CN109608301A - 一种丁烷催化脱氢制备丁烯和丁二烯的方法 - Google Patents
一种丁烷催化脱氢制备丁烯和丁二烯的方法 Download PDFInfo
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- CN109608301A CN109608301A CN201710964985.3A CN201710964985A CN109608301A CN 109608301 A CN109608301 A CN 109608301A CN 201710964985 A CN201710964985 A CN 201710964985A CN 109608301 A CN109608301 A CN 109608301A
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- dehydrogenation
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- butylene
- butanes
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 59
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 235000013844 butane Nutrition 0.000 title claims abstract description 40
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 33
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 29
- 239000001273 butane Substances 0.000 claims abstract description 25
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 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
- 238000004519 manufacturing process Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 3
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- 230000008859 change Effects 0.000 description 3
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- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
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- 101150116295 CAT2 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 229920005987 OPPANOL® Polymers 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- SHGUVJPXKKRMRP-UHFFFAOYSA-N [O].CCCC Chemical compound [O].CCCC SHGUVJPXKKRMRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J35/615—100-500 m2/g
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- B01J37/082—Decomposition and pyrolysis
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- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
本发明提供一种丁烷催化脱氢制备丁烯和丁二烯的方法,使用包含锆和镓的双活性组分复合催化剂,丁烷进行高效脱氢,产物中丁二烯的选择性达到17%,总丁烯的选择性达到81.5%,而且催化剂在高温下表现出良好的稳定性和再生性。
Description
技术领域
本发明涉及一种制备丁烯和丁二烯的方法,特别涉及一种丁烷催化脱氢制备丁烯和丁二烯的方法。
背景技术
丁烯是石油化工基础原料,在石油化工烯烃原料中地位仅次于乙烯和丙烯,是合成橡胶和高分子材料的重要单体。一般说来,丁烯主要有几种异构体,例如正丁烯(1-丁烯),异丁烯,顺式二丁烯和反式二丁烯四种。正丁烯主要用于制造甲基乙基酮、仲丁醇、环氧丁烷及丁烯聚合物和共聚物。异丁烯主要用于制造丁基橡胶、聚异丁烯橡胶及各种塑料。一般说来,1-丁烯和2-丁烯无需分离,可一起进行化学加工生产许多重要基本有机化工产品,如水合为仲丁醇进而生产甲基乙基酮,氧化脱氢制丁二烯,催化氧化制顺丁烯二酸酐以及醋酸。此外,丁烯还可以作为原料制造丁二烯。丁二烯是石化工业的基础原料,在石油化工烯烃原料中地位仅次于乙烯和丙烯,是合成橡胶和高分子材料的重要单体。工业上丁烯的生产主要由碳四馏分分离获得。不同来源碳四馏分中丁烯质量有所不同。随着我国石油工业飞速发展,石油价格居高不下,石油基产品生成成本过高,丁烯产能已经远远落后实际需求,丁烯供求短缺的局面愈发严重,在极大程度上制约了国民经济的发展。
实际上,自上世纪开始,科学家就在努力开发新的制备丁烯的工艺,例如利用正丁烷为原料,通过脱氢的方式制备相应的丁烯,并且已经实现产业化。近年来,随着页岩气的不断勘探,全世界可开采的页岩气总量巨大。相关数据表明:全球可开采的页岩气总量高达207立方米,其中我国的储量高居世界第一,总量达32万亿立方米。页岩气的主要成分为甲烷、乙烷、丙烷和丁烷,这些低碳烷烃可通过氧化偶联的方式进一步合成其他化学中间体,因此为现代化工业提供了丰富而廉价的原料。因此以丁烷为原料制备丁烯的工艺受到更大的关注。目前较为流行的有两种工艺路线:直接脱氢和氧化脱氢。氧化脱氢虽然在一定程度上能减缓积碳生成,但是引入的氧化剂往往容易生成一氧化碳和二氧化碳,造成丁烯的选择性很低。而直接脱氢可有效避免其他含氧产物的生成,烯烃选择性可高达95%以上。虽然直接脱氢往往需要较高的温度,这样就可能导致丁烷过度脱氢甚至断链生成小分子的烃类,但是通过催化剂调控往往可实现C-H键和C-C选择性活。此外生成的积炭可通过催化剂再生实现。因此丁烷直接脱氢制备丁烯受到了广泛的青睐,并且该工艺已经实现工业化生成。
目前常用的丁烷脱氢催化剂有以下几种:(1)Pt基催化剂,贵金属催化剂在脱氢反应起到了至关重要的作用,但是成本较高。实际应用的有UOP公司和Philips石油公司,他们选用Pt作为催化剂活性组分,通过加入助剂、载体提高催化剂的稳定性。其中较为著名的助剂就是Sn,目前已经商业化的催化剂为Pt-Sn-Al2O3;(2)V基催化剂,这种催化剂一般是用氧化钒负载在氧化铝或者氧化硅上;(3)Cr基催化剂。Cr基催化剂是另外一种重要的非金属催化剂,目前Catofin已经将其商业化。虽然目前关于直接脱氢催化剂的报道屡见不鲜,但是丁烷脱氢仍然面临着诸多问题和挑战。例如,在热力学上,直接脱氢是个强吸热反应,需要在高温下进行。高温容易造成催化剂烧结而失活,因此要求催化剂具有高稳定性。另一方面,高温容易造成丁烷过度脱氢形成积炭,因此要实现选择性脱氢对催化剂的设计也提出了更高的要求。就目前工业催化剂而言,Pt催化剂容易积炭,虽然高温再生可烧除积炭,但是高温易造成Pt烧结而失活。虽然有报道说添加Sn能有效阻止Pt烧结,但是再生过程需要氯化,此过程对设备有腐蚀作用。Cr基催化剂也存在类似的问题,高温条件下Cr会迁移到载体氧化铝中造成活性组分丧失。另一方面Cr的使用Cr的使用也会造成环境污染。
综上所述,新型催化剂的开发是实现丁烷脱氢制备烯烃的关键步骤。理想的催化剂应具备优异的C-H活化性能,而且还能迅速转移中间产物以避免过度脱氢甚至断链;此外,催化剂应具备优异的高温抗烧结能力,这样在循环再生中能保持活性;而且还应该着重开发以非贵金属为基础的、环境友好的催化剂,以体现更大的工业价值。
发明内容
针对现有技术的上述问题,本发明的目的是提供一种丁烷催化脱氢制备丁烯和丁二烯的方法,实现丁烷的高效转化。
为了解决上述问题,本发明的技术方案如下:
一种丁烷催化脱氢制备丁烯和丁二烯的方法,在脱氢催化剂的存在下,将丁烷进行脱氢反应,并从得到的脱氢产物中分离丁烯和丁二烯;所述脱氢催化剂包含锆和镓中的一种或两种作为活性组分。
进一步地,所述脱氢催化剂中的活性组分占催化剂总质量的1-10%。
优选的,所述脱氢催化剂中的活性组分占催化剂总质量的3-5%。
优选的,所述脱氢催化剂中的活性组分为锆和镓,且锆和镓的质量比例为0.1-10。
优选的,所述脱氢催化剂中的活性组分中锆和镓的质量比例为0.2-5。
脱氢催化剂包含活性组分锆和镓,该脱氢催化剂为一种双活性组分复合催化剂。该复合催化剂以非贵金属锆和镓为基础,通过锆镓协同作用实现丁烷高效脱氢。通过调控复合催化剂的界面,实现C-H键和C-C的选择活化,从而提高丁烯的选择性。
氧化锆和氧化镓不但具备优异的热稳定性,而且其在氢气处理下会产生大量的氧空位,可有效促进C-H键活化。
上述活性组分以金属或金属氧化物形式存在,可以单独作脱氢催化剂,也可以负载在载体上,所述的载体并没有特别的限制,优选使用硅铝复合载体,例如,ZSM系列分子筛、MCM系列分子筛、β-沸石等。负载型催化剂中所述脱氢催化剂中的活性组分占催化剂总质量的1-10%,优选3-5%,特别优选4.5%。
上述脱氢催化剂可以按照现有的各种方法制得,例如根据本发明的一种具体实施方式,所述脱氢催化剂按如下方法制备:
1)称取一定量的锆和镓的可溶性盐并配制成混合溶液;
2)将上述混合溶液等体积浸渍在硅铝复合载体上;
3)浸渍后老化、干燥,高温煅烧,即得催化剂固体粉末;
4)将上述催化剂固体粉末经过H2/N2混合气体高温活化处理。
根据本发明的一种具体实施方式,丁烷催化脱氢制备丁烯和丁二烯的反应条件为:反应温度为500-750℃,反应压力为0-0.3Mpa,气体时体积空速为20-300h-1。所述丁烷与氢气共同进料,其中氢气与丁烷的摩尔比为0.1-10。
在催化脱氢反应过程中还可以使用惰性气体稀释氢气和丁烷的浓度,以减缓反应过程中的温度上升。所述惰性气体的用量将反应温度控制在500-750℃以内为准,所述惰性气体可以为氮气、氦气和氩气中的一种或多种。
在本发明中所述脱氢产物中含有C3以下组分和C4组分。C4组分主要含有丁烯(包括1-丁烯、2-丁烯和异丁烯),丁二烯以及未反应的丁烷。在本发明中可以采用本领域技术人员公知的方法从脱氢产物中分离出正丁烯和丁二烯。
本发明的优点如下:
1)采用非贵金属锆和镓为催化剂的活性组分,环境友好,成本低,具有更大的工业价值和应用前景。
2)通过锆镓协同作用实现丁烷高效脱氢,产物中丁二烯的选择性达到17%左右,总丁烯的选择性达到81.5%。
3)催化剂在高温下表现出良好的稳定性和再生性。
附图说明
图1是本发明实施例提供的不同活性组分含量的催化剂的X射线衍射图;
图2是本发明实施例提供的不同活性组分含量的催化剂催化丁烷脱氢反应中丁烷的转化率和选择性图;
图3是本发明实施例提供的不同活性组分含量的催化剂催化丁烷脱氢的产物分布图;
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
称取一定量硝酸锆,并配制成溶液,然后等体积浸渍于硅铝复合载体上。浸渍后老化1小时然后置于100℃烘箱中过夜干燥,所得催化剂经过750℃高温焙烧2小时,得催化剂cat 1。
本实施例所得到的催化剂中锆质量分数为4.47%,该催化剂的比表面积、孔容和孔径如表1所示,X射线衍射图如图1所示。
实施例2
按金属锆和金属镓的质量比为3.5:1,称取一定量的锆和镓的前驱体硝酸锆和硝酸镓并配制成混合溶液,然后等体积浸渍于硅铝复合载体上。浸渍后老化1小时然后置于100℃烘箱中过夜干燥,所得催化剂经过750℃高温焙烧2小时,得催化剂cat 2。
本实施例所得到的催化剂中锆的质量分数为3.53%,镓的质量分数为0.81%。该催化剂的比表面积、孔容和孔径如表1所示,X射线衍射图如图1所示。
实施例3
按金属锆和金属镓的质量比为2:2.5,称取一定量的锆和镓的前驱体硝酸锆和硝酸镓并配制成混合溶液,然后等体积浸渍于硅铝复合载体上。浸渍后老化1小时然后置于100℃烘箱中过夜干燥,所得催化剂经过750℃高温焙烧2小时,得催化剂cat 3。
本实施例所得到的催化剂中锆的质量分数为1.89%,镓的质量分数为2.23%。该催化剂的比表面积、孔容和孔径如表1所示,X射线衍射图如图1所示。
实施例4
按金属锆和金属镓的质量比为1:3.5,称取一定量的锆和镓的前驱体硝酸锆和硝酸镓并配制成混合溶液,然后等体积浸渍于硅铝复合载体上。浸渍后老化1小时然后置于100℃烘箱中过夜干燥,所得催化剂经过750℃高温焙烧2小时,得催化剂cat 4。
本实施例所得到的催化剂中锆的质量分数为0.97%,镓的质量分数为3.25%。该催化剂的比表面积、孔容和孔径如表1所示,X射线衍射图如图1所示。
实施例5
按金属锆和金属镓的质量比为0.5:4,称取一定量的锆和镓的前驱体硝酸锆和硝酸镓并配制成混合溶液,然后等体积浸渍于硅铝复合载体上。浸渍后老化1小时然后置于100℃烘箱中过夜干燥,所得催化剂经过750℃高温焙烧2小时,得催化剂cat 5。
本实施例所得到的催化剂中锆的质量分数为0.51%,镓的质量分数为3.34%。该催化剂的比表面积、孔容和孔径如表1所示,X射线衍射图如图1所示。
实施例6
称取一定量硝酸镓并配制成溶液,然后等体积浸渍于硅铝复合载体上。浸渍后老化1小时然后置于100℃烘箱中过夜干燥,所得催化剂经过750℃高温焙烧2小时,得催化剂cat 6。
本实施例所得到的催化剂中镓的质量分数为4.34%。该催化剂的比表面积、孔容和孔径如表1所示,X射线衍射图如图1所示。
表1不同催化剂的化学物理性质
实施例7
将上述实施例1至实施例6制备的催化剂cat 1~cat 6在制备好以后,经过压片过筛,选择60-80目的催化剂0.4g与石英砂按照1:3质量比混合均匀后放入石英反应器中。
催化剂在反应前需要经过H2/N2(10%)处理30分钟到600摄氏度。然后将丁烷,氢气和氮气按照1:1:8的体积比引入反应管中,总流量为100ml/min。反应在常压下进行,温度为600℃,气体时体积空速为20-300h-1。
将产物进行气相分析所得结果如图2和3所示。如图2所示丁烷的转化率达到90%以上、选择性最高可达60%;如图3所示,产物中丁二烯的选择性最高达到17%左右,总丁烯的选择性最高达到81.5%。
上述说明已经充分揭露了本发明的具体实施方式。需要指出的是,熟悉该领域的技术人员对本发明的具体实施方式所做的任何改动均不脱离本发明的权利要求书的范围。相应地,本发明的权利要求的范围也并不仅仅局限于前述具体实施方式。
Claims (8)
1.一种丁烷催化脱氢制备丁烯和丁二烯的方法,其特征在于:在脱氢催化剂的存在下,将丁烷进行脱氢反应,并从得到的脱氢产物中分离丁烯和丁二烯;所述脱氢催化剂包含锆和镓中的一种或两种作为活性组分。
2.根据权利要求1所述丁烷催化脱氢制备丁烯和丁二烯的方法,其特征在于:所述脱氢催化剂中的活性组分占催化剂总质量的1-10%。
3.根据权利要求2所述丁烷催化脱氢制备丁烯和丁二烯的方法,其特征在于:所述脱氢催化剂中的活性组分占催化剂总质量的3-5%。
4.根据权利要求1所述丁烷催化脱氢制备丁烯和丁二烯的方法,其特征在于:所述脱氢催化剂中的活性组分为锆和镓,且锆和镓的质量比例为0.1-10。
5.根据权利要求4所述丁烷催化脱氢制备丁烯和丁二烯的方法,其特征在于:所述脱氢催化剂中的活性组分中锆和镓的质量比例为0.2-5。
6.根据权利要求1-5任一项所述丁烷催化脱氢制备丁烯和丁二烯的方法,其特征在于,所述脱氢催化剂按如下方法制备:
1)称取一定量的锆和镓的可溶性盐并配制成混合溶液;
2)将上述混合溶液等体积浸渍在硅铝复合载体上;
3)浸渍后老化、干燥,高温煅烧,即得催化剂固体粉末;
4)将上述催化剂固体粉末经过H2/N2混合气体高温活化处理。
7.根据权利要求1所述丁烷催化脱氢制备丁烯和丁二烯的方法,其特征在于:所述丁烷与氢气共同进料,其中氢气与丁烷的摩尔比为0.1-10。
8.根据权利要求1所述丁烷催化脱氢制备丁烯和丁二烯的方法,其特征在于:反应温度为500-750℃,反应压力为0-0.3Mpa,气体时体积空速为20-300h-1。
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