CN1074304C - 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 monooxideInfo
- Publication number
- CN1074304C CN1074304C CN96115579A CN96115579A CN1074304C CN 1074304 C CN1074304 C CN 1074304C CN 96115579 A CN96115579 A CN 96115579A CN 96115579 A CN96115579 A CN 96115579A CN 1074304 C CN1074304 C CN 1074304C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sio
- ethanolaldehyde
- synthesis
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Abstract
The present invention relates to a catalyst for the synthesis of C2 oxygen-containing compounds of alcohol, ethanolaldehyde by adding H2 into carbon monooxide (CO). The constitute of the catalyst is Rh-V-M/SiO, wherein the content of the metallic element is 0.01 to 3% of Rh, 0.1 to 10% of V and 0.01 to 10% of M, and the rest is a carrier SiO2. M in the constitute is one kind or several kinds of complex elements in Ru, Fe, Ir, Mo, Mn, K, Li and Zr or Cu. Using the catalyst can make CO and H2 synthesized into C2 oxygen-containing compounds of alcohol, acetaldehyde, etc. at high conversion rate and high selectivity under the mild reaction condition. The reaction can use natural gas as the raw material and provides a method suitable for industrialization for reasonably and effectively utilizing a natural gas resource.
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 as 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, J61178936, 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, Zr or Cu a kind of element or multiple element auxiliary agent wherein, the content of Rh is 0.01～3% by weight percentage 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. carbon monoxide such as hydrogen system c_2-oxygen compound catalyst is characterized in that containing V and M metallic element as auxiliary agent, 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 percentage by weight of catalyst is:
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 according to the described Preparation of catalysts method of claim 1, it 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 CN1175479A (en) | 1998-03-11 |
| CN1074304C true CN1074304C (en) | 2001-11-07 |
Family
ID=5122815
Family Applications (1)
| 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) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19929281A1 (en) * | 1999-06-25 | 2000-12-28 | Basf Ag | Process and catalyst for the production of C¶2¶ oxygenates from synthesis gas |
| BR112012010203A2 (en) * | 2009-11-02 | 2019-09-24 | Dow Global Technologies Inc | supported catalyst composition |
| WO2011126545A1 (en) | 2010-04-09 | 2011-10-13 | Dow Global Technologies Llc | Catalyst compositions for producing mixed alcohols |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1502891A (en) * | 1974-02-07 | 1978-03-08 | Exxon Research Engineering Co | Heavy crude conversion catalysts therefor and their preparation |
| US4096164A (en) * | 1976-08-30 | 1978-06-20 | Union Carbide Corporation | Process for producing ethanol, acetic acid and/or acetaldehyde, from synthesis gas |
| AU551644B2 (en) * | 1982-01-30 | 1986-05-08 | Hoechst A.G. | Acetic acid, ethanol and acetaldehyde from carbon monoxide and hydrogen |
-
1996
- 1996-09-04 CN CN96115579A patent/CN1074304C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1502891A (en) * | 1974-02-07 | 1978-03-08 | Exxon Research Engineering Co | Heavy crude conversion catalysts therefor and their preparation |
| US4096164A (en) * | 1976-08-30 | 1978-06-20 | Union Carbide Corporation | Process for producing ethanol, acetic acid and/or acetaldehyde, from synthesis gas |
| AU551644B2 (en) * | 1982-01-30 | 1986-05-08 | Hoechst A.G. | Acetic acid, ethanol and acetaldehyde from carbon monoxide and hydrogen |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1175479A (en) | 1998-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4591578A (en) | Catalyst of molybdenum on wide-pore carbon support | |
| CN1219733C (en) | Method and catalyst for preparing oxide containing two carbon atoms from synthetic gas | |
| JPS61183237A (en) | Hydrogenation of acetic acid | |
| CN1024666C (en) | Production of alcohols and ethers by the catalysed hydrogenation of esters | |
| CN104011002A (en) | Process for preparing 1, 6-hexanediol | |
| CN1074304C (en) | Catalyst for synthesis of C2 oxy-compound, e. g. ethanolaldehyde by hydrogenation of carbon monooxide | |
| CN100503534C (en) | Method for synthesis of isopropanol | |
| US4217249A (en) | Supported heteronuclear noble metal cluster catalysts and method for preparing same | |
| EP0079132A1 (en) | Process for the production of oxygenated hydrocarbons by the catalytic conversion of synthesis gas | |
| US4444898A (en) | Heterocatalyst system | |
| US4187168A (en) | Hydrocarbon conversion processes utilizing supported heteronuclear cluster complex catalysts | |
| Ichikawa et al. | Ensemble and ligand effects in selective alkane hydrogenolysis catalysed on well characterised RhIr and RhFe bimetallic clusters inside NaY zeolite | |
| CN1035240C (en) | Catalyst for synthesizing methyl isobutyl ketone/diisobutyl ketone from isopropanol and preparing process thereof | |
| CN1074306C (en) | Catalyst for synthesizing alcohol, acetic acid and acetaldehyde etc. dicarbonic oxy-combound by carbon monoxide hydronation | |
| Grushin et al. | Chemospecific, biphasic reduction of. alpha.,. beta.-unsaturated aldehydes and ketones catalyzed by rhodium complex (Cy3P) 2Rh (H) Cl2 | |
| US4302400A (en) | Heteronuclear noble metal cluster catalysts | |
| GB2269116A (en) | A process for the production of aromatic alcohol by selective hydrogenation of aromatic ketone | |
| CN1088402C (en) | Dicarbonic oxygen-contained compound catalyst such as alcohols, acetic acid, acetaldehyde etc. made from synthetic gas and process thereof | |
| CN1249008C (en) | Method for preparing cyclopentanone from cyclopentanol | |
| US4271302A (en) | Supported heteronuclear noble metal cluster catalysts and method for preparing same | |
| CN111871428B (en) | Rhodium catalyst for preparing d, l-menthol and preparation method of d, l-menthol | |
| JPH01190638A (en) | Production of hydrocarbon by hydrogenation of carbon dioxide | |
| CN100473462C (en) | Catalyst for hydroisomerization reaction of alkane and preparation method thereof | |
| CN1046436C (en) | Catalyst for preparing synthetic gas by natural gas partial oxidation and its preparation method | |
| EP0220477A2 (en) | Novel bimetallic catalysts for the reaction of carbon monoxide and hydrogen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
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 |
|
| CX01 | Expiry of patent term |
Granted publication date: 20011107 |
|
| EXPY | Termination of patent right or utility model |