CN1225853A - Catalyst for synthesizing low-carbon mixed alcohol - Google Patents

Catalyst for synthesizing low-carbon mixed alcohol Download PDF

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Publication number
CN1225853A
CN1225853A CN 98104989 CN98104989A CN1225853A CN 1225853 A CN1225853 A CN 1225853A CN 98104989 CN98104989 CN 98104989 CN 98104989 A CN98104989 A CN 98104989A CN 1225853 A CN1225853 A CN 1225853A
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CN
China
Prior art keywords
catalyst
carbon mixed
mixed alcohol
alcohol
synthesizing low
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CN 98104989
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Chinese (zh)
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CN1075398C (en
Inventor
孙予罕
陈小平
王秀芝
任杰
钟炳
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Priority to CN 98104989 priority Critical patent/CN1075398C/en
Publication of CN1225853A publication Critical patent/CN1225853A/en
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Publication of CN1075398C publication Critical patent/CN1075398C/en
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Abstract

The catalyst for synthesis of low-carbon mixed alcohol comprises (mole percentage) Cu 40-50%, Zr 20-35%, Fe 10-15%, K 0-5% and Mn 10-20%. Said catalyst features easily available raw material, low cost, simple preparation, mild reaction condition and the selectivity of C2+ is greater than 35 wt%.

Description

A kind of catalyst of synthesizing low-carbon mixed alcohol
The invention belongs to a kind of catalyst, relate in particular to a kind of catalyst of MAS.
By the synthetic MAS of CO+H2 is to improve the desirable additive of leadless gasoline octane rating, has vast market prospect, the modification Cu-Zn-Al catalyst system and catalyzing of German Lurgi company and the Zn-Cr-K catalyst system and catalyzing of Italian Snam company are arranged in the at present ripe technical process of this reaction, it is the methanol synthesis catalyst modification that this two classes catalyst all belongs to, employed modified additive is alkali metal or alkaline-earth metal, but C 2+The selectivity of alcohol in total alcohol only is 30wt%, and another problem is that this type of catalyst service condition is comparatively harsh, and temperature requirement is higher than 400 ℃, and pressure is more than the 10MPa.
Goal of the invention of the present invention provides C in a kind of product 2+The selectivity of alcohol is good, the catalyst of the synthesizing low-carbon mixed alcohol that reaction condition relaxes.
Goal of the invention of the present invention is achieved in that at Cu/ZrO 2Add the VIII family element that strong carbochain growing ability is arranged in the series catalysts, and alkali metal, alkaline-earth metal, C when improving the CO hydrogenation reaction 2+The selectivity of alcohol.
Catalyst of the present invention consists of (molar percentage)
Cu 40-50％ Zr 20-35％ Fe 10-15％
K 0-5％ Mn 10-20％
Preparation method of the present invention adopts coprecipitation, the predecessor of Zr is a zirconium oxychloride, all the other are the predecessor of nitrate, be dissolved in the distilled water by above-mentioned composition, 60-90 ℃ down with the sodium carbonate liquor co-precipitation, fully stir in the precipitation process and keep pH=9-12, precipitation is washed till do not have chlorion through distilled water, 120 ℃ of dry down and 350 ℃ of roastings, be crushed to the 20-40 order and get final product.
The present invention compared with prior art has following advantage:
1. raw material is easy to get, and cost is low.2. preparation is simple.
3. reaction condition gentleness.4.C 2+The selectivity of alcohol is greater than 35wt%.
5. the good stability of catalyst.
Embodiments of the invention are as follows:
Embodiment 1
Press the composition of Cu 40%, Zr 30%, Mn 20%, Fe 10% (percentage by weight), the predecessor zirconium oxychloride of Zr, all the other do not have plain predecessor is nitrate, be dissolved in the distilled water, 70 ℃ down with 30% sodium carbonate liquor co-precipitation, precipitation process needs fully to stir and keep pH=9, precipitation is washed till do not have chlorion and detect through distilled water, 120 ℃ of dry down and 350 ℃ of roastings, be crushed to the 20-40 order.The catalyst of producing reduced 10 hours at 300 ℃ with pure hydrogen before reaction, and service condition is P=6.0MPa, T=280 ℃, GHSV=4000h -1, H 2/ CO=2, the product that obtains through the gas chromatographic analysis result is: CO conversion ratio alcohol space-time yield product total pure selectivity that distributes distributes
(g/ml catalh) pure hydrocarbon CO 2Methanol propyl alcohol butanols (isobutanol) amylalcohol hexanol 43 0.20 63.64 13.25 23.11 63.93 8.97 7.40 13.85 (11.30) 5.83--
Embodiment 2
Catalyst consists of Cu 40%, and Zr 30%, and Mn 15%, and Fe 10%, K 5% (percentage by weight), and service condition is P=6.0MPa, T=260 ℃, GHSV=3000h -1, H 2/ CO=2, all the other are with implementing
Example 1, the result is: CO conversion ratio alcohol space-time yield product total pure selectivity that distributes distributes
(g/ml catalh) pure hydrocarbon CO 2Methanol propyl alcohol butanols (isobutanol) amylalcohol hexanol 51.24 0.18 50.05 14.35 35.60 42.48 23.34 13.79 11.88 (2.96) 6.63 1.85
Embodiment 3
Catalyst consists of Cu 45%, and Zr 30%, and Mn 10%, Fe 15% (percentage by weight), and service condition is P=8.0MPa, T=280 ℃, GHSV=40000h -1, H 2/ CO=2, all the other are with embodiment 1, and the result is: CO conversion ratio alcohol space-time yield product total pure selectivity that distributes distributes
(g/ml catalh) pure hydrocarbon CO 2Methanol propyl alcohol butanols (isobutanol) amylalcohol hexanol 42.76 0.25 49.55 14.64 35.81 68.83 7.45 5.13 8.99 (7.28) 4.73 4.01

Claims (1)

1. the catalyst of a synthesizing low-carbon mixed alcohol is characterized in that consist of (molar percentage) of catalyst
Cu 40-50％ Zr 20-35％ Fe 10-15％
K 0-5％ Mn 10-20％
CN 98104989 1998-02-12 1998-02-12 Catalyst for synthesizing low-carbon mixed alcohol Expired - Fee Related CN1075398C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 98104989 CN1075398C (en) 1998-02-12 1998-02-12 Catalyst for synthesizing low-carbon mixed alcohol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 98104989 CN1075398C (en) 1998-02-12 1998-02-12 Catalyst for synthesizing low-carbon mixed alcohol

Publications (2)

Publication Number Publication Date
CN1225853A true CN1225853A (en) 1999-08-18
CN1075398C CN1075398C (en) 2001-11-28

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CN 98104989 Expired - Fee Related CN1075398C (en) 1998-02-12 1998-02-12 Catalyst for synthesizing low-carbon mixed alcohol

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CN (1) CN1075398C (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100384964C (en) * 2000-06-20 2008-04-30 Sasol技术股份有限公司 Hydrocarbon synthesis catalyst and process
WO2009094935A1 (en) * 2008-01-23 2009-08-06 Accelergy Shanghai R & D Center Co., Ltd. Fe/mn catalyst for fischer-tropsch synthesis and its preparation method
CN102872881A (en) * 2012-09-17 2013-01-16 中国科学院山西煤炭化学研究所 Copper-based catalyst used in process of synthesizing low carbon mixed alcohol and preparation method and application of catalyst
CN109772329A (en) * 2019-02-14 2019-05-21 国家能源投资集团有限责任公司 Catalyst, preparation method and its application in the synthetic reaction of low carbon alcohol by synthetic gas

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100384964C (en) * 2000-06-20 2008-04-30 Sasol技术股份有限公司 Hydrocarbon synthesis catalyst and process
WO2009094935A1 (en) * 2008-01-23 2009-08-06 Accelergy Shanghai R & D Center Co., Ltd. Fe/mn catalyst for fischer-tropsch synthesis and its preparation method
CN102872881A (en) * 2012-09-17 2013-01-16 中国科学院山西煤炭化学研究所 Copper-based catalyst used in process of synthesizing low carbon mixed alcohol and preparation method and application of catalyst
CN109772329A (en) * 2019-02-14 2019-05-21 国家能源投资集团有限责任公司 Catalyst, preparation method and its application in the synthetic reaction of low carbon alcohol by synthetic gas

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Publication number Publication date
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