JP2019188340A - Process for producing catalyst for producing hydrocarbon from carbon dioxide and hydrogen, and process for producing hydrocarbon from carbon dioxide and hydrogen - Google Patents
Process for producing catalyst for producing hydrocarbon from carbon dioxide and hydrogen, and process for producing hydrocarbon from carbon dioxide and hydrogen Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 185
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 84
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 84
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 73
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000001257 hydrogen Substances 0.000 title claims abstract description 69
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 23
- 150000002431 hydrogen Chemical class 0.000 title claims description 7
- 230000008569 process Effects 0.000 title abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000010941 cobalt Substances 0.000 claims abstract description 49
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 49
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 40
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 23
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 82
- 238000004519 manufacturing process Methods 0.000 claims description 77
- 239000011734 sodium Substances 0.000 claims description 49
- 229910052708 sodium Inorganic materials 0.000 claims description 47
- 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 45
- 229910052700 potassium Inorganic materials 0.000 claims description 42
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 40
- 239000011591 potassium Substances 0.000 claims description 40
- 229910052791 calcium Inorganic materials 0.000 claims description 39
- 239000011575 calcium Substances 0.000 claims description 39
- 229910052749 magnesium Inorganic materials 0.000 claims description 39
- 239000011777 magnesium Substances 0.000 claims description 39
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 159000000021 acetate salts Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 41
- 239000002994 raw material Substances 0.000 abstract description 34
- 230000009849 deactivation Effects 0.000 abstract description 2
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- 239000002245 particle Substances 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 17
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- 150000001340 alkali metals Chemical class 0.000 description 16
- 238000011282 treatment Methods 0.000 description 16
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- 238000006722 reduction reaction Methods 0.000 description 13
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- 238000005406 washing Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 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 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- -1 oxides Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 230000001154 acute effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、二酸化炭素と水素を反応させて炭化水素を製造するための触媒の製造方法、及び該製造方法で製造された触媒を用いた、二酸化炭素と水素から炭化水素を製造する方法に関する。 The present invention relates to a method for producing a catalyst for producing hydrocarbons by reacting carbon dioxide and hydrogen, and a method for producing hydrocarbons from carbon dioxide and hydrogen using the catalyst produced by the production method.
近年、地球温暖化への関心が高まっている。特に、温室効果ガス排出削減等の国際的枠組みを協議する気候変動枠組条約締約国会議（ＣＯＰ）では、世界共通の長期目標として産業革命前からの平均気温の上昇を２℃よりも十分下方に保持することを目的とし、排出ピークをできるだけ早期に抑え、最新の科学に従って急激に削減することを目標とされている。ＣＯＰ２１パリ協定では、全ての国が長期の温室効果ガス低排出開発戦略を策定・提出するように努めるべきとされており、我が国の日本では長期的目標として２０５０年までに８０％の温室効果ガスの排出削減を目指すこととされた。 In recent years, interest in global warming has increased. In particular, at the Conference of the Parties to the Framework Convention on Climate Change (COP), which discusses international frameworks such as greenhouse gas emission reductions, the global average long-term goal is to keep the average temperature rise from before the industrial revolution well below 2 ° C. The goal is to maintain, aiming to reduce the emission peak as early as possible and reduce it rapidly according to the latest science. According to the COP21 Paris Agreement, all countries should endeavor to formulate and submit a long-term greenhouse gas emission development strategy. In Japan, 80% of greenhouse gases will be achieved by 2050 as a long-term goal. It was decided to aim to reduce emissions.
このような背景の下、人為的に排出されている温室効果ガスの中では、二酸化炭素の影響量が最も大きいと見積もられており、二酸化炭素の排出削減のための対策技術開発が各所で精力的に行われている。このような対策技術の一つとして、排出された二酸化炭素を有用物に変換する幾つかの試みが提案されているが、二酸化炭素を別の物質に変換させるためには大きなエネルギーが必要であり、反応を促進させるための有効な触媒の開発が望まれていた。 Against this background, it is estimated that the amount of carbon dioxide influence is the largest among the artificially emitted greenhouse gases. It is done vigorously. As one of such countermeasure technologies, some attempts to convert discharged carbon dioxide into useful substances have been proposed, but large energy is required to convert carbon dioxide into another substance. Therefore, development of an effective catalyst for promoting the reaction has been desired.
また、二酸化炭素の排出削減に資する技術とするためには、二酸化炭素から需要の多い有用物を製造する必要がある。炭化水素（メタンやガソリン等の燃料）は二酸化炭素を炭素源として製造可能な有用物の中でも最も需要が多く、二酸化炭素と水素を原料として炭化水素を製造する技術は二酸化炭素の排出削減のための対策技術として位置付けられる。 In addition, in order to achieve a technology that contributes to the reduction of carbon dioxide emissions, it is necessary to produce useful products with high demand from carbon dioxide. Hydrocarbons (fuels such as methane and gasoline) are most in demand among useful materials that can be produced using carbon dioxide as a carbon source, and the technology for producing hydrocarbons using carbon dioxide and hydrogen as raw materials is to reduce carbon dioxide emissions. It is positioned as a countermeasure technology.
化学反応によって炭化水素を製造する技術としては、一酸化炭素と水素の混合ガス、いわゆる合成ガスを原料として、触媒を用いて変換するＦｉｓｃｈｅｒ−Ｔｒｏｐｓｃｈ（フィッシャー・トロプシュ、Ｆ−Ｔ）合成反応が知られている。この際の触媒としては、コバルト系、鉄系が有効であり、世界中で精力的に技術開発が行われてきた。主触媒であるコバルト、鉄の微細構造、助触媒の機能等、触媒性能に対する触媒組成、構造の詳細が明らかにされている。
一方、二酸化炭素と水素を原料とした炭化水素への変換においても、従来のＦ−Ｔ合成用の触媒に似た組成の鉄系触媒を使用する試みについての報告（非特許文献１、２）や、コバルト系触媒を使用する報告（非特許文献３）がある。しかしながら、二酸化炭素と水素を原料とした炭化水素の製造技術に関しては、地球温暖化への関心の高まりを受けて取り組みの始まった研究が多く、特に使用する触媒の性能に対する詳細な検討は十分とは言えない状況である。
As a technology for producing hydrocarbons by chemical reaction, Fischer-Tropsch (Fischer-Tropsch, FT) synthesis reaction is known in which a mixed gas of carbon monoxide and hydrogen, so-called synthesis gas, is used as a raw material and converted using a catalyst. It has been. Cobalt-based and iron-based catalysts are effective as catalysts at this time, and technological development has been vigorously carried out all over the world. Details of the catalyst composition and structure with respect to the catalyst performance, such as the main catalyst cobalt and iron microstructure, the function of the promoter, etc. have been clarified.
On the other hand, even in the conversion to hydrocarbons using carbon dioxide and hydrogen as raw materials, reports on attempts to use iron-based catalysts having a composition similar to conventional catalysts for FT synthesis (Non-Patent Documents 1 and 2) There is also a report (Non-patent Document 3) using a cobalt-based catalyst. However, with regard to hydrocarbon production technology using carbon dioxide and hydrogen as raw materials, many studies have been started in response to the growing interest in global warming. It is a situation that cannot be said.
二酸化炭素と水素を原料とした炭化水素の製造における化学反応は、従来の一酸化炭素と水素を原料としたＦ−Ｔ合成反応と同様に発熱反応であるが、プラントの安定操業のためには反応熱を効果的に除去することが重要である。反応形式としては、気相合成プロセス（固定床、噴流床、流動床）と、液相合成プロセス（スラリー床）があり、それぞれ特徴を有しているが、熱除去効率が高く、生成した高沸点炭化水素の触媒上への蓄積やそれに伴う反応管閉塞が起こらないスラリー床が有利であると予想される。しかし、二酸化炭素を排出する発生源において、炭化水素への変換プラントを併設する場合には、天然ガス田を対象とした従来のＦ−Ｔ合成プラントと比較して炭化水素の生産量は少なくなると考えられ、この場合にはマイクロチャネル反応器が有利となる可能性も考えられる。マイクロチャネル反応器は、極微細な溝を多数有しており、化学反応の効率化の向上が期待できる反応器として近年、特に注目されている。 The chemical reaction in the production of hydrocarbons using carbon dioxide and hydrogen as raw materials is an exothermic reaction similar to the conventional FT synthesis reaction using carbon monoxide and hydrogen as raw materials. It is important to effectively remove the heat of reaction. The reaction formats include gas phase synthesis process (fixed bed, spouted bed, fluidized bed) and liquid phase synthesis process (slurry bed). A slurry bed that does not accumulate boiling-point hydrocarbons on the catalyst or concomitant reaction tube blockage is expected to be advantageous. However, in the generation source that emits carbon dioxide, when a conversion plant for hydrocarbons is installed, the production amount of hydrocarbons is reduced compared to a conventional FT synthesis plant for natural gas fields. In this case, a microchannel reactor may be advantageous. The microchannel reactor has many ultrafine grooves and has recently attracted particular attention as a reactor that can be expected to improve the efficiency of chemical reactions.
一般的に触媒の活性は、高ければ高いほど好ましいことは言うまでもないが、特にスラリー床では、良好なスラリー流動状態を保持するためにはスラリー濃度を一定の値以下にする必要があるという制限が存在するため、触媒の高活性化は、プロセス設計の自由度を拡大する上で、非常に重要な要素となる。 In general, it is obvious that the higher the activity of the catalyst is, the more preferable it is. However, especially in the slurry bed, there is a restriction that the slurry concentration needs to be a certain value or less in order to maintain a good slurry flow state. Therefore, high activation of the catalyst is a very important factor in expanding the degree of freedom in process design.
また、一般的に触媒の粒子径は、熱や物質の拡散が律速となる可能性を低くするという観点からは、小さいほど好ましい。しかし、スラリー床による炭化水素の製造では、生成する炭化水素の内、高沸点炭化水素は反応容器内に蓄積されるため、触媒と生成物との固液分離操作が必ず必要になることから、触媒の粒子径が小さ過ぎる場合、分離操作の効率が大きく低下するという問題が発生する。よって、スラリー床用の触媒には最適な粒子径範囲が存在することになり、一般的に２０〜２５０μｍ程度、平均粒径として４０〜１５０μｍ程度が好ましいとされているが、以下に示すように、反応中に触媒が破壊、粉化を起こして、粒子径が小さくなることがあり、注意が必要である。 In general, the particle diameter of the catalyst is preferably as small as possible from the viewpoint of reducing the possibility that the diffusion of heat or substance becomes rate-limiting. However, in the production of hydrocarbons using a slurry bed, among the hydrocarbons produced, high boiling point hydrocarbons accumulate in the reaction vessel, so a solid-liquid separation operation between the catalyst and the product is indispensable. When the particle diameter of the catalyst is too small, there arises a problem that the efficiency of the separation operation is greatly reduced. Therefore, there is an optimum particle size range for the catalyst for the slurry bed, and it is generally preferred that the average particle size is about 20 to 250 μm and the average particle size is about 40 to 150 μm. The catalyst may be destroyed or pulverized during the reaction, and the particle size may be reduced.
即ち、スラリー床では相当高い原料ガス空塔速度（０．１ｍ／秒以上）で運転されることが多く、触媒粒子は反応中に激しく衝突するため、触媒粒子の物理的な強度や耐摩耗性（耐粉化性）が不足すると、反応中に触媒粒径が低下して、上記分離操作に不都合をきたすことがある。更に、スラリー床では液媒体として有機物を使用するが、炭素源として二酸化炭素、一酸化炭素のいずれを使用する場合でも多量の水を副生するため、耐水性が低く、水により強度低下や破壊、粉化を起こし易い触媒を用いる場合は、反応中に触媒粒径が細かくなることがあり、上記と同様に分離操作に不都合をきたすことになる。 That is, the slurry bed is often operated at a considerably high raw material gas superficial velocity (0.1 m / second or more), and the catalyst particles collide violently during the reaction, so that the physical strength and wear resistance of the catalyst particles are increased. If (dust resistance) is insufficient, the catalyst particle size may decrease during the reaction, which may cause inconvenience in the separation operation. In addition, organic substances are used as the liquid medium in the slurry bed, but even if carbon dioxide or carbon monoxide is used as a carbon source, a large amount of water is by-produced, so the water resistance is low, and the strength is reduced or destroyed by water. When a catalyst that easily causes pulverization is used, the particle size of the catalyst may become fine during the reaction, resulting in inconvenience in the separation operation as described above.
また、一般的に、スラリー床用の触媒は、上記したような最適粒径となるように粉砕して粒度調整をして実用に供することが多い。ところが、このような破砕状の触媒には予亀裂が入っていたり、鋭角な突起が生じていたりすることが多く、機械的強度や耐摩耗性に劣る。そのため、破砕状の触媒をスラリー床に用いた場合には、触媒が破壊して微粉が発生することになり、生成する高沸点炭化水素と触媒との分離が著しく困難になるという欠点を有していた。 In general, the catalyst for the slurry bed is often put to practical use after being pulverized to adjust the particle size so as to have the optimum particle size as described above. However, such a crushed catalyst is often pre-cracked or has a sharp protrusion, and is inferior in mechanical strength and wear resistance. Therefore, when a crushed catalyst is used in the slurry bed, the catalyst is destroyed and fine powder is generated, and it is difficult to separate the produced high boiling point hydrocarbon from the catalyst. It was.
また、二酸化炭素と水素を原料として炭化水素を製造する反応においては、一酸化炭素と水素を原料として炭化水素を製造する反応と比較して副生する水の量が多くなる。一般的に炭化水素製造のための触媒の活性種は金属状態であることから、炭化水素の原料として二酸化炭素を用いる場合は、副生する水と金属状態の活性種が反応して金属酸化物に変化することによる触媒失活が起こり易くなる。
以下に、一酸化炭素と水素を原料とした炭化水素の製造時の化学反応式と、二酸化炭素と水素を原料とした炭化水素の製造時の化学反応式を示す。
In addition, in the reaction for producing hydrocarbons using carbon dioxide and hydrogen as raw materials, the amount of water produced as a by-product is increased compared to the reaction for producing hydrocarbons using carbon monoxide and hydrogen as raw materials. In general, the active species of catalysts for hydrocarbon production are in the metal state. Therefore, when carbon dioxide is used as a hydrocarbon raw material, the by-product water reacts with the active species in the metal state to produce metal oxides. The catalyst deactivation due to the change to is likely to occur.
The chemical reaction formula at the time of manufacturing hydrocarbons using carbon monoxide and hydrogen as raw materials and the chemical reaction formula at the time of manufacturing hydrocarbons using carbon dioxide and hydrogen as raw materials are shown below.
上述したように、二酸化炭素と水素を原料とする炭化水素の製造においては、触媒性能に及ぼす因子に関する知見は十分ではない。その上、一酸化炭素と水素を原料とする炭化水素の製造時と同等の転化率で比較すると、二酸化炭素と水素を原料とする場合の反応では副生する水が多い状況となる。このような反応における触媒活性は未だ十分ではない上、鉄系触媒では炭素数が５以上（Ｃ５以上）の液状生成物は得られるものの反応温度が３００℃程度と厳しく、一方、コバルト系触媒を使用すると反応温度は２２０℃程度と比較的緩やかになるもののＣ５以上の液状生成物の生成量はわずかという状況である。このような状況下から、炭化水素への変換プラントの設計自由度を拡大する観点からも、二酸化炭素と水素を原料とした炭化水素の製造時に使用可能な高性能触媒の開発が急務である。
即ち、本発明は、十分なＣ５以上の液状生成物が製造可能であり、活性、選択性、耐久性の高い、二酸化炭素と水素から炭化水素を製造する触媒の製造方法、及び、当該触媒を用いた二酸化炭素と水素から炭化水素を製造する方法を提供することを目的とする。
As described above, in the production of hydrocarbons using carbon dioxide and hydrogen as raw materials, knowledge about factors affecting catalyst performance is not sufficient. In addition, when compared at the same conversion rate as in the production of hydrocarbons using carbon monoxide and hydrogen as raw materials, the reaction when carbon dioxide and hydrogen are used as raw materials has a large amount of water by-produced. The catalytic activity in such a reaction is not yet sufficient, and an iron-based catalyst can produce a liquid product having 5 or more carbon atoms (C5 or more), but the reaction temperature is as severe as about 300 ° C. When used, the reaction temperature becomes relatively low at about 220 ° C., but the amount of liquid product of C5 or higher is small. Under such circumstances, it is urgent to develop a high-performance catalyst that can be used in the production of hydrocarbons using carbon dioxide and hydrogen as raw materials from the viewpoint of expanding the degree of freedom in designing a conversion plant for hydrocarbons.
That is, the present invention is capable of producing a sufficient liquid product of C5 or higher, and having a high activity, selectivity, and durability, a method for producing a catalyst for producing hydrocarbons from carbon dioxide and hydrogen, and the catalyst. It aims at providing the method of manufacturing a hydrocarbon from the carbon dioxide and hydrogen which were used.
本発明者らは、シリカを主体とする触媒担体にコバルト成分が担持される触媒を、酢酸コバルトを主体とする前駆体溶液を用いて製造するとともに、前駆体溶液のｐＨを適正範囲に調整することにより、二酸化炭素と水素を原料とする炭化水素の製造において触媒の活性、耐久性が向上し、炭素数５以上の液状炭化水素を十分に製造できることを見出し、本発明に至った。 The present inventors produce a catalyst in which a cobalt component is supported on a catalyst carrier mainly composed of silica using a precursor solution mainly composed of cobalt acetate, and adjust the pH of the precursor solution to an appropriate range. As a result, it has been found that the activity and durability of the catalyst are improved in the production of hydrocarbons using carbon dioxide and hydrogen as raw materials, and liquid hydrocarbons having 5 or more carbon atoms can be sufficiently produced, leading to the present invention.
本発明は、二酸化炭素と水素からの炭化水素の製造時に使用する、高い活性、選択性、耐久性を有する触媒の製造方法及び該触媒を用いた炭化水素の製造方法に関する。更に詳しくは、以下に記す通りである。 The present invention relates to a method for producing a catalyst having high activity, selectivity and durability, which is used when producing a hydrocarbon from carbon dioxide and hydrogen, and a method for producing a hydrocarbon using the catalyst. Further details are as described below.
（１）シリカを主成分とする触媒担体に、コバルトを担持させる際に、酢酸コバルトを主体とする前駆体溶液を用いて前記触媒担体に担持する工程を有し、前記酢酸コバルトを主体とする前駆体溶液のｐＨが４．０〜７．３であることを特徴とする、二酸化炭素と水素から炭化水素を製造する触媒の製造方法。
（２）前記触媒中のナトリウム、カリウム、カルシウム、及びマグネシウムの含有量合計が０．０８〜３．５質量％であることを特徴とする上記（１）に記載の二酸化炭素と水素から炭化水素を製造する触媒の製造方法。
（３）前記触媒中のナトリウム、カリウム、カルシウム、及びマグネシウムの含有量合計が０．１５〜３．５質量％であることを特徴とする上記（１）に記載の二酸化炭素と水素から炭化水素を製造する触媒の製造方法。
（４）前記酢酸コバルトを主体とする前駆体が酢酸塩であることを特徴とする上記（１）〜（３）のいずれか１項に記載の二酸化炭素と水素から炭化水素を製造する触媒の製造方法。
（５）前記酢酸コバルトを主体とする前駆体が酢酸塩及び硝酸塩であり、前記酢酸コバルトを主体とする前駆体溶液のｐＨが４．０〜７．３の範囲であることを特徴とする上記（１）〜（４）のいずれか１項に記載の二酸化炭素と水素から炭化水素を製造する触媒の製造方法。
（６）前記触媒担体中のナトリウム、カリウム、カルシウム、及びマグネシウムの含有量の合計が、金属換算で０．０８〜２．０質量％であることを特徴とする上記（１）〜（５）のいずれか１項に記載の二酸化炭素と水素から炭化水素を製造する触媒の製造方法。
（７）前記触媒担体中のナトリウムの含有量が、金属換算で０．２〜１．９質量％であることを特徴とする上記（１）〜（６）のいずれか１項に記載の二酸化炭素と水素から炭化水素を製造する触媒の製造方法。
（８）上記（１）〜（７）のいずれかに記載の製造方法にて製造した触媒を用いた反応により、二酸化炭素と水素から炭化水素を製造する方法。
（９）前記反応がスラリー床を用いた液相反応であることを特徴とする上記（８）に記載の二酸化炭素と水素から炭化水素を製造する方法。
(1) When cobalt is supported on a catalyst carrier mainly composed of silica, the catalyst carrier has a step of supporting the catalyst carrier using a precursor solution mainly composed of cobalt acetate, and mainly composed of the cobalt acetate. A method for producing a catalyst for producing hydrocarbons from carbon dioxide and hydrogen, wherein the pH of the precursor solution is 4.0 to 7.3.
(2) The total content of sodium, potassium, calcium, and magnesium in the catalyst is 0.08 to 3.5% by mass, and the hydrocarbons from carbon dioxide and hydrogen according to (1) above The manufacturing method of the catalyst which manufactures.
(3) The total content of sodium, potassium, calcium, and magnesium in the catalyst is 0.15 to 3.5% by mass, and the hydrocarbon from carbon dioxide and hydrogen according to (1) above The manufacturing method of the catalyst which manufactures.
(4) The catalyst for producing hydrocarbons from carbon dioxide and hydrogen according to any one of (1) to (3) above, wherein the precursor mainly composed of cobalt acetate is acetate. Production method.
(5) The precursor characterized in that the precursor mainly composed of cobalt acetate is acetate and nitrate, and the pH of the precursor solution mainly composed of cobalt acetate is in the range of 4.0 to 7.3. The manufacturing method of the catalyst which manufactures a hydrocarbon from the carbon dioxide and hydrogen of any one of (1)-(4).
(6) The total content of sodium, potassium, calcium and magnesium in the catalyst carrier is 0.08 to 2.0% by mass in terms of metal, (1) to (5) above The manufacturing method of the catalyst which manufactures a hydrocarbon from the carbon dioxide and hydrogen of any one of these.
(7) The content of sodium in the catalyst carrier is 0.2 to 1.9% by mass in terms of metal, and the dioxide as described in any one of (1) to (6) above A method for producing a catalyst for producing hydrocarbons from carbon and hydrogen.
(8) A method for producing a hydrocarbon from carbon dioxide and hydrogen by a reaction using the catalyst produced by the production method according to any one of (1) to (7) above.
(9) The method for producing hydrocarbons from carbon dioxide and hydrogen as described in (8) above, wherein the reaction is a liquid phase reaction using a slurry bed.
本発明によると、二酸化炭素と水素を原料とする炭化水素の製造時に使用することができ、反応温度が低くても活性、Ｃ５以上の液状炭化水素の選択性に優れ、耐久性の高い触媒の製造方法、及び、当該触媒を用いた二酸化炭素と水素から炭化水素を製造する方法を提供することができる。従って、本発明の製造方法によって製造された触媒は、耐久性が高く、比較的低い反応温度でも十分な活性を発揮できるため、十分な量の炭化水素を生産することが可能となる。 According to the present invention, a catalyst that can be used in the production of hydrocarbons using carbon dioxide and hydrogen as raw materials, is active even when the reaction temperature is low, has excellent selectivity for liquid hydrocarbons of C5 or higher, and has high durability. A production method and a method for producing hydrocarbons from carbon dioxide and hydrogen using the catalyst can be provided. Therefore, the catalyst produced by the production method of the present invention has high durability and can exhibit sufficient activity even at a relatively low reaction temperature, so that a sufficient amount of hydrocarbons can be produced.
以下、本発明の、二酸化炭素を水素から炭化水素を製造する触媒の製造方法、ならびに二酸化炭素と水素からから炭化水素を製造する方法の実施形態を更に詳述する。 Hereinafter, embodiments of the method for producing a catalyst for producing hydrocarbons from carbon dioxide and hydrogen and the method for producing hydrocarbons from carbon dioxide and hydrogen according to the present invention will be described in more detail.
まず、二酸化炭素と水素から炭化水素を製造する触媒の製造方法（以下、単に触媒の製造方法とも称する。）によって製造する触媒について説明する。
本実施形態の製造方法によって製造する触媒は、二酸化炭素と水素を原料とする炭化水素製造時の化学反応に活性を有する金属としてコバルトを含むものである。すなわち、触媒活性種としてコバルト成分を触媒担体に担持してなるものである。
また、触媒担体としては、シリカを主成分とするものである。ここでいうシリカを主成分とする担体（以下、シリカ担体とも称する。）とは、シリカ含有量が５０質量％以上で１００質量％未満のものであり、シリカ以外にアルミナを含有するシリカ−アルミナ担体や、シリカ担体の製造工程における不可避的不純物を少量含むものであっても構わない。触媒中、及び触媒担体中のシリカ含有量の測定方法は、酸分解やアルカリ溶融等の前処理後にＩＣＰ発光分光分析法（ＩＣＰ−ＡＥＳ法）にて測定する方法とする。
First, a catalyst produced by a production method of a catalyst for producing hydrocarbons from carbon dioxide and hydrogen (hereinafter also simply referred to as a catalyst production method) will be described.
The catalyst produced by the production method of the present embodiment contains cobalt as a metal having activity in a chemical reaction during hydrocarbon production using carbon dioxide and hydrogen as raw materials. That is, a cobalt component is supported on a catalyst carrier as a catalytically active species.
Further, the catalyst carrier is mainly composed of silica. The carrier having silica as a main component (hereinafter also referred to as a silica carrier) is a silica-alumina having a silica content of 50% by mass or more and less than 100% by mass and containing alumina in addition to silica. The carrier or the silica carrier may contain a small amount of inevitable impurities in the production process. The method for measuring the silica content in the catalyst and in the catalyst carrier is a method of measuring by ICP emission spectroscopic analysis (ICP-AES method) after pretreatment such as acid decomposition or alkali melting.
触媒中には、ナトリウム、カリウム、カルシウム、及びマグネシウムが含まれる場合があり、これら元素は各製造工程において混入してしまうものであるが、特に触媒担体の製造工程においては、ナトリウム、カリウム、カルシウム、及びマグネシウムは当該工程で使用される洗浄水に含有されるものや、シリカ担体の出発原料に含有される金属によるものがある。 The catalyst may contain sodium, potassium, calcium, and magnesium, and these elements are mixed in each manufacturing process. In particular, in the manufacturing process of the catalyst support, sodium, potassium, calcium. , And magnesium may be contained in the washing water used in the process, or may be due to the metal contained in the starting material of the silica support.
また、触媒担体にコバルト等の金属系化合物を担持する工程の際には、ナトリウム、カリウム、カルシウム、及びマグネシウムは、担持する金属系化合物の前駆体や、担持の際の処理水や洗浄水、担持後の乾燥工程や焼成工程で入り込む可能性がある。
従来では、これらナトリウム、カリウム、カルシウム、及びマグネシウム等は活性低下を招く不純物元素として、触媒中の含有量を極力低減するようされてきた。しかしながら本発明者らの検討の結果、二酸化炭素を水素から炭化水素を製造するための触媒が、ナトリウム、カリウム、カルシウム、マグネシウム等のアルカリ金属及びアルカリ土類金属を適切な範囲で含有することで、液状生成物の選択率が向上することが分かった。なお、触媒性能へ最も影響が大きいのは、アルカリ金属のナトリウム、及びカリウムであり、次に影響が大きいのはアルカリ土類金属のカルシウムとマグネシウムである。
In the process of supporting a metal compound such as cobalt on the catalyst support, sodium, potassium, calcium, and magnesium are precursors of the metal compound to be supported, treated water and washing water at the time of loading, There is a possibility of entering in a drying process or a baking process after loading.
Conventionally, sodium, potassium, calcium, magnesium and the like have been tried to reduce the content in the catalyst as much as possible as impurity elements that cause a decrease in activity. However, as a result of the study by the present inventors, the catalyst for producing hydrocarbons from carbon dioxide from hydrogen contains alkali metals and alkaline earth metals such as sodium, potassium, calcium and magnesium in an appropriate range. It has been found that the selectivity of the liquid product is improved. It is to be noted that alkali metals sodium and potassium have the largest influence on the catalyst performance, and alkaline earth metals calcium and magnesium have the next largest influence.
以上述べたように、本実施形態の製造方法によって製造する触媒においては、ナトリウム、カリウム、カルシウム、及びマグネシウムの合計含有量を適切な範囲に制御することが好ましい。これらのうち、カリウムは、シリカを主成分とする担体から製造した触媒中には、ごく僅かしか含まれていないことが多く、ナトリウム、カルシウム、マグネシウムの含有量が比較的多い。なお、これらの不純物金属は、酸化物等の化合物となって存在するものも多いが、全て金属換算した量で含有量を算出する。
触媒中において、ナトリウム、カリウム、カルシウム、及びマグネシウムの総含有量は、活性低下の抑制ならびに選択性の向上のバランスを考慮して、０．０８〜３．５質量％（８００〜３５０００ｐｐｍ）が好ましく、より好ましくは０．１５〜３．５質量％、更に好ましくは０．２〜２．０質量％、最も好ましくは０．２〜１．２質量％である。なお、ナトリウム、カリウム、カルシウム、及びマグネシウムの含有量は総含有量であり、これらの中でいずれかが含まれない場合もあるが、その場合においてもこれらの総含有量が０．０８〜３．５質量％であると好ましい。
As described above, in the catalyst produced by the production method of the present embodiment, it is preferable to control the total content of sodium, potassium, calcium, and magnesium within an appropriate range. Of these, potassium is often very little contained in a catalyst produced from a carrier mainly composed of silica, and the contents of sodium, calcium and magnesium are relatively high. In addition, although many of these impurity metals exist as compounds such as oxides, the content is calculated in an amount converted into metal.
In the catalyst, the total content of sodium, potassium, calcium, and magnesium is preferably 0.08 to 3.5% by mass (800 to 35000 ppm) in consideration of the balance between suppressing the decrease in activity and improving the selectivity. More preferably, it is 0.15-3.5 mass%, More preferably, it is 0.2-2.0 mass%, Most preferably, it is 0.2-1.2 mass%. In addition, content of sodium, potassium, calcium, and magnesium is a total content, and any of these may not be included, but even in that case, the total content is 0.08 to 3 .5% by mass is preferable.
次に、本実施形態の触媒の製造方法について説明する。
本実施形態の触媒の製造方法は、シリカを主成分とする触媒担体に、酢酸コバルトを主体とする前駆体溶液を用いて、コバルト成分を担持する工程を有する。
シリカを主成分とする担体へコバルト成分を担持する方法は、通常の含浸法、インシピエントウェットネス（Ｉｎｃｉｐｉｅｎｔ Ｗｅｔｎｅｓｓ）法、沈殿法、イオン交換法等によればよい。担持において使用する原料（前駆体）であるコバルト成分は、酢酸コバルトを主体とするものである。
Next, the manufacturing method of the catalyst of this embodiment is demonstrated.
The manufacturing method of the catalyst of this embodiment has the process of carrying | supporting a cobalt component on the catalyst support | carrier which has a silica as a main component, using the precursor solution which has cobalt acetate as a main component.
A method for supporting a cobalt component on a carrier containing silica as a main component may be a normal impregnation method, an incipient wetness method, a precipitation method, an ion exchange method, or the like. The cobalt component, which is a raw material (precursor) used for loading, is mainly composed of cobalt acetate.
本実施形態による触媒の製造方法は、シリカ担体に対し、コバルト前駆体溶液のｐＨが４．０〜７．３の範囲になるように調整した上でコバルト成分を担持するものである。
コバルト前駆体溶液のｐＨを上記範囲に調整することにより、触媒担体全体に渡り、均質な分散をさせることが可能となる。コバルト前駆体溶液のｐＨが４．０未満となると、コバルト担持後の触媒ではコバルトが触媒担体に不均質に担持されることになり、二酸化炭素から炭化水素を製造する反応において副生する水が存在する雰囲気下では、近接したコバルト粒子が合体凝集（シンタリング）を起こしやすく、反応表面積の低下等により長時間安定した活性を示すことが不可能になる。一方、コバルト前駆体溶液のｐＨが７．３を超えると、シリカ担体自体の溶解、溶出が起こり、コバルトが担持されるべき細孔が減ること等により、コバルト粒子が不均質に担持されてしまうため、同様に、反応中の高い副生水分圧下では、コバルト粒子のシンタリングが起こって、長時間の安定した活性を示すことが不可能になる。そのため、コバルト前駆体溶液のｐＨは４．０以上、７．３以下とし、好ましくは４．５以上、７．３以下とし、さらに好ましくは５．０以上、７．３以下とする。
In the method for producing a catalyst according to the present embodiment, the cobalt component is supported on the silica support after adjusting the pH of the cobalt precursor solution to be in the range of 4.0 to 7.3.
By adjusting the pH of the cobalt precursor solution to the above range, it is possible to achieve uniform dispersion over the entire catalyst support. When the pH of the cobalt precursor solution is less than 4.0, cobalt is supported on the catalyst support in a non-homogeneous manner in the catalyst after supporting the cobalt, and water produced as a by-product in the reaction for producing hydrocarbons from carbon dioxide is generated. Under the existing atmosphere, adjacent cobalt particles are likely to cause coalescence aggregation (sintering), and it becomes impossible to exhibit stable activity for a long time due to a reduction in the reaction surface area or the like. On the other hand, when the pH of the cobalt precursor solution exceeds 7.3, dissolution and elution of the silica support itself occurs, resulting in a decrease in the number of pores on which cobalt is to be supported. Therefore, similarly, under high by-product water pressure during the reaction, sintering of the cobalt particles occurs, and it becomes impossible to show stable activity for a long time. Therefore, the pH of the cobalt precursor solution is 4.0 or more and 7.3 or less, preferably 4.5 or more and 7.3 or less, and more preferably 5.0 or more and 7.3 or less.
酢酸コバルトを主体する前駆体溶液を用いてコバルト成分を担体に担持させる方法について説明する。
まず、酢酸コバルトを主体する前駆体としては、酢酸塩からなるものを用いることが好ましく、または酢酸塩及び硝酸塩からなるものを用いることも好ましい。
具体的には、コバルト化合物である、酢酸コバルト、硝酸コバルト、ギ酸コバルト、シュウ酸コバルト、塩化コバルト、炭酸コバルト、硫酸コバルトからなる群のうち、酢酸コバルトを少なくとも含み、かつ酢酸コバルトが重量比で過半となるような割合で混合した混合物を用い、この混合物を溶媒に溶解させた溶液をコバルト前駆体溶液とする。そしてこのコバルト前駆体溶液を用いて、シリカを主成分とする担体に担持する。ここで、混合物を溶解させる溶媒としては、上記コバルト化合物を溶解することができ、かつ最終的な５００℃前後の焼成工程で除去できるものであればよく、例えば、水やアルコール、有機酸などを好適に用いることができる。
A method for supporting a cobalt component on a carrier using a precursor solution mainly composed of cobalt acetate will be described.
First, as a precursor mainly composed of cobalt acetate, it is preferable to use one made of acetate, or one made from acetate and nitrate.
Specifically, among the group consisting of cobalt acetate, cobalt nitrate, cobalt nitrate, cobalt formate, cobalt oxalate, cobalt chloride, cobalt carbonate, and cobalt sulfate, at least cobalt acetate, and cobalt acetate in weight ratio. A mixture in which the mixture is mixed at a ratio such that it is a majority is used as a cobalt precursor solution. Then, the cobalt precursor solution is used to carry it on a carrier mainly composed of silica. Here, the solvent for dissolving the mixture may be any solvent that can dissolve the cobalt compound and can be removed in the final baking process at around 500 ° C., for example, water, alcohol, organic acid, and the like. It can be used suitably.
コバルト前駆体溶液のｐＨを４．０〜７．３の範囲に調整する方法について説明する。
酢酸コバルトを主体とするコバルト化合物を溶解させた時点の溶液のｐＨは、その溶解量に比例するものの、一般にはｐＨが４．０を下回ると予想される。その場合にはアルカリ溶液を適宜混合することでｐＨを調整する方法などが挙げられる。しかしながら、前述のシリカ担体中の不純物として触媒活性に悪影響を及ぼす元素であるアルカリ金属、中でもナトリウム、カリウムが成分中に含まれる化合物を溶解させたアルカリ溶液は適当でなく、例えば、硝酸アンモニウム、エチレンジアミン四酢酸やテトラメチルアンモニウムを水に溶解させたものやアンモニア水溶液などが好適に用いられる。また、本前駆体溶液中のｐＨを測定する手法としては、一般的な手法で測定することが可能であるが、例えば、ｐＨメーター等を好適に用いることができる。
A method for adjusting the pH of the cobalt precursor solution to a range of 4.0 to 7.3 will be described.
Although the pH of the solution at the time when the cobalt compound mainly composed of cobalt acetate is dissolved is proportional to the amount of dissolution, it is generally expected that the pH is lower than 4.0. In that case, the method of adjusting pH by mixing an alkali solution suitably is mentioned. However, an alkali solution in which a compound containing an alkali metal, particularly sodium or potassium, which is an element having an adverse effect on the catalytic activity as an impurity in the silica support, is not suitable. For example, ammonium nitrate, ethylenediamine A solution in which acetic acid or tetramethylammonium is dissolved in water or an aqueous ammonia solution is preferably used. Moreover, as a method for measuring the pH in the precursor solution, it can be measured by a general method. For example, a pH meter or the like can be preferably used.
コバルト成分の担持後は必要に応じて乾燥処理を行い、引き続き還元処理、又は焼成処理及び還元処理を行う。 After loading the cobalt component, a drying process is performed as necessary, followed by a reduction process, or a firing process and a reduction process.
コバルトの担持率は、５〜５０質量％であり、好ましくは１０〜４０質量％である。この範囲を下回ると活性を十分発現しない場合があり、また、この範囲を上回ると分散度が低下して、担持したコバルトの利用効率が低下することがあり、不経済となるため、好ましくない。ここでいうコバルトの担持率とは、担持したコバルトが最終的に１００％還元されるとは限らないため、１００％還元されたと考えた場合の金属コバルトの質量が触媒質量全体に占める割合を指す。触媒中のコバルトの定量方法は、酸分解やアルカリ溶融等の前処理後にＩＣＰ−ＡＥＳ法にて測定する方法とする。 The loading rate of cobalt is 5-50 mass%, Preferably it is 10-40 mass%. If the content is below this range, the activity may not be sufficiently expressed. If the content is above this range, the degree of dispersion may be reduced, and the utilization efficiency of the supported cobalt may be reduced, which is not preferable. The cobalt loading rate here refers to the ratio of the mass of metallic cobalt to the total mass of the catalyst when it is assumed that the loaded cobalt is not 100% reduced in the end. . The cobalt in the catalyst is quantified by the ICP-AES method after pretreatment such as acid decomposition or alkali melting.
上述のようにして得られた触媒の寿命延長効果（耐久性）を評価する方法としては、触媒をオートクレーブに溶媒と共に仕込み強撹拌状態として、二酸化炭素と水素を供給しながら昇温・昇圧することでオートクレーブ内を完全混合状態に保ちながら炭化水素を製造する反応を行い、断続的に撹拌を停止する手法が挙げられる。完全混合状態では、活性点で副生した水は直ちに原料ガス、生成ガスと混合されるが、撹拌を停止した状態では副生した水とガスとの混合が進まず、副生した水は活性点近傍に滞留することになり、水への耐性が低い触媒は急速に活性低下することとなる。撹拌停止によって触媒を活性低下させた後、再度撹拌を開始し、完全混合状態として触媒活性を評価し、撹拌停止前後での活性低下の度合を評価することで副生水への耐性を把握できる。 As a method for evaluating the life extension effect (durability) of the catalyst obtained as described above, the catalyst is charged into an autoclave together with a solvent, and the mixture is vigorously stirred and heated and heated while supplying carbon dioxide and hydrogen. And a method of performing a reaction for producing hydrocarbons while keeping the inside of the autoclave in a completely mixed state and intermittently stopping the stirring. In the fully mixed state, the water produced as a by-product at the active point is immediately mixed with the raw material gas and the product gas, but when the stirring is stopped, the by-product water and the gas are not mixed and the by-produced water is activated. The catalyst stays in the vicinity of the point, and the activity of the catalyst having low resistance to water is rapidly reduced. After reducing the activity of the catalyst by stopping the stirring, start stirring again, evaluate the catalyst activity as a complete mixing state, and evaluate the degree of the decrease in activity before and after stopping the stirring, so that the resistance to by-product water can be grasped .
その他には、高圧ポンプで強制的に水をオートクレーブ内に導入して、水分圧が高い条件を作り出す手法でも評価することができる。いずれも副生水への耐性は、水分圧を高い条件とした前後での活性の比率で評価する。 In addition, it can be evaluated by a method of forcibly introducing water into the autoclave with a high-pressure pump to create a condition with a high water pressure. In any case, the resistance to by-product water is evaluated by the ratio of the activity before and after the moisture pressure is high.
以下に、本実施形態の触媒を得る方法の一例を示す。
まず、酢酸コバルト水溶液を調製後、必要に応じて、酸性溶液を加えてｐＨが４．０〜７．３のコバルト前駆体溶液を調製する。次いで、該コバルト前駆体溶液を、シリカを主成分とする触媒担体に含浸させた後、乾燥、又は乾燥と焼成処理を行い、必要に応じて乾燥と還元処理、又は乾燥と焼成と還元処理を行うことで、二酸化炭素と水素を原料として炭化水素を製造する触媒を得ることができる。
Below, an example of the method of obtaining the catalyst of this embodiment is shown.
First, after preparing an aqueous cobalt acetate solution, an acidic solution is added as necessary to prepare a cobalt precursor solution having a pH of 4.0 to 7.3. Next, after impregnating the cobalt precursor solution into a catalyst carrier mainly composed of silica, drying or drying and firing treatment is performed, and drying and reduction treatment, or drying, firing and reduction treatment are performed as necessary. By carrying out, a catalyst for producing hydrocarbons using carbon dioxide and hydrogen as raw materials can be obtained.
コバルトの含浸を行った後、必要に応じて乾燥処理を行い、引き続き担体表面のコバルト化合物をコバルト金属に還元（例えば、常圧水素気流中４５０℃−１５ｈ、通常は２５０〜６００℃程度の範囲であるが、特に限定されない。）することで触媒が得られるが、焼成して酸化物に変化させた後にこの還元処理を行っても、焼成せずに直接還元処理を行ってもよい。 After impregnation with cobalt, if necessary, a drying treatment is performed, and then the cobalt compound on the surface of the support is reduced to cobalt metal (for example, 450 ° C. to 15 h in a normal pressure hydrogen stream, usually in a range of about 250 to 600 ° C. However, it is not particularly limited.) The catalyst can be obtained by performing the reduction treatment after calcination to change to an oxide, or the reduction treatment may be performed directly without calcination.
還元処理の温度を高くしたり時間を長くしたりすることにより還元条件を厳しくすると、還元処理後に金属系化合物が酸化物の状態から金属状態まで還元される比率が高くなり、さらに極端に厳しい還元処理を行うと活性金属のみの状態にすることも可能となる。しかし、一般的な還元条件ではコバルト酸化物を一部含有する化学状態となることが多い。 If the reduction conditions are tightened by increasing the temperature of the reduction treatment or lengthening the time, the ratio of reduction of the metal compound from the oxide state to the metal state after the reduction treatment increases, and the reduction becomes extremely severe. When the treatment is performed, it becomes possible to make only the active metal. However, in general reducing conditions, the chemical state often contains a part of cobalt oxide.
還元処理後の触媒は、大気に触れて酸化失活しないように取り扱う必要があるが、担体上のコバルト金属の表面を大気から遮断するような安定化処理を行うと、大気中での取り扱いが可能となり好適である。この安定化処理には、低濃度の酸素を含有する窒素、二酸化炭素、不活性ガスを触媒に触れさせて、担体上の活性金属の極表層のみを酸化するいわゆるパッシベーション（不動態化処理）を行ったり、二酸化炭素と水素を原料として炭化水素を製造する反応を液相で行う場合には反応溶媒や溶融したワックス等に浸漬して大気と遮断したりする方法があり、状況に応じて適切な安定化処理を行えばよい。 The catalyst after the reduction treatment must be handled so as not to be oxidized and deactivated by exposure to the atmosphere. However, if the stabilization treatment is performed to block the surface of the cobalt metal on the support from the atmosphere, the catalyst will not be handled in the atmosphere. It is possible and preferable. In this stabilization treatment, so-called passivation (passivation treatment) is performed in which only the extreme surface layer of the active metal on the support is oxidized by bringing nitrogen, carbon dioxide, and inert gas containing low concentrations of oxygen into contact with the catalyst. Or when the reaction to produce hydrocarbons using carbon dioxide and hydrogen as raw materials is conducted in the liquid phase, there are methods of immersing them in a reaction solvent or molten wax, etc. to shut off from the atmosphere. The stabilization process may be performed.
また、コバルト成分、担体構成元素以外の触媒中のアルカリ金属、アルカリ土類金属を所定の範囲内に制御することが、活性や液状炭化水素の選択性の向上および触媒コストに対して極めて効果的である。すなわち、触媒活性の低下を抑制するためには触媒中のアルカリ金属、アルカリ土類金属の含有量は低い方が望ましいが、極度に低減することは製造コスト面で望ましくない。その上、ナトリウム、カリウム、カルシウム、マグネシウムは液状炭化水素の選択性に好影響を及ぼす因子であることから、アルカリ金属、アルカリ土類金属の含有量は、これらの効果をバランスよく享受できるよう適正の範囲内に制御することが望ましい。
本実施形態のようにシリカを主成分とする担体では、前記したように、ナトリウム、カリウム、カルシウム、マグネシウムが担体中に含まれることが多い。活性、選択性への影響はナトリウム、カリウムが強く、中でもナトリウムの存在の影響が最も強い。すなわち、ナトリウム、カリウム、カルシウム、マグネシウムは、活性の低下を抑制する観点からはその含有量は少ない方が望ましいが、選択性を向上させる因子でもあることから、特にナトリウムはその含有量を適切な範囲となるよう制御することが望ましい。なお、カリウムは、上記作用の影響が強いものの、製造方法や担体の種類によって、担体中に存在しないことも多い。
In addition, controlling the alkali metal and alkaline earth metal in the catalyst other than the cobalt component and the carrier constituent element within a predetermined range is extremely effective for improving the activity and selectivity of liquid hydrocarbons and for the catalyst cost. It is. That is, in order to suppress a decrease in catalyst activity, it is desirable that the content of alkali metal and alkaline earth metal in the catalyst is low, but it is not desirable in terms of production cost to reduce it extremely. In addition, sodium, potassium, calcium, and magnesium are factors that have a positive effect on the selectivity of liquid hydrocarbons, so the content of alkali metals and alkaline earth metals is adequate to enjoy these effects in a balanced manner. It is desirable to control within the range.
In the carrier having silica as a main component as in the present embodiment, sodium, potassium, calcium, and magnesium are often contained in the carrier as described above. The influence on activity and selectivity is strong for sodium and potassium, and the presence of sodium is the strongest. In other words, sodium, potassium, calcium, and magnesium are preferably low in content from the viewpoint of suppressing the decrease in activity, but are also factors that improve selectivity, so sodium has an appropriate content. It is desirable to control the range. In addition, although potassium has the strong influence of the said effect | action, depending on a manufacturing method and the kind of support | carrier, it does not exist in a support | carrier often.
シリカを主成分とする触媒担体中のナトリウム、カリウム、カルシウム、及びマグネシウムの合計含有量は、金属換算で０．０８〜２．０質量％（８００〜２００００ｐｐｍ）が好ましく、より好ましくは０．２〜２．０質量％、更に好ましくは０．２〜１．２質量％である。触媒担体中のナトリウム、カリウム、カルシウム、及びマグネシウムの合計含有量が２．０質量％を上回ると、反応活性が低下するため、ナトリウム、カリウム、カルシウム、及びマグネシウムの合計含有量は２．０質量％以下とすることが好ましい。
また、前述のように、活性や選択性等の触媒性能へ最も影響が大きいのは、アルカリ金属のナトリウムである。そのため、本実施形態において、触媒担体中のナトリウムの含有量は、金属換算で０．２〜１．９質量％であることが好ましく、より好ましくは、０．２〜１．８質量％である。
なお、触媒担体中のナトリウム、カリウム、カルシウム、及びマグネシウムの含有量は、後に詳述するに、シリカ担体の製造時に使用する洗浄水を調整することで制御することが可能であるが、触媒担体中のこれら元素の含有量が上記範囲未満であっても、後述するように、担体に担持すること所望の含有量に調整することも可能である。
The total content of sodium, potassium, calcium, and magnesium in the catalyst carrier mainly composed of silica is preferably 0.08 to 2.0 mass% (800 to 20000 ppm), more preferably 0.2 in terms of metal. It is -2.0 mass%, More preferably, it is 0.2-1.2 mass%. If the total content of sodium, potassium, calcium, and magnesium in the catalyst support exceeds 2.0 mass%, the reaction activity decreases, so the total content of sodium, potassium, calcium, and magnesium is 2.0 mass. % Or less is preferable.
Further, as described above, the alkali metal sodium has the greatest influence on the catalyst performance such as activity and selectivity. Therefore, in the present embodiment, the content of sodium in the catalyst support is preferably 0.2 to 1.9% by mass in terms of metal, and more preferably 0.2 to 1.8% by mass. .
The contents of sodium, potassium, calcium, and magnesium in the catalyst carrier can be controlled by adjusting the washing water used during the production of the silica carrier, as will be described in detail later. Even if the content of these elements is less than the above range, as described later, it is possible to adjust the content to a desired content supported on a carrier.
また、コバルトの担持操作中に、少量であればナトリウム、カリウム、カルシウム、及びマグネシウムが混入してもよく、具体的には、上記のとおり金属換算で２．０質量％以下であれば許容される。また本実施形態にかかる触媒の製造方法においては、極端に純度の高いコバルト前駆体を使用せずとも一定の作用効果を享受できる。すなわち、ナトリウム、カリウム、カルシウム、及びマグネシウムの含有量が極度に低減された純度の高いコバルト前駆体を用いることは製造コストを徒に高めることとなるため、触媒コストの観点から一定量以上のナトリウム、カリウム、カルシウム、及びマグネシウムが含有されることが好ましい。また、液状炭化水素の選択性を向上させる観点から、ナトリウム、カリウム、カルシウム、及びマグネシウムの含有量を０．０８質量％以上とすることが好ましい。ここで、触媒担体中のナトリウム、カリウム、カルシウム、及びマグネシウムの定量方法としては、例えば酸分解やアルカリ溶融等の前処理後にＩＣＰ−ＡＥＳ法にて測定する方法が挙げられる。 In addition, during the cobalt loading operation, sodium, potassium, calcium, and magnesium may be mixed in a small amount. Specifically, as described above, it is acceptable if it is 2.0% by mass or less in terms of metal. The Moreover, in the manufacturing method of the catalyst concerning this embodiment, a fixed effect can be enjoyed even if it does not use an extremely high purity cobalt precursor. That is, using a high purity cobalt precursor with extremely reduced contents of sodium, potassium, calcium, and magnesium increases the manufacturing cost. Therefore, a certain amount or more of sodium is required from the viewpoint of catalyst cost. Preferably, potassium, calcium, and magnesium are contained. Moreover, it is preferable to make content of sodium, potassium, calcium, and magnesium into 0.08 mass% or more from a viewpoint of improving the selectivity of liquid hydrocarbon. Here, as a method for quantifying sodium, potassium, calcium, and magnesium in the catalyst carrier, for example, a method of measuring by ICP-AES method after pretreatment such as acid decomposition or alkali melting may be mentioned.
また、シリカを主成分とする触媒担体中のナトリウム、カリウム、カルシウム、及びマグネシウムの合計含有量が少ない場合には、これら成分を触媒担体に担持することで上記範囲内の含有量に調整することができる。
シリカを主成分とする担体へナトリウム、カリウム、カルシウム、及びマグネシウムを担持する方法は、通常の含浸法、インシピエントウェットネス（Ｉｎｃｉｐｉｅｎｔ Ｗｅｔｎｅｓｓ）法、沈殿法、イオン交換法等によればよい。担持において使用する原料（前駆体）としては、担持後に乾燥処理又は、乾燥処理及び焼成処理を行う際に、カウンターイオン（例えば炭酸ナトリウムであればＮａ２ＣＯ３中の（ＣＯ３）２−）が揮散するものであり、溶媒に溶解するものであれば特に制限はなく、硝酸塩、炭酸塩、酢酸塩等が使用可能であるが、担持操作をする際に水溶液を用いることができる水溶性の化合物を用いることが製造コストの低減や安全な製造作業環境の確保のためには好ましい。
When the total content of sodium, potassium, calcium, and magnesium in the catalyst support mainly composed of silica is small, the content should be adjusted to the above range by supporting these components on the catalyst support. Can do.
A method of supporting sodium, potassium, calcium, and magnesium on a carrier containing silica as a main component may be a normal impregnation method, an incipient wetness method, a precipitation method, an ion exchange method, or the like. The raw material (precursor) used in the loading is a counter ion (for example, (CO 3 ) 2− in Na 2 CO 3 in the case of sodium carbonate) when performing drying treatment or drying treatment and firing treatment after loading. Is volatilized and is not particularly limited as long as it dissolves in a solvent, and nitrates, carbonates, acetates, and the like can be used. It is preferable to use a compound in order to reduce the manufacturing cost and secure a safe manufacturing work environment.
このような担体を用いて製造する触媒中のナトリウム、カリウム、カルシウム、マグネシウムの総量としては０．０８〜３．５質量％が好ましい。触媒中の不純物量の定量方法は前記触媒担体中の方法と同様であり、酸分解やアルカリ溶融等の前処理後にＩＣＰ−ＡＥＳ法にて測定する。 The total amount of sodium, potassium, calcium and magnesium in the catalyst produced using such a carrier is preferably 0.08 to 3.5% by mass. The method for quantifying the amount of impurities in the catalyst is the same as the method in the catalyst carrier, and is measured by the ICP-AES method after pretreatment such as acid decomposition and alkali melting.
一般にシリカの製造方法は、乾式法と湿式法に大別される。乾式法としては燃焼法、アーク法等、湿式法としては沈降法、ゲル法等があり、いずれの製造方法でも触媒担体を製造することは可能である。しかしながら、ゲル法を除く上記方法では球状に成形することが技術的、経済的に困難である為、シリカゾルを気体媒体中又は液体媒体中で噴霧させて容易に球状に成形することが可能であるゲル法が好ましい。 In general, silica production methods are roughly classified into a dry method and a wet method. Examples of the dry method include a combustion method and an arc method, and examples of the wet method include a sedimentation method and a gel method. The catalyst carrier can be produced by any production method. However, since it is technically and economically difficult to form into a sphere in the above methods except the gel method, it is possible to easily form into a sphere by spraying silica sol in a gas medium or a liquid medium. The gel method is preferred.
例えば、上記ゲル法にてシリカ担体を製造する際には、製造工程で多量の硫酸ナトリウムが生成するため、これを取り除くために通常多量の洗浄水を用いる。一方、上述したようなアルカリ金属、アルカリ土類金属の不純物の含有量を適切な範囲とする観点からは、全く洗浄しない方法や、使用する洗浄水を極端に少なくすることで硫酸ナトリウムを適切な範囲で残存させる方法が考えられる。しかし、硫酸ナトリウムを多量に含有したシリカ担体は比表面積、細孔容積、細孔径の物性制御が困難となり、活性や触媒の機械特性が不安定となるおそれがある。従って、シリカ担体の物性も同時に適切な範囲とするためには、硫酸ナトリウムの除去が必要であり、多量の洗浄水を用いた洗浄工程が必要である。なおこの洗浄工程において、工業用水等のアルカリ金属、アルカリ土類金属を多く含んだ洗浄水のみを用いると、担体中に多量のアルカリ金属、アルカリ土類金属が残留することになり、シリカ担体中のナトリウム、カリウム、カルシウム、マグネシウムの含有量を上記範囲とすることが可能である。しかし、この洗浄工程において必ずしもナトリウム、カリウム、カルシウム、マグネシウムの含有量を確保しなければならないわけではないので、洗浄水としてイオン交換水等のアルカリ金属、アルカリ土類金属を全く含まないものを使用することもできる。洗浄水としてイオン交換水を用いる場合は、後述するように、シリカ担体を製造後に、ナトリウム、カリウム、カルシウム、マグネシウムの含有量を上記範囲となるよう担持させることができる。
このように、シリカ担体中のアルカリ金属、アルカリ土類金属の含有率制御の方法としては、適切な含有率の工業用水を選択する他、イオン交換水などのアルカリ金属、アルカリ土類金属を全く含まないものを工業用水と組み合わせて用いることもできる。
For example, when a silica carrier is produced by the gel method, a large amount of sodium sulfate is produced in the production process, and thus a large amount of washing water is usually used to remove this. On the other hand, from the viewpoint of setting the content of alkali metal and alkaline earth metal impurities as described above to an appropriate range, sodium sulfate can be appropriately used by a method that does not clean at all, or by extremely reducing the amount of cleaning water used. A method of remaining in the range is conceivable. However, a silica support containing a large amount of sodium sulfate makes it difficult to control the physical properties of the specific surface area, pore volume, and pore diameter, and the activity and mechanical properties of the catalyst may become unstable. Therefore, in order to bring the physical properties of the silica support to an appropriate range at the same time, it is necessary to remove sodium sulfate, and a washing step using a large amount of washing water is necessary. In this cleaning step, if only cleaning water containing a large amount of alkali metal and alkaline earth metal such as industrial water is used, a large amount of alkali metal and alkaline earth metal will remain in the support, and the silica support The content of sodium, potassium, calcium, and magnesium can be within the above range. However, it is not always necessary to ensure the sodium, potassium, calcium, and magnesium contents in this washing process, so use washing water that does not contain alkali metals such as ion-exchanged water or alkaline earth metals at all. You can also When ion-exchanged water is used as the washing water, as described later, after the silica carrier is produced, it can be supported so that the contents of sodium, potassium, calcium, and magnesium are in the above range.
As described above, as a method for controlling the content of alkali metals and alkaline earth metals in the silica support, in addition to selecting industrial water having an appropriate content, alkali metals such as ion-exchanged water and alkaline earth metals are not used at all. What is not included can also be used in combination with industrial water.
洗浄工程によって、ナトリウム、カリウム、カルシウム、マグネシウムの含有量が適切な範囲を下回る場合には、シリカ担体を製造後、これら成分を担持することで含有させることができる。シリカを主成分とする担体へこれら成分を担持する方法は、通常の含浸法、インシピエントウェットネス（Ｉｎｃｉｐｉｅｎｔ Ｗｅｔｎｅｓｓ）法、沈殿法、イオン交換法等によればよい。担持において使用する原料（前駆体）である化合物としては、溶媒に溶解するものであれば特に制限はなく、硝酸塩、炭酸塩、酢酸塩、塩化物、水酸化物等が使用可能であるが、担持操作をする際に水溶液を用いることができる水溶性の化合物を用いることが製造コストの低減や安全な製造作業環境の確保のためには好ましい。なお、水溶液にした際にアルカリ性が強すぎるものは、シリカ担体を溶解させることがあるため、アルカリ性であっても弱いもの、例えば炭酸塩が好ましい。 When the contents of sodium, potassium, calcium, and magnesium are below an appropriate range by the washing step, they can be contained by supporting these components after producing the silica carrier. A method of supporting these components on a carrier containing silica as a main component may be a normal impregnation method, an incipient wetness method, a precipitation method, an ion exchange method, or the like. The compound that is a raw material (precursor) used in the support is not particularly limited as long as it is soluble in a solvent, and nitrates, carbonates, acetates, chlorides, hydroxides, and the like can be used. It is preferable to use a water-soluble compound that can be used as an aqueous solution during the carrying operation in order to reduce manufacturing costs and to ensure a safe manufacturing work environment. In addition, since the thing with too strong alkalinity when made into aqueous solution may dissolve a silica support | carrier, even if it is alkaline, a weak thing, for example, carbonate, is preferable.
シリカ担体は鉄、アルミニウム等のアルカリ金属、アルカリ土類金属以外の不純物が含まれることが多く、これら不純物の含有量を低下させることで触媒性能を向上させることが好ましい。
また、触媒中のナトリウム、カリウム、カルシウム、マグネシウムを適切な範囲に制御する方法としては、シリカ担体の製造段階においては、担体の物性制御の観点から、これらのアルカリ金属およびアルカリ土類金属を含めて可能な限り不純物量を低下させておき、その後に、アルカリ金属、アルカリ土類金属を担持させることが好ましい。
Silica supports often contain impurities other than alkali metals such as iron and aluminum and alkaline earth metals, and it is preferable to improve the catalyst performance by reducing the content of these impurities.
In addition, as a method for controlling sodium, potassium, calcium, and magnesium in the catalyst to an appropriate range, in the production stage of the silica support, these alkali metals and alkaline earth metals are included from the viewpoint of controlling the physical properties of the support. It is preferable to reduce the amount of impurities as much as possible, and then support an alkali metal or alkaline earth metal.
以上述べたような担体を用いて触媒を製造することにより、二酸化炭素と水素を原料として炭化水素を製造する反応において液状炭化水素の選択性や活性、耐久性を高めることができるため、液状炭化水素の生産量が高い触媒を得ることが可能となる。 By producing a catalyst using the carrier as described above, the selectivity, activity, and durability of liquid hydrocarbons can be increased in the reaction of producing hydrocarbons using carbon dioxide and hydrogen as raw materials. It is possible to obtain a catalyst having a high hydrogen production amount.
シリカ担体の物理性状としては特に限定されないが、触媒活性の観点からは、金属の分散度を高く保ち、さらに、担持したコバルト金属の反応に寄与する効率を向上させるためには、高比表面積の担体を使用することが好ましい。しかし、担体の比表面積を大きくするためには、気孔径を小さくする、細孔容積を大きくする必要があるものの、この二つの要因を増大させると、耐摩耗性や強度が低下することになるため、以下に示す範囲とすることが、活性、強度の両面から好ましい。すなわち、担体の物理性状としては、細孔径が８〜５０ｎｍ、比表面積が８０〜４５０ｍ２／ｇ、細孔容積が０．３〜２．０ｍＬ／ｇを同時に満足するものが、触媒用の担体として好適である。細孔径が８〜３０ｎｍ、比表面積が１００〜４００ｍ２／ｇ、細孔容積が０．４〜１．５ｍＬ／ｇを同時に満足するものであればより好ましく、細孔径が１０〜２０ｎｍ、比表面積が１５０〜３５０ｍ２／ｇ、細孔容積が０．４〜１．２ｍＬ／ｇを同時に満足するものであれば更に好ましい。上記の比表面積はＢＥＴ法で、細孔容積は水銀圧入法で測定することができる。また、細孔径はガス吸着法で測定することが可能である。 The physical properties of the silica support are not particularly limited, but from the viewpoint of catalytic activity, in order to keep the metal dispersibility high and further improve the efficiency of contributing to the reaction of the supported cobalt metal, a high specific surface area is required. It is preferred to use a carrier. However, in order to increase the specific surface area of the carrier, it is necessary to reduce the pore diameter and increase the pore volume. However, if these two factors are increased, the wear resistance and strength will be reduced. Therefore, the range shown below is preferable in terms of both activity and strength. That is, the physical properties of the carrier are those that simultaneously satisfy the pore diameter of 8 to 50 nm, the specific surface area of 80 to 450 m 2 / g, and the pore volume of 0.3 to 2.0 mL / g. It is suitable as. More preferably, the pore diameter is 8 to 30 nm, the specific surface area is 100 to 400 m 2 / g, and the pore volume is 0.4 to 1.5 mL / g at the same time. The pore diameter is 10 to 20 nm, the specific surface area. Is more preferably 150 to 350 m 2 / g and a pore volume satisfying 0.4 to 1.2 mL / g at the same time. The specific surface area can be measured by the BET method, and the pore volume can be measured by the mercury intrusion method. The pore diameter can be measured by a gas adsorption method.
二酸化炭素と水素を原料として炭化水素を製造する反応に十分な活性を発現する触媒を得るためには、触媒担体の比表面積は８０ｍ２／ｇ以上であることが望ましい。この比表面積を下回ると、担持した金属の分散度が低下してしまい、活性金属の反応への寄与効率が低下するため好ましくない。また、比表面積を４５０ｍ２／ｇ超とすると、細孔容積と細孔径が上記範囲を同時に満足することが困難となり好ましくない。そのため、触媒担体の比表面積は８０〜４５０ｍ２／ｇとすることが好ましい。 In order to obtain a catalyst that exhibits sufficient activity for the reaction of producing hydrocarbons using carbon dioxide and hydrogen as raw materials, the specific surface area of the catalyst carrier is desirably 80 m 2 / g or more. Below this specific surface area, the dispersity of the supported metal decreases, and the contribution efficiency to the reaction of the active metal decreases, which is not preferable. On the other hand, if the specific surface area exceeds 450 m 2 / g, it is difficult to satisfy the above ranges of the pore volume and the pore diameter, which is not preferable. Therefore, the specific surface area of the catalyst carrier is preferably 80 to 450 m 2 / g.
触媒担体の細孔径を小さくするほど比表面積を大きくすることが可能となるが、８ｎｍを下回ると、細孔内のガス拡散速度が水素と二酸化炭素では異なり、細孔の奥へ行くほど水素分圧が高くなるという結果を招き、メタン等の軽質炭化水素が多量に生成することになることに加えて、生成した炭化水素の細孔内拡散速度も低下し、結果として、見かけの反応速度を低下させることとなるため、細孔径は８ｎｍ以上とすることが好ましい。また、一定の細孔容積で比較を行うと、細孔径が大きくなるほど比表面積が低下するため、細孔径が５０ｎｍを超えると、比表面積を増大させることが困難となり、活性金属の分散度が低下してしまうため、細孔径は５０ｎｍ以下とすることが好ましい。 The specific surface area can be increased as the pore diameter of the catalyst support is reduced. However, if the diameter is less than 8 nm, the gas diffusion rate in the pore differs between hydrogen and carbon dioxide, and the hydrogen content increases toward the depth of the pore. As a result, the pressure increases, and a large amount of light hydrocarbons such as methane are produced. In addition, the diffusion rate of the produced hydrocarbons in the pores decreases, resulting in an apparent reaction rate. In order to reduce the pore diameter, the pore diameter is preferably 8 nm or more. In addition, when the comparison is made with a constant pore volume, the specific surface area decreases as the pore diameter increases. Therefore, when the pore diameter exceeds 50 nm, it is difficult to increase the specific surface area, and the dispersity of the active metal decreases. Therefore, the pore diameter is preferably 50 nm or less.
触媒担体の細孔容積は０．３〜２．０ｍＬ／ｇの範囲内にあるものが好ましい。触媒担体が０．３ｍＬ／ｇを下回るものでは、細孔径と比表面積が上記範囲を同時に満足することが困難となり好ましくなく、また、触媒担体の２．０ｍＬ／ｇを上回る値とすると、強度が低下してしまうため、好ましくない。 The pore volume of the catalyst support is preferably in the range of 0.3 to 2.0 mL / g. When the catalyst support is less than 0.3 mL / g, it is not preferable because the pore diameter and the specific surface area satisfy the above ranges at the same time, and when the value exceeds 2.0 mL / g of the catalyst support, Since it falls, it is not preferable.
前述したように、スラリー床を用いた液相反応用の触媒には、耐摩耗性、強度が要求される。また、二酸化炭素と水素を原料として炭化水素を製造する反応では、水が副生するために、水の存在下で破壊、粉化するような触媒又は担体を用いると、前述したような不都合が生じることになるために注意を要する。よって、予亀裂が入っている可能性が高く、鋭角な角が折損、剥離し易い破砕状の担体ではなく、球状の担体を用いた触媒が好ましい。球状の度合については、例えば、形状の複雑さを測る指標の１つであって、粒子を画像解析した際の二次元画像における面積と周囲長を元に数値で表現する円形度を用いて規定した場合、この円形度が０．７以上の担体が好ましい。球状の担体を製造する際には、一般的なスプレードライ法等の噴霧法を用いればよい。特に、２０〜２５０μｍ程度の粒径の球状シリカ担体を製造する際には、噴霧法が適しており、耐摩耗性、強度、耐水性に優れた球状シリカ担体が得られる。 As described above, wear resistance and strength are required for a catalyst for a liquid phase reaction using a slurry bed. In addition, in the reaction of producing hydrocarbons using carbon dioxide and hydrogen as raw materials, since water is by-produced, the use of a catalyst or carrier that breaks and pulverizes in the presence of water has the disadvantages described above. Care must be taken to make it happen. Therefore, a catalyst using a spherical support is preferable instead of a crushed support that is highly likely to have a pre-crack and has an acute angle that easily breaks and peels off. The degree of sphericity is specified using, for example, a degree of circularity expressed as a numerical value based on an area and a perimeter in a two-dimensional image when a particle is image-analyzed. In this case, a carrier having a circularity of 0.7 or more is preferable. When producing a spherical carrier, a spraying method such as a general spray drying method may be used. In particular, when producing a spherical silica carrier having a particle size of about 20 to 250 μm, a spraying method is suitable, and a spherical silica carrier excellent in wear resistance, strength and water resistance can be obtained.
本実施形態による製造方法によって製造した触媒は、高い耐久性を有するため、反応によって副生する水が流動上の滞留域において分圧が高くなるスラリー床の他、通常の固定床や、マイクロチャネル反応器での反応においても、副生水によって一定の分圧を持つため、良好な寿命特性を示す。 Since the catalyst produced by the production method according to the present embodiment has high durability, in addition to a slurry bed in which the partial pressure of water produced as a by-product of the reaction is increased in the flow retention region, a normal fixed bed or a microchannel reaction Even in the reaction in the vessel, since it has a constant partial pressure due to by-product water, it exhibits good life characteristics.
二酸化炭素を排出する発生源において、炭化水素への変換プラントを併設する比較的小規模なプラントの場合、極微細な溝を多数有するマイクロチャネル反応器が有利となる可能性が考えられるが、ミリオーダー以下の流路に触媒を充填することを考慮すると、スラリー床の場合と同様に、シリカ担体の粒径は２０〜２５０μｍ程度が好ましい。 In the case of a relatively small plant with a conversion plant for hydrocarbons that emits carbon dioxide, a microchannel reactor with a large number of extremely fine grooves may be advantageous. Considering that the catalyst is filled in the flow path below the order, the particle size of the silica support is preferably about 20 to 250 μm, as in the case of the slurry bed.
このようなシリカ担体の製造法を以下に例示する。
珪酸アルカリ水溶液と酸水溶液とを混合し、ｐＨが２〜１０．５となる条件で生成させたシリカゾルを、空気等の気体媒体中又は前記ゾルと不溶性の有機溶媒中へ噴霧してゲル化させ、次いで、酸処理、水洗、乾燥する。ここで、珪酸アルカリとしては珪酸ソーダ水溶液が好適で、Ｎａ２Ｏ：ＳｉＯ２のモル比は１：１〜１：５、シリカの濃度は５〜３０質量％が好ましい。用いる酸としては、硝酸、塩酸、硫酸、有機酸等が使用できるが、製造する際の容器への腐食を防ぎ、有機物が残留しないという観点からは、硫酸が好ましい。酸の濃度は１〜１０ｍｏｌ／Ｌが好ましく、この範囲を下回るとゲル化の進行が著しく遅くなり、また、この範囲を上回るとゲル化速度が速過ぎてその制御が困難となり、所望の物性値を得ることが難しくなるため、好ましくない。また、ゲル化させる際に有機溶媒中へ噴霧する方法を採用する場合には、有機溶媒として、ケロシン、パラフィン、キシレン、トルエン等を用いることができる。
A method for producing such a silica carrier is exemplified below.
A silica sol produced by mixing an alkali silicate aqueous solution and an acid aqueous solution and having a pH of 2 to 10.5 is gelled by spraying it in a gaseous medium such as air or an organic solvent insoluble in the sol. Then, acid treatment, washing with water and drying. Here, a sodium silicate aqueous solution is suitable as the alkali silicate, and the molar ratio of Na 2 O: SiO 2 is preferably 1: 1 to 1: 5, and the concentration of silica is preferably 5 to 30% by mass. As the acid to be used, nitric acid, hydrochloric acid, sulfuric acid, organic acid, and the like can be used, but sulfuric acid is preferable from the viewpoint of preventing corrosion of the container during production and leaving no organic matter. The concentration of the acid is preferably 1 to 10 mol / L, and if it falls below this range, the progress of gelation becomes remarkably slow. On the other hand, if it exceeds this range, the gelation rate becomes too fast and difficult to control, and the desired physical property value This is not preferable because it is difficult to obtain. Moreover, when employ | adopting the method sprayed in an organic solvent when making it gelatinize, kerosene, paraffin, xylene, toluene etc. can be used as an organic solvent.
以上、本実施形態に係る触媒の製造方法を説明してきたが、上記のような構成あるいは製造法を用いれば、強度や耐摩耗性を損なうことなく、高い活性を発現し、高い選択性を有する、二酸化炭素と水素を原料として炭化水素を製造する触媒の提供が可能となる。
また、このような触媒を用い、二酸化炭素と水素を原料として炭化水素を製造することにより、比較的低い反応温度でも十分な活性を発揮できるため、十分な量の炭化水素を生産することが可能となる。
As mentioned above, although the manufacturing method of the catalyst which concerns on this embodiment was demonstrated, if the above structures or manufacturing methods are used, it will express high activity, and will have high selectivity, without impairing intensity | strength and abrasion resistance. It is possible to provide a catalyst for producing hydrocarbons using carbon dioxide and hydrogen as raw materials.
In addition, by using such a catalyst and producing hydrocarbons using carbon dioxide and hydrogen as raw materials, sufficient activity can be exhibited even at relatively low reaction temperatures, so that a sufficient amount of hydrocarbons can be produced. It becomes.
なお、炭化水素への変換プラントとして、マイクロチャネル反応器ではない通常の固定床を採用する場合には、反応器内での圧力損失を勘案して、触媒はペレット状の形状に成型することが好ましく、例えば、シリカを主成分とする触媒担体を含有する前駆体を押出成型にて加工することが可能である。 In addition, when adopting a normal fixed bed that is not a microchannel reactor as a hydrocarbon conversion plant, the catalyst may be formed into a pellet shape in consideration of pressure loss in the reactor. Preferably, for example, a precursor containing a catalyst carrier mainly composed of silica can be processed by extrusion molding.
なお、本実施形態の炭化水素の製造方法で使用する二酸化炭素と水素の混合ガスには、二酸化炭素と水素の合計が全体の５０体積％以上であるガスが生産性の面から好ましく、特に、水素と二酸化炭素のモル比（水素／一酸化炭素）が０．５〜４．０の範囲であることが望ましい。これは、水素と二酸化炭素のモル比が０．５未満の場合には、原料ガス中の水素の存在量が少な過ぎるため、二酸化炭素の水素化反応が進み難く、生産性が高くならないためであり、一方、水素と二酸化炭素のモル比が４．０を超える場合には、原料ガス中の二酸化炭素の存在量が少な過ぎるため、触媒活性に関わらず液状炭化水素の生産性が高くならないためである。 The mixed gas of carbon dioxide and hydrogen used in the hydrocarbon production method of the present embodiment is preferably a gas having a total of 50% by volume or more of carbon dioxide and hydrogen from the viewpoint of productivity, The molar ratio of hydrogen to carbon dioxide (hydrogen / carbon monoxide) is preferably in the range of 0.5 to 4.0. This is because when the molar ratio of hydrogen to carbon dioxide is less than 0.5, the amount of hydrogen in the raw material gas is too small, so that the hydrogenation reaction of carbon dioxide is difficult to proceed and productivity is not increased. On the other hand, when the molar ratio of hydrogen to carbon dioxide exceeds 4.0, the amount of carbon dioxide in the raw material gas is too small, and the productivity of liquid hydrocarbons does not increase regardless of the catalyst activity. It is.
以下、実施例により本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
酢酸コバルト四水和物を前駆体として、コバルト濃度として５％の水溶液を調製し、さらに５ｍｏｌ／Ｌの硝酸水溶液を混合して、ｐＨが１．１〜７．０となるように調整した。この水溶液を用い、表１に示すような、シリカを主成分とする触媒担体（比表面積：３００ｍ２／ｇ、平均粒径：１００μｍ）にインシピエントウェットネス法でコバルト成分を担持した。なお、触媒担体中のナトリウム、カリウム、カルシウム、マグネシウムの含有量は、担体製造時の洗浄工程の制御することで調整した。
その後、乾燥処理、焼成処理、還元処理、パッシベーション処理を施し、触媒を調整した。得られた触媒Ａ〜Ｋについては表１〜３に示す通りである。
Using cobalt acetate tetrahydrate as a precursor, an aqueous solution having a cobalt concentration of 5% was prepared, and a 5 mol / L nitric acid aqueous solution was further mixed to adjust the pH to 1.1 to 7.0. Using this aqueous solution, a cobalt component was supported on a catalyst carrier (specific surface area: 300 m 2 / g, average particle size: 100 μm) mainly composed of silica as shown in Table 1 by the incipient wetness method. The contents of sodium, potassium, calcium, and magnesium in the catalyst carrier were adjusted by controlling the washing process during the production of the carrier.
Then, the drying process, the baking process, the reduction process, and the passivation process were performed, and the catalyst was adjusted. The obtained catalysts A to K are as shown in Tables 1 to 3.
触媒の反応性を評価するため、内容積３００ｍＬのオートクレーブを用い、上述のようにして調製した１．５ｇの触媒（Ｃｏ担持率は２０〜３０質量％）と１００ｍＬのｎ−Ｃ１６（ｎ−ヘキサデカン）を仕込んだ後、２２０℃、２．０ＭＰａ−Ｇの条件下、撹拌子を８００ｍｉｎ−１で回転させながら、Ｗ（触媒質量）／Ｆ（二酸化炭素と水素の混合ガス流量）＝３．０（ｇ・ｈ／ｍｏｌ）となるように当該混合ガス（Ｈ２／ＣＯ２＝３．０（モル比））を調整して流通させた。そして、反応中、供給ガス及びオートクレーブ出口ガスの組成をガスクロマトグラフィーにより求め、ＣＯ２転化率、ＣＨ４選択率、Ｃ２選択率、Ｃ３選択率、Ｃ４選択率、Ｃ５＋選択率、炭素数５以上の液状炭化水素の生産性（Ｃ５＋生産性（ｇ／ｋｇ−ｃａｔ．ｈ））を得た。 In order to evaluate the reactivity of the catalyst, an autoclave having an internal volume of 300 mL was used, and 1.5 g of the catalyst prepared as described above (Co support ratio was 20 to 30% by mass) and 100 mL of n-C 16 (n- Hexadecane) was charged, and then W (catalyst mass) / F (mixed gas flow rate of carbon dioxide and hydrogen) = 3 while rotating the stir bar at 800 min −1 under the conditions of 220 ° C. and 2.0 MPa-G. The mixed gas (H 2 / CO 2 = 3.0 (molar ratio)) was adjusted and circulated so as to be 0 (g · h / mol). During the reaction, the composition of the feed gas and the autoclave outlet gas was determined by gas chromatography, and CO 2 conversion, CH 4 selectivity, C 2 selectivity, C 3 selectivity, C 4 selectivity, C 5+ selectivity, Productivity (C5 + productivity (g / kg-cat.h)) of liquid hydrocarbons having 5 or more carbon atoms was obtained.
また、触媒の耐水性を評価するため、以下の実験を実施した。
内容積３００ｍＬのオートクレーブを用い、上述の方法で調整した１．５ｇの触媒と１００ｍＬのｎ−Ｃ１６を仕込んだ後、２３０℃−２．２ＭＰａ−Ｇ、オートクレーブの撹拌速度を８００ｍｉｎ−１に保持した条件で、ＣＯ２転化率が２５％となるようにＷ／ＦのＦ（Ｈ２／ＣＯ２＝３．０の混合ガス）を調整し、数時間の安定運転後、撹拌を停止して６ｈ保持した。その後、再度、撹拌速度を８００ｍｉｎ−１に設定し、さらに数時間の安定運転を実施した。撹拌停止中は活性点近傍では局所的に副生する水が滞留し、触媒が失活し易い条件となるため、撹拌停止による活性低下の度合を把握することで、触媒寿命を評価することが可能である。反応中は供給ガス及びオートクレーブ出口ガスの組成をガスクロマトグラフィーにより求め、撹拌停止前のＣＯ２転化率、撹拌再開後のＣＯ２転化率を得て活性保持率を求めた。
この活性保持率が高い触媒である程、活性の低下が抑制され耐水性（耐久性）に優れたた触媒であると評価できる。
Moreover, the following experiment was implemented in order to evaluate the water resistance of a catalyst.
Using an autoclave with an internal volume of 300 mL, charging 1.5 g of the catalyst adjusted by the above method and 100 mL of n-C 16 , then maintaining the stirring speed of the autoclave at 230 ° C.-2.2 MPa-G and 800 min −1 . Under these conditions, the W / F F (a mixed gas of H 2 / CO 2 = 3.0) was adjusted so that the CO 2 conversion rate was 25%, and after a stable operation for several hours, the stirring was stopped. Hold for 6 h. Thereafter, the stirring speed was set again at 800 min −1 and a stable operation for several hours was performed. While stirring is stopped, water by-produced locally remains in the vicinity of the active point, and it becomes a condition that the catalyst tends to be deactivated, so it is possible to evaluate the catalyst life by grasping the degree of decrease in activity due to stirring stop. Is possible. During the reaction determined the composition of the feed gas and the autoclave outlet gas by gas chromatography, CO 2 conversion rate before the stirring was stopped to obtain a CO 2 conversion after stirring resumed seeking activity retention rate.
It can be evaluated that the higher the activity retention rate, the more excellent the water resistance (durability) of the catalyst since the decrease in activity is suppressed.
表１〜３に記載したＣＯ２転化率、ＣＨ４選択率、Ｃ２選択率、Ｃ３選択率、Ｃ４選択率、Ｃ５＋選択率、活性保持率は、それぞれ次に示す式により算出した。 The CO 2 conversion, CH 4 selectivity, C 2 selectivity, C 3 selectivity, C 4 selectivity, C 5+ selectivity, and activity retention described in Tables 1 to 3 were calculated by the following formulas, respectively. .
以上説明した製造方法によって、表１〜３に示す触媒Ａ〜Ｋそれぞれを調整し、以上の評価方法によって選択性、活性保持率を評価した。表１〜３に実施例、比較例の反応結果をまとめた。 Each of the catalysts A to K shown in Tables 1 to 3 was prepared by the production method described above, and the selectivity and activity retention rate were evaluated by the above evaluation methods. Tables 1 to 3 summarize the reaction results of Examples and Comparative Examples.
（実施例１）
表１のＡに示すような触媒を用いて反応を行ったところ、ＣＯ２転化率２４．４％、ＣＨ４選択率９０．１％、Ｃ２選択率０．９％、Ｃ３選択率０．３％、Ｃ４選択率０．１％、Ｃ５＋選択率８．６％、Ｃ５＋生産性３０ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率９０．３％であった。実施例１では担体中のＮａ、Ｋ、Ｃａ、Ｍｇの合計含有量（濃度）が、好ましい範囲未満だったので、他の実施例に比べてＣ５＋選択率が少々低い結果となった。
(Example 1)
When the reaction was carried out using a catalyst as shown in A of Table 1, CO 2 conversion 24.4%, CH 4 selectivity 90.1%, C 2 selectivity 0.9%, C 3 selectivity 0 .3%, C 4 selectivity 0.1%, C 5+ selectivity 8.6%, C 5+ productivity 30 g / kg-cat. h, Activity retention was 90.3%. In Example 1, since the total content (concentration) of Na, K, Ca, and Mg in the support was less than the preferred range, the C 5+ selectivity was slightly lower than in the other examples.
（実施例２）
表１のＢに示すような触媒を用いて反応を行ったところ、ＣＯ２転化率２２．５％、ＣＨ４選択率８３．５％、Ｃ２選択率２．５％、Ｃ３選択率２．６％、Ｃ４選択率１．０％、Ｃ５＋選択率１０．４％、Ｃ５＋生産性３３ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率８９．９％であった。
(Example 2)
When the reaction was carried out using a catalyst as shown in B of Table 1, CO 2 conversion 22.5%, CH 4 selectivity 83.5%, C 2 selectivity 2.5%, C 3 selectivity 2 .6%, C 4 selectivity was 1.0%, C 5+ selectivity of 10.4%, C 5+ productivity 33g / kg-cat. h, activity retention was 89.9%.
（実施例３）
表１のＣに示すような触媒を用いて反応を行ったところ、ＣＯ２転化率２０．２％、ＣＨ４選択率８１．７％、Ｃ２選択率２．１％、Ｃ３選択率１．８％、Ｃ４選択率１．１％、Ｃ５＋選択率１３．３％、Ｃ５＋生産性３８ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率９１．３％であった。
(Example 3)
When the reaction was carried out using a catalyst as shown in Table 1 C, CO 2 conversion 20.2%, CH 4 selectivity 81.7%, C 2 selectivity 2.1%, C 3 selectivity 1 .8%, C 4 selectivity 1.1%, C 5+ selectivity 13.3%, C 5+ productivity 38 g / kg-cat. h, Activity retention was 91.3%.
（実施例４）
表１のＤに示すような触媒を用いて反応を行ったところ、ＣＯ２転化率１８．１％、ＣＨ４選択率８２．１％、Ｃ２選択率１．７％、Ｃ３選択率１．８％、Ｃ４選択率１．０％、Ｃ５＋選択率１３．４％、Ｃ５＋生産性３４ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率９０．６％であった。
Example 4
When the reaction was carried out using a catalyst as shown in Table 1 D, the CO 2 conversion was 18.1%, the CH 4 selectivity was 82.1%, the C 2 selectivity was 1.7%, and the C 3 selectivity was 1. .8%, C 4 selectivity was 1.0%, C 5+ selectivity of 13.4%, C 5+ productivity 34g / kg-cat. h, Activity retention was 90.6%.
（実施例５）
表１のＥに示すような触媒を用いて反応を行ったところ、ＣＯ２転化率１４．９％、ＣＨ４選択率８５．１％、Ｃ２選択率２．７％、Ｃ３選択率１．６％、Ｃ４選択率０．７％、Ｃ５＋選択率９．９％、Ｃ５＋生産性２１ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率８７．４％であった。実施例５では担体中のＮａ、Ｋ、Ｃａ、Ｍｇの合計含有量（濃度）が、好ましい範囲を超えたので、他の実施例に比べて活性保持率が少々低い結果となった。
(Example 5)
When the reaction was carried out using a catalyst as shown in E of Table 1, CO 2 conversion 14.9%, CH 4 selectivity 85.1%, C 2 selectivity 2.7%, C 3 selectivity 1 .6%, C 4 selectivity 0.7%, C 5+ selectivity 9.9%, C 5+ productivity 21 g / kg-cat. h, activity retention was 87.4%. In Example 5, the total content (concentration) of Na, K, Ca, and Mg in the carrier exceeded the preferred range, so the activity retention rate was slightly lower than in the other examples.
（実施例６）
表２のＦに示すような触媒を、コバルト前駆体のｐＨが４．０となるように５．０ｍｏｌ／Ｌの硝酸水溶液を混合して調整した水溶液を用いて調製し、反応を行ったところ、ＣＯ２転化率１９．１％、ＣＨ４選択率７９．１％、Ｃ２選択率２．０％、Ｃ３選択率１．３％、Ｃ４選択率１．０％、Ｃ５＋選択率１６．６％、Ｃ５＋生産性４５ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率８２．１％であった。
(Example 6)
A catalyst as shown in F of Table 2 was prepared using an aqueous solution prepared by mixing a 5.0 mol / L nitric acid aqueous solution so that the pH of the cobalt precursor was 4.0, and the reaction was performed. CO 2 conversion 19.1%, CH 4 selectivity 79.1%, C 2 selectivity 2.0%, C 3 selectivity 1.3%, C 4 selectivity 1.0%, C 5+ selectivity 16.6%, C 5+ productivity 45 g / kg-cat. h, activity retention was 82.1%.
（実施例７）
表２のＧに示すような触媒を、酢酸コバルト四水和物と硝酸コバルト六水和物が重量比で４：１の割合で用いてｐＨが４．５となるように調整した水溶液を用いて調製し、反応を行ったところ、ＣＯ２転化率１９．６％、ＣＨ４選択率７８．７％、Ｃ２選択率２．１％、Ｃ３選択率１．５％、Ｃ４選択率１．１％、Ｃ５＋選択率１６．６％、Ｃ５＋生産性４６ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率８４．８％であった。
(Example 7)
Using an aqueous solution prepared by using a catalyst as shown in G of Table 2 at a pH ratio of 4.5 using cobalt acetate tetrahydrate and cobalt nitrate hexahydrate in a weight ratio of 4: 1. And the reaction was carried out to obtain a CO 2 conversion of 19.6%, a CH 4 selectivity of 78.7%, a C 2 selectivity of 2.1%, a C 3 selectivity of 1.5%, and a C 4 selectivity. 1.1%, C 5+ selectivity 16.6%, C 5+ productivity 46 g / kg-cat. h, activity retention was 84.8%.
（実施例８）
表２のＨに示すような触媒を、コバルト前駆体のｐＨが７．０となるように５．０ｍｏｌ／Ｌの硝酸水溶液を混合して調整した水溶液を用いて調製し、反応を行ったところ、ＣＯ２転化率２１．０％、ＣＨ４選択率８２．２％、Ｃ２選択率２．２％、Ｃ３選択率１．７％、Ｃ４選択率１．０％、Ｃ５＋選択率１２．９％、Ｃ５＋生産性３８ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率９２．４％であった。
(Example 8)
A catalyst as shown in H of Table 2 was prepared by using an aqueous solution prepared by mixing a 5.0 mol / L nitric acid aqueous solution so that the pH of the cobalt precursor was 7.0, and the reaction was performed. CO 2 conversion 21.0%, CH 4 selectivity 82.2%, C 2 selectivity 2.2%, C 3 selectivity 1.7%, C 4 selectivity 1.0%, C 5+ selectivity 12.9%, C 5+ productivity 38 g / kg-cat. h, activity retention was 92.4%.
（実施例９）
表２のＩに示すような触媒を用いて反応を行ったところ、ＣＯ２転化率１６．４％、ＣＨ４選択率８５．１％、Ｃ２選択率１．８％、Ｃ３選択率１．３％、Ｃ４選択率０．７％、Ｃ５＋選択率１１．１％、Ｃ５＋生産性２６ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率９１．５％であった。
Example 9
When the reaction was carried out using a catalyst as shown in I of Table 2, CO 2 conversion 16.4%, CH 4 selectivity 85.1%, C 2 selectivity 1.8%, C 3 selectivity 1 .3%, C 4 selectivity of 0.7%, C 5+ selectivity of 11.1%, C 5+ productivity 26g / kg-cat. h, Activity retention was 91.5%.
（比較例１）
表３のＪに示すような触媒を、酢酸コバルト四水和物と硝酸コバルト六水和物が重量比で１：５の割合で用いてｐＨが２．０となるように調整した水溶液を用いて調製し、反応を行ったところ、ＣＯ２転化率１８．８％、ＣＨ４選択率７９．１％、Ｃ２選択率２．０％、Ｃ３選択率１．３％、Ｃ４選択率１．１％、Ｃ５＋選択率１６．５％、Ｃ５＋生産性４４ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率７６．２％であった。
(Comparative Example 1)
Using an aqueous solution prepared by using a catalyst as shown in J of Table 3 with cobalt acetate tetrahydrate and cobalt nitrate hexahydrate in a weight ratio of 1: 5 so that the pH is 2.0. And the reaction was carried out to obtain a CO 2 conversion of 18.8%, a CH 4 selectivity of 79.1%, a C 2 selectivity of 2.0%, a C 3 selectivity of 1.3%, and a C 4 selectivity. 1.1%, C 5+ selectivity 16.5%, C 5+ productivity 44 g / kg-cat. h, Activity retention was 76.2%.
（比較例２）
表３のＫに示すような触媒を、硝酸コバルト六水和物を前駆体として調製し、反応を行ったところ、ＣＯ２転化率１８．５％、ＣＨ４選択率７８．５％、Ｃ２選択率２．１％、Ｃ３選択率１．２％、Ｃ４選択率１．０％、Ｃ５＋選択率１７．３％、Ｃ５＋生産性４５ｇ／ｋｇ−ｃａｔ．ｈ、活性保持率７４．３％であった。
(Comparative Example 2)
When a catalyst as shown in K of Table 3 was prepared using cobalt nitrate hexahydrate as a precursor and reacted, the CO 2 conversion was 18.5%, the CH 4 selectivity was 78.5%, C 2 selectivity of 2.1%, C 3 selectivity of 1.2%, C 4 selectivity was 1.0%, C 5+ selectivity of 17.3%, C 5+ productivity 45g / kg-cat. h, activity retention was 74.3%.
Claims (9)
前記酢酸コバルトを主体とする前駆体溶液のｐＨが４．０〜７．３であることを特徴とする、二酸化炭素と水素から炭化水素を製造する触媒の製造方法。 When loading cobalt on a catalyst carrier mainly composed of silica, a step of loading the catalyst carrier using a precursor solution mainly composed of cobalt acetate,
The method for producing a catalyst for producing hydrocarbons from carbon dioxide and hydrogen, wherein the precursor solution mainly composed of cobalt acetate has a pH of 4.0 to 7.3.
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| JPH01190638A (en) * | 1988-01-26 | 1989-07-31 | Nkk Corp | Production of hydrocarbon by hydrogenation of carbon dioxide |
| JPH0352825A (en) * | 1989-07-19 | 1991-03-07 | Nkk Corp | Production of propane by hydrogenation of carbon dioxide |
| JP2011517426A (en) * | 2008-03-27 | 2011-06-09 | コリア リサーチ インスティテュート オブ ケミカル テクノロジー | Cobalt / zirconium-phosphorus / silica catalyst for Fischer-Tropsch synthesis and method for producing the same |
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| JPH01190638A (en) * | 1988-01-26 | 1989-07-31 | Nkk Corp | Production of hydrocarbon by hydrogenation of carbon dioxide |
| JPH0352825A (en) * | 1989-07-19 | 1991-03-07 | Nkk Corp | Production of propane by hydrogenation of carbon dioxide |
| JP2011517426A (en) * | 2008-03-27 | 2011-06-09 | コリア リサーチ インスティテュート オブ ケミカル テクノロジー | Cobalt / zirconium-phosphorus / silica catalyst for Fischer-Tropsch synthesis and method for producing the same |
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