CN114471692A - 一种加氢异构催化剂及其载体的制备方法 - Google Patents
一种加氢异构催化剂及其载体的制备方法 Download PDFInfo
- Publication number
- CN114471692A CN114471692A CN202011264516.9A CN202011264516A CN114471692A CN 114471692 A CN114471692 A CN 114471692A CN 202011264516 A CN202011264516 A CN 202011264516A CN 114471692 A CN114471692 A CN 114471692A
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- China
- Prior art keywords
- molecular sieve
- acid
- catalyst carrier
- solution
- hydroisomerization catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000002808 molecular sieve Substances 0.000 claims abstract description 101
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 239000012684 catalyst carrier precursor Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000003929 acidic solution Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000011812 mixed powder Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 238000000265 homogenisation Methods 0.000 claims abstract description 10
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000007522 mineralic acids Chemical class 0.000 claims description 17
- 150000007524 organic acids Chemical class 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 11
- 239000011975 tartaric acid Substances 0.000 claims description 11
- 235000002906 tartaric acid Nutrition 0.000 claims description 11
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 230000007547 defect Effects 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 229910016341 Al2O3 ZrO2 Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000003637 basic solution Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 abstract description 3
- 239000002199 base oil Substances 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 238000006317 isomerization reaction Methods 0.000 description 9
- 241000219782 Sesbania Species 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011363 dried mixture Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- B01J29/80—Mixtures of different zeolites
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/708—MRE-type, e.g. ZSM-48
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- 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
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- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- B01J2229/30—After treatment, characterised by the means used
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/7073—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/7092—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7096—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
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- 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
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- 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
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
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Abstract
本发明公开一种加氢异构催化剂载体的制备方法,包括以下步骤:将原料分子筛放置在酸性溶液或碱性溶液中,充分搅拌后获得含有分子筛碎片结构单元的浑浊液A;将步骤S1所得的浑浊液A继续由酸性溶液或碱性溶液调节至pH值为6~8,获得含有分子筛碎片结构单元的浑浊液B;将分子筛、无定形无机多孔材料和粘结剂粉末在容器中机械混匀得到混合粉末,然后将助剂与去离子水混匀后滴加到上述混合粉末中,再进行混捏成型、均化、干燥、焙烧成为催化剂载体前体;在步骤S2所得的浑浊液B中加入去离子水后浸渍到步骤S3所得的催化剂载体前体上,然后经过均化、干燥和焙烧得到催化剂载体。本发明还公开一种加氢异构催化剂。
Description
技术领域
本发明涉及加氢异构催化剂领域,尤其涉及一种加氢异构催化剂及其载体的制备方法,该加氢异构催化剂适用于作为炼油行业择型催化的催化剂,尤其适合于生产润滑油基础油的催化剂。
背景技术
润滑油基础油生产的常用技术有溶剂脱蜡、催化脱蜡和加氢异构。加氢异构技术于20世纪90年代出现生产高质量第Ⅱ、Ⅲ类润滑油基础油的一项新技术,已经成为主流的高档润滑油基础油生产技术。
加氢异构技术的特点是,把油中的蜡通过异构化反应转化成润滑油基础油。它不是像溶剂脱蜡那样,通过物理方法把蜡与油分开;也不是像催化脱蜡那样,把蜡裂化为气体和石脑油等轻组分。同一种原料油,采用加氢异构、溶剂脱蜡、催化脱蜡技术进行脱蜡,生产粘度指数相同、倾点相同的基础油,加氢异构技术得到的基础油收率最高。与催化脱蜡技术相比,加氢异构脱术不仅得到的基础油收率和粘度指数高(相同生产条件下),而且副产的中间馏分油(如副产柴油或溶剂油)收率要高得多,经济效益也高。溶剂脱蜡副产石蜡,难以生产凝点很低的基础油,投产和操作费用最高。因此加工加氢裂化尾油或高含蜡油采用异构脱蜡技术来生产APIⅡ、Ⅲ类润滑油基础油已经成为技术首选。
加氢异构的技术核心就是异构脱蜡催化剂,该种催化剂以具有择型功能的分子筛为主作为载体,加氢活性较强的贵金属作为金属活性中心。在金属择型催化过程中,催化剂的金属活性中心与载体功能需要进行合理的匹配。
ZL201310645847.0公开了一种非贵金属异构化催化剂,由十元环分子筛和负载雷尼镍的过渡金属氧化物组成,十元环分子筛和负载雷尼镍的过渡金属氧化物的重量组成比为0.2-5:1,过渡金属氧化物与雷尼镍的重量组成比为0.05-2:1。
ZL201410812484.X公开了一种加氢异构脱蜡催化剂制备方法,将无定形硅铝、氧化铝、硝酸、助剂和水混合得到混合物进行混捏、挤条成型、干燥和焙烧得到载体前体,载体前体在水蒸气存在下进行改性获得了改性载体,在再改性载体上引入金属活性组分经过干燥和焙烧获得催化剂前体。
ZL02109409.8公开一种加氢异构催化剂制备方法,以SAPO-11作为主要载体,通过有机胺对催化剂载体预处理来保留分子筛的酸性来提高催化剂的活性。
US7141529B2、US5246566公开了利用碱性金属或者碱土金属对分子筛改性,调节分子筛酸量的办法来提高催化剂的选择性。
对于加氢异构脱蜡催化剂载体的处理主要通过分子筛表面修饰手段,用毒化或者钝化催化剂的外表面的非选择性的酸性中心,如磷沉积、碳沉积、金属氧化物修饰以及烷基化处理等技术,对于以上技术能对生产的基础油某一方面性质有影响,如基础油收率、倾点、粘度或者粘度指数,如何能够降低重质基础油的低温流动性能、降低浊点又同时保证基础油的粘度指数损失少,已经成为一个需要解决的技术问题,而载体作为异构脱蜡催化剂一个重要组成部分,对载体进行行之有效的改性可能会解决上述技术问题。
发明内容
为了现有技术中的上述问题,本发明的目的在于提供一种加氢异构催化剂载体的制备方法,在催化剂载体制备过程中直接引入分子筛碎片结构单元,这种分子筛碎片结构单元具有丰富的分子筛缺陷位,而这些分子筛缺陷位(defect zeolite)在某些催化领域具有特殊的催化性能,在催化剂载体上引入更多具有择型催化作用的分子筛缺陷位,使得催化剂的整体催化性能得到提高,在这里需要说明,分子筛缺陷位是指在规整的分子筛结构中通过改性方法造成这种分子筛结构的不规整性。
本发明的目的还在于提供一种加氢异构催化剂。该催化剂在异构脱蜡领域应用中发现,这种具有更多分子筛碎片结构单元的催化剂载体制备的催化剂具有更好的催化性能。
为此,本发明提供一种加氢异构催化剂载体的制备方法,包括以下步骤:
S1:将原料分子筛放置在H+浓度为0.5~5mol/L的酸性溶液或OH+浓度为0.5~5mol/L的碱性溶液中,充分搅拌后获得含有分子筛碎片结构单元的浑浊液A;
S2:将步骤S1所得的浑浊液A继续由酸性溶液或碱性溶液调节至pH值为6~8,获得含有分子筛碎片结构单元的浑浊液B;
S3:将分子筛、无定形无机多孔材料和粘结剂粉末在容器中机械混匀得到混合粉末,然后将助剂与去离子水混匀后滴加到上述混合粉末中,再进行混捏成型、均化、干燥、焙烧成为催化剂载体前体;
S4:在步骤S2所得的浑浊液B中加入去离子水后浸渍到步骤S3所得的催化剂载体前体上,然后经过均化、干燥和焙烧得到催化剂载体。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,以催化剂载体质量为百分百计,所述催化剂载体中的各组分及含量为:分子筛碎片结构单元1~10%,分子筛20~80%,无定形无机多孔材料10~50%,助剂1~10%。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,以催化剂载体质量为百分百计,所述催化剂载体中的各组分及含量为:分子筛碎片结构单元2~8%,分子筛30~70%,无定形无机多孔材料20~40%,助剂2~8%。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,步骤S1中,所述原料分子筛带有十元环结构;步骤S3中,所述分子筛带有十元环结构。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,所述原料分子筛和所述分子筛分别独立地选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,所述无定形无机多孔材料选自Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2和Al2O3-ZrO2中的一种或几种。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,所述分子筛碎片单元为经酸或碱处理过但不经干燥焙烧的具有分子筛缺陷位的分子筛。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,所述碱性溶液为氨水。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,所述酸性溶液为有机酸或无机酸,当所述酸性溶液为有机酸时,选自柠檬酸、醋酸、酒石酸中一种或几种;当所述酸性溶液为无机酸时,选自硝酸、硫酸、盐酸和磷酸中一种或几种。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,所述助剂为有机酸或无机酸,当所述助剂为有机酸时,选自柠檬酸、醋酸、酒石酸中一种或几种;当所述助剂为无机酸时,选自硝酸、硫酸、盐酸和磷酸中一种或几种。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,所述搅拌的时间为10min~60min、温度为20~80℃;所述均化的时间为20min~120min。
本发明所述的加氢异构催化剂载体的制备方法,其中优选的是,所述搅拌的时间为20min~40min、温度为40~60℃;所述均化的时间为30min~60min。
为此,本发明还提供一种加氢异构催化剂,该催化剂的载体由上述的加氢异构催化剂载体的制备方法制得。
具体地,本案采取以下技术方案:
在本发明中,加氢异构载体的制备过程中,分子筛碎片结构单元的制备是催化剂载体制备的重要一环,前两个步骤为分子筛碎片结构单元的制备过程,步骤S1:将含十元环结构的分子筛放置在一定量的酸性或碱性溶液中,充分搅拌5min~60min后获得浑浊液A,其中搅拌时间优选10min~30min;步骤S2:将浑浊液A通过酸或碱调节至pH值为6~8,获得含有分子筛碎片结构单元的浑浊液B;步骤S3:将分子筛粉末、无定形无机多孔材料粉末进行机械混匀、然后将一定量助剂和去离子水配制成溶液滴加到到机械混匀的粉末中,然后进行混捏成型、均化、再经过干燥、焙烧得到加氢异构催化剂载体前体;步骤S4:将步骤S2的浑浊液B加入一定量水浸渍到步骤S3的催化剂载体前体上,经过均化、干燥和焙烧得到异构脱蜡催化剂载体。
其中,以催化剂载体质量为百分百计,催化剂载体包含以下组分:
S1步骤分子筛为1~10%,S3步骤分子筛为20~80%,S3步骤无定形无机多孔材料为10~50%,助剂为1~10%;进一步优化为:S1步骤分子筛为2~8%;S3步骤分子筛为30~70%;S3步骤无定形无机多孔材料为20~40%;助剂为2~8%。
其中,步骤S1中搅拌时间为10min~60min;搅拌温度为20~80℃;均化时间为20min~120min;进一步优化为步骤S1中搅拌时间为20min~40min,搅拌温度为40~60℃;均化时间为30min~60min。
其中,S1步骤分子筛的质量即为分子筛碎片结构单元的质量。
其中,在催化剂载体制备过程中S1步骤分子筛和S3步骤所使用的分子筛可以是相同分子筛,也可以是不同分子筛。
其中,S1步骤分子筛和S3步骤分子筛为带有十元环结构的分子筛,该种分子筛选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23一种或几种。
其中,粘结剂为田菁粉。
其中,用于制备分子筛碎片结构单元的碱为氨水。
其中,用于制备分子筛碎片结构单元的酸为无机酸或有机酸,
其中,无机酸选自硝酸、硫酸、盐酸和磷酸中一种或几种。
其中,有机酸选自柠檬酸、醋酸、酒石酸中一种或几种。
其中,在催化剂载体制备中所用到的助剂可以为酸、碱或盐中的一种或几种,酸可以为有机酸,又可以是无机酸;碱可以是有机碱,也可以是无机碱。
其中,在催化剂载体制备中所用到的无定形无机多孔材料包含Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2或Al2O3-ZrO2中的一种或几种。
其中,在催化剂载体制备过程中所使用的助剂为酸,进一步优选:当为有机酸时,选自柠檬酸、醋酸、酒石酸中一种或几种;当为无机酸时,选自硝酸、硫酸、盐酸和磷酸中一种或几种。
其中,均化时间为20min~120min,优选30min~60min。
本发明的有益效果如下:
本案通过酸性或碱性溶蚀具有十元环结构的分子筛,制备出含有分子筛碎片结构单元的浑浊液,这些分子筛碎片结构单元一方面保持了分子筛一定的结晶度,另一方面这些碎片结构单元又具有更多的缺陷位,而这些缺陷位通常具有特殊的择型催化活性,将这些分子筛碎片结构单元引入到催化剂载体外表面,使得催化剂载体具有更多的分子筛缺陷位,使得催化剂具有更高的催化活性。在异构脱蜡领域应用中发现,这种具有更多分子筛碎片结构单元的催化剂载体制备的催化剂具有更好的催化性能,生产的基础油具有硫、氮含量低、基础油黏度高、粘度指数损失少、基础油的低温流动性能好(凝点和倾点低)、浊点更低和总基础油收率高的优点。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
本发明提供的加氢异构催化剂载体的制备方法,包括以下步骤:
S1:将原料分子筛放置在H+浓度为0.5~5mol/L的酸性溶液或OH+浓度为0.5~5mol/L的碱性溶液中,充分搅拌后获得含有分子筛碎片结构单元的浑浊液A;
S2:将步骤S1所得的浑浊液A继续由酸性溶液或碱性溶液调节至pH值为6~8,获得含有分子筛碎片结构单元的浑浊液B;
S3:将分子筛、无定形无机多孔材料和粘结剂粉末在容器中机械混匀得到混合粉末,然后将助剂与去离子水混匀后滴加到上述混合粉末中,再进行混捏成型、均化、干燥、焙烧成为催化剂载体前体;
S4:在步骤S2所得的浑浊液B中加入去离子水后浸渍到步骤S3所得的催化剂载体前体上,然后经过均化、干燥和焙烧得到催化剂载体。
在一些实施例中,以催化剂载体质量为百分百计,所述催化剂载体中的各组分及含量为:分子筛碎片结构单元1~10%,分子筛20~80%,无定形无机多孔材料10~50%,助剂1~10%。
在一些实施例中,以催化剂载体质量为百分百计,所述催化剂载体中的各组分及含量为:分子筛碎片结构单元2~8%,分子筛30~70%,无定形无机多孔材料20~40%,助剂2~8%。
在一些实施例中,步骤S1中,所述原料分子筛带有十元环结构;步骤S3中,所述分子筛带有十元环结构。
在一些实施例中,所述原料分子筛和所述分子筛分别独立地选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种。
在一些实施例中,所述无定形无机多孔材料选自Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2和Al2O3-ZrO2中的一种或几种。
在一些实施例中,所述分子筛碎片单元为经酸或碱处理过但不经干燥焙烧的具有分子筛缺陷位的分子筛。
在一些实施例中,所述碱性溶液为氨水。
在一些实施例中,所述酸性溶液为有机酸或无机酸,当所述酸性溶液为有机酸时,选自柠檬酸、醋酸、酒石酸中一种或几种;当所述酸性溶液为无机酸时,选自硝酸、硫酸、盐酸和磷酸中一种或几种。
在一些实施例中,所述助剂为有机酸或无机酸,当所述助剂为有机酸时,选自柠檬酸、醋酸、酒石酸中一种或几种;当所述助剂为无机酸时,选自硝酸、硫酸、盐酸和磷酸中一种或几种。
在一些实施例中,所述搅拌的时间为10min~60min、温度为20~80℃;所述均化的时间为20min~120min。
在一些实施例中,所述搅拌的时间为20min~40min、温度为40~60℃;所述均化的时间为30min~60min。
本发明提供的加氢异构催化剂,该催化剂的载体由上述的加氢异构催化剂载体的制备方法制得。
实施例1
以制备100g催化剂载体为例,本实施例中制作分子筛碎片结构单元的分子筛为ITQ-13,载体成型所使用的分子筛为市售工业用分子筛ZSM-48。使用的无定形无机多孔材料为Al2O3-SiO2,助剂为硝酸和酒石酸。
制备ITQ-13型碎片结构单元:步骤S1:取ITQ-13分子筛5g放置15ml含1mol/L盐酸溶液中,在20℃的水浴中充分搅拌30min获得浑浊液A;步骤S2:将浑浊液A通过2mol/L氨水调节至pH值为6~8获得含有ZSM-5型碎片结构单元的浑浊液B。
步骤S3:取市售工业用分子筛ZSM-48型分子筛80g、10g Al2O3、田8g菁粉在容器中进行混匀,将浓度为37%的硝酸10g、酒石酸2g与57g去离子水配制成溶液滴加入上述混匀的粉末中,进行混捏后挤压成型、均化20min后,120℃干燥3小时、550℃焙烧4小时到催化剂载体前体K1。
步骤S4:将浑浊液B加入40ml去离子水浸渍到催化剂载体前体上,均化20min后,120℃干燥3小时、550℃焙烧4小时得到催化剂载体Z1。
实施例2
以制备100g催化剂载体为例,本实施例中制作分子筛碎片结构单元的子筛为市售工业用分子筛NU-87,载体成型所使用的市售工业用分子筛为ZSM-5。使用的无定形无机多孔材料为Al2O3和ZrO2,助剂为硫酸。
制作NU-87型分子筛碎片结构单元:步骤S1:取NU-87型分子筛1g放置10ml含5mol/L氨水溶液中,在30℃的水浴中充分搅拌60min获得浑浊液A;步骤S2:将浑浊液A通过醋酸调节至pH值为6~8获得含有NU-87型分子筛碎片结构单元的浑浊液B。
步骤S3:取ZSM-5型分子筛为30g、30g Al2O3、30g ZrO2为和12g田菁粉在容器中进行混匀,将浓度为98%硫酸6g与63g去离子水配制成溶液,滴加入上述混匀的粉末中,进行混捏、挤压成型后均化120min后,120℃干燥3小时、550℃焙烧4小时得到催化剂载体前体K2。
步骤S4:将浑浊液B加入45ml去离子水浸渍到催化剂载体前体上,均化60min后,120℃干燥3小时、550℃焙烧4小时得到催化剂载体Z2。
实施例3
以制备100g催化剂载体为例,本实施例中制备分子筛碎片结构单元的分子筛为市售工业用分子筛EU-1,载体成型所使用的市售工业用分子筛为MCM-22分子筛。使用的无定形无机多孔材料为TiO2和Al2O3-ZrO2,助剂为磷酸和柠檬酸。
制备EU-1型分子筛碎片结构单元:步骤S1:取EU-1分子筛10g放置15ml含3mol/L磷酸溶液中,在60℃的水浴中充分搅拌20min获得浑浊液A;步骤S2:将浑浊液A通过5mol/L氨水调节至pH值为6~8获得含有EU-1分子筛碎片结构单元的浑浊液B。
步骤S3:取MCM-22分子筛20g、20g TiO2、44g Al2O3-ZrO2和12g田菁粉在容器中进行混匀,将磷酸4g与柠檬酸4g和68ml去离子水配制成溶液,滴加入上述混匀的粉末中,进行混捏,然后挤压成型后均化60min,再120℃干燥3小时、550℃焙烧4小时得到催化剂载体前体K3。
步骤S4:将浑浊液B加入53ml去离子水浸渍到催化剂载体前体上,均化120min后120℃干燥3小时、550℃焙烧4小时得到催化剂载体Z3。
实施例4
以制备100g催化剂载体为例,本实施例中制备分子筛碎片结构单元的分子筛为市售工业用分子筛为ZSM-35,载体成型所使用的分子筛为市售工业用分子筛ZSM-35。使用的无定形无机多孔材料为Al2O3和TiO2,助剂为酒石酸和硝酸。
制备SAPO-11型分子筛碎片结构单元:步骤S1:取ZSM-35型分子筛2g放置10ml含1mol/L硝酸溶液中,在80℃的水浴中充分搅拌10min获得浑浊液A;步骤S2:将浑浊液A通过5mol/L氨水调节至pH值为6~8获得含有ZSM-35分子筛碎片结构单元的浑浊液B。
步骤S3:取ZSM-35型分子筛60g、20g Al2O3、10g TiO2和8g田菁粉在容器中进行混匀,将磷酸5g和柠檬酸5g与60ml去离子水配制成浑浊液,滴加入上述混匀的粉末中,进行混捏然成条型后均化100min,再120℃干燥3小时、550℃焙烧4小时得到催化剂载体前体K4。
步骤S4:将浑浊液B加入55ml去离子水浸渍到催化剂载体前体上,均化80min后120℃干燥3小时、550℃焙烧4小时得到催化剂载体Z4。
实施例5
以制备100g催化剂载体为例,本实施例中制作分子筛碎片结构单元的分子筛为市售工业用分子筛SAPO-11,载体成型所使用的分子筛为市售工业用分子筛ZSM-23。使用的无定形无机多孔材料为Al2O3和ZrO2,助剂为硝酸。
制备SAPO-11分子筛碎片结构单元:步骤S1:取SAPO-11分子筛8g放置20ml含1mol/L硫酸溶液中,在60℃的水浴中充分搅拌20min获得浑浊液A;步骤S2:将浑浊液A通过2mol/L氨水调节至pH值为6~8获得含有ZSM-35型分子筛碎片结构单元的浑浊液B。
步骤S3:取ZSM-23型分子筛70g、15g Al2O3和3g ZrO2和10g田菁粉在容器中进行混匀,将37%的硝酸11g与50ml去离子水配制成溶液,滴加入上述混匀的粉末中,进行混捏然后挤压成条型后均化60min、再120℃干燥3小时、550℃焙烧4小时得到催化剂载体前体K5。
步骤S4:将浑浊液B加入25ml去离子水浸渍到催化剂载体前体上,均化30min后120℃干燥3小时、550℃焙烧4小时得到催化剂载体Z5。
实施例6
以制备100g催化剂载体为例,本实施例中制作分子筛碎片结构单元的分子筛为市售工业用分子筛ZSM-22,载体成型所使用的分子筛为市售工业用分子筛ZSM-22。使用的无定形无机多孔材料为Al2O3和TiO2,助剂为磷酸和醋酸。
制备ZSM-22分子筛碎片结构单元:步骤S1:取ZSM-22型分子筛2g放置15ml含5mol/L氨水溶液中,在40℃的水浴中充分搅拌40min获得浑浊液A;步骤S2:将浑浊液A通过磷酸调节至pH值为6~8获得含有ZSM-22型分子筛碎片结构单元的浑浊液B。
步骤S3:取ZSM-22型分子筛50g、30g Al2O3和10g TiO2和12g田菁粉在容器中进行混匀,将磷酸5g和醋酸4g与65ml去离子水配制成溶液,滴加入上述混匀的粉末中,进行混捏然后挤压成条型后均化30min、120℃干燥3小时、550℃焙烧4小时得到催化剂载体前体K6。
步骤S4:将浑浊液B加入35ml去离子水浸渍到催化剂载体前体上,均化60min后120℃干燥3小时、550℃焙烧4小时得到催化剂载体Z6。
对比例1
与实施例5的区别在于,没有步骤S1、步骤S2和步骤S4,而是将用于制备分子筛结构单元的8g SAPO-11直接加入到步骤S3中,具体实施方式是:取8g SAPO-11分子筛、70gZSM-23分子筛、15g Al2O3、3g ZrO2和10g田菁粉在容器中进行混匀,将80ml去离子滴加入上述混匀的粉末中,进行混捏然后挤压成条型后均化60min、再120℃干燥3小时、550℃焙烧4小时,其余步骤与实施例5相同,制备得到催化剂载体B5。
对比例2
与实施例6的区别在于,没有步骤S1、步骤S2和步骤S4,而是将用于制备分子筛结构单元的2g ZSM-22直接加入到步骤S3中,具体实施方式是:取52g ZSM-22分子筛、30gAl2O3和10g TiO2和12g田菁粉在容器中进行混匀,将80ml去离子滴加入上述混匀的粉末中,进行混捏然后挤压成条型后均化60min、再120℃干燥3小时、550℃焙烧4小时,其余步骤与实施例6相同,制备得到催化剂载体B6。
实施例7
各取50g制备好的催化剂载体Z5、Z6、B5和B6,通过等体积浸渍方法,将氯铂酸溶液浸渍到载体上,制备获得催化剂C5、C6、BC5和BC6,各催化剂中,铂金属含量占催化剂质量的0.5%,并通过异构脱蜡技术将催化剂应用到生产润滑油基础油领域,采用固定床反应器进行加氢评价研究工作,以经过加氢处理的减三线蜡油为原料,反应条件:反应温度330℃、氢分压12MPa、氢油体积比:560:1、体积空速1.0h-1,原料油性质参见表1,评价结果列于表2。
表1原料油性质
密度(20℃),g/ml | 0.8595 |
馏程 | |
HK,℃ | 428 |
50%,℃ | 485 |
KK,℃ | 528 |
硫,μg/g | 10.5 |
氮,μg/g | 6.4 |
黏度(100℃),mm<sup>2</sup>/s | 4.46 |
粘度指数 | 137 |
凝点,℃ | 3 |
加氢评价装置运转20小时后取样分析,经过实沸点切割后大于360℃馏分段,分析结果于表2所示。
表2评价结果
从表2的评价结果看,相比于不引入分子筛碎片结构单元的催化剂载体来说,在催化剂载体外表面引入分子筛碎片结构单元后使得生产的润滑油基础油具有硫和氮含量低、黏度高、粘度指数损失更少(原料粘度指数137,产品分别为126和122),同时产品的低温流动性能更好(凝点和倾点更低)、浊点更低、总基础油收率更高。
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的保护范围。
Claims (13)
1.一种加氢异构催化剂载体的制备方法,其特征在于,包括以下步骤:
S1:将原料分子筛放置在H+浓度为0.5~5mol/L的酸性溶液或OH+浓度为0.5~5mol/L的碱性溶液中,充分搅拌后获得含有分子筛碎片结构单元的浑浊液A;
S2:将步骤S1所得的浑浊液A继续由酸性溶液或碱性溶液调节至pH值为6~8,获得含有分子筛碎片结构单元的浑浊液B;
S3:将分子筛、无定形无机多孔材料和粘结剂粉末在容器中机械混匀得到混合粉末,然后将助剂与去离子水混匀后滴加到上述混合粉末中,再进行混捏成型、均化、干燥、焙烧成为催化剂载体前体;
S4:在步骤S2所得的浑浊液B中加入去离子水后浸渍到步骤S3所得的催化剂载体前体上,然后经过均化、干燥和焙烧得到催化剂载体。
2.根据权利要求1所述的加氢异构催化剂载体的制备方法,其特征在于,以催化剂载体质量为百分百计,所述催化剂载体中的各组分及含量为:分子筛碎片结构单元1~10%,分子筛20~80%,无定形无机多孔材料10~50%,助剂1~10%。
3.根据权利要求2所述的加氢异构催化剂载体的制备方法,其特征在于,以催化剂载体质量为百分百计,所述催化剂载体中的各组分及含量为:分子筛碎片结构单元2~8%,分子筛30~70%,无定形无机多孔材料20~40%,助剂2~8%。
4.根据权利要求1所述的加氢异构催化剂载体的制备方法,其特征在于,步骤S1中,所述原料分子筛带有十元环结构;步骤S3中,所述分子筛带有十元环结构。
5.根据权利要求4所述的加氢异构催化剂载体的制备方法,其特征在于,所述原料分子筛和所述分子筛分别独立地选自ZSM-5、SAPO-11、EU-1、ITQ-13、ZSM-35、ZSM-48、ZSM-22、MCM-22、NU-87和ZSM-23中一种或几种。
6.根据权利要求1所述的加氢异构催化剂载体的制备方法,其特征在于,所述无定形无机多孔材料选自Al2O3、SiO2、Al2O3-SiO2、TiO2、Al2O3-TiO2、ZrO2和Al2O3-ZrO2中的一种或几种。
7.根据权利要求1所述的加氢异构催化剂载体的制备方法,其特征在于,所述分子筛碎片单元为经酸或碱处理过但不经干燥焙烧的具有分子筛缺陷位的分子筛。
8.根据权利要求1所述的加氢异构催化剂载体的制备方法,其特征在于,所述碱性溶液为氨水。
9.根据权利要求1所述的加氢异构催化剂载体的制备方法,其特征在于,所述酸性溶液为有机酸或无机酸,当所述酸性溶液为有机酸时,选自柠檬酸、醋酸、酒石酸中一种或几种;当所述酸性溶液为无机酸时,选自硝酸、硫酸、盐酸和磷酸中一种或几种。
10.根据权利要求1所述的加氢异构催化剂载体的制备方法,其特征在于,所述助剂为有机酸或无机酸,当所述助剂为有机酸时,选自柠檬酸、醋酸、酒石酸中一种或几种;当所述助剂为无机酸时,选自硝酸、硫酸、盐酸和磷酸中一种或几种。
11.根据权利要求1所述的加氢异构催化剂载体的制备方法,其特征在于,所述搅拌的时间为10min~60min、温度为20~80℃;所述均化的时间为20min~120min。
12.根据权利要求11所述的加氢异构催化剂载体的制备方法,其特征在于,所述搅拌的时间为20min~40min、温度为40~60℃;所述均化的时间为30min~60min。
13.一种加氢异构催化剂,其特征在于,该催化剂的载体由权利要求1-12任一项所述的加氢异构催化剂载体的制备方法制得。
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CN105289704A (zh) * | 2015-11-09 | 2016-02-03 | 中国海洋石油总公司 | 一种c8芳烃异构化催化剂的制备方法 |
CN106669803A (zh) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | 生产高粘度指数加氢裂化尾油的催化剂及其制备方法 |
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