CN1260007C - 一种微球状费托合成铁基催化剂及制法和应用 - Google Patents
一种微球状费托合成铁基催化剂及制法和应用 Download PDFInfo
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- CN1260007C CN1260007C CN 200410012349 CN200410012349A CN1260007C CN 1260007 C CN1260007 C CN 1260007C CN 200410012349 CN200410012349 CN 200410012349 CN 200410012349 A CN200410012349 A CN 200410012349A CN 1260007 C CN1260007 C CN 1260007C
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- Prior art keywords
- catalyst
- fischer
- based catalyst
- iron
- deionized water
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title abstract description 6
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- 239000011806 microball Substances 0.000 title 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 45
- 229910021641 deionized water Inorganic materials 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 20
- 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 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 238000005299 abrasion Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- DCJAPNLJBXPBCU-UHFFFAOYSA-N [Fe].[Cu].[Ce] Chemical compound [Fe].[Cu].[Ce] DCJAPNLJBXPBCU-UHFFFAOYSA-N 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 5
- 239000006188 syrup Substances 0.000 claims description 5
- 235000020357 syrup Nutrition 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 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 claims description 3
- 238000005304 joining Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 238000001694 spray drying Methods 0.000 abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001062233 Salmonella enterica subsp. enterica serovar Texas Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 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
- 230000008021 deposition Effects 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
催化剂编号 | 实施例l | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
粒度分布(%)(50~120μm比例)磨损指数(%h-1)BET比表面积(m2/g)孔体积(ml/g) | 95.21.51820.18 | 96.51.61690.22 | 96.31.11950.21 | 96.81.71560.23 | 95.11.51330.26 | 97.01.42010.16 |
催化剂编号 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | ||||||||
运转时间(小时) | 300 | 800 | 200 | 750 | 500 | 1000 | 400 | 900 | 800 | 1500 | 900 | 3000 | ||
反应温度(℃)反应压力(MPa)反应空速(h-1) | 3201.51000 | 2803.52500 | 2504.01500 | 2203.03000 | 2752.02000 | 2551.52000 | ||||||||
CO转化率,%碳氢化物产率(g-HC/g-Fe/h) | 72.50.75 | 69.90.73 | 79.30.80 | 77.50.79 | 81.60.81 | 79.30.72 | 69.20.68 | 68.00.65 | 80.20.82 | 79.00.78 | 85.20.86 | 76.50.80 | ||
烃类选择性,wt%(on HC basis) | ||||||||||||||
CH4C2-C4C5-C11C12 +烯烃含氧化物选择性,mol%(on Cbasis) | 3.715.7918.9461.87673.8 | 3.315.7317.8162.76654.0 | 3.914.1015.8866.12623.6 | 3.314.0215.9966.69673.4 | 3.413.3915.3967.82703.9 | 3.313.2115.5567.94684.0 | 2.912.4814.2070.42734.9 | 2.712.8014.0470.46704.9 | 3.714.7618.7162.93663.9 | 3.515.3216.8564.33654.1 | 3.314.2616.3864.06694.0 | 3.214.3316.6865.79683.9 |
Claims (9)
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CN 200410012349 CN1260007C (zh) | 2004-06-11 | 2004-06-11 | 一种微球状费托合成铁基催化剂及制法和应用 |
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CN 200410012349 CN1260007C (zh) | 2004-06-11 | 2004-06-11 | 一种微球状费托合成铁基催化剂及制法和应用 |
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CN1583259A CN1583259A (zh) | 2005-02-23 |
CN1260007C true CN1260007C (zh) | 2006-06-21 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8506895B2 (en) | 2007-09-29 | 2013-08-13 | Synfuels China Technology Co. Ltd. | Gas-liquid-solid three-phase suspension bed reactor for fischer-tropsch synthesis and its applications |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101829580B (zh) * | 2009-03-12 | 2012-10-03 | 中科合成油技术有限公司 | 一种费托合成催化剂、其制备方法和应用 |
CN101869840A (zh) * | 2009-04-22 | 2010-10-27 | 中科合成油技术有限公司 | 一种费托合成催化剂、其制备方法和应用 |
CN101993707B (zh) * | 2009-08-31 | 2014-03-05 | 中国石油化工股份有限公司 | 费托合成重质烃的方法 |
CN102482583B (zh) * | 2009-08-31 | 2015-05-13 | 日本石油天然气·金属矿物资源机构 | 浆料制备方法、浆料制备装置、烃合成反应装置以及烃合成反应*** |
CN102371155B (zh) * | 2010-08-23 | 2013-04-10 | 中国石油化工股份有限公司 | 费托合成重质烃的铁基催化剂及其制备方法 |
CN102453492B (zh) * | 2010-10-21 | 2014-03-26 | 中国石油化工股份有限公司 | 费托合成重质烃的方法 |
CN102649079B (zh) * | 2011-02-25 | 2015-09-09 | 中国石油化工股份有限公司 | 用铁锰基催化剂将合成气转化为低碳烯烃的方法 |
CN103170341A (zh) * | 2013-04-22 | 2013-06-26 | 神华集团有限责任公司 | 一种微球状沉淀铁含钕费托催化剂及其制备方法 |
CN103240093A (zh) * | 2013-04-23 | 2013-08-14 | 神华集团有限责任公司 | 一种沉淀铁含钕费托催化剂及其制备方法 |
CN103301839B (zh) * | 2013-06-16 | 2015-10-28 | 复旦大学 | 一种制备纳米线泡沫堆积结构的费托催化剂的方法 |
CN105879875A (zh) * | 2016-04-21 | 2016-08-24 | 武汉凯迪工程技术研究总院有限公司 | 用于费托合成反应的负载型铁基催化剂及其制备方法 |
CN110732329B (zh) * | 2018-07-20 | 2022-12-27 | 国家能源投资集团有限责任公司 | 含钾硅溶胶及其制备方法和费托合成铁基催化剂及其制备方法和费托合成方法 |
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2004
- 2004-06-11 CN CN 200410012349 patent/CN1260007C/zh not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8506895B2 (en) | 2007-09-29 | 2013-08-13 | Synfuels China Technology Co. Ltd. | Gas-liquid-solid three-phase suspension bed reactor for fischer-tropsch synthesis and its applications |
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Address after: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Zhongke synthetic oil Technology Co.,Ltd. Address before: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. |
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CX01 | Expiry of patent term |
Granted publication date: 20060621 |