CN1175479A - Catalyst for synthesis of C2 oxy-compound, e. g. ethanolaldehyde by hydrogenation of carbon monooxide - Google Patents
Catalyst for synthesis of C2 oxy-compound, e. g. ethanolaldehyde by hydrogenation of carbon monooxide Download PDFInfo
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- CN1175479A CN1175479A CN 96115579 CN96115579A CN1175479A CN 1175479 A CN1175479 A CN 1175479A CN 96115579 CN96115579 CN 96115579 CN 96115579 A CN96115579 A CN 96115579A CN 1175479 A CN1175479 A CN 1175479A
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Abstract
A catalyst for synthesizing C2 compound containing oxygen such as alcohol and acetaldehyde by hydrogenation of CO contains Rh (0.01-3%), V (0.1-10%), M )0.01-10%) and SiO2 as carrier, where M is one or more of Ru, Fe, Ir, Mo, Mn, K, Li, Zr or Cu. With said catalyst, CO and H2 has high conversion rate and selectivity in mild reaction condition. In said reaction natural gas can be used as raw material.
Description
The present invention provides a kind of Rh-V-M/SiO for c_2-oxygen compounds such as co hydrogenation synthesizing alcohol, acetaldehyde
2Catalysts and its preparation method.
The oxygenatedchemicals that contains two carbon atoms by co hydrogenation synthesizing alcohol, acetaldehyde, acetate etc. all adopts the catalyst based on metal rhodium basically, add some other element in addition again catalyst is modified, to reach the purpose that improves activity of such catalysts and product selectivity.GB1 for example, 501,891 is to add component to have synthesized loaded Rh-Fe catalyst with Fe, and carbon monoxide hydrogenation is improved to the selectivity of ethanol.US4,096,164 has synthesized loaded Rh-Mo catalyst, and J 61178936, J61178941 uses compound rhodium base catalyst, and such as Rh-Se, Ir, Li/ carry and Rh-Ir, Fe, Mo/ carry mixing or divide two sections fillings to use, and obtain selectivity and space-time yield preferably.AU551,644 is to add synthetic the supporting on the rhodium catalyst of component with the rare earth element, the selectivity of oxygenatedchemicals such as ethanol reaches 82%.But the rhodium-containing amount of the rhodium base catalyst that uses in the above-mentioned patent is all higher, and generally more than 4% (wt), and the space-time yield of Unit Weight rhodium is lower, makes troubles to industrial applications, and disposable input is excessive.
The objective of the invention is to add H for CO
2System ethanol, C such as acetaldehyde
2The oxygenatedchemicals reaction provides a kind of Catalysts and its preparation method of low Rh content.Utilize this Catalyst for CO and H
2But C such as the synthesizing alcohol of high conversion, acetaldehyde
2Oxygenatedchemicals.
Novel co hydrogenation system ethanol of the present invention, the composition of the catalyst of c_2-oxygen compounds such as acetaldehyde is Rh-V-M/SiO
2Wherein M represents Ru, Fe, and Ir, Mo, Mn, K, Li, a kind of element among Zr or the Cu or multiple element auxiliary agent, the content of Rh is 0.01～3% in the catalyst, and the content of V is 0.1～10%, and the content of M is 0.01～10%, and all the other are carrier S iO
2
Rh-V-M/SiO
2The Preparation of catalysts method is:
1. the various elemental constituents of selecting for use are made into the certain density aqueous solution with the form of chloride or nitrate.
2. SiO
2Drop into rapidly among the above-mentioned aqueous solution, slowly stir.
3. at 10 ℃ to 100 ℃ baking temperature, kept 1～20 day, can make finished catalyst.
With the catalyst that makes in reactor or reactor external application H
2Gas reduced 3～16 hours down at 100～400 ℃, promptly can be used for CO and added H
2System ethanol, C such as acetaldehyde
2The oxygenatedchemicals reaction, reaction can be undertaken by the conventional method of such synthetic reaction.The Rh content of this catalyst is low, ethanol, the space-time yield height of c_2-oxygen compounds such as acetaldehyde, selectivity height.Below by example technology of the present invention is given to illustrate further.
Example 1 Rh-V-Fe-Ir-K/SiO
2Preparation of catalysts
Certain density RhCl
3, VO (NO
3)
2, Fe (NO
3)
3, H
2IrCl
6, the aqueous solution of KCl adds quantitative SiO then
2, dipping stirs, 18 ℃ of dryings 6 days, and 60 ℃ of dryings 16 hours, 80 ℃ of dryings 16 hours.Acquisition consists of 1%Rh-1.5%V-0.5%Fe-0.1%Ir-0.1%K/SiO
2The catalyst of (all the other).
Example 2 Rh-V-Ru-Li/SiO
2Preparation of catalysts
Certain density RhCl
3, VO (NO
3)
2, RuCl
3, the aqueous solution of LiCl adds quantitative SiO then
2, dipping stirs, 30 ℃ of dryings 7 days, and 80 ℃ of dryings 16 hours, 100 ℃ of dryings 8 hours obtain to consist of 0.5%Rh-1.2%V-0.2%Ru-0.1%Li/SiO
2Catalyst.
Example 3～10 Rh-V-M/SiO
2Preparation of catalysts
Press the method for example 1, prepare the Rh-V-M/SiO of different metal constituent content
2Catalyst, wherein the content of each element is represented with percentage by weight, all the other are carrier S iO
2, the composition of catalyst is listed in table 1.
The performance test of embodiment 11 catalyst
Get the above-mentioned catalyst of 1.0ml, the internal diameter of packing into is the fixed bed reactors of 6mm.Use H at 300 ℃
2Reduced 3 hours, and reduced to 280 ℃ then by going into H
2+ CO (H
2: CO=2: 1, the ratio of volume), pressure is 3.0MPa, air speed is 15000h
-1Reaction the results are shown in table 1, wherein ethanol and acetaldehyde with space-time yield (gram/kilogram. hour), the selectivity of ethanol and acetaldehyde is represented with %.
Comparative example 1～4 comparative example Preparation of catalysts
Prepare as a comparative example catalyst by the method for example 1, the composition of its catalyst is with listing in table 1.
The performance of comparative example 5～8 comparative example catalyst
Press the method for example 11, catalyst is as a comparative example estimated, its result is with listing in table 1.
By the result of table 1 as can be seen, the content of noble metal Rh is low in the catalyst of the present invention, and the preparation method is simple, is used for CO and adds H
2C such as system ethanol, acetaldehyde
2The oxygenatedchemicals reaction has higher activity and selectivity.Utilize this catalyst can natural gas for raw material through synthesis gas ethanol production, C such as acetaldehyde
2Oxygenatedchemicals provides a kind of new method that industrialization is adopted that is suitable for for utilizing natural gas resource rationally and effectively.
The catalyst of table 1. embodiment and comparative example and performance reaction condition: H thereof
2/ CO=2,280 ℃, 3.0MPa, air speed 15000h
-1
| Embodiment | (weight %, surplus be SiO to the catalyst composition 2) | Space-time yield (gram/kilogram. hour) | Selectivity (%) |
| ????1 | ?1％Rh-1.5％V-0.5％Fe-0.1％Ir-0.1％K/SiO 2 | ????390 | ????86 |
| ????2 | ?0.5％Rh-1.2％V-0.2％Ru-0.1％Li/SiO 2 | ????308 | ????82 |
| ????3 | ?1％Rh-1.5％V/SiO 2 | ????312 | ????78 |
| ????4 | ?1％Rh-0.3％V-0.5％Zr/SiO 2 | ????278 | ????75 |
| ????5 | ?1％Rh-10％V-0.5％K/SiO 2 | ????322 | ????78 |
| ????6 | ?3％Rh-1.5％V-0.5％Fe-/SiO 2 | ????463 | ????76 |
| ????7 | ?1％Rh-6％V-1.0％Fe-0.1％Ru-0.6％K/SiO 2 | ????379 | ????79 |
| ????8 | ?1％Rh-2％V-0.2％Mo-0.5％Mn/SiO 2 | ????289 | ????72 |
| ????9 | ?1％Rh-2％V-0.5％Fe-0.8％Cu/SiO 2 | ????251 | ????68 |
| ????10 | ?1％Rh-2％V-0.2％Fe-0.1％Zr/SiO 2 | ????308 | ????80 |
| Comparative example 1 | ?1％Rh-0.5％Fe-0.1％Ir/SiO 2 | ????158 | ????48 |
| ????2 | ?1％Rh-0.5％Fe-0.1％Ir-0.1％K/SiO 2 | ????228 | ????71 |
| ????3 | ?1％Rh-0.5％Fe-0.1％Ir-0.1％K/Al 2O 3 | ????241 | ????52 |
| ????4 | ?3％Rh/SiO 2 | ????129 | ????55 |
Claims (3)
1. a CO adds H
2C such as synthesizing alcohol, acetaldehyde
2Oxygenatedchemicals is characterized in that containing V and M metallic element as auxiliary agent with containing the Rh catalyst, catalyst consist of Rh-V-M/SiO
2, wherein M is one or more complex elements in Ru, Fe, Ir, Mo, Mn, K, Li or the Cu metallic element, and the weight of catalyst consists of:
Rh：0.01～3％，
V：0.1～10％，
M:0.01～10%, all the other are carrier S iO
2
2. according to the described Preparation of catalysts method of claim 1, it is characterized in that after the chloride or nitrate impregnated carrier with the metallic element that contains each component, keep making in 1～20 day finished catalyst down in 10～100 ℃ of baking temperatures.
3. one kind is utilized the described catalyst of claim 1 to carry out CO to add H
2Synthesizing alcohol, C such as acetaldehyde
2The oxycompound reaction is characterized in that reacting procatalyst H
2Gas reduced 3～16 hours down in 100～400 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115579A CN1074304C (en) | 1996-09-04 | 1996-09-04 | Catalyst for synthesis of C2 oxy-compound, e. g. ethanolaldehyde by hydrogenation of carbon monooxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115579A CN1074304C (en) | 1996-09-04 | 1996-09-04 | Catalyst for synthesis of C2 oxy-compound, e. g. ethanolaldehyde by hydrogenation of carbon monooxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175479A true CN1175479A (en) | 1998-03-11 |
| CN1074304C CN1074304C (en) | 2001-11-07 |
Family
ID=5122815
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115579A Expired - Lifetime CN1074304C (en) | 1996-09-04 | 1996-09-04 | Catalyst for synthesis of C2 oxy-compound, e. g. ethanolaldehyde by hydrogenation of carbon monooxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1074304C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500781B2 (en) * | 1999-06-25 | 2002-12-31 | Basf Aktiengesellschaft | Process and catalyst for preparing C2-oxygenates from synthesis gas |
| CN102553613A (en) * | 2010-12-30 | 2012-07-11 | 中国科学院大连化学物理研究所 | Catalyst for use in preparation of methane from synthesis gas and coproduction of low-carbon mixed alcohol and preparation and application methods thereof |
| CN102596396A (en) * | 2009-11-02 | 2012-07-18 | 陶氏环球技术有限责任公司 | Supported rhodium synthesis gas conversion catalyst compositions |
| US9415375B2 (en) | 2010-04-09 | 2016-08-16 | Dow Global Technologies Llc | Catalyst compositions for producing mixed alcohols |
| CN106238048A (en) * | 2011-08-31 | 2016-12-21 | 积水化学工业株式会社 | Oxide catalyst for synthesizing and manufacture method, the manufacture device of oxide and the manufacture method of oxide |
| CN106268856A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application |
| CN111434382A (en) * | 2019-01-15 | 2020-07-21 | 天津大学 | Carrier-supported vanadium oxide promoted Rh-based catalyst and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2504248A1 (en) * | 1974-02-07 | 1975-08-21 | Exxon Research Engineering Co | CATALYST MIXTURE AND PROCESS FOR THE CONVERSION OF HEAVY PETROLEUM RAW MATERIALS |
| US4096164A (en) * | 1976-08-30 | 1978-06-20 | Union Carbide Corporation | Process for producing ethanol, acetic acid and/or acetaldehyde, from synthesis gas |
| DE3203060A1 (en) * | 1982-01-30 | 1983-08-04 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING ACETIC ACID, ACETALDEHYDE AND ETHANOL |
-
1996
- 1996-09-04 CN CN96115579A patent/CN1074304C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500781B2 (en) * | 1999-06-25 | 2002-12-31 | Basf Aktiengesellschaft | Process and catalyst for preparing C2-oxygenates from synthesis gas |
| EP1064997A3 (en) * | 1999-06-25 | 2004-02-25 | Basf Aktiengesellschaft | Process and catalyst for the preparation of C2-oxygenates from synthetic gas |
| CN102596396A (en) * | 2009-11-02 | 2012-07-18 | 陶氏环球技术有限责任公司 | Supported rhodium synthesis gas conversion catalyst compositions |
| US9415375B2 (en) | 2010-04-09 | 2016-08-16 | Dow Global Technologies Llc | Catalyst compositions for producing mixed alcohols |
| CN102553613A (en) * | 2010-12-30 | 2012-07-11 | 中国科学院大连化学物理研究所 | Catalyst for use in preparation of methane from synthesis gas and coproduction of low-carbon mixed alcohol and preparation and application methods thereof |
| CN102553613B (en) * | 2010-12-30 | 2014-06-25 | 中国科学院大连化学物理研究所 | Catalyst for use in preparation of methane from synthesis gas and coproduction of low-carbon mixed alcohol and preparation and application methods thereof |
| CN106238048A (en) * | 2011-08-31 | 2016-12-21 | 积水化学工业株式会社 | Oxide catalyst for synthesizing and manufacture method, the manufacture device of oxide and the manufacture method of oxide |
| CN107020088A (en) * | 2011-08-31 | 2017-08-08 | 积水化学工业株式会社 | The manufacture method of oxide catalyst for synthesizing and its manufacture method, the manufacture device of oxide and oxide |
| CN106238048B (en) * | 2011-08-31 | 2020-05-29 | 积水化学工业株式会社 | Catalyst for synthesizing oxide, method for producing same, apparatus for producing oxide, and method for producing oxide |
| CN106268856A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application |
| CN111434382A (en) * | 2019-01-15 | 2020-07-21 | 天津大学 | Carrier-supported vanadium oxide promoted Rh-based catalyst and preparation method and application thereof |
| CN111434382B (en) * | 2019-01-15 | 2023-04-28 | 天津大学 | Rh-based catalyst promoted by vanadium oxide supported by carrier, and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1074304C (en) | 2001-11-07 |
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Assignee: Jiangsu Sopo (Group) Co., Ltd. Assignor: Dalian Institute of Chemical Physics, Chinese Academy of Sciences Contract record no.: 2012320000391 Denomination of invention: Catalyst for synthesis of C2 oxy-compound, e. g. ethanolaldehyde by hydrogenation of carbon monooxide Granted publication date: 20011107 License type: Exclusive License Open date: 19980311 Record date: 20120405 |
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