oil product' in the presence of one or more catalysts, wherein the crude oil product is a liquid mixture at the pit and 0 (i) i Mb; and controlling the contact conditions so that the Crude oil feed is in contact with hydrogen under the first hydrogen uptake conditions and then under the second hydrogen uptake conditions. The first gas uptake conditions are different from the second hydrogen uptake conditions. 'Control the net uptake of hydrogen 200535221 in the first nitrogen uptake conditions to prevent The p-value of the crude oil feed / total product mixture is reduced to less than 1 $, and one or more properties of the crude oil product are at most compared to the individual properties of the crude oil feed- A change of 90/0. The present invention also provides a method for producing a crude oil product, which includes contacting a crude oil feed with one or more catalysts at a first temperature and then contacting at a second temperature to produce crude oil containing The total product of the product, wherein the crude product is a liquid mixture at 25 C and 0.101 MPa, the crude feed has a TAN of at least 0.3, and the contact conditions are controlled such that the first contact temperature is at least 30 seconds lower than the second contact temperature ° C, so that the crude oil product has a TAN of up to 90% compared to the tan of the crude oil feed, in which butyl AN is determined by the astm method D664. The present invention also provides a method for producing a crude oil product, comprising: The crude oil feed is contacted with one or more catalysts to produce a total product containing crude oil products, wherein the crude oil product is a liquid mixture at 2 cavities and 0.1 (1 MPaT), the crude oil feed has a TAN of at least 0.3, and the crude oil feed Have a sulfur content of at least 0.0001 grams of sulfur in the parent gram crude oil feed, the at least one catalyst comprises one or more metals in the sixth table of the periodic table, one or more subordinate or multiple compounds in column 6 of the periodic table, or A mixture; and controlling contact conditions so that the crude oil product has a TAN of up to 90% of the crude oil feed and the crude product has a sulfur content of 70 to 130% of the crude oil feed, wherein TAN is measured by ASTM & D664, and sulfur content is measured by ASTM method D4294. The present invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing the crude product, 15 200535221 wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa The crude oil feed has a TAN of at least 0.1, the crude oil feed has a residue that is at least 0.1 grams of residues in the parent gram crude feed, and the at least one catalyst includes the sixth block of the periodic table. One or more metals, one or more compounds of one or more metals of the periodic table, or a mixture thereof; and controlling the contact conditions so that the crude oil product has a TAN of TAN of up to 90% of the crude oil feed ′ The crude product is made to have a residual content of 70 to 130% of the crude feed, wherein TAN is determined by ASTM method D664 and residue content is determined by ASTM method D5307. _ The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, The crude feed has a TAN of at least 0. The crude feed has a VG. The parent gram of crude feed has at least 0.1 gram of VGO. The at least one catalyst contains one or A plurality of metals, one or more compounds of one of the columns of the periodic table, or one or more compounds thereof, or a mixture thereof; and controlling the contact conditions so that the crude oil product has a TAN of TAN of up to 90% of the crude oil feed, so that The crude oil product has a VGO content of the crude oil feed having a VG0 content of 70 to 30%, wherein the VG0 content is determined by aSTm method D5307. The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product is at 25 ° C and 0.11 MPa, Liquid mixture, the crude oil feed has a TAN of at least 0.3, the at least one catalyst can be obtained by the following 16 200535221 column: the carrier and the sixth metal of the periodic table-or more metals, in column 6 of the periodic table- One or more compounds of one or more metals, or a mixture thereof to produce a catalyst precursor; heating the catalyst precursor at a temperature of less than 50 ° C. in the presence of one or more sulfur-containing compounds to form a catalyst; and The contact conditions are controlled so that the crude product has a TAN of the crude feed of up to 9q%. The present invention also provides a method of producing a crude product, comprising: contacting the crude feed with-or catalysts to produce crude oil containing The total product of the product, where the crude product is a liquid mixture at 25 ° C. and 0.101 MPa, the crude feed has a viscosity of at least 10 cSt at 37.8 aC (10 (rF), and the crude feed has: 10's API specific gravity, the at least one catalyst comprising one or more metals of the sixth table of the periodic table, one or more compounds of one or more metals of the sixth table of the periodic table, or a mixture thereof; and controlling the contact conditions so that the crude oil product has The viscosity at 37. is at most 90% of the viscosity of the crude oil feed at 37.8 ° C, and the crude oil product has an API specific gravity of 70 to 130% of the crude oil feed, wherein the specific gravity of Apl is Determined by ASTM method D6822, and viscosity is determined by astm method D2669. The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, Wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, the crude oil feed has a T AN of at least 0.1, and the one or more catalysts include: one or more compounds containing tritium, one or more hungry compounds, or A catalyst of a mixture thereof; and an additional catalyst, wherein the additional catalyst comprises one or more compounds of column 6 metal, 17 200535221 or one or more compounds of group 6 metal, or a combination thereof; and controlled contact The conditions are such that the crude oil product has a TAN of 90% of the crude oil feed, where TAN is determined by ASTM method D664. The present invention also provides a method for producing a crude oil product, comprising: A variety of catalysts are contacted to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the crude feed has a TAN of at least 0.1; hydrogen is generated during the contact; and controlled contact Conditions are such that the crude product has a TAN of up to 90% of the crude feed, where TAN is determined by ASTM method D664. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the The crude oil feed has a TAN of at least 0, the at least one catalyst comprising vanadium, or a vanadium compound, or a mixture thereof; and controlling the contact conditions such that the contact temperature is at least 20 (rc, such that the crude oil product has a maximum TAN) It is 90% of the TAN of the crude oil feed, where TAN is determined by the D31 method D664. The present invention also provides a method for producing a crude oil product, which comprises: contacting the crude oil feed with one or more catalysts to produce A total product containing a crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, the crude oil feed has a TAN of at least 0, and the at least one catalyst comprises vanadium, or a plurality of vanadium compounds, or Mixture; supply of hydrogen and gas sources during contact, 4 gas streams are supplied in the opposite direction of crude oil feed flow; and control of contact conditions so that the crude product has a maximum TAN of 90% of the 18 200535221 TAN of crude oil feed, wherein TAN is determined by the method of D81. The invention also provides a method for producing a crude oil product, which comprises: contacting the crude oil feed with one or more catalysts to Production of a total product containing a crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0.101 MPa, and the crude oil feed has a total Ni / V / g of at least 20000 grams per gram of crude oil feed Fe content, the at least one catalyst contains vanadium, one or more vanadium compounds, or a mixture thereof, the vanadium catalyst has a pore size distribution with a median pore size of at least ^ human, and the contact conditions are controlled so that the crude oil product has a total Ni / The Ni / V / Fe content of the crude oil feed with a V / Fe content of up to 90%, wherein the Ni / V / Fe content is determined by ASTM method D5708. The present invention also provides a method for producing a crude oil product, comprising: The crude feed is contacted with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the at least one catalyst comprises vanadium, one or more vanadium compounds, or Its mixture, the original The oil feed comprises one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or a mixture thereof, and the crude oil feed has at least 0.0000 per gram of crude oil feed. 001 grams of the total content of alkali metals and alkaline earth metals in the form of metal salts of organic acids; and controlling the contact conditions so that the crude oil product has the total content of alkali metals and alkaline earth metals in the form of metal salts of organic acids at most 90/0 The content of metal and soil in the form of organic acid metal salt in the feed, among which the content of alkali metal and alkaline earth metal in the form of metal salt of organic acid is determined by ASTM method D 丨 3 丨 8. The present invention also provides the production of crude oil products. A method comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, 19 200535221 wherein the crude oil product is a liquid mixture at 25 ° C and 0.11 MPa, the crude oil feed The feed contains one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or a mixture thereof. The material has a total organic acid metal salt content of at least 10,000 g of the organic acid and the metal content of the metal and metal. The at least one catalyst has a pore size with a median pore size in the range of 90 to 1 80 A. Distribution, at least 60% of the total number of pores in the pore size distribution has a pore size in the 45 A median pore size range, wherein the pore control distribution is determined by ASTM method D4282; and the contact conditions are controlled so that the crude oil product has an organic acid The total content of alkali metal and soil test metal in the form of metal salt is up to 90%. The metal and soil test metal content of the organic acid metal salt form of the crude oil feed, among which the content of metal test and alkaline earth metal in the form of organic acid metal salt It was measured by ASTM method D 1 3 1 8. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the The crude oil feed has a total Ni / V / Fe content of at least 20000 grams per gram of crude oil feed, and the at least one catalyst has a pore size with a median pore size ranging from 90a to 280 people. Distribution, at least 60% of the total number of pores in the pore size distribution has a pore size in the median pore size range of 45 people, wherein the pore size distribution is determined by ASTM method D4282; and the contact conditions are controlled so that the crude oil product has total Ni The Ni / V / Fe content of the crude oil feed at which the / V / Fe content is at most 90%, wherein the Ni / V / Fe content is determined by ASTM method D5708. The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing the crude oil product, 20 200535221 wherein the crude oil product is liquid at 25t and 〇ΗΠ MPa The crude oil feed has a total alkali metal and alkaline earth metal content in the form of an organic acid metal salt per gram of crude oil feed, the at least one catalyst having a median pore size of at least 4 180 #Pore size distribution, which is determined by the astm method D4282 'The catalyst has a pore size distribution containing one or more metals in column 6 of the periodic table, one or more metals in column 6 of the periodic table—or multiple compounds, or mixtures thereof ; And controlling the contact conditions so that the crude oil product has an organic acid metal salt in the form of alkali metals and alkaline earth metals with a total content of up to 90% of the organic acid metal salt in the crude oil feed in the form of alkali metals and alkaline earth metals containing 1, The metal and soil metal content of the organic acid metal salt is determined by ASTM method D1318. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the A crude oil feed comprising one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or a mixture thereof, the crude oil feed having at least 0.00001 grams of organic per gram of crude oil feed The total content of alkali metals and alkaline earth metals in the form of acid metal salts. The at least one catalyst has a pore size distribution with a median pore size of at least 230A. It is measured by ASTM method D4282. The catalyst has a Pore size distribution of one or more metals, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof; and control of the contact conditions so that the crude oil product has the form of an organic acid metal salt The content of alkali metals and alkaline earth metals in the form of metal salts of organic acids in the crude oil feed with a maximum content of 90% is 21 200535221, of which the metal salts of organic acids The alkali metal and alkaline earth metal contents in the form were measured by ASTM method D1318. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the The crude feed has a total Ni / V / Fe content of at least 0.00002 grams of Ni / V / Fe per gram of crude feed. The at least one catalyst has a pore size distribution with a median pore size of at least 230A. D4282 determined that the catalyst has a pore size distribution comprising one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof; and controlling the contact conditions so that the crude oil The product has a Ni / V / Fe content of the crude oil feed with a total Ni / V / Fe content of up to 90%, where the Ni / V / Fe content is determined by ASTM method D5708. The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product is at 25 ° C and 0.1 MPa Is a liquid mixture, the crude oil feed comprises one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or a mixture thereof, the crude oil feed is in a mother gram crude oil feed A total metal content and soil metal content of at least 100,000 g of organic acid metal salt. The at least one catalyst has a pore size distribution with a median porosity of at least 90 A, which is determined by ASTM method D4282. The catalyst has a total molybdenum content of 0.0001 g to 0.3 g of molybdenum, one or more molybdenum compounds, or a mixture thereof, based on the weight of molybdenum per gram of the catalyst; and controlling contact conditions so that the crude oil The product has organic acid metal 22 200535221 The total content of test metal and soil test metal in salt form is up to 90%. The content of alkali metal and alkaline earth metal in the form of organic acid metal salt in the crude oil feed is as follows. The content of the bad test metal and the test metal was determined by the D 1 3 1 8 method. The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product is a liquid mixture at 25 ° C and 0. 101 MPa The crude feed has a TAN of at least 0.3 and the crude feed has a total Ni / V / Fe content of at least 0.00002 grams per gram of crude feed, and the at least one catalyst has a pore size with a median pore size of at least 90A Distribution, which is determined by ASTM method D4282, 'The catalyst has a total key content of 0.0001 to 0.3 g of molybdenum, one or more molybdenum compounds, based on the weight of molybdenum per gram of catalyst, or A mixture; and controlling the contact conditions so that the crude oil product has a TAN of at most 90% of the crude oil feed and the crude product has a total Ni / V / Fe content of at most 90% of the crude oil feed Ni / V / Fe content, where Ni / V / Fe content is measured by ASTM method D5708, and TAN is measured by ASTM method D664. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the The crude oil feed comprises one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or a mixture thereof, the crude oil feed having at least 0.0000 per gram of crude oil feed. The total content of alkali metals and alkaline earth metals in the form of 0.001 g of an organic acid metal salt, the at least one catalyst package 23 200535221 containing (a) one or more metals in column 6 of the periodic table, or in column 6 of the periodic table, or One or more compounds of the genus, or mixtures thereof; and (b) one or more metals of the 10th periodic table, one or more compounds of one or more metals of the periodic table, or a mixture thereof, The molar ratio of the total metal content of the 10th metal to the total metal of the 6th metal is in the range of 1 to 10; and the contact conditions are controlled so that the crude oil product has an organic acid metal salt and a metal detection metal. The content of alkali metals and alkaline earth metals in the form of organic acid metal salts in the crude oil feed with a content of up to 90%, among which the metal and metal content of organic acid metal salts are measured by ASTM method D1 3 1 8 · set. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the The crude feed has a total Ni / V / Fe content of at least 0.00002 grams of Ni / V / Fe per gram of crude feed, and the at least one catalyst comprises: (a) one or more metals in column 6 of the periodic table, One or more compounds of one or more metals of the Periodic Table, or mixtures thereof; and (b) ® one or more metals of the tenth Table of the Periodic Table, one or more of one or more metals of the tenth Table of the Periodic Table A compound, or a mixture thereof, in which the molar ratio of the total metal in column 10 to the total metal in column 6 is in the range of 1 to 10; and controlling the contact conditions so that the crude oil product has a total Ni / V / Fe content The Ni / V / Fe content of the crude oil feed is at most 90%, where the Ni / V / Fe content is determined by ASTM method D5708. The present invention also provides a method for producing a crude oil product, which includes: contacting a crude oil 24 200535221 feed with one or more contact J spirals to produce a total product containing a shoulder, a mountain, and a ^ wherein the crude product is at a total product of 2, , C and 0 · 1 0 1 MPa are light energy, the β-human crude feed contains one or more night-heart compounds, and the female α-α-one or more alkali metal hafnium of an organic acid, One or more of a variety of organic acids ^ ^ $ .. ^ ^ ^ Alkaline earth metal salts, or mixtures thereof, ^, 由, 碱 +, and 原油 in the form of crude salt per gram of crude oil and crude salt Metal and final "" organic metal containing eight grams of gram: containing the first catalyst, Xi Dilu ... / or Xi catalyst package based on metal weight, containing: in the first catalyst per gram,

… · 000… · 06 grams of the Goethe metal in the sixth table of the periodic table, one or more compounds of one or more of the metals in the column of the periodic table & the bow buckle work table, or a mixture thereof · (h ^ ^ ^ ^, And (b) the first catalyst, the second catalyst

In the second catalyst of the mother gram, 'based on the weight of the metal, it contains at least 002 grams of column 6 of the periodic table-or more metals, and the sixth table of the periodic table-or more metals-or multiple compounds' or A mixture; and controlling the contact conditions so that the crude oil product has an alkali metal and alkaline earth metal content in the form of organic acid metal salts of a total of 90% of the alkali metal and alkaline earth metal content in the form of organic acid metal salts in the crude oil feed, where organic The content of alkali metals and soil metals in the form of acid metal salts is determined by ASTM method D 13 1 8. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the The crude oil feed comprises one or more metallographic salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or a mixture thereof. The crude oil feed has at least 0.000 per gram of crude oil feed. 0001 grams of organic acid metal isolated metal and soil test metal content 'the at least one catalyst in every 25 200535221 grams of catalyst, based on the weight of the metal, contains at least 0. 001 grams of column 6 of the periodic table Or more metals, one or more compounds of one or more metals of the periodic table, or a mixture thereof; and controlling the contact conditions so that the liquid space velocity in the contact zone exceeds 10 1T1, and the crude oil product has an organic acid metal The total content of alkali metal and alkaline earth metal in salt form is the metal and soil metal content of organic acid metal salt form in the crude oil feed, of which organic acid metal The content of alkali metals and alkaline earth metals in salt form was determined by ASTM method D13 18. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the The crude oil feed has a total / V / Fe of at least 20000 grams per gram of crude oil feed, and at least one catalyst contains at least 0.001 per gram of catalyst based on the weight of the metal Grams of one or more metals of the periodic table, one or more compounds of one or more metals of the periodic table, or a mixture thereof, and controlling the contact conditions so that the liquid space velocity in the contact zone exceeds 10 h And make the crude product have a total Ni / v / Fe content of at most

Determined by ASTM method D5708.

Oxygen, sulfur with a sulfur content of at least 0.0000 g, and a liquid mixture at 0.1 101 MPa, the r has free sulfur with an oxygen content of at least 0.0001 g, and the at least one catalyst contains week 26 200535221 One or more metals in column 6 of the Periodic Table, one or more metals in column 6 of the Periodic Table. Metal or metal compounds, or mixtures thereof; and controlling the contact conditions so that the crude oil product has an oxygen content of at most 9%. % Of the oxygen content of the crude oil feed, and the crude product has a sulfur content of 70% to 130% of the original, sulfur content of the feed, wherein the oxygen content is determined by ASTM method E385 The sulfur content is measured by ASTM method D4294. The present invention also provides a method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product having crude oil productivity, wherein the crude oil product is at 25. It is a liquid mixture at 0 and 0.11 Mpa. The Lu crude oil feed has a total Ni / V / Fe content of at least 20000 grams per gram of crude oil feed and a sulfur content of at least 0. 0.01 g of sulfur, the at least one catalyst comprising the sixth or more metals of the periodic table, the one or more metals of the sixth table of the periodic table, or a compound thereof, or a mixture thereof; and controlling the contact conditions so that The crude oil product has a maximum Ni / V / Fe content of the Ni / V / Fe content of the crude oil feed, and the crude product has a sulfur content of 70 to 130% of the sulfur content of the crude oil feed. Amount, where the Ni / v / Fe content is measured by ASTM method D, and the sulfur content is measured by M · _ method D4294. The present invention also provides a method for producing a crude oil product, which comprises: contacting crude oil, feedstock with-or a plurality of catalysts to produce a total product containing the crude oil product, wherein the crude oil product is a liquid mixture in the pit and Om MPaT, and the crude oil is The feed contains-or more organic acids-or more metal test passes, one or more: one or more soil test metals of organic acids, or a mixture thereof, the crude oil, which has at least, 0 00001 in the parent gram crude oil feed. Organic acid metal of t 27 200535221 The total content of alkali metals and alkaline earth metals in salt form with a residue content of at least 0 μg and a residue of at least one catalyst containing one or more metals in column 6 of the periodic table, the periodic table Column 6-One or more compounds of the metal or mixtures thereof; and the contact conditions so that the crude oil product has an organic acid metal salt form with a total metal and earth metal content of up to 90% of the crude oil The alkali metal and alkaline earth metal content in the form of a metal salt of an organic acid in the feed, and the crude oil product has a residue content of 70 to 30% of the crude feed, The content of metal and metal in the form of metal salts of organic acids is determined by ASTM method Xichuan, and the content of residues is determined by ASTM method D5307. The present invention also provides a method for producing crude oil products, including: feeding Contact with—or multiple catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 2 cavities and 0.1 (1) MPa, and the crude feed has residues per gram of crude feed A residue of at least 0 μg, a total Ni / V / Fe content of at least 0.00002 g, the at least one catalyst comprising one or more metals in column 6 of the periodic table, one or more metals in column 6 of the periodic table -Or more compounds, or mixtures thereof; and controlling and contacting conditions so that the crude product has a total Ni / V / Fe content of up to 90% = the Ni / V / Fe content of the crude feed, and the crude product The residue content of the crude oil feed having a residue content of 70 to 130%, wherein the Ni / V / Fe content is determined by ASTM method D57008, and the residue content is determined by ASTM method D5307. The present invention Methods of producing crude oil products are also provided, which Including ... contacting a crude oil feed with one or more catalysts to produce a total product containing crude oil products, 28 200535221 where the crude oil product is a liquid mixture at 251 and 0.101 MPa, and the crude oil feed contains one or more organic acids One or more alkali metal salts, one or more organic acid one or more alkaline earth metal salts, or a mixture thereof, the crude oil feed has at least 0.1 grams of vacuum gas oil ("VGO ") Content, the total content of alkali metals and soil test metals in the form of organic acid metal salts of 0. 0001 grams, the at least one catalyst comprising one or more metals in column 6 of the periodic table, one or more metals in column 6 of the periodic table One or more compounds' or mixtures thereof; and controlling the contact conditions so that the crude oil product has an organic acid metal salt form of alkali metal and alkaline earth metal with a total content of at most _90% of the organic acid metal salt form in the crude oil feed Alkali metal and soil metal content, and the crude oil product has a VGO content of 70 to 13% of the VG0 content of the crude oil feed, where the VG0 content is determined by ast to D5307, and there is Metal content test metal acid metal salt and posterior aspect of the soil series measured by ASTM method D1318. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the Crude oil feed has a total Ni / V / Fe content of at least 20000 grams per gram of crude oil feed, and a VG0 content of at least 0] grams, the at least one catalyst comprising One or more metals, one or more compounds of one of the columns of the periodic table or one or more compounds thereof, or a mixture thereof; and controlling the contact conditions so that the crude oil product has a total Ni / V / Fe content of up to 90% The Ni / V / Fe content of the crude oil feed and the crude product has a VGO content of 70 to 130% of the crude oil feed with a VG content of 70 to 130%, wherein the VGO content of 29 200535221 is determined by ASTM method D5307, The Ni / V / Fe content is measured by ASTM method D5708. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the A crude oil feed comprising one or more alkali metal salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or a mixture thereof, the crude oil feed having at least 0.0001 per gram of crude oil feed The total content of alkali metals and alkaline earth metals in the form of a metal salt of an organic acid. The at least one catalyst can be obtained by combining the carrier with one or more metals in column 6 of the periodic table and one or more metals in column 6 of the periodic table. One or more compounds, or mixtures thereof, to produce a catalyst precursor, heating the catalyst precursor at a temperature below 400 C in the presence of one or more sulfur-containing compounds to form a catalyst; and controlling the contact conditions so that Alkali metal and soil test which make the crude oil product have organic acid metal salt form and the total content of test metal and alkaline earth metal is at most 90% in the form of organic acid metal salt in the crude oil feed Metal content, wherein the alkali metal and alkaline earth metal content of organic acid metal salt-based aspect of the method by ASΤΜ Determination 1318 d. The invention also provides a method for producing a crude product, comprising: contacting a crude feed with one or more catalysts to produce a total product containing a crude product, wherein the crude product is a liquid mixture at 25 ° C and 0.101 MPa, the The crude oil feed has a discriminating Ni / V / Fe content of at least 200000 grams per gram of crude oil feed, and the at least one catalyst can be obtained by: Multiple metals, one or more of the 30th of the Periodic Table 30 200535221 metals or one or more compounds, or mixtures thereof, to produce catalyst precursors; in the presence of one or more sulfur-containing compounds, at less than 400 Heating the catalyst precursor to form a catalyst; and controlling the contact conditions so that the crude oil product has a Ni / V / Fe content of the crude oil feed with a total Ni / V / Fe content of up to 90%, where Ni / The V / Fe content is measured by ASTM method D5708. The present invention also provides a crude oil composition containing per gram of crude oil composition: at least 0.001 g of a hydrocarbon having a boiling range distribution between 95 ° C: and 260 ° C at 0,001 MPa; at least 0.001 g of Hydrocarbons with boiling range distribution between 260 ° C and 320 ° C at 001 Mpa; at least 0.001 grams of hydrocarbons with boiling range distribution between 32 ° C and 650t at 0.101 MPa; and Each gram of crude oil product contains more than 0 grams, but less than 0.001 grams of one or more catalysts. The present invention also provides a crude oil composition containing the following in each gram of crude oil composition: at least 0.01 grams of sulfur, which borrows Determined by ASTM method D4294; at least 0.2 g of residue, determined by ASTM method D5307, the composition has a weight ratio of MCR content of at least 1.5 to 0: 5 asphaltene content, wherein the MCR content is determined by ASTM method. As measured at 4530, the c5 asphaltene content is determined by ASTM method D2007. The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the Crude products are condensable at 25 ° C and 0.101 MPa. The crude oil feed has an MCR content of at least 0.001 grams per gram of crude oil feed, and the at least one catalyst can be obtained by: the carrier and one or more metals in the sixth table of the periodic table, One or more compounds of one or more metals in column 6 2005200521 21 'combinations' or mixtures thereof to produce a catalyst precursor; in the presence of one or more sulfur-containing compounds, the contact is heated at a temperature below 50 (rc). The precursor of the medium forms a catalyst, and the contact conditions are controlled so that the crude product has an Mcr content of the crude feed of up to 90%, where the MCR content is determined by ASTM method D4530.

The present invention also provides a method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil product can be produced at 25 ° C and 0.1 MPa Condensing, the crude feed has an MCr content of at least 0.001 grams per gram of crude feed, the at least one catalyst has a pore size distribution with a median pore size in the range of 70 people to i 800A, the At least 60% of the total number of pores in the pore size distribution has a pore size in the median pore size range of 45, wherein the pore size distribution is determined by ASTM method D4282; and the contact conditions are controlled so that the crude oil product has an MCR of at most 90% The MCR of this crude oil feed, where MCR is determined by ASTM method D4530. The present invention also provides a crude oil composition containing the following in each gram of composition: up to 0.004 g of oxygen, as measured by ASTM method E385; up to 0.003 g of sulfur, as measured by ASTM method D4294; And at least 0.3 g of residue as determined by ASTM method D5307. The present invention also provides a crude oil composition containing the following in each gram of composition: up to 0.004 g of oxygen, as measured by ASTM method E385; up to 0.003 g of sulfur, as measured by ASTM method D4294; Up to 0.04 grams of basic nitrogen, which is determined by ASTM method D2896; at least 0.2 grams of residue, which is measured by ASTM method D5307; and the composition has a maximum of 32 200535221 and a TAN of 0.5, which is determined by Determined by ASTM method D664. The present invention also provides a crude oil composition containing at least 0.001 g of sulfur per gram of composition, which is determined by ASTM method D4294; a residue of at least 0.2 g, which is determined by astM method D5307; the composition Has a weight ratio of MCR content to c5 asphaltene content of at least 1.5, and the composition has a TAN of up to 0.5, where TAN is determined by ASTM method D664, and the weight of MCR is measured by ASTM method D4530, and The weight of C5 asphaltene was measured by ASTM method D2007. In several specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide the following crude oil feeds: (a) those that have not been processed, distilled and / or fractionated in a refinery; (b) contain carbon For components with a number greater than 4, the crude oil feed contains at least 0.5 grams of this type of feed per gram of crude oil feed. '(C) Contains smoke, and part of it has: less than 1 at 0 10 MPa 〇〇 Boiling range distribution, 0.101 MPa between 10 (TC and 200 ° C boiling range distribution, 0.101 MPa between 200 ° C and 300 ° C boiling range distribution, at 0.101 Boiling range distribution between 300 ° C and 400 ° C at MPa, and boiling range distribution between 400 ° C and 650 ° C at 0.101 MPa; (d) Contained in each gram of crude oil feed At least 0.001 grams of hydrocarbons with a boiling range distribution below 0.101 MPa at 0.101 MPa, 0.001 grams of hydrocarbons with a boiling range distribution at 0.101 MPa between 100 and 200 ° C, 〇01 grams of hydrocarbons with a boiling range distribution between 200 ° C and 30.0 ° at 0.101 MPa, and 0.001 grams of a boiling range distribution between 3,000 ° C and 0.10 MPa Hydrocarbons between 400 ° C, and 0.001 grams of hydrocarbons with a boiling range distribution between 400 ° C and 650 ° C at 010i Mpa; (e) have at least 〇1, to 200535221 less Is 0.3, or a TAN in the range of 0.3 to 20, 04 to 10 milk U. 5 to 5; (f) has an onset of at least 200 qc at 0.1 MPa

Boiling point; (g) contains nickel, vanadium and iron; (h) contains at least 0.00002 grams of total Ni / V / Fe per gram of crude feed; ⑴ contains sulfur; ⑴ contains at least 0.0001 per 1 of crude feed Gram or 0.05 gram of sulfur; (k) containing at least 0.1 g of VG0 per gram of crude oil feed; 至少 containing at least 0.1 gram of residue per gram of crude oil feed; (m) containing oxygenated hydrocarbons (Η) one or more metal test salts of one or more organic acids, one or more alkaline earth metal salts of one or more organic acids, or a mixture thereof; (0) at least two zinc salts containing organic acids; and / or (P) At least one kun salt containing an organic acid. In several specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide crude oil feeds that can be obtained by removing naphtha and more volatile compounds than naphtha from crude oil. material.

In certain specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide a method of contacting a crude oil feed with one or more catalysts to produce a total product containing a crude oil product, wherein the crude oil feed And crude oil products both have C5 asphaltene content and MCR content, and: (a) the sum of the C5 asphaltene content of the crude oil feed and the MCR content of the crude oil feed is s, the C5 asphaltene content of the crude oil product and the crude oil product The sum of the mcr content is to control the contact conditions so that S is at most 99% of s; and / or (b) restrain the contact conditions so that the weight ratio of the mcr content of the crude oil product to the c-cyanocyanine content of the crude product is between 1-2 to 2.0, or h3 to ι · 9. 5 In several specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide a hydrogen source, wherein the hydrogen source is (a) gaseous, ((dagger) 34 200535221 hydrogen; (C) Methane; (d) light hydrocarbons; (e) inert gases; and / or mixtures. In a few specific examples, the present invention and one or more methods or compositions combining the present invention also provide a method of connecting raw materials with—or multiple catalysts to produce a total product containing crude oil products, wherein the crude oil is The material is contacted in a contact zone located or connected to the offshore equipment.

In some specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide a method comprising contacting a crude oil feed with one or more catalysts in the presence of a gas and / or hydrogen source and Controlled Contact :: In order to: (a) The ratio of gaseous hydrogen source to crude oil feed is 5 to 800 standard cubic meters of gaseous hydrogen source per cubic meter of crude oil feed in contact with one or more catalysts. Within the range; (b) controlling the selection of hydrogen by changing the partial pressure of the hydrogen source > Yin absorption rate; (c) the hydrogen absorption rate makes the crude oil product have a less than TAN, but the hydrogen absorption system is less than that during contact will cause The amount of hydrogen uptake that is substantially phase separated between the crude oil feed and the total product; (d) Selected uptake of hydrogen = 1 to 30 or 1 to 80 standard cubic meters of hydrogen source per cubic meter of crude feed Within the range; (e) the liquid space velocity of the gas and / or hydrogen source is at least 11 1T1, at least 15 ^, or at most 20 h- !; (f) controlling the partial pressure of the gas and / or hydrogen source during contact (G) the total liquid space velocity of the gas and / or hydrogen source in the range of contact temperature in the range of 50 to 5001: The temperature is in the range of 0 to 1 and the total pressure of the gas and / or hydrogen source is in the range of to 20 MPa; (h) the flow of the gas and / or hydrogen source is in the direction opposite to the flow of the crude oil feed (I) the crude oil product has an H / C of 70 to 130% of the crude oil feed; (j) the hydrogen absorbed by the crude oil feed is 35 200535221 per cubic meter;

The crude oil feed contains a maximum of 80 and / or 1 to 80 or 1 to 50 standard cubic meters of chlorine; (k) the crude product has a total Ni / V / Fe content of at most / ° Yuan Xi is 50%, Or up to 10% of the Ni / v / Fe content of the crude oil feed, the crude oil product has a sulfur content of 70 to no% or 80 to 120% Content; (m) the crude oil product has a content of 70 to 130% or 90 to 110% of the crude oil to 13.0% or 9 VG of the feed; (n) the crude product has a residue content of 700 To Π0% ^ residue content of the crude oil feed; (〇) the crude oil product has an oxygen content of 90%, up to 70%, up to 50%, up to peach, or 10 / 〇 the oxygen content of the crude oil feed; the crude oil product has an organic acid metal salt in the form of a total alkali metal and alkaline earth metal content of at most 50 / 〇, or at most 10% of the organic acid of the crude oil feed Contents of alkali metals and alkaline earth metals in the form of metal salts; ⑷ During the contact, the P value of the crude oil feed is at least 15; ⑴ The crude oil product has a viscosity of up to 9G% at 37 8 ° Or at most & the original: the viscosity of the feed at 37 · 8 C; Yan Yanhai crude product has an Aρ specific gravity of 70 to 130% of the crude oil feed, and / or the crude oil The product has a TAN of at most 90%, at most 50%, at most% = at most 20%, or at most 10% of the tan and / or 0 of the crude oil feed in the range of 0.001 to 0.5, 0 · The range is from 01 to 0.2, or from 0.05 to 0.001. In some specific examples, the present invention and one or more methods or compositions combining the present invention also provide a method comprising contacting crude oil feed fish with a catalyst and controlling the contact conditions to reduce the content of organic oxygen compounds. Of each! 'Which ... ⑷ reduces the content of selected organic oxygen compounds so that the oxygen content of the crude oil feed which has an oxygen content of up to 90% to 36 200535221; ⑻: right, at least one compound of the compound contains a carboxylic acid metal Salt; (c) at least one compound of the bismuth compound contains an alkali metal salt of a carboxylic acid; ⑷: at least one compound of the organic oxygen compound contains at least one compound of the acid metal, and at least one compound of the organic oxygen compound contains the compound Acid gold: where this metal includes one or more metals in the twelfth table of the periodic table; ⑴ = the oil product has an acidic organic compound content of up to $ ㈣ this = the organic compound content in the feed; and 蜮 ㈦ At least one oxygen-containing compound in the original η is an organic oxygen-containing compound produced from a cyclic burning acid or a non-rebel acid. In some specific examples, the present invention and one or more methods or compositions combining the present invention also provide a method comprising contacting a crude oil feed tray with a catalyst, wherein: at a temperature of- The crude oil enters, at least-the catalyst is contacted, and then contacted at a second temperature, and the contact conditions are controlled so that the first contact temperature is at least lower than the second contact temperature. ㈨ Under the first hydrogen absorption conditions and then at the second Under nitrogen absorption conditions, the cough crude oil feed is brought into contact with hydrogen. The temperature of the first extraction condition is at least lower than the temperature of the second extraction condition 3 (TC; at a temperature of _, the crude oil feed is contacted with at least- Medium contact, then contact at the second temperature, control the contact conditions so that the first-contact temperature is at most lower than the second contact temperature fan. C. 产生 generate hydrogen during the contact; ⑷ 纟 generate hydrogen during the contact, and control the contact conditions so that The crude oil feed is allowed to absorb at least a part of the produced gas; ⑺ 2 The crude oil feed is contacted with the first and second catalysts, and the contact of the crude oil feed with the first catalyst forms a phase crude product, where this initial original The product has 37 200535221 The crude oil feed is contacted with-or more than one type of bed reactor; make the-or more catalysts are sharp touches: after contact with additional catalysts; after contact, in ^^ Contact with _ catalyst for cubic meters of crude oil: contact the additional catalyst with each contact to make the crude oil feed with:

(M) The opposite of the oil feed ㈣ and the money maker ㈣ is at the i-th; T feed is contacted with the catalyst at the first temperature, and then the temperature tr is contacted with the catalyst to control the contact conditions so that the first ^ 1 is lower than: temperature 3G ° C; 产生 generates hydrogen during the contact, so that the crude oil feed is attached to the boat as the 4 t main soil and the catalyst is sucked up;, ==, control the contact conditions so that the Feed the crude oil at a temperature of 2 = chlorine; and / or subsequently contact the catalyst at a temperature of ηη7 at a second temperature to control the contact conditions so that the degree of exposure is at least 1801: 〇

In some specific cases, the method or composition of the present invention is also: hair month < or more than one or more catalysts contact, two of the methods' which include the crude oil feed and-Γ Γ oxygen cut oxygen ㈣, oxygen ㈣, oxidation dream, Oxygen picker or its mixture, the catalyst is a supported catalyst ': This method still includes at least one catalyst called Qian before the vulcanization, and / or (e) the at least _insert_ catalysts Tied in a fixed bed or suspended in the original 38 200535221 oil feed. In several specific examples, the present invention and a combination of the methods of the present invention also provide a method that includes feeding crude oil into And at least one of the catalysts, the at least one catalyst being a loaded catalyst or a bulk metal catalyst, the loaded catalyst or a bulk metal catalyst ... containing one or Multiple metals, one or more compounds of columns _ or multiple metals, or mixtures thereof, in columns 5 to 10 of the Periodic Table; (b) at least 0.0001 g, 0.0001 to 0.6 g, or 0.001 to 0 per gram of catalyst 3 grams of one or more metals in columns 5 to 10 of the periodic table, in columns 5 to w of the periodic table One or more compounds of one or more metals, or mixtures thereof; (c) one or more metals including blocks 6 to 10 of each periodic table, one or more compounds of one or more metals of periodic table 6 to T, or Mixtures; (d) one or more metals including one or more of the seventh to tenth of the power table, one or more compounds of the seventh group of metals of the periodic table, or a mixture thereof; (e) in: g catalyst contains 0 · 00〇1 to 0.6 grams or 0.001 to 0.3 grams: week ^ = = 7 to 10 blocks of one or more metals, Periodic Table 7 to 丨 ❻ one or more metals 6 -1 cycle, or evening compounds , Or mixtures thereof; (f) containing-or up to 6 bars-or more metals, the first compound of the Periodic Table 5 to 6 of the periodic table, or mixtures thereof; (g) one-, metal containing metals , Block 5 of the periodic table-or more compounds or compounds, or pots containing at least 0〇ΛΛ1 A Feiba * *, (h) in the mother gram catalyst in the evening 0_〇00〇1 gram, 〇. 0001 to 0.6 g to 0.1 g, Shi η where υ · υυι to 0.3 g, 0.005 d or 0.001 to 0.08 g: the period 矣 筮 s is absorbed from the metal, week Periodic Table SW One or more cousins of Periodic Table 5-or more of metal-or compounds, 39 200535221 or mixtures thereof; (i) 4 u) Contains No. 6 of the Periodic Table ό 拦 — or 6 or more metals, perimeters; (j) 0.0000 g per gram of catalyst, or a mixture of 0.005 to 〇i ancient Λ A main 0.6 g, 0.001 to 0 · 3 • ϋ · 01 to 0.08 incense >, net # + or more metals, a compound of the 6th column of the J table this week, or a mixture thereof; ik〗 ^ or of a metal —Or one or more genus, one or more of gold or mixtures thereof in column 10 of Periodic Table 13—Column 10 of Periodic Table: — — or more metals — or more compounds, to 0.003 gm catalyst contains 0.00. 〇1 to 0.6 grams or 0.001 main: · 3 charge: one or more metals, one or more of the present compounds, or compounds, or mixtures thereof, in the tenth block of the periodic table; (m ) Bao Xi or Xi a vanadium compound, or a mixture thereof; (η) contains nickel, a 5: a kind of nickel compound 'or a mixture thereof; (. ) & Contains Cobalt,-or more Cobalt to 0 1 Gypsum ·, · Molybdenum, into a variety of molybdenum compounds, or mixtures thereof; (r) compounds; (s) per gram of contact or Mixture · '(P) contains molybdenum, one or more Gu compounds, or a combination thereof; (cl) contains 0.001 to 0.3 g or 0.000 ί to * 0 · 1 g per gram of catalyst ·· Molybdenum, a saccharin and sulphate compound; m sentence, or more tungsten compounds, or more metals and its containing cranes,-or more crane compounds, or a mixture thereof: from 0.001 to 0.3 g : Crane, one = compound; (t) one or more metals containing column 6 of the periodic table and one or more metals of column / 0, wherein the metal in column 10 and the metal in column 6 < The ear ratio is 1 to 5; ⑻ contains one or more compounds of one or more elements in column 15 of the periodic table, or more, 4, 5, or 8; (v) per gram The catalyst contains 0.00001 to 0.06 grams: one or more of the elements listed in Table 15, one or more compounds of the type i element in column 15 of the periodic table, or a mixture thereof; (w) phosphorus, i 200535221 A stone compound, or a mixture thereof · Plant, —— 乂 this article, (X) contains up to 0j grams of α alumina in the master gram catalyst; and / or fv, Tai 夂 * 金 Η 丄 and (y) in the master gram catalyst It contains at least 0.5 arsine alumina. In some specific examples, the present invention and the combination of the present day and month or more: the method or the composition also provides a method for forming a catalyst, including combining a carrier with one or more metals to form a carrier / metal mixture, wherein the Carrier pack 3 is oxidized at least thoroughly. The heat treatment is carried out at a temperature of c. The carrier / metal is oxidized, and further includes: (i) combining the carrier / metal mixture with water to form a paste, and extruding the paste; The alumina is obtained by heat-treating alumina at a temperature of 0; and / or the catalyst is vulcanized.

In some specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide a method comprising contacting a crude oil feed with one or more catalysts, wherein the pore size distribution of the one or more catalysts Have: at least 60 A, at least 90 A, at least 180 A, at least 200 A, at least 230 A, at least 300 people, at most 230 A, and at most 500 , Or a median aperture in the range of 90 to 180 A, 100 to 140 A, 120 to 130 A, 230 to 25〇A, 180 to 500 A, 230 to 500 A; or 60 to 300 A; (b ) At least 60% of the total number of pores have a pore size in the range of 45 people, 35 A, or 25 A; (c) at least 60 m2 / g, at least 90 m2 / g, at least 100 m2 / g, at least 120 m2 / g, at least 150 m2 / g, at least 200 m2 / g, or at least 220 m2 / g of surface area; and / or (d) at least 0.3 cm3 / g, at least The total volume of all pore diameters of 0.4 cm3 / g, at least 0-5 cm3 / g 'or at least 0.7 cm3 / g. 41 200535221 In some specific examples, the present invention and a combination of one or more methods or compositions of the present invention also provide a method comprising contacting a crude oil feed with one or more X-loaded catalysts, wherein the carrier: (a ) Contains alumina, silica, silica-alumina, titania, zirconia, magnesia, or mixtures thereof, and / or zeolites; (b) contains gamma alumina and / or delta alumina; Contains at least 0.5 grams of gamma alumina; (d) at least 0.3 grams or at least 0.5 grams of Θ alumina per gram of support; (e) contains alpha alumina, gamma alumina, δ Alumina, theta alumina, or mixtures thereof; (f) containing up to 0.1 g of alumina per gram of support. ® In several specific examples, the present invention and those who combine one or more methods or compositions of the present invention also provide a vanadium catalyst: (a) having a pore size distribution with a median pore size of at least 60A; (b) containing a carrier, which The carrier contains thorium oxide, and the thallium catalyst has a pore size distribution with a median pore diameter of at least 60 A; and ⑷ contains one or more metals in the sixth table of the periodic table, and one or more of the one or more metals in the sixth table of the periodic table. Multiple compounds, or mixtures thereof; and / or (d) at least 0.001 grams per gram of catalyst: one or more metals in column 6 of the periodic table, one or more compounds in one or more metals in column 6 of the periodic table , Lu or its mixture. In several specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide a crude oil product having: ⑷ at most 0.1 0.001 to 0.5, 0.01 to 〇2; or 〇5 To 〇 ”TAN; 最多 in each gram of crude oil product is at most Q_ grams of organic acid metal salt in the form of metal and soil test metal; A Yidudu rabbit, (C) in the mother gram of crude oil products at most 0.0_2 grams of Nl / V / Fe; and / or at least one catalyst that is greater than 42 200535221 grams per gram of crude oil product but less than 0.01 grams. In several specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide one or more metal test salts of one or more organic acids: or more of the organic acid-or more metal test salts, Or a mixture thereof, (1), (2), (2), and (2) the test metal is bell, sodium, or potassium; and / or (b) the at least one alkaline earth metal is magnesium or calcium. In several specific examples, the present invention and those combining one or more methods or compositions of the present invention are also provided-锸 ^ ^ a / method, which includes contacting a crude oil feed with one or more catalysts to produce The total product of crude oil products, the method further comprises: (i) combining the crude oil product with the same or different crude oil feed to form a blend suitable for transportation; (ii) making the crude oil product the same or different from the crude oil feed The crude oil is combined to form a blend suitable for processing equipment; (i) fractionating the crude oil product; and (ii) rendering the crude product into one or more ethics, scoring at least 7 miles, and producing from the at least one fraction. Fuel for transportation. In some specific examples, the present invention and those combining one or more methods or compositions of the present invention also provide a supported catalyst composition, which contains at least 0.3 g or at least 0.05 g of tritium oxide per gram of carrier. Ming; 包含 contains δ alumina in the carrier; ⑷ contains a maximum of 0 μg of α alumina per gram of carrier; (d) has a pore size distribution with a median pore size of at least 23 OA; Pores with a pore volume of at least 0.3 cmVg or at least 0 7 cW / g; (f) a surface area of at least 60 mVg or at least 90 m2 / g; ⑻ containing one or more metals in the seventh to tenth of the periodic table, the periodic table One or more compounds of one or more metals of the seventh to tenth, or mixtures thereof; 43 200535221 (h) One or more metals containing a β of the periodic table, β < Multi-metallic, only one of the five columns of Shi Shao said one or more compounds, or a mixture of them. R, the catalyst contains 〇〇〇y '(1) in the mother 々c L 1 to 0 · 6 grams or 0.001 to 0 · 3 * ♦ · bucket, various 5th bar metal, ~, brother of one or l _, ·, a ~ or more than five column metal compounds, ω; ω includes periodic nasal μ or a mixture thereof

la ★ 々 'One or more metals in column 6 and one or more metals in column A of the weekly diary, one or more compounds in the schedule table 6 ^^, or mixtures thereof; (k) in each The gram catalyst contains 0, 0.001 U to 0.001 to 0.6 g or 0.001 to 03 or more of the 6th metal, 1 g of 1 metal, one or more 6th metal compound,

⑴ contains vanadium, a little bit of your milk 'or one or more vanadium compounds' or mixtures thereof; ㈣㈣ network' one or more indium compounds of each order, or mixtures thereof; (n) contains tungsten, one or A plurality of crane compounds, or mixtures thereof; (0) containing cobalt, a compound, or a mixture thereof; and / or, a nickel compound, one or more nickel compounds, or a mixture thereof.

In some specific examples, the present invention and the method or composition combining the present invention also provide a crude oil composition, which: (a) has a maximum of 1, a maximum of 0.5, a maximum of 0.3, or a maximum of Tan of 〇1; containing at least 0.001 grams of boiling range distribution of hydrocarbons between 95 C and 260 ° C per gram of composition; at least 0.001 grams, at least 〇. 〇5 grams' or at least 0.001 grams of Buddhism distributed hydrocarbons between 26 ° C and 320 ° C at 0.101 Mpa; and at least 0.001 grams boiling range distribution at 001 Mpa Hydrocarbons between 320 ° C and 650 ° C, (c) contains at least 0.0005 grams of basic nitrogen per gram of composition; (d) contains at least 0.001 grams or at least gram per gram of composition. · A total nitrogen amount of 0.001 g, and / or (e) a total mirror and vanadium amount of up to 0.0005 g per gram of the composition. 44 200535221 In several examples of If IY,, the present invention and the combination of the method or composition of the present invention may also be based on ... a crude oil composition containing-or multiple catalysts 5 the at least one 6η ί + 4- Dental catalysts: (a) Porosity distribution with a median pore size of at least 500 A, and another / Tenshi ^ 180 Α 180 Α, 100 to 140 people, 120 to ⑻; a median pore size of at least 90 Α , The pore size distribution has more than 60% of the total number of pores having a pore size in the 45A, 35, or M median pore size range; ⑷ has at least 100-, to, Bu- / g 'or at least 22. m2 / g surface area; ⑷ contains the carrier core; the carrier contains alumina, silica, silica_alumina, titania, zirconia, magnesia 'zeolite' and / or mixtures thereof; ⑷ contains the fifth to tenth periodic table 襕One or more metals, one or more compounds of the periodic table, or one or more compounds of the metal, or mixtures thereof; (f) one or more metals containing the periodic table ^ 5, one of the five or more metals of the periodic table, —Or multiple metals—or more compounds, or mixtures thereof; (g) contained in each gram of catalyst At least 0.0001 g of:-or more than 5th metal,-or more than 5th metal compound 'or a mixture thereof; (h) containing column 6 of the periodic table-or more metals, in column 6 of the periodic table One or more compounds or mixtures of one or more metals; (0 contains at least 0,0001 g per gram of catalyst. Brother:-or more of the 6th column metal, one or more 6th metal compounds, compounds (J) one or more metals containing one or more metals of the tenth column of the periodic table, one or more compounds of one or more metals of the periodic table, or a mixture thereof; and / or (k) One or more elements, one or more compounds of one or more elements in the column of the periodic table, or a mixture thereof. In a few specific examples, the characteristics of the specific embodiment of the present invention are as follows: 200535221 and other specific embodiments of the present invention. The features of the examples are combined. For example, the characteristics of the specific examples of the present invention can be combined with the characteristics of other specific examples μ. In further specific examples, crude oil products can be obtained by any of the methods and systems described herein. Specific in progress In the examples, additional features can be added to specific specific examples described herein. [Embodiment] Specific specific examples of the present invention will be described in more detail here. The terms used herein are defined as follows. "ASTM" refers to the US material test Standard. "API Specific Gravity" refers to the specific gravity of Aρι at 15.5t (60 ° F). Nano specific gravity is determined by ASTM method D6822.… The percentages of atomic hydrogen and atomic carbon of crude oil feeds and crude oil products are derived from AST M method D 5 2 91 1. Unless otherwise stated, the boiling range distribution of crude oil feed, total product, and / or crude product is determined by ASTM method D5307. Asphaltene refers to asphaltenes that are insoluble in pentane. The C5 asphaltene content was measured by ASTM method D2007. `` Column X metal '' means one or more metals of the periodic table χ and / or one or more compounds of one or more metals of the periodic table X, where X is the number corresponding to the periodic table ( For example 丨 to 丨 2). For example, "metal" refers to one or more metals in the sixth table of the periodic table and / or one or more compounds of one or more metals in column 6 of the periodic table. "Element in column X" refers to one or more compounds of one or more elements in the X column of the periodic table, and 46 200535221 / or Zhou "cousin X or one or more elements of the X column, and in the X series corresponds to Numbers of the periodic table (for example, 13 to 18). For example, "the 7L element in column 15々 refers to one or more elements of the 15th cycle of the periodic table and / or the 15th of Yiyi—or one of the multiple elements Or multiple compounds. — ’Within the scope of this application, the metal weight of a periodic table, the weight of a metal compound, the person who loves the Lord-Ben Ren ° ° Elementalization of the periodic table. 5 The reset of objects is calculated by the metal weight or element weight. For example, if

The mother gram catalyst is used (M gram of 〇03, then the amount of metal turned in this catalyst is 0.067 grams per gram of catalyst. 3 li is expressed as the weight fraction or weight based on the total weight of the substrate Percentage weight of ingredients in the matrix (such as crude feed, total product, or crude product). `` Wtppm, means parts per million by weight. "Crude feed / total product mixture" The mixture that was in contact with the catalyst during the period. "Distillate" refers to hydrocarbons with a lag range of 0 generations between 20 generations (Salix F) and 343 ° C (650T). The storage content is determined by the astm method D5307 "Heteroatom" refers to the oxygen, nitrogen, and / or sulfur contained in the molecular structure of a hydrocarbon. Heteroatom content is determined by ASTM method for E385 for oxygen and D for sulfur for 4. "Experimental nitrogen total Amount, refers to nitrogen compounds with less than 40. Basic nitrogen ("bn") is determined by astm method d2896. "Hydrogen source" means hydrogen, and / or compounds and / or when crude oil is fed and catalyst A compound that reacts in the presence of a compound to provide hydrogen to the crude feed. 47 200535221 Hydrogen sources can include, but are not limited to For hydrocarbons (eg _ UJ female C1 to C4 hydrocarbons, such as methane, ethane, propane, butane), water, or 1, 1, 4 compounds. Mass balance can be performed to estimate the crude oil feed The amount of net hydrogen provided by the compound in the catalyst. The compressive force required by the catalyst. Flat plate resistance measurement. Flat plate crushing strength refers to crushing strength by ASTM method D4179 LHSV refers to the volume liquid feed rate / catalyst The total volume is shown in hours. The total volume of the catalyst is calculated by summing up all the volume of the catalyst in the contact area, as described herein.

"Liquid mixture" means Bai Mo +,, Shi, > 5 before showing the quasi temperature and pressure (25 ℃, 0.101

MPa, hereinafter referred to as "STP ,," TA. ^ AJ Bu Feng composition of one or more compounds, or containing 纟 STP is liquid-or more compounds and solid under STP-or A combination of multiple compounds. The periodic table refers to the periodic table stipulated by the International Union of Pure and Applied Chemistry (IUPAC) in November 2003. "Metals in the form of metal salts of organic acids refer to alkali metals and alkaline earth metals. ,

词, arsenic, @ ’or a combination thereof. The metal content in the form of a metal salt of an organic acid was measured by ASTM method D1 3 1 8. Residual stone ('MCR') content refers to the amount of residual carbon left after evaporation and pyrolysis of the substrate. MCR content is determined by ASTM method 0453〇. "Naphtha" refers to the boiling range distribution Smoke composition between 38 ° c (100 F) and 200 C (392 F) at 0.101 MPa. The naphtha content is determined by the ASTM method D 5 3 0 7.

"Ni / V / Fe" means nickel, vanadium, iron, or a combination thereof.

Ni / V / Fe combination refers to the content of nickel, vanadium, iron, or a combination thereof. 48 200535221

The Ni / V / Fe content is measured by ASTM method D5708. "NmVm3" refers to standard cubic meters of gas per cubic meter of crude oil feed. The "non-carboxylic acid-containing organic oxygen compound" means an organic oxygen compound containing no carboxyl group (-C02-). Non-carboxylic acid-containing organic oxygen compounds include, but are not limited to, ethers, cyclic ethers, alcohols, aromatic alcohols, ketones, aldehydes, or combinations thereof, which do not contain a carboxyl group. By "non-condensable gas" is meant a component that is gaseous under STP and / or a mixture of these components. "P (peptide) value" or "P value" means a value indicating the tendency of asphaltenes to flocculate in a crude oil feed. The measurement of the P value is described by J. J. Heithaus in "Measurement and Significance of Asphaltene Peptization" described in "/ ⑽r_ / 〇 / Institute of Petroleum, Vol. 48, Number 458, February 1962, pp. 45-33. "Aperture diameter", "median pore diameter" and "pore volume" refer to the pore diameter, median pore diameter, and pore volume determined by ASTM method D4284 (mercury porosity method at a contact angle of 140 °). A micromeritics® A9220 instrument (Micromeritics Inc., Norcross Georgia, U.S.A.) can be used to determine these values. "Residue" means a component with a boiling range distribution above 538 ° C (1000 ° F), as determined by ASTM method D5307. "SCFB" means the standard cubic feet of gas in a barrel of crude oil feed. The "surface area" of the catalyst was measured by ASTM method D3663. "TAN" refers to the total acid value, expressed in milligrams of KOH ("mg") per gram ("g") of the sample. TAN is measured by ASTM method D664. "VGO" refers to hydrocarbons with a boiling range distribution between 343 ° C (650 200535221 F) and 538 C (1_τ) at 0.101 MPa. The vg0 content was determined by the μD. method D5307. "Viscosity" means at 37.8 t⑽. F) Dynamic viscosity. The viscosity is measured by ASTM method 0445. In the case of this application, it should be understood that if the values obtained for the properties of the tested substrate are outside the limits of the test method, the test method may be modified and / or re-authorized to test such properties. Crude oil can be produced and / or dried in the self-contained structure, and then freshened. Crude oil may include crude oil. Crude oil is usually solid, semi-solid, and / or liquid spring. Stabilization may include, but is not limited to, removing non-condensable gases, water, salts ', or combinations thereof, in the crude oil to form a stable crude oil. This type of stabilization may often occur at or near production and / or retorting sites. Stable crude oils typically have not been steamed and / or branched in processing facilities to produce multi-components with specific boiling range distributions (e.g., naphtha, fractions, vg0, and / or lubrication: origin). Distillation includes, but is not limited to, atmospheric distillation and / or vacuum distillation. Undistilled and / or unfractionated stable crude oil may contain components having a carbon number greater than 4 per gram of crude oil in an amount of at least 0.5 grams. Examples of Shandong stable crude oil include whole crude oil, distillate crude oil, desalted crude oil, desalted distillate crude oil, or a combination thereof. "Distillate residue" refers to crude oil that has been processed and therefore has been removed at least-partly with a boiling point below 35 at G.1G1 Mpa. 〇 (95 at 1 atm). Typically, distillate crudes have such ingredients in amounts of up to 0.1 g, up to 0.05 g, or up to 0.02 g per gram of distillate. The nature of a number of stable raw materials by which permissible stable crude oil is transported by wheeled carriers (such as 50 200535221 pipelines, trucks, or ships) to conventional processing equipment. Other crude oils have one or more inappropriate properties that make them unfavorable. Inferior crude oil may be unacceptable for transportation vehicles and / or processing equipment, and therefore will give the inferior crude oil a low economic value. This economic value may be like thinking that the production, transportation, and / or processing of a container containing inferior crude oil is too expensive. The properties of inferior crude oil may include, but are not limited to: a) a TAN of at least 0.1, at least 0.3; b) a viscosity of at least 10 cSt; c) an API specific gravity of up to 19; d) a total Ni / V / Fe content per Gram of crude oil has at least 0.2 g or at least 0.0001 gram of Ni / V / Fe; e) the total content of heteroatoms is at least 0.005 grams of heteroatoms per gram of crude oil; f) the content of residues per gram Crude oil has at least 0.01 grams of residue; g) C5 asphaltene content of at least 0.04 grams of q asphaltene per gram of crude oil; h) MCR content of at least 0.002 grams of MCR per gram of crude oil; i) organic acids The metal content in the form of a metal salt is at least 0.00001 grams of metal per gram of crude oil; or j) a combination thereof. In several specific examples, the 'inferior crude oil' may contain at least 0.2 g of residue, at least 0.3 g of residue, at least 0.5 g of residue, or at least 0.9 g of residue per gram of inferior crude oil. In several specific examples, inferior crude oil may have a tan in the range of 0.1 or 0.3 to 20, 0.3 or 0.5 to 10, or 0.4 or 0.5 to 5. In certain specific examples, inferior crude oil may have a sulfur content of at least 0.05 g, at least 0.00 g, or at least 0.02 g per gram of inferior crude oil. In several specific examples, inferior crude oil has properties including, but not limited to: a) a TAN of at least 0-5; b) an oxygen content of at least 0.005 grams of oxygen per gram of crude oil feed; c) c5 The asphaltene content is at least 0.04 grams of Cs asphalt per gram of crude oil feed 51 200535221. η, + μ «For May shellfish, M is greater than the desired viscosity (for example, for crude oil feeds with an API specific gravity of at least 10) Words > ιο ″; metal content in the form of a metal organic acid salt is at least 10,000 grams of metal per gram of crude oil; or f) a combination thereof. Inferior crude oil may be included in each gram of inferior crude oil. : At least 0.001 g, at least 0.005 g, or at least 0.001 g of a hydrocarbon having a boiling range distributed between 90 ° C and 200 ° C at 010 mρ & at least 0.01 g, At least 005 grams, or at least 0.001 grams of a hydrocarbon having a distribution between 200 ° C and 300 ° C at 0.11 MPa; at least 0.001 g, at least 0.005 g, or Hydrocarbons with a boiling range distribution of at least 0.001 g between 300 ° C and 400 ° C at 0.101 MPa; and at least 0.001 g, at least 0.005 g, or to 〇ιιgram boiling range distribution of hydrocarbons between 400 ° C and 650 ° C at 0.101 MPa. Inferior crude oil may include per gram of inferior crude oil: at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams of boiling Hydrocarbons with a range of up to 100 ° C at o.ioi MPa; at least 0.001 g, at least 0.005 g, or at least 0.001 g of boiling range distribution between 0.1 ° C and 200 ° C at 0.101 MPa Hydrocarbons; at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams of hydrocarbons having a boiling range distribution between 200 ° C and 300 ° C at 0.101 MPa; at least 0.001 grams, at least 0.005 grams, or at least 0.01 grams boiling range distributions Hydrocarbons between 300 ° C and 400 ° C at 0.101 MPa; and a boiling range distribution of at least 0.0001 g, at least 0.005 g, or at least 0.01 g between 400 ° at 0.101 MPa Hydrocarbons between C and 650 ° C. In addition to the higher boiling point components, a number of inferior crudes may contain at least 0.001 grams, at least 0.0005 grams, or at least 0.01 200535221 grams of boiling range per gram of inferior crude oil. Hydrocarbons up to 100 ° C at 0.101 MPa. Typically, inferior crude oil has the most per gram of inferior crude oil. 0.2 g or a maximum of 0.1 g of this hydrocarbon content. Several poor crude oils may contain at least 0.001 grams, at least 0.005 grams, or at least 0.001 grams of boiling range distribution per gram of poor crude oil. Hydrocarbons of at least 200 ° C at .101 MPa. Several inferior crudes may contain at least 0.0000 g, at least 0.005 g, or at least 0.01 g of a hydrocarbon having a boiling range distribution of at least 650 ° C per gram of inferior crude. Examples of inferior crudes that can be processed using the methods described herein include, but are not limited to, crudes from the following regions of the world: U.S. Gulf Coast and southern California, Canada Tar sands, Brazilian Santos and

Campos basins, Egyptian Gulf of Suez, Chad, United

Kingdom North Sea, Angola Offshore, Chinese Bohai Bay, Venezuelan Zulia, Malaysia, and Indonesia Sumatra. Processing of poor quality crude oil can enhance the properties of the poor quality crude oil so that the crude oil is acceptable for transportation and / or processing. The crude oil and / or inferior crude oil to be processed is referred to herein as the "crude feed". This crude feed can be a distillate crude as described herein. Crude products derived from processing crude feeds as described herein are generally suitable for transportation and / or processing. The properties of crude oil products produced as described herein are closer to the corresponding properties of West Texas Intermediate crude oil than the crude oil feed, or closer to the corresponding properties of Brent crude oil than the crude oil feed, thereby improving the crude oil feed Economic Value. This type of crude oil product can be refined with little or no pretreatment, thereby improving the refining efficiency and removing impurities. Pre-treatment may include desulfurization, demetalization and / or atmospheric distillation to remove

= The processing of the crude oil feed of the present invention may include contacting the crude oil feed with the catalyst in a contact zone and / or a combination of two contact zones. In the contact zone, at least one property of the crude oil feed may be altered by contacting the crude oil feed with one or more catalysts compared to the same properties of the crude oil feed. Yu Qiang actually shot and contacted in the presence of a hydrogen source. In several specific examples, the ' hydrogen source provides a relatively small amount of hydrocarbon—or multiple hydrocarbons—to the original to react under specific contact conditions τ. ° FIG. 1 is a simplified diagram of a contact system 100 including a contact area 102. The crude oil feed enters the contact zone 102 via a conduit 104. The contact zone may be a reactor, a trowel, multiple parts of the reactor, or a combination thereof. Contact area

Examples include stacked bed reactors, fixed bed reactors, ebullated bed reactors, continuous stirred tank reactors ("CSTR,"), fluidized bed reactors, spray reactors, and liquid / liquid contactors. In a specific embodiment, the contact system is located or connected to offshore equipment. In the contact system 100, the contact of the crude oil feed with the catalyst may be continuous or batch. This contact zone may contain one or more catalysts (eg, Two catalysts). In several specific examples, the contact of the crude oil feed with the first catalyst of the two catalysts can reduce the TAN of the crude oil feed. The crude oil feed that has been reduced by the TAN and the first catalyst Subsequent contact is to reduce the heteroatom content and increase the API specific gravity. In other specific examples, after contacting the crude oil feed with one or more catalysts, the TAN, viscosity, Ni / V / Fe content, and heteroatom content of the crude oil feed歹 歹 @ @content, API gravity, or a combination of these properties will change at least 10% compared to the same properties of the crude oil feed 2005 200535221. In the example, the contact area in the contact area is 10 to Λ at 60 total oil feed volume. In the contact area of $ 3G to 4G% by volume, Zhongyuan, 隹 ^ will be in several specific examples, catalyst and crude oil ^ spoon of water in each 100 grams of crude oil feed in the contact area may include 001 GIGANET. • 005 to 5 grams, or 0.01 to 3 grams of catalyst. The contact conditions in the driver can include, but are not limited to, temperature, pressure, medium :: crude oil feed flow, or a combination thereof. Controls several specific Examples, and 1 conditions to produce characteristic crude oil products. The temperature in the contact zone is in the range of 50 to 500 C, 60 to 440 ° C, 70 to 430 ° C, or 80 to E. In the contact zone The pressure can be distributed in the range of 0 "to 20 MPa, MPa '4 to 10 MPa, or 6 to 8 MPa. The LHSV of crude oil is usually distributed in the range of 0-1 to 30, 0.5 to by, 0.5 to 20 to 15 h, or 2 to 10 h · 1. In several specific examples, the LHSV is at least 5 f, at least n w, at least f, or at least 20 ir1. In the specific example where the hydrogen source is supplied as a gas (such as hydrogen), the ratio of the gaseous hydrogen source to the crude oil feed is typically distributed from 01 to 100,000 NmVm, 0.5 to 10, _ Nm3 / m3, i to 800 Nm3 / m3, 2 to $ '

NmW ′ 5 to 3,000 NmVm3, or 10 to _ Nm3 / in3 range of contact with the catalyst. This hydrogen originates from several specific examples in combination with a carrier gas and recycled through the contact zone. The carrier gas may be, for example, f, & m ^ ^ ^, and / 戍 lice. The carrier gas can promote the flow of crude oil feed and / or gas in the contact zone. The carrier gas can also enhance mixing in the contact zone. Yu-source flow in Yuqian concrete 55 200535221 In the example, a hydrogen source (such as hydrogen, pinane or ethane) can be used as a carrier gas and recycled through the contact zone. The hydrogen source may enter the contact zone 102 concurrently with the crude oil feed in the conduit 104 or via the conduit 106, respectively. In the contact zone 102, the contact of the crude oil feed with the catalyst produces a crude product containing crude oil, and in a few specific examples a total product of gas. In several specific examples, the carrier gas system is combined with a crude oil feed and / or a hydrogen source in a conduit 106. The total product can leave the contact zone ⑽ and enter the separation zone 108 via the conduit 110.

In the separation zone 108, crude oil products and gases can be separated from the total product using generally known separation techniques, such as gas-liquid separation '. Crude oil products can exit the branch 108 through the conduit U2, and then be transported to a transportation vehicle, pipeline, storage container, refined hemp, other processing areas, or a combination thereof. The gas may include a gas generated during the treatment (e.g., hydrogen sulfide, carbon dioxide, and / or oxygen = anorexia), a source of hydrogen and / or a carrier gas. Excess gas can be recycled to the contact system 100, which can be purified 'and transported to other processing areas, storage containers, or a combination thereof.

In the specific example, contacting the crude feed with the catalyst to produce the total product is performed in two or more contact zones. This total product can be separated to produce crude oil products and gases. Figures 2 to 3 are simplified diagrams of specific examples of contact systems including two or three contact areas. In s 1 Λ < ^ θ 2A and 2B, the contact system 100 includes contact areas 102 and 114. Figures from and 3B are included. Contact area 1 () 2, 114, 116. In Figs. 2A and 3A, the contact areas 102, 114, and 116 are depicted as individual joints in a reactor. The crude oil feed line enters the contact area 102 via the conduit 04 2005 200521. In several specific examples, a carrier gas is combined with a hydrogen source in a conduit 106 and introduced into the contact zone as a mixture. In certain specific examples, as shown in FIGS. 1, 3A, and 3B, the hydrogen source and / or carrier gas may pass through the conduit 106 and / or via the conduit 106, in a direction opposite to the flow of crude oil feed, as opposed to crude oil. The feed enters one or more contact zones, respectively. Addition of a hydrogen source and / or carrier gas in reverse to the flow of the crude oil feed can improve the mixing and / or contact of the crude oil feed with the catalyst.

In the contact zone 102, the contact of the crude oil feed with the catalyst generates a feed stream. This raw material stream flows from the contact area 102 to the contact area 14. In Figs. 3A and 3B, the 'feed stream' flows from the contact zone 丨 4 to the contact zone 丨 6. The contact areas 102, 114, 116 may include one or more catalysts. As shown in FIG. 2β, the raw material stream leaves the contact area 102 through the conduit 118 and enters the contact area 114. As shown in FIG. 3B, the raw material stream leaves the contact area π 4 through the conduit 118 and enters the contact area 丨 6.

The feed stream may be contacted with additional catalyst in the contact zone 114 and / or the contact zone 116 to form a total product. The total product leaves contact zone 114 and / or contact zone j via conduit 110 and enters separation $ 108. Crude products and / or gas systems are separated from the total products. The crude product leaves separation zone 108 via conduit 112. —Figure 4 is a simplified illustration of a specific example of the separation zone upstream of the contact system. “Shell crude oil (distilled or non-distilled) enters the separation item via the guide f 122. = = & 12G towel, at least-part of the disadvantages f Crude oil is separated using two known techniques (such as mouth cloth, membrane separation, decompression). For example, water can be at least partially dislodged from inferior crude oil. 57 200535221 / τρ. In another example, a wm training knife can be used to at least partially separate crude oil from crude oil to produce a crude feed. In several specific examples [at least-part of naphtha and compounds more volatile than naphtha were separated from inferior crude oil. In several specific examples, at least a portion of the separated components are separated from the zone 120 via the conduit 124. The crude oil feed known from the knife-off zone 120 has a boiling range distribution of at least ⑽ in several specific examples. c, or in some specific examples, a mixture of ingredients whose boiling range is 120 C. Typically, the separated crude oil feed contains a boiling range distribution between 100 and 1000. (:, A mixture of ingredients of 120 to 900 c or 200 to 800 ° c. At least a part of the crude oil feed, the guide & 126 leaves the separation zone 12G into the contact system ⑽ (see contact in Figures 1 to 3) Zone) for further processing to produce crude oil products. In several specific examples, the separation zone 120 may be located upstream or downstream of the desalination unit. After: the original W leaves the contact system through the product line via conduit i J 2. In the example, the crude oil product is made the same as or different from the crude oil feed. For example, t, the crude oil product can be combined with M with different viscosities to thereby produce a viscosity between the viscosity of the crude product and the viscosity of the crude oil. In another example, a crude product may be blended with crude oil having different TANs, thereby producing a product having a tan between the crude product and β mAN. This blended product may be suitable for transportation and As shown in Fig. 5, in a specific embodiment, the crude oil feed enters the contact system 100 via the guide 104, and at least a portion of the crude product leaves the receiver via the 58 200535221 conduit 128. The system 100 is introduced into a blending zone 130. In the blending zone 13, at least a portion of the crude oil product is combined with one or more industrial production streams (eg, hydrocarbon streams, such as naphtha produced by separating one or more crude feeds). Oil), crude oil, crude oil feeds, or mixtures thereof to produce blended products. Industrial production streams, crude oil feeds, crude oils, or mixtures thereof are directed into the blending zone 130 or such blending zone via conduit 132 Upstream. The mixing system can be located at or near the blending zone 130. The blended product can meet the product specifications specified by the refinery and / or conveyor. The product specifications include, but are not limited to, the specific gravity, tan, viscosity, or combinations thereof The range or limit of the blended product is via the conduit 1 3 4 Φ leaving the blending area 130 for transport or processing. In FIG. 6, the inferior crude oil enters the separation area 120 through the conduit 122, as previously described. The inferior crude oil is separated to produce a crude oil feed. The crude oil feed then enters the contact system 100 through a conduit 126. At least several components of the inferior crude oil leave the separation zone 120 via the conduit 124. At least a portion of the crude oil The system exits the contact system 100 via the conduit 128 and enters the blending zone 13. Other industrial production streams and / or crude oil enter the blending zone 13G directly or via the conduit 132 to combine with the crude oil product to produce a blended product. Blended products It exits the blending zone 130 via a piping conduit 134. In several specific examples, crude oil products and / or blended products are delivered to refining and / or processing equipment. Crude oil products and / or blended products can be processed to produce industry Products, such as transportation fuels, heating fuels, lubricants, or chemicals. Processing may include distilling and / or fractionating crude oil products and / or complex products to produce-or multiple locations. In several specific examples, crude oil production: : Combined product and / or one or more fractions can be hydrotreated. '59 200535221 In several specific examples, the crude oil product has a TAN of at most 90%, at most 50/0, at most 30%, or at most 10% of the crude feed TAN. In several specific examples, the crude product has a TAN in the range of i to 80%, 20 to 70%, 30 to 60%, or 40 to 50% of the TAN of the crude feed. In a specific embodiment, the crude oil product has a TAN of at most 丨, at most 0.5 ', at most 03, at most 02, at most 01, or at most 0.05. The TAN of the crude product is usually at least 0.0000, and more often at least 0.001. In several specific examples, the ταν of the crude product may be in the range of 0.001 to 0.5, 0.001 to 0.02, or 005 to 0.001. In several specific examples, the crude oil product has a total Ni / V / Fe content of up to 90%, up to 50%, up to 10%, up to 5%, or up to 3% of the Ni / V / Fe content. This crude oil product has a total Ni / V / Fe content of 1 to 80%, 10 to 70%, 20 to 600/0 'or 30 to 50% of the Ni / V / Within the range of Fe content. In certain specific examples, the crude oil product has between 1 x 10 7 g to 5 X 10.5 g, 3 x 10-7 g to 2 x 1 0-5 g, or i x 1 0 per gram of crude product. Total Ni / V / Fe content in the range of 6 grams to 1 x 1 (T5 grams. In certain specific examples, this crude oil contains a maximum of 2 X 1 0.5 grams of Ni / V / Fe. In several specific examples 'The total Ni / V / Fe content of the crude oil product is 70 to 130%, and the Ni / V / Fe content of the crude oil feed is 80 to 120/0 or 90 to 110%. In several specific examples, the crude oil product has The total metal content in the form of organic acid metal salt is up to 90%, up to 50%, up to 10%, or up to 5% of the total metal content in the form of organic acid metal salt in the crude oil feed. In specific specific examples The crude oil product has an organic acid metal salt form of gold 60 200535221 is a total metal content of organic acid metal salt form in the crude oil feed in the range of i to 8G%, 1G to 28%, 2G to 6G%, or 3q to 50% of the crude oil feed. The range is within the range. Often: organic acids that form metal salts include, but are not limited to, carboxylic acids, thiols, imines, and phosphonates. Examples of carboxylic acids include, but Limited to naphthenic acid, phenanthronic acid and benzoic acid. The metal part of the metal salt may include alkali metals (such as lithium, sodium, and potassium) 'alkaline earth metals (such as magnesium, calcium, and barium), and the 12th metal (such as Ci and cadmium) , The 15th metal (such as arsenic), the 6th metal (such as chromium), or a mixture thereof. In a specific embodiment, the total content of the metal in the form of the organic acid metal salt per gram of crude oil product is There are 0, · 0000001 g to 0.0005 g of crude oil products, 0.03 g to 0.02 g ', or 0.00 g to 0.1 g of metal in the form of organic acid metal salt. In several specific examples, the organic acid metal salt of the crude oil product has a total metal content of 70 to 13 ()%, 8 () to, or 9 g to the organic acid metal salt in the crude oil feed. The total metal content in the form. In the specific example, the API ratio of the crude oil product produced by the crude oil feed and the catalyst under the contact conditions is / 4-π- 艏 ′, which is 70% to 130%. '90 to 110% 'or 100 to 13% of the crude oil feedstock. The specific gravity of the crude oil feed. The nano specific gravity is ^ buckle, 15 to 30, or 16 to 25. ^ In the specific example of the crude oil product, the crude oil product has a viscosity of at most ㈣, bulk srv, or a viscosity of 70% of the crude oil feed. Among several examples, Crude oil products have viscosities in the range of 10 to 60%, 20m, or 30 to 40% of the crude oil feed point. In a number of cases, the number of solid oil products in 2005 200535221 was' the viscosity of the crude oil products. V & is the viscosity of 90% of the crude oil feed, and the Apj of this crude product was observed on the same day; the specific gravity of 90, 1100_ was 70 to 130%, 80 to 120%, or 90 to 12 /. API weight of crude oil feed. For example, in the example, the crude oil product has a total heteroatom content of 50% at most and 10% at most. The heteroatoms in the feed will fly away from the crude heteroatoms at 5/0. In a specific embodiment, the crude oil product has a total heteroatom content of at least A 1%, at least 3G%, and at least the total heteroatom content of the crude oil feed of the shaft. . Or in some specific examples, the crude oil production is 90%, and the maximum is 50%. Zheng Xiyan 3 has the latest sulfur content. In specific examples of crude oil products Ai 2 to 10%, or at most 5%, the crude oil product has a sulfur content of at least 1% and a sulfur content of at least 30 / y feed. In some examples, the crude oil product has a sulfur content of at least 99% of the crude oil and 8 () to:%. . Or 90 to 90% of the crude oil feed contains 90% of the total nitrogen content of the crude oil product in the latest example; the total nitrogen content of the crude oil product may be at most two; is at least ", to; = the total nitrogen content of the actual crude oil feed 8〇 /。 Or at least 99% of the specific examples of the right ,; §, Shan Liyan 95% of the original, the basic nitrogen content of oil products may be up to 90%, up to 5% of crude oil. The nitrogen content of the raw material is expected to be greater than 2 ::: or the most oil product has a nitrogen content of 2; in the examples, the original is 1 / 〇, at least 30%, at least 62 200535221 80%, or at least 9 ^ Ma 99 /. Alkaline nitrogen content of crude oil feed. In several specific examples φ 〇〇〇 /, ^. 'The oxygen content of crude oil products may be at most Chuan / 0, which is more than 5000 / county 5% of $, FREE, # α is taken as 30%, up to 10%, or up to 3/0 of the crude oil route containing Hongdan Guba # 里. In specific examples, crude oil products and The oxygen content is at least 30%, at least 30%, at least 80%, or at least 99 /) of crude oil feed. In some specific examples, crude oil Produce The lice content of the product is within the range of 1 to 80. ^ 0 to 70%, 20 to 60%, or 30 to 50/0 of crude oil feed Hedan lice. In several specific examples ,

The final acid of the μ / product can be up to 90%, and the maximum temperature can be up to 90%, and the maximum is 1G%, or up to 5% of the carboxylic acid in the crude oil feed. For example, the crude oil product has a total carboxylic acid compound content of at least 1%, at least 1 n 0 /. Xi Ma 30 /., At least 80%, or at least 99% of the carboxylic acid in the crude feed Total acid compounds.

In several specific examples, selected organic oxygen compounds in a crude oil feed can be reduced. In several specific examples, the meta-acid and / or lauric acid metal salts can be chemically reduced before the non-carboxylic acid-containing organic oxygen compound. Carboxylic acids and non-fluorene-containing organic oxygen compounds in crude oil products can be identified by analyzing crude oil products using generally known spectroscopic methods (such as infrared analysis, mass spectrometry, and / or gas chromatography). This crude oil product has a maximum oxygen content of 90% in most specific examples, a maximum of 7%, a maximum of 7G%, or a maximum of 5G% of the oxygen content of the crude oil feed, and a maximum TAN of 9 for this crude product 0%, up to 70%, up to 50%, or up to $ 40% of the TAN of crude oil feed. In a specific embodiment, the crude oil product has an oxygen content of at least 1%, at least 63 200535221 μ ° 〇%, or at least "% of the crude oil feed oxygen content and the crude product has a TAN of at least 1%, ΤΑΝ of at least 30%, to Xiaozhen 80%, or at least 99% of crude oil feed. 'Besides, crude oil products can have m acid and / or rhenium metal oil. The maximum feed is rhenium, the most is dove, the most is guan = peach, the content of non-organic oxygen compounds is 7G to i3g% = to 120%, Or 90 $ lino / # m 10 / ° crude oil feed in the range containing non-carboxylic organic oxygen compounds. Lization In several specific examples, the crude product contains in its molecular structure grams of crude product with 0.05 to 0.15 grams or 009 to 013 grams of hydrogen. This crude oil product may contain in its molecular structure 0.8 to 0.9 grams or 0.82 to 0.88 grams of carbon per gram of crude product. The atomic hydrogen to atomic carbon ratio (H / C) of the crude oil product can be in the range of 70 to 130%, 80 to 120%, or 90 to ιιη% of the atomic H / C ratio of the crude oil feed. . The original + H / c ratio of the crude oil product within the range of the atomic H / C ratio of 30% of the crude oil feed shows that the hydrogen absorbed and / or consumed in the excess% is relatively small, and / Or hydrogen-based on-site production of crude oil products contains components in a certain boiling point range. In several specific examples, the 'crude oil product contains per gram of crude oil product: at least 0.0000 g, or a boiling range distribution of 0.001 to 0.5 g at a maximum of 0.10 MPa pyrotechnics, at least 0.0000 g, or 0.001-0.5 g boiling range distribution Hydrocarbons between 10 (rc and 20 (rc) at 0 MPa; at least 0.001 g, or 0.000 g ι to 0.5 g boiling range distribution hydrocarbons between 200 ° C and 300 ° C at 0.11 MPa; at least 0.001 g, or 0.001 to 0.5 g boiling range distribution 0 to 101 64 200535221 MPa Hydrocarbons between 300 ° C and 400 ° C; and at least o.ooi grams, or 0.001 to 0.5 grams of hydrocarbons with a boiling range distribution between 0.101 MPa and 400 ° C and 538 ° C. In a specific example, the crude oil product contains at least 0.001 grams of hydrocarbons with a boiling range distribution of 0.101 MPa per gram of crude oil product and a maximum of 100 ° C hydrocarbons and / or J. 0.001 grams of Fodang distribution between 0 and 200 at 0101 MPa ° C hydrocarbons.

In several specific examples, the crude product may contain at least 0.001 grams, or at least 0.01 grams of naphtha per gram of crude product. In other specific examples, the crude product may have a naphtha content of up to 0.6 grams per gram of crude product, or up to 0.8 grams. In several specific examples, the crude product has a distillate content of 70 to 130% ' 80 to 120%, or 90 to 110% of the distillate content of the crude feed. The distillate content of the crude product may be in the range of 0.001 to 0.5 g, 0.001 to 0.3 g, or 2000 g to 0.2 per gram of crude product.

In certain specific examples, the crude product has a vGO content of 70 to 130%, 80 to 120/100, or 90 to 110% of the crude oil feed. In several specific examples, the crude oil product has 0.00001 to 0.8 grams per gram of crude oil product, and has a VG in the range of 0.0001 to 0.5 grams, or 0.002 to 0.4 grams, or 0.001 to 0.3 grams. content. In several specific examples, the crude oil product has a residual content of 70 to 130%, 80 to 120%, or Qn wide, 490 to 110% of the crude feed. This crude oil product may have from 0.00000 to 0.88 grams, 0.0001 to 0.5 grams, η 0.005 to 0.4 grams, 0.001 to 0.33 grams, 65 200535221 in the Beigu π crude oil product. Residue content in the range of 005 to 0.2 g, or 0.01 to u g. In a specific embodiment, the crude product has an MCR content of 70 to

1 MCR content of 30%, 80% to 120%, or 90% to 110% of crude oil feed. At the same time, this product has a G asphaltene content of up to 90%, up to 嶋, or up to 50%. In the specific example, the A asphaltene content of the crude oil feed is determined to be at least 10%, at least 60%, or at least please. Of crude oil. 5 Cyanite content, while the war content of crude oil products is within the range of 1 to the mcr: amount of crude oil feed. In several specific examples, reduce the ~ calendar month quality content of crude oil feed while maintaining Relatively stable warfare content can increase the stability of the crude oil feed / total product mixture.-In several specific examples, the 05 asphaltene content and the mcr content can be combined to produce a viscosity that is in comparison to the high viscosity components in the crude oil feed. Mathematical relationship between high viscosity components of crude oil products. For example, the sum of the A-cyanine content of the crude oil feed and the MCR content of the crude oil feed can be expressed as s. The A asphaltene content of the crude oil product and the crude product The sum of the MCR content can be expressed as S. These sums (S, and S) can be compared to estimate the net reduction of high viscosity components caused by crude oil feed. The crude product S can range from 1 to 99%, 10 to 90%, or 20 to 80% of s. In several specific examples, the ratio of the MCR content to the C5 asphaltene content of the crude product is from 1.0 to 30, 12 to 20, or J 3 to Within the range of 1 · 9. In certain specific examples, crude oil products have the most MCR content 90%, up to 80%, up to 50%, or up to 10% of the MCR content of the crude oil feed. In several specific examples, the crude product has an mcr content of 66 200535221 and an amount of 1 to 80%, 10 to 70% '20 to 60%, or 30 to 50% of the MCR content of the crude feed. Crude oil products, in several specific examples, contain 0.0001 to 0 "grams per gram of crude product, 0.0000. 5 to 008 grams, or 0.01 to 0.05 grams of MCR. In several specific examples, the crude oil product contains greater than 0 grams, but less than 0.01 grams, 0.0001 to 0.001 grams, or 0.0000 grams per gram of crude oil product. The total amount of catalyst is from 0.0001 to 0.0001 grams. The catalyst can help stabilize the crude oil product during transportation and / or processing. The catalyst can inhibit corrosion, inhibit friction, and / or enhance the water separation capacity of the crude product. The methods described herein can be configured to add one or more catalysts described herein to crude oil products during processing. The crude oil products produced in contact with the contact system 100 have properties that are different from the properties of the crude oil feed. Such properties Can include, but is not limited to: a) lowering TAN; b) lowering Degrees; C) reduced total Ni / V / Fe content; d) reduced sulfur, oxygen, nitrogen, or combinations thereof; reduced residue content; f) reduced & asphaltene content; g) reduced MCR content; h) increased API specific gravity; o reduced metal content in the form of a metal salt of an organic acid, or j) a combination thereof. In several specific examples, one or more properties of the crude oil product may be selectively changed compared to the crude oil feed, while other properties are not changed or substantially unchanged. For example, it may be desirable to selectively reduce only the TAN in a crude oil feed without significantly altering the amount of other components such as sulfur, residues, Ni / V / Fe, or VGO. In this way, the hydrogen uptake during the contact can be "concentrated" according to the reduction of TAN, without affecting the reduction of other components. Therefore, although less hydrogen is used, the crude oil feed can still be reduced. TAN, because a smaller amount of this kind of hydrogen will also be used to reduce other components in the 200535221 crude oil feed. For example, if a poor quality crude oil has a high TAN, but the sulfur content is within the processing and / or transportation specifications Recipients, this type of crude feed can be processed more efficiently to reduce TAN without also reducing sulfur. The catalyst used in one or more embodiments of the present invention may include one or more bulk metals and / or One or more metals on the carrier. The metal can be in the form of an element or a metal compound. The catalyst described herein can be introduced into the contact zone as a precursor, and then becomes an active catalyst in the contact zone (for example, and (When sulfur and / or sulfur-containing crude oil feeds come into contact with precursors). The catalyst or catalyst combination used as described herein may or may not be a commodity catalyst. It covers the commodity catalysts used in this description. Examples include HDS3; HDS22; HDN60; C234; C311; C344; C411; C424; C344; C444; C447; C454; C448; C524; C534; DN110; DN120; DN130; DN140; DN190; DN18; DN800; DN3100; DN3110; DN3300; DN3310; RC400; RC410; RN412; RN400; RN420; RN440; RN450; RN650; RN5210; RN5610; RN5650; RM430; RM5030; Z; Z ;; Z763, available from CRI International, Inc. (Houston, Texas, US.A.). In several specific examples, the catalyst used to modify the properties of the crude oil feed contains one or more of columns 5 to 10 on the carrier. Metals. Columns 5 to 10 include, but are not limited to, vanadium, chromium, molybdenum, tungsten, manganese, chromium, baht, iron, cobalt, nickel, ruthenium, barium, osmium, osmium, iridium, indium, or mixtures thereof. The catalyst may have at least 0.0001 grams, at least 0.001 grams, at least 0.01 68 200535221 grams per gram of catalyst, or 0.0001 to 0.6 grams, 0.005 to 0.3 grams, 0.0000 grams to 0 grams, or 0.01 Total metal content from 5th to 10th to 0.08 grams. In several specific examples, the catalyst contains elements in columns 15 in addition to the 5th to 10th metal. Examples of elements in column 15 include phosphorus. The catalyst may have a total content of elements in column 15 in the range of o.oooooi to 0.001 g, 0.00001 to 0.06 g, 0.00005 to 0.03 g, or 0.0001 to 0.0001 g per gram of catalyst. Within range.

In a specific embodiment, the catalyst includes a column 6 metal. The catalyst may have at least 0.0001 grams, at least 0.01 grams, at least 002 grams and / or 0.0001 to 0.6 grams, 0.001 to 0.3 grams, and 0.05 to gram grams per gram of catalyst. , Or 0.01 to 0.08 grams of the total content of the 6th metal. In some specific examples, the catalyst contains 0.0001 to 2006 grams of the sixth column metal per gram of catalyst. In some specific examples, the catalyst includes elements in column 15 in addition to the sixth metal.

In some specific examples, the catalyst includes a combination of metal in column 6 and one or more metals in column 5 and or 7-10. Moore ratios of the 6th metal and the 6th metal can range from 0.1 to 20, 1 to 10, or 2 to 5. The mole ratio of the metal in the sixth column to the metal in the 7th to 10th may be in the range of 0 to 1, 1 to 10 ', or 2 to 5. In a few specific examples +, the catalyst includes elements in column 15 in addition to the metals in column 6 and one or more metals in columns 5 and / or 7 to 10. In other specific examples, the catalyst includes column 6 metal and column 1 () metal. In the catalyst, the molar ratio of the total amount of the shack and the sixth metal block can be in the range of i to 10, or. In a specific embodiment, the catalyst includes a fifth metal and a second metal. The molar ratio of the total amount of metal in column 10 to the total amount of metal in column 5 can be in the range of 1 to 10, or 2 to 5. In some specific examples, the 5th to 1G metal blocks are deposited on or on the carrier to form a catalyst. In some specific examples, a combination of 5th to 0th metal and 15th element is incorporated or deposited on a carrier to form a catalyst. In the specific example of metal and / or element loading, the weight of the catalyst includes all carriers, all metals and all elements. The support may be porous and may include a refractory oxide, a porous carbon-based material, a stone, or a combination thereof. : Pyrogenic oxides can include, but are not limited to, alumina, silica, silica_emulsified aluminum, titanium oxide, hafnium oxide, magnesium oxide, and mixtures thereof. The carrier can be # t t ^ Criterion Catalysts and Technologies LP (Houston, Texas, USA). Porous carbon-based materials include, but are not limited to, activated carbon and / or porous graphite. Examples of zeolites include gamma zeolite, zeolite, mordenite, zeolite, and magnesite. Zeolites can be obtained from industrial manufacturers, such as Zeolyst (Valley Forge, Pennsylvania, Us A). In several specific examples, carriers are prepared so that the carriers have an average pore size of at least 150 to 'at least 170 A' or at least 180 A. . In a specific embodiment, the carrier is prepared by forming an aqueous slurry of the carrier. In several specific examples ' acid is added to the slurry to facilitate extrusion of the slurry. Water and dilution 7 acids are added in the required amount and by the required method to provide the desired consistency of the water that can be separated. Examples of acids include, but are not limited to, nitric acid, acetic acid, sulfuric acid, and hydrochloric acid. The conventionally known catalyst extrusion method and catalyst cutting method are used to extrude and cut to form an extrudate. The extrudate may be S 5 to 260. (: Or heat treatment at a temperature in the range of 85 200535221 to 235 C for a period of time (such as 0.5 to 8 hours) and / or until the humidity of the extrudate reaches the desired value. The heat-treated extrudate can be at 800 to 1200 ° C or 900 to no 〇t

Further heat treatment at a temperature of 50 ° C. to form a support having an average pore size of at least 150 A. In a specific embodiment, the carrier comprises gamma alumina, hafnium oxide, alumina, alpha alumina, or a mixture thereof. The amount of γ alumina, δ alumina, carbon oxide, or a mixture thereof may be in the range of 0.000 to 0.199 g, 0.001 to 0.5 g, and 0.01 to 0.1 g per gram of the catalyst carrier. Or at most 0.01 g, which is determined by X-ray diffraction. In some specific examples, the carrier contains alone or in combination with other forms of alumina, Θ alumina content per gram of carrier is from 0.1 to 0.99 g, 0.5 In the range of 0.9 g, or 0-6 g, it is determined by X-ray diffraction. In some specific examples, the carrier may contain at least 0.1 g, at least 0.3 g, at least 0.5 g, or at least 0 · 8 grams of Θ alumina, which is determined by X-ray diffraction. The supported catalyst can be prepared using commonly known catalyst preparation techniques. Examples of catalyst preparation methods are found in the U.S. patent issued to Gabrielov et al. Case No. 6,218,333; 6,290,841 to Gabrielov et al .; 5,744,025 to Bon, and U.S. Patent Application Publication No. 20031 1 1391 to Bhan. In several specific examples, the carrier can be impregnated with metal to form Catalyst. In a specific embodiment, Prior to metal, the carrier is heat-treated at a temperature in the range of 400 to 1200, 450 to 1000 ° C, or 600 to 900 ° C. In some specific examples, the impregnation aid can be used in the preparation of catalyst 71 200535221 Used during the period. Examples of impregnation aids include EDTA, ammonia, or mixtures thereof. In some specific examples, ethylene glycol is added or incorporated into the catalyst. The reason is 5 to 10. The metal is heat-treated to form an open-formed carrier mixture ("cover ,,"). The top surface of the carrier of the uniform and agricultural genus is covered with metal to have a substantial or relative uniformity. All genus: Γ often gives catalysts Favorable catalytic properties. In each coating, the formed support tends to improve the catalytic activity of the catalyst. The special coating method for preparing the catalyst is described in the issued ... j patent patent application notice No. 3Gui39i. The 5th to 1 () metal and carrier can be mixed with appropriate mixing equipment to form a metal / carrier mixture. The 5th to 1th shed metal / carrier :: ,, I are mixed using appropriate mixing equipment. Examples of suitable mixing equipment Batch hopper,. _ Λ or trough, grinding mixer (such as batch or continuous = old impact type this combined machine, and any other generally known that can properly form columns 5-10) Mixer, or generally known device. In the case of the dioxin, the materials are mixed until the 5th to 10th metal is substantially uniformly dispersed in the carrier. In the specific example of the right, after the carrier and the metal are combined, the The catalyst is heat treated at a temperature of 150 to 750 t C '200 to 740 ° C, or 400 to 730 ° C. In the specific example on the right, the catalyst can be heat treated in the range of 40 ° C and 1000 ° C in the presence of hot air and / or oxygen-enriched air to remove volatiles f in order to At least-part of the 5th to 10th metal is converted into the corresponding metal oxide. 72 200535221; ,,, and: In other specific examples, the catalyst can be in the presence of air at 3 to 500 C (for example, less than 300 ° C, less than 400, or less than 500). 〇) heat treatment at a temperature within the fc range! A period of time from U to H to remove most of the volatiles without converting the 5th to 0th metal into metal oxides. The catalysts prepared by this method are commonly referred to as "uncalcined, catalysts. When combined in this way to form catalysts, the active metal can be substantially dispersed in the carrier. This type of catalyst The preparation of the catalyst is described in U.S. Patent No. 6,218,333 'to Gabrielov et al. And 6,29 (), 841 to Gabriel () v et al. _ In a specific embodiment, theta alumina The support can be combined with the 5th to 10th metal to form a Θ alumina support / column 5 to 10 metal mixture. The alumina support / column 5 to 10 metal mixture can be heat treated at a temperature of at least 400. Form a catalyst with a pore size distribution with a median pore size of at least 23 people. Typically, this type of heat treatment is performed at a temperature of up to 12,000. In several specific examples, the carrier (commercial carrier or as described herein) The carrier to be prepared) can be combined with the text catalyst and / or bulk metal catalyst. In some specific examples, the supported catalyst may include the 15th metal. For example, the supported catalyst and / or The bulk metal catalyst can be crushed to an average particle size of 丨 to 5 Rice, 2 to 45 microns, or 5 to 40 microns powder. The powder can be combined with a carrier to form an embedded metal catalyst. In several specific examples, the powder can be combined with the carrier and then extruded using standard techniques to Form a catalyst with a pore size distribution with a median pore size in the range of 80 to 200 A or 90 to 180 A, or 120 to 130 A. 73 200535221 Contacting the catalyst with the carrier in at least some of the specific examples allows for at least _ Metal is present below the surface of the buried metal catalyst (for example, it is buried in the carrier, which results in less metal on the surface than in other methods where the metal catalyst is not buried. In several specific examples, on the surface of the catalyst Those with less metal on it will extend the life and / or catalytic activity of the catalyst by allowing at least part of the metal to move to the surface of the catalyst during use. Metals can be used on the surface of the catalyst during contact between the catalyst and the crude oil feed. Invasion and move to the surface of the catalyst. The central and / or mixed catalyst components in several specific examples will make the structure of the 6th metal in the 6th emulsion crystal structure into the embedded catalyst structure. in The substantial random order of the 6 columns of metals. The 6th metal can be determined using powder X-ray diffraction. Compared with the order of the metals in the metal oxides, the order of the metal elements in the catalyst can be compared by comparing the 6th metal. The order of the metal peaks in column 6 in the x-ray diffraction spectrum of objects and the order of the metal peaks in column 6 in the X-ray diffraction spectrum of the catalyst are determined. From column 6 of the x-ray diffraction spectrum, this is an ancient pass From the perspective of broadening and / or pattern-free metal-related patterns, it is possible to estimate the metal in column 6, which is substantially randomly arranged in the crystal structure. # For example, barium trioxide and median pore size are at least ΐ8〇 The emulsified aluminum support of A can be combined to form an alumina / molybdenum trioxide mixture. Molybdenum trioxide has a well-defined pattern (such as a well-defined D, _D2G (), and / or D wave peak). The ... trioxide mixture can be at least 538. "1 00." and heat treatment at a temperature to produce a catalyst that does not show a molybdenum dioxide pattern in the x-ray diffraction spectrum (for example, without a Di⑽ peak). In several specific examples, the characteristics of the catalyst may be The parameters of the pore structure of the pore type include, but are not limited to, pore size, pore volume, surface area 200535221, or a combination thereof. The catalyst can be the right disk f ... ± L, and the total pore size distribution relative to the pore size. The median pore size of the pore size distribution It can be in the range of 30 to A, 50 to 500 a, or 60 to 300 A. In several examples, the mother gram catalyst contains at least 0.5 grams of gamma alumina catalyst and the J 碉 姝 /, there is a pore size distribution with a median pore size in the range of 60 to 200 A; 90 to 180 A, 100 to 140 A, or u to 130 A. In other specific examples, prepare the ancient ^ J τ mother gram catalyst contains at least 0.1 grams of Θ alumina catalyst having a median pore size of 180 to 500 A, 2㈧ to 3㈧A,

Or pore size distribution in the range of 230 to 250 A. In several specific examples, the median pore size of the pore size distribution is at least 120 A, to -A, ^ 2ooA ,, ^ 22〇a ^^ 2A3 / a; and ^ is at least 300A. Such median pore sizes are typically up to 1000 A.

The catalyst may have a pore size distribution with a median pore size of at least 60 people or at least 90 people. In some specific examples, the catalyst has a pore size distribution with a median pore size ranging from 9 () to 80A, 100 to 140 people, or 120 to 130 A, and at least 60% of the total pores in the pore distribution Numbers have pore sizes in the 45 A, 35, or 25 A median pore size range. In a specific embodiment, the catalyst has a pore size distribution with a median pore size ranging from 70 to 180 people, and at least 60% of the total pore size in the pore size distribution has a median pore size of 45 A, 35 A, or 25 A Aperture within range. In specific examples where the median pore size is at least 1 80 A, at least 200 people, or at least 230 A, more than 60% of the total number of pores in the pore size distribution has 50 people, 70 A, or 90 A Aperture within the median aperture range. In some specific examples, the catalyst has a pore size with a median pore size ranging from 1 80 to 500 A, 200 to 400 people, or 230 to 300 A. 75 200535221 cloth, at least 60% of the total number of pores in the pore size distribution Has a pore size in the 50A, 70A, or 90 A median pore size range. In several specific examples, the pore volume of the pores may be at least 0.3 cm3 / g, at least 0.7 cmVg, or at least 0.9 cmVg. In a specific embodiment, the pore volume of the pores may be in a range of 0.3 to 〇_99 cm3 / g, 0.4 to 0 μs 芏 8_8 cm3 / g, or 0.5 to 0.7 cm3 / g.

Catalysts with a pore size distribution having a median pore size in the range of 90 to 180 A may have at least 100 m2 / g, at least 120 m / g, at least 170 m2 / g, at least 220 in some specific examples m2 / g or at least the surface area. Such surface areas can range from 100 to 300 m2 / g, 120 to m2 / g '130 to 250 m2 / g, or 170 to 220 m2 / g. In a specific embodiment, a catalyst having a pore size distribution with a median pore size in the range of 180 to 300 people may have at least 60 m2 / g, at least 90 m2 / g ', and at least 100 m2 / g, a surface area of at least 120 m2 / g, or at least 27. Such surface areas can range from 60 to 300 m2 / g, 90 to 280 m2 / g, 100 to 270 m2 / g, or 120 to 250 m2 / g.

In a specific embodiment, the catalyst exists in a shaped form, such as a pellet shape, a cylindrical shape, and / or an extrudate. The catalyst typically has a flat resistance in the range of 50 to 500 N / cm '60 to 400 N / cm, 100 to 350 N / cm, 200 to 300 N / cm', or 220 to 280 N / cm. Crushing strength. In several specific examples, catalysts and / or catalyst precursors are 'Lized' using techniques known in the art (e.g. ACTICATTM method, CRI International, nC ') to form metal sulfides (before use). In several embodiments, the 'catalyst can be dried and then vulcanized. Alternatively, the catalyst may be vulcanized in situ by contacting Catalyst 76 200535221 2 crude oil feed containing sulfur compounds. In-situ cleavage can use gaseous thorium sulfide in the presence of hydrogen, or a liquid phase vulcanizing agent, such as organic & compounds (including alkyl sulfur, polysulfide compounds, thiols, and maple). The off-site vulcanization system is described in U.S. Patent No. 5,468,372 issued to Seamans et al. And 5,688,736 issued to Seamans et al. In a specific embodiment, the first type of catalyst ("the first catalyst,") contains the 5th to the 10th metal bound to the carrier and has a pore size distribution with a median pore size in the range of 15 to 250 A The first catalyst may have a surface area of at least m / g. The pore volume of the first catalyst may be at least 0.5 cm3 / g. The first catalyst may have the first type of gamma alumina content per gram. The catalyst has at least 0.5 grams of gamma alumina, and typically a maximum of 9999 grams of alumina. The first catalyst has, in several specific examples, from 0.0000 to 1.00 per gram of catalyst. The total metal content in column 6 in the range of 0 · 1 g. The first catalyst can remove a part of Ni / V / Fe in the crude oil feed, remove the tritium components that cause the TAN of the crude oil feed, and remove crude oil. At least a portion of the c5 asphaltene in the feed removes at least a portion of the metal in the form of an organic acid metal salt in the crude feed, or / and a combination. When the crude feed is in contact with the first catalyst, other properties (such as Sulfur content, VGO content, API specific gravity, residue content, or a combination thereof) can only show a relatively small amount Variations. The ability to selectively change the raw scallops of the crude oil feed, while only changing other properties in relatively small amounts, allows more efficient processing of the crude oil feed. In several specific examples, one or more of the first catalysts may be in any order In a specific specific example, the second type of catalyst ("the second type of catalyst,") contains columns 5 to 10 of the metal combined with the carrier, and has a median pore size in the range of 90 to 180 77 200535221 A Pore size distribution. The pore diameter of the second catalyst =: the number of pores has a pore diameter in the range of the median pore diameter. In the second case, the contact between the lower crude oil feed and the second catalyst can produce a crude oil product that has significant changes compared to the same properties as the crude oil, and other crude oil products with only small changes in other properties. In several specific examples, a source of hydrogen may be present during the contact.

The second catalyst can reduce at least a part of the TAN that causes the crude oil feed to cause at least a part of the relatively high viscosity component, and reduce the Ni / V / Fe content from the original to the J-part. In addition, the contact of the crude oil feed with the second catalyst can produce a crude product with a slightly changed sulfur content compared to the sulfur content of the crude oil feed. For example, a crude oil product may have a sulfur content of 70% to 130% of a crude oil feed. The crude oil product may also show only relatively small changes in the fraction content, VG0 content, and residue content compared to the crude oil feed.

— In several specific examples, the crude oil feed may have a relatively low amount (e.g., up to 50 wtppm), but a relatively high metal content in the form of TAN, asphaltene content ', or a metal salt of an organic acid. Relatively high #tantans (such as TAN of G.3) may make crude oil feed unacceptable for transportation and / or refining. Poor crude oils with relatively high c5 asphaltene content may show lower stability during processing compared to other crude oils with relatively low c5 asphaltene f content. The contact between the H crude oil feed and the second catalyst is removable. 'The acid content of the TAN and / or q asphaltenes in the crude feed. In several specific examples, reducing (: 5 asphaltenes and / or the viscosity of the ingredients that cause TAN compared to the viscosity of crude oil feeds' may reduce the viscosity of the crude feed / total product mixture by 78 200535221. Used in specific specific examples to treat The crude oil feed described in this article; the stability of the catalyst-or multiple-composition mixture can improve the minimum net uptake of the total product / crude oil production. In the stomach catalyst dance, the hydrogen that provides crude oil feed is used in several specific In the example, the first one makes the carrier washer &#; the second type of catalyst ("the third catalyst,") can be made by the carrier and the 6 metal precursor can be-or more jr catalyst precursor In the presence of the catalyst ㈣4 compound in the presence of a compound below t (for example, less than 482 ° C); the pimple sacral irradiance has not been held for a relatively short period of time to produce a Three kinds of catalysts. Industry ^, /, i and §, the catalyst precursor system is heated to the time. For specific specific wealth, t kinds of catalysts can have ㈣i to ask for 5 to 0 0.008 in the master gram catalyst. To 〇〇1 Bang Xi Fan Rong • (The content of the 15th bar element in the range of H grams. The third catalyst ::: 理 本When the crude oil is fed, it can show significant live stability. In several specific examples, the catalyst precursor is based on one or more sulfur, and the presence of the compound τ is heated at a temperature lower than ㈢. The first catalyst can reduce the formation of at least a part of the TAN of the crude oil feed, reduce at least a part of the metal in the form of a metal salt of an organic acid, reduce the Ni / V / Fe content of the crude oil product, and reduce the viscosity of the crude oil product. In addition, the contact of the crude oil feed with a third catalyst can produce a crude oil product that has a relatively small change in sulfur content and a relatively small net absorption of hydrogen from the crude oil feed compared to the sulfur content of the crude oil feed. For example, a crude oil product may have a sulfur content of a crude oil feed with a sulfur content of 70% to 1300/0. The crude oil product produced using the third catalyst has a specific gravity in Aρι compared to the crude oil feed. , Distillate content, VG0 content, and residue content may also show only small changes ^ 79 200535221. Reduce crude oil ·, 'tank of organic acids, metals of organic acid metal salt form, Ni / V / Fe content Jin, monthly office by grapefruit office The ability to change the distillate content and the VG0 content H 1 ^ * at the same time with only a small amount of residue can be used for a variety of processing equipment. Crude oil products can be used in various processing equipment.卞 In the specific example, the MCR content of at least a part of the crude oil feed can be reduced, and at the same time, the crude oil feed / total product stability is maintained at 1 ± ° In the specific specific example, two-a catalyst in the master gram catalyst It may have column 6 in the range of 0.0001 to 0 ″, 0.005, a main unit of 5 grams, or 0.000 to ο · οι grams, all of which belong to He Wu v Λ Λ Mi metal 3 li and The 10th metal content in the range of 0.001 to 0.05 grams, 0.005 denier = grams', or 0.001 to 0.01 grams. Brother γ and 10 metal catalysts can promote the reduction of at least a part of the temperature in the range of 300C or 350 to 450 C and the range of 0 to 10 MPa, 1 i 8 MPa, or 2 to 5 MPa. The composition of the MCR in the crude oil feed under pressure. / In the specific example, the fourth type of catalyst ("fourth catalyst") contains 5 columns of metal combined with emulsified carrier. The fourth catalyst has a pore size distribution with a median = at least $ 18G A. In some specific examples, the median pore diameter of the fourth catalyst may be at least A, at least A 2 50 A 7 A ′, or at least 300 A. The carrier may contain at least grams to> 0.5 grams' at least 0.8 grams, or at least 0.9 grams of theta oxidation per gram of carrier. The fourth catalyst may include per gram of catalyst in several specific examples. The most "] grams of the 5th metal, and each gram of the catalyst is at least 0.001 g of 苐 5 metal. Ut; in specific examples, the 5th metal is hungry. In several specific examples In contact with the fourth catalyst, the crude oil 80 200535221 feed can be contacted with the additional catalyst. The additional catalyst can be: the first catalyst, the second catalyst, the third catalyst: or more The fifth catalyst, the sixth catalyst, the seventh catalyst, and the second: the catalyst, the product catalyst, or a combination thereof. In a few specific examples, chlorine can be used in crude oil feed and During the first touch, the catalyst will be connected to the host at 400 to 400 ° C, 320 to 380, or 33 °.

Temperature. The product of crude oil produced by e α _ ό / Ό C by contact with type A can be

The maximum is 90%, the maximum A 8π〇 / take Xi also /, with TAN is 80 / 〇, the maximum is 50%, or the TAN for crude oil feed.气 # 政 丄 丄 1 w / 〇 之 τ 顶 湖. Lice can occur at 1 to 50 breaks, 3, 1

NmVm3 'or 15 to 25 Nm3 / m3. Crude oil products can have a total test / Fe content of up to 90%, up to 80%, up to dove, up to 50%, up to 10%, or at least 1% of crude oil

Ni / V / Fe content. . In a specific embodiment, the fifth type of catalyst (the "fifth catalyst") includes a sixth metal in combination with a rhenium alumina carrier. The fifth catalyst has a pore size distribution with a median pore size of at least 18 A, at least 22 B, at least 23 A, at least 250 A, at least 300 A, or at most 500 A. The carrier may contain at least 0.1 g, at least 0.5 g, or at least 0.999 g of theta alumina per gram of the carrier. In several specific examples, the carrier has an alpha oxide content of less than 0 gram alpha alumina per gram of catalyst. In some specific examples, the catalyst includes a column 6 metal of up to 0.1 g per gram of catalyst and a column 6 metal of at least 0.0001 g per gram of catalyst. In some specific examples, the metal in column 6 is molybdenum and / or tungsten. In a specific specific example, when the crude oil feed and the fifth catalyst are connected to 400 ° C at a temperature of 3 i 〇81 200535221 or 3 30 to 3 60 ° c, and 320 to 370 contacts, the hydrogen of the crude oil feed The net pickup may be relatively low (for example, please go to 100 Nm3 / m3, 1 to 80 NmW, 5 to 50NmVm3, or 10 to 30Nm / m). The net absorption of hydrogen from crude oil feed can be in the range of ^ to 20 NmVm3, 2 to 15 Nm3 / m3, or 3 to ι〇, 3 in some specific examples.

Inside. The crude oil product produced by contacting the crude oil feed with the fifth catalyst may have a TAN of a crude oil feed of at most 90%, at most 80%, at most 50%, or at most 10 / ◦. The TAN of the crude product may be in the range of 0 to, 0.03 to 0.05, or 0.02 to 0.03. In a specific embodiment, the sixth type of catalyst (the "sixth catalyst") includes a rhenium metal and a column 6 metal combined with a rhenium alumina carrier. The sixth kind of j has a pore size distribution with a median pore size of at least i 80. In several specific examples, the median pore size of the pore size distribution can be at least 220 A, at least 23 A, at least 250 A, at least 300 A, or at most 500 people. The carrier may contain at least 0 "grams, at least 0.5 grams, at least 0.8 grams per gram of carrier.

^, At least 0.9 g, or at most 0.99 g of rhenium alumina. The carrier in: specific examples may contain up to 0.1 per gram of catalyst {the total amount of metal in column 5 and column 6 '' and at least Q grams per gram of catalyst Column 6 Total amount of metal. In some specific examples, the molar ratio of the total amount of the metal in the 6th column to the total amount of the metal in the fifth column may be in the range of 0. to 10.0, 1 to 10, λ8, or 2 to 5. In a specific embodiment, the metal in column 5 is vanadium and the metal in column 6 is molybdenum and / or tungsten. . When crude oil is fed with the sixth catalyst at 310 to 400 x :, 320 to 37, or 33 to 360. (When contacted at the temperature, the net hydrogen of crude oil feed can be absorbed at _10 NmVm; to 20 Nm3 / m3, _7 Nm3 / m3 to

Nm3 / m3, or -5 Nm3 / m3 to 5 NmVm3. The negative net absorption of argon is a sign of hydrogen produced in the field. The crude oil product produced by the contact of the feed with the catalyst can have a TAN of at most 90%, at most, at most 50%, and at most The TAN of 10%, or at least 1% of crude oil products, can range from 0.01 to 0.04.的 A small net uptake of ticks during periods when the crude feed is in contact with the fourth, fifth, or sixth catalyst will reduce the overall demand for hydrogen during processing to produce and / or process acceptable crude oil products. Because the cost of producing and / or rotating hydrogen is expensive, minimizing the amount of hydrogen used in the process will reduce the total processing—in a specific example, a seventh type of catalyst ("the seventh catalyst,") has The total content of the 6th metal is within the range of 0.0 to 0_06g of the 6th metal per gram of catalyst. The 6th column of metal is the key and / or crane. The seventh catalyst is beneficial to the production of tools. # TAN is a maximum of 90% of crude oil feed,

Oil products. The fourth, fifth, and seventh types of catalysts can be manufactured and / or used as other specific examples of the first, second, third, and seventh catalysts, as described in this article. The catalysts for this application were selected and controlled. “Rrrr Μ Gravy produces crude oil products that have changed TAN and / or selected properties compared to crude oil feeds, while other properties of the feedstock have not changed significantly. The resulting crude oil produced crude oil Material may have a strengthening f, so it is more acceptable for transportation and / 83 200535221. The configuration of two or more catalysts in a selected order can control the order of improving the properties of crude oil feed. For example, crude oil Tan, api specific gravity, at least-part of c5 cyanide, at least part of iron, at least part of nickel, and / or at least part of hunger in the feed can be reduced before reducing at least part of the heteroatoms in the crude feed. 77 Configuration and / or selection of catalysts can improve catalyst life and / or stability of crude oil feeds / total product mixtures in several specific examples. Increase catalyst life and / or crude oil feeds / total product mixtures during processing Stability can allow the contact system to operate for at least 3 months, at least 6 months, or at least 1 year without changing the catalyst in the contact zone. Combined with the selected catalyst, it can be used in other crude oil feeds. Before the qualitative change, at least part of the Ni / V / Fe in the oil feed, at least part of the c5 asphaltene, at least part of the metal in the form of a metal salt of an organic acid, and at least part of the w to form a component of TAN 'at least-part of the residue Reduction of crude oil, or a combination thereof, while maintaining the stability of the crude oil feed / total product mixture during processing (for example, maintaining a crude oil feed p-value higher than 1.5). Alternatively, C5 asphaltenes, taN, and / or API specific gravity may be The ability to gradually and / or selectively change the properties of a crude oil feed by contacting the crude oil feed with a selected catalyst may allow the stability of the crude oil feed / total product mixture to be maintained during processing. In several specific examples In the first catalyst (the above) can be arranged upstream of a series of catalysts. This configuration of the first catalyst allows the removal of 3 dyes, metal contaminants, and / or organic acid metal salts in the polymer. Form of the metal and at the same time maintain the stability of the crude oil feed / total product mixture. 84 200535221 The first catalyst, in several specific examples, allows the removal of at least a portion of the Nl / v / in the crude oil feed. Fe, removes acidic components, removes components that reduce the life of other catalysts in the system, or a combination thereof. For example, t, and crude oil

Compared with the feed, reducing at least a part of the C asphaltene in the crude oil feed / total product mixture will inhibit the clogging of other catalysts arranged downstream, so I increase 5 The contact system can still operate without supplemental catalyst Ongoing; removing at least a portion of the Ni / V / Fe in the crude feed may increase the life of one or more catalysts arranged behind the first catalyst in several specific examples.

The second catalyst and / or the third catalyst may be arranged downstream of the first catalyst. Further contact of the crude oil feed / total product mixture with the second catalyst and / or the third catalyst can further reduce the TAN, lower the Ni / V / Fe content, lower the 3 & mile, lower the oxygen content, and / Or reduce the metal content of the organic acid metal salt. : In the specific example on the right, 'the contact between the crude oil feed and the second catalyst and / or the second catalyst can produce a crude oil feed / total product mixture, which is related to the individual properties of the crude oil feed &# TAN, reduced sulfur content, reduced oxygen content, reduced metal content in the form of metal salt of organic acid, reduced asphaltene content, reduced viscosity, or a combination thereof, while maintaining crude oil feed during processing / The stability of the total product mixture. The second catalyst can be juxtaposed—the first catalyst is located upstream of the third catalyst, or vice versa. The ability to transport gas to a particular contact zone tends to minimize the use of hydrogen during the contact. Combining the catalyst that promotes the occurrence of hydrogen during the contact with the catalyst that absorbs a relatively small amount of hydrogen during the contact can be used to change the same properties as the crude oil 85 200535221 feed. In contrast, the fourth catalyst can be compared with the first Catalyst, second catalyst, fifth catalyst, sixth catalyst, and / or third catalyst to change selected properties of crude oil feed and use other properties of oil feed, And / style /, selectively change the original nature. You can choose to maintain the stability of the crude oil feed / total product, t select the sequence and / or number of catalysts to reduce the net hydrogen absorption to the maximum / Kli 'while maintaining the crude oil feed / total product. &Amp; The minimum net of hydrogen and the enemy system make the crude oil feed residue content, vg

tb t > 4 ^ έΒ yv ^ 4 * ^ Distillation knife contains ϊ, in API, 22: ° TAM TAN and / or TAN with a viscosity of up to 9G% of crude oil feed And / or viscosity. The net absorption of hydrogen from the crude oil feed of TZT can produce crude oil products with a boiling range distribution similar to that of the crude oil feed, which reduces TAN compared to the TAN of the crude oil feed. The atomic politics of crude oil products can also be changed only slightly compared to the atomic H / C of the crude oil feed.

The occurrence of hydrogen in the special contact zone may allow selective addition of hydrogen to other contact zones and / or allow selective reduction of the properties of the crude oil feed. The fourth catalyst in several specific shellfish can be deployed on the additional catalyst described herein * downstream or in between. Hydrogen may occur during contact of the crude feed with the fourth catalyst ' ' The hydrogen may be transported to a contact zone containing additional catalyst. The hydrogen transport can reverse the flow of the crude oil feed. In several specific examples, the transport of thorium may be in the same direction as the flow of crude oil feed. For example, in a stacked structure (see FIG. 2B), hydrogen can be generated in a contact zone (such as the contact zone 102 in FIG. 2B) during contact, and hydrogen can be reversed in the flow of crude oil 86 200535221 Contact area m). In several and to the additional contact zone (for example, the flow of the material is in the same direction. Or, in the reactor: two ::: hydrogen flow can be in a contact zone during the contact (:: structure in (see Figure 3B) Hydrogen can be formed. The gas h _ £ (for example, the contact zone in FIG. 3B is formed. The lice source can be transported in the crude oil feed stream L raw hammer F ~ 丨 to the first additional rescue zone (for example, in the figure In 3B, the first additional connection 114) is added to the contact area with a shield and 丄 # 工 田 导 官 106 (for example, the wheel is sent to the second additional contact area in the direction of the H ^ + gate (for example, in FIG. 3B, Add the specific catalyst ^ to the contact area 116). # 京 The fourth catalyst is used in parallel with the sixth catalyst system, and the fourth catalyst system can be used. Combine the fourth catalyst with two or In the case of net absorption, in the case of net absorption, reduce 2 = expected gas, lower TAN, lower Ni / V / Fe content, and / or reduce the metal acid in the form of organic acid metal salt. A small amount of lice Other properties of the net absorption allowable crude oil product; g, 丄, I, are only slightly changed compared to the same properties of the raw and oil feeds. In several specific examples, two different seventh catalysts may be used in combination. The seventh catalyst used upstream rather than the seventh catalyst downstream may have a range of 0 to 0.06 grams per gram of catalyst. The total content of the sixth metal in the range. The seventh catalyst downstream may have a content per gram of the seventh catalyst downstream or greater than the total metal content of the sixth catalyst in the seventh catalyst upstream, or The total content of the sixth metal of the sixth metal in the gram catalyst is at least 0.02 grams. In some specific examples, the seventh catalyst upstream and the seventh catalyst downstream can be reversed. The downstream The ability of the seventh catalyst to use a relatively small amount of catalytically active metals may allow other properties of crude oil products to be compared to the same properties of crude oil 87 200535221, APJ hh, down, some) changes (such as heteroatom content, 1 Specific gravity, residue content, VGO content of 詈, 洸, change). 3 / ,,, and a relatively small amount of crude oil feed and the seventh upstream and downstream contact with Ding is at most ㈣, at most 80%, Up to t production or at least 1% crude oil feed Take xi as the origin / product of '^, r.'. The TAN of Yu Ruoqian's contact with ΓΓ feed can be reached by contacting the seventh upstream and downstream ==: = low (for example, crude oil feed and The contact of the catalyst to produce a product of -1 crude crude oil product, followed by crude crude oil product.): Jin = compared with Guangyou product has the ability to help with the experience / can hold crude oil during processing The stability of the feed / total product mixture. In the specific example of the contact body ΓΓ, the combination of catalyst selection and / or catalyst sequence and control of the contact conditions (such as temperature and flow rate) Helps reduce the intake of raw and natural gas 'helps maintain the stability of the crude oil feed / total product during processing' and changes the nature of the w σ species or species compared to the individual properties of the crude oil feed. Stability of crude oil feed / total product mixture: Once subjected to various phase separations from the crude oil feed / total product mixture ^: said. Phase separation may be caused by, for example, crude oil feed in the crude feed / total product mixture, or insolubility of the crude product, crude feed / total mixture in the crude product / precipitation of ingredients in the feed / total product mixture, or Caused by their combination. α At certain times during the contact, the MM and / or total product concentration in the crude feed / total product mixture may change. When the crude product feed / total 88 200535221 product total product concentration changes due to the formation of crude product, the solubility of the crude feed component and / or the total product component in the crude feed / total product mixture will tend to change . For example, a crude feed may contain ingredients that are soluble in the crude feed at the beginning of processing. When the properties of the crude oil feed (such as TAN, MCR, C5 asphaltenes, P-values, or a combination thereof) change, these ingredients may have a tendency to become less soluble in the crude oil feed / total product mixture. In several examples, the crude feed and total product may form two phases and / or become insoluble with each other. Changes in solubility may also cause the crude feed / total product mixture to form two or more phases. The formation of two phases due to flocculation of asphaltenes, changes in crude oil feed and total product concentration, and / or precipitation of ingredients tends to reduce the life of one or more catalysts. In addition, process efficiency may be reduced. For example, it may be necessary to repeatedly process the crude feed / total product mixture to produce a crude product with the desired properties. During processing, the P value of the crude feed / total product mixture can be monitored and the stability of the process, crude feed, and / or crude feed / total product mixture can be evaluated. Typically, the maximum $ p value indicates that the flocculation of the asphaltenes of the crude feed usually occurs. If the * p value is at least 15 at the beginning, and these P values increase or are fairly stable during the contact period, this means that the crude oil feed is quite stable during the contact period. The stability of the crude feed / total product mixture, as assessed by the P value, can be controlled by controlling the contact conditions, by the choice of catalyst, by the selective ordering of the catalyst, or a combination thereof. Such controlled contact conditions may include controlling LHSV, temperature, pressure, nitrogen uptake, crude oil feed flow rate, or a combination thereof. In the concrete example on the right, the contact temperature is controlled in order to remove asphaltenes 89 200535221 and / or other asphaltenes, 同 ^,, ′ keep the MCR content of the crude oil feed. By hydrogen uptake and / or higher exposure, lowering the MCR content may lead to the formation of two phases, which can be combined to reduce the stability of the crude oil feed / total product mixture. … The life of the catalyst. Control the contact temperature and the absorption of hydrogen. The catalysts described in the oral text allow to reduce the cyanide quality while at the same time only changing the MCR content of the crude oil feed in a relatively small amount. In several specific examples, the contact conditions are controlled so that the temperature in one or more contact zones may be} s soil is different. Operation at different temperatures allows selection

The crude oil feedability has been changed over time while maintaining the stability of the crude oil feed / total product mixture. Crude oil feed enters the first contact zone at the beginning of the process. The first contact temperature f is a temperature in the first contact region. Other contact temperatures (e.g., second temperature, third temperature, fourth temperature, etc.) are temperatures in the contact area disposed behind the first contact area. The first contact temperature may be in the range of 100 to 4200 t, and the second contact temperature may be different from the first contact temperature by 20 to 100 t, such as

To 90 C, or 40 to 60 ° C. In some specific examples, the first contact temperature is greater than the first contact temperature. Having different contact temperatures can reduce the TAN and / or Cs asphaltene content in the crude oil product to the ratio of the TAN and / or Cs asphaltene content of the crude oil feed, if any, between the first and the first When the two contact temperatures are the same or differ by less than 10 t, the TAN and / or C5 asphaltenes are reduced to a greater extent. For example, the first contact area may include a first catalyst and / or a fourth catalyst, and the second contact area may include other catalysts described herein. The first contact temperature may be 350 ° C, and the second contact temperature may be 300 ° c. Crude oil feed contacted with the first catalyst in the first contact zone and / or contacted with other catalysts in the contact zone with the second contact 90 200535221 A, and the catalyst was contacted with the fourth catalyst at a higher temperature The contact can result in a decrease in TAN and / or c5 asphaltenes in the crude oil feed compared with the phase difference between the first and second contact temperatures within 10 c. There is more reduction in TAM »^ or C5 asphaltenes. EXAMPLES Non-limiting examples of carrier preparation, catalyst preparation, and systems with selected catalyst configurations and controlled contact conditions are presented below. The carrier system uses 585 grams of water and 8 grams of glacial acid to convert 576 grams of oxygen (aluminum) (Criterion Catalysts and Technogies Lp,

Chy, Mlchigan, U.s.a.) was prepared by milling for 35 minutes. The resulting milled mixture was extruded through a 1.3 Tril0beTM template, dried between 90 and 25 and then calcined at 918 ° C to obtain 650 g of a calcined support having a median pore size of 182 A. This calcined carrier was placed in a Lindbq furnace. The temperature of the furnace was raised to 1,000 to 11,000 t during 1.5 hours, and then kept in this range for 2 hours to produce a carrier. This support contained 0.0003 g of gamma alumina, 0.0008 g of alpha alumina, 0.0008 g of $ _ alumina, and 0.9781 g of theta alumina per gram of the carrier. Diffraction measurement. This support has a surface area of 110 m2 / g and a total pore volume of 0.82 cmVg. This carrier has a pore size distribution with a median pore size of 232 A, and 66.7% of the total number of pores in the pore size distribution has a pore size in the range of 85 A median pore size. This example illustrates how to prepare a support having a pore size distribution of at least 80 A and containing at least 0.1 g of Θ alumina. Example 2 · __1 Prepare a hole with a median pore diameter of at least 230 people. 91 200535221 Hungry catalysts are prepared using the following catalysts: VSO4 prepared by the method described in Example 1. 82 grams of μ and Belling's solution were impregnated, which was prepared by combining 7.69 grams of ionized water. The pH value of the solution was 2.27. The emulsified carrier (100) was aged for 2 hours. It was impregnated with hunger ... solution, dried under accidental sand for several hours, and then at 480 μM. The obtained catalyst contained 0.001 g of hunger per gram of catalyst, and ::: part was used as a carrier. This catalyst has a pore volume knife with a median pore diameter of 350 A <, a pore volume of 0.69 cm3 / g, and a reduced surface area. In addition, 66.7% of the total pore numbers in the pore size distribution of the europium catalyst have pore sizes in the middle pore size range of Chuan A. This example illustrates the preparation of a fifth catalyst having a pore size distribution with a median pore size of at least 23 people. ^^ 歹 " · ~~ Manufacture-Prepare an iJL molybdenum contact with a hole diameter of at least 230 A. The molybdenum catalyst was prepared in the following manner. The alumina support prepared by the method described in Example 丨 was impregnated with a molybdenum impregnation solution. The molybdenum immersion solution was prepared by using 4.26 g of (NΗ4) 2Mο207, 6.38 g of Mο03, and 1.12 g of 30% Η202, 0.27 g of monoethanolamine (ΜΕΑ). It was prepared by forming a slurry with 6.51 grams of deionized water. This slurry was heated to 65 ° C until the solids were dissolved. The heating solution was allowed to cool to room temperature. The pH of this solution was 5.36. Adjust the solution volume to 82 mL with ionized water. The alumina carrier (100 g) was impregnated with a molybdenum impregnation solution, aged by accidental agitation for 2 hours, and dried at 125 ° C for several hours, and then at 480 c 92 200535221; Contains 0.04 grams of molybdenum, and the remainder is the carrier. This indium catalyst has a pore volume with a median pore diameter of 25 G A and a pore volume of cm / g, and a surface area of 6 m2 / g. In addition, the pore size of the indium catalyst is 67.7% of the total number of pores in the cloth, which has a pore size in the median pore size range of 86 people. This example illustrates the preparation of a sixth catalyst having a pore size distribution with a median pore size of at least 4 230 A. f. Molybdenum / vanadium catalysts with a median pore size of at least 23 people are prepared in the following manner. The oxide support prepared by the method described in Example 1 was impregnated with a molybdenum / vanadium impregnation solution prepared as follows. The first solution was obtained by combining 2.14 grams of (NH4) 2M0207, 3.21 grams of Mo03, / 6 grams of 30 / 〇hydrogen peroxide (n), and 014 grams of monoethanolamine (mea). Deionized water is produced as a slurry. This slurry was heated to 6 5 C until the solids were dissolved. The heating solution was allowed to cool to room temperature. The first / valley solution was produced by combining 3.57 g of VS04 and 40 g of deionized water. The first solution was combined with the second solution, and sufficient deionized water was added to bring the volume of the combined solution to 82 ml to produce a molybdenum / vanadium impregnated solution. The alumina was impregnated with a molybdenum / vanadium impregnation solution, aged by accidental agitation for 2 hours, dried at 125 ° C for several hours, and then calcined at 48 ° C for 2 hours. The obtained catalyst contained 0.02 g of vanadium and 0.02 g of molybdenum per gram of the catalyst, and the remainder was a carrier. This molybdenum / vanadium catalyst has a pore size distribution with a median pore size of 300 A. This example illustrates the preparation of Column 6 metal and Column 5 metal catalysts with a pore size with a median pore size of at least 230 A. 93 200535221 distribution. The case of Fuhuang L ~~ Yuan went into the body ^ after touching with a touch. A tubular reactor with a temperature-measuring insert in the center is equipped with a thermocouple to measure the temperature of the entire catalyst bed. This catalyst bed is filled with catalyst and carbonized carbide (20_gnd, stanf〇rd) in the space between the temperature measuring sleeve and the inner wall.

Materials; Aliso Viej〇, CA). It is believed that such carbides, if any, have low catalytic properties under the operating conditions described herein. Before placing the mixture in the contact area of the reactor,

An equal volume of silicon carbide is blended. The crude oil feed flow of the μ reactor is from the top of the reactor to the bottom of the reactor. The carbon cutting system is arranged at the bottom of the reactor as a bottom support. A catalyst / carbide (42 em3) at the bottom is disposed above the thorium carbide to form a bottom contact area. The bottom catalyst has a hole with a median pore diameter of 77 A. Distribution: 66.7% of the pore size distribution has a pore size in the range of 20 A median pore diameter. The bottom catalyst contained 0.095 g of indium and 25 g of G.G in each gram of catalyst, and the rest was an oxide carrier.

. The middle catalyst / silicon carbide mixture (56 series is arranged on / side of the bottom box area to form the middle contact area. The middle catalyst has a pore size distribution with a median pore size of 98 J. The pore size distribution is 彳 66 · 7% The total number of pores has a pore diameter within the pores of M ^ < pores. The intermediate catalyst contains • 0.02 grams of brocade and G. G8 grams per gram of catalyst, and the rest is oxidized! Lu carrier. The catalyst / carbon-cut mixture (42em3) = is placed in the middle contact area. ^ The top contact area. The top catalyst has an exhaust hole with a median pore size of S 192 A. It contains 0.04 grams of pins per gram of catalyst. 94 200535221 To be a gamma alumina carrier. The silicon carbide system is arranged above the top contact area to fill the vacant space and serves as a preheating zone. The catalyst bed is loaded into the Lindberg furnace, which includes the corresponding preheating zone, top, middle, and bottom. The contact zone, and the five heating zones of the bottom carrier.

The catalyst is a rate of 1.5 liters of a gaseous mixture per unit volume (mL) of the gaseous mixture of 5 vol% hydrogen sulfide and 95 vol% hydrogen gas (silicon carbide is not considered as a volume part of the catalyst). The contact area is introduced to form a sulfide. The temperature in the contact area is below! During the course of the hour it was increased to 204 (400) and kept at 204 t: 2 hours. After being held at 204 t, the contact zone gradually increased to 316 it (600 ° F) at a rate of 10 t (50 ° F) per hour. Keep the contact area at 316. Mouth-hour, gradually rose to 37G t (τ) during the i-hour and stayed at 37G t for two days ^ ° to cool the contact area to the surrounding temperature.

The crude oil from the Mars rig in GulfOfMexic0 was filtered and then heated in an oven for 12 to 24 hours under us to generate a crude feed having the properties summarized in Table 7 below. The crude feed is fed into the reactor. The top 4 raw materials flow through the preheating zone, the top contact zone, the middle contact zone, the bottom contact and the bottom support of the reactor. The crude feed is contacted with each catalyst in the presence of hydrogen. The contact conditions are as follows: gas to shore supply ^ nw ™ m3 / m3 (2GG () SCFB) = fv is 1 h 'and pressure is 6.9 MPa no 14 7., 孰 to 37 MPa (1G14.7 just. 3) Each contact zone was supplemented with F) and kept at 37 ° C. for one hour. Temperature of three contact zones # f a

', The following sequence increases and maintains: 379 ° C 00 hours, followed by 388 ° C (730 0F) 500 hours, 95 200535221 followed by 390 t (734 卞) 180 hours, followed by 3 materials (M). ° F) 2400 hours. The total products (in other words, crude oil products and gases) leave the catalyst bed. The total product was introduced into a gas-liquid separator. The total product is separated into a crude product and a gas in a gas-liquid separator. The gas input to the system is measured by a mass flow controller. The gas system leaving the system is determined by a hygrometer. Crude oil products are periodically analyzed to determine the weight percent of crude oil product components. The results listed are averages of the measured weight percentages of the components. Crude product properties are summarized in Table 1 of FIG. g As shown in Table 1, the crude oil product has 0.0075 grams of a stone melon in each gram of crude oil product, a residue content of 0.255 grams, and an oxygen content of 0.0007 grams. The crude product has a TAN with a ratio of MCR content to q asphaltene content of 19 and 0.09. The total amount of nickel and vanadium was 22.4 wtppm. The catalyst oddity is determined by measuring the weighted average bed temperature ("wabt") versus the operating time of the crude feed. The catalyst life may be related to the temperature of the catalyst bed. Xianxin WABT will increase when the catalyst life is shortened. Head 8 is a graphical representation of the WABT versus time _ () used to improve the crude oil feed in the contact zone described in this example. 1 3 6 shows the average WABt of the three contact zones versus crude oil feed and top and middle. 'The running time of the contact with the bottom catalyst was in the course of the operating hours of Daxi, the WABT in the contact zone changed only about ° C. From the relatively stable WABT, it can be judged that the catalytic activity of the catalyst is not affected. Typically, 3 to 3,500 hours of mid-hours plant operation time is related to one-year sanitation. θ This example illustrates the contact of crude oil feed 96 200535221 with a catalyst having a pore size distribution with a median pore size of at least 1 80 A and the contact with a median pore size between 90 and 1 80 A under controlled contact conditions A pore size distribution within the range. At least 60% of the total pore numbers in the pore size distribution have additional catalyst contacts with pore sizes in the 45 A median pore size range to produce a total product containing crude oil products. As measured by the P value, the stability of the crude oil feed / total product mixture was maintained. Compared with the crude oil feed, the crude oil product has a reduced TAN, a reduced Ni / V / Fe content, a reduced sulfur content, and a reduced oxygen content, while the crude product residue content and VG0 content are 9 These properties are from 0% to 11% of the crude oil feed. _ Example 6. Crude oil has a median pore diameter free from the contact of two catalysts with a pore diameter within the range of 90 to ί 8 () Α Huang Sewei. The reactor equipment (except for the number and content of the contact zones), the catalyst-forming sulfide method, the method for isolating the total product, and the method for analyzing the crude product are the same as those described in the implementation of M5. Each catalyst type is mixed with an equal volume of carbonized fossils.

The reacted crude feed flow is from the top of the reactor to the bottom of the reactor. The reactor was filled from bottom to top in the following manner. The carbonization system is arranged at the bottom of the reaction 作为 as a bottom support. The catalyst / carbonized mixture at the bottom is disposed above the carbon cut to form the bottom junction. The bottom catalyst has a pore size distribution with a median pore size of 127 A. 66.7% of the total number of pores in the cloth has a median pore size of 32 A to control. The bottom catalyst contains G n gram of indium and osmium 2 nickel per gram of catalyst, and the rest is a carrier. The catalyst / carbon fossil mixture at the top (80 cm3) is arranged at the contact area with 97 200535221 ⑽4 at the bottom. The top catalyst has a median pore size of woven cloth. The total number of pores in this pore size distribution is 彳 66 7%. The top catalyst contained Gamma / core. 12 grams of molybdenum per gram of catalyst and the remainder was alumina. SiC-based configuration is too LV on the first contact area, it really fills two positions and acts as a preheating area. The catalyst bed system, the inlet and the mdberg furnace 'includes four heating zones corresponding to a preheating zone, two contact zones, and a bottom carrier.

的 The BS-4 crude oil (Venezuela) with the properties summarized in Table 2 and Figure 9 is a human reaction | g top. Crude oil feeds flow through the preheat zone, top contact :, bottom contact zone, and bottom carrier of the reactor. Crude oil feed is under hydrogen gas contact "for each catalyst contact. The contact conditions are as follows: the ratio of radon gas to the crude oil feed to the reactor is i60Nm3 / m3 (1000 SCFB), ^ HSV is 1 h1, and The pressure is 6.9 MPa (1014.7 psi). The two contact zones are heated to 260 ° C (500 ° F) and maintained at 260 ° C (500 ° F).

Under 287 hours. The temperature of the two contact zones was then increased and maintained in the following order: 270 t (525 T) for 19 hours, followed by 288 t (5500 ° F) for 216 hours' followed by 315 ° C (600 ° F) for 360 hours , Followed by 120 hours at 343 ° C (650 ° F) to achieve a total operating time of 1173 hours. The total product left the reactor and was separated as described in Example 5. Crude products have an average tan of 0.42 and an average API specific gravity of 12.5 during processing. This crude product contained 0.0023 g of sulfur '0.0034 g of oxygen, 0.441 g of VGO, and 0.378 g of residue per gram of crude product. Additional properties of the crude product series are shown in Table 2 of FIG. This example shows that contacting a crude oil feed with a catalyst having a pore size distribution with a median pore size in the range of 90 to 98 200535221 180 A to produce a crude oil product, compared with the properties of the feedstock, has a reduced TAN, Reduced Ni / V / Fe 3 > and reduced oxygen content while the crude oil product has a residual content and V⑽ content of 99% and 100% of the individual properties of the crude oil feed. Example 7. ~~ a kind of stump. The reactor equipment (except the number and content of the contact zones), catalyst, total product separation method, crude oil product analysis, and catalyst sulfide formation system are the same as those described in Example 6. ^ The crude oil feed (BC_10 crude oil) with properties summarized in Table 3 and Figure 10 is supplied to the top of the reactor. The crude oil feed flows through the preheating zone, top contact zone, bottom contact zone, and bottom carrier of the reactor. The contact conditions are as follows: the ratio of hydrogen to the crude oil feed to the reactor is 80Nm3 / m3 (5⑻8 咖), ^ is 211-1, and the pressure is 69% (10147). Two Each contact zone was gradually heated to 343 t (65 ° F). The total operating time was 1,007 hours. The crude oil product had an average TAN of 016 and an average API specific gravity of 16.2 during processing. The crude product contained 9 wtppm㈣, 6% sodium, 0.6 wtppm zinc, and 3 wtppm potassium. This crude product contained 0.0033 grams of sulfur, 0.02 grams of oxygen, 376 grams of VGO, and 0.401 grams of residue per gram of crude product. Additional properties of the crude product are listed in Table 3 of FIG. This example shows that a crude oil feed is contacted with a selected catalyst having a pore size distribution in the range of 90 to 80 A to produce a crude oil product with reduced TAN, reduced total calcium, sodium, zinc, and potassium Content, while the crude oil product has 99 200535221 sulfur content, VGO content and residue content of 76%, 94% and 103% of the individual properties of the crude oil feed. fExamples 8 to 1 1-Contact of crude oil feed with four catalyst systems under various contact conditions. The parent reactor equipment (except for the number and content of contact zones), each catalyst-forming sulfide method, each total product separation method, and each crude product analysis system are the same as those described in Example 5. Unless otherwise stated, all catalysts were mixed with silicon carbide in a volume ratio of 2 parts silicon carbide to 1 part catalyst. The crude feed flow through each reactor is from the top of the reactor to the bottom of the reactor. The tritiated silicon system is arranged at the bottom of each reactor as a bottom carrier. Each reactor has a bottom contact zone and a top contact zone. After the catalyst / silicon carbide mixture was placed in the contact area of each reactor, the silicon carbide system was arranged above the top contact area to fill the voids and serve as a preheating area for each reactor. Each reactor was housed in a Lindberg furnace, which included four heating zones corresponding to a preheating zone, two contact zones, and a bottom carrier. In Example 8, an uncalcined molybdenum / nickel catalyst / silicon carbide mixture (48 actinide is disposed in the bottom contact area. The catalyst contains 0.146 grams of nickel per gram of catalyst and 0.047 grams of nickel ㈣.21 grams of phosphorus, the rest is an alumina support. A pin catalyst / carbonized compound containing a catalyst having a pore size distribution with a median pore diameter of 180 Å (12 ㈣ series, is arranged in the top contact zone. This flip catalyst has a total content of 0_04 grams per gram of catalyst, and the rest is a carrier containing at least 0.50 grams of gamma oxide in the mother gram carrier. In Example 9, the unfired Fan / catalyst / carbonized fossil mixture (48 100 200535221 cm) is arranged in two contact areas. 0.143 g of molybdenum, 0.0043 g of cobalt, is the carrier of the oxide. The uncalcined molybdenum / cobalt The catalyst contains 0.021 grams of phosphorus, and the rest of the molybdenum catalyst / silicon carbide mixture (12 cm3) is arranged at the top to contact the 5 MH molybdenum catalyst, which is the same as the top contact area of Example 8. In Example 1G 'The pin catalyst system as described in the top contact area of Example 8 is mixed with carbonized carbide and arranged in two In the contact area 3).

In Example U, an uncalcined flip / nickel catalyst / silicon carbide mixture (48⑽3) was disposed in the bottom contact region. The non-calcined rhenium / nickel catalyst contains a gram of the per gram catalyst, a record of 0.5 g, and a scale of 0.01 gram. The remainder is an alumina carrier. A molybdenum catalyst / silicon carbide mixture (12 cm3) is placed in the top contact area. The molybdenum catalyst is the same as that in the top contact area of Example 8.

Crude oil from the Mars rig (GulfOfMexic〇) was filtered and then heated in an oven at% C (200 ° F) for 12 to 24 hours to generate a summary for Examples 8 to 11 in Table 4, Figure A crude oil feed of n nature. Crude oil feed was fed to the top of the reactors of these examples. Crude oil feeds flow through the preheat zone, top contact zone, bottom contact zone, and bottom carrier of the reactor. The crude feed is contacted with each catalyst in the presence of hydrogen. The contact conditions for each example were as follows: the ratio of hydrogen to crude oil feed during the contact was 160 NmVm3 (1000 SCFB), and the total pressure of each system was 6.9 MPa (1014.7 psi). During the first 200 hours of exposure, LHsvg was 20 h · 1, and then the HSV decreased to ι · 〇 during the remaining exposure time. The temperature in all contact areas was 343 ° C (650 ° F) for 500 hours of contact. After 500101 200535221 hours, the temperature of all contact zones was controlled as follows: the temperature of the contact zone was raised to 354 ° C (670 T) and kept at 354 ° C for 200 hours; it was raised to 3 66 C (690 ° F) 'Hold at 366 ° C for 200 hours; rise to 371 ° C (700 T) for 1,000 hours at 371 ° C; rise to 385 ° C (725 F) and hold at 385 ° C for 200 hours; It was then raised to a final temperature of 399 ° C (750 ° F) and held at 399 ° C for 200 hours to achieve a total contact time of 2300 hours. Crude oil products are regularly analyzed to determine the TAN, hydrogen uptake of the crude oil feed, P value, VGO content, residue content, and oxygen content. The series of average values of the properties of the crude oil products produced in Example 8 are shown in Table 5 in Figure u. FIG. 12 is a graphical representation of the crude product P value ("P") versus operating time ("t") for each catalyst system of Examples 8 to n. The crude feed has a p-value of at least]. Curves 140, 142, 144, and 146 represent the p-values of the crude oil products obtained by contacting the feeds individually with the four catalyst systems of Example 8 to n / ', ^, ^^^. For the catalyst system that is carefully reached, the main 10

The p-value of the crude oil product at / h is at least at least the p-values ^, Μ η, AA t +% 1 · 5 of most operating times in Example 11. At the end of the 1st revolution (2300 hours) in Example 11, from the p value of ρ *, it can be inferred that the crude oil production in each trial solid test is quite stable (for example, crude oil entering and leaving two: during the contact period Example ... In addition to the increase in P value ::: Production: As shown in Figure 12, the P value in each test is kept fairly constant. The P value of the substance is large. Figure U shows four kinds of plutonium, anion, and antecedent in the presence of hydrogen. A graph of the hydrogen of crude oil feed, 102 200535221 absorption (H2) vs. operating time ("t ,,"). The curves I ", 15, 152, and '15 4 show that the crude oil feed is not related to The net absorption of hydrogen obtained by each of the catalyst systems of Examples 8 to 11 was achieved. The net absorption of hydrogen from crude oil feed was between 7 and 48 Nm3 / m3 (43.8 to 300) during a 2,300-hour operation. SCFB). As shown in Figure 13, the net uptake of hydrogen from the crude feed was fairly constant in each test. Figure 14 shows the crude oil expressed in weight percent for each catalyst system from Examples 8 to The plot of the product's residue content ("R") versus run time ("t") is shown. In each of the four tests, crude oil The product has a residual content of 88 to 90 ° /. The residual content of the crude oil feed. The curves 56, 158, and 6 indicate that the crude oil feed was individually contacted with the catalyst systems of Examples 8 to 11 The residue content of the obtained crude oil product. As shown in Fig. 14, the residue content of the raw / derived product remained fairly constant in most of each test. Fig. 15 shows each catalyst system of Examples 8 to U. A graph showing the change in API specific gravity of crude oil products ("Δ API") versus operating time ("t"). Curves 164, 1 66, 168, and 170 indicate that the crude oil feeds are individually compared to Examples 8 to Φ " The APF proportion of the crude oil product obtained by contacting the catalyst system. In each of the four tests: each crude product has a viscosity within the dry range of 58.3 to 72.7 cSt. Each crude product @ Αρι specific gravity system Increase M to 4.1 degrees. The increased API specific gravity corresponds to the API specific gravity of crude oil products in the range of 217 to a%. The specific gravity of Aρ in this range is ιι0 to " 7% of the crude oil feed API ratio. Figure 16 Weight percentage for each catalyst system of Example 8 in 103 200535221 The rate of oxygen content of crude oil products ("〇2 ,," vs. operating time ("t") is not shown. Curves 1 72, 1 74, 1 76, 1 78 series, showing that by feeding crude oil The oxygen content of the crude oil products obtained by contacting with the catalyst systems of Examples 8 to 11 individually. Each crude oil product has an oxygen content of up to 16% of the crude oil feed. Each crude oil product has during each test period The oxygen content is in the range of 0.0014 to 0.0015 grams per gram of crude product. As shown in Figure 16, the oxygen content of the crude product remained fairly constant after a contact time of 200 hours. The relatively constant oxygen content of the crude oil product shows a reduction in the selected organic oxygen compounds during the contact. Since the TAN is also reduced in these examples, it can be inferred that at least a portion of the carboxylic acid-containing organic oxygen compound has a more selective decrease than the non-carboxylic acid-containing organic oxide. In Example 11, the reaction conditions were: 371 (700 MPa), pressure was 6.9 MPa (1014.7 psi), and the ratio of hydrogen and crude oil feed was NmVm3 (1000 SCFB). Based on the weight of the crude feed, The reduction in mcr content in the crude feed was 17.5 wt%. At 399. (: At a temperature of (750 ° F), at the same pressure and the ratio of hydrogen and crude oil feed, the reduction in MCR content of crude oil feed by crude oil feed weight was 25.4 wt%. In Example 9, the reaction The conditions are: 371 t (700 MPa), pressure is 6.9 MPa (1014.7 psi), and the ratio of hydrogen to crude oil feed is NmVm3 (1000 SCFB). 'Based on the weight of crude oil feed, the mcr content of crude oil feed is reduced. It is 17.5 wt%. At a warm production of 399 ° C (750 ° F), at the same pressure and the ratio of hydrogen and crude oil feed, the reduction in MCR content of crude oil feed is 1 9 wt. The increase in these reductions in the MCR content of crude oil feeds shows that uncalcined 104 200535221 has passed 6 and 10 metal catalysts at higher temperatures than the uncalcined 6 and 9 metal catalysts Promote a reduction in MCR content. These examples show that a crude oil feed having a relatively high TAN㈣ @ tan) is contacted with one or more catalysts to produce crude oil products while maintaining the stability of the crude oil feed / total product mixture and having a relatively small amount Net uptake of hydrogen. The selected crude oil product has a maximum of 70% of the same properties of the crude oil feed, and at the same time, the selected crude oil product has the same properties within the range of 20-30% of the crude oil. Specifically, as shown in Table 4, each crude oil product is produced with a net uptake of hydrogen from a crude oil feed of up to 44 M1113 (M SCFB). This type of production has an average TAN of up to 4% of the crude oil feed and an average total Ni / V content of up to the total v content of the crude oil feed, while maintaining a P value above 3 scoops of crude oil feed. The average residue content of each crude product is from M to 90% of the residue content of the crude feed. The average VGO of each crude oil product is 115 to 117% of the vg0 crude oil feed. The average API of the oily product is 110 to 117% of the original gas weight. The crude oil feed has an API weight and the viscosity of each crude oil product is at most 45% of the viscosity of the crude oil feed. < 1 /, the connection of catalysts with good holes ^^ In the examples 12 to 14, each reactor equipment (except the inner spear valley in the contact area), each catalyst forms a sulfide method 2. Each total product separation method and each crude oil product analysis system are the same as those described in Example 5. All catalysts were mixed with an equal volume of carbonized fossils. Crude feed stream for each reactor 105 200535221 The drive train runs from the top of the reactor to the bottom of the reactor. The silicon carbide system is arranged at the bottom of each reactor as a bottom carrier. Each reactor contains a contact zone. After the catalyst / carbonized carbide mixture is placed in the contacted zone of each reactor, the carbonized carbide is arranged above the top contacting zone to fill the voids and serve as a preheating zone for each reactor. . Each reactor was charged into a Lindberg furnace, which included three heating zones corresponding to a preheating zone, a contact zone, and a bottom carrier. The crude oil feed was contacted with each catalyst in the presence of hydrogen. The catalyst / silicon carbide mixture (40 cm3) is placed over the silicon carbide to form the contact area. The catalyst used in Example 12 was the Lu vanadium catalyst prepared in Example 2. The catalyst used in Example 3 was the molybdenum catalyst prepared in Example 3. The catalyst used in Example 14 was the molybdenum / vanadium catalyst prepared in Example 4. The contact conditions of Examples 12 to 14 were as follows: the ratio of hydrogen to the crude oil feed supplied to the reactor was 160 Nm3 / m3 (100 SCFB), the LHSV was 1, and the pressure was 6.9 MPa (1014 7 psi). The contact zone was gradually heated to 343 (65 τ) over a period of time and maintained at 120 hrs below 343 to achieve a total operating time of 36 hours. The φ total product leaves the contact zone and separates as described in Example 5. The net uptake of hydrogen by each catalyst system was measured during the contact period. In Example U, the net absorption of 'hydrogen' was 107 Sc 3 (· 65 scfb), and the crude oil product had a TAN of 6.75. In Example 13, the net absorption of hydrogen was in the range of 2.2 to 3.0 NmVm3 (13.9 to 187 SCFB), and the crude product had a TAN in the range of 0.3 to 0.5. In Example 14, the net absorption of hydrogen during the contact of the indium / starch catalyst in the crude oil feed was in the range of Nm3 / m3 to 106 200535221 0.6 Nm3 / m3 (-0.36 SCFB to 4.0 SCFB). —A 1 > There is tan in the range of 0.2 to 0.5. From the net absorption value of hydrogen during the contact period, it is estimated that during the contact between the crude oil feed and the vanadium catalyst, the hydrogen system was generated at a rate of 10.7 Nm3 / m3 (65 SCFB) ^. Where the hydrogen generation during the contact is compared with the amount of hydrogen used in the conventional process: it is acceptable to use less hydrogen in the process to improve the properties of the inferior crude oil. The need for less hydrogen during the contact tends to reduce the cost of processing crude oil. > TAN of the crude product of the π throne crude product of TAN crude oil JliL with vanadium catalyst and additional ^

In addition, the contact system production of crude oil feeds with molybdenum / vanadium catalysts has lower contact than that produced by the single ^-· ,. Each reactor device (except for the number and content of contact zones), each catalyst sulfide formation method, each total product separation method, and each crude oil product analysis system are the same as those described in the implementation of W5. Unless otherwise stated, all catalysts are mixed with carbon cut at a volume ratio of 2 parts carbon cut to 1 part catalyst. The crude oil feed flow of each reactor is from the top of the reactor to the bottom of the reactor. Anaerobic fossils are disposed at the bottom of each reactor as a bottom carrier. Each reactor has a bottom contact zone and a top contact zone. After the catalyst / carbonite mixture was placed in the contact area of each reactor, the carbonite group was placed above the top contact area to fill the voids and serve as a preheating area for each reactor. Each reactor is housed in a Lindberg furnace and includes four heating zones corresponding to a preheating zone, two contact zones' and a bottom carrier. In each implementation, the vanadium catalyst is prepared and used in conjunction with the additional catalyst as described in the implementation report. 107 200535221; In Example 15 only, the additional catalyst / carbonite mixture (45 cm3) was prepared in the bottom contact area, and the additional catalyst was a radon catalyst prepared by the method described in Example 3. . The catalyst / carbonite mixture (15⑽3) is arranged in the top contact area. In Embodiment 16, the additional catalyst / silicon carbide mixture (30 em3) is disposed in the bottom contact area. The additional catalyst is a rhenium catalyst prepared by the method described in Example 3. The catalyst / carbonite mixture (30 cm3) is arranged in the top contact area. In Example 17, an additional catalyst / silicon carbide mixture (30 cm3) is disposed in the bottom contact area. The additional catalyst is the molybdenum / rhenium catalyst prepared in Example 4. The # 1 catalyst / carbon fossil evening mixture (30 cm3) was placed in the top contact area. In Example 18, Pyre, (Glass WorkCorp New York, U.S.A.) beads (30 cm3) were arranged in each contact area. Crude oil (Santos Basin, Brazil) having the properties summarized in Tables 5 and 17 used in Examples 15 to 18 was supplied to the top of the reactor. The crude oil feed flows through the preheat zone, the top contact zone, the bottom contact zone, and the bottom carrier of the reactor. The crude feed is contacted with each catalyst in the presence of hydrogen. The contact conditions for each example were as follows: the ratio of hydrogen to crude oil feed to the reactor was 160 Nm3 / m3 (1000 SCFB) for the first 86 hours and 80 Nm3 / m3 (500 SCFB) for the remaining time period , LHSV is 1 h-1, and pressure is 6.9 MPa (1014.7 psi). The contact zone is gradually heated to 343 C (650 ° F) and maintained at 343 over a period of time. (: To achieve a total operating time of 1400 hours. 108 200535221 These examples show that in the presence of a hydrogen source, the crude oil feed and the fifth metal catalyst with a pore size distribution with a median and pore size of 350 A combined with Additional catalysts with a pore size distribution with a median pore size in the range of 250 to 300 A are contacted to produce crude oil products that have altered properties compared to the same properties of the crude oil feed, and other properties of the crude oil product are similar to those of the crude oil feed. The same properties are only slightly changed. In addition, a relatively small amount of hydrogen uptake of the crude oil feed was observed during processing. Specifically, as shown in Table 5, FIG. 17, the crude oil products of Examples 15 to 17 had the most TAN. It is a tan of 15% crude oil feed. Compared with the same properties of the crude oil feed, the crude oil products produced in Examples 15 φ to 17 have a total Ni / V / Fe content of up to 44%, respectively. 50% oxygen-containing star 'and a viscosity of up to 75%. In addition, the crude oil products produced in Examples 15 to 17 have APIs having a API gravity of 100 to 103% of the crude oil feed, respectively. In contrast, in non-catalytic strips (Example 1 8) The crude oil product produced under the viscosity and API specific gravity of the crude oil feed produced a product with increased viscosity and decreased API specific gravity. From the perspective of increasing viscosity and decreasing API specific gravity, it can be inferred that Initiate coking and / or polymerization of crude oil feed. _ Contact of Star Ait feed under various LHSVs. The contact system and catalyst system are the same as those described in Example 6. The crude oil feed is shown in Figure 18 Table 6. The contact conditions are as follows: the ratio of hydrogen to the crude oil feed to the reaction benefit is 160 Nm3 / m3 (1000 SCFB), the force is 6.9MPa (10i4.7psi), and the temperature of the contact zone The total operating time was 371 ° C (700F). In Example 19, the LHS V during the contact was increased from 109 200535221 over a period of time from h! To 12 ρ and maintained at 12 h-1 at 48. The small daily inch 'then increased the LHSV to 20.7 h · 1 and maintained it at 20.7 hr1 for 96 hours. In Example 19, the crude oil product was analyzed to determine the TAN during the time period when the LHSV was 12 hi and 20.7 h · 1. , Viscosity, density, VGO content, residue content, heteroatom content, and gold in the form of organic acid metal salts Weight. The average value of the properties of crude oil products is shown in Table 6, Figure 18. As shown in Table 6, Figure 18, the crude oil product of Example 19 has a reduced TAN and a reduced TAN and viscosity compared to the crude oil feed. Viscosity, and · API specific gravity of crude oil product is 104% to 80% of Aρι of crude oil feed. The weight ratio of MCR content to Cs asphaltene content is at least ι.5. The sum of mcr content and asphaltene content Compared with the sum of MCR content and c5 asphaltene content of crude oil feed. From the weight ratio of the MCR content to the q asphaltene content and the reduction of the sum of the MCR content and the C5 asphaltene, it can be inferred that it is the asphalt shells rather than the components with a tendency to form coke. Crude products also have a total potassium, sodium, zinc and calcium content of up to 60% of the same metal in the crude feed. The crude product has a sulfur content of 80 to 90% of the sulfur content of the crude feed. Examples 6 and I9 show that the contact conditions can be controlled so that the LHSV through the contact zone is greater than 0 h i compared to a process with an LHsv of 1 h-m to produce crude products with similar properties. The ability to selectively change the feedability f of crude oil at liquid space velocities greater than 10 h-1 allows the contact method to be carried out in a container that is smaller in size than a commercially available container. The smaller container size allows the processing of inferior crude oils to be performed at production sites with size restrictions (for example, offshore facilities 110 200535221). ‘20. —Contact of crude oil feed at various contact temperatures. The contact system and the catalyst system are the same as those described in the sixth embodiment. A crude oil feed having the properties listed in Table 7 of Figure 19 was added to the top of the reactor and contacted with two catalysts in two contact zones in the presence of hydrogen to produce a crude oil product. The two contact zones operate at different temperatures. The contact conditions in the top contact zone are as follows: LHSV is 1 h-1; the temperature in the top contact zone is 260 t (500 T); the ratio of hydrogen to crude oil feed is 160 NmW (1_ SCFB); and the pressure is 6 9 gallons ( ι〇ΐ4 7 ㈣. The contact conditions of the bottom contact area are as follows: LHSV is 1 lr1; the temperature of the bottom contact area is 315 t (600 ° F); the ratio of hydrogen to crude oil feed is 160 Nm / m3 (100%). SCFB); and the pressure is 6 9 MPa (1014 7 Torr). The total product leaves the bottom contact zone and is introduced into the gas-liquid separator. In the gas-liquid separator, the total product is separated into crude oil products and gases. Crude oil products are regularly analyzed to determine the TAN and c5 asphaltene content. The average value of the properties of the crude oil products obtained during operation is shown in Table 7. Figure B crude oil feed has a TAN and q asphaltene content of 9 · 3 per gram. Lu crude oil feed has 0.055 grams of C5 asphaltenes. Crude oil products have a flat sentence of TAN and c5> calendar f quality average content of grams of asphaltenes per gram of crude oil products. Q of crude oil products q C5 asphaltene content in crude oil feeds with a maximum asphaltene content of 71. Total content of potassium and sodium in crude oil products The total content of 2 metals in the crude oil feed. The crude oil product with a TAN of at most 1G% crude oil feed N maintained a P value of 1.5 or higher during the contact. 111 200535221 As shown in Examples 6 and 20 A first (top in this example) contact temperature having a contact temperature 50 lower than the contact temperature of the second (bottom in this example) zone tends to make the c5 asphaltene content of the crude oil product better than the q asphalt of the crude oil feed The quality content is more reduced. In addition, the use of a controlled temperature difference will reduce the metal content of the organic acid metal salt form. For example, in each embodiment, the stability of the crude oil feed / total product mixture is quite stable (As measured by p-value)

The total potassium and sodium content of the crude oil product of Example 20 is lowered than the total potassium and sodium content of the crude oil product of Example 6 is reduced. The use of a lower temperature first contact zone allows the removal of high molecular weight names (such as Cs asphaltenes and 7 or organic acid metal salts), which will have physical properties that form aggregates and / or have softness and / or stickiness Properties of compounds (such as gums and or tars). Removal of these compounds at lower temperatures may allow this to happen: the substances are removed before they clog and cover the catalyst, thereby increasing the life of the catalyst configured to operate at higher temperatures behind the first contact zone. ~ Contact of catalyst in suspension.

Monthly metal catalysts and / or catalysts (per 100 grams of radon feed contains 0 · 0001 to s Gudou, Λ — main 1 2 3 grams or 0.02 to 4 grams ) In several examples, the crude oil feed can be used to suspend it and react under the following conditions: The degree is 85 to 425 V " η. (185 to 797 T), a pressure in the range of 0 to 10 MPa allows you to snore, and the ratio of lice source to crude oil feed is 1 to 16 (

Nm / m reaches 112 1 in one paragraph. After a reaction time sufficient to produce the crude product, the crude product is separated from the equipment by a knife, such as a filter and / or centrifuge: the catalyst and / or residual horses 3, and the oil feed is separated. Crude products and crude feed phases] 200535221 May have altered TAN, iron, nickel, and / or vanadium content, and reduced cyanidin content. It will be apparent to those skilled in the art that further modifications and substitutions can be made in various aspects of the invention in light of the present specification. Therefore, this description is only to be used as an illustration and for the purpose of teaching a person skilled in the art to implement the general method of the present invention. It should be understood that the form of the invention shown and described herein is an example of a specific example. Can replace the elements and materials illustrated and described in this article, can reverse parts and procedures of the present invention, can use some features of the invention alone, all of which should be familiar with the technology after the benefits of the description of the invention This is obvious. Changes to the documents described herein can be made without departing from the spirit and scope of the invention as described in the scope of the attached patent application. [Brief description of the drawing] For the person skilled in the art, the advantages of the present invention with the following detailed description will become obvious after referring to the drawings, where: Figure 1 is the specific of the contact system Simplified illustration of the example. Figures 2A and 2B are simplified diagrams of a specific example of a contact system including two contact areas. Figures 3 A and 3B are specific examples of a contact system including three contact areas.

Simple diagram. J Figure 4 is a simplified diagram of a specific example of a separation zone incorporating a contact system. Fig. 5 is a schematic diagram of a specific example of a blending zone of a contact system. Figure 6 is a specific example of the combination of separation zone, contact system and blending zone.

Figure 7 is a representative f list of crude feeds and three feeds and crude products. A specific example of contacting crude oil Figure 8 is a graphical representation of a specific example of contacting a crude oil feed with a weighted average bed-production ff ^ 'catalyst at 隹 9 beds / deck versus operating time. Figure 9 is a list of representative properties of crude oil feeds and crude oil products for specific examples of contacting two crude oil feed trays with two fishermen and two catalysts. 10 is another list of representative properties of crude oil feeds in contact with two catalysts < feed and crude oil products.

Figure 11 is a list of specific actual crude oil feeds and crude oil products that contact the crude oil feed with four different catalyst systems. Figure 12 is a graphical representation of the P value of a specific set of crude oil products versus operating time for contacting the crude oil feed with four different contact systems. Figure 13 is a graphical representation of the net uptake of hydrogen from the crude feed versus operating time for a specific example of contacting the crude feed with four different catalyst systems.

• Figure 14 is a graphical representation of specific examples of contacting crude oil feeds with four different catalyst systems, with the residual content of crude oil products expressed as weight percentages versus operating time. Figure 15 is a graphical representation of the change in API specific gravity of crude oil products versus operating time for a specific example of contacting a crude feed with four different catalyst systems. Fig. 16 is a graphic illustration of the specific example of contacting the crude oil feed with four different catalyst systems, the oxygen content of the crude oil product expressed as a percentage by weight versus operating time. Figure 17 shows a specific example of crude oil contacting the crude oil feed with the catalyst system. 114 200535221 The feedstock and crude oil product #a ... list, the catalyst system contains various quantities, ',. All catalysts, and catalyst systems containing vanadium catalysts and molybdenum / vanadium catalysts, and glass beads. Figure 18 is a list of properties of a shoulder oil booster / crude feedstock and crude oil product for a specific example of contacting a crude oil feed with krypton or catalysts at various liquid space velocities. Figure 19 is a list of properties of crude oil feeds and crude oil products for specific examples of contacting crude oil feeds at various contact temperatures.

Although the invention allows various modifications and alternative forms, specific specific examples thereof are shown by way of example in the drawings. The illustrations may not be drawn to scale. It should be understood that its illustrations and detailed descriptions are not intended to limit the present invention to the specific forms disclosed, but, on the contrary, it is intended to cover all modifications and equivalents that fall within the spirit and scope as defined by the appended claims. And alternatives. [Description of main component symbols] 100: contact system 102: contact area 104: conduit 106; conduit 106 ': conduit: separation area 110: conduit 112: conduit 1 14: contact area 1 1 6: contact area 115 200535221 1 18 : Duct 120: separation zone 122: duct 124: duct 126: duct 128: duct 130: blending region 132: duct 134: duct 136: curve of weighted average bed temperature (WABT) versus operating time 140-146: P value vs. running time curve 148_ 154: Net absorption of argon vs. running time 15 6-162: Residual content of crude oil product vs. running time 164-170: API specific gravity of crude oil product vs. running time 172 -178: Curve of oxygen content of crude oil product versus operating time

Claims (1)

200535221 10. Scope of patent application: 1. A method for producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a core product containing a crude oil product, wherein the crude oil product is at 25. 〇 and 〇⑻ are in liquid state. This product 1 2 3 Hai crude oil feed has a total acid value (TAN) of at least 0.1, the crude oil feed has a residue content of at least 0.001 grams per gram of crude oil feed And the at least one catalyst comprises one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof, and controlling the contact conditions so that the crude oil The product has the TAN of the crude oil feed with the largest TAN, and the crude oil product has the residue content of the crude oil feed with a residue content of up to 130%, where the TAN is determined by the astm method D664 and the residue content is Determined by ASTM method D5307. 2. The method according to item 1 of the scope of patent application, wherein the crude oil product is 50% at the latest, at most 30%, or the TAN of crude oil feed of 100/0 at most 〇 117 1 The method of item 1, wherein the Lu Tan of the crude product is in! To 80%, 20 to 70%, 30 to 60%, or 50% of the TAN of the crude oil feed. 2. The method according to any one of claims 1 to 3, wherein the TAN of the crude product is in the range of 0.001 to 0.05, 0.001 to 0.2, or 0M to ο · 1. Inside. 3. The method according to any one of claims 1 to 4, wherein the crude oil feed TAN is in the range of 200535221 from 0.3 to 20, 0.4 to 10, or 0.5 to 5. 6 · A method of producing a crude oil product, comprising: contacting a crude oil feed with one or more catalysts to produce a total product containing the crude oil product 'wherein the crude oil product is a liquid mixture at 25 and 〇 丨 〇1 The crude oil feed contains one or more organic acids, one or more alkali metal salts, one or more organic acid one or more alkaline earth metal salts, or a mixture thereof. The crude oil feed has at least 0.00001 per gram of crude oil feed. The total content of alkali metals and alkaline earth metals in the form of organic acid metal salt, the residue contains at least 0.1 grams of residue, the at least one catalyst contains one or more metals in the sixth table of the periodic table, column 6 of the periodic table One or more compounds of one or more metals, or a mixture thereof; and ^ controlling the contact conditions so that the crude oil product has an organic acid metal salt in the form of a total alkali metal and alkaline earth metal content of up to 90% in the crude oil feed Contents of alkali metals and alkaline earth metals in the form of metal organic acids, the crude oil product has a residue content of 70 to 130% of the crude oil feed, wherein organic Alkali metal and alkaline earth metal content of the metal-based form by astm & D1318 measured, and the content-based residue, still by ast ^ Julius measured. 7. The method according to the scope of patent application f6, wherein the total content of alkali metals and alkaline earth metals in the form of organic acid metal in the crude oil product is, at most, 10% ', or at most 5% of organic in the crude oil feed. Alkali and alkaline earth metal content in acid metal form. 8. The method according to the scope of patent application f6, wherein the total content of alkali metals and alkaline earth metals in organic acid metal form in the crude oil product is i to ⑼%, 118 200535221 is organic to 10 to 70%, 2G to 6G%, or The content of the alkali metal and alkaline earth metal in the acid metal form of the crude oil feed is in the range of 3G to 5G%. ^ 9_ The method according to any one of claims 6 to 8 in the scope of the patent application, wherein 4 crude oil products contain 0.00000 to 100,000 per gram of crude oil products, 0_0000003 to 0.00000 Grams, or 10,000 to 10,000 grams of alkali metal and alkaline earth metal in organic acid metal form. 10 · —A method for producing crude oil products, including: The crude oil feed is contacted with one or more catalysts to produce a total product ' . And this compound is liquid at 0101 MPa, and the rhenium crude oil feed has a residue content of 0.1 g per gram of crude oil feed, and a total Ni / V / Fe content of at least 0 0000002 g, The at least one catalyst comprises one or more metals in column 6 of the periodic table, one or more compounds of one or more metals in column 6 of the periodic table, or a mixture thereof; and controlling the contact conditions so that the crude oil product has a total Ni / The V / Fe content is more than 90% of the Ni / V / Fe content of the crude oil feed, and the crude oil product has a residue content of the crude oil feed of 70 to 130% mullite content, where Ni / The V / Fe content is measured by ASTM method D57008, and the residue S i is measured by ASTM method D5307. 11. The method according to item 10 of the patent application range, wherein the Ni / V / Fe content of the crude product is at most 50%, at most 10%, or at most 5% of the Ni / V / Fe of crude oil feed content. 12. The method of claim 10, wherein the Ni / V / Fe content of the crude product is 1 to 80%, 10 to 70%, 20 to 60%, or 30119 200535221 to Within the range of 50% Ni / V / Fe content of the crude oil feed. 13. The method as claimed in any one of claims 10 to 12 in the scope of the patent application, wherein the crude oil product contains 〇〇〇〇〇1 〇0005 gram in the mother gram crude oil product, 0.0000005 to o.ooool grams, or Ni / V / Fe from 0,001,001 to 0,000 μ. 5 grams 14. The residue content of the crude oil product in the method basin according to any one of claims 1 to 13 is 80 to 120% or 90 to ^. The residue content of this crude oil feed. 15. The method according to any one of the claims i to 14 of the scope of patent application, the crude oil product contains 0.001 g to 0.0001 g to 0.5 g, 0.0005 g to 0.4 g per gram of crude oil product, ( ) G to 0.005 g to 0.2 g, or 0.001 g to 0.01 g of residue. > 16. According to the method of any one of claims 15 to 15, the crude oil feed in beans contains at least G2 grams, at least '㈠ grams, at least 0.5 grams, or at least 0 grams per gram of crude oil feed. 9 g of residue. -P. The method of any one of claims i to 16 in the scope of patent application, wherein one or more of the metals in column 6 is molybdenum and / or tungsten. // 18. The method according to any one of the items i to 17 of the scope of patent application, wherein the 6th & metal catalyst has a median pore diameter of at least 90A, and, to: A 'or at least 230 A Pore size distribution. # 19. The method according to any one of claims 18 to 18, wherein the metal catalyst of No. 6 has a total pore number of at least 60% in the pore size distribution with 70 A, 45 people, 35 A, 弋, "λ 丄 Α or 25 Α pore size in the median pore size range. 120 200535221 2．If the metal catalyst in the sixth column of any of the items 1 to 19 of the scope of the application for a patent contains a method of periodic items, it does not contain 1 or 5 columns_ $ 夕 属, one or more of the 5th column One or more compounds of metals, one or more metals of gold to 10 columns in the next night, one or more compounds of 7 to 10 or more in the seventh table of the periodic table, or a mixture thereof. 21 of the remaining rabbits. As described in the patent application scope of any of the 1st to 20th of the _ metal catalyst in the 6th method additionally contains Zhou's method, its J only He 丄 5 _ Xi element, one or more One or more compounds of elements in column 15. Eve species 22 · If any of the items in the scope of patent applications 1 to 21-the-or more catalysts additionally include additional catalysts, the appendix: ancient: pore size distribution of at least 60A, or at least 18GA . Yes No 23. If any one of claims i to 22 of the scope of patent application, the crude oil feed is brought into contact in a contact zone located or connected to the offshore equipment. U〒 进 仃 24. As in any of the items 1 to 23 of the scope of the patent application, the middle method also includes combining the crude oil product with the same or different crude oil feed to form a blend. —! To 2: item = oil: substance or blend, which can be obtained by the method of any one of items 1 to 2 in the scope of patent application. . Part 2 of 6 :: The method for transporting fuel, heating fuel, lubricating oil or chemical plutonium, including processing patent or blending. ≪ Crude oil product 27. The method according to item 26 of the patent application, wherein the processing includes distilling the crude oil product or blended product into one or more fractions. 121 200535221 28. The method of claim 26 or 27, wherein the processing includes hydrotreating. Η • 一 、 Schematic: Like the next page 122