CN114522716A - 一种双金属负载型催化剂及其制备方法和在棕榈油加氢转化制备生物航空煤油中的应用 - Google Patents
一种双金属负载型催化剂及其制备方法和在棕榈油加氢转化制备生物航空煤油中的应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 54
- 239000003350 kerosene Substances 0.000 title claims abstract description 35
- 235000019482 Palm oil Nutrition 0.000 title claims abstract description 22
- 239000002540 palm oil Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003921 oil Substances 0.000 claims abstract description 5
- 235000019198 oils Nutrition 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011973 solid acid Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 239000002244 precipitate Substances 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 16
- 239000004519 grease Substances 0.000 abstract description 12
- 238000006317 isomerization reaction Methods 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 25
- 238000005984 hydrogenation reaction Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 239000002808 molecular sieve Substances 0.000 description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 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 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 238000007033 dehydrochlorination reaction Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910003962 NiZn Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 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 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- 229910003289 NiMn Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- WTQFIWBPGZZVFN-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] Chemical compound O.O.O.O.O.O.O.O.O.[N+](=O)([O-])[O-].[Cu+2].[N+](=O)([O-])[O-] WTQFIWBPGZZVFN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- -1 fatty acid esters Chemical class 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
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- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
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- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/123—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on nickel or derivates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Life Sciences & Earth Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明设计制备适用于油脂加氢转化制备生物航空煤油的非贵双金属负载型催化剂,将其应用在棕榈油加氢脱氧、裂化/异构化反应中生产C8~C16烃类范围的生物航空煤油。本发明以镍为主要金属,添加第二过渡金属,以碱液沉淀负载在酸性载体上制备而得的双金属负载型催化材料,金属高度分散在载体表面,大大提高了催化剂加氢脱氧性能,在棕榈油的加氢脱氧、裂化异构化反应中,油脂转化率高达100%,生物航空煤油收率可达60%,并减少碳损失,因而在油脂加氢转化生产生物航空煤油工艺上具有良好的应用前景。
Description
技术领域
本发明涉及一种加氢脱氧催化剂的制备,主要是用于油脂一步加氢脱氧裂化异构化生产生物航空煤油,属于能源化工技术领域。
背景技术
航空业作为21世纪的造碳大户之一,在化石能源危机及减碳目标的双重压力下,发展可持续航空燃料势在必行。传统航空煤油是石油经加氢裂化和催化裂化加工成的产品,主要组成成分是碳数范围为C8~C16的正构烷烃、带支链的异构烷烃、环烷烃及少量芳烃,而生物航空煤油是从生物质原料直接或间接转化而来。生物航空煤油在燃烧热值、能量密度、冷凝点、润滑性能满足石油基航空煤油的性能指标基础上,同时具有较低的硫氮含量,热稳定性较高,低温流动性较好,在整个生命周期中至少可以减少80%的碳排放,可持续和环境友好。
目前,制备生物航空煤油的技术路线有四种,分别是根据原料的特点而命名的醇类制备路线(ATJ)、合成气制备路线(GTJ)、糖类制备路线(STJ)以及油脂类制备路线(OTJ)。OTJ技术路线的整体投资成本相对于ATJ、STJ及GTJ路线低,工艺流程相对简单,产品质量较好,且收率高,是目前最具竞争力优势的制备生物航空煤油的技术路线。发明专利CN113004953A、EP3795657A1、KR20210158492A、US10793785B2中公布的生产生物航空燃料的方法均是采用油脂加氢脱氧技术。
油脂制备生物航空煤油的技术路线有两段加氢工艺和一步加氢工艺。两段加氢工艺中,反应条件不同,催化剂不同,第一段加氢完成不饱和双键的加氢及脂肪酸酯的脱氧,得到的长链烷烃在第二段加氢中裂化、异构化得到航空煤油碳数范围的烃类。一步加氢工艺,能在同个反应器、同种催化剂下,一步实现油脂的加氢脱氧、裂化异构化,这将大大简化生产流程,提高生产效率,同时降低能耗,减少生产成本。因此,构建高效且稳定的具有双键加氢、酯基脱氧、烷烃裂化/异构化性能的催化剂是油脂制生物航空煤油的关键。
发明专利(CN103920528A)公开了一种用于油脂一步加氢脱氧裂化异构化制航空煤油组分的催化剂及其制备方法。其采用贵金属Pt、Pd、Ru作为活性组分负载于复合载体Beta-Al2O3上,对于油脂的转化率能达到100%,航空煤油组分收率可达72.3%,尽管贵金属类催化剂表现了优异的加氢脱氧活性及产物选择性,但贵金属成本较高,且对反应环境中的杂质、水等敏感,易中毒失活,不利于在加氢脱氧生产生物航空煤油工业上的广泛应用。
发明专利(CN111250156A)公布的一种磷化镍负载在SAPO-11载体上的催化剂的制备方法在脂肪酸甲酯的加氢脱氧-异构化反应中具有较高的加氢活性及异构烷烃选择性,具有优良的耐硫、耐水性,但磷化物类催化剂制备过程相对不可控,在空气中易氧化,稳定性差。
单一金属组分的催化剂存在着不稳定金属组分易流失、易失活及结焦的问题,利用第二种金属组成双金属催化剂能够产生协同效应、几何结构效应、电子结构效应及稳定效应,表现出两种金属的组合性能,极大地提高催化活性,增强催化剂稳定性。文献Renewable Energy. 180(2021)1-13中,将Cu引入到Ni/Al2O3中,Ni金属的分散性和电子密度都得到了提高,在脂肪酸酯的加氢脱氧反应中,双金属Ni1Cu1/Al2O3催化剂表现出优于单金属Ni/Al2O3、贵金属Pd/C及硫化态NiMo/Al2O3催化剂的加氢脱氧活性。文献AppliedCatalysis B: Environmental. 224(2018)88-100. 将亲氧性Zn原子加入到Ni/Al2O3催化剂中,二者形成合金,提高了催化活性,由于几何和电子效应的影响,形成NiZn合金,电子由Ni转移到Zn,导致Ni位周围电子云密度减小,从而利于吸附C=O,且不利于C-C键的氢解,在NiZn/Al2O3在对月桂酸甲酯的加氢脱氧反应中,促进了HDO脱氧路线,DCO/DCO2脱羰脱羧路线受抑制。然而上述催化剂制备所用载体为氧化铝,不具备异构化裂化反应所需的B酸及孔道结构,不适用于成分复杂的棕榈油加氢转化制备生物航空煤油。
发明专利(CN105921168A)公布了一种加氢脱氧异构化催化剂NiFeCNTSAPO-11的制备方法及其在植物油加氢转化为生物航空煤油中的应用,生物航煤收率可达78~85%,但该催化剂制备过程相对复杂,其所用的镍盐和铁盐为有机酞菁盐,价格昂贵且不够绿色环保,不利于工业生产应用。
发明内容
在上述背景技术下,本发明的目的在于提供一种制备方法简单、催化性能稳定高效的用于棕榈油生产生物航空煤油的催化剂,
为实现上述目的,本发明的技术方案如下:
一种双金属负载型催化剂的制备方法包括以下步骤:
(1)将镍盐和第二种金属盐按照一定金属摩尔比均匀溶解于去离子水中,形成混合金属盐溶液;
(2)配制一定浓度的碱溶液;
(3)称取适量的固体酸载体,加入到步骤(1)所得的混合盐溶液中;
(5)将碱液匀速逐滴滴加至步骤(3)所得的混合液中;
(6)步骤(1)中所用的镍盐和第二种金属盐的量按摩尔比9:1~1:9进行混合。所述镍盐为乙酸镍、氯化镍、硝酸镍、硫酸镍中的任意一种,第二种金属盐为铜盐、铁盐、镁盐、锌盐、锰盐中的任意一种。所得混合金属盐溶液的总摩尔浓度为0.1~1 mol/L;
(7)步骤(2)中所述碱溶液所用的碱为碳酸钠、碳酸氢钠、氢氧化钠、氢氧化钾、尿素、氨水中的一种或两种,碱液浓度为0.05~5.0mol/L;
(8)步骤(3)中所述固体酸性载体为Beta(Si/Al=25~300)、ZSM-5(Si/Al=20~300)、USY(Si/Al=15~200)、SAPO-11(Si/Al=25~300)中的任意一种,与步骤(1)混合盐溶液充分搅拌均匀。
(9)将步骤(5)得到的混合液放于水浴锅中,水浴温度25~95℃,然后将碱液逐滴滴加进去,同时保证搅拌速度不低于300 rpm,调节pH不低于8,之后在密封状态下继续水浴4~12 h。
(10)将步骤(9)所得混合液室温陈化2~8 h后,抽滤洗涤至中性,烘箱干燥时间不低于6 h,温度不低于60℃;马弗炉焙烧时间不低于2 h(优选为3~5 h),温度不低于400℃(优选为450~600℃)。
(11)步骤(10)所得固体样品于管式炉中氢气进行还原,还原温度450~700℃,还原时间2~5 h,得到双金属负载型催化剂。
(12)步骤(11)所得的双金属负载型催化剂中,金属负载量为1~20 wt.%。
本发明所得双金属负载型催化剂可应用于棕榈油加氢脱氧制备生物航空煤油,其应用方法具体是以棕榈油(24、33、44、52、58度中的一种)为原料油,将固体催化剂粉体与棕榈油共同加入到反应釜中,用氮气吹扫反应器及管路中的空气,再用氢气置换残留氮气,然后向反应釜中充入普氢进行反应,所得产物经离心分离固体物质。所述反应过程的操作条件为:反应温度250~400℃(优选为300~380℃),氢气压力2~8 MPa(优选为4~8 MPa),搅拌速率300~800 rpm,催化剂用量为1~20 wt.%(优选为3 wt.%)。
本发明具有如下优点:
(1)本发明提供的双金属负载型催化剂的制备工艺绿色简单,成本低廉,制得的催化剂金属颗粒更小且均匀分散在载体表面,提高了金属位点与酸性位点协同作用,从而加氢脱氧、裂化、异构化性能优异,且抗积碳性能好。
(2)本发明制得的高活性双金属催化剂在棕榈油加氢转化制备生物航空煤油的应用中,能实现油脂的完全转化,生物航空煤油收率高,促进加氢脱氧路径向HDO转化,能减少碳损失,在工业生产中应用前景良好。
具体实施方式
为了进一步了解本发明,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
对比例
将0.01 mol六水合氯化镍,搅拌溶解于100 mL去离子水中,形成溶液A,然后将5.3g Beta分子筛粉末加入到A溶液中,以一定速度搅拌均匀形成悬浊液B。然后配制0.05mol/L的NaOH碱溶液C,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6 h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得单金属Ni/Beta催化剂。
取50 g棕榈油原料油和3.0 g制备的单金属Ni/Beta催化剂,装入高温高压反应釜中,用氮气吹扫反应器及管路中的空气,再用氢气置换残留氮气,然后向反应釜中充入普氢进行加氢反应,反应条件为:温度350℃,氢气压力5.0 MPa,搅拌速率500 rpm,反应4 h后产物经过过滤分离,液相产物进行GC-MS分析产物组成。
实施例1
将0.009 mol六水合氯化镍,0.001 mol六水合氯化铁,共同搅拌溶解于100 mL去离子水中,形成溶液A,然后将5.3 g Beta分子筛粉末加入到A溶液中,以一定速度搅拌均匀形成悬浊液B。然后配制0.05mol/L的NaOH碱溶液C,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6 h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得双金属NiFe/Beta催化剂。
取50 g棕榈油原料油和3.0 g制备的双金属NiFe/Beta催化剂,装入高温高压反应釜中,用氮气吹扫反应器及管路中的空气,再用氢气置换残留氮气,然后向反应釜中充入普氢进行加氢反应,反应条件为:温度350℃,氢气压力5.0 MPa,搅拌速率500 rpm,反应4 h后产物经过过滤分离,液相产物进行GC-MS分析产物组成。
实施例2
将0.008 mol六水合氯化镍,0.002mol六水合氯化铁,共同搅拌溶解于100 mL去离子水中,形成溶液A,然后将5.2 g Beta分子筛粉末加入到A溶液中,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6 h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得单金属NiFe/Beta催化剂。
取50 g棕榈油原料油和3.0 g制备的双金属NiFe/Beta催化剂,装入高温高压反应釜中,用氮气吹扫反应器及管路中的空气,再用氢气置换残留氮气,然后向反应釜中充入普氢进行加氢反应,反应条件为:温度350℃,氢气压力5.0 MPa,搅拌速率500 rpm,反应4 h后产物经过过滤分离,液相产物进行GC-MS分析产物组成。
实施例3
将0.007 mol六水合氯化镍,0.003 mol六水合氯化铁,共同搅拌溶解于100 mL去离子水中,形成溶液A,然后将5.2 g Beta分子筛粉末加入到A溶液中,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6 h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得单金属NiFe/Beta催化剂。
取50 g棕榈油原料油和3.0 g制备的双金属NiFe/Beta催化剂,装入高温高压反应釜中,用氮气吹扫反应器及管路中的空气,再用氢气置换残留氮气,然后向反应釜中充入普氢进行加氢反应,反应条件为:温度350℃,氢气压力5.0 MPa,搅拌速率500 rpm,反应4 h后产物经过过滤分离,液相产物进行GC-MS分析产物组成。
实施例4
将0.008 mol硝酸镍六水合物,0.002 mol硝酸铁九水合物,共同搅拌溶解于100mL去离子水中,形成溶液A,然后将5.2 g Beta分子筛粉末加入到A溶液中,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得双金属NiFe/Beta催化剂。
取50 g棕榈油原料油和3.0 g制备的双金属NiFe/Beta催化剂,装入高温高压反应釜中,用氮气吹扫反应器及管路中的空气,再用氢气置换残留氮气,然后向反应釜中充入普氢进行加氢反应,反应条件为:温度350℃,氢气压力5.0 MPa,搅拌速率500 rpm,反应4 h后产物经过过滤分离,液相产物进行GC-MS分析产物组成。
实施例5
将0.008 mol硝酸镍六水合物,0.002 mol硝酸铁九水合物,共同搅拌溶解于100mL去离子水中,形成溶液A,然后将5.2 g Beta分子筛粉末加入到A溶液中,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得双金属NiFe/Beta催化剂。
取50 g棕榈油原料油和3.0 g制备的双金属Ni/Beta催化剂,装入高温高压反应釜中,用氮气吹扫反应器及管路中的空气,再用氢气置换残留氮气,然后向反应釜中充入普氢进行加氢反应,反应条件为:温度370℃,氢气压力5.0 MPa,搅拌速率500 rpm,反应4 h后产物经过过滤分离,液相产物进行GC-MS分析产物组成。
实施例6
将0.008 mol硝酸镍六水合物,0.002 mol硝酸铜九水合物,共同搅拌溶解于100mL去离子水中,形成溶液A,然后将5.2 g Beta分子筛粉末加入到A溶液中,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得双金属NiCu/Beta催化剂。
催化剂对棕榈油加氢转化制备生物航空煤油的实验条件同实施例5,反应结果见表1。
实施例7
将0.008 mol硝酸镍六水合物,0.002 mol硝酸锌六水合物,共同搅拌溶解于100mL去离子水中,形成溶液A,然后将5.2 g Beta分子筛粉末加入到A溶液中,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得双金属NiZn/Beta催化剂。
催化剂对棕榈油加氢转化制备生物航空煤油的实验条件同实施例5,反应结果见表1。
实施例8
将0.008 mol硝酸镍六水合物,0.002 mol硝酸镁六水合物,共同搅拌溶解于100mL去离子水中,形成溶液A,然后将5.2 g Beta分子筛粉末加入到A溶液中,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得双金属NiMg/Beta催化剂。
催化剂对棕榈油加氢转化制备生物航空煤油的实验条件同实施例5,反应结果见表1。
实施例9
将0.008 mol硝酸镍六水合物,0.002 mol硝酸锰四水合物,共同搅拌溶解于100mL去离子水中,形成溶液A,然后将5.2 g Beta分子筛粉末加入到A溶液中,在800 rpm的搅拌速度、30℃水浴条件下将其逐滴滴加进悬浊液B中,调节pH至8.5,水浴6 h后,静置陈化6h,抽滤洗涤至中性,80℃干燥 8 h,将固体研磨成粉末后,于马弗炉中500℃焙烧4 h,管式炉中600℃还原3 h既得双金属NiMn/Beta催化剂。
催化剂对棕榈油加氢转化制备生物航空煤油的实验条件同实施例5,反应结果见表1。
由表1可见,与对比例1相比,本发明非贵双金属负载型催化剂相比于单金属镍基催化剂的加氢脱氧活性更优异,油脂转化率更高,且具有更高的生物航空煤油收率。n-C15+17/n-C16+18比值代表了加氢脱氧反应路径,对比例的数据结果表明,单金属Ni基催化剂对油脂的加氢脱氧路径主要是以脱除一个碳原子的DCO/CO2过程,而加入第二金属合成的双金属催化剂的脱氧路径向HDO过程转变,只是脱除氧原子,保留碳原子,从而减少了碳损失。
以上所述实例仅为本发明的较佳实施例,还可以实施其它类型实例,熟悉本领域的相应人员可以依据本发明做出相应改变,但这些改变皆应属于本发明的保护范围。
Claims (10)
1.一种双金属负载型催化剂的制备方法,其特征在于:包括以下步骤:
(1)将镍盐和第二种金属盐溶解于去离子水中,形成混合金属盐溶液;
(2)配制碱溶液;
(3)将固体酸载体加入到步骤(1)所得的混合盐溶液中;
(4)将步骤(2)的碱溶液匀速逐滴滴加至步骤(3)所得的混合液中,并进行水浴搅拌得到悬浊液;
(5)将步骤(4)中所得悬浊液陈化得到沉淀物,经过滤、洗涤、干燥,焙烧还原得到双金属负载型催化剂。
2.根据权利要求1所述的双金属负载型催化剂的制备方法,其特征在于:金属的负载量为1~30 wt.%。
3.根据权利要求1所述的双金属负载型催化剂的制备方法,其特征在于:步骤(1)中所用的镍盐和第二种金属盐的中金属摩尔比为9:1~1:9,所述镍盐为乙酸镍、氯化镍、硝酸镍、硫酸镍中的任意一种,第二种金属盐为铜盐、铁盐、镁盐、锌盐、锰盐中的任意一种,所得混合金属盐溶液的总摩尔浓度为0.1~1 mol/L。
4.根据权利要求1所述的双金属负载型催化剂的制备方法,其特征在于:步骤(2)中所述碱溶液所用的碱为碳酸钠、碳酸氢钠、氢氧化钠、氢氧化钾、尿素、氨水中的一种或两种,碱溶液浓度为0.05~5.0mol/L。
5.根据权利要求1所述的双金属负载型催化剂的制备方法,其特征在于:步骤(3)中所述固体酸性载体为Beta、ZSM-5、USY、SAPO-11中的任意一种。
6.根据权利要求1所述的双金属负载型催化剂的制备方法,其特征在于:步骤(4)具体为:步骤(3)所得的混合液在25~95℃的水浴温度下,将碱液逐滴滴加进去的同时保证搅拌速度不低于300 rpm,调节pH不低于8,之后在密封状态下继续水浴4~12 h。
7.根据权利要求1所述的双金属负载型催化剂的制备方法,其特征在于:步骤(5)中陈化是在室温陈化2~8 h,陈化后得到的沉淀物用去离子水抽滤洗涤至中性,烘箱干燥时间不低于6 h,温度不低于60℃;马弗炉焙烧时间不低于2 h,温度不低于400℃,还原温度450~700℃,还原时间2~5 h。
8.一种如权利要求1-7任一项所述的制备方法制得的双金属负载型催化剂。
9.一种如权利要求8所述的双金属负载型催化剂在棕榈油加氢转化生产生物航空煤油中的应用,其特征在于:以棕榈油为原料油,与双金属负载型催化剂共同放入高温高压反应釜中,用氮气排空反应釜及管路中的气体,之后充入普氢进行反应,所得反应产物进行固液分离,得到液体生物航空煤油。
10.根据权利要求9所述的双金属负载型催化剂在棕榈油加氢转化生产生物航空煤油中的应用,其特征在于:所述反应条件为:反应温度250~400℃,氢气压力2~8 MPa,搅拌速率300~800 rpm,双金属负载型催化剂用量1~20 wt.%。
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