CN105435773B - 用于异丁烷脱氢制异丁烯的催化剂及其制备方法 - Google Patents
用于异丁烷脱氢制异丁烯的催化剂及其制备方法 Download PDFInfo
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 53
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000001282 iso-butane Substances 0.000 title claims abstract description 27
- 235000013847 iso-butane Nutrition 0.000 title claims abstract description 27
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 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 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 15
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 8
- 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 claims abstract description 7
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 239000003426 co-catalyst Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 238000005360 mashing Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000037396 body weight Effects 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000003643 water by type Substances 0.000 description 11
- 238000010792 warming Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- -1 C 4 olefin Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical class [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
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Abstract
本发明属于化工催化剂技术领域,具体为一种用于异丁烷脱氢制备异丁烯的催化剂及其制备方法。本发明在氧化铝载体上添加质量分数0.5%~10.0%的氧化硅,然后负载钒含量为3.0%~11.0%的氧化钒,并且添加0.1%~5.0%的碱金属或碱土金属作为助催化剂。本发明将氧化硅引入氧化铝载体上,改善了氧化铝载体的孔结构和表面性质,调变了氧化钒活性中心的分布;碱金属和碱土金属的加入,协同改善了催化剂的表面酸碱性和电子性质,提高了异丁烷脱氢制异丁烯钒基催化剂的转化率和选择性,延长了催化剂的寿命。
Description
技术领域
本发明属于化工催化剂技术领域,具体涉及一种用于异丁烷脱氢制备异丁烯的催化剂及其制备方法。
背景技术
异丁烯是一种重要的化工原料,国内外市场对异丁烯的需求量巨大,且呈逐年递增的态势。传统异丁烯生产主要是从石油催化裂化装置和石脑油催化裂化装置副产碳四馏分中提取,这些方法中异丁烯都是作为副产品生产,产量受制于主反应的规模和碳四烯烃产率。我国液化气资源丰富,其中异丁烷作为一种主要成分,其大部分随着液化气作为民用燃料被消耗掉,得不到合理的利用。因而采用异丁烷作为原料,通过脱氢反应制备异丁烯具有先天的优势和社会意义。
从二十世纪六十年代起,国外公司相继开始开发异丁烷脱氢制异丁烯的催化剂以及催化脱氢工艺,具有代表性并且已经实现工业化的包括Snamprogetti公司的FBD-4工艺、Lummus/UCI开发的Catofin工艺、UOP的Oleflex工艺、Phillips的STAR工艺和Linde AG的Linde工艺等。他们所使用的催化剂主要分为两类:一种是将氧化铬负载在氧化铝载体上,还有一种是将贵金属Pt负载在氧化铝或者其他载体上。应用于催化脱氢时,反应温度在500-650℃之间,反应压力在0.1-6.0MPa之间,异丁烷转化率在40-60%之间,异丁烯的选择性在91-95%之间。虽然目前这些工艺已经实现工业化,可是贵金属的高成本、金属铬的高毒性以及二类催化剂所共有的较易失活的特点仍促使着人们寻求更合适的催化剂。
金属钒与金属铬在元素周期表中相邻,在多价态和氧化性上具有相似性,但其毒性更低,对环境污染性更小,工业上钒催化剂已被用于二氧化硫氧化制硫酸、醇氧化制醛等反应;同时也有很多学者和机构进行研究将钒用于低碳烷烃脱氢,试图用其替代铂催化剂和铬催化剂。但是目前钒基催化剂在转化率、选择性和稳定性上依旧存在可提高的空间,而提高载体的比表面和高温热稳定性对提高钒催化剂的催化性能有重要的作用。
专利US5273949中公开了一种提高氧化铝作为载体的高温热稳定性的方法,该方法采用氧化硅作为载体稳定剂,通过制备氧化铝载体过程中添加1% ~ 20%含量的氧化硅,提高了催化剂的等电点pH, 降低了催化剂烯烃异构化能力,提高了氧化硅在高温时的稳定性。以此方法制备的氧化铝可以用作废气处理催化剂载体。但这种方法制备的载体,硅在氧化铝宏观颗粒的表面,分布也不够均匀,因此用于制备催化异丁烷脱氢的钒催化剂不够理想。
发明内容
本发明的目的在于提供一种转化率高、选择性好、使用寿命长的用于异丁烷脱氢制备异丁烯的催化剂及其制备方法。
本发明采用拟薄水铝石为铝源,加入去离子水后打浆,加入盐酸,使酸铝比为0.15-0.25,然后进一步打浆。采用这样的处理方案,拟薄水铝石形成胶粒约为70纳米的溶胶。然后在溶胶中加入硅源,使硅均匀修饰纳米氧化铝胶粒,在碱性条件下水热处理后得到高稳定性的含硅氧化铝载体。以此为载体制得的钒基催化剂具有异丁烷脱氢的高活性、高选择性和高稳定性。
本发明提供的异丁烷脱氢制异丁烯催化剂,以钒为活性金属组分,以氧化铝为载体,以氧化硅作为载体改良剂,以碱金属或碱土金属作为助催化剂;以氧化铝载体重量为基准,氧化硅的含量为0.5% ~ 10.0%,以催化剂重量为基准,钒含量为3% ~ 11%,碱金属或碱土金属含量为0.1% ~ 5%。
本发明所述的异丁烷脱氢制异丁烯催化剂的制备方法,具体步骤如下:
(1)在一定量的拟薄水铝石中加入10-20倍质量的去离子水,打浆20-40分钟;然后加入一定量的盐酸,使酸铝比为0.15-0.25,继续打浆20-40分钟;
(2)用含有氧化硅前驱体的溶液与上述拟薄水铝石浆液均匀混合,搅拌下调节pH为9-11,然后密闭,在95-100℃下保持1-48小时,然后过滤、干燥、焙烧,得到含有氧化硅的氧化铝载体;
(3)采用浸渍法,把氧化钒前驱体、碱金属或碱土金属分别或共同负载到步骤(2)得到的含氧化硅的氧化铝载体上,经过干燥、焙烧、压片、过筛,得到异丁烷脱氢制异丁烯的催化剂。
本发明中,步骤(2)和步骤(3)所述的干燥和焙烧是在空气、富氧或者氧气气氛下进行。所述干燥是在80 ~ 120℃下持续1 ~ 12小时;所述焙烧采用程序升温,首先从室温升到500-550℃,升温速率为1 ~ 5℃/min,接下来在500-550℃持续焙烧3 ~ 9小时。
本发明中,步骤(1)所采用的拟薄水铝石的BET比表面积不低于100m2/g,平均孔径不低于5nm。
本发明中,步骤(2)所采用的氧化硅前驱体溶液包括正硅酸乙酯(TEOS)溶液或者硅溶胶溶液,溶剂为浓度0% ~ 90%的乙醇水溶液。
本发明中,步骤(3)所采用的氧化钒前驱体为偏钒酸铵草酸水溶液,碱金属或碱土金属包括锂、钠、钾、铷、铯、镁、钙、锶、钡等一种或多种,采用相应的硝酸盐或者碳酸盐等可溶性盐作为前驱体。
本发明中,步骤(3)所采用的浸渍方法是等量浸渍法、过量浸渍法或喷浸法。
本发明方法制得的异丁烷脱氢催化剂,比表面积50 ~ 400m2/g,孔容0.3 ~1.5mL/g,平均孔径5 ~25nm。
本发明中,氧化硅被均匀引入氧化铝载体上,改善了氧化铝载体的孔结构和表面性质,调变了氧化钒活性中心的分布;碱金属和碱土金属的加入,协同改善了催化剂的表面酸碱性和电子性质,提高了异丁烷脱氢制异丁烯钒基催化剂的转化率和选择性,延长了催化剂的寿命。
具体实施方式
下面结合实施例,对本发明进行详细说明。
实施例1
(1)称取134.3g拟薄水铝石,加入1500mL去离子水打浆20分钟后,加入11.5mL浓盐酸(37wt%)继续打浆40分钟。
(2)加入1.8g TEOS搅拌均匀后,用氨水调节至pH = 9。将物料放置于水热釜中,置于95℃的烘箱中恒温6小时。然后过滤、烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温6小时。
(3)称取6.89g偏钒酸铵、14g草酸和0.26g硝酸钾,加入83mL去离子水,搅拌溶解后与步骤(1)中制得的载体充分混合,置于90℃的烘箱中恒温3小时烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温6小时。得到的催化剂压片后粉碎过筛,取20 ~ 30目的颗粒C1进行测试。
实施例2
(1)称取127.7g拟薄水铝石,加入1500mL去离子水打浆20分钟后,加入14.6mL浓盐酸(37wt%)继续打浆40分钟。
(2)加入3.47g TEOS搅拌均匀后,用氨水调节至pH = 10。将物料放置于水热釜中,置于96℃的烘箱中恒温12小时。然后过滤、烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温3小时。
(3)称取11.48g偏钒酸铵、22g草酸和2.95g硝酸钙,加入78mL去离子水,搅拌溶解后与步骤(1)中制得的载体充分混合,置于90℃的烘箱中恒温3小时烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温6小时。得到的催化剂压片后粉碎过筛,取20 ~ 30目的颗粒C2进行测试。
实施例3
(1)称取116.9g拟薄水铝石,加入1300mL去离子水打浆20分钟后,加入10.0mL浓盐酸(37wt%)继续打浆20分钟。
(2)加入11.76g硅溶胶溶液(34wt%)搅拌均匀后,用氨水调节至pH = 11。将物料放置于水热釜中,置于97℃的烘箱中恒温24小时。然后过滤、烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温9小时。
(3)称取16.07g偏钒酸铵、22g草酸和10.55g硝酸镁,加入72mL去离子水,搅拌溶解后与步骤(1)中制得的载体充分混合,置于90℃的烘箱中恒温3小时烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温9小时。得到的催化剂压片后粉碎过筛,取20 ~ 30目的颗粒C3进行测试。
实施例4
(1)称取102.7g拟薄水铝石,加入2000mL去离子水打浆20分钟后,加入11.7mL浓盐酸(37wt%)继续打浆40分钟。
(2)加入23.53g硅溶胶溶液(34wt%)搅拌均匀后,用氨水调节至pH = 9。将物料放置于水热釜中,置于98℃的烘箱中恒温1小时。然后过滤、烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温3小时。
(3)称取20.67g偏钒酸铵、40g草酸和11.09g硝酸钠,加入63mL去离子水,搅拌溶解后与步骤(1)中制得的载体充分混合,置于90℃的烘箱中恒温3小时烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温6小时。得到的催化剂压片后粉碎过筛,取20 ~ 30目的颗粒C4进行测试。
实施例5
(1)称取92.5g拟薄水铝石,加入1000mL去离子水打浆20分钟后,加入13.2mL浓盐酸(37wt%)继续打浆30分钟。
(2)加入34.68g TEOS搅拌均匀后,用氨水调节至pH = 10。将物料放置于水热釜中,置于100℃的烘箱中恒温48小时。然后过滤、烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温6小时。
(3)称取25.26g偏钒酸铵、50g草酸和9.52g硝酸钡,加入57mL去离子水,搅拌溶解后与步骤(1)中制得的载体充分混合,置于90℃的烘箱中恒温3小时烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温6小时。得到的催化剂压片后粉碎过筛,取20 ~ 30目的颗粒C5进行测试。
对比例6
称取1.102g偏钒酸铵、2.0g草酸和0.09g硝酸钾,加入3.7mL去离子水,搅拌溶解后与步骤6.0g拟薄水铝石充分混合,置于90℃的烘箱中恒温3小时烘干,置于马弗炉内,以2℃/min的速率升温到550℃,恒温6小时。得到的催化剂压片后粉’碎过筛,取20 ~ 30目的颗粒C6进行测试。
表1 催化剂成分
。
取实施例和对比例各催化剂C1, C2, C3, C4, C5, C6,在高压微型固定床反应器上进行活性测试,取2g催化剂装填在内径8mm的不锈钢反应管内,反应管尾接气相色谱进行产物分析。用氮气作为排空气,异丁烷与氮气体积比为1:15进行稀释,反应温度550℃,压力为常压,气时空速530h-1。不同时间下异丁烷的转化率和选择性列于表2。
表2催化剂活性评价
。
从表2催化剂评价结果中可以看出,本发明催化剂C1 ~ C5活性、选择性和稳定性都要好于比较例中的催化剂C6。
Claims (7)
1.一种用于异丁烷脱氢制备异丁烯的催化剂的制备方法,其特征在于具体步骤为:
(1)在拟薄水铝石中加入10-20倍质量的去离子水,打浆20-40分钟;然后加入盐酸,使酸铝比为0.15-0.25,继续打浆20-40分钟;
(2)用含有氧化硅前驱体的溶液与上述拟薄水铝石浆液均匀混合,搅拌下调节pH为9-11,然后密闭,在95-100℃下保持1-48小时,然后过滤、干燥、焙烧,得到含有氧化硅的氧化铝载体;
(3)采用浸渍法,把氧化钒前驱体、碱金属或碱土金属分别或共同负载到步骤(2)得到的含氧化硅的氧化铝载体上,经过干燥、焙烧、压片、过筛,即得到异丁烷脱氢制异丁烯的催化剂;
该催化剂,以钒为活性金属组分,以氧化铝为载体,以氧化硅作为载体改良剂,以碱金属或碱土金属作为助催化剂;以氧化铝载体重量为基准,氧化硅的含量为0.5% ~ 10.0%,以催化剂重量为基准,钒含量为3% ~ 11%,碱金属或碱土金属含量为0.1% ~ 5%;比表面积50~ 400m2/g,孔容0.3 ~ 1.5mL/g,平均孔径5 ~25nm。
2.根据权利要求1所述的用于异丁烷脱氢制备异丁烯的催化剂的制备方法,其特征在于步骤(2)和步骤(3)所述的干燥和焙烧是在空气、富氧或者氧气气氛下进行;所述干燥是在80 ~ 120℃下持续1 ~ 12小时;所述焙烧采用程序升温,首先从室温升到500-550℃,升温速率为1 ~ 5℃/min,接下来在500-550℃持续焙烧3 ~ 9小时。
3.根据权利要求2所述的用于异丁烷脱氢制备异丁烯的催化剂的制备方法,其特征在于步骤(1)所采用的拟薄水铝石的BET比表面积不低于100m2/g,平均孔径不低于5nm。
4.根据权利要求3所述的用于异丁烷脱氢制备异丁烯的催化剂的制备方法,其特征在于步骤(2)所采用的氧化硅前驱体溶液包括正硅酸乙酯溶液或者硅溶胶溶液,溶剂为浓度0% ~ 90%的乙醇水溶液。
5.根据权利要求3所述的用于异丁烷脱氢制备异丁烯的催化剂的制备方法,其特征在于步骤(3)所采用的氧化钒前驱体为偏钒酸铵草酸水溶液,碱金属或碱土金属包括锂、钠、钾、铷、铯、镁、钙、锶、钡中一种或多种,采用相应的硝酸盐或者碳酸盐可溶性盐作为前驱体。
6.根据权利要求3所述的用于异丁烷脱氢制备异丁烯的催化剂的制备方法,其特征在于步骤(3)所采用的浸渍方法是等量浸渍法、过量浸渍法或喷浸法。
7.一种由权利要求1-6之一所述制备方法得到的用于异丁烷脱氢制备异丁烯的催化剂。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5273949A (en) * | 1991-05-14 | 1993-12-28 | Rhone-Poulenc Chimie | Silica-stabilized alumina |
CN102614864A (zh) * | 2012-03-01 | 2012-08-01 | 河南科技大学 | 异丁烷脱氢催化剂及其制备方法 |
CN102850169A (zh) * | 2012-09-19 | 2013-01-02 | 复旦大学 | 一种异丁烷脱氢制异丁烯的方法 |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5273949A (en) * | 1991-05-14 | 1993-12-28 | Rhone-Poulenc Chimie | Silica-stabilized alumina |
CN102614864A (zh) * | 2012-03-01 | 2012-08-01 | 河南科技大学 | 异丁烷脱氢催化剂及其制备方法 |
CN102850169A (zh) * | 2012-09-19 | 2013-01-02 | 复旦大学 | 一种异丁烷脱氢制异丁烯的方法 |
Non-Patent Citations (3)
Title |
---|
V2O5/γ-Al2O3和V2O5/SiO2负载型催化剂对异丁烷的催化脱氢性能;马红超 等;《应用化学》;20041231;第21卷(第12期);第1221页摘要 * |
Vanadium and alumina modified with groups I and II elements for for CO2 and coke reaction under fluid catalytic cracking process;Thiago Crispim da Silva et al.;《Applied Catalysis B: Environmental》;20140929;第164卷;第225-233页 * |
异丁烷脱氢制异丁烯催化剂的研究;张波;《天津大学硕士学位论文》;20121211;摘要,正文第13、21-24、43-49页 * |
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