CN104226342B - Heavy oil hydrotreating catalyst and preparation and application - Google Patents

Abstract

A heavy oil hydrotreating catalyst and its preparation and application, the catalyst contains a halogen bimodal porous alumina carrier and a hydrogenation active metal component loaded on the carrier, wherein, characterized by mercury porosimetry, the pores of the carrier The volume is 0.95-1.2 ml/g, the specific surface area is 50-300 ^m2 /g, the carrier has a bimodal pore distribution with a diameter of 10-30nm and a diameter of 300-500nm, wherein the diameter of the pore is 10-30nm The pore volume accounts for 55-80% of the total pore volume, the pore volume of pores with a diameter of 300-500nm accounts for 10-35% of the total pore volume, and the hydrogenation active metal component is selected from at least one VIB group metal component and at least one Group VB metal component, calculated as an oxide and based on the catalyst, the content of the VIB Group metal component is 0.2-15% by weight, and the content of the Group VB metal component is 0.2-12% weight%. Compared with the catalyst provided by the prior art, the hydrogenation demetallization and deasphaltene activities of the catalyst provided by the invention are obviously improved.

Description

A kind of heavy oil hydrogenation treatment catalyst and its preparation and application

technical field

The invention relates to a hydrogenation catalyst, its preparation and application, in particular to a hydrogenation treatment catalyst suitable for heavy oil processing, its preparation and its application.

Background technique

As the world-wide contradiction between heavy and low-quality crude oil and diversified and light-weight demand for petrochemical products becomes increasingly acute, the main task of the petrochemical industry will focus on lightening heavy oil. Residual oil is the heaviest fraction in crude oil. After crude oil is distilled, species with large molecular weight and complex structures are enriched in the residual oil. These impurities have an important impact on the subsequent processing and product properties. These impurities are removed. Compared with distillate oil, in addition to impurities such as sulfur and nitrogen, heavy oil also contains a higher proportion of metal impurities such as Ni and V, and has a higher asphaltene content and higher carbon residue value. Among them, if metal impurities such as Ni and V are not effectively removed, they will have an adverse effect on the downstream catalyst, block the pores of the downstream catalyst, and cause the deactivation of the downstream catalyst. Therefore, the development of hydrodemetallization catalysts with high demetallization activity can effectively prolong the service life of downstream catalysts, thereby protecting downstream catalysts and prolonging the operation period of the device. Due to the above-mentioned characteristics of residual oil, the activity and stability of residual oil hydrogenation catalysts are very important in industrial applications. Many patent companies at home and abroad have launched a variety of residual oil hydrodemetallization agents.

CN1054393C discloses a method for preparing a residual oil hydrodemetallization catalyst, which is characterized in that the pore structure of the residual oil hydrodemetallization agent is improved by means of physical and chemical methods.

CN1267537C discloses a method for preparing a residual oil hydrodemetallization catalyst, which is characterized in that the carrier used contains a halogen, and the proportion of the halogen accounts for 0.1-5% by weight of the carrier, so that the acidity of the carrier is less than 0.2 mmol/ grams (the amount of carrier acid is low), so that the catalyst maintains a high hydrodemetallization activity and at the same time, the amount of carbon deposition is low.

CN1946831A and US7608558 disclose a hydrotreating catalyst containing VB group metals, characterized in that the metal components (calculated as oxides) constitute at least 50% by weight of the catalyst, wherein the molar ratio between the metal components conforms to the following formula: (Group VIB + Group VB): (Group VIII) = 0.5-2:1.

US5275994 describes a hydroprocessing catalyst suitable for hydrocarbon feedstocks comprising a Group VIII metal component, a Group VIB metal component and a Group VB metal component. Such trimetallic catalysts must be supported on silica or alumina and are preferably characterized by comprising less than 28% by weight of metal components (calculated as oxides). In catalyst preparation, the Group VB metal component must be added as an alkoxide in an anhydrous environment, and the catalyst as a whole is preferably calcined at at least 500°C.

Contents of the invention

The technical problem to be solved by the present invention is to provide a new catalyst with high activity and stability of hydrogenation demetallization and deasphaltene, the preparation and application of the catalyst.

The present invention relates to the following inventions:

1. A heavy oil hydrotreating catalyst, comprising a carrier and a hydrogenation active metal component supported on the carrier, wherein the hydrogenation active metal component is selected from at least one Group VIB metal component and at least A metal component of Group VB, the carrier contains alumina and halogen, characterized by mercury intrusion porosimetry, the pore volume of the carrier is 0.95-1.2 ml/g, and the specific surface area is 50-300 ^m2 /g, The carrier has a bimodal pore distribution with a diameter of 10-30nm and a diameter of 300-500nm, wherein the volume of pores with a diameter of 10-30nm accounts for 55-80% of the total pore volume, and the pores with a diameter of 300-500nm The volume accounts for 10-35% of the total pore volume, based on oxides and catalysts, the content of the VIB group metal component is 0.2-15% by weight, and the content of the VB group metal component is 0.2-12% by weight. weight%.

2. The catalyst according to 1, characterized in that the pore volume of the carrier is 0.95-1.15 ml/g, the specific surface area is 80-200 ^m2 /g, and the pore volume of the pores with a diameter of 10-30nm accounts for the total pore volume 60-75% of the total pore volume, and the pore volume of the pores with a diameter of 300-500nm accounts for 15-30% of the total pore volume; the metal component of the VIB group is selected from molybdenum and/or tungsten, and the metal component of the VB group is selected from From vanadium and/or niobium, calculated as oxides and based on the catalyst, the content of the group VIB metal component is 0.5-12% by weight, and the content of the group VB metal component is 0.5-9% by weight.

3. The catalyst according to 1, characterized in that the halogen component is selected from one or more of fluorine, chlorine, bromine, iodine and astatine, based on the support and in terms of elements, the The content of halogen in the carrier is 0.1-6% by weight.

4. The catalyst according to 3, characterized in that the halogen is preferably fluorine, and the content of the halogen is 0.3-4% by weight in terms of elements and based on the support.

5. The catalyst according to 4, characterized in that based on the carrier and calculated as elements, the content of halogen in the carrier is 0.5-2.5% by weight.

6. The catalyst according to 1 or 2, characterized in that the metal component of Group VIB is molybdenum or tungsten, and the metal component of Group VB is vanadium, calculated as oxide and based on catalyst, said The content of the Group VIB metal component is 5-12% by weight, and the content of the Group VB metal component is 1-9% by weight.

7. The preparation method of the catalyst according to 1, comprising the steps of:

(1) Preparation of the carrier, including mixing the hydrated alumina P1 containing pseudoboehmite and the modified product P2 of P1 and introducing a halogen-containing compound into the mixture, followed by shaping, drying and calcining, the P1 and P2 The weight mixing ratio is 20-95:5-80, the κ value of P2 is 0 to less than or equal to 0.9, the κ=DI ₂ /DI ₁ , DI ₁ is the acid of hydrated alumina P1 containing pseudo-boehmite Peptization index, DI2 is the acid peptization index of the modification P2 of the hydrated alumina P1 containing pseudoboehmite;

(2) introducing hydrogenation active metal components on the support obtained in step (1) by impregnation, including preparing an impregnation solution containing a hydrogenation active metal compound and impregnating the support with the solution, followed by drying, roasting or no roasting, The hydrogenation active metal component is selected from at least one metal component of Group VIB and at least one metal component of Group VB, calculated as oxide and based on catalyst, the concentration and amount of the impregnating solution The content of the metal component of Group VIB in the final catalyst is 0.2-15% by weight, and the content of the metal component of Group VB is 0.2-12% by weight;

Wherein, the drying conditions in the step (1) include: the temperature is 40-350°C, and the time is 1-24 hours; the roasting conditions include: the temperature is greater than 500 to less than or equal to 1200°C, and the time is 1-8 hours; The drying conditions in the step (2) include: the temperature is 100-250° C., and the time is 1-10 hours; the roasting conditions include: the temperature is 360-500° C., and the time is 1-10 hours.

8. The method according to 7, characterized in that the weight mixing ratio of P1 and P2 is 70-95:5-25; the k value of P2 is 0 to less than or equal to 0.6; the step (1) The drying conditions include: the temperature is 100-200°C, the time is 2-12 hours, the roasting conditions include: the temperature is greater than 800 to less than or equal to 1000°C, and the roasting time is 2-6 hours; the drying of the step (2) Conditions include: a temperature of 100-140°C.

9. The method according to 7, characterized in that the halogen component is selected from one or more of fluorine, chlorine, bromine, iodine and astatine, calculated as oxides and based on the carrier, so The introduction amount of said halogen compound makes the content of halogen in the final carrier be 0.1-6% by weight.

10. The method according to 9, characterized in that the halogen is preferably fluorine, calculated as an oxide and based on the support, and the introduction amount of the halogen compound is such that the content of halogen in the final support is 0.3-4 weight%.

11. The method according to 7 or 8, characterized in that the hydrated alumina P1 containing pseudoboehmite has a pore volume of 0.9-1.4 ml/g and a specific surface of 100-350 ^m2 /g, The most accessible pore diameter is 8-30nm.

12. The method according to 11, characterized in that the hydrated alumina P1 containing pseudo-boehmite has a pore volume of 0.95-1.3 ml/g and a specific surface of 120-300 ^m2 /g, most And the hole diameter is 10-25nm.

13. The method according to any one of 7 or 8, characterized in that the P2 is 80-300 mesh particles.

14. The method according to 13, wherein the P2 is 100-200 mesh particles.

15. The method according to 7, characterized in that one of the methods for modifying P1 to P2 is to shape and dry the hydrated alumina P1 containing pseudo-boehmite, and then grind all or part of it , sieving, and the obtained powder is P2, and the drying conditions include: the temperature is 40-350° C., and the time is 1-24 hours; the second method is to roast the molded product obtained by method one, and the roasting temperature is greater than 350 To be less than or equal to 1400°C, the roasting time is 1-8 hours, and then all or part of it is ground and sieved to obtain a powder P2; the third method is to flash the hydrated alumina P1 containing pseudo-boehmite dry, the flash-drying temperature is greater than 150 to less than or equal to 1400°C, the flash-drying time is 0.05-1 hour, and the obtained powder is P2; One or a combination of several substances.

16. The method according to 15, characterized in that the drying conditions in the first method include: the temperature is 100-200°C, and the time is 2-12 hours; the calcination temperature in the second method is 500-1200°C , the calcination time is 0.1-6 hours; the flash-drying temperature in method 3 is 200-1000° C., and the flash-drying time is 0.1-0.5 hours.

17. The method according to 15 or 16, characterized in that the P2 is the 80-300 mesh particulate matter in the modified product of P1.

18. The method according to 17, characterized in that the P2 is the 100-200 mesh particulate matter in the modified P1.

19. The method according to 7, characterized in that, based on the oxide and the catalyst, the concentration and dosage of the impregnating solution in the step (2) are such that the content of the VIB group metal component in the final catalyst is 0.5-12% by weight, and the content of the VB group metal component is 0.5-9% by weight.

20. The method according to 19, characterized in that, based on the oxide and the catalyst, the concentration and dosage of the impregnation solution in the step (2) are such that the content of the Group VIB metal component in the final catalyst is is 5-12% by weight, and the content of Group VB metal components is 1-9% by weight.

21. The application of the hydrotreating catalyst according to any one of claims 1-6 in the hydrotreating of hydrocarbon oil.

Depending on different requirements, the carrier in the catalyst of the present invention can be made into various easy-to-handle shapes, such as spherical, honeycomb, bird's nest, tablet or strip (clover, butterfly, cylindrical, etc.). Wherein, the method of mixing the hydrated alumina P1 containing pseudoboehmite and the modified product P2 of P1 is a conventional method, for example, the powder P1 and P2 are put into a stirring mixer according to the feeding ratio and mixed . The method of introducing the halogen compound into the mixture of P1 and P2 is a conventional method, for example, directly mixing the required amount of the halogen compound in the aforementioned mixing process of P1 and P2.

In a specific embodiment of preparing the support, the method of introducing the halogen compound into the mixture of the hydrated alumina P1 containing pseudo-boehmite and the modified product P2 of P1 is to prepare the halogen compound into an aqueous solution, and the The aqueous solution is mixed in while the P1 and P2 are mixed or mixed in after the P1 and P2 are mixed, and then shaped, dried and fired. The halogen compound may be one or more of any halogen water-soluble compounds. For example, one or more of the water-soluble inorganic salts of halogens.

In the present invention, the molding can be carried out by conventional methods, for example, one method or a combination of several methods among ball rolling, tablet pressing and extrusion molding. When molding, such as extrusion molding, in order to ensure that the molding is carried out smoothly, water, extrusion aids and/or adhesives, with or without pore-expanding agents, can be added to the mixture, and then extrusion molding, followed by Dried and roasted. The type and amount of the extrusion aid and the peptizing agent are well known to those skilled in the art, for example, the common extrusion aid can be selected from one of squash powder, methyl cellulose, starch, polyvinyl alcohol, polyethanol or several, the peptizer can be inorganic acid and/or organic acid, and the pore-enlarging agent can be one or more of starch, synthetic cellulose, polymeric alcohol and surfactant. Wherein the synthetic cellulose is preferably one or more in hydroxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxycellulose fatty alcohol polyvinyl ether, and the polymeric alcohol is preferably polyethylene glycol, polypropylene alcohol, One or more of polyvinyl alcohol, the surfactant is preferably one of fatty alcohol polyvinyl ether, fatty alcohol amide and its derivatives, acrylic alcohol copolymer and maleic acid copolymer with a molecular weight of 200-10000 or several.

The acid peptization index DI in the preparation of the carrier refers to the hydrated alumina containing pseudoboehmite that is peptized within a certain reaction time after adding nitric acid at a certain acid-aluminum ratio. The percentage of aluminum oxide in Al ₂ O ₃ , DI=(1-W ₂ /W ₁ )×100%, W ₁ and W ₂ are respectively before and after the reaction of pseudo-both aluminum and acid with Al ₂ O ₃ gauge weight.

The determination of DI includes: (1) Determination of the ignited base content of hydrated alumina containing pseudo-boehmite (the ignited base (also called dry base) content refers to roasting quantitative pseudo-boehmite at 600°C for 4 hours , the ratio of the weight after burning to the weight before burning), counted as a; (2) Weigh the hydrated alumina W ₀ grams containing pseudo-boehmite with an analytical balance, and the amount of W ₀ meets the W calculated in Al ₂ O _{3 1} is 6 grams (W ₁ /a=W ₀ ), weigh W grams of deionized water, W=40.0-W ₀ , add the weighed hydrated alumina containing pseudo-boehmite and deionized water under stirring Mix in a beaker; (3) Use a 20mL pipette to pipette 20mL of dilute nitric acid solution with a concentration of 0.74N, add the acid solution into the beaker of step (2), and react for 8 minutes under stirring; (4) Reaction of step (3) The final slurry was centrifuged in a centrifuge, and the precipitate was placed in a weighed crucible. After that, it was dried at 125°C for 4 hours, baked in a muffle furnace at 850°C for 3 hours, and weighed to obtain an ignited sample. Amount W ₂ grams; (5) Calculated according to the formula DI=(1-W ₂ /W ₁ )×100%.

On the premise that the final carrier is sufficient to meet the requirements of the present invention, the present invention has no special requirements for the hydrated alumina P1 containing pseudo-boehmite, which can be any pseudo-boehmite prepared in the prior art, or A mixture of pseudo-boehmite and other hydrated alumina, wherein the other hydrated alumina is selected from one or more of alumina monohydrate, alumina trihydrate and amorphous hydrated alumina. For example, the pore volume is 0.9-1.4 ml/g, the specific surface is 100-350 ^m2 /g, and the most accessible pore diameter is 8-30 nm; the preferred pore volume is 0.95-1.3 ml/g, and the specific surface is 120-300 m Alumina hydrates containing pseudo ^- boehmite having a most accessible pore diameter of 10-25 nm are particularly suitable for use in the present invention. In the present invention, the pore volume, specific surface area and most accessible pore diameter of the hydrated alumina containing pseudo-boehmite are determined by BET after calcination of the hydrated alumina containing pseudo-boehmite at 600°C for 4 hours. Nitrogen adsorption was characterized.

In a further preferred embodiment, as characterized by X-ray diffraction, the content of pseudo-boehmite in the hydrated alumina containing pseudo-boehmite is not less than 50%, more preferably not less than 60%.

The inventors of the present invention have surprisingly found that after heat treatment and modification of alumina hydrate P1 containing pseudo-boehmite, the peptization index of the modified product changes. After P1 was mixed and molded, dried and calcined, the obtained support had an obvious bimodal pore distribution. Especially after the 80-300 mesh particles, preferably 100-200 mesh particles and the non-heat-treated part are mixed and formed, dried and calcined, the pore distribution of each unimodal in the bimodal of the obtained carrier is particularly concentrated . Here, the 80-300 mesh particles, preferably 100-200 mesh particles mean that the modified product has been sieved (including the step of crushing or grinding if necessary), and the sieved material (undersize) meets the 80-300 mesh Particles, preferably 100-200 mesh particles, account for a percentage (by weight) of not less than 60% of the total, more preferably not less than 70%.

In specific implementation, the P2 can be easily obtained by the following methods:

(1) Obtaining P2 based on drying, including the tailings produced by drying during the preparation of conventional alumina carriers from hydrated alumina P1 containing pseudoboehmite according to conventional methods, for example: in extrusion molding, strip forming The tailings (customarily called dry waste) that are by-produced in the drying and shaping process are ground and sieved to obtain P2.

(2) Obtained on the basis of roasting, including the tailings (customarily called roasting waste) produced by roasting during the preparation of conventional alumina carriers from hydrated alumina P1 containing pseudo-boehmite according to conventional methods, for example, in tumbling In ball molding, the tailings produced by the spherical particles during the roasting process are ground and sieved to obtain P2; or obtained by flashing P1 directly. When directly flashing P1, the flashing time is the best 0.05-1 hour, more preferably 0.1-0.5 hour.

(3) Obtained based on the mixture of two or more of the modified substances P2 obtained by the aforementioned method. When using the mixing method to obtain P2, there is no limit to the mixing ratio of the modified P2 obtained by the above-mentioned methods.

The VIB group metal component is preferably molybdenum and/or tungsten, more preferably molybdenum or tungsten, and the VB group metal component is preferably vanadium and/or niobium, more preferably vanadium. Based on the oxide and based on the catalyst, the content of the Group VIB metal component is preferably 0.2-15% by weight, more preferably 0.5-12% by weight, and even more preferably 5-12% by weight; the Group VB metal The content of the component is preferably 0.2-12% by weight, more preferably 0.5-9% by weight, still more preferably 1-9% by weight.

On the premise that the hydrogenation active metal component is sufficient to be loaded on the alumina carrier, the present invention has no particular limitation on the loading method, and the preferred method is the impregnation method, which includes preparing the metal-containing compound impregnation solution, and then impregnate the alumina support with this solution. The impregnation method is a conventional method, for example, it may be impregnation with excess liquid or pore saturation method.

Wherein, the metal-containing compound is selected from one or more of their water-soluble compounds (including water-soluble compounds in the presence of a co-solvent). Taking the molybdenum of the VIB group as an example, it can be selected from one or more of molybdenum oxide, molybdate, and paramolybdate, preferably molybdenum oxide, ammonium molybdate, and ammonium paramolybdate; For example, it can be selected from one or more of tungstate, metatungstate, ethyl metatungstate, preferably ammonium metatungstate and ethyl ammonium metatungstate; For example, it can be selected from one or more of vanadium pentoxide, ammonium vanadate, ammonium metavanadate, vanadium sulfate, and vanadium heteropolyacid, among which ammonium metavanadate and ammonium vanadate are preferred.

The catalyst provided by the present invention may also contain any material that does not affect the performance of the catalyst provided by the present invention or that can improve the catalytic performance of the catalyst provided by the present invention. If phosphorus and other components may be included, the content of the above-mentioned components is not more than 10% by weight, preferably 0.5-5% by weight, based on the oxide and the catalyst.

When the catalyst also contains components such as phosphorus, the introduction method of components such as phosphorus can be any method, such as directly mixing the compound containing components such as phosphorus with the pseudo-boehmite Mixing, molding and roasting; it may be that the compound containing the phosphorus and other components and the compound containing the hydrogenation active metal component are formulated into a mixed solution and then contacted with the carrier; it may also be that the compound containing phosphorus and other components After the solution is prepared separately, it is contacted with the carrier and calcined. When components such as phosphorus and the hydrogenation active metal are respectively introduced into the carrier, it is preferable to first contact the carrier with a solution containing an auxiliary agent compound and roast it, and then contact with a solution containing a compound of the hydrogenation active metal component, for example By impregnation, the calcination temperature is 400-600°C, preferably 420-500°C, and the calcination time is 2-6 hours, preferably 3-6 hours.

According to the heavy oil hydrotreating method provided by the present invention, the reaction conditions for the heavy oil hydrotreating are not particularly limited. In a preferred embodiment, the hydrotreating reaction conditions are: reaction temperature 300-550°C, further Preferably 330-480°C, hydrogen partial pressure 4-20 MPa, more preferably 6-18 MPa, volume space velocity 0.1-3.0 h ^-1 , more preferably 0.15-2 h ^-1 , hydrogen-oil volume ratio 200-2500, More preferably 300-2000.

The device for the hydrogenation reaction can be carried out in any reactor sufficient to make the feedstock oil contact with the catalyst under the hydrotreating reaction conditions, for example, in the fixed bed reactor, moving bed reactor or carried out in an ebullating bed reactor.

According to conventional methods in this field, before use, the hydrotreating catalyst can be presulfurized with sulfur, hydrogen sulfide or sulfur-containing raw materials at a temperature of 140-370° C. in the presence of hydrogen, such presulfurization It can be vulcanized outside or in-situ, and the active metal components supported by it can be converted into metal sulfide components.

Compared with the catalyst provided by the prior art, the double peaks of the carrier adopted by the catalyst provided by the invention are concentrated in 10nm-30nm and 300nm-500nm. When it is used in heavy oil processing, the catalyst shows good performance of hydrodeasphaltene. The catalyst provided by the invention can be used alone or in combination with other catalysts. The catalyst is especially suitable for hydrotreating heavy oil, especially inferior residue oil, so as to provide qualified raw material oil for subsequent processes (such as catalytic cracking process).

detailed description

The following examples will further illustrate the present invention, but should not be construed as a limitation of the present invention.

The reagents used in the examples are chemically pure reagents unless otherwise specified.

The pseudo-boehmite used in the following examples includes:

P1-1: Dry rubber powder produced by Changling Catalyst Branch (pore volume is 1.2ml/g, specific surface is ^280m2 /g, most accessible pore diameter is 15.8nm. Dry basis is 73%, of which pseudo-thin water The content of gibbsite is 68%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 15.8).

P1-2: Dry rubber powder produced by Yantai Henghui Chemical Co., Ltd. (pore volume is 1.1 ml/g, specific surface is 260 ^m2 /g, most accessible pore diameter is 12nm. Dry basis is 71%, of which pseudo-thin water The content of gibbsite is 67%, the content of gibbsite is 5% by weight, and the balance is amorphous alumina (DI value 17.2).

Examples 1-5 illustrate the preparation of the modification P2 of the P1 used in the carrier of the present invention and its preparation method.

Example 1

Weigh 1000 g of P1-1, then add 1440 ml of aqueous solution containing 10 ml of nitric acid (product of Tianjin Chemical Reagent No. Dry the wet strips at 120°C for 4 hours to obtain dry strips, shape the dry strips, sieve, grind and sieve the dry strip materials (generally called industrial dry strip waste) with a length of less than 2mm, and take 100-200 Mesh sieving to obtain the modified product P2A of P1-1. The k values of P2A are shown in Table 1.

Example 2

Weigh 1000 g of P1-1, and flash dry at 240°C for 6 minutes to obtain P2B, a modified product of P1-1. See Table 1 for the k values of P2B.

Example 3

200 grams each of P2A obtained in Example 1 and P2B obtained in Example 2 were evenly mixed to obtain the modified product P2C of P1-1. See Table 1 for the k value of P2C.

Example 4

Weigh 1000 grams of P1-2, add 1440 ml of aqueous solution containing 10 ml of nitric acid (product of Tianjin Chemical Reagent No. The wet strips were dried at 120°C for 4 hours, and roasted at 1200°C for 4 hours to obtain the carrier. The carrier strips were shaped and sieved, and the carrier strip materials (generally called industrial carrier waste) with a length of less than 2mm were ground, sieved, and collected. Among them, 100-200 mesh sieves can obtain the modified product P2D of P1-2. See Table 1 for the k value of P2D.

Example 5

Weigh 1000 g of P1-2, and flash dry at 650°C for 10 minutes to obtain P2E, a modified product of P1-2. See Table 1 for the k value of P2E.

Table 1

Example raw material k 1 P2A 0.5 2 P2B 0.4 3 P2C 0.4 4 P2D 0 5 P2E 0.3

Examples 6-13 illustrate the preparation method of the halogen bimodal porous alumina support for the catalyst of the present invention. Comparative Examples 1-3 illustrate the preparation of conventional catalyst supports.

Example 6

Take by weighing 800 grams of P1-1, mix evenly with 200 grams of raw material P2A obtained in Example 1, add 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. 3 Factory), 1440 milliliters of aqueous solution containing 9.8 g of ammonium fluoride, On the screw extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120° C. for 4 hours to obtain a shaped product, which was calcined at 900° C. for 3 hours to obtain a carrier Z1. The properties of carrier Z1 are listed in Table 2.

Example 7

Take 200 grams of P1-1, mix evenly with the 800 grams of raw material P2B obtained in Example 2, add 10 milliliters of the aqueous solution containing 9.8 g of ammonium fluoride containing nitric acid (Tianjin Chemical Reagent No. Extrude into a butterfly-shaped strip with an outer diameter of φ1.4mm on the extruder. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 900° C. for 3 hours to obtain a carrier Z2. The properties of carrier Z2 are listed in Table 2.

Example 8

Take 500 grams of P1-1, mix evenly with the 500 grams of raw material P2C obtained in Example 3, add 10 milliliters of aqueous solution containing 10 milliliters of nitric acid, 1440 milliliters of ammonium chloride 7.6 g in the twin-screw Extrude into a butterfly-shaped strip with an outer diameter of φ1.4mm on the extruder. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 950° C. for 3 hours to obtain a carrier Z3. The properties of carrier Z3 are listed in Table 2.

Comparative example 1

Weigh 1000 grams of P1-1, add 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. 3 Factory), 1440 milliliters of aqueous solution containing 9.8 g of ammonium fluoride, and extrude it into a butterfly-shaped strip with an outer diameter of φ1.4 mm on a twin-screw extruder. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 900°C for 3 hours to obtain a carrier DZ1. The properties of vector DZ1 are listed in Table 2.

Example 9

Weigh 800 grams of P1-2, mix evenly with 200 grams of raw material P2D obtained in Example 4, add 10 milliliters of nitric acid (product of Tianjin Chemical Reagent No. 3 Factory) and 1440 milliliters of aqueous solution containing 19.6 g of ammonium fluoride, On the screw extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 1000° C. for 3 hours to obtain a carrier Z4. The properties of carrier Z4 are listed in Table 2.

Example 10

Take by weighing 900 grams of P1-1, mix evenly with 100 grams of raw material P2E obtained in Example 5, add 10 milliliters of aqueous solution containing 19.6 g of ammonium fluoride containing 10 milliliters of nitric acid (the product of Tianjin Chemical Reagent No. Extrude into a butterfly-shaped strip with an outer diameter of φ1.4mm on the extruder. The wet strip was dried at 120° C. for 4 hours to obtain a shaped product, which was calcined at 1000° C. for 3 hours to obtain a carrier Z5. The properties of vector Z5 are listed in Table 2.

Example 11

Take by weighing 850 grams of P1-2, after mixing evenly with 150 grams of raw material P2C that embodiment 3 makes, add 10 milliliters containing nitric acid, 1440 milliliters of aqueous solution containing 15.2 g of ammonium chloride, in twin-screw On the extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 850°C for 3 hours to obtain a carrier Z6. The properties of carrier Z6 are listed in Table 2.

Comparative example 2

Weigh 1000 g of P1-2, add 10 ml of nitric acid (product of Tianjin Chemical Reagent No. 3 Factory) and 1440 ml of aqueous solution containing 19.6 g of ammonium fluoride, and extrude it into a butterfly bar with an outer diameter of φ1.4 mm on a twin-screw extruder. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 1000°C for 3 hours to obtain a carrier DZ2. The properties of vector DZ2 are listed in Table 2.

Example 12

Take by weighing 900 grams of P1-2, after mixing evenly with 100 grams of raw material P2D obtained in Example 4, add 10 milliliters of aqueous solution containing 39.2 g of ammonium fluoride containing nitric acid (Tianjin Chemical Reagent No. On the extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 1000°C for 3 hours to obtain a carrier Z7. The properties of carrier Z7 are listed in Table 2.

Example 13

Take by weighing 850 grams of P1-2, after mixing evenly with 150 grams of raw material P2E obtained in Example 5, add 10 milliliters of aqueous solution containing 39.2 g of ammonium fluoride containing 10 milliliters of nitric acid, and 1440 milliliters of aqueous solution containing 39.2 g of ammonium fluoride. On the extruder, it is extruded into a butterfly-shaped strip with an outer diameter of φ1.4mm. The wet strip was dried at 120° C. for 4 hours to obtain a molded product, which was calcined at 900° C. for 3 hours to obtain a carrier Z8. The properties of carrier Z8 are listed in Table 2.

Comparative example 3

According to the method provided in Example 7 of patent CN1782031A, a butterfly-shaped strip with an outer diameter of φ1.4mm is extruded on a twin-screw extruder. The wet strip was dried at 120°C for 4 hours to obtain a molded product, which was calcined at 900°C for 3 hours to obtain the carrier DZ3. The properties of vector DZ3 are listed in Table 2.

Table 2

Examples 14-21 are used to illustrate that the present invention provides heavy oil hydrotreating catalysts and preparation methods thereof.

Among them, the content of active metal components in the catalyst was measured by X-ray fluorescence spectrometer (all instruments are X-ray fluorescence spectrometer 3271 of Japan Rigaku Electric Industry Co., Ltd., for specific methods, see petrochemical analysis method RIPP133-90).

Example 14

Take 200 grams of carrier Z1, impregnate with 220 milliliters of ammonium heptamolybdate and ammonium metavanadate mixed solution containing MoO ₃ 80 g/L, V ₂ O ₅ 16 g/L for 1 hour, dry at 120°C for 4 hours, and then dry at 400°C Calcined for 3 hours to obtain hydrodemetallization catalyst C1, the composition of which is listed in Table 3.

Example 15

Take 200 grams of carrier Z2, impregnate with 220 ml of mixed solution of ammonium heptamolybdate and ammonium metavanadate containing 80 g/L MoO ₃ and 16 g/L V ₂ O ₅ for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain hydrodemetallization catalyst C2, the composition of C2 is listed in Table 3.

Example 16

Take 200 grams of carrier Z3, impregnate with 220 ml of mixed solution of ammonium heptamolybdate and ammonium metavanadate containing MoO ₃ 80 g/L, V ₂ O ₅ 16 g/L for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain hydrodemetallization catalyst CZ3, the composition of C3 is listed in Table 3.

Comparative example 4

Take 200 grams of carrier DZ1, impregnate 220 milliliters of ammonium heptamolybdate and nickel nitrate mixed solution containing 80 grams/liter MoO ₃ and 16 grams/liter NiO for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 2 hours to obtain the added Hydrodemetallization catalyst DC1, the composition of DC1 is listed in Table 3.

Comparative example 5

Take 200 grams of DZ2, impregnate with 220 ml of mixed solution of ammonium heptamolybdate and nickel nitrate containing MoO ₃ 80 g/L, NiO 16 g/L for 1 hour, dry at 120°C for 4 hours, and roast at 400°C for 2 hours to obtain hydrogenation Demetallization catalyst DC2, the composition of DC2 is listed in Table 3.

Comparative example 6

Take 200 grams of carrier DZ3, impregnate with 500 ml of mixed solution of ammonium heptamolybdate and ammonium metavanadate containing MoO ₃ 80 g/L, V ₂ O ₅ 16 g/L for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain the hydrodemetallization catalyst DC3, the composition of DC3 is listed in Table 3.

Example 17

Take 200 grams of carrier Z4, impregnate with 220 ml of mixed solution of ammonium heptamolybdate and ammonium metavanadate containing 90 g/L MoO ₃ and 20 g/L V ₂ O ₅ for 1 hour, dry at 120°C for 4 hours, and dry at 400°C Calcined for 3 hours to obtain hydrodemetallization catalyst C4. The composition of hydrodemetallization catalyst C4 is listed in Table 3.

Example 18

Take 200 grams of Z5, soak in 220 ml of ammonium tungstate and ammonium metavanadate mixed solution containing WO ₃ 90 g/L, V ₂ O ₅ 20 g/L for 1 hour, dry at 120°C for 4 hours, and bake at 400°C for 3 hours. hours, the hydrodemetallization catalyst C5 was obtained. The composition of hydrodemetallization catalyst C5 is listed in Table 2.

Example 19

Take 200 grams of Z6, soak it in 220 ml mixed solution of ammonium tungstate and ammonium metavanadate containing WO ₃ 100 g/L, V ₂ O ₅ 30 g/L for 1 hour, dry at 120°C for 4 hours, and bake at 400°C for 3 hours. hours, the hydrodemetallization catalyst C6 was obtained. The composition of hydrodemetallization catalyst C6 is listed in Table 2.

Example 20

Take 200 grams of Z7, soak it in 220 ml mixed solution of ammonium tungstate and ammonium metavanadate containing MoO ₃ 60 g/L, V ₂ O ₅ 60 g/L for 1 hour, dry at 120°C for 4 hours, and bake at 400°C for 3 hours. hours, the hydrodemetallization catalyst C7 was obtained. The composition of hydrodemetallization catalyst C7 is listed in Table 2.

Example 21

Take 200 grams of Z8, soak it in 220 ml of ammonium tungstate and ammonium metavanadate mixed solution containing WO ₃ 60 g/L, V ₂ O ₅ 60 g/L for 1 hour, dry at 120°C for 4 hours, and bake at 400°C for 3 hours. hours, the hydrodemetallization catalyst C8 was obtained. The composition of hydrodemetallization catalyst C8 is listed in Table 2.

table 3

Examples 22-29

Examples 22-29 illustrate the demetallization rate, deasphaltene rate, carbon residue removal rate and desulfurization rate of the hydrotreating catalyst provided by the present invention.

Using Kuwaiti slag as raw material, the protective agent was evaluated in a 100ml small fixed-bed reactor.

Catalysts C1, C2, C3, C4, and C5 are broken into particles with a diameter of 2-3 mm, and the catalyst loading is 100 milliliters. The reaction conditions are as follows: reaction temperature 380°C, hydrogen partial pressure 14 MPa, liquid hourly space velocity 0.7 hr ^-1 , hydrogen-oil volume ratio 1000, and samples were taken after 200 hours of reaction.

The specific calculation methods of demetallization rate, deasphaltene rate, residual carbon removal rate and desulfurization rate are as follows:

The properties of raw oil are listed in Table 4, and the evaluation results are listed in Table 5.

Comparative example 7-9

According to the method of Example 22, the catalysts DC1, DC2, and DC3 were evaluated for their demetallization rate, deasphaltene rate, carbon residue removal rate and desulfurization rate. The results are shown in Table 5.

Table 4

Raw oil name Kuwait often slag Density (20℃), kg/ ^m3 0.998 average molecular weight 804 Carbon residue, %(m) 15.9 Four components, %(m) Saturation 20 Aroma 49.3 colloid twenty three Asphaltenes 7.7 S, m% 5.0 N, m% 0.21 Ni, ppm 26.5 V, ppm 80

table 5

The result given in table 5 is the result after evaluating the reaction for 200 hours. It can be seen from comparison that, with respect to the reference catalyst, the hydrodemetallization activity, deasphaltene and residual carbon removal activity of the hydrotreating catalyst provided by the invention Significantly higher than the reference agent.

Claims (19)

1. a kind of heavy oil hydrogenating treatment catalyst, containing carrier and load hydrogenation active metals component on this carrier, wherein, Described hydrogenation active metals group is selected from the metal component of at least one vib metals component and at least one Group VB, Described carrier contains aluminium oxide and halogen, is characterized with mercury injection method, and the pore volume of described carrier is 0.95-1.2 ml/g, specific surface Amass as 50-300 rice²/ gram, described carrier is in bimodal pore distribution in a diameter of 10-30nm and a diameter of 300-500nm, wherein, directly Footpath is that the pore volume in 10-30nm hole accounts for the 55-80% of total pore volume, and the pore volume in a diameter of 300-500nm hole accounts for the 10- of total pore volume 35%, counted and on the basis of catalyst by oxide, the content of described vib metals component is 0.2-15 weight %, VB The content of race's metal component is 0.2-12 weight %.

2. catalyst according to claim 1 it is characterised in that described carrier pore volume be 0.95-1.15 ml/g, Specific surface area is 80-200 rice²/ gram, the pore volume in a diameter of 10-30nm hole accounts for the 60-75% of total pore volume, a diameter of 300- The pore volume in 500nm hole accounts for the 15-30% of total pore volume；The metal component of described vib is selected from molybdenum and/or tungsten, Group VB gold Genus group is selected from vanadium and/or niobium, is counted and on the basis of catalyst by oxide, and the content of described vib metals component is 0.5-12 weight %, the content of Group VB metal component is 0.5-9 weight %.

3. catalyst according to claim 1 is it is characterised in that described halogen component is selected from fluorine, chlorine, bromine, iodine and astatine One or more, on the basis of described carrier and in terms of element, in described carrier the content of halogen be 0.1-6 weight %.

4. catalyst according to claim 3 is it is characterised in that described halogen is preferably fluorine, in terms of element and with described On the basis of carrier, the content of described halogen is 0.3-4 weight %.

5. catalyst according to claim 4 is it is characterised in that on the basis of described carrier and in terms of element, described load In body, the content of halogen is 0.5-2.5 weight %.

6. catalyst according to claim 1 and 2 it is characterised in that described vib metal component be molybdenum or tungsten, Group VB metal component is vanadium, is counted and on the basis of catalyst by oxide, and the content of described vib metals component is 5-12 Weight %, the content of Group VB metal component is 1-9 weight %.

7. the preparation method of catalyst according to claim 1, comprises the steps：

(1) prepare carrier, be incorporated in this and mix including mixing the modifier P2 of hydrated alumina P1 and P1 containing boehmite Introduce halogen-containing compound in compound, aftershaping, drying roasting, the Mixing ratio by weight of described P1 and P2 is 20-95：5- 80, P2 κ value for 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁It is the hydrated alumina P1 containing boehmite Sour peptization index, DI₂It is the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite；

(2) hydrogenation active metals component is introduced on the carrier that step (1) obtains using infusion process, contain hydrogenation activity including preparing The dipping solution of the compound of metal simultaneously uses this solution impregnating carrier, is dried afterwards, roasting or not roasting, and described hydrogenation is lived Property metal component be selected from the metal component of at least one group VIB and the metal component of at least one Group VB, in terms of oxide And on the basis of catalyst, the concentration of described dipping solution and consumption make the metal component of group VIB in final catalyst Content is 0.2-15 weight %, content 0.2-12 weight % of the metal component of described Group VB；

Wherein, the drying condition of described step (1) includes：Temperature is 40-350 DEG C, and the time is 1-24 hour, roasting condition bag Include：Temperature is that the time is 1-8 hour more than 500 to less than or equal to 1200 DEG C；The drying condition of described step (2) includes：Temperature For 100-250 DEG C, the time is 1-10 hour；Roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 hour.

8. method according to claim 7 is it is characterised in that the Mixing ratio by weight of described P1 and P2 is 70-95：5-25； The κ value of described P2 is for 0 to less than or equal to 0.6；The drying condition of described step (1) includes：Temperature is 100-200 DEG C, and the time is 2-12 hour, roasting condition includes：Temperature is that roasting time is 2-6 hour more than 800 to less than or equal to 1000 DEG C；Described step Suddenly the drying condition of (2) includes：Temperature is 100-140 DEG C.

9. the method according to claim 7 or 8 is it is characterised in that the described hydrated alumina P1 containing boehmite Pore volume be 0.9-1.4 ml/g, specific surface area be 100-350 rice²/ gram, most probable bore dia 8-30nm.

10. method according to claim 9 is it is characterised in that the described hydrated alumina P1 containing boehmite Pore volume is 0.95-1.3 ml/g, and specific surface area is 120-300 rice²/ gram, most probable bore dia 10-25nm.

11. methods according to claim 7 or 8 any one are it is characterised in that described P2 is the granule of 80-300 mesh Thing.

12. methods according to claim 11 are it is characterised in that described P2 is the particulate matter of 100-200 mesh.

13. methods according to claim 7 are it is characterised in that P1 is modified as one of method of P2 is to contain described It is completely or partially ground, sieves, obtaining powder thing by the hydrated alumina P1 molding of boehmite, drying afterwards For P2, the condition of described drying includes：Temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are to obtain one of method The article shaped roasting arrived, sintering temperature is that roasting time is 1-8 hour, afterwards that it is complete more than 350 to less than or equal to 1400 DEG C Portion or part are ground, sieve, and obtaining powder thing is P2；The three of method are by the hydrated alumina P1 containing boehmite Dodge dry, dodging dry temperature is that flash-off time is 0.05-1 hour more than 150 to less than or equal to 1400 DEG C, and obtaining powder thing is P2；Side The four of method are to be mixed to get several in three modifiers obtaining of one of method, the two of method and method.

14. methods according to claim 13 are it is characterised in that the condition of drying in one of methods described includes：Temperature Spend for 100-200 DEG C, the time is 2-12 hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1- 0.5 hour.

15. methods according to claim 13 or 14 are it is characterised in that described P2 is 80-300 purpose in P1 modifier Grain thing.

16. methods according to claim 15 are it is characterised in that described P2 is the granule of 100-200 mesh in P1 modifier Thing.

17. methods according to claim 7 it is characterised in that being counted and on the basis of catalyst by oxide, described step (2) it is 0.5-12 weight that the concentration of dipping solution and consumption make the content of group vib metal component described in final catalyst Amount %, the content of VB race metal component is 0.5-9 weight %.

18. methods according to claim 17 it is characterised in that being counted and on the basis of catalyst by oxide, described step Suddenly the concentration of the dipping solution of (2) and consumption make the content of vib metals component described in final catalyst is 5-12 weight Amount %, the content of Group VB metal component is 1-9 weight %.

Application in hydrocarbon oil hydrogenation process for the hydrotreating catalyst described in any one in 19. claim 1-6.