WO2014047753A1 - 一种使不饱和化合物选择加氢的方法 - Google Patents
一种使不饱和化合物选择加氢的方法 Download PDFInfo
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- WO2014047753A1 WO2014047753A1 PCT/CN2012/001508 CN2012001508W WO2014047753A1 WO 2014047753 A1 WO2014047753 A1 WO 2014047753A1 CN 2012001508 W CN2012001508 W CN 2012001508W WO 2014047753 A1 WO2014047753 A1 WO 2014047753A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 50
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 130
- 239000002253 acid Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 16
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- -1 VIB metal oxide Chemical class 0.000 claims description 8
- 229910021472 group 8 element Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 230000004584 weight gain Effects 0.000 claims description 3
- 235000019786 weight gain Nutrition 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 20
- 238000009826 distribution Methods 0.000 abstract description 5
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 150000001993 dienes Chemical class 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000005673 monoalkenes Chemical class 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000012698 colloidal precursor Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
-
- 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
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten 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
- C10G45/32—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
- C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
Definitions
- This invention relates to a process for the selective hydrogenation of unsaturated compounds.
- the raw materials may contain a certain amount of sulfides in addition to the unsaturated compounds, all or part of which are light sulfides, which may be under the action of the hydrogenation catalyst and the raw materials.
- the polyunsaturated compounds react to form heavy sulfides which can be removed by fractional distillation.
- the polyunsaturated compounds in the above materials are very unstable in nature and are easily polymerized during storage and subsequent processing. This portion of the polyunsaturated compound can be selectively hydrogenated to a monounsaturated compound by the action of a hydrogenation catalyst.
- the polyunsaturated compound is hydrogenated to a monounsaturated compound
- a small amount of the polyunsaturated compound or the monounsaturated compound is hydrogenated to a saturated compound, and the optimization of the catalyst can minimize the occurrence of the reaction.
- CN03815240 A method of selectively hydrogenating a polyunsaturated compound to a monounsaturated compound using a homogeneous catalyst is proposed. This method uses at least one salt selected from the group consisting of transition metal elements of Groups IB, IIB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements, at least one ligand and at least one organometallic reducing agent.
- a selective hydrogenation process for a catalyst having controlled porosity employs a supported catalyst comprising at least one Group VIB metal and at least one Group VI II non-noble metal used in a sulfided form, deposited on a support, having controlled porosity, wherein: The weight content of the oxide of the Group VIB element is strictly higher than 12% by weight, the weight content of the oxide of the Group VIII element is less than 15% by weight, the metal component of the catalyst has a degree of sulfurization at least equal to 60%, and the diameter is larger than The catalyst pore volume of 0. 05 microns is 10 to 40% of the total pore volume.
- a selective hydrogenation process using a sulfurization catalyst employs a catalyst comprising at least one Group VIB metal and at least one Group VI II non-noble metal deposited on a support, wherein: the Group VIB element has an oxide content strictly above 12% by weight, VIII 5 ⁇ //.
- the molar ratio of the non-precious metal to the Group VIB metal is 0. 2 ⁇ 0. 5 ⁇ / Moore.
- CN200610064397. 6 respectively, a selective hydrogenation process using a catalyst of a specific support, which uses a supported catalyst comprising at least one Group VIB metal and at least one Group VI II used in a sulfur-containing form Non-noble metals, which are deposited on a special support containing a ruthenium metal aluminate selected from the group consisting of nickel and cobalt.
- CN200910170584. 6 proposes a selective hydrogenation method using a sulfurization catalyst having a prescribed composition
- the catalyst comprises at least one Group VIB metal supported on alumina and at least one Group VII I non-noble metal, wherein the Group VIB metal oxide is from 4% to 20% by weight of the catalyst; Group VIII 4 ⁇ 1. 4 cmVg
- the catalyst has a catalyst having a molar ratio of 0. 4 ⁇ 1. 4 cmVg.
- the catalyst has a catalyst having a molar ratio of 0. 4 ⁇ 1. 4 cmVg Total pore volume.
- the present invention proposes a method of optimizing the surface acid distribution and the like so that the unsaturated compound can selectively hydrogenate, and at the same time, it can achieve the purpose of light sulfide weight gain and isomerization of a monounsaturated compound.
- a method for selectively hydrogenating an unsaturated compound wherein, while selectively hydrogenating, performing light sulfide weight gain and monounsaturated compound isomerization reaction, wherein the method uses at least one type of support on the support a catalyst of a Group VIB metal and at least one Group VIII non-noble metal, wherein:
- the amount of the oxide of the group VIB element is 4% to 10% by weight, preferably 6% to 8%;
- the amount of the non-noble element oxide of Group VIII is 6% to 15% by weight, preferably 8% to 12% by weight;
- the ratio of B acid to L acid in the acid center of the catalyst surface B, a / L, a is not more than 0.4, preferably 0.05 to 0.3.
- the molar ratio of the Group VIII non-noble metal to the Group VIB metal oxide in the catalyst is preferably more than 3.0, 5.0 mol/mol or less, particularly 3.2 or more and 5.0 mol/mol or less;
- the density of the Group VIII element is not less than 8 X 10 ⁇ 4 g of the Group VIII element oxide / m 2 catalyst, especially not less than 10 X 10" 4 g of the Group VIII element oxide / m 2 catalyst, the effect will be better .
- the catalyst is first vulcanized during use, and the vulcanization conditions are the same as in the prior art, such as converting a metal oxide to a sulfide.
- the vulcanization conditions are generally as follows: a pressure of 0.5 MPa and 3.0 MPa, a vulcanization temperature of 200 ° C to 500 ° C, a vulcanization space velocity of 0.5 11 -1 to 5.011 -1 ; vulcanization under a hydrogen atmosphere and a hydrogen sulfide atmosphere.
- the catalyst is used under the conditions of a pressure of 1.0 to 5.0 MPa, a hydrogen/polyunsaturated compound molar ratio of 1 to 20 mol/mol, a weight of 3 to 4 2.0 to 6.0 h- 1 , and a temperature of 50 to 250 °C.
- the process when treating an unsaturated compound or comprising a mixture of unsaturated compounds, allows operation at a relatively high molar ratio of oxygen/polyunsaturated compound, such as greater than 5.0, and the degree of hydrogenation of the monounsaturated compound to a saturated compound is low. , the operation is flexible.
- polyunsaturated compounds are very active, they are easily reacted with other compounds in the system to form molecules. A larger amount of compound.
- the reaction system contains a sulfide, especially a light sulfide, the addition reaction of the polyunsaturated compound can produce a sulfide having a higher boiling point, and these sulfides can be removed by fractional distillation.
- the polyunsaturated compound is selectively hydrogenated to a monounsaturated compound
- the polyunsaturated compound can be selectively hydrogenated to a monounsaturated compound by the action of a catalyst.
- the monounsaturated compound can undergo an isomerization reaction which helps to improve the stability of the monounsaturated compound.
- While the polyunsaturated compound is hydrogenated to form a monounsaturated compound, a small amount of the monounsaturated compound is hydrogenated to a saturated compound. In most cases, monounsaturated compounds are desirable to be retained. Hydrogenation of monounsaturated compounds is therefore minimized by optimization of catalysts and conditions.
- Unsaturated compounds in the processing raw materials are prone to polymerization to form colloidal precursors such as colloids under the action of the acid center of the catalyst. These materials will cover the surface active center of the catalyst and affect the catalytic action.
- the catalyst has a certain acid center. Therefore, in the design of the catalyst, in order to meet the requirements of different reactions, it is necessary to adjust the composition of the acidic center of the catalyst and the distribution of strong and weakly acidic centers.
- the invention does not limit the method for adjusting the ratio of B acid to L acid in the acid center of the catalyst surface, the ratio of weak L acid and strong L acid, and is also introduced in the book "Hydrogenation Process and Engineering” published by the petrochemical press.
- the technique of the present invention for example, the modification of the carrier by using a non-metal oxide, the hydrothermal treatment of the catalyst carrier, etc., may be carried out by the present invention, but is not limited to the above method. Therefore, the present invention does not particularly limit the carrier composition as long as it satisfies the ratio of the B acid to the L acid, the ratio of the weak L acid and the strong L acid which satisfy the requirements of the present invention.
- the carrier recommended by the present invention is alumina or predominantly alumina.
- the alumina content is preferably not less than 80% by weight, more preferably not less than 90% by weight.
- Different carrier compositions there are many ways to adjust the surface acid center, which is the basic means of carrier modification.
- the acid center adjustment methods of the carrier surface such as CN102039151, CN1597093, etc., so it is required that the carrier has a specific surface acidity center which can be fully realized in the prior art, and Manufacturers can provide the corresponding products according to user needs.
- the catalyst carrier is prepared by a method known in the art: if necessary, the carrier may be modified with a non-metal oxide or a precursor, or the obtained carrier may be treated with steam at 400 to 600 ° C for 4 to 6 hours. It can also be calcined at a temperature of 500 to 70 (TC and or 700 to 900 ° C and or 900 to 1100 for 4 to 6 hours.
- the total pore volume of the catalyst is preferably 0.2 ⁇ 0.5cm 3 / g, preferably 0.2 ⁇ 0.45cm 3 / g, more preferably 0.2 ⁇ 0.39cm 3 / g; specific surface
- the surface is preferably 50 to 200 m 2 /g, preferably 50 to 150 m 2 /g.
- the acid center of the catalyst was analyzed by pyridine infrared analysis. This method is described in detail in Chapter 7, In-situ Infrared Spectroscopy, of Modern Catalytic Research Methods published by Science Press.
- the catalyst carrier can be prepared by various techniques such as tableting, kneading, rolling into balls, extrusion, and spray molding.
- the catalyst support may be modified by various technical means to meet the requirements of the catalyst for the properties of the catalyst.
- the present invention does not particularly limit the preparation method of the catalyst, and a general impregnation method such as a salt of the active component nickel and/or molybdenum may be added to water or other solution capable of forming a complex to prepare an active metal impregnation. Solution.
- the catalyst carrier is impregnated with an active metal impregnation solution, then dried at 120 to 300 ° C, and calcined at 400 to 800 ° C. detailed description
- the carrier in the catalyst of the present invention except for the description, the carrier in the examples and the comparative examples were respectively calcined at 500 ° C or high-temperature treatment at 600 to 1000 ° C or treated with steam at 400 to 600 ° C. 4 to 6 hours, the carrier obtained by the inorganic oxide precursor modification treatment.
- the physical properties are shown in Table 1.
- all of the example catalysts and comparative catalysts are based on the expected active metal loading of the catalyst, the molar ratio of the Group VIII non-noble metal and the Group VIB metal oxide, etc., the Group VIII non-noble metal, Group VIB metal.
- the salt was mixed with different concentrations of the impregnation liquid to impregnate the catalyst carrier, and then aged at normal temperature for 12 hours, then dried at 120 ° C and calcined at 500 ° C to obtain a catalyst product.
- the catalyst carrier was added to the above impregnation liquid, and after immersing for 3 hours at normal temperature, it was taken out, aged for 12 hours, then dried at 12 CTC, and calcined at 50 CTC for 4 hours to obtain a catalyst A.
- the specific surface area of the catalyst is 148 m 2 /g, the total pore volume is 0.41 cmVg, the content of Mo0 3 is 6.4%, and the content of NiO is 10.6%. Comparative Example 2 Catalyst Preparation
- the catalyst carrier was added to the above immersion liquid, and after immersing for 3 hours at normal temperature, it was taken out, aged for 12 hours, then dried at 120 ° C, and calcined at 500 ° C for 4 hours to obtain a catalyst B.
- the specific surface area of the catalyst is 240 m 2 /g, the total pore volume is 0.38 cmVg, the Mo0 3 content is 6.4%, and the NiO content is 10.6%.
- the catalyst carrier was added to the above immersion liquid, and after immersing for 3 hours at normal temperature, it was taken out, aged for 12 hours, then dried at 12 CTC, and calcined at 500 Torr for 4 hours to obtain a catalyst E.
- the specific surface area of the catalyst is 101 m 2 /g, the total pore volume is 0.38 cm 3 /g, the Mo0 3 content is 6.4%, and the NiO content is 10.6%.
- the catalyst carrier was added to the above immersion liquid, and after immersing for 3 hours at normal temperature, it was taken out, aged for 12 hours, and then 12 (TC was dried, and calcined at 500 ° C for 4 hours to obtain a catalyst F.
- the catalyst specific surface was 97 m 2 /g, The total pore volume is 0.35 cm 7 g, the MoO 3 content is 9.1%, and the CoO content is 14.8%.
- Catalysts A, B, C, D, E, F, G, H, I the physical composition of which is shown in Table 1.
- catalysts A, B, C, D are not part of the catalyst of the invention.
- the catalyst was packed in the middle of a reaction tube having an inner diameter of 15 mm and a height of 320 mm, and the upper and lower portions of the catalyst were loaded with 20 to 40 mesh quartz sand support.
- the catalyst is first vulcanized prior to use.
- the sulfurized oil is a mixture of cyclohexane and carbon disulfide (CS 2 content is 2%).
- the vulcanization conditions are: pressure 2.0 MPa, liquid hourly space velocity 4 h - hydrogen oil volume ratio 200: 1, temperature 32 (TC, vulcanization time test mixture of unsaturated compounds has the following composition: propyl mercaptan 100 ppm by weight, pentadiene 1% Weight, heptene-1 3% by weight, cyclohexane balance.
- Propanthiol conversion % (1 - propanethiol content in product / propanethiol content in raw material) *100
- Monoolefin isomerization rate % isomerized olefin content / (isomerized olefin content + hydrazine hydrocarbon content) *100
- Hydrogenation selectivity % diene conversion / (diene conversion + monoene conversion) * 100
- the method of the present invention has a higher conversion rate of propanethiol and diene, and the isomerization ratio of monoolefin and the selectivity of hydrogenation are also significantly higher. The method of the comparison.
- Example 6-8
- the catalyst shown in Example 1 of the present invention has better adaptability.
- the unsaturated compound is hydrotreated by this catalyst, it can be operated in a relatively wide range, and high conversion rate and selectivity of the reaction product can be obtained.
- the invention optimizes the surface acid distribution of the catalyst by selecting the active component of the catalyst, in particular, further selecting a suitable ratio of the catalyst VIII/VIB metal, the density of the non-precious metal of the group VIII per unit catalyst surface, and improving the hydrogenation conversion of the polyunsaturated compound. Rate and selectivity increase the isomerization rate of monounsaturated compounds. Isoolefins generally have higher stability and higher enthalpy values, which are often very important for improving the properties of unsaturated compounds or mixtures containing unsaturated compounds.
- the hydrotreating effect is significantly improved by the method of the present invention, and has higher thiol conversion rate, higher diene saturation ratio, and better diene when used for hydrogenation of unsaturated compounds or mixtures containing unsaturated compounds.
- the selectivity of hydrogenation is significantly improved.
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Abstract
本发明涉及一种使不饱和化合物选择加氢的方法，特别是一种不饱和化合物或含有不饱和化合物的混合物中轻硫化物增重、多不饱和化合物加氢、单不饱和化合物异构化的方法，所述方法使用的负载型催化剂，所述负载型催化剂包含在载体上沉积的至少一种第VIB族和至少一种第VIII族非贵金属氧化物，催化剂具有优化的催化剂表面酸分布，更优选的是具有优化的VIII/VIB族金属比率、每单位催化剂表面积第VIII族非贵金属密度。
Description
一种使不饱和化合物选择加氢的方法
技术领域
本发明涉及一种使不饱和化合物选择加氢的方法。
背景技术
在不饱和化合物选择加氢工艺过程中， 原料可能除不饱和化合物外还含有一定数量 的硫化物， 其中全部或部分是轻硫化物， 这些轻硫化物可以在加氢催化剂的作用下和原 料中的多不饱和化合物反应生成重硫化物， 这些重硫化物可以采用分馏的办法除去。
上述原料中多不饱和化合物性质很不稳定， 容易在储存和后续加工过程中聚合。 在 加氢催化剂的作用下， 可以将这部分多不饱和化合物选择加氢成单不饱和化合物。
在多不饱和化合物加氢成单不饱和化合物的同时，有少量多不饱和化合物或单不饱和 化合物被加氢成饱和化合物， 通过催化剂的优化设计可以尽量避免此反应的发生。
以下专利或专利申请中提出了不饱和化合物加氢处理的方法。
CN03815240. 1 提出了一种使用均相催化剂将多不饱和化合物选择性氢化为单不饱 和化合物的方法。 此方法使用至少一种选自元素周期表中第 IB、 IIB、 VB、 VIB、 VIIB和 VIII族的过渡金属元素的盐， 至少一种配位体和至少一种有机金属还原剂。
CN200610064286. 5提出了一种具有控制空隙度的催化剂的选择性氢化方法。 所述方 法使用一种载体上的催化剂，它含有以硫化形式使用的至少一种第 VIB族金属和至少一种 第 VI II族非贵金属， 它们沉积在载体上， 具有控制的孔隙度， 其中： 第 VIB族元素的氧 化物的重量含量严格高于 12重量％，第 VIII族元素的氧化物的重量含量低于 15重量％， 所述催化剂的金属组分的硫化度至少等于 60%，直径大于 0. 05微米的所述催化剂孔体积 是总孔体积的 10〜40%。
CN200610064287. x提出了使用硫化催化剂的选择性氢化方法。 所述方法采用含有沉 积在载体上的至少一种第 VIB族金属和至少一种第 VI I I族非贵金属的催化剂， 其中： 第 VIB族元素的氧化物含量严格高于 12重量％，第 VI I I族元素的氧化物含量低于 15重量％， 所述催化剂的金属组分的硫化度至少等于 60%， 第 VIH族非贵金属与第 VIB族金属的摩 尔比是 0. 2〜0. 5摩尔 /摩尔。
CN200610064397. 6分别提出了使用特定载体的催化剂的选择性氢化方法， 所述方法 使用一种载带催化剂，它含有以含硫形式使用的至少一种第 VIB族金属和至少一种第 VI I I 族非贵金属，它们沉积在含有 ΜΑ1Λ类金属铝酸盐的特别载体上，其中金属 M选自镍和钴。
CN200910170584. 6提出了一种利用具有规定组成的硫化催化剂的选择加氢方法， 所
述催化剂包含在氧化铝上负载的至少一种第 VIB族金属和至少一种第 VII I族非贵金属， 其中第 VIB族金属氧化物以重量计为催化剂重量的 4%〜20%； 第 VIII族非贵金属氧化物 以重量计小于催化剂重量的 15%; 第 VII I族非贵金属和第 VIB族金属的摩尔比为 0. 6至 3. 0摩尔 /摩尔， 催化剂具有 0. 4〜1. 4 cmVg的总孔体积。
发明内容
本发明提出一种使用优化表面酸分布等方法， 以使不饱和化合物使选择加氢， 同时还 可以达到轻硫化物增重、 以及单不饱和化合物异构化的目的。
一种使不饱和化合物选择加氢的方法， 在选择加氢的同时， 进行轻硫化物增重、单不 饱和化合物异构化反应， 其特征在于所述方法使用了载体上负载至少一种第 VIB族金属 和至少一种第 VIII族非贵金属的催化剂， 其中：
第 VIB族元素氧化物以重量计的量为 4%~10%， 最好是 6%~8%；
第 VIII族非贵元素氧化物以重量计的量为 6%~15%重量， 最好是 8%~12%；
催化剂表面酸性中心中 B酸与 L酸的比率 B ,a/L ,a不大于 0.4， 最好为 0.05~0.3。 催化剂表面酸性中心中弱 L酸和强 L酸的比率 L ¾/L强为 0.5〜2.0， 最好是 0.5〜1.5； 载体是氧化铝或主要是氧化铝。
本发明中，催化剂中第 VIII族非贵金属和第 VIB族金属氧化物的摩尔比最好大于 3.0， 小于等于 5.0摩尔 /摩尔， 特别是大于等于 3.2且小于等于 5.0摩尔 /摩尔； 每单位催化剂 表面积的第 VIII族元素密度不小于 8 X 10·4克第 VIII族元素氧化物 /m2催化剂， 特别是不 小于 10 X 10"4克第 VIII族元素氧化物 /m2催化剂， 效果会更好。
和现有技术相同， 催化剂在使用时要先硫化， 硫化条件同现有技术， 如将金属氧化物 转变为硫化物。 硫化条件一般为： 压力在 0.5MPa和 3.0MPa， 硫化温度 200°C至 500°C， 硫化空速 0.5 11—1至5.011—1 ; 在氢气、 硫化氢气氛下进行硫化。
催化剂的使用条件为压力 1.0〜5.0MPa、氢 /多不饱和化合物摩尔比 1〜20摩尔 /摩尔、 $¾ 2.0~6.0h-1 , 温度为 50〜250°C。
本方法在处理不饱和化合物或包含不饱和化合物混合物时，允许在相对较高譬如大于 5.0的氧 /多不饱和化合物摩尔比下操作，其单不饱和化合物的加氢成饱和化合物的程度很 低， 操作弹性大。
在一个不饱和化合物选择加氢过程中， 可能发生 （包含但不仅限于） 以下几种反应: ( 1 ) 多不饱和化合物加成反应；
由于多不饱和化合物非常活泼，容易与体系中的其他化合物发生加成反应，生成分子
量更大的化合物。当反应体系中含有硫化物尤其是轻硫化物时，利用多不饱和化合物的加 成反应可生成沸点更高的硫化物， 这些硫化物可以利用分馏的方式除去。
( 2 ) 多不饱和化合物选择加氢成单不饱和化合物；
在催化剂的作用下， 可以将多不饱和化合物选择加氢成单不饱和化合物。
( 3 ) 单不饱和化合物的异构化；
在加氢的过程中，单不饱和化合物可以发生异构化反应，此反应有助于提高单不饱和 化合物的稳定性。
(4 ) 单不饱和化合物的加氢；
在多不饱和化合物加氢生成单不饱和化合物的同时，少量单不饱和化合物被加氢成饱 和化合物。在大多数情况下， 单不饱和化合物是希望被保留的。 因此要通过催化剂及条件 的优化将单不饱和化合物的加氢减少到最低程度。
加工原料中的不饱和化合物在催化剂酸性中心的作用下易发生聚合反应生成胶质等 一些生焦前驱物， 这些物质会覆盖在催化剂的表面活性中心上， 影响催化作用的发挥。但 是对于硫化物增重反应、异构化反应来说， 又需要催化剂具有一定的酸性中心。 因此， 在 催化剂的设计中， 为了满足不同反应的要求， 调节催化剂酸性中心构成、 强、 弱酸性中心 的分布是十分必要的。
本发明并不限制调节催化剂表面酸性中心中 B酸与 L酸的比率、弱 L酸和强 L酸的比 率的方法， 在石化出版社出版的《加氢工艺与工程》一书中也介绍了这方面的技术， 譬如 使用非金属氧化物对载体进行改性、对催化剂载体进行水热处理等，本发明可使用其中的 方法， 但并不局限于上述方法。 因此本发明并不特别限定载体组成， 只要能满足本发明要 求的 B酸与 L酸的比率、弱 L酸和强 L酸的比率即可。本发明推荐的载体是氧化铝或主要 是氧化铝。 氧化铝含量最好不小于 80wt%， 更优选为不小于 90 wt %。 不同的载体组成， 其表面酸性中心调节方法也可多种， 它是载体改性的基本手段。 除《加氢工艺与工程》之 外， 有大量文献都涉及了载体表面酸性中心调节方法， 如 CN102039151、 CN1597093等， 因此要求载体具有特定的面酸性中心在现有技术中已完全能实现，并且生产厂商能根据用 户需求来提供相应的产品。如采用业内公知的方法制备催化剂载体： 根据需要， 可以用非 金属氧化物、 或前驱物对载体进行改性， 亦可将制得的载体在 400〜600°C用水蒸气处理 4〜6小时， 亦可在 500〜70(TC且或 700〜900°C且或 900〜1100温度下焙烧 4〜6小时。 通过上述方法， 可以对催化剂酸性中心的性质、 强、 弱酸中心分布进行调节。本发明中催 化剂的总孔体积优选为 0.2~0.5cm3/g， 最好是 0.2~0.45cm3/g， 更好是 0.2〜0.39cm3/g; 比表
面优选 50〜200 m2/g， 最好是 50〜150 m2/g。
通过对不饱和化合物或含有不饱和化合物混合物加氢反应体系的研究我们发现，当催 化剂具有本发明所述特征时， 加氢处理的效果显著改善。
催化剂的酸性中心分析采用吡啶红外分析法。此方法在科学出版社出版的《现代催化 研究方法》 第 7章原位红外光谱方法中有详细的介绍。
其他指标采用业内公知的分析与计算方法。
可采用压片、 混捏、 滚动成球、 挤出、 喷雾成型等各种技术手段制备催化剂载体。 可 可以采取各种技术手段对催化剂载体进行改性， 以满足此方法对催化剂性质的要求。
本发明并不特别限定催化剂的制备方法，可以采用通用的浸渍方法，如可将活性组分 镍和 /或钼的盐类加入水或其他可形成络合物的溶液中， 制成活性金属浸渍溶液。 用活性 金属浸渍溶液浸渍催化剂载体， 然后在 120〜300°C烘干， 在 400〜800°C焙烧制成的。 具体实施方式
实施例 1〜5与对比例 1〜4
本发明的催化剂中的载体除加有说明的外，实施例及对比例中的载体分别是在 500°C 进行焙烧或 600〜1000°C载体进行高温处理或使用 400〜600°C用水蒸气处理 4〜6小时、 无机氧化物前驱物改性处理得到的载体。 物性如表 1所示。
除特别说明外，所有实施例催化剂、对比例催化剂均根据催化剂预期的活性金属负载 量、 第 VIII族非贵金属和第 VIB族金属氧化物的摩尔比等将第 VIII族非贵金属、 第 VIB 族金属盐配成不同浓度的浸渍液浸渍催化剂载体， 然后在常温下陈化 12小时， 然后在 120°C干燥， 在 500°C焙烧， 得到催化剂产品。
为进一步说明催化剂的得到过程， 在此详细说明几例， 其余均可参照所述步骤， 按要 求得到所需催化剂。
对比例 1催化剂制备
取工业 Si02 A1203粉 ( Si02含量 14%) 100g, 加入 50g水， 捏合、 挤出成型， 120°C 烘干， 600°C焙烧 4小时， 得到催化剂载体。
将 14g工业钼酸铵加入 45g水中搅拌溶解， 再加入 75g工业硝酸镍、 12g工业柠檬 酸， 搅拌溶解， 制成催化剂活性金属浸渍液。
将催化剂载体加入上述浸渍液中， 常温下浸渍 3小时后取出， 陈化 12小时， 然后 12CTC烘干， 50CTC焙烧 4小时，制得催化剂 A。催化剂比表面 148m2/g，总孔体积 0.41 cmVg, Mo03含量 6. 4%, NiO含量 10. 6%, 更多性质分析数据见表 1。
对比例 2催化剂制备
取工业氧化铝粉 100g， 加入 50g水， 捏合、 挤出成型， 120°C烘干， 50CTC焙烧 4小 时， 得到催化剂载体。
将 14g工业钼酸铵加入 45g水中搅拌溶解， 再加入 75g工业硝酸镍、 12g工业柠檬 酸， 搅拌溶解， 制成催化剂活性金属浸渍液。
将催化剂载体加入上述浸渍液中， 常温下浸渍 3小时后取出， 陈化 12小时， 然后 120'C烘干， 500°C焙烧 4小时，制得催化剂 B。催化剂比表面 240m2/g，总孔体积 0.38 cmVg, Mo03含量 6. 4%， NiO含量 10. 6%， 更多性质分析数据见表 1。
实施例 1催化剂制备
取工业氧化铝粉 100g， 加入 50g水， 捏合、 挤出成型， 120Ό烘干， 50(TC焙烧 4小 时， 再在 90CTC焙烧 4小时， 得到催化剂载体。
将 14g工业钼酸铵加入 45g水中搅拌溶解， 再加入 75g工业硝酸镍、 12g工业柠檬 酸， 搅拌溶解， 制成催化剂活性金属浸渍液。
将催化剂载体加入上述浸渍液中， 常温下浸渍 3小时后取出， 陈化 12小时， 然后 12CTC烘干， 500Ό焙烧 4小时，制得催化剂 E。催化剂比表面 101m2/g，总孔体积 0.38 cm3/g， Mo03含量 6. 4%， NiO含量 10. 6%， 更多性质分析数据见表 1。
实施例 2催化剂制备
取工业氧化铝粉 100g， 加入 50g水， 捏合、 挤出成型， 120Ό烘干， 500Ό焙烧 4小 时， 再在 450Ό的水蒸气中处理 4小时， 得到催化剂载体。
将 18g工业钼酸铵加入 45g水中搅拌溶解， 再加入 95g工业硝酸钴、 16g工业柠檬 酸， 搅拌溶解， 制成催化剂活性金属浸渍液。
将催化剂载体加入上述浸渍液中， 常温下浸渍 3小时后取出， 陈化 12小时， 然后. 12(TC烘干， 500°C焙烧 4小时，制得催化剂 F。催化剂比表面 97m2/g，总孔体积 0.35cm7g， Mo03含量 9. 1%， CoO含量 14. 8%， 更多性质分析数据见表 1。
其余催化剂的制备方法不再详述， 按所需性能得到各自催化剂。
催化剂 A、 B、 C, D、 E、 F、 G、 H、 I， 其物性组成如表 1所示。
催化剂 A、 B、 C、 D、 E、 F、 G、 H、 I物性组成
Si02
A1203 A1203 A1203 A1203 A1203 (2%) (5%) - ： A1203
A1A 总孔体积 cmVg 0.41 0.38 0.38 0.38 0.38 0.35 0.42 0.39 0.28 比表面 m2/g 148 240 101 101 101 97 96 142 165 o ^
Mo03 % 6. p4 6.4 5.0 11.0 6.4 9.1 6.3 5.6
NiO % 10.6 10.6 5.8 4.0 10.6 11.7 11.5 13.2
W03 % 7.0
CoO % 14.8
VIII族/ VIB族金
3.2 3.2 2.2 0.7 3.2 3.1 3.6 5.0 4.5 属摩尔比 d第 VIII族元素氧化物
0.7 0.4 0.6 0.4 1.1 1.5 1.2 0.8 0.8 (10— 3g/m2)
B总 /L总 0.47 0 0 0 0 0 0.06 0.28 0
L弱 / 强 0.8 2.3 1.2 1.2 1.2 2.0 0.6 0.8 0.7 上述催化剂中， 催化剂 E 八
、 F、 G、 H、 I为本发明的催化剂； 相比之下， 催化剂 A、 B、 C、 D不属于本发明的催化剂。
催化剂的加氢：
将催化剂装填在内径 15mm、 高 320mm的反应管中部， 催化剂的上、 下部装填 20~40 目的石英砂支撑。
使用前首先对催化剂进行硫化。硫化油为环己烷和二硫化碳混合物（CS2含量为 2%)。 硫化条件为： 压力 2.0MPa、 液时空速 4h— 氢油体积比 200: 1， 温度 32(TC， 硫化时间 试验用不饱和化合物的混合物具有以下组成： 丙硫醇 lOOppm重量、 戊二烯 1%重量、 庚烯 -1 3%重量、 环己烷余量。
在本发明中， 评价催化剂性能的重要技术指标表示如下：
丙硫醇转化率％ = (1-产品中丙硫醇含量 /原料中丙硫醇含量） *100
双烯转化率％ = (1-产品中双烯含量 /原料中双烯含量） *100
单烯转化率％ = (1-产品中单烯含量 /原料中单烯含量） *100
单烯异构化率％ = 异构化烯烃含量 / (异构化烯烃含量 +垸烃含量） *100
加氢选择性％ =双烯转化率 / (双烯转化率 +单烯转化率） *100
在压力 2.0MPa、 空速 4.0h 温度 12(TC、 氢 /双烯摩尔比 5: 1条件下进行加氢处理， 然后分析加氢产品中丙硫醇、 双烯、 单烯、 异构化单烯、 垸烃的含量。
分别使用对比例 1〜4、 实施例 1〜5的催化剂进行加氢实验， 得到的实验结果如表 2 所示。
表 2 不同对比例、 实施例实验结果
使用催化剂实施例 1的催化剂 E， 采用相同的硫化方法、 采用相同组成的进料， 改 变反应的条件， 取得的实验结果如表 3所示。
表 3 催化剂 E不同条件下实验结果
实施例 6 7 8 催化剂编号 E E E
压力 MPa 1.5 2.0 3.0 空速 h—1 2.0 4.0 3.0 温度 V 100 120 110 氢 /双烯摩尔比 10.0 5.0 15.0 丙硫醇转化率 ％ 100 100 100
双烯转化率 ％ 89.2 88.5 88.2 单烯异构化率％ 53.1 52.5 52.7
001508
从上面数据可以看出， 本发明实施例 1所示的催化剂具有较好的适应性。 采用此催 化剂对不饱和化合物进行加氢处理时，在比较宽的范围内进行操作，都可以得到很高的反 应产物转化率和选择性。
工业实用性
本发明通过选择催化剂活性组分， 优化催化剂表面酸分布， 特别是进一步选择合适的 催化剂 VIII/VIB族金属比率、每单位催化剂表面积第 VIII族非贵金属密度，提高了多不 饱和化合物加氢的转化率和选择性，提高了单不饱和化合物的异构化率。异构烯烃通常具 有更高的稳定性和更高的辛垸值,这通常对改进不饱和化合物或含有不饱和化合物混合物 的性质是非常重要的。
使用本发明的方法，加氢处理的效果显著改善，用于不饱和化合物或含有不饱和化合 物混合物加氢时具有更高的硫醇转化率、 更高的双烯饱和率以及更好的双烯加氢的选择 性。
Claims
1. 一种使不饱和化合物选择加氢的方法， 在选择加氢的同时， 进行轻硫化物增重、 单不 饱和化合物异构化反应， 其特征在于所述方法使用了载体上负载至少一种第 VIB族金属 和至少一种第 VIII族非贵金属的催化剂， 其中：
第 VIB族元素氧化物以重量计的量为 4%~10%；
第 VIII族非贵元素氧化物以重量计的量为 6%~15%重量；
催化剂表面酸性中心中 B酸与 L酸的比率 B fi/L 不大于 0.4;
催化剂表面酸性中心中弱 L酸和强 L酸的比率 L /L强为 0.5〜2.0;
载体是氧化铝或主要是氧化铝。
2.根据权利要求 1所述的方法，其特征在于催化剂中第 VIII族非贵金属和第 VIB族金属 氧化物的摩尔比大于 3.0， 小于等于 5.0摩尔 /摩尔； 每单位催化剂表面积的第 VIII族元 素密度不小于 8 X 10"4克第 VIII族元素氧化物 /m2催化剂。
3.根据权利要求 2所述的方法，其特征在于催化剂中第 VIII族非贵金属和第 VIB族金属 氧化物的摩尔比为大于等于 3.2且小于等于 5.0摩尔 /摩尔。
4. 根据权利要求 1所述的方法， 其特征在于催化剂中第 VIB族金属选自钼和 /或钨， 优 选为钼。
5. 根据权利要求 1所述的方法， 其特征在于催化剂中第 VIII族非贵金属选自镍和 /或钴， 优选为镍。
6. 根据权利要求 1所述的方法， 其特征在于催化剂中第 VIB族元素氧化物以重量计为 6%〜8%。
7. 根据权利要求 1所述的方法， 其特征在于催化剂中第 VIII族非贵金属氧化物以重量计 为 8%〜12%。
8. 根据权利要求 1所述的方法， 其特征在于催化剂中每单位催化剂表面积的第 VIII族元 素密度不小于 10X 10— 4克第 VIII族元素氧化物 /m2。
9. 根据权利要求 1所述的方法 ， 其特征在于催化剂表面酸性中心中 B酸与 L酸的比率 B总 /L总为 0.05-0.3
10. 根据权利要求 1所述的方法， 其特征在于催化剂表面酸性中心中弱 L酸和强 L酸的 比率 L弱 /L强为 0.5〜1.5。
11. 根据权利要求 1中所述的方法， 其特征在于催化剂的总孔体积为 0.2~0.5cm3/g ， 优
选为 0.2 cm3/g〜0.45cm3/g， 更好是 0.2 cm3/g〜0.39cm3/g。
12. 根据权利要求 1中所述的方法， 其特征在于催化剂的比表面为 50~200 m2/g， 优选为 50〜150 m2/g。
13. 根据权利要求 1中所述的方法， 其特征在于催化剂载体中氧化铝不小于 80wt%， 优 选为不小于 90 wt %。
14. 根据权利要求 1中所述的方法， 其特征在于催化剂载体中氧化铝的晶型为 Υ、 δ、 θ 或以上的混晶。
15. 根据权利要求！〜 14中的任何一项方法， 其特征在于催化剂在使用时先硫化，硫化条 件为压力 0.5MPa和 3.0MPa, 温度 200°C至 500 °C， 空速 0.5 h 1至 5.0h 。
16. 根据权利要求 15 中的任何一项方法， 其特征在于催化剂的使用条件为压力 1.0〜 5.0MPa、氢 /多不饱和化合物摩尔比 1〜20摩尔 /摩尔、空速 2.0〜6.0h— 温度为 50〜250°C。
17. 根据权利要求 16中所述的方法， 其特征在于催化剂的使用条件为压力 2.0〜4.0MPa、 氢 /多不饱和化合物摩尔比 1〜10摩尔 /摩尔、 空速 2.0〜5.0h— 温度为 70〜200°C。
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