JP2004322085A - 合成ガスから炭化水素を製造する触媒と該触媒の製造方法及び炭化水素の製造方法 - Google Patents
合成ガスから炭化水素を製造する触媒と該触媒の製造方法及び炭化水素の製造方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 58
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 58
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
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- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
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- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
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- 229920003303 ion-exchange polymer Polymers 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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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
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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Abstract
【解決手段】 触媒担体上に金属系化合物を担持してなる触媒であって、該触媒の不純物含有量が0.01〜0.15質量%であることを特徴とする合成ガスから炭化水素を製造する触媒とその製造方法及び該触媒を用いた炭化水素の製造方法。
【選択図】 図1
Description
表1のAに示すような物性を有するシリカ担体にCoを20質量%担持して、F−T合成反応を行ったところ、CO転化率75.9%、CH4選択率5.3%、CO2選択率1.4%であった。
表1のBに示すような物性を有するシリカ担体にCoを20質量%担持して、F−T合成反応を行ったところ、CO転化率75.8%、CH4選択率4.6%、CO2選択率1.0%であった。
表1のGに示すような物性を有するシリカ担体を、塩酸水溶液及びイオン交換水にて洗浄して、表1のCに示すようなシリカ担体を得た。この担体にCoを20質量%担持して、F−T合成反応を行ったところ、CO転化率74.1%、CH4選択率4.8%、CO2選択率1.0%であった。
表1のDに示すような細孔径が30nmであるシリカ担体にCoを20質量%担持して、F−T合成反応を行ったところ、CO転化率46.4%、CH4選択率7.8%、CO2選択率1.0%であった。
Coの担持率を30質量%とし、W/Fを1.5(g・h/mol)とする以外は実施例3と同様に反応を行ったところ、CO転化率74.7%、CH4選択率3.7%、CO2選択率0.6%であり、炭素数5以上の炭化水素生産性は2.1(kg−炭化水素/kg−触媒・時間)であった。
表1のEに示すようなシリカ担体にCOを30質量%担持し、W/Fを1.5としてF−T合成反応を行ったところ、CO転化率71.7%、CH4選択率4.4%、CO2選択率0.7%であり、炭素数5以上の炭化水素生産性は1.9(kg−炭化水素/kg−触媒・時間)であった。
表1のFに示すようなシリカ担体にCOを16質量%担持し、W/Fを2としてF−T合成反応を行ったところ、CO転化率74.8%、CH4選択率4.9%、CO2選択率1.1%であり、炭素数5以上の炭化水素生産性は1.4(kg−炭化水素/kg−触媒・時間)であった。
表1のGに示すような不純物を多量に含むシリカ担体にCoを20質量%担持して、F−T合成反応を行ったところ、CO転化率24.0%、CH4選択率8.3%、CO2選択率0.84%であった。
Claims (13)
- 触媒担体上に金属系化合物を担持してなる触媒であって、該触媒の不純物含有量が0.01〜0.15質量%であることを特徴とする合成ガスから炭化水素を製造する触媒。
- 前記触媒担体中のアルカリ金属又はアルカリ土類金属の含有量が0.01〜0.1質量%であることを特徴とする請求項1に記載の合成ガスから炭化水素を製造する触媒。
- 前記触媒担体が、細孔径が8〜50nm、表面積が80〜550m2/g、細孔容積が0.5〜2.0mL/gを同時に満足することを特徴とする請求項1又は2に記載の合成ガスから炭化水素を製造する触媒。
- 水中に分散させた触媒に室温で超音波を4時間照射した際に、前記触媒の破壊あるいは粉化する率が10%以下の触媒担体を用いることを特徴とする請求項1〜3の何れか1項に記載の合成ガスから炭化水素を製造する触媒。
- 前記触媒担体が球状のシリカであることを特徴とする請求項1〜4の何れか1項に記載の合成ガスから炭化水素を製造する触媒。
- 前記金属系化合物が、鉄、コバルト、ニッケル、ルテニウムの少なくとも一つからなることを特徴とする請求項1〜5の何れか1項に記載の合成ガスから炭化水素を製造する触媒。
- 前記金属系化合物が、アルカリ金属又はアルカリ土類金属の含有量が5質量%以下である金属系化合物前駆体を原料とすることを特徴とする請求項6に記載の合成ガスから炭化水素を製造する触媒。
- 請求項1〜7の何れか1項に記載の合成ガスから炭化水素を製造する触媒を製造する方法であって、触媒担体の不純物濃度を低下させる前処理をしてから、触媒を担持させることを特徴とする合成ガスから炭化水素を製造する触媒の製造方法。
- 前記前処理が、酸又はイオン交換水の一方又は双方を用いた洗浄であることを特徴とする請求項8に記載の合成ガスから炭化水素を製造する触媒の製造方法。
- 前記触媒担体を製造する工程で、アルカリ金属又はアルカリ土類金属の含有量が0.06質量%以下である洗浄水を用いて得られる触媒担体を用いて触媒を調製することを特徴とする請求項8又は9に記載の合成ガスから炭化水素を製造する触媒の製造方法。
- 前記触媒担体が、噴霧法により球状に整形されたものであることを特徴とする請求項8〜10の何れか1項に記載の合成ガスから炭化水素を製造する触媒の製造方法。
- 前記触媒担体がシリカであることを特徴とする請求項8〜11の何れか1項に記載の合成ガスから炭化水素を製造する触媒の製造方法。
- 請求項1〜7の何れか1項に記載の合成ガスから炭化水素を製造する触媒を用いて、合成ガスから炭化水素を製造することを特徴とする炭化水素の製造方法。
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JP2006297273A (ja) * | 2005-04-20 | 2006-11-02 | Nippon Steel Corp | F−t合成反応用触媒 |
JP2007061770A (ja) * | 2005-09-01 | 2007-03-15 | Nippon Steel Corp | 合成ガスから炭化水素を製造する触媒とその触媒の製造方法、及び当該触媒を用いた合成ガスから炭化水素を製造する方法 |
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JP2018187556A (ja) * | 2017-05-01 | 2018-11-29 | 新日鉄住金エンジニアリング株式会社 | 合成ガスから炭化水素を製造する触媒の製造方法、合成ガスから炭化水素を製造する炭化水素の製造方法 |
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RU2005134237A (ru) | 2007-05-20 |
JP4429063B2 (ja) | 2010-03-10 |
US8524788B2 (en) | 2013-09-03 |
US20100184876A1 (en) | 2010-07-22 |
CN100479917C (zh) | 2009-04-22 |
RU2311230C2 (ru) | 2007-11-27 |
KR101054604B1 (ko) | 2011-08-04 |
CN1771086A (zh) | 2006-05-10 |
US20120289615A1 (en) | 2012-11-15 |
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US8178589B2 (en) | 2012-05-15 |
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