CN1247305C - Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed - Google Patents
Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed Download PDFInfo
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- CN1247305C CN1247305C CN 200410012199 CN200410012199A CN1247305C CN 1247305 C CN1247305 C CN 1247305C CN 200410012199 CN200410012199 CN 200410012199 CN 200410012199 A CN200410012199 A CN 200410012199A CN 1247305 C CN1247305 C CN 1247305C
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- catalyst
- gas
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- fischer
- synthesis gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 100
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 99
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 14
- 239000002002 slurry Substances 0.000 title claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 230000009467 reduction Effects 0.000 claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 12
- 238000006073 displacement reaction Methods 0.000 claims description 12
- 239000006188 syrup Substances 0.000 claims description 12
- 235000020357 syrup Nutrition 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 2
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011946 reduction process Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 239000012071 phase Substances 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241001062233 Salmonella enterica subsp. enterica serovar Texas Species 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 101100004280 Caenorhabditis elegans best-2 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010041954 Starvation Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
A | Running time, hour | 0 | 100 | 300 | 500 | 1000 | 1500 | 2000 | 2500 |
The CO conversion ratio, % | - | 65.56 | 69.80 | 69.66 | 68.24 | 66.58 | 63.69 | 60.05 | |
CH 4Selectivity, wt% | - | 4.54 | 4.02 | 3.89 | 4.35 | 3.98 | 4.17 | 4.33 | |
C 4 +Selectivity, wt% | - | 78.56 | 80.55 | 82.12 | 79.51 | 82.11 | 80.05 | 79.86 | |
Deactivation rate, %/sky | - | - | - | - | 0.08 | 0.11 | 0.14 | 0.17 | |
Reduction back breakage rate, % | 0.05 | - | - | - | - | - | - | - | |
Reaction back breakage rate, % | - | - | - | - | - | - | - | 10 |
B | Running time, hour | 0 | 100 | 300 | 500 | 800 | 1000 | 1200 | 1600 |
The CO conversion ratio, % | - | 66.67 | 71.56 | 72.08 | 71.35 | 70.88 | 70.01 | 67.67 | |
CH 4Selectivity, wt% | - | 4.67 | 4.77 | 4.23 | 4.15 | 4.89 | 4.68 | 4.96 | |
C 4 +Selectivity, wt% | - | 77.67 | 77.98 | 79.03 | 79.64 | 77.08 | 77.52 | 76.89 | |
Deactivation rate, %/sky | - | - | - | - | 0.06 | 0.06 | 0.11 | 0.14 | |
Reduction back breakage rate, % | 0.06 | - | - | - | - | - | - | - | |
Reaction back breakage rate, % | - | - | - | - | - | - | - | 0.98 | |
C | Running time, hour | 0 | 100 | 300 | 500 | 800 | 1000 | 1200 | 1500 |
The CO conversion ratio, % | - | 65.67 | 71.66 | 71.48 | 70.35 | 69.88 | 68.81 | 67.07 | |
CH 4Selectivity, wt% | - | 5.01 | 4.88 | 4.59 | 4.96 | 4.92 | 5.08 | 4.65 | |
C 4 +Selectivity, wt% | - | 76.88 | 77.46 | 76.98 | 78.00 | 78.04 | 76.45 | 77.83 | |
Deactivation rate, %/sky | - | - | - | - | 0.09 | 0.06 | 0.15 | 0.15 | |
Reduction back breakage rate, % | 0.03 | - | - | - | - | - | - | - | |
Reaction back breakage rate, % | - | - | - | - | - | - | - | 0.88 | |
D | Running time, hour | 0 | 100 | 300 | 500 | 1000 | 1200 | 1500 | 1800 |
The CO conversion ratio, % | - | 75.78 | 77.89 | 77.09 | 76.68 | 76.04 | 75.02 | 74.16 | |
CH 4Selectivity, wt% | - | 5.0 | 4.45 | 4.54 | 4.69 | 5.02 | 4.89 | 4.73 | |
C 4 +Selectivity, wt% | - | 76.26 | 78.49 | 78.47 | 78.40 | 77.03 | 77.59 | 77.07 | |
Deactivation rate, %/sky | - | - | - | - | 0.07 | 0.08 | 0.09 | 0.07 | |
Reduction back breakage rate, % | 0.07 | - | - | - | - | - | - | - | |
Reaction back breakage rate, % | - | - | - | - | - | - | - | 0.98 | |
E | Running time, hour | 0 | 100 | 300 | 500 | 1000 | 1500 | 1800 | 2200 |
The CO conversion ratio, % | - | 72.38 | 74.88 | 75.96 | 74.32 | 7245 | 71.18 | 69.66 | |
CH 4Selectivity, wt% | - | 4.87 | 4.55 | 4.96 | 5.04 | 4.43 | 4.78 | 4.80 | |
C 4 +Selectivity, wt% | - | 78.65 | 79.04 | 78.49 | 77.95 | 79.82 | 78.88 | 7857 | |
Deactivation rate, % days | - | - | - | - | 0.08 | 0.09 | 0.11 | 0.10 | |
Reduction back breakage rate, % | 0.04 | - | - | - | - | - | - | - | |
Reaction back breakage rate, % | - | - | - | - | - | - | - | 1.0 |
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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CN 200410012199 CN1247305C (en) | 2004-03-19 | 2004-03-19 | Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed |
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Application Number | Priority Date | Filing Date | Title |
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CN 200410012199 CN1247305C (en) | 2004-03-19 | 2004-03-19 | Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed |
Publications (2)
Publication Number | Publication Date |
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CN1562484A CN1562484A (en) | 2005-01-12 |
CN1247305C true CN1247305C (en) | 2006-03-29 |
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CN 200410012199 Expired - Lifetime CN1247305C (en) | 2004-03-19 | 2004-03-19 | Method for deoxidizing iron base catalyst of Fisher-Tropsch synthesis in slurry bed |
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Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100404137C (en) * | 2005-06-21 | 2008-07-23 | 上海兖矿能源科技研发有限公司 | Industrial reduction method of particle iron-base fischer-tropsch synthesis catalyst |
CN102371189B (en) * | 2010-08-19 | 2013-06-26 | 中国石油化工股份有限公司 | Reactivation method for Fishcer-Tropshc synthesis catalyst |
CN102553657B (en) * | 2012-01-06 | 2013-11-20 | 神华集团有限责任公司 | Reduction method of fischer tropsch catalyst |
CN103084219B (en) * | 2013-02-04 | 2016-02-24 | 中科合成油技术有限公司 | A kind of method of reducing of syrup state bed Fischer Tropsch synthesis iron base catalyst |
CN103071543B (en) * | 2013-02-04 | 2015-07-01 | 中科合成油技术有限公司 | Reduction method for iron-based catalyst for Fischer-Tropsch synthesis in fixed bed |
CN104549559B (en) * | 2013-10-28 | 2017-03-15 | 中国石油化工股份有限公司 | Fluid bed syngas directly prepare the activation method of low-carbon alkene ferrum-based catalyst |
CN103769241A (en) * | 2014-02-18 | 2014-05-07 | 神华集团有限责任公司 | Fixed-bed Fischer-tropsch catalyst reduction activation system and technology |
CN106552632B (en) * | 2015-09-30 | 2019-04-16 | 神华集团有限责任公司 | A kind of restoring method of Fischer-Tropsch synthetic iron-based catalyst |
CN110201673B (en) * | 2018-02-28 | 2022-02-18 | 国家能源投资集团有限责任公司 | Method for reducing iron-based Fischer-Tropsch synthesis catalyst and reduced iron-based Fischer-Tropsch synthesis catalyst |
CN113893860A (en) * | 2021-11-11 | 2022-01-07 | 兖矿榆林精细化工有限公司 | Reduction method of low-temperature Fischer-Tropsch synthesis iron-based catalyst |
-
2004
- 2004-03-19 CN CN 200410012199 patent/CN1247305C/en not_active Expired - Lifetime
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CN1562484A (en) | 2005-01-12 |
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Denomination of invention: Reducing method of slurry bed Fischer-Tropsch synthesis iron-based catalyst Effective date of registration: 20101206 Granted publication date: 20060329 Pledgee: China Development Bank Co. Pledgor: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. Registration number: 2010990000994 |
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. Address before: 030006, Shanxi, Taiyuan hi tech Zone, South Central Cyberport 2, port 4, A, B District Patentee before: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. |
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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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