JP2010526653A - 触媒 - Google Patents
触媒 Download PDFInfo
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- JP2010526653A JP2010526653A JP2010507050A JP2010507050A JP2010526653A JP 2010526653 A JP2010526653 A JP 2010526653A JP 2010507050 A JP2010507050 A JP 2010507050A JP 2010507050 A JP2010507050 A JP 2010507050A JP 2010526653 A JP2010526653 A JP 2010526653A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 claims abstract description 58
- 230000003647 oxidation Effects 0.000 claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 39
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 24
- 230000001172 regenerating effect Effects 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000011069 regeneration method Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 5
- 238000000638 solvent extraction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000005243 fluidization Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 description 32
- 238000005470 impregnation Methods 0.000 description 20
- 239000012018 catalyst precursor Substances 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 17
- 239000002002 slurry Substances 0.000 description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000005517 carbenium group Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005229 chemical vapour deposition Methods 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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/30—Treating with free oxygen-containing gas in gaseous suspension, e.g. fluidised bed
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
第1活性化段階において、酸化触媒粒子を、水素含有還元性ガスまたは窒素含有ガスを用いて、第1加熱速度HR1で、酸化触媒粒子が温度T1(但し80℃ < T1 < 180℃)に達するまで処理して、部分的に処理した触媒前駆体を得、
第2活性化段階において、部分的に処理した触媒前駆体を、水素含有還元性ガスを用いて、第2加熱速度HR2(但し0 < HR2 < HR1)で、時間t1(但しt1は0.1〜20時間)の間処理して、部分的に還元した触媒前駆体を得、そして、
第3活性化段階において、部分的に還元した触媒前駆体を、水素含有還元性ガスを用いて、第3加熱速度HR3(但しHR3 > HR2)で、部分的に還元した触媒前駆体が温度T2に達するまで処理し、また、温度T2に時間t2(但しt2は0〜20時間)の間維持して、再生触媒である、活性化したフィッシャー-トロプシュ合成用担持コバルト触媒を得る。
第1活性化段階において、仮焼された状態の還元可能な酸化コバルトを含み、コバルト原子1モル当たりの酸素原子のモル数が4/3モルを超える式単位を有し、還元可能な酸化コバルトの比表面積がCo3O4スピネルの比表面積と少なくとも等しい酸化触媒粒子を、純粋水素である還元性ガスを用い、特定の第1供給ガス空間速度SV1を用い、第1加熱速度HR1で処理して、部分的に還元した触媒前駆体を得、そして
第2活性化段階において、部分的に還元した触媒前駆体を、純粋水素である還元性ガスを用い、特定の第2供給ガス空間速度SV2を用い、第2加熱速度HR2で処理して、活性化したフィッシャー-トロプシュ合成用担持コバルト触媒を得る(但しSV2 < < SV1、及び/又はHR2 > 2 > HR1、但しSV2=SV1の場合、HR2≠HR1であり、HR2=HR1の場合、SV2≠SV1である)。
下記一般式(1):
HOOC−C*R1C*R2−COOH (1)
式中:
C*R1とC*R2中のC*はsp2炭素であり、そして
R1とR2は同じでも異なってもよく、各々、水素、カルベニウムまたはアルキルである、
で表わされる多官能性カルボン酸またはその前駆体を、粒状触媒担体の内部及び/又は表面に導入し、その際、多官能性カルボン酸の粒状触媒担体に対する比率を0.3〜4.4μmolのカルボン酸/担体の1m2とし、
所望により、得られたカルボン酸含有触媒担体を乾燥させ、
多官能性カルボン酸を粒状触媒担体の内部及び/又は表面に導入するのと同時に、または、その後で、触媒担体にコバルト塩及び、所望により、還元促進剤を含浸させ、得られた含浸担体を部分的に乾燥させ、そして
得られた部分的乾燥含浸担体を仮焼する、ことを含む方法。
反応器圧力 : 21バール
(H2+CO)転化率(%) : 60±10
H2 : 50〜60容量%
CO : 30〜40容量%
他の成分 : CH4及び/又はCO2
ワックス被覆された使用済み触媒サンプルの10gを実験室スケールの固定床還元ユニットにおいて水素化分解工程に付してワックスを除去した。その際、純粋水素の空間速度は1500ml n/触媒1g/1時間とし、同時に以下の温度プログラムを用いた。加熱速度1℃/分で加熱して220℃に昇温し、220℃を2時間等温に維持し、次に加熱速度1℃/分で加熱して350℃に昇温し、350℃を2時間等温に維持し、その後25℃に冷却する。水素をアルゴンで置換し、得られた乾燥触媒粉体をドライアイス(即ちCO2)に入れて不動態化した。
不動態化した触媒を次に実験室スケールの流動床仮焼ユニット(反応室)において酸化に付した。その際、空気の空間速度は1780ml n/触媒1g/1時間とし、同時に以下の温度プログラムを用いた。加熱速度1℃/分で加熱して250℃に昇温し、250℃を6時間等温に維持した。流動床還元ユニットを0.9バール(絶対圧)に維持し、酸素濃度を21容量%とした。
酸化触媒サンプルを次に実験室スケールの固定床還元ユニットにおいて以下の還元工程に付した。水素の空間速度は1500ml n/触媒1g/1時間とした。加熱速度1℃/分で加熱して425℃に昇温し、425℃を16時間等温に維持した。水素中で室温(±25℃)まで冷却したのち、得られた還元(活性化)触媒を取り出してワックス中に入れ、その後再使用した。
RFT − (kFT pH2 PCO)/(1 + kpCO)2
を適用し、報告された実験についてのアレニウス前指数項(Arrhenius derived pre-exponential factor)kFTを推定した。
Claims (13)
- 使用済みのフィッシャー‐トロプシュ合成用コバルト触媒を再生するための方法であって、使用済みのフィッシャー‐トロプシュ合成用コバルト触媒粒子に対して、ワックス除去処理、4〜30バール(絶対圧)の圧力下での酸化処理、及び還元処理を順次行なうことにより触媒を再生することを含むことを特徴とする方法。
- 4〜30バール(絶対圧)の圧力下での酸化処理及びその後の還元処理を含む少なくとも1回の更なる再生サイクルを行なうことを更に含むことを特徴とする請求項1に記載の方法。
- ワックス除去処理が、水素化分解、溶媒洗浄または溶媒抽出、並びに溶媒洗浄または溶媒抽出及びその後の水素化分解からなる群より選ばれる1種を含むことを特徴とする請求項1または2に記載の方法。
- ワックス除去処理の後で、酸化処理の前に、触媒を不動態化することを更に含むことを特徴とする請求項1〜3のいずれかに記載の方法。
- 酸化処理が、ワックス除去した触媒粒子を、高温下と4〜30バール(絶対圧)の高圧力下の酸素含有ガス中で流動させることにより仮焼することによって触媒粒子を酸化させることを含むことを特徴とする請求項1〜4のいずれかに記載の方法。
- ワックス除去した触媒粒子の流動化を該高圧力下の反応室中で行ない、その際、触媒粒子を加熱して温度Tまで昇温し、触媒粒子を温度Tに一定時間維持することにより仮焼することを特徴とする請求項5に記載の方法。
- 触媒粒子の流動中の反応室における空間速度が100〜20000mln/触媒1g/1時間の範囲内であることを特徴とする請求項6に記載の方法。
- 触媒粒子を加熱して温度Tまで昇温する速度が0.1〜10℃/分であることを特徴とする請求項5または6に記載の方法。
- 温度Tが150℃〜400℃の範囲内であることを特徴とする請求項6〜8のいずれかに記載の方法。
- 触媒粒子を温度Tに維持する時間が0.1時間〜24時間の範囲内であることを特徴とする請求項6〜9のいずれかに記載の方法。
- 酸化処理を行なう高圧力が4〜12バール(絶対圧)の範囲内であることを特徴とする請求項1〜10のいずれかに記載の方法。
- 酸化処理における酸素レベルを、約1%の低酸素濃度から始めて、約21%の酸素濃度まで上昇させることを特徴とする請求項1〜11のいずれかに記載の方法。
- 還元処理が、高温下と圧力P(但しP > 0.8バール(絶対圧))下の水素含有還元性ガスで酸化触媒粒子を処理することを含むことを特徴とする請求項1〜12のいずれかに記載の方法。
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US8809215B2 (en) | 2014-08-19 |
WO2008139407A2 (en) | 2008-11-20 |
UA98644C2 (ru) | 2012-06-11 |
RU2009144160A (ru) | 2011-06-20 |
WO2008139407A3 (en) | 2009-03-12 |
US20100304955A1 (en) | 2010-12-02 |
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