CN112295596B - 含介孔-大孔zsm-5分子筛的催化汽油加氢改质催化剂及其制备方法 - Google Patents
含介孔-大孔zsm-5分子筛的催化汽油加氢改质催化剂及其制备方法 Download PDFInfo
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- CN112295596B CN112295596B CN201910698177.6A CN201910698177A CN112295596B CN 112295596 B CN112295596 B CN 112295596B CN 201910698177 A CN201910698177 A CN 201910698177A CN 112295596 B CN112295596 B CN 112295596B
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- macroporous
- zsm
- mesoporous
- molecular sieve
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 67
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000004048 modification Effects 0.000 title abstract description 7
- 238000012986 modification Methods 0.000 title abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 239000005060 rubber Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 10
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims 2
- 239000000306 component Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- 150000001336 alkenes Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical group S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及一种含介孔‑大孔ZSM‑5分子筛的催化汽油加氢改质催化剂及其制备方法。该催化剂以钴和钼为金属组分，以氧化铝与介孔‑大孔ZSM‑5分子筛构成的混合物为载体，以介孔‑大孔ZSM‑5分子筛为酸性组分。该催化剂的制备方法是先将硅源、铝源、无机酸或无机碱、去离子水配制成凝胶并使其老化，在老化后的凝胶中加入橡胶微乳液，经晶化、过滤、水洗、干燥、焙烧、离子交换后获得介孔‑大孔ZSM‑5分子筛；然后将该介孔‑大孔ZSM‑5分子筛与氧化铝粉制成载体；将钴盐和钼盐的浸渍液浸渍到载体后，经陈化、干燥和焙烧，获得目标催化剂。该催化剂对催化重汽油及其全馏分汽油均表现出了优良的加氢改质性能。
Description
技术领域
本发明涉及一种含分子筛的汽油加氢催化剂及其制备方法。
背景技术
国外汽油池中催化裂化(FCC)汽油约占33％，而我国汽油池中FCC汽油约占75％，且硫和烯烃的含量较高。因此，国外普遍采用的FCC汽油加氢改质技术在用于国内汽油质量升级时，产品在烯烃含量大幅降低的同时其辛烷值损失也较大。
CN200610083283.6介绍了综合改性HZSM-5沸石催化剂及其制备方法和用途。该综合改性HZSM-5沸石催化剂的制备方法包括：将HZSM-5沸石与粘结剂按重量比1:1-4:1混合，向形成的混合物中加入田菁粉和HNO3水溶液，以重量计使田菁粉的终浓度为1-3％和HNO3的终浓度为2-5％，再经混捏、挤压成型、干燥和焙烧后，制成催化剂载体中间体；将所述催化剂载体中间体依次进行水热改性和有机酸处理，制成催化剂载体；在所述催化剂载体上负载金属活性组分，再经干燥、焙烧，制成催化剂成品。该综合改性HZSM-5沸石催化剂适用于FCC汽油的加氢改质，可降低其烯烃和硫含量，改善其抗爆指数。
CN200610083284.0报道了ZSM-5/SAPO-11复合沸石和FCC汽油加氢改质催化剂及其制备方法。将硫酸铝、硫酸和水配成溶液A，将水玻璃、四乙基氢氧化铵和水配成溶液B；然后，在强烈搅拌的情况下，将溶液A缓慢加入溶液B中，形成均匀胶体；再将胶体混合物在150-180℃下晶化24-72小时，然后于晶化产物中加入磷酸、拟薄水铝石、硅溶胶以及合成SAPO-11的模板剂，再在170-200℃下晶化24-48小时后，得到一种钠型复合沸石。以该复合沸石为载体制备的催化剂具有良好的加氢脱硫性能、优异的稳定性、较高的汽油收率、高度的异构化和一定的芳构化活性，可用于生产低硫、低烯烃的优质清洁汽油产品。
200710177579.9公开了一种选择性加氢脱硫催化剂及其制备方法，该催化剂以氧化铝和含有有序介孔结构的硅铝介孔分子筛为载体，以钴和钼为活性组分，以镁为助剂。该催化剂的制备方法包括：将氧化铝和硅铝介孔分子筛混合，加入田菁粉和硝酸，再经混捏、成型、干燥和焙烧后，制成氧化铝和硅铝介孔分子筛组合物；将上述组合物经有机酸处理并负载助剂镁以及活性组分钴和钼，再经陈化、干燥和焙烧，制成催化剂。本发明的催化剂通过引入有序介孔分子筛调变催化剂的孔结构和酸性，引入镁调变催化剂的酸性，引入有机酸调变载体和活性组分之间的相互作用；该催化剂呈现出良好的选择性加氢脱硫活性，产品的研究法辛烷值损失低且液体收率高。
以上专利CN200610083283.6和CN200610083284.0报道的催化剂均表现出了较好的加氢改质性能，但所用微孔ZSM-5分子筛的狭窄孔道不利于大分子反应物、中间体和产物的扩散及反应，其酸性太强会导致较多裂化、积碳等反应。CN200610083283.6说明含有有序介孔结构的介孔硅铝分子筛的选择性加氢脱硫催化剂展现出了良好的选择性加氢脱硫性能。如果在ZSM-5分子筛中同时引入介孔和大孔并使其具有适宜酸性才能使含ZSM-5分子筛的FCC汽油加氢改质催化剂表现出更好的催化活性、选择性和稳定性。然而未见含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂的研究报道。
发明内容
本发明的目的是提供一种含介孔-大孔ZSM-5分子筛的FCC汽油加氢改质催化剂，该催化剂的载体为氧化铝与介孔-大孔ZSM-5分子筛构成的混合物，该催化剂的酸性组分为介孔-大孔ZSM-5分子筛，该催化剂的金属组分为钴和钼。
为了实现上述目的，本发明以便宜的橡胶微乳液为介孔-大孔模板剂，制备出了介孔-大孔ZSM-5分子筛，该分子筛的孔径分布、总比表面积、硅/铝原子比分别为2-100nm、300-400m2/g、10:1-100:1。
本发明所提供的FCC汽油加氢改质催化剂，由于采用氧化铝和介孔-大孔ZSM-5分子筛的混合物作为载体，催化剂载体的孔结构更加合理，更有利于活性金属的分散和大分子的扩散与反应，因而对FCC汽油具有更好的加氢改质性能。优选地，所述介孔-大孔ZSM-5分子筛与氧化铝混合物中，介孔-大孔ZSM-5分子筛的含量为60-80wt％，氧化铝含量为20-40wt％；更优选地，可以控制介孔-大孔ZSM-5分子筛与氧化铝的干基重量比为3.0-3.7:1。
根据本发明的方案，基于催化剂总重量，金属活性组分钴和钼在催化剂中的含量以氧化物计分别为：CoO 1-3wt％、MoO3 5-7wt％。
本发明的目的还在于提供所述FCC汽油加氢改质催化剂的制备方法，所述方法主要包括以下步骤：
(1)氧化铝与介孔-大孔ZSM-5分子筛混合物载体的制备
首先，将硅源、铝源、无机酸或无机碱、去离子水配制成混合物凝胶并使其老化，在老化后的混合凝胶中加入一定量的橡胶微乳液，经晶化、过滤、水洗、干燥、焙烧、离子交换后，获得介孔-大孔ZSM-5分子筛；
然后，将该介孔-大孔ZSM-5分子筛与氧化铝原粉混合，加入助挤剂和胶溶剂水溶液，经成型、干燥和焙烧后，制得含氧化铝与介孔-大孔ZSM-5分子筛的催化剂载体。
(2)含介孔-大孔ZSM-5分子筛的FCC汽油加氢改质催化剂的制备
依据上述混合物载体的吸水率及目标催化剂钴钼金属含量，配置适合浓度的钴盐和钼盐的浸渍液，将浸渍液浸渍到载体后，经陈化、干燥和焙烧，得所述催化剂成品。
其中，步骤(1)中，混合物凝胶组成为1.0SiO2:0.005-0.05Al2O3:0.04-0.55Na2O:5-50H2O，混合物凝胶pH值为9.5-13.0；
步骤(1)中，橡胶微乳液干基质量与硅源中硅元素质量的比值(R)为0.5-50；
步骤(1)中，混合物凝胶60-100℃老化约2-48小时、150-200℃晶化约12-72小时；
步骤(1)中，晶化产物过滤水洗后80-140℃干燥约2-12小时、500-600℃焙烧约4-10小时；
步骤(1)中，所述介孔-大孔ZSM-5分子筛的孔径分布、总比表面积、硅/铝原子比分别为2-100nm、300-400m2/g、10:1-100:1；
步骤(1)中，所述氧化铝原粉可以是常用的铝源，如拟薄水铝石粉、氢氧化铝粉、SB粉等；
步骤(1)中，在成型过程中，可控制介孔-大孔ZSM-5分子筛与氧化铝的干基重量比为3.0-3.7:1；以催化剂载体干基总重量计，助挤剂和胶溶剂的重量含量分别为6-8wt％、3-4wt，助挤剂可以是田菁粉、聚丙烯酰胺、石墨、润滑油等，胶溶剂可以是硝酸、盐酸、乙酸、柠檬酸等；
步骤(1)中，经120-150℃干燥约3-5小时、500-550℃焙烧约3-5小时后，制得氧化铝和介孔-大孔ZSM-5分子筛的混合物载体；
步骤(1)中所述橡胶微乳液为丁苯橡胶微乳液、丁腈橡胶微乳液、顺丁橡胶微乳液等；
步骤(2)中，浸渍活性组分时采用的钴盐可以包括硝酸钴、碳酸钴等，钼盐可选用正钼酸铵、仲钼酸铵、四钼酸铵等；
步骤(2)中，浸渍液的配置过程是在90-100℃去离子水中，加入适当量的钴盐和钼盐后再加入浓氨水调节pH值使钴盐和钼盐全部溶解；
步骤(2)中，可以采用等体积共浸渍或等体积分步浸渍的方法浸渍钴盐和钼盐浸渍液。
步骤(2)中，浸渍后，经陈化约8-10小时，120-150℃干燥约3-5小时、500-550℃焙烧约3-5小时后，制得含介孔-大孔ZSM-5分子筛的FCC汽油加氢改质催化剂。
与现有技术相比，本发明提供的一种含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂及其制备方法具有以下特点：
(1)以便宜的橡胶微乳液为介孔-大孔模板剂，制备出了介孔-大孔ZSM-5分子筛，并以介孔-大孔ZSM-5分子筛作为FCC汽油加氢改质催化剂载体的酸性组分；
(2)该催化剂与现有含介孔ZSM-5分子筛的工业FCC汽油加氢改质催化剂相比，在馏分油脱硫率(80-90％)、烯烃降量(4.0-10.0v％)、液体收率(>99.0wt％)相当的情况下，研究法辛烷值(RON)损失降低0.3-0.7个单位；异构烷烃含量高0.4-1.5v％。
具体实施方式
下面通过实施例对本发明的一种含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂及其制备方法给予进一步的说明，但并不能限制本发明的可实施范围。
实施例1
本实施例制备的催化剂A，以催化剂重量计，CoO 1.9wt％，MoO36.0wt％，71.1wt％介孔-大孔ZSM-5分子筛，21.0wt％氧化铝。
先将2084g正硅酸乙酯、28g偏铝酸钠、9900g去离子水和24g氢氧化钠配制成各组分以氧化物摩尔比计为1.0SiO2:0.01Al2O3:0.08Na2O:55.0H2O的混合物凝胶，在容器中85℃搅拌回流22h，在晶化之前，按R＝5.0的比例向混合物凝胶中加入丁苯橡胶微乳液，然后在185℃晶化40h时，将合成产物过滤、水洗、110℃干燥7h、540℃焙烧5h、用0.5mol/L氯化铵水溶液离子交换在60℃交换4h后，即得介孔-大孔ZSM-5分子筛(硅铝原子摩尔比30，比表面积325m2/g)。
称取上述介孔-大孔ZSM-5分子筛375g、拟薄水铝石粉HC-07(山东星都化工有限公司生产，制成氧化铝失水约30wt％)150g、田菁粉32.5g，混合均匀，再加入16.9g浓硝酸(65wt％)和180g去离子水，充分混捏后在挤条机中挤成1.7mm的三叶草条型，经120℃干燥约4小时、520℃焙烧约4小时，冷却筛分，制成3-10mm长的氧化铝与介孔-大孔ZSM-5分子筛混合物载体。
然后，根据该载体吸水率、目标催化剂钼的含量、所用载体量，配制含有30.38g七钼酸铵和90g浓氨水浸渍液，将该浸渍液浸渍到450g载体上，经室温陈化约8小时、120℃干燥约4小时、520℃焙烧约4小时后，得一浸半成品。
根据一浸半成品吸水率、目标催化剂钴的含量、所用半成品量，将34.5g硝酸钴、18.3g磷酸二氢氨、47.2g硝酸铵加入到90-100℃的170.1g去离子水中配置成浸渍液，将该浸渍液浸渍到472.7g一浸半成品上，经室温陈化约8小时、120℃干燥约4小时、520℃焙烧约4小时后，得成品催化剂A。
实施例2
本实施例制备的催化剂为B，其制备方法与实施例1相同，所不同的是ZSM-5分子筛的制备过程如下：先将2084g正硅酸乙酯、35g偏铝酸钠、9900g去离子水和24g氢氧化钠配制成各组分以氧化物摩尔比计为1.0SiO2:0.01Al2O3:0.08Na2O:55.0H2O的混合物凝胶，在容器中90℃搅拌回流12h，在晶化之前，按R＝6.0的比例向混合物凝胶中加入丁腈橡胶微乳液，然后在190℃晶化40h时，将合成产物过滤、水洗、120℃干燥5h、550℃焙烧4h、用0.5mol/L氯化铵水溶液离子交换在60℃交换4h后，即得硅铝原子摩尔比为40、比表面积为322m2/g的介孔-大孔ZSM-5分子筛。
实施例3
本实施例制备的催化剂为C，其制备方法与实施例1相同，所不同的是ZSM-5分子筛的制备过程如下：先将1000g水玻璃、88g硫酸铝、7640g去离子水和200g浓硫酸(95-98wt％)配制成各组分以氧化物摩尔比计为1SiO2:0.01Al2O3:0.55Na2O:62.4H2O的混合物凝胶，在容器中80℃搅拌回流24h，在晶化之前，按R＝2.5的比例向混合物凝胶中加入丁苯橡胶微乳液，然后在185℃晶化48h时，将合成产物过滤、水洗、130℃干燥4h、560℃焙烧3h、、用0.5mol/L氯化铵水溶液离子交换在60℃交换4h后，即得硅铝原子摩尔比为50、比表面积为318m2/g的介孔-大孔ZSM-5分子筛。
实施例4
本实施例制备的催化剂为工业FCC汽油加氢改质催化剂D，其制备方法与实施例1相同，所不同的是将混合物载体中的大孔-介孔ZSM-5分子筛变为介孔ZSM-5分子筛(硅/铝原子摩尔比30，比表面积329m2/g)。
实施例5
本实施例说明本发明催化剂A、B、C与工业剂D对FCC重汽油加氢改质的对比评价结果。
将上述催化剂分别装入两通道小型等温固定床反应器中，催化剂装填为10mL，气密合格后，首先进行催化剂的器内硫化。硫化油为直馏石脑油，硫化剂为二硫化碳，其浓度为1.5wt.％；硫化压力为2.0MPa，氢油体积比为300:1；硫化油体积空速为1.5h-1。升温过程是在氮气气氛下，以30℃/h的升温速率从室温升温至150℃，恒温2小时，然后将氮气气氛切换为氢气气氛，开始注入硫化油，以20℃/h的升温速率从150℃升温至230℃，恒温4小时，随后以20℃/h的升温速率从230℃升温至280℃，恒温8小时，硫化结束。
硫化结束后，切换为FCC重汽油置换2h，将反应压力降至1.8MPa，氢油体积比调整到400:1，反应温度升至340℃，体积空速保持1.5h-1，反应72小时后取样分析。
表1本发明催化剂与工业剂对FCC重汽油的加氢改质数据
表1是本发明催化剂与工业剂对FCC重汽油加氢改质数据。由表1可知，在340℃的反应温度下，本发明催化剂随ZSM-5分子筛Si/Al原子比增加，产品的烯烃和芳烃含量、RON、液体收率逐渐降低，异构烃和硫含量逐渐增加；A与D相比，其产品的脱硫率(80.2-80.9％)、烯烃降量(3.7-4.9v％)、RON增量(0.6)、液体收率(99.7wt％)基本相同。这说明ZSM-5分子筛Si/Al原子比对催化剂加氢改质性能具有重要影响，且当Si/Al原子比为30时，本发明的催化剂具有较好的加氢改质性能。
为了进一步比较催化剂A和D的加氢改质性能，在不同反应温度下评价了这两种催化剂对FCC重汽油的加氢改质性能。表2是不同温度下催化剂A和D对FCC重汽油的加氢改质数据。由表2可知，随着反应温度升高，产品的烯烃降量、异构烷烃含量、芳烃含量、RON增加，产品液体收率、硫含量逐渐降低；A与D相比，在其产品的烯烃降量和脱硫率基本相同的情况下，其产品的异构烃含量、RON、液体收率较高，这说明本法发明催化剂A对FCC重汽油具有较好的加氢改质性能。
表2在不同温度下催化剂A和D对FCC重汽油的加氢改质数据
实施例6
表3在不同温度下催化剂A和D对FCC全馏分汽油的加氢改质数据
本实施例说明催化剂A与工业剂D对FCC全馏分汽油加氢改质的对比评价结果。该实施例采用FCC全馏分汽油，其它操作程序与实施例1相同。表3是不同温度下催化剂A和D对FCC全馏分汽油的加氢改质数据。由表3可知，在不同反应温度下，A产品的烯烃含量、异构烷烃含量、芳烃含量、RON损失、液体收率、硫含量等指标均优于D产品的，这说明本法发明催化剂A与工业剂D相比，对FCC全馏分汽油具有更好的加氢改质性能。
当然，本发明还可有其它多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (6)
1.一种含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂，其特征在于以氧化铝与介孔-大孔ZSM-5分子筛混合物为载体，以介孔-大孔ZSM-5分子筛为酸性组分，以钴和钼为金属活性组分，其中所述介孔-大孔ZSM-5分子筛以橡胶微乳液为模板剂合成；
其中，基于催化剂总重量，金属活性组分钴和钼在催化剂中的含量以氧化物计分别为：CoO 1-3wt％、MoO3 5-7wt％；所述介孔-大孔ZSM-5分子筛与氧化铝混合物中，介孔-大孔ZSM-5分子筛的含量为60-80wt％，氧化铝含量为20-40wt％；
以橡胶微乳液为介孔-大孔模板剂制备介孔-大孔ZSM-5分子筛，橡胶微乳液是丁苯橡胶乳液和/或丁腈橡胶乳液。
2.根据权利要求1所述的含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂，其特征在于所述介孔-大孔ZSM-5分子筛的孔径分布、总比表面积、硅/铝原子比分别为2-100nm、300-400m2/g、(10:1)-(100:1)。
3.权利要求1所述含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂的制备方法，其特征在于主要包括以下步骤：
(1)氧化铝与介孔-大孔ZSM-5分子筛混合物载体的制备
首先，将硅源、铝源、无机酸或无机碱、以及去离子水配制成混合物凝胶并使其老化，在老化后的混合凝胶中加入一定量的橡胶微乳液作为模板剂，经晶化、过滤、水洗、干燥、焙烧、离子交换后，获得介孔-大孔ZSM-5分子筛；
然后，将该介孔-大孔ZSM-5分子筛与氧化铝原粉混合，加入助挤剂和胶溶剂水溶液，经成型、干燥和焙烧后，制得含氧化铝与介孔-大孔ZSM-5分子筛的催化剂载体；
(2)含介孔-大孔ZSM-5分子筛的FCC汽油加氢改质催化剂的制备
依据上述混合物载体的吸水率及目标催化剂钴钼金属含量，配置适合浓度的钴盐和钼盐的浸渍液，将浸渍液浸渍到载体后，经陈化、干燥和焙烧，得所述催化剂成品。
4.根据权利要求3所述的含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂的制备方法，其特征在于所述的橡胶微乳液加入量是橡胶微乳液干基质量与硅源中硅元素质量的比值为0.5-50。
5.根据权利要求3所述的含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂的制备方法，其特征在于在配置浸渍液时，采用的钴盐选自硝酸钴、碳酸钴，钼盐选自正钼酸铵、仲钼酸铵、四钼酸铵。
6.根据权利要求3所述的含介孔-大孔ZSM-5分子筛的催化汽油加氢改质催化剂的制备方法，其特征在于浸渍液的配置过程是在90-100℃去离子水中，加入适当量的钴盐和钼盐后再调节pH值使钴盐和钼盐全部溶解。
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