US3619408A - Hydroisomerization of motor fuel stocks - Google Patents
Hydroisomerization of motor fuel stocks Download PDFInfo
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- US3619408A US3619408A US859561A US3619408DA US3619408A US 3619408 A US3619408 A US 3619408A US 859561 A US859561 A US 859561A US 3619408D A US3619408D A US 3619408DA US 3619408 A US3619408 A US 3619408A
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- hydroisomerized
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- 239000000446 fuel Substances 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000012808 vapor phase Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 150000001993 dienes Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Definitions
- this invention relates to hydroisomerization of stocks in the motor fuel range for the purpose of quality improvement.
- Catalytically cracked and pyrolysis gasolines normally contain olefins and diolefins which have a deleterious effect on the gasoline inasmuch as they tend to form gums.'Such materials are particularly prevalent in certain deisopentanized stocks, derived from the cracking, having an initial boiling point of about 100 F. and anend point of about 400 F. While the total stock can be hydroisomerized for olefin, acetylene, and diolefin conversion to other forms of hydrocarbons, it has now been determined that improved results are realized if this raw gasoline is divided into two portions, each of which is individually hydroisomerized, the two portions being recombined thereafter to provide a motor gasoline blending stock. The method of this invention provides such a process.
- a process for hydroisomerizing a cracked gasoline containing olefins which comprises separating the stock into two portions of different boiling ranges, hydroisomerizing each portion individually over different hydroisomerization catalysts and combining the hydroisomerized streams to produce a gasoline blending stock having a higher octane number than can be produced by hydroisomerizing the total stock over either of the catalysts.
- the method of this invention in one of its aspects, contemplates treating cracked gasoline obtained by cracking a stream comprising substantially virgin gas oil over a cracking catalyst such as silica-alumina, molecular sieve, etc. in a fluid catalytic cracking unit. This product stream will comprise C s through about 400 F.
- the catalytically cracked gasoline-to be isomerized is divided into two portions.
- the first portion is a 200 F. end point material and comprising olefinic materials.
- the second portion is a 2000 F.400 F. El. cut comprising substantially aromatics and some small amount of olefins. Both portions contain diolefins.
- This invention can be carried out in any of the usual processing sequences, including series or parallel flow of the individual reactants.
- Catalysts suitable for promoting the reactions involved are the conventional palladium on alumina-type catalysts and the nickel sulfide-type catalysts.
- Palladium on alumina catalysts can be employed in any convenient form, such as pelleted or spherical shapes.
- the catalysts will contain about 0.005 to about 1.0 weight percent palladium on alumina, preferably about 0.01 to about 0.1 percent.
- the alumina will be of controlled pore diameter and will contain about 41.5 weight percent alumina. It will weigh about 40-52 pounds per cubic foot, will have a surface area of about 340-350 square meters per gram, a pore volume ofabout 0.50 to 0.60 milliliters per gram, and a pore diameter of about 60 to about 70 A. While this catalyst will be spoken of herein as the palladium catalyst, it is to be understood that equally suitable catalysts include the noble metals of.
- Group VIII of the Periodic Table of Elements Handbook of Chemistry and Physics, Chemical Rubber Company, 45th Edition (1964), page 8-2, and include ruthenium, rhodium palladium, osmium, iridium and platinum on such supports as alumina, silicaalumina, glass beads and carbon.
- the second catalyst employed in the method of this invention will be referred to herein as the nickel sulfide catalyst. It will comprise a solid acid isomerization catalyst containing a sulfide of one or more of the metals of the left-hand column of Group Vl including chromium, molybdenum, tungsten and/or a sulfide of one or more of the metals of Group VIII, for example, iron, cobalt, nickeL of the Periodic Table.
- Such catalysts contain the metal sulfide in the range of about 0.5 to about 15 percent by weight based upon the total catalyst, the support being any suitable support such as silica, alumina, etc. Both the catalysts employed herein are well known and their preparation and use is described in the prior art.
- This invention contemplates the separation of the cracked product into two individual stocks which are individually hydroisomerized. . Any suitable method of separating the cracked stock into the individual stocks is satisfactory, fractionation being preferably employed to produce a first stock, the 200 F. end point stock having an end point of from about 200250 F., and a second stock, the "400 F. end point stock having an IB? of from about200-250 F. and an end point of about 375-450 F.
- The-200 F. end point stock is contacted with a palladium catalyst in a catalytic contacting zone in substantially the vapor phase to hydrogenate the diolefins and to isomerize the olefins to internal olefins.
- the reaction is conducted at a temperature of about 200300 F., at a pressure of about 10 to 200 p.s.i.g., in the presence off hydrogen in an amount of from about 2 to about 10 mols of hydrogen per mol of diolefins plus acetylenes, at a liquid space velocity, vol./vol./hr., of from about 1 to about 4.
- the 400 F. end point stock is contacted in a catalytic contacting zone with the sulfide catalyst in substantially the vapor phase at a temperature of about 400-750" F .,-at a pressure of about 200-1000 p.s;i.g. in the presence of hydrogen in an amount from about 2 to about 10 mols of hydrogen per mol of I hydrocarbon, at a liquid space velocity, vol./vol./hr., of about
- the individually isomerized stocks are combined to produce a motor fuel blending stock.
- the practice of the method of this invention produces a motor fuel blending stock having a higher octane member than is obtainable when treating the unproportioned cracked stock, as-such, with either of the catalysts under comparable conditions.
- This is indicated by the following runs in which a catalytically cracked gasoline containing C through 400 F. end point material, having an olefin content of about 55 volume percent, a diolefin-acetylene content of about 1 percent, and a research octane number, with 3 cc. of tetraethyllead per gallon, of 97.0 was treated in its entiretywith the two catalysts concerned under the following conditions.
- the hydrogen can be introduced at a plurality of points into the reaction zone; a plurality of catalyst beds can be employed, the various beds having different operating temperatures; the generous stream containing the hydrogen can be composed of various percentages of hydrogen and can include inert materials.
- a method of hydroisomerizing a cracked gasoline containing olefins, diolefins and aromatics and having a boiling range from about C through about 400 F. to produce a product having an improved octane number which comprises:
- said cracked gasoline into a first portion and a second portion, said first portion having an end point within the range of about 200-250 F. comprising olefins and diolefins, said second portion having an initial boiling point within range of about 200-250 F. and an end point within the range of 375-450 F. and comprising a minor amount of olefins and a substantial amount of aromatics;
- a hydroisomerizing said first portion by contacting said first portion with hydrogen and a catalyst consisting essentially of a supported noble metal of Group VIII of the Periodic Table to hydrogenate said diolefins and to isomerize said olefins to internal olefins and to produce a first hydroisomerized stream;
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method of obtaining an improved octane rating by hydroisomerization which involves separating a stock into two portions, individually hydroisomerizing the portions for olefin conversion and combining the two hydroisomerized streams.
Description
United states Patent Lewis G. Larson Bartlesville, Okla.
Sept. 19, 1969 Nov. 9, 1971 Phillips Petroleum Company inventor Appl. No. Filed Patented Assignee l-IYDROISOMERIZATION OF MOTOR FUEL STOCKS 5 Claims, No Drawings US. Cl 208/80, 208/57, 208/138, 260/683.65, 260/683.67 Int. Cl C07c 5/24, ClOg 39/00 Field of Search 208/79, 80,
I l37l38; 260/683.65, 683.67
Primary ExaminerDelbert E. Gantz Assistant Examiner-G. E. Schmitkons An0rneyYoung and Quigg ABSTRACT: A method of obtaining an improved octane rating by hydroisomerization which involves separating a stock into two portions, individually hydroisomerizing the portions for olefin conversion and combining the two hydroisomerized streams.
HYDROISOMERIZATION F MOTOR FUEL STOCKS This invention relates to motor fuel production.
In one of its more specific aspects, this invention relates to hydroisomerization of stocks in the motor fuel range for the purpose of quality improvement.
Catalytically cracked and pyrolysis gasolines normally contain olefins and diolefins which have a deleterious effect on the gasoline inasmuch as they tend to form gums.'Such materials are particularly prevalent in certain deisopentanized stocks, derived from the cracking, having an initial boiling point of about 100 F. and anend point of about 400 F. While the total stock can be hydroisomerized for olefin, acetylene, and diolefin conversion to other forms of hydrocarbons, it has now been determined that improved results are realized if this raw gasoline is divided into two portions, each of which is individually hydroisomerized, the two portions being recombined thereafter to provide a motor gasoline blending stock. The method of this invention provides such a process.
According to the method o this invention there is provided a process for hydroisomerizing a cracked gasoline containing olefins which comprises separating the stock into two portions of different boiling ranges, hydroisomerizing each portion individually over different hydroisomerization catalysts and combining the hydroisomerized streams to produce a gasoline blending stock having a higher octane number than can be produced by hydroisomerizing the total stock over either of the catalysts. The method of this invention, in one of its aspects, contemplates treating cracked gasoline obtained by cracking a stream comprising substantially virgin gas oil over a cracking catalyst such as silica-alumina, molecular sieve, etc. in a fluid catalytic cracking unit. This product stream will comprise C s through about 400 F. end point material, and will have an olefin content of about 55 percent and a diolefin-acetylene content of about 1 percent. A g if 7 7W The catalytically cracked gasoline-to be isomerized is divided into two portions. The first portion is a 200 F. end point material and comprising olefinic materials. The second portion is a 2000 F.400 F. El. cut comprising substantially aromatics and some small amount of olefins. Both portions contain diolefins.
Accordingly, it is an object of this invention to provide an improved method of hydroisomerizing olefins present in cracked gasolines.
It is another object of this invention to provide an improved motor fuel blending stock.
This invention can be carried out in any of the usual processing sequences, including series or parallel flow of the individual reactants. Catalysts suitable for promoting the reactions involved are the conventional palladium on alumina-type catalysts and the nickel sulfide-type catalysts.
Palladium on alumina catalysts can be employed in any convenient form, such as pelleted or spherical shapes. The catalysts will contain about 0.005 to about 1.0 weight percent palladium on alumina, preferably about 0.01 to about 0.1 percent. The alumina will be of controlled pore diameter and will contain about 41.5 weight percent alumina. It will weigh about 40-52 pounds per cubic foot, will have a surface area of about 340-350 square meters per gram, a pore volume ofabout 0.50 to 0.60 milliliters per gram, and a pore diameter of about 60 to about 70 A. While this catalyst will be spoken of herein as the palladium catalyst, it is to be understood that equally suitable catalysts include the noble metals of. Group VIII of the Periodic Table of Elements, Handbook of Chemistry and Physics, Chemical Rubber Company, 45th Edition (1964), page 8-2, and include ruthenium, rhodium palladium, osmium, iridium and platinum on such supports as alumina, silicaalumina, glass beads and carbon.
The second catalyst employed in the method of this invention will be referred to herein as the nickel sulfide catalyst. It will comprise a solid acid isomerization catalyst containing a sulfide of one or more of the metals of the left-hand column of Group Vl including chromium, molybdenum, tungsten and/or a sulfide of one or more of the metals of Group VIII, for example, iron, cobalt, nickeL of the Periodic Table. Such catalysts contain the metal sulfide in the range of about 0.5 to about 15 percent by weight based upon the total catalyst, the support being any suitable support such as silica, alumina, etc. Both the catalysts employed herein are well known and their preparation and use is described in the prior art.
This invention contemplates the separation of the cracked product into two individual stocks which are individually hydroisomerized. .Any suitable method of separating the cracked stock into the individual stocks is satisfactory, fractionation being preferably employed to produce a first stock, the 200 F. end point stock having an end point of from about 200250 F., and a second stock, the "400 F. end point stock having an IB? of from about200-250 F. and an end point of about 375-450 F.
The-200 F. end point stock is contacted with a palladium catalyst in a catalytic contacting zone in substantially the vapor phase to hydrogenate the diolefins and to isomerize the olefins to internal olefins. Generally the reaction is conducted at a temperature of about 200300 F., at a pressure of about 10 to 200 p.s.i.g., in the presence off hydrogen in an amount of from about 2 to about 10 mols of hydrogen per mol of diolefins plus acetylenes, at a liquid space velocity, vol./vol./hr., of from about 1 to about 4.
The 400 F. end point stock is contacted in a catalytic contacting zone with the sulfide catalyst in substantially the vapor phase at a temperature of about 400-750" F .,-at a pressure of about 200-1000 p.s;i.g. in the presence of hydrogen in an amount from about 2 to about 10 mols of hydrogen per mol of I hydrocarbon, at a liquid space velocity, vol./vol./hr., of about The individually isomerized stocks are combined to produce a motor fuel blending stock.
The practice of the method of this invention produces a motor fuel blending stock having a higher octane member than is obtainable when treating the unproportioned cracked stock, as-such, with either of the catalysts under comparable conditions. This is indicated by the following runs in which a catalytically cracked gasoline containing C through 400 F. end point material, having an olefin content of about 55 volume percent, a diolefin-acetylene content of about 1 percent, and a research octane number, with 3 cc. of tetraethyllead per gallon, of 97.0 was treated in its entiretywith the two catalysts concerned under the following conditions.
'Hydrogcn/Diolefins plus Acctylenes Mol Ratio is 5:!
In contrast to this method and in accordance with the method of this invention, the same stock was fractionated to produce a C -200 F. end point material which was isomerized with a palladium catalyst in accordance with -the procedure described-below,'and 200-400 F. out which was treated with the nickel sulfide catalyst under the conditions indicated below. The octane number indicated is on the stream after the treated portions were recombined in their entirety.
Stock Conditions C,-'200 F. End point 200-400 F. End Point Catalyst Palladium-alumina Nickel Sulfide Temperature, F. 250 600 Pressure, p.s.i.g. 50 500 Hydrogen/Diolcfins plus Acetylenes Mol Ratio is it will be seen from the above data that the resulting blend of the two individually isomerized streams has an octane number greater than that of the product produced by treating the total stock with either of the catalysts concerned.
it will be appreciated that normal variations can be employed in the carrying out of the process. For example, the hydrogen can be introduced at a plurality of points into the reaction zone; a plurality of catalyst beds can be employed, the various beds having different operating temperatures; the generous stream containing the hydrogen can be composed of various percentages of hydrogen and can include inert materials.
Other modifications of a related nature will be evident. However, such modifications are considered to be within the scope of the invention.
What is claimed is:
l. A method of hydroisomerizing a cracked gasoline containing olefins, diolefins and aromatics and having a boiling range from about C through about 400 F. to produce a product having an improved octane number which comprises:
a. separating said cracked gasoline into a first portion and a second portion, said first portion having an end point within the range of about 200-250 F. comprising olefins and diolefins, said second portion having an initial boiling point within range of about 200-250 F. and an end point within the range of 375-450 F. and comprising a minor amount of olefins and a substantial amount of aromatics;
b. a hydroisomerizing said first portion by contacting said first portion with hydrogen and a catalyst consisting essentially of a supported noble metal of Group VIII of the Periodic Table to hydrogenate said diolefins and to isomerize said olefins to internal olefins and to produce a first hydroisomerized stream;
c. hydroisomerizing said second portion by contacting said second portion with hydrogen and a catalyst consisting essentially of a supported sulfide of a metal of the lefthand column of Group VI of the Periodic Table to produce a second hydroisomerized stream;
d. combining said first hydroisomerized stream and said second hydroisomerized stream; and,
e. recovering the combined stream as said produce.
2. The method of claim 1 in which said cracked gasoline has an olefin content of about 55 percent and a diolefin-acetylene content of about lpercent.
3. The method of claim 1 which said first portion is hydroisomerized by contact with a catalyst consisting essentially of supported palladium and said second portion is hydroisomerized by contact with a catalyst consisting essentially of supported nickel sulfide.
4. The method of claim 1 in which said first portion is hydroisomerized in the vapor phase at a temperature within the range of about 200-300 F. at a pressure of about 10 to 200 p.s.i.g. and a said second portion is hydroisomerized in the vapor phase at a temperature in the range of about 400-750 F. at a pressure of about 200-1 000 p.s.i.g.
5. The method of claim 3 in which said first portion is hydroisomerized at a temperature of about 250 F. at a pressure of about 50 p.s.i.g., at a space velocity of about 2 and at a hydrogen to hydrocarbon mol ratio of about 0.05 and said second portion is hydroisomerized at a temperature of about 600F. at a pressure of about 500 p.s.i.g., at a space velocity of about 1 and at a hydrogen to hydrocarbon mol ratio of about 6.
UNITED STATES PATEJT OFFICE CERTIFICATE OF CORRECTION Date November 9, 1971 Patent No. 3,619, 08
Lewis G. Larson It is certified that error appears in the above-identified patent and that 5.1; Letters Patent are hereby corrected as shown below:
Column h, line 2, delete the word "a"; line 15, the word "produce" should reac product Signed and sealed this 11th day of April 1972.
(SEAL) Attest:
ROBERT GOTTSCHALK EDWARD M.FLETCHER,JR. Atte sting Officer Commissioner of Patents
Claims (4)
- 2. The method of claim 1 in which said cracked gasoline has an olefin content of about 55 percent and a diolefin-acetylene content of about 1percent.
- 3. The method of claim 1 which said first portion is hydroisomerized by contact with a catalyst consisting essentially of supported palladium and said second portion is hydroisomerized by contact with a catalyst consisting essentially of supported nickel sulfide.
- 4. The method of claim 1 in which said first portion is hydroisomerized in the vapor phase at a temperature within the range of about 200-300* F. at a pressure of about 10 to 200 p.s.i.g. and a said second portion is hydroisomerized in the vapor phase at a temperature in the range of about 400-750* F. at a pressure of about 200-1000 p.s.i.g.
- 5. The method of claim 3 in which said first portion is hydroisomerized at a temperature of about 250* F. at a pressure of about 50 p.s.i.g., at a space velocity of about 2 and at a hydrogen to hydrocarbon mol ratio of about 0.05 and said second portion is hydroisomerized at a temperature of about 600*F. at a pressure of about 500 p.s.i.g., at a space velocity of about 1 and at a hydrogen to hydrocarbon mol ratio of about 6.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US85956169A | 1969-09-19 | 1969-09-19 |
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US3619408A true US3619408A (en) | 1971-11-09 |
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Application Number | Title | Priority Date | Filing Date |
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US859561A Expired - Lifetime US3619408A (en) | 1969-09-19 | 1969-09-19 | Hydroisomerization of motor fuel stocks |
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US6274029B1 (en) | 1995-10-17 | 2001-08-14 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
US6309432B1 (en) | 1997-02-07 | 2001-10-30 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
FR2828205A1 (en) * | 2001-08-06 | 2003-02-07 | Inst Francais Du Petrole | Hydro-isomerization of hydrocarbon charge involves initial separation into two fractions separately treated, to produce high octane petrol base with low aromatic content |
US6822131B1 (en) | 1995-10-17 | 2004-11-23 | Exxonmobil Reasearch And Engineering Company | Synthetic diesel fuel and process for its production |
US20150094510A1 (en) * | 2012-05-29 | 2015-04-02 | Haldor Topsøe A/S | Process for synthesis of alcohols |
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US4832819A (en) * | 1987-12-18 | 1989-05-23 | Exxon Research And Engineering Company | Process for the hydroisomerization and hydrocracking of Fisher-Tropsch waxes to produce a syncrude and upgraded hydrocarbon products |
US6607568B2 (en) | 1995-10-17 | 2003-08-19 | Exxonmobil Research And Engineering Company | Synthetic diesel fuel and process for its production (law3 1 1) |
US6274029B1 (en) | 1995-10-17 | 2001-08-14 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
US6296757B1 (en) | 1995-10-17 | 2001-10-02 | Exxon Research And Engineering Company | Synthetic diesel fuel and process for its production |
US6822131B1 (en) | 1995-10-17 | 2004-11-23 | Exxonmobil Reasearch And Engineering Company | Synthetic diesel fuel and process for its production |
US6309432B1 (en) | 1997-02-07 | 2001-10-30 | Exxon Research And Engineering Company | Synthetic jet fuel and process for its production |
US6669743B2 (en) | 1997-02-07 | 2003-12-30 | Exxonmobil Research And Engineering Company | Synthetic jet fuel and process for its production (law724) |
WO2003014265A1 (en) * | 2001-08-06 | 2003-02-20 | Institut Francais Du Petrole | Method for the isomerisation of a c5-c8 fraction involving two parallel reactors |
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US20040254415A1 (en) * | 2001-08-06 | 2004-12-16 | Christophe Bouchy | Method for the isomerisation of a c5-c8 fraction involving two parallel reactors |
US7429685B2 (en) | 2001-08-06 | 2008-09-30 | Institut Francais Du Petrole | Method for the isomerisation of a C5-C8 fraction involving two parallel reactors |
US20150094510A1 (en) * | 2012-05-29 | 2015-04-02 | Haldor Topsøe A/S | Process for synthesis of alcohols |
US10150714B2 (en) * | 2012-05-29 | 2018-12-11 | Haldor Topsoe A/S | Process and catalyst for upgrading gasoline |
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