CN109395769B - Iron-based hydrogenation catalyst and preparation method thereof - Google Patents
Iron-based hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN109395769B CN109395769B CN201710704764.2A CN201710704764A CN109395769B CN 109395769 B CN109395769 B CN 109395769B CN 201710704764 A CN201710704764 A CN 201710704764A CN 109395769 B CN109395769 B CN 109395769B
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- active metal
- iron
- hydrogenation catalyst
- alpo
- based hydrogenation
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 239000003054 catalyst Substances 0.000 title claims abstract description 182
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 113
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 137
- 239000002184 metal Substances 0.000 claims abstract description 137
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 128
- 239000002808 molecular sieve Substances 0.000 claims abstract description 66
- 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 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910017119 AlPO Inorganic materials 0.000 claims abstract description 38
- 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 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 32
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010937 tungsten Chemical group 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 52
- 238000005470 impregnation Methods 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 44
- 239000011701 zinc Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002244 precipitate Substances 0.000 claims description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052750 molybdenum Chemical group 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011733 molybdenum Chemical group 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000284 resting effect Effects 0.000 claims 1
- 238000002791 soaking Methods 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 28
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 19
- 238000003756 stirring Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 13
- 238000000921 elemental analysis Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 9
- 239000000295 fuel oil Substances 0.000 description 9
- 238000007654 immersion Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000011280 coal tar Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 3
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 3
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 3
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 3
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 3
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 3
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 3
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 3
- 108091006231 SLC7A2 Proteins 0.000 description 3
- 108091006230 SLC7A3 Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000005078 molybdenum compound Substances 0.000 description 3
- 150000002752 molybdenum compounds Chemical class 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
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 206010033307 Overweight Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005987 sulfurization reaction 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
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides an iron-based hydrogenation catalyst and a preparation method thereof. The catalyst comprises a carrier and an oxide of an active metal, the carrier comprising alumina and AlPO modified with nickel and tungsten4-5 molecular sieve, the active metal comprising a main active metal and an auxiliary active metal, the main active metal being Fe and the auxiliary active metal being Zn; nickel and tungsten modified AlPO4-5 mass ratio of molecular sieve to alumina (5-21): 50, the molar ratio of Fe to Zn is (2-6): 1, taking the total weight of the catalyst as 100 percent and the total weight of the active metal oxide as 15 to 32 percent; the preparation method of the molecular sieve comprises the following steps: ni was first introduced into AlPO4In-5 molecular sieve to obtain Ni/AlPO4-5 molecular sieves; soaking in Ni/AlPO with W water solution in the same volume4On-5 molecular sieve to obtain W-Ni/AlPO4-5 molecular sieves.
Description
Technical Field
The invention relates to the field of hydrogenation catalysis, in particular to an iron-based hydrogenation catalyst and a preparation method thereof.
Background
The hydrogenation technology is a key technology for deep processing of heavy oil, and plays an important role in deep processing of heavy raw oil, product quality improvement, raw material adaptability enhancement and operation flexibility enhancement. A number of new refinery hydrogenation catalysts and processes for their preparation have emerged in succession.
The patent CN105772005A provides a hydrogenation catalyst, a preparation method thereof and a heavy oil hydrodesulfurization method, wherein the catalyst comprises a carrier and active metal components loaded on the carrier, the active metal components are distributed in a double-layer manner along the radial direction of the carrier, and the active metal components of a nuclear layer are CoO and MoO3The active metal component of the shell layer is NiO and MoO3And/or WO3The catalyst has the activities of hydrogenation demetallization, desulfurization, carbon residue removal and denitrification, wherein the carrier comprises alumina or a mixture of alumina and at least one of silica, titania and zirconia, and the preparation method comprises the steps of immersing the carrier subjected to hydrothermal treatment in a first alkaline solution containing a nickel compound, a molybdenum compound and/or a tungsten compound and drying to obtain the carrier loaded with the nickel compound, the molybdenum compound and/or the tungsten compound; the above-mentioned carrier is immersed in an acidic second solution containing a cobalt compound and a molybdenum compound, followed by drying and calcination, so that the metal compound supported on the carrier is converted into the corresponding metal oxide.
CN106140293A discloses a coal tar hydro-upgrading catalyst and a preparation method thereof, wherein the catalyst consists of an active metal component, a promoter component and a carrier, wherein the active metal component is one or more metal elements selected from Ni, Mo, Co and W, the promoter component is P2O3 and one or more metal elements selected from Fe and Mn, and the carrier is kaolin modified by phosphoric acid; the weight of the active metal component is 10-30% of the weight of the carrier, the weight of the metal element in the promoter component is 3-7% of the weight of the carrier, and the dosage of the phosphoric acid is 1-4 times of the weight of the carrier, so that the catalyst shows good hydrodesulfurization, denitrification and degumming activities, and simultaneously has strong aromatic saturation ring-opening capability.
In the patent, the hydrogenation active component is mainly Co (Ni) xMo (W) y composite oxide or sulfide; the hydrogenation metal active phase has higher hydrogenation activity than the supported Co (Ni) Mo (W) oxide or sulfide of the traditional impregnation method, but the high cost is another problem to be solved urgently. Especially, the development of low-cost hydrogenation catalysts has wider significance in the face of increasing heavy oil production and heavy components in crude oil.
CN103877999A discloses a coal tar heavy oil hydrogenation catalyst and a preparation method thereof, wherein, iron sulfide and iron oxide with higher weight proportion are added into coal powder and are uniformly mixed, mineral powder or metal salt aqueous solution with proper concentration such as molybdenum, nickel, tungsten, cobalt and the like is respectively added according to different coal tar, and water is added to prepare slurry. And the slurry is subjected to wet-type crushing, so that the molybdenum, nickel, tungsten and cobalt active components can be uniformly dispersed on the surface of the carrier coal dust, and meanwhile, the high-weight percentage content and the iron sulfide and iron oxide active components are uniformly dispersed on the surface of the carrier coal dust. The coal tar heavy oil hydrogenation catalyst prepared by the method has good overall dispersibility in coal tar heavy oil and higher catalytic hydrogenation activity, and can prevent catalyst agglomeration and deposition in a coal tar heavy oil hydrogenation reactor, thereby achieving good effect.
CN104918698B discloses an iron-based heavy oil hydrogenation catalyst, which uses iron as a main active metal and zinc and potassium as first auxiliary active component metals; based on the total weight of the iron-based hydrogenation catalyst, the total amount of the main active component metal and the auxiliary active component element is 5-100%, and the balance is binder or carrier in oxide form; the co-active component element comprises a first co-active component metal; wherein the main activityThe molar ratio of the metal of the sexual component to the metal of the first coactive component is 0.5-200: 1; the iron-based hydrogenation catalyst is subjected to vulcanization treatment, the vulcanization treatment temperature is 200-450 ℃, the pressure is 0.1-10Mpa, the vulcanization treatment time is 2-48 hours, and the liquid hourly space velocity is 0.1-20 hours-1The volume ratio of hydrogen to oil is 100-800.
In view of the above, researchers have made a lot of research on the modification of a supported catalyst carrier and an auxiliary agent, and the preparation of a breakthrough unsupported catalyst, which has appeared in recent years, and also made many efforts to reduce the production and preparation costs of the catalyst. But the basic combination of metals of molybdenum and tungsten as main active components is not broken by taking nickel and cobalt as assistants. Therefore, the development of a gasoline-diesel oil and heavy oil hydrogenation catalyst with both cost and activity is still one of the problems to be solved in the field.
Disclosure of Invention
It is an object of the present invention to provide an iron-based hydrogenation catalyst;
the invention also aims to provide a preparation method of the iron-based hydrogenation catalyst.
In order to achieve the above object, in one aspect, the present invention provides an iron-based hydrogenation catalyst, wherein the catalyst comprises a support and an oxide of an active metal supported on the support, and the support comprises alumina and AlPO modified with nickel and tungsten4-5 molecular sieves, the active metals comprising a primary active metal and a co-active metal, the primary active metal being Fe and the co-active metal being Zn; the AlPO modified with nickel and tungsten4-5 mass ratio of molecular sieve to alumina (5-21): 50, the molar ratio of Fe element to Zn element is (2-6): 1, taking the total weight of the catalyst as 100 percent, and taking the total weight of the oxide of the active metal as 15 to 32 percent; the AlPO modified with nickel and tungsten4The preparation method of the molecular sieve comprises the following steps:
(a) introduction of nickel element into AlPO4In-5 molecular sieve to obtain Ni/AlPO4-5 molecular sieve, wherein the nickel element accounts for 0.5-3% of NiO based on 100% of the weight of the molecular sieve;
(b) with water-soluble salts of metallic tungstenSoaking the Ni/AlPO obtained in the step (a) in solution in equal volume4-5 molecular sieve, then drying and roasting to obtain W-Ni/AlPO4-5 molecular sieves of W-Ni/AlPO45 total weight of molecular sieves, calculated as 100%, WO33 to 7 percent.
According to some embodiments of the invention, wherein the AlPO modified with nickel and tungsten4-5 mass ratio of molecular sieve to alumina (18-20): 50.
according to some embodiments of the present invention, the molar ratio of Fe element and Zn element is (4-6): 1.
according to some embodiments of the present invention, the nickel element in the step (a) is 1.0-2.0% calculated as NiO.
According to some embodiments of the invention, wherein in step (b) W-Ni/AlPO is used45 total weight of molecular sieves, calculated as 100%, WO3Is 3-5%.
According to some embodiments of the invention, the water-soluble salt of metallic tungsten in step (b) is ammonium metatungstate.
According to some embodiments of the present invention, wherein the calcination temperature in step (b) is 450-550 ℃.
According to some embodiments of the invention, wherein the drying temperature of step (b) is 90-120 ℃.
According to some embodiments of the invention, step (a) is an equal volume impregnation of AlPO with an aqueous nickel salt solution4-5 molecular sieve, then drying and roasting to obtain the Ni/AlPO4-5 molecular sieves.
According to some embodiments of the invention, wherein the drying temperature in step (a) is 90-120 ℃.
According to some embodiments of the present invention, wherein the calcination temperature in step (a) is 450-550 ℃.
According to some embodiments of the invention, the water-soluble salt of nickel in step (a) is nickel nitrate hexahydrate.
According to some embodiments of the present invention, the preparation method of the iron-based hydrogenation catalyst comprises the following steps:
preparing co-impregnation solution of main active metal and auxiliary active metal, then loading the main active metal and the auxiliary active metal on pseudo-boehmite by an isometric impregnation method, and roasting to obtain the iron-based hydrogenation catalyst;
or uniformly mixing main active metal oxide powder and auxiliary active metal oxide powder with a carrier to obtain the iron-based hydrogenation catalyst;
or uniformly mixing the main active metal oxide powder and the auxiliary active metal oxide powder with the pseudo-boehmite, and roasting to obtain the iron-based hydrogenation catalyst.
According to some embodiments of the present invention, the calcination temperature after loading the primary active metal and the secondary active metal to the pseudo-boehmite is 450-550 ℃.
According to some embodiments of the present invention, the calcination temperature after uniformly mixing the primary active metal oxide and the auxiliary active metal oxide powder with the pseudo-boehmite is 450-550 ℃.
According to some embodiments of the present invention, the roasting time after the primary active metal and the secondary active metal are loaded to the pseudo-boehmite is 2 to 12 hours; of these, 4 to 8 hours are preferred.
According to some embodiments of the present invention, the roasting time after uniformly mixing the main active metal oxide and the auxiliary active metal oxide powder with the pseudo-boehmite is 2-12 hours; of these, 4 to 8 hours are preferred.
According to some embodiments of the present invention, the step of loading the carrier with the primary active metal and the secondary active metal comprises: preparing co-impregnation solution of main active metal and auxiliary active metal, then loading the main active metal and the auxiliary active metal on the pseudo-boehmite by an equal-volume impregnation method, drying the pseudo-boehmite loaded with the main active metal and the auxiliary active metal, and then roasting to obtain the iron-based hydrogenation catalyst.
According to some embodiments of the invention, the step of preparing a co-impregnation solution of the primary active metal and the secondary active metal comprises: and dissolving the water-soluble salt of the main active metal and the water-soluble salt of the auxiliary active metal in water to obtain the co-impregnation solution.
According to some embodiments of the invention, the water-soluble salt of the primary reactive metal is a mixture of one or more of ferric nitrate nonahydrate, ferric chloride and ferric sulfate.
According to some embodiments of the invention, the water-soluble salt of the coactive metal is a mixture of one or more of zinc nitrate hexahydrate, zinc chloride and zinc sulfate.
According to some embodiments of the present invention, the temperature at which the pseudo-boehmite loaded with the primary active metal and the secondary active metal is dried is 90 to 120 ℃.
According to some embodiments of the present invention, the pseudo-boehmite loaded with the primary active metal and the secondary active metal is dried for 4 to 12 hours.
According to some embodiments of the present invention, after the pseudo-boehmite is impregnated with the primary active metal and the secondary active metal, the pseudo-boehmite impregnated with the primary active metal and the secondary active metal is allowed to stand, and then dried and calcined.
According to some embodiments of the invention, the time of standing is 4 to 24 hours.
According to some embodiments of the present invention, the step of uniformly mixing the primary active metal oxide and the secondary active metal oxide powders with the carrier or the pseudo-boehmite comprises: the water soluble salt of the main active metal and the water soluble salt of the auxiliary active metal are uniformly mixed in water to obtain a mixed solution, the mixed solution reacts under an alkaline condition to obtain a hydroxide precipitation mixture of the main active metal and the auxiliary active metal, then the hydroxide precipitation mixture is roasted to obtain an oxide mixture of the main active metal and the auxiliary active metal, and then the oxide mixture is uniformly mixed with the carrier or the pseudo-boehmite.
According to some embodiments of the invention, the water-soluble salt of the primary reactive metal is a mixture of one or more of ferric nitrate nonahydrate, ferric chloride and ferric sulfate.
According to some embodiments of the invention, the water-soluble salt of the coactive metal is a mixture of one or more of zinc nitrate hexahydrate, zinc chloride and zinc sulfate.
According to some embodiments of the invention, the alkaline condition is that the pH of the mixed solution is 10 or more.
According to some embodiments of the present invention, the calcination temperature after the reaction under alkaline conditions to obtain the hydroxide precipitate mixture of the primary active metal and the secondary active metal is 450-550 ℃.
According to some embodiments of the present invention, the calcination time after the reaction under alkaline conditions to obtain the hydroxide precipitation mixture of the main active metal and the auxiliary active metal is 2 to 12 hours; preferably 4-8 h.
According to some embodiments of the present invention, the step of uniformly mixing the primary active metal oxide and the secondary active metal oxide powders with the carrier or the pseudo-boehmite comprises: dissolving water soluble salt of main active metal and water soluble salt of auxiliary active metal in water, adding alkali to react to obtain precipitate, filtering after complete reaction, roasting the precipitate to obtain iron-zinc oxide powder, and mixing the iron-zinc oxide powder with carrier or pseudo-boehmite uniformly.
According to some embodiments of the invention, the base is ammonia or urea.
According to some embodiments of the invention, the water-soluble salt of the primary reactive metal is a mixture of one or more of ferric nitrate nonahydrate, ferric chloride and ferric sulfate.
According to some embodiments of the invention, the water-soluble salt of the coactive metal is a mixture of one or more of zinc nitrate hexahydrate, zinc chloride and zinc sulfate.
According to some embodiments of the invention, wherein the reaction temperature of the reaction is 75-95 ℃.
According to some embodiments of the invention, the reaction time of the reaction is 4 to 8 hours.
According to some embodiments of the invention, the precipitate is obtained after aging after the reaction is completed.
According to some embodiments of the invention, wherein the aging is standing at 50-80 ℃ for 20-30 h; preferably, the mixture is allowed to stand at 60 ℃ for 24 hours.
According to some embodiments of the present invention, the step of uniformly mixing the iron-zinc oxide powder and the carrier further comprises a step of tabletting the mixed iron-zinc oxide powder and the carrier.
According to some embodiments of the present invention, before the co-impregnation of the carrier with the co-impregnation solution of the primary active metal and the secondary active metal in the same volume, the method further comprises the step of adding alumina and AlPO modified with nickel and tungsten4-5 a step of mixing the molecular sieves.
According to some embodiments of the invention, wherein the alumina and the AlPO modified with nickel and tungsten45 after the molecular sieve is mixed, the step of extruding the mixture into strips is also included.
In another aspect, the invention also provides a preparation method of the iron-based hydrogenation catalyst, which comprises the step of using nickel and tungsten to perform reaction on AlPO4-5 a step of modifying the molecular sieve, said step comprising:
(a) introduction of nickel element into AlPO4In-5 molecular sieve to obtain Ni/AlPO4-5 molecular sieves to obtain Ni/AlPO45, calculated by 100% of the weight of the molecular sieve, the nickel element is 0.5-3% calculated by NiO;
(b) isovolumetrically impregnating the Ni/AlPO obtained in step (a) with a water-soluble salt solution of metallic tungsten4-5 molecular sieve, then drying and roasting to obtain W-Ni/AlPO4-5 molecular sieves of W-Ni/AlPO45 total weight of molecular sieves, calculated as 100%, WO33 to 7 percent.
In conclusion, the invention provides an iron-based hydrogenation catalyst and a preparation method thereof. The catalyst of the invention has the following advantages:
the invention adopts an iron-based catalyst to replace the traditional hydrogenation catalyst which takes molybdenum and tungsten of VIB group as active component metals and cobalt and nickel of VIII group as auxiliary metals. The iron is used as a main active component metal, and the zinc is used as an auxiliary active component metal; and modified W-Ni/AlPO4The-5 molecular sieve is introduced into the alumina carrier, so that the interaction between the carrier and the hydrogenation metal active component FeZn can be effectively improved, and the activity of the catalyst is improved. Compared with the traditional hydrogenation catalyst, the iron-based catalyst has the advantages of cheap and easily obtained raw materials, simple manufacturing process and the like, can greatly reduce the production cost of the hydrogenation catalyst, has higher hydrogenation activity, and has long-term industrial application value.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
Example 1
An iron-based hydrogenation catalyst, the preparation method comprises the following steps:
Ni/AlPO4-5(1) preparation: 1.07g of nickel nitrate hexahydrate is dissolved in 42.5g of distilled water to prepare a solution, and the solution is slowly dripped into 50g of AlPO by an isovolumetric immersion method4Standing in-5 molecular sieve with air for 3 hr, drying at 110 deg.C for 12 hr, and calcining at 540 deg.C for 3 hr. Elemental analysis showed Ni/AlPO4The mass percentage of NiO in the (5) and (1) is 0.55 wt%.
W-Ni/AlPO4-5(1) preparation: 0.98g of ammonium metatungstate is dissolved in 21g of distilled water to prepare a solution, and the solution is slowly added dropwise to 25g of Ni/AlPO by an equal volume impregnation method4And (5) standing in air for 3h, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 3 h. Elemental analysis showed W-Ni/AlPO4WO in (5) to (1)3The mass percentage of (B) is 3.3 wt%.
Preparing a catalyst carrier: pseudo-boehmite 63.9g (in terms of weight percent of alumina content in consideration of loss on ignition) and 15W-Ni/AlPO45(1) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 15: 50.
Preparing an iron-based hydrogenation catalyst: 18.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolutionPreparing co-impregnation solution in a proper amount of deionized water, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-1; iron oxide (Fe) in the catalyst CAT-12O3) And zinc oxide (ZnO) in an amount of 15.1 wt%, with a metal molar ratio of Fe to Zn of 2.1: 1.
Example 2
Ni/AlPO4-5(2) preparation: 1.95g of nickel nitrate hexahydrate is dissolved in 42.5g of distilled water to prepare a solution, and the solution is slowly dripped into 50g of AlPO by adopting an isovolumetric immersion method4Standing in-5 molecular sieve with air for 3 hr, drying at 110 deg.C for 12 hr, and calcining at 540 deg.C for 3 hr. Elemental analysis showed Ni/AlPO4The mass percentage of NiO in the (5) and (2) is 0.98 wt%.
W-Ni/AlPO4-5(2) preparation: dissolving 1.33g ammonium metatungstate in 21g distilled water to obtain solution, and slowly adding 25g Ni/AlPO dropwise by the same volume immersion method4And (5) standing in air for 3h, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 3 h. Elemental analysis showed W-Ni/AlPO4WO in (5) to (2)3The mass percentage of (B) is 4.5 wt%.
Preparing a catalyst carrier: pseudo-boehmite 63.9g (in terms of weight percent of alumina content in consideration of loss on ignition) and 17W-Ni/AlPO45(2) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 17: 50.
Preparing an iron-based hydrogenation catalyst: 22.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-2; iron oxide (Fe) in the catalyst CAT-22O3) And zinc oxide (ZnO)) Is 17.0 wt%, and the metal molar ratio of Fe to Zn is 2.7: 1.
Example 3
Ni/AlPO4-5(3) preparation: preparing nickel-containing AlPO by adopting hydrothermal synthesis method of patent CN200710009684.14-5 molecular sieves. The iron source is nickel nitrate hexahydrate and triethylamine (Et) is adopted3N) is a template agent; the proportion of the synthetic gel is (atomic ratio): 0.03Ni:1Al2O3:1.06P2O5:1.47Et3N:45H2O, the crystallization temperature is 190 ℃, and the crystallization time is 16 hours. Filtering, washing, drying (90 ℃) and roasting the obtained product at 500 ℃; the elemental analysis shows that the mass content of NiO in the product is 1.3 wt%.
W-Ni/AlPO4-5(3) preparation: dissolving 1.69g ammonium metatungstate in 21g distilled water to obtain solution, and slowly adding 25g Ni/AlPO dropwise by the same volume immersion method4And (3) standing in air for 3h, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 3 h. Elemental analysis showed W-Ni/AlPO4WO in (5) to (3)3The mass percentage of (B) is 5.6 wt%.
Preparing a catalyst carrier: pseudo-boehmite 63.9g (in terms of weight percent of alumina content in consideration of loss on ignition) and 19W-Ni/AlPO45, (3) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 19: 50.
Preparing an iron-based hydrogenation catalyst: 32.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 5.30g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing for 5 hours in air, drying at 100 ℃ for 6 hours, and roasting at 500 ℃ for 5 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-3; iron oxide (Fe) in the catalyst CAT-32O3) And the weight content of zinc oxide (ZnO) was 20.8 wt%, and the metal molar ratio of Fe to Zn was 4.5: 1.
Example 4
Ni/AlPO4-5(4) preparation: preparing nickel-containing AlPO by adopting hydrothermal synthesis method of patent CN200710009684.14-5 molecular sieves. The iron source is nickel nitrate hexahydrate and triethylamine (Et) is adopted3N) is a template agent; the proportion of the synthetic gel is (atomic ratio): 0.05Ni:1Al2O3:1.06P2O5:1.47Et3N:45H2O, the crystallization temperature is 190 ℃, and the crystallization time is 16 hours. Filtering, washing, drying (90 ℃) and roasting the obtained product at 500 ℃; elemental analysis showed that the product NiO mass content was 2.3 wt%.
W-Ni/AlPO4-5(4) preparation: dissolving 1.89g ammonium metatungstate in 21g distilled water to obtain solution, and slowly adding 25g Ni/AlPO dropwise by the same volume immersion method4And (5) standing in air for 3h, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 3 h. Elemental analysis showed W-Ni/AlPO4WO 5(4) in (1)3The mass percentage of the component (B) is 6.3 wt%.
Preparing a catalyst carrier: pseudo-boehmite 63.9g (in terms of weight percent of alumina content in consideration of loss on ignition) and 20W-Ni/AlPO45(4) mechanically mixing to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 20: 50.
Preparing an iron-based hydrogenation catalyst: mixing 38.5g ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 8.30g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) and 30g of the prepared catalyst carrier are uniformly mixed and roasted for 5 hours at 500 ℃ to obtain the hydrogenation catalyst which is marked as catalyst CAT-4; iron oxide (Fe) in the catalyst CAT-42O3) And zinc oxide (ZnO) in an amount of 24.8 wt%, with a metal molar ratio of Fe to Zn of 3.4: 1.
Example 5
Ni/AlPO4-5(5) preparation: 5.64g of nickel nitrate hexahydrate is dissolved in 42.5g of distilled water to prepare a solution, and the solution is slowly dripped into 50g of AlPO by an isometric immersion method4Standing in-5 molecular sieve with air for 3 hr, drying at 110 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr. Elemental analysis showed Ni/AlPO4The mass percentage of NiO in the (5) and the (5) is 2.9wt percent.
W-Ni/AlPO4-5(5) preparation: dissolving 2.01g ammonium metatungstate in 21g distilled water to obtain solution, and slowly adding 25g Ni/AlPO dropwise by the same volume immersion method4And (5) standing in air for 3h, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 3 h. Elemental analysis showed W-Ni/AlPO4WO 5(5)3The mass percentage of (B) is 6.9 wt%.
Dissolving 32.2g of ferric chloride and 5.22g of zinc chloride in 250mL of deionized water to obtain an aqueous solution of the ferric chloride and the zinc chloride; slowly adding 62g of ammonia water solution into the aqueous solution of ferric chloride and zinc chloride while stirring; stirring and reacting for 4 hours in a water bath at the temperature of 80 ℃, then cooling to 60 ℃, standing and aging for 24 hours to obtain a precipitate; filtering the precipitate while the precipitate is hot, washing the precipitate with deionized water until the pH value is about 9, drying the precipitate in a drying oven at 120 ℃, heating the dried precipitate at the speed of 5 ℃/min, and roasting the dried precipitate for 2 hours at 500 ℃ in the air atmosphere to obtain iron-zinc oxide powder; wherein the metal molar ratio of Fe to Zn in the resulting oxide is 5.4: 1.
Calcining 9.8g of oxide powder of iron-based hydrogenation catalyst at 550 ℃ for 4 hours to obtain 14.9g of pseudo-boehmite, 6.24g W-Ni/AlPO45, (5) mixing and stirring uniformly, adding into a tablet press, pressing and forming, and marking as catalyst CAT-5; iron oxide (Fe) in the catalyst CAT-52O3) And the weight content of zinc oxide (ZnO) was 31.7 wt%.
Comparative example 1
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
with Ni/AlPO prepared as in example 24-5(2) AlPO as modification4-type 5 molecular sieves.
Preparing a catalyst carrier: pseudo-boehmite 63.9g (in terms of weight percent of alumina content in consideration of loss on ignition) and 17W-Ni/AlPO45(2) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 17: 50.
Preparing an iron-based hydrogenation catalyst: 22.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R1; iron oxide (Fe) in the catalyst CAT-R12O3) And the weight content of zinc oxide (ZnO) was 17.0 wt%, and the metal molar ratio of Fe to Zn was 2.7: 1.
Comparative example 2
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
with W/AlPO4-5 AlPO as modification4-type 5 molecular sieves.
W/AlPO4-5 preparation: 0.98g of ammonium metatungstate is dissolved in 21g of distilled water to prepare a solution, and the solution is slowly added dropwise to 25g of AlPO by an isometric immersion method4Standing in-5 deg.C, drying at 110 deg.C for 12 hr, and calcining at 500 deg.C for 3 hr. Elemental analysis showed W/AlPO4WO in (5) to (1)3The mass percentage of (B) is 3.2 wt%.
Preparing a catalyst carrier: pseudo-boehmite 63.9g (in terms of weight percent of alumina content in consideration of loss on ignition) and 15W/AlPO4And 5, mechanically mixing, extruding and molding to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 15: 50.
Preparing an iron-based hydrogenation catalyst: 18.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R2; iron oxide (Fe) in the catalyst CAT-R22O3) And zinc oxide (ZnO) in an amount of 15.1 wt%, with a metal molar ratio of Fe to Zn of 2.1: 1.
Comparative example 3
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
preparing a catalyst carrier: pseudo-boehmite 63.9g (in terms of loss on ignition, calculated as alumina content 78.1 wt.%) was mixed with 19 AlPO4And 5, mechanically mixing, extruding and molding to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 19: 50.
Preparing an iron-based hydrogenation catalyst: 32.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 5.30g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing for 5 hours in air, drying for 6 hours at 100 ℃, and roasting for 5 hours at 500 ℃ to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R3; iron oxide (Fe) in the catalyst CAT-R32O3) And the weight content of zinc oxide (ZnO) was 20.8 wt%, and the metal molar ratio of Fe to Zn was 4.5: 1.
Comparative example 4
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
W-Ni/AlPO4-5(4) is modified AlPO4-5 molecular sieves
Preparing a catalyst carrier: 68.5g of pseudoboehmite (calculated as the alumina content of 78.1 wt% in consideration of loss on ignition) was mixed with 9g W-Ni/AlPO45(4) mechanically mixing, extruding and forming to obtain the catalyst carrier, wherein the mass ratio of the molecular sieve to the alumina is 8.8: 50.
Preparing an iron-based hydrogenation catalyst: 15.2g of iron nitrate nonahydrate (Fe (NO)3)3·9H2O) and 7.5g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 6h, drying at 110 ℃ for 6h, and roasting at 520 ℃ for 5h to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R4; in the catalyst CAT-R4Iron oxide (Fe)2O3) And zinc oxide (ZnO) in an amount of 14.5 wt%, with a metal molar ratio of Fe to Zn of 1.4: 1.
Comparative example 5
The present comparative example provides a hydrogenation catalyst, the method of preparation comprising the steps of:
with W-Ni/AlPO as in example 54-5(5) is modified AlPO4-5 molecular sieves.
Dissolving 34.2g of ferric chloride and 5.92g of zinc chloride in 250mL of deionized water to obtain an aqueous solution of the ferric chloride and the zinc chloride; slowly adding 62g of ammonia water solution into the aqueous solution of ferric chloride and zinc chloride while stirring; stirring and reacting for 5 hours in a water bath at the temperature of 80 ℃, then cooling to 60 ℃, standing and aging for 24 hours to obtain a precipitate; filtering the precipitate while the precipitate is hot, washing the precipitate with deionized water until the pH value is about 9, drying the precipitate in a drying oven at 110 ℃, heating the dried precipitate at the speed of 5 ℃/min, and roasting the dried precipitate for 2 hours at 500 ℃ in the air atmosphere to obtain iron-zinc oxide powder; wherein the metal molar ratio of Fe to Zn in the obtained oxide is 4.9: 1.
Calcining 10.5g of oxide powder of iron-based hydrogenation catalyst at 550 ℃ for 4 hours to obtain 14.9g of pseudo-boehmite, 6.24g W-Ni/AlPO45, (5) mixing and stirring uniformly, adding into a tablet machine, pressing and forming, and marking as catalyst CAT-R5; iron oxide (Fe) in the catalyst CAT-R52O3) And the weight content of zinc oxide (ZnO) was 33.1 wt%.
Comparative example 6
An iron-based hydrogenation catalyst, the preparation method comprises the following steps:
Ni/AlPO4-5(1) preparation: 1.07g of nickel nitrate hexahydrate is dissolved in 42.5g of distilled water to prepare a solution, and the solution is slowly dripped into 50g of AlPO by an isovolumetric immersion method4Standing in-5 molecular sieve with air for 3 hr, drying at 110 deg.C for 12 hr, and calcining at 540 deg.C for 3 hr. Elemental analysis showed Ni/AlPO4The mass percentage of NiO in the (5) and (1) is 0.55 wt%.
W-Ni/AlPO4-5(1) preparation: dissolving 0.98g ammonium metatungstate in 21g distilled water to obtain solution, and slowly adding dropwise 25g Ni/based on the same volume of the solutionAlPO4And (5) standing in air for 3h, drying at 110 ℃ for 12h, and roasting at 500 ℃ for 3 h. Elemental analysis showed W-Ni/AlPO4WO in (5) to (1)3The mass percentage of (B) is 3.3 wt%.
Preparing a catalyst carrier: 63.9g of pseudo-boehmite (considering loss on ignition, calculated by the content of alumina of 78.1 wt%) and 15g of USY are mechanically mixed and extruded to form a catalyst carrier, and the weight ratio of the molecular sieve to the alumina is 15: 50.
Preparing an iron-based hydrogenation catalyst: 18.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R6; iron oxide (Fe) in the catalyst CAT-R62O3) And zinc oxide (ZnO) in an amount of 15.1 wt%, with a metal molar ratio of Fe to Zn of 2.1: 1.
Comparative example 7
63.9g of pseudo-boehmite (in consideration of loss on ignition, in terms of alumina content of 78.1 wt%) was bar-extruded to be shaped into a catalyst carrier.
Preparing an iron-based hydrogenation catalyst: 22.5g of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) and 6.3g of zinc nitrate hexahydrate (Zn (NO)3)2·6H2O) dissolving in a proper amount of deionized water to prepare a co-impregnation solution, slowly pouring the co-impregnation solution into 30g of the prepared catalyst carrier, continuously stirring to realize equal-volume impregnation, standing in air for 4 hours, drying at 110 ℃ for 9 hours, and roasting at 480 ℃ for 4 hours to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R7; iron oxide (Fe) in the catalyst CAT-R72O3) And the weight content of zinc oxide (ZnO) was 17.0 wt%, and the metal molar ratio of Fe to Zn was 2.7: 1.
Comparative example 8
Preparing an iron-based hydrogenation catalyst: 22.5g of ferric nitrate nonahydrate(Fe(NO3)3·9H2O), 6.3g zinc nitrate hexahydrate (Zn (NO)3)2·6H2O), 0.34g of nickel nitrate hexahydrate and 0.42g of ammonium metatungstate are dissolved in a proper amount of deionized water to prepare a co-impregnation solution, the co-impregnation solution is slowly poured into 30g of the prepared catalyst carrier, constant stirring is carried out, equal-volume impregnation is realized, after air standing is carried out for 4 hours, drying is carried out for 9 hours at 110 ℃, and then roasting is carried out for 4 hours at 480 ℃, so as to obtain the hydrogenation catalyst, which is marked as catalyst CAT-R8; iron oxide (Fe) in the catalyst CAT-R82O3) And zinc oxide (ZnO) in an amount of 17.0 wt%, WO3The weight content is 0.91 wt%, the weight content of NiO is 0.23 wt%, and the metal molar ratio of Fe to Zn is 2.71: 1.
Test example
The iron-based hydrogenation catalysts of examples 1-5 and comparative examples 1-8 were evaluated for hydrogenation performance. The hydrotreatment of the example was carried out by using a 50mL high-temperature high-pressure hydrogenation micro-reactor, and the evaluation raw material was sand medium-pressure and normal-pressure residue oil, and the density (20 ℃ C.) was 0.987g/cm33.89 wt% of sulfur and 0.36 wt% of total nitrogen. Before application, the catalyst is sulfurized to make it have hydrogenation activity. The sulfurized oil is a mixture containing 5 wt% of CS2The sulfuration temperature of the n-decane solution is 380 ℃, the time is 8h, the pressure is 4MPa, and the liquid hourly space velocity is 1.5h-1The volume ratio of hydrogen to oil was 300. The hydrogenation reaction raw material is pumped by a plunger pump, and the oil sample after reaction is cooled by a high separator and then is collected and analyzed by a low separator. The temperature of the hydrotreatment is 400 ℃, the pressure is 10MPa, and the liquid hourly space velocity is 1h-1The volume ratio of hydrogen to oil was 800. The evaluation results of the catalysts after hydrotreating of the example catalysts and the comparative catalysts are shown in tables 1 and 2.
Table 1 evaluation results of catalysts in examples
| CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-5 | |
| Desulfurization rate% | 50.8 | 50.6 | 50.7 | 50.7 | 53.3 |
| Denitrification rate% | 32.1 | 32.5 | 32.6 | 32.9 | 32.7 |
Table 2 evaluation results of comparative example catalysts
| CAT-R1 | CAT-R2 | CAT-R3 | CAT-R4 | CAT-R5 | CAT-R6 | CAT-R7 | CAT-R8 | |
| Desulfurization rate% | 47.1 | 48.0 | 44.0 | 41.7 | 41.9 | 43.2 | 36.6 | 46.5 |
| Denitrification rate% | 29.9 | 30.7 | 29.5 | 28.1 | 29.1 | 28.9 | 24.9 | 29.3 |
Test example 2
The iron-based hydrogenation catalysts of examples 1-5 and comparative examples 1-5 were evaluated for hydrogenation performance. The hydrotreatment of this example employed 10mL of high temperature, high pressure hydrogenation catalystThe evaluation is carried out by a reverse device, the raw material is Daqing catalytic cracking diesel oil, and the specific gravity of the catalytic cracking diesel oil
0.8796, sulfur content 890ppm, total nitrogen content 920ppm, total aromatics content 55.2 v%. The raw materials are pumped by a plunger pump, and the reacted oil sample is cooled by a high separator and then collected and analyzed by a low separator. The temperature of the hydrotreatment is 390 ℃, the pressure is 6MPa, and the liquid hourly space velocity is 1.0h-1The volume ratio of hydrogen to oil was 800. The results of evaluation of the catalyst after hydrotreatment are shown in tables 3 and 4.
Table 3 evaluation results of catalysts in examples
| CAT-1 | CAT-2 | CAT-3 | CAT-4 | CAT-5 | |
| Desulfurization rate% | 79.2 | 77.1 | 78.4 | 83.6 | 82.5 |
| Denitrification rate% | 58.2 | 57.9 | 59.0 | 58.3 | 57.6 |
| Dearomatization ratio of% | 43.0 | 42.3 | 42.9 | 43.3 | 42.1 |
Table 4 evaluation results of comparative example catalysts
| CAT-R1 | CAT-R2 | CAT-R3 | CAT-R4 | CAT-R5 | CAT-R6 | CAT-R7 | CAT-R8 | |
| Desulfurization rate% | 63.2 | 66.9 | 70.9 | 72.1 | 64.3 | 61.7 | 58.3 | 73.1 |
| Denitrification rate% | 50.9 | 52.4 | 49.9 | 53.3 | 54.7 | 50.2 | 43.9 | 55.0 |
| Dearomatization ratio of% | 39.9 | 38.3 | 38.9 | 36.3 | 39.0 | 34.3 | 33.7 | 40.1 |
As can be seen from the evaluation results of tables 1 to 4, the iron-based hydrogenation catalysts of the examples have high catalytic hydrogenation activity as compared with the iron-based hydrogenation catalyst of the comparative example. The iron-based hydrogenation catalyst of the embodiment of the invention breaks through the limitation of active component metals of the traditional hydrogenation catalyst for decades, and has important theoretical research value and industrial application value.
Claims (30)
1. An iron-based hydrogenation catalyst, wherein the catalyst comprises a support comprising alumina and AlPO modified with nickel and tungsten and a supported oxide of an active metal4-5 molecular sieves, the active metals comprising a primary active metal and a co-active metal, the primary active metal being Fe and the co-active metal being Zn; the AlPO modified with nickel and tungsten4-5 mass ratio of molecular sieve to alumina (5-21): 50, the molar ratio of Fe element to Zn element is (2-6): 1, taking the total weight of the catalyst as 100 percent, and taking the total weight of the oxide of the active metal as 15 to 32 percent; AlPO modified with nickel and tungsten4The preparation method of the molecular sieve comprises the following steps:
(a) is to use the water soluble salt solution of nickel to soak AlPO in the same volume4-5 molecular sieve, then drying and roasting to obtain Ni/AlPO4-5 molecular sieve, the roasting temperature is 450-45, calculated by 100% of the weight of the molecular sieve, the nickel element is 0.5-3% calculated by NiO;
(b) isovolumetrically impregnating the Ni/AlPO obtained in step (a) with a water-soluble salt solution of metallic tungsten4-5 molecular sieve, then drying and roasting to obtain W-Ni/AlPO4-5 molecular sieves of W-Ni/AlPO45 total weight of molecular sieves, calculated as 100%, WO33 to 7 percent.
2. The iron-based hydrogenation catalyst of claim 1, wherein the water-soluble salt of metallic tungsten is ammonium metatungstate.
3. The iron-based hydrogenation catalyst of claim 1, wherein the AlPO modified with nickel and tungsten4-5 mass ratio of molecular sieve to alumina is 18-20: 50; the molar ratio of Fe element to Zn element is (4-6): 1.
4. the iron-based hydrogenation catalyst of claim 1, wherein the calcination temperature in step (b) is 450-550 ℃.
5. The iron-based hydrogenation catalyst of claim 1, wherein the drying temperature of step (b) is 90-120 ℃.
6. The iron-based hydrogenation catalyst of claim 1, wherein the drying temperature of step (a) is 90-120 ℃.
7. The iron-based hydrogenation catalyst of claim 1, wherein the water-soluble salt of nickel of step (a) is nickel nitrate hexahydrate.
8. The iron-based hydrogenation catalyst of claim 1, wherein the nickel element in step (a) is 1.0-2.0% calculated as NiO.
9. The iron-based hydrogenation catalyst of claim 1, wherein WO is applied in step (b)33 to 5 percent.
10. The iron-based hydrogenation catalyst of any one of claims 1-9, wherein the preparation method of the iron-based hydrogenation catalyst comprises the following steps:
preparing co-impregnation solution of main active metal and auxiliary active metal, then loading the main active metal and the auxiliary active metal on a carrier by an isometric impregnation method, and roasting to obtain the iron-based hydrogenation catalyst;
or uniformly mixing the main active metal oxide powder and the auxiliary active metal oxide powder with a carrier to obtain the iron-based hydrogenation catalyst.
11. The iron-based hydrogenation catalyst of claim 10, wherein the calcination temperature is 450-550 ℃.
12. The iron-based hydrogenation catalyst of claim 10, wherein the calcination time is 2-12 hours.
13. The iron-based hydrogenation catalyst of claim 10, wherein the step of loading the primary active metal and the secondary active metal on the support comprises: preparing co-impregnation solution of main active metal and auxiliary active metal, then loading the main active metal and the auxiliary active metal on a carrier by an equal-volume impregnation method, drying the carrier loaded with the main active metal and the auxiliary active metal, and then roasting to obtain the iron-based hydrogenation catalyst.
14. The iron-based hydrogenation catalyst of claim 13, wherein the step of formulating a co-impregnation solution of the primary active metal and the secondary active metal comprises: and dissolving the water-soluble salt of the main active metal and the water-soluble salt of the auxiliary active metal in water to obtain the co-impregnation solution.
15. The iron-based hydrogenation catalyst of claim 13, wherein the support loaded with the primary active metal and the co-active metal is dried at a drying temperature of 90-120 ℃; the drying time is 4-12 h.
16. The iron-based hydrogenation catalyst of claim 13, wherein, after impregnating the support with the primary active metal and the co-active metal, the method further comprises the step of allowing the support impregnated with the primary active metal and the co-active metal to stand, and then drying and calcining the support; standing for 4-24 h.
17. The iron-based hydrogenation catalyst of claim 10, wherein the step of uniformly mixing the primary and secondary active metal oxide powders with the support comprises: the water soluble salt of the main active metal and the water soluble salt of the auxiliary active metal are uniformly mixed in water to obtain a mixed solution, the mixed solution reacts under an alkaline condition to obtain a hydroxide precipitation mixture of the main active metal and the auxiliary active metal, then the hydroxide precipitation mixture is roasted at the temperature of 450-550 ℃ to obtain an oxide mixture of the main active metal and the auxiliary active metal, and then the oxide mixture and the carrier are uniformly mixed.
18. The iron-based hydrogenation catalyst of claim 14 or 17, wherein the water-soluble salt of the primary active metal is a mixture of one or more of ferric nitrate nonahydrate, ferric chloride, and ferric sulfate.
19. The iron-based hydrogenation catalyst of claim 14 or 17, wherein the water-soluble salt of a co-active metal is a mixture of one or more of zinc nitrate hexahydrate, zinc chloride, and zinc sulfate.
20. The iron-based hydrogenation catalyst of claim 17, wherein the pH of the mixed solution under alkaline conditions is 10 or greater.
21. The iron-based hydrogenation catalyst of claim 17, wherein the calcination time is 2-12 hours.
22. The iron-based hydrogenation catalyst of claim 17, wherein the step of uniformly mixing the primary and secondary active metal oxide powders with the support comprises: dissolving water soluble salt of main active metal and water soluble salt of auxiliary active metal in water, adding alkali to react to obtain precipitate, filtering after complete reaction, roasting the precipitate to obtain iron-zinc oxide powder, and mixing the iron-zinc oxide powder and the carrier uniformly.
23. The iron-based hydrogenation catalyst of claim 22, wherein the base is ammonia or urea.
24. The iron-based hydrogenation catalyst of claim 22, wherein the reaction temperature of the reaction is 75-95 ℃.
25. The iron-based hydrogenation catalyst of claim 22, wherein the reaction time of the reaction is 4-8 hours.
26. The iron-based hydrogenation catalyst of claim 22, wherein the iron-based hydrogenation catalyst is further aged to precipitate after the reaction is completed.
27. The iron-based hydrogenation catalyst of claim 26, wherein the aging is resting for 20-30 hours at 50-80 ℃.
28. The iron-based hydrogenation catalyst of claim 10, further comprising impregnating alumina and AlPO modified with nickel and tungsten before impregnating the support with equal volumes of co-impregnation solutions of the formulated primary and secondary active metals4-5 a step of mixing the molecular sieves.
29. The iron-based hydrogenation catalyst of claim 28, wherein alumina and AlPO modified with iron and molybdenum are mixed45 after the molecular sieve is mixed, the step of extruding the mixture into strips is also included.
30. A method of making the iron-based hydrogenation catalyst of any one of claims 1-29, the method comprising the pairing of AlPO with nickel and tungsten4-5 a step of modifying the molecular sieve, said step comprising:
(a) introduction of nickel element into AlPO4In-5 molecular sieve to obtain Ni/AlPO4-5 molecular sieves;
(b) isovolumetrically impregnating the Ni/AlPO obtained in step (a) with a water-soluble salt solution of metallic tungsten4-5 molecular sieve, then drying and roasting to obtain W-Ni/AlPO4-5 molecular sieves.
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