CN112844448A - 一种催化合成气与甲苯直接转化制乙苯的催化剂及其应用 - Google Patents
一种催化合成气与甲苯直接转化制乙苯的催化剂及其应用 Download PDFInfo
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- CN112844448A CN112844448A CN201911194576.5A CN201911194576A CN112844448A CN 112844448 A CN112844448 A CN 112844448A CN 201911194576 A CN201911194576 A CN 201911194576A CN 112844448 A CN112844448 A CN 112844448A
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- Prior art keywords
- catalyst
- component
- synthesis gas
- mno
- ethylbenzene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000007036 catalytic synthesis reaction Methods 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims description 19
- 150000004706 metal oxides Chemical class 0.000 claims description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 239000002808 molecular sieve Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
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- 229910016978 MnOx Inorganic materials 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
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- 239000002131 composite material Substances 0.000 claims description 5
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- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 230000018109 developmental process Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000001914 filtration 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
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 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 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UTARHJMVJBSOKZ-UHFFFAOYSA-N [O-2].[Al+3].[Zn+2].[Cu+2] Chemical compound [O-2].[Al+3].[Zn+2].[Cu+2] UTARHJMVJBSOKZ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052792 caesium Inorganic materials 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
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- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
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- 239000012716 precipitator Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000007320 rich medium Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011734 sodium Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- WDNRWJRRUZRRNB-UHFFFAOYSA-K tricesium;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cs+].[Cs+].[Cs+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WDNRWJRRUZRRNB-UHFFFAOYSA-K 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- B01J37/082—Decomposition and pyrolysis
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- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- 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
- B01J23/24—Chromium, molybdenum or tungsten
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- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供一种催化合成气与甲苯直接转化制乙苯的催化剂及其应用,属于合成气与甲苯直接制备乙苯,具体涉及一种催化剂及合成气与甲苯直接转化制乙苯的方法,其以合成气和甲苯为反应原料,在固定床、移动床或者流化床上进行转化反应,所述催化剂为复合催化剂I+II,组分I与组分II以机械混合方式复合,组分I的活性成份为金属氧化物,组分II为分子筛。反应过程具有很高的产品收率和选择性,芳烃选择性可以达到40‑80%,乙苯在芳烃中比例可以达到50‑90%,具有很好的应用前景。
Description
技术领域
本发明属于合成气与甲苯制备乙苯,具体涉及一种催化剂及合成气与甲苯转化制乙苯的方法。
背景技术
乙苯是重要的有机化合物,主要用途是作为生产苯乙烯的中间体,所制成的苯乙烯一般被用来制备常用的塑料制品——聚苯乙烯。目前,工业生产乙苯主要通过酸催化苯与乙烯反应。而乙烯是合成纤维、合成橡胶、合成塑料(聚乙烯及聚氯乙烯)、合成乙醇(酒精)的基本化工原料,其主要来源于石油。而由于我国富媒贫油的能源结构,我国石油大量依赖于进口。随着我国经济的快速发展,原油需求量逐年增加,原油对外依存度接近70%。因此,从煤、天然气、生物质等非石油资源制备乙苯将具有重要的战略意义。通过先将煤、天然气、生物质等非石油资源转化为合成气(CO和H2的混合气),而后通过合成气制备芳烃可以实现从非石油资源制备芳烃。金属氧化物与ZSM-5分子筛的复合催化剂可以实现合成气直接制芳烃。但是这两种路线中乙苯选择性很低,不超过5%。因此,开发可从合成气出发生产高乙苯选择性的催化剂对我国能源、纺织、化纤、塑料等行业都具有十分重要的意义。
发明内容
针对上述问题,本发明提供了一种催化剂及合成气与甲苯转化制乙苯的方法。
本发明的技术方案为:
一种催化剂,所述催化剂为复合催化剂I+II,组分I与组分II以机械混合方式复合。组分I的活性成份为金属氧化物,组分II为碱金属Cs改性的X型分子筛。
所述的金属氧化物为MnOx、MnxCryO(x+1.5y)、MnxAlyO(x+1.5y)、MnxZryO(x+2y)、MnxInyO(x+1.5y)、ZnO、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CeO2、CeZryO2、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、In2O3、InyAlzMnO(1+1.5y+1.5z)、InyGazMnO(1+1.5y+1.5z)中的一种或二种以上;所述x的取值范围是1~3.5,y的取值范围是0.1-10;z的取值范围是0.1-10;
所述MnOx、ZnO、CeO2、In2O3的比表面积是1-100m2/g;
所述MnxCryO(x+1.5y)、MnxAlyO(x+1.5y)、MnxZryO(x+2y)、MnxInyO(x+1.5y)、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CeZryO2、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、In2O3、InyAlzMnO(1+1.5y+1.5z)、InyGazMnO(1+1.5y+1.5z)的比表面积是5-150m2/g。
基于以上技术方案,优选的,所述通过碱金属Cs改性处理的X型分子筛,碱金属原子取代X型分子筛B酸上的H原子,碱金属的取代程度为20%-90%,优选30%-80%。
基于以上技术方案,优选的,其中碱金属Cs的取代程度为样品中碱金属Cs的摩尔量与Al的摩尔量的比例,其中Cs和Al的含量可以但不限于采用ICP、XRF表征手段获取。
基于以上技术方案,优选的,所述Cs原子可以通过离子交换法引入X型分子筛中,所述Cs的前驱体可以是但不限于硝酸铯,碳酸铯,柠檬酸铯,氯化铯,溴化铯,氟化铯,碳酸氢铯。
基于以上技术方案,优选的,所述组分II与组分I中的活性组分之间的重量比为0.1-20,优选为0.3-5。
基于以上技术方案,优选的,所述组分I中还添加有分散剂,金属氧化物分散于分散剂中;所述分散剂为Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3、活性炭、石墨烯、碳纳米管中的一种或二种以上。
基于以上技术方案,优选的,所述组分I中,分散剂的含量在0.05-90wt%,其余为金属氧化物。
本发明还提供一种合成气与甲苯直接转化制乙苯的方法,以合成气和甲苯为反应原料,在固定床、流化床或者移动床上进行转化反应,所述合成气的压力为0.5-10MPa,优选为1-8MPa;反应温度为300-600℃,优选为350-500℃;合成气空速为300-12000ml/gcat/h,优选为300-9000ml/gcat/h,更优选为300-7000ml/gcat/h;所述合成气为H2/CO混合气,H2/CO比例为0.2-3.5,优选为0.3-2.5;甲苯液时空速为0.5-10h-1,优选为0.5-5h-1。
基于以上技术方案,优选的,所述方法以合成气和甲苯为反应原料一步法直接转化制乙苯,反应过程具有很高的产品收率和选择性,芳烃选择性可以达到30-80%,乙苯在芳烃中比例可以达到40-80%,具有很好的应用前景。
本发明具有如下优点:
1、本技术与传统的苯与乙烯制备乙苯方法相比,避免使用高价值的乙烯作为原料,并且
可以实现非石油路线制备乙苯。
2、催化剂中组分I的活性成分金属氧化物具有较高的比表面积,因此金属氧化物表面上具有更多的活性位点,更有利于催化反应的进行。
3、本发明所述的催化剂为双功能催化剂,组分I为金属氧化物,主要用于活化CO生成含氧化合物中间体,组分II为改性的分子筛,用于甲苯与该含氧化合物中间体的侧链烷基化,生成乙苯。只有组分I和组分II协同作用时,才能实现本发明的功能。单独分别使用本发明中所述的组分I或者组分II皆不能完全实现本发明的功能,例如单独使用I组分产物中甲烷选择性非常高,且转化率很低,而单独使用II组不能活化转化合成气。
4、本发明的组分I为金属氧化物,与金属,例如铜相比,氧化物具有较弱的加氢和裂解能力,因此低碳烷烃的选择性低,芳烃选择性高,并且稳定性优于铜催化剂。
5、本发明的复合催化剂的制备过程简单、条件温和;且反应过程具有很高的产品收率和选择性,芳烃选择性可以达到30-80%,乙苯在芳烃中比例可以达到40-80%,具有很好的应用前景。
具体实施方式
下面通过实施例对本发明做进一步阐述,但是本发明的权利要求范围不受这些实施例的限制。同时,实施例只是给出了实现此目的的部分条件,但并不意味着必须满足这些条件才可以达到此目的。
样品的比表面积可以通过氮气或氩气物理吸附的方法进行测试。
本发明所述的金属氧化物可以通过购买市售的高比表面积的金属氧化物获得,也可以通过下述几种方法获得:
一、催化剂组分I的制备
(一)、沉淀法合成具有高比表面的ZnO材料:
(1)分别称取3份、每份0.446g(1.5mmol)Zn(NO3)2·6H2O于3个容器中,再分别称取0.795g(7.5mmol)、1.272g(12mmol)、1.908g(18mmol)的NaCO3依次加入上述3个容器中,再各量取30ml去离子水加入到3个容器中,70℃搅拌0.5h以上使溶液混合均匀,自然冷却至室温。反应液离心分离,收集离心分离后的沉淀物,用去离子水洗涤2次获得ZnO金属氧化物前驱体;
(2)焙烧:上述获得的产物在空气中烘干以后,在气氛中进行焙烧处理,即得到高比表面的ZnO材料。气氛为惰性气体、还原性气体或者氧化性气体;惰性气体为N2、He和Ar中的一种或二种以上;还原性气体为H2、CO中的一种或二种,还原气中也可以含有惰性气体;氧化性气体是O2、O3、NO2中的一种或两种以上,氧化气体中也可以含有惰性气体。焙烧温度为300-700℃,时间为0.5h-12h。
焙烧的目的是为了将沉淀后的金属氧化物前驱体在高温下分解为高比表面积的氧化物纳米粒子,并且通过焙烧的高温处理可以将分解生成的氧化物表面吸附物种处理干净。
具体样品及其制备条件如下表1,作为对比例,表中ZnO4是市售低比表面积的ZnO单晶。
表1 ZnO材料的制备及其参数性能
(二)共沉淀法合成具有高比表面积的MnOx材料:
制备过程同上述ZnO 2,不同之处在于将Zn的前驱体换成了Mn的对应的前驱体,可为硝酸锰、氯化锰、醋酸锰中的一种,在此为硝酸锰,对应产物定义为MnOx;x=1;比表面积是:43m2/g。
(三)共沉淀法合成具有高比表面积的CeO2材料:
制备过程同上述ZnO 2,不同之处在于将Zn的前驱体换成了Ce的对应的前驱体,可为硝酸铈、氯化铈、醋酸铈中的一种,在此为硝酸铈,对应产物定义为CeO2;比表面积是:92m2/g。
(四)共沉淀法合成具有高比表面积的In2O3材料:
制备过程同上述ZnO 2,不同之处在于将Zn的前驱体换成了In的对应的前驱体,可为硝酸铟、氯化铟、醋酸铟中的一种,在此为硝酸铟,对应产物定义为In2O3;比表面积是:52m2/g。
(五)沉淀法合成具有高比表面积的MnCryO(x+1.5y)、MnAlyO(x+1.5y)、MnZryO(x+2y)、MnInyO(x+1.5y)、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CeZryO2、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、InyAlzMnO(x+1.5y+1.5z)、InyGazMnO(x+1.5y+1.5z):
采用硝酸锌、硝酸铝、硝酸铬、硝酸锰、硝酸锆、硝酸镓、硝酸铟、硝酸钴、硝酸铁为前驱体,与碳酸铵,在室温下于水中相互混合(其中碳酸铵作为沉淀剂,投料比例为碳酸铵过量或者优选铵离子与金属离子的比例为1:1);将上述混合液陈化,然后取出洗涤、过滤和干燥,所得的固体在空气气氛下焙烧,获得高比表面的金属氧化物,具体样品及其制备条件如下表2。
表2高比表面积金属氧化物的制备及其性能参数
(六)、分散剂Cr2O3、Al2O3或ZrO2分散的金属氧化物
以分散剂Cr2O3、Al2O3或ZrO2为载体,沉淀沉积法制备Cr2O3、Al2O3或ZrO2分散的金属氧化物。以分散ZnO的制备为例,将商业Cr2O3(比表面积约为5m2/g)、α-Al2O3(比表面积约为20m2/g)或ZrO2(比表面积约为10m2/g)作为载体预先分散于水中,然后采用硝酸锌为原料,与碳酸钠沉淀剂在室温下混合沉淀,Zn2+的摩尔浓度为0.067M,Zn2+与沉淀剂的摩尔份数比为1:8;然后在160℃下陈化24小时,获得Cr2O3、α-Al2O3或ZrO2为载体分散的ZnO(分散剂于组分Ⅰ中的含量依次为0.1wt%、20wt%、85wt%)。得到的样品在空气下500℃焙烧1h,产物依次定义为分散氧化物1-3,其比表面积依次为:148m2/g,115m2/g,127m2/g。
以同样的方法,可以获得SiO2(比表面积约为2m2/g)、双组分Ga2O3(比表面积约为10m2/g)与γ-Al2O3(比表面积约为10m2/g)、TiO2(比表面积约为15m2/g)分别为载体分散的MnO氧化物(分散剂于组分Ⅰ中的含量依次为5wt%、20wt%与10wt%、60wt%),产物依次定义为分散氧化物4-6。其比表面积依次为:97m2/g,68m2/g,56m2/g。
以同样的方法,可以获得活性炭(比表面积约为1000m2/g)、石墨烯(比表面积约为500m2/g)和碳纳米管(比表面积约为300m2/g)为载体分散的ZnO氧化物(分散剂于组分Ⅰ中的含量依次为5wt%、30wt%、60wt%),产物依次定义为分散氧化物7-9。其比表面积依次为:177m2/g,245m2/g,307m2/g。
(七)铜锌铝催化剂的制备:将一定浓度的硝酸铜、硝酸锌以及硝酸铝按照CuO/ZnO/Al2O3的摩尔比为3/3/0.3的比例溶于容器中,加入适当浓度的碳酸钠溶液控制pH值为8,滴加完毕后老化一段时间,经过洗涤、过滤,110℃干燥,350℃焙烧4小时得到铜锌铝催化剂。记为CuZnAl。
二、组分II的制备
本发明所描述的碱金属以及Al含量,可以有XRF或者ICP等方法测得。但含量的测试方法不限于上述测试方法。
本发明组分Ⅱ的X型分子筛可以是购买的商品化产品(选择其中符合权利要求的的分子筛),也可以是自行制备的分子筛。
本发明组分Ⅱ的X型分子筛的Cs的引入方式这里以离子交换法为例,但不限于离子交换的方式,所述X型分子筛可以为氢型,Na型也可以是铵型等,这里以商业Na型X分子筛的离子交换法为例。
离子交换法制备Cs改性的X型分子筛CsX:取NaX分子筛,将其与0.1mol/L的硝酸铯溶液混合,搅拌,离心分离,用去离子水将催化剂表面未交换的离子洗涤干净,在60℃烘干过夜,随后在110℃烘箱中干燥除水。上述获得的产物在空气中烘干以后,在气氛中进行焙烧处理,得到含CsX分子筛。气氛为惰性气体、还原性气体或者氧化性气体;惰性气体为N2、He和Ar中的一种或二种以上;还原性气体为H2、CO的一种或二种,还原气中也可以含有惰性气体;氧化性气体是O2、O3、NO2中的一种或两种以上,氧化气体中也可以含有惰性气体。交换温度为20-80℃,交换时间为2-10h,交换次数为1-8次,焙烧温度为300-700℃,时间为0.5h-12h。
表3 Cs改性的X型分子筛的制备及其性能参数
三、催化剂的制备
将所需比例的组分I和组分II加入容器中,利用这些物料和/或容器的高速运动产生的挤压力、撞击力、裁剪力、摩擦力等中的一种或两种以上作用实现分离、破碎、混匀等目的,通过调变温度与载气气氛实现机械能、热能与化学能的转换,进一步调节不同组分间的相互作用。
机械混合过程中,可以设置混合温度为20-100℃,可以在气氛中或者直接在空气中进行,气氛选自以下任意的气体:
a)氮气和/或惰性气体;
b)氢气与氮气和/或惰性气体的混合气,其中氢气于混合气中的体积为5~50%;
c)CO与氮气和/或惰性气体的混合气,其中CO于混合气中的体积为5~20%;
d)O2与氮气和/或惰性气体的混合气,其中O2于混合气中的体积为5-20%,所述惰性气体为氦气、氩气、氖气中的一种或两种以上。
机械混合可采用机械搅拌、球磨、摇床混合、机械研磨中的一种或二种以上进行复合,具体如下:
机械搅拌:在搅拌槽中,采用搅拌棒将组分I和组分II进行混合,通过控制搅拌时间(5min-120min)和速率(30-300转/min),可以调节组分I和组分II的混合程度和相对距离。
球磨:利用磨料与催化剂在研磨罐内高速翻滚,对催化剂产生强烈冲击、碾压,达到分散、混合组分I和组分II的作用。通过控制磨料(材质可以是不锈钢、玛瑙、石英。尺寸范围:5mm-15mm)与催化剂的比例(质量比范围:20-100:1),可以调节催化剂的粒度及相对距离。
摇床混合法:将催化剂A和B预混合,并装入容器中;通过控制摇床的往复振荡或圆周振荡,实现组分I和组分II的混合;通过调节振荡速度(范围:1-70转/分)和时间(范围:5min-120min),实现均匀混合并调节其相对距离。
机械研磨法:将组分I和组分II预混合,并装入容器中;在一定的压力(范围:5公斤-20公斤)下,通过研具与混合的催化剂进行相对运动(速率范围:30-300转/min),达到调节催化剂粒度、相对距离和实现均匀混合的作用。
具体的催化剂制备及其参数特征如表4所示。
表4 I+II复合催化剂的制备及其参数特征
催化反应实例
该固定床反应装置配备气体质量流量计、在线产物分析色谱(反应器的尾气直接与色谱的定量阀连接,进行周期实时采样分析)。催化剂III置于催化剂I+II的下方,原料气方向由上到下。
将上述本发明的催化剂2g,置于固定床反应器中,使用Ar置换反应器中的空气,然后再在H2气氛中升温至300℃,切换原料气,合成气(H2/CO摩尔比=0.3-3.5)和甲苯,反应的压力为1-8MPa,反应温度350-500℃,调节合成气空速为300-7000ml/gcat/h,甲苯液时空速为0.5-5h-1。
改变温度、压力和空速和合成气中H2/CO的摩尔比,可以改变反应性能。表5列出了催化剂的具体应用及其效果数据。
表5催化剂的具体应用及其效果数据
注:实施例8和实施例9的催化剂和反应条件相同,反应时间不同,实施例8反应时间为2h,实施例9的反应时间为15h;对比例4和对比例5的催化剂和反应条件相同,反应时间不同,对比例4反应时间为2h,对比例4的反应时间为15h;其他实施例和对比例的反应时间均为反应2h的结果。
对比例1催化剂组份I为ZnO4。
对比例2采用的催化剂中不包含组分II。
对比例3采用的催化剂中不包含组分I。
对比例1采用的催化剂组分I是低比表面积的ZnO 4,CO转化率很低。
对比例2采用的催化剂中不包含组分II。其产物中芳烃选择性很低,不具备本发明所述的优异反应性能。
对比例3采用的催化剂中不包含组分I。CO不转化,并且产物中乙苯选择性很低,不具备本发明所述的优异反应性能。
对比例4采用的催化剂中组分Ⅰ为铜锌铝氧化物,由于Cu的加氢能力强于氧化物,因此其产物中烷烃选择性比较高,但是芳烃选择性低。并且对比对比例4和对比例5可以看出,由于铜易烧结,因此其CO转化率经过15h后,下降明显。对比实施例8和实施例9可以看出,本发明中氧化物的稳定性要明显由于铜锌铝。由上表可以看出氧化物的组成、结构,CsX分子筛中Cs的交换程度,以及催化剂组分I和II之间的匹配至关重要,直接影响一氧化碳的转化率、甲苯转化率、芳烃的选择性以及其中乙苯的选择性。
Claims (8)
1.一种催化剂,其特征在于:所述催化剂为复合催化剂I+II,组分I与组分II以机械混合方式复合;组分I的活性成份为金属氧化物,组分II为碱金属Cs改性的X型分子筛;
所述的金属氧化物为MnOx、MnxCryO(x+1.5y)、MnxAlyO(x+1.5y)、MnxZryO(x+2y)、MnxInyO(x+1.5y)、ZnO、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CeO2、CeZryO2、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、In2O3、InyAlzMnO(1+1.5y+1.5z)、InyGazMnO(1+1.5y+1.5z)中的一种或二种以上;所述x的取值范围是1~3.5,y的取值范围是0.1-10;z的取值范围是0.1-10;
所述MnOx、ZnO、CeO2、In2O3的比表面积是1-100m2/g;
所述MnxCryO(x+1.5y)、MnxAlyO(x+1.5y)、MnxZryO(x+2y)、MnxInyO(x+1.5y)、ZnCryO(1+1.5y)、ZnAlyO(1+1.5y)、ZnGayO(1+1.5y)、ZnInyO(2+1.5y)、CeZryO2、CoAlyO(1+1.5y)、FeAlyO(1+1.5y)、In2O3、InyAlzMnO(1+1.5y+1.5z)、InyGazMnO(1+1.5y+1.5z)的比表面积是5-150m2/g。
2.按照权利要求1所述的催化剂,其特征在于:所述的改性为Cs原子取代X型分子筛中的B酸上的H原子,碱金属Cs的取代程度为20%-90%,优选30%-80%;所述取代程度为催化剂中,碱金属Cs的摩尔量与Al的摩尔量的比例。
3.按照权利要求1所述的催化剂,其特征在于:组分II与组分I中的活性组分之间的重量比为0.1-20:1,优选为0.3-5:1。
4.按照权利要求1所述的催化剂,其特征在于:所述组分I中还添加有分散剂,金属氧化物分散于分散剂中;所述分散剂为Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3、活性炭、石墨烯、碳纳米管中的一种或二种以上。
5.按照权利要求4所述的催化剂,其特征在于:所述组分I中,分散剂的含量在0.05-90wt%,其余为金属氧化物。
6.一种合成气与甲苯直接转化制乙苯的方法,其特征在于:以合成气和甲苯为反应原料,在固定床、流化床或者移动床上进行转化反应,所采用的催化剂为权利要求1-5任一所述的催化剂。
7.按照权利要求6所述的方法,其特征在于:所述合成气的压力为0.5-10MPa,优选为1-8MPa;反应温度为300-600℃,优选为350-500℃;空速为300-12000ml/gcat/h,优选为300-9000ml/gcat/h,更优选为300-7000ml/gcat/h;所述合成气为H2/CO混合气,H2/CO比例为0.2-3.5,优选为0.3-2.5;甲苯液时空速为0.5-10h-1,优选为0.5-5h-1。
8.按照权利要求7所述的方法,其特征在于:所述方法以合成气和甲苯为反应原料一步法直接转化制乙苯,芳烃选择性为30-80%,乙苯在芳烃中的比例为40-80%。
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