CN115301234B - 表面活性剂诱导合金制备催化剂及用于油脂一步加氢异构 - Google Patents
表面活性剂诱导合金制备催化剂及用于油脂一步加氢异构 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 49
- 239000000956 alloy Substances 0.000 title claims abstract description 49
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 30
- 239000004519 grease Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000002808 molecular sieve Substances 0.000 claims abstract description 50
- 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 50
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001868 water Inorganic materials 0.000 claims abstract description 24
- 229910002847 PtSn Inorganic materials 0.000 claims abstract description 21
- 239000000084 colloidal system Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 238000005303 weighing Methods 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 239000003225 biodiesel Substances 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 10
- 241001465754 Metazoa Species 0.000 claims description 9
- 239000010775 animal oil Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 9
- 239000008158 vegetable oil Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 7
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 44
- 238000010438 heat treatment Methods 0.000 description 25
- 239000011135 tin Substances 0.000 description 21
- 238000000227 grinding Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 229910019029 PtCl4 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/08—Heat treatment
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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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
表面活性剂诱导合金制备催化剂及用于油脂一步加氢异构,属于催化材料领域。将商业的SAPO‑11分子筛在马弗炉中煅烧;称取Pt与Sn的可溶性盐溶液置于容器中,加入表面活性剂,充分混合后将混合样品转移至水热釜中水热;将备用的SAPO‑11分子筛,完全浸于水热反应后的胶体中超声,水浴条件下持续搅拌,再将样品干燥、焙烧、研磨封存,获得高分散、小颗粒的PtSn合金/SAPO‑11多功能催化剂,可在油脂一步法加氢催化异构化反应中获得近100%脱氧率、98%以上的C15‑C18烃选择性和60%以上的C15‑C18异构烷烃选择性。操作简单,合金颗粒分散均匀、尺寸小,高度分散,活性、稳定性、目标产物的选择性高。
Description
技术领域
本发明属于催化材料领域,具体涉及一种表面活性剂诱导合金制备催化剂及用于油脂一步加氢异构。
背景技术
随着我国经济和工业的迅速发展,化石资源的需求和消耗逐渐增加,能源供应的不稳定性和地缘政治等的影响使得原油的价格持续增长,导致柴油的价格也不段攀升。石化柴油是国际上目前需求量最大的液体燃料,作为一个国家的战略性物资,是十分重要的能源资源。为缓解能源短缺、保障能源安全,研发可再生的高品质烃基生物柴油显得尤为重要。
动植物油脂经加氢脱氧和临氢异构化反应可得到高热值、低冷滤点的烃基生物柴油。目前,世界各国已相继开展了催化加氢法制高品质烃基生物柴油,美国UOP公司、芬兰Neste公司等均已实现动植物油脂加氢异构制高品质生物柴油的工业化应用。然而他们制备的高品质烃基生物柴油的工艺主要采用两步法:第一步,将动植物油脂在加氢反应器中进行加氢反应,让油脂中的碳碳双键或叁键饱和、去除氧,然后转化成长链正构烷烃和副产物丙烷、二氧化碳、水、一氧化碳等(专利US5705722、WO2006075057、US009567264B2等);其中油脂加氢饱和、脱氧过程所采用的催化剂均为预硫化NiMo/Al2O3或CoMo/Al2O3等。第二步,主要是将分离净化后的长链正构烷烃在釜式反应器或固定床反应器中进行临氢裂化/异构化反应,然后得到低凝点的异构烷烃(专利WO2009156452、US2010000908、US008142527B2等),此过程目前使用的催化剂多为非贵金属/分子筛多功能催化剂,如Co、Mo、Ni基/SAPO-11等。传统的两步法虽然能够获得高品质生物柴油,但在实际运用当中存在着氢气消耗高、工艺复杂繁琐、投资成本较高等问题。为了解决上述问题,研究人员提出一步法加氢催化异构制备高品质烃基生物柴油技术,该技术多在贵金属/分子筛多功能催化剂的催化作用下催化动植物油脂发生加氢脱氧裂化异构化反应获得高热值、低冷滤点的生物柴油。其中,一步法加氢催化异构化工艺的关键在于高活性、高选择性催化剂的研发。
当前,一步法工艺所用的催化剂多以SAPO-11分子筛为载体,再进行贵金属如铂、钯等的负载,从而得到贵金属/分子筛型多功能催化剂。SAPO-11分子筛是一种人工合成的磷酸硅铝择型分子筛,属于典型的AEL拓扑结构,具有一维十元环孔道结构,已被广泛应用于烷烃的异构化反应。然而研究发现脂肪酸甘油脂加氢反应主要以加氢脱氧、加氢脱羰、加氢脱羧的方式进行,其中加氢脱氧方式生成的水会导致贵金属/分子筛催化剂中毒失活。以Pt为活性金属负载在SAPO-11分子筛上的催化剂在进行动植物油脂加氢异构化的过程中主要是以加氢脱羧和加氢脱羰的方式进行,能有效避免水的生成,同时Pt较强的加氢和脱氢能力可有效完成直链烷烃的异构化反应,实现动植物油脂一步加氢制备异构烷烃。专利CN201210048253对此进行详细的概述。但仅将Pt负载在SAPO-11分子筛上制备而成的催化剂存在着催化活性不佳、异构烷烃选择性低的缺点。而现有的研究多采取通过添加第二种金属助剂,如:铁、钴、镍、铜、锡等进行金属位点调控;或改变载体的合成方法从而调节酸量,进而提高催化剂的活性和目标烷烃选择性。然而过量金属助剂的添加容易造成颗粒的团聚,而分子筛的合成过程调控又十分复杂、对整个设备要求较高,不利于大规模的进行工业化生产。
发明内容
本发明的目的是针对现有技术存在的上述问题,提供一种表面活性剂诱导合金制备催化剂的方法。通过表面活性剂水热诱导生成合金,随后负载在商业SAPO-11分子筛上制备而成的高热值、高十六烷值、低冷凝点的合金/分子筛多功能催化剂。具体工艺操作简单,合金颗粒分散均匀、尺寸小,活性、稳定性、目标产物的选择性高等特点。
本发明的另一目的在于提供所述催化剂用于油脂一步加氢异构。该催化剂在催化油脂制备高品质烃基生物柴油时具有较高的脱氧活性和异构烷烃选择性。
一种表面活性剂诱导合金制备催化剂的方法,包括如下步骤:
1)在表面活性剂的存在下,使可溶性Pt盐的水溶液与可溶性Sn盐的水溶液进行水热诱导合金生成反应,得到PtSn合金胶体;
2)对SAPO-11分子筛载体进行干燥和煅烧,加入到步骤1)所得到的PtSn合金胶体中进行催化剂成型,得到PtSn合金/分子筛多功能型催化剂。
在步骤1)中,所述得到PtSn合金胶体的具体步骤可为:称取Pt溶液与Sn溶液置于容器中;加入表面活性剂,搅拌2~4h,充分混合;将混合的胶体转移至聚四氟乙烯水热釜中,在烘箱中于150~180℃的条件下,水热反应4~8h;
所述表面活性剂可选自聚乙烯吡咯烷酮、聚乙二醇、十二烷基磺酸钠等中的至少一种;所述可溶性Pt盐的水溶液为氯铂酸、硝酸四氨合铂、氯亚铂酸钾等中的至少一种,可溶性Pt盐的水溶液的浓度可为5%~10%,Pt的负载量可为1wt%~3wt%;所述可溶性Sn盐的水溶液为氯化锡、乙酸亚锡等中的至少一种,可溶性Sn盐的水溶液的浓度可为1%~5%,Sn的负载量可为1wt%~5wt%;所述溶液中Pt与Sn的原子比可为1︰1,1︰2,1︰3,1︰4,2︰3,3︰1中的一种;所述表面活性剂的添加量与Pt的质量比可为1︰5或1︰10。
在步骤2)中,所述SAPO-11分子筛载体为商业分子筛,煅烧的条件是于400~700℃的马弗炉中煅烧2~4h;
所述催化剂成型,将煅烧后的SAPO-11分子筛,完全浸于水热反应后的PtSn合金胶体中,超声30~60min后,在60~80℃的恒温水浴锅中,转速250~400r/min的水浴条件下持续搅拌6~8h,然后置于80℃的烘箱中干燥2h,转移到105~110℃的烘箱中过夜干燥,再转移至马弗炉中进行煅烧,在升温速率为3℃/min的条件下升温至350℃,恒温2h,之后在升温速率为1℃/min的条件下升温至500℃,恒温2~4h,自然降温,研磨过筛进行封存;
优选的,在80℃、300r/min的水浴条件下持续搅拌4~6h。
所述制备的催化剂结构通式为PtxSny/SAPO-11-SFT,其中SFT为所采用的表面活性剂名称的缩写;所述制备的催化剂主要由PtSn合金与SAPO-11载体两部分构成,合金由表面活性剂在水热条件下诱导合成;所制备的催化剂的PtSn合金纳米颗粒小于2nm。
所制备的催化剂可在油脂一步加氢催化异构化制烃基生物柴油中的应用。
所述加氢催化异构化的反应温度为200~400℃,氢压为1~10MPa。
所述油脂包括动植物油脂。
本发明采用表面活性剂诱导生成合金,随后负载在商业SAPO-11分子筛上制备而成的合金/分子筛多功能催化剂,用于动植物油脂一步法加氢催化异构化制备高热值、高十六烷值、低冷滤点的生物柴油的合金催化剂。该催化剂在催化油脂制备高品质烃基生物柴油时具有较高的脱氧活性和异构烷烃选择性。
与现有技术相比,本发明具有的以下优点:
1、本发明制备方法操作简单,所制备催化剂的合金纳米颗粒小于2nm,合金颗粒分散均匀、尺寸小,高度分散,活性、稳定性、目标产物的选择性高等特点。
2、本发明所采用的表面活性剂来源范围广,价格低廉,可有效降低一步法工艺中贵金属催化剂的生产成本。
3、本发明制备的催化剂具有100%的脱氧率、98%以上的C15-C18烃选择性和60%以上的异构烷烃选择性。
附图说明
图1为本发明对比例2、实施例1和实施例8合成的催化剂的X射线衍射图(XRD);
图2为本发明对比例2、实施例1和实施例8合成的催化剂的高分辨透射电子显微镜图(TEM)。其中,(a)A1(Pt/SAPO-11-PEG)、(b)A9(Pt1Sn1/SAPO-11-SDS)、(c)A3(Pt2Sn3/SAPO-11-PVP)。
具体实施方式
以下实施例将结合附图对本发明作进一步的说明,本发明内容并不局限于此。
对比例1
取商业SAPO-11分子筛5g在500℃下煅烧4h,以5%浓度的H2PtCl6溶液进行等体积浸渍,Pt的负载量为3wt%,取计量好的H2PtCl6溶液逐滴滴加到分子筛载体上,在80℃、300r/min的条件下水浴搅拌2h,后将样品于80℃下干燥2h,再转移至105℃烘箱中过夜干燥,之后再于500℃马弗炉中煅烧4h,最后将所得样品研磨至40-60目封存,制得活性金属含量为2wt%的Pt/SAPO-11催化剂,编号为A0。
对比例2
取商业SAPO-11分子筛5g在600℃下煅烧2h备用,取适量的10%浓度的Pt(NH3)4(NO3)2溶液置于烧杯中,Pt的负载量为3wt%,加入的表面活性剂聚乙二醇与Pt的质量比例为1:5,搅拌4h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于180℃的条件下,水热4h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声30min后,在80℃、300r/min的水浴条件下持续搅拌6h,后将样品于80℃下干燥2h,再转移至110℃烘箱中过夜干燥,之后再于500℃马弗炉中煅烧4h,自然降温;最后将所得样品充分研磨至40~60目封存,制得活性金属含量为2wt%的Pt/SAPO-11-PEG催化剂,编号为A1。
实施例1
取商业SAPO-11分子筛10g在550℃下煅烧3.5h备用。取适量的10%浓度的Pt(NH3)4(NO3)2溶液与5%浓度的SnCl45H2O溶液置于烧杯中,Pt负载量为3wt%,PtSn合金的原子比为1:1,加入的表面活性剂聚乙烯吡咯烷酮与Pt的比例为1:5,搅拌4h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于180℃的条件下,水热5h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声30min后,在80℃、300r/min的水浴条件下持续搅拌4h,后将样品于80℃下干燥2h,再转移至110℃烘箱中过夜干燥。后从室温30℃,以3℃/min的升温速率升至350℃,恒温2h,然后以1℃/min升温速率升至500℃,恒温4h,自然降温。最后将所得样品充分研磨至40-60目封存,制得合金Pt1Sn1/SAPO-11-PVP催化剂,编号为A2。
实施例2
取商业SAPO-11分子筛10g,在550℃下煅烧2.5h备用。称取适量5%浓度的Pt(NH3)4(NO3)2溶液与4%浓度的SnCl45H2O溶液和1%浓度的C4H6O4Sn溶液置于烧杯中,Pt负载量为3wt%,PtSn合金的原子比为2:3,加入的表面活性剂聚乙烯吡咯烷酮与Pt的比例为1:5,搅拌4h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于180℃的条件下,水热6h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声40min后,在60℃、400r/min的水浴条件下持续搅拌8h,后将样品于80℃烘箱中干燥2h,再转移至105℃烘箱中过夜干燥。后从室温30℃,以3℃/min的升温速率上升至350℃,恒温2h,再以1℃/min速率升温至500℃,恒温2.5h,自然降温。最后将所得样品充分研磨至40~60目进行封存,制得合金Pt2Sn3/SAPO-11-PVP催化剂,编号为A3。
实施例3
取商业SAPO-11分子筛5g,在500℃下煅烧4h备用。称取适量5%浓度的Pt(NH3)4(NO3)2溶液和5%浓度的H2PtCl6溶液与2%浓度的SnCl45H2O溶液置于烧杯中,Pt负载量为2wt%,PtSn合金的原子比为3:1,加入的表面活性剂聚乙烯吡咯烷酮与Pt的比例为1:10,搅拌3h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于170℃的条件下,水热7h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声50min后,在60℃、400r/min的水浴条件下持续搅拌7h,后将样品于80℃烘箱中干燥2h,再转移至108℃烘箱中过夜干燥。后从室温30℃,以3℃/min的升温速率上升至350℃,恒温2h,再以1℃/min速率升温至500℃,恒温3h,自然降温。最后将所得样品充分研磨至40~60目进行封存,制得合金Pt3Sn1/SAPO-11-PVP催化剂,编号为A4。
实施例4
取商业SAPO-11分子筛5g,在550℃下煅烧3.5h备用。称取适量9%浓度的Pt(NH3)4(NO3)2溶液与4%浓度的SnCl45H2O溶液置于烧杯中,Pt负载量为2.5wt%,PtSn合金的原子比为1:2,加入的表面活性剂聚乙烯吡咯烷酮与Pt的比例为1:10,搅拌2h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于180℃的条件下,水热8h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声60min后,在60℃、300r/min的水浴条件下持续搅拌6.5h,后将样品于80℃烘箱中干燥2h,再转移至108℃烘箱中过夜干燥。后从室温30℃,以3℃/min的升温速率上升至350℃,恒温2h,再以1℃/min速率升温至500℃,恒温3.5h,自然降温。最后将所得样品充分研磨至40~60目进行封存,制得合金Pt1Sn2/SAPO-11-PVP催化剂,编号为A5。
实施例5
取商业SAPO-11分子筛6g,在700℃下煅烧2.5h备用。称取适量7%浓度的K2PtCl4溶液和5%浓度的H2PtCl6溶液与5%浓度的C4H6O4Sn溶液置于烧杯中,Pt负载量为1wt%,PtSn合金的原子比为1:3,加入的表面活性剂聚乙烯吡咯烷酮和聚乙二醇与Pt的比例为1:5,搅拌2h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于160℃的条件下,水热4h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声30min后,在70℃、250r/min的水浴条件下持续搅拌7h,后将样品于80℃烘箱中干燥2h,再转移至107℃烘箱中过夜干燥。后从室温30℃,以3℃/min的升温速率上升至350℃,恒温2h,再以1℃/min速率升温至500℃,恒温4h,自然降温。最后将所得样品充分研磨至40~60目进行封存,制得合金Pt1Sn3/SAPO-11-PEG-PVP催化剂,编号为A6。
实施例6
取商业SAPO-11分子筛8g,在600℃下煅烧3h备用。称取适量9%浓度的Pt(NH3)4(NO3)2溶液和8%浓度的K2PtCl4溶液与1%浓度的C4H6O4Sn溶液及2%浓度的SnCl45H2O溶液置于烧杯中,Pt负载量为1.5wt%,PtSn合金的原子比为1:4,加入的表面活性剂聚乙烯吡咯烷酮、聚乙二醇、十二烷基磺酸钠与Pt的比例为1:10,搅拌2h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于150℃的条件下,水热5h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声40min后,在80℃、350r/min的水浴条件下持续搅拌5.5h,后将样品于80℃烘箱中干燥2h,再转移至105℃烘箱中过夜干燥。后从室温30℃,以3℃/min的升温速率上升至350℃,恒温2h,再以1℃/min速率升温至500℃,恒温3.5h,自然降温。最后将所得样品充分研磨至40~60目进行封存,制得合金Pt1Sn4/SAPO-11-PEG-PVP-SDS催化剂,编号为A7。
实施例7
取商业SAPO-11分子筛3g,在550℃下煅烧3.5h备用。称取适量5%浓度的Pt(NH3)4(NO3)2溶液、7%浓度的K2PtCl4溶液和5%浓度的H2PtCl6溶液与3%浓度的SnCl45H2O溶液置于烧杯中,Pt负载量为2wt%,PtSn合金的原子比为1:1,加入的表面活性剂聚乙二醇与Pt的比例为1:10,搅拌2h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于180℃的条件下,水热5h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声35min后,在80℃、350r/min的水浴条件下持续搅拌6.5h,后将样品于80℃烘箱中干燥2h,再转移至110℃烘箱中过夜干燥。后从室温30℃,以3℃/min的升温速率上升至350℃,恒温2h,再以1℃/min速率升温至500℃,恒温2.5h,自然降温。最后将所得样品充分研磨至40~60目进行封存,制得合金Pt1Sn1/SAPO-11-PEG催化剂,编号为A8。
实施例8
取商业SAPO-11分子筛3g,在550℃下煅烧2.5h备用。称取适量10%浓度的Pt(NH3)4(NO3)2溶液与4%浓度的SnCl45H2O溶液置于烧杯中,Pt负载量为3wt%,PtSn合金的原子比为1:1,加入的表面活性剂十二烷基磺酸钠与Pt的比例为1:5,搅拌2h,使其充分混合,将混合的样品转移至水热釜中,在烘箱中于180℃的条件下,水热6h。将备用的商业SAPO-11分子筛,完全浸于水热反应后的胶体中,超声45min后,在80℃、300r/min的水浴条件下持续搅拌6h,后将样品于80℃烘箱中干燥2h,再转移至110℃烘箱中过夜干燥。后从室温30℃,以3℃/min的升温速率上升至350℃,恒温2h,再以1℃/min速率升温至500℃,恒温2.5h,自然降温。最后将所得样品充分研磨至40~60目进行封存,制得合金Pt1Sn1/SAPO-11-SDS催化剂,编号为A9。
测试与表征
1、材料表征分析
如图1和2所示,对比对比例2、实施例1和实施例8合成的催化剂的XRD图与TEM图,可以看到实施例1与8制备的合金纳米颗粒呈现颗粒分布均匀、高度分散,且颗粒小于2nm。
2、加氢反应评价结果
以脂肪酸甲酯为模型,对比对比例1、对比例2、实施例1~8合成的催化剂,进行一步加氢催化异构化反应评价,加氢异构催化反应条件为:温度320℃、氢压4MPa、转速400r/min、反应时间6h、原料/催化剂比10:1。结果见表1。
表1.不同催化剂对应的一步加氢反应评价结果
本发明通过采用表面活性剂水热法诱导生成合金,再负载于商业SAPO-11分子筛上制备而成高分散、小颗粒的PtSn合金/SAPO-11多功能催化剂,在油脂一步法加氢催化异构化反应中获得近100%脱氧率、98%以上的C15-C18烃选择性和60%以上的C15-C18异构烷烃选择性。
Claims (6)
1.一种表面活性剂诱导合金制备催化剂的方法,其特征在于包括如下步骤:
1)在表面活性剂的存在下,使可溶性Pt盐的水溶液与可溶性Sn盐的水溶液进行水热诱导合金生成反应,得到PtSn合金胶体;具体步骤为:称取Pt溶液与Sn溶液置于容器中;加入表面活性剂,搅拌2~4 h,充分混合;将混合的胶体转移至聚四氟乙烯水热釜中,在烘箱中于150~180℃的条件下,水热反应4~8 h;所述可溶性Pt盐的水溶液的浓度为5%~10%,Pt的负载量为1 wt%~3 wt%;所述可溶性Sn盐的水溶液的浓度为1%~5%,Sn的负载量为1 wt%~5 wt%;
2)对SAPO-11分子筛载体进行干燥和煅烧,加入到步骤1)所得到的PtSn合金胶体中进行催化剂成型,得到PtSn合金/分子筛型催化剂;所述SAPO-11分子筛载体为商业分子筛,煅烧的条件是于500~700℃的马弗炉中煅烧2~4h;所述催化剂成型,将煅烧后的SAPO-11分子筛,完全浸于水热反应后的PtSn合金胶体中,超声30~60min后,在60~80℃的恒温水浴锅中,转速250~400 r/min的水浴条件下持续搅拌6~8h,然后置于80℃的烘箱中干燥2h,转移到105~110℃的烘箱中过夜干燥,再转移至马弗炉中进行煅烧,在升温速率为3℃/min的条件下升温至350℃,恒温2h,之后在升温速率为1℃/min的条件下升温至500℃,恒温2~4h,自然降温,研磨过筛进行封存。
2.如权利要求1所述一种表面活性剂诱导合金制备催化剂的方法,其特征在于在步骤1)中,所述表面活性剂选自聚乙烯吡咯烷酮、聚乙二醇、十二烷基磺酸钠中的至少一种;所述可溶性Pt盐的水溶液为氯铂酸、硝酸四氨合铂、氯亚铂酸钾中的至少一种,所述可溶性Sn盐的水溶液为氯化锡、乙酸亚锡中的至少一种。
3.如权利要求1所述一种表面活性剂诱导合金制备催化剂的方法,其特征在于在80℃、300 r/min的水浴条件下持续搅拌4~6 h。
4.如权利要求1~3中任一项所述的制备方法制备的PtSn合金/分子筛型催化剂;其特征在于其结构通式为PtxSny/SAPO-11-SFT,其中SFT为所采用的表面活性剂名称的缩写;所述催化剂的合金纳米颗粒小于2 nm。
5.如权利要求4所述PtSn合金/分子筛型催化剂在油脂一步加氢催化异构化制烃基生物柴油中的应用。
6.如权利要求5所述应用,其特征在于所述加氢催化异构化的反应温度为200~400℃,氢压为1~10 MPa;所述油脂包括动植物油脂。
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