CN1088402C - Dicarbonic oxygen-contained compound catalyst such as alcohols, acetic acid, acetaldehyde etc. made from synthetic gas and process thereof - Google Patents
Dicarbonic oxygen-contained compound catalyst such as alcohols, acetic acid, acetaldehyde etc. made from synthetic gas and process thereof Download PDFInfo
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- CN1088402C CN1088402C CN98113757A CN98113757A CN1088402C CN 1088402 C CN1088402 C CN 1088402C CN 98113757 A CN98113757 A CN 98113757A CN 98113757 A CN98113757 A CN 98113757A CN 1088402 C CN1088402 C CN 1088402C
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- catalyst
- rhodium
- carrier
- oxygen
- acetaldehyde
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a catalyst for producing dicarbide oxygen-containing compounds of alcohol, acetic acid, acetaldehyde, etc. from the reaction of synthetic gas. The constitute of the catalyst is Rh-(a)-(b)-(c)-(d) and a carrier, wherein (a) is an element Ti or V, (b) is one kind or a plurality of kinds of rare earth elements of La, Ce, Y, Sm or Nd, etc., (c) is one of transition metal elements of Ru, Ni, Co, Pd, and (d) is one kind or two kinds of alkali metal elements Li and Na or K. The loading of Rh is 0.01w% to 4.0w% weight of the carrier, the loading of the elements (a), (b), (c) is 0.01 to 10% weight of the carrier, and the loading of the (d) element is 0 to 5% weight of the carrier. Using the catalyst can make CO and H2 react at high activity and high selectivity to prepare the dicarbide oxygen-containing compounds of the alcohol, the acetic acid, the acetaldehyde, etc.
Description
The invention provides a kind of multicomponent and contain supporting rhodium catalyst and on this catalyst, carrying out the catalyst and the process of c_2-oxygen compounds such as CO preparation of ethanol by hydrogenating, acetate, acetaldehyde of rare earth element.
As everyone knows, the rhodium catalyst that supports of promotion has unique selectivity in c_2-oxygen compounds such as CO hydrogenation synthesizing alcohol, be subjected to paying attention to widely.Once having the people just to contain rare-earth compound does the rhodium catalyst application that supports of the synthetic c_2-oxygen compound of auxiliary agent and crosses patent of invention, having described with one of Y, Pr, Sc, Nd, Sm, Dy, Ho, Er, Yb or Ce element as J57-062233 is the rhodium catalyst that supports of auxiliary agent, DE-3203060 once described period of element atom ordinal number be 21,39 and one of the element (being Ce, Y, Ce, Pr, Sm, Eu, Gd, Th, Dy, Ho, Er, Tm, Yb, Lu) of 58-71 as the rhodium catalyst that supports of auxiliary agent.J57-109731 has applied for the rhodium catalyst that supports that one of rare earth element y and element Zr, Ag, RE, U, Co, Ni, Th promote, J60-255741 has applied for one of alkali metal Li, Na, K, and one of rare earth element Lu, Y, Dy, Ho, Tb, Gd and alkaline-earth metal Mg reach the rhodium catalyst that supports of one of transition metal Ir, Ru promotion; Patent J61-178939, J61-178940, J61-178941, J60-259232 have applied for two kinds of catalyst that series connection is used, and four parts of patents are with identical first kind of catalyst and different second kind of catalyst.First kind with Rh, Li, Ir or/and x (x=Mg, Y, Yb, Lu, V, Cr) forms, second kind is respectively to support iron catalyst, Rh-Ir is or/and Fe, Mo catalyst, Rh-Ir is or/and the Mo catalyst, the Cu-Zn that supports is or/and the Cr catalyst.The catalysis efficiency that a significant disadvantages of these catalyst is rhodiums is not high enough, needs to use higher rhodium carrying capacity.Because rhodium is expensive metal, and is too much with the rhodium amount, must cause the investment cost of catalyst too high, influences their application in actual industrial process.
The objective of the invention is to reach and use the reaction that this catalyst carried out for the catalyst of a kind of high activity and high selectivity is provided from the reaction of c_2-oxygen compounds such as synthesis gas system ethanol, acetic acid, acetaldehyde.
Provided by the present inventionly be used for above-mentioned catalyst for reaction and form by Rh-(a)-(b)-(c)-(d) and carrier.(a) is V or Ti element in this catalyst, (b) be one of rare earth elements such as La, Sm, Nd, Y or Ce, (c) be one of Ru, Pd, Ni or Co metallic element, (d) alkali metal Li, Na or K a kind of or two kinds, carrier are carriers such as the silica gel used always, aluminium oxide, molecular sieve, active carbon.The content of rhodium is 0.01～4.0% of vehicle weight, be preferably 0.1～3%, the content of (a) and (b), (c) element is respectively 0.01～10% of vehicle weight, and preferably 0.1～5%, (d) content of element is 0～5% of vehicle weight, preferably 0.01～3%.The rhodium compound that is used for preparing catalyst is salts such as the chloride of rhodium, nitrate, oxalates, acetate, and vanadium compounds is NH
4VO
3, VOCL
2.xH
2O, VO (NO
3)
2.xH
2Compounds such as O, titanium compound are TiCL
4, TiCl
3, Ti (SO
4)
2, Ti (OC
4H
9)
4Etc. inorganic and organic compound, the compound of rare earth elements such as La, Sm, Nd, Y, Ce is their chloride or salt such as nitrate.The compound of Ru, Pd, Ni, Co metallic element and Li, Na, K element is salts such as their chloride, nitrate, acetate.
The method for preparing catalyst of the present invention preparation method of supported catalyst routinely carries out: the compound of the element of rhodium and other promotion is dissolved in water or the organic solvent, carrier is added in the solution floods, evaporation removes and desolvates, and drying and roasting can obtain required catalyst.Dipping process can once be finished, and also can be impregnated into some component earlier earlier and flood other component on the carrier after the drying roasting again.Wherein, baking temperature is 10～200 ℃, and 1～24 hour time, roasting is at 200～600 ℃, and the time is 1～60 hour, is preferably 2～40 hours.
These catalyst reduced earlier and make the catalyst activation before the input reaction bed reacts.Reducing agent can be other reducing agents such as hydrogen or hydrogeneous gaseous mixture, or hydrazine, preferably hydrogen or hydrogeneous gaseous mixture.Preference temperature with hydrogen or the reduction of hydrogeneous gaseous mixture is 100～600 ℃, preferably 200～500 ℃, and 1～80 hour recovery time, best 2～50 hours.
The suitable condition that carries out the synthetic c_2-oxygen compound reaction of CO hydrogenation is: raw material is hydrogeneous and CO gas, H
2/ CO (molecular proportion) is 0.1～15.0,100～500 ℃ of reaction temperatures, preferably 150～350 ℃; Reaction pressure 0.1～30.0 MPa, preferably 1.0～20.0 MPa; Air speed 500～50000 hr
-1, 1000～40000 hr preferably
-1
The catalyst rhodium-containing amount that makes with the method is low and catalytic activity and selectivity are good, and the catalysis efficiency height of rhodium helps the economic benefit of the process that improves.Give further instruction below by specific embodiment to technology of the present invention.
Embodiment 1, certain density rhodium chloride, samaric nitrate, the dichloro vanadyl, the aqueous solution of cobalt nitrate mixes in proportion, adds the silica-gel carrier of requirement then, 120 ℃ of dryings 4 hours, 250 ℃ of roastings 5 hours made 1%Rh-0.3% Sm-0.5% V-0.5% Co/SiO
2, 2%Rh-0.05% Sm-1% V-1% Co and 0.5% Rh-0.5% Sm-4%V-3% Co/SiO
2Catalyst.
Embodiment 2, certain density rhodium chloride, samaric nitrate, titanium tetrachloride, cobalt nitrate, sodium-chloride water solution mixes in proportion, the silica-gel carrier that adds requirement then makes 1% Rh-0.3% Sm-0.5%Ti-0.5% Co-0.07% Na/SiO by embodiment 1 program
2Catalyst.
Embodiment 3, and certain density titanium tetrachloride aqueous solution is flooded silica-gel carrier in proportion, 120 ℃ of dryings and make Ti/SiO earlier 400 ℃ of roastings
2Carrier mixes the aqueous solution of certain density rhodium chloride, lanthanum nitrate, nickel nitrate then in proportion, the Ti/SiO of requirement
2The carrier adding wherein makes 1% Rh-0.3% La-0.1% Ti-0.6% Ni/SiO by embodiment 1 program
2Catalyst.
Embodiment 4, mix in proportion with certain density rhodium chloride, yttrium nitrate, titanium tetrachloride, nickel nitrate, the lithium nitrate aqueous solution, add then and need heavy silica-gel carrier, make 1% Rh-0.3% Y-0.1% Ti-0.6% Ni-0.01% Li/SiO by embodiment 1 program
2Catalyst.
Embodiment 5, mix in proportion with certain density rhodium chloride, neodymium nitrate, dichloro vanadyl, the ruthenium trichloride aqueous solution, and the heat back adds the absorbent charcoal carrier of requirement, makes 0.3% Rh-0.3% Nd-0.5% V-1.0% Ru/SiO by embodiment 1 program
2Catalyst.
Embodiment 6, mix in proportion with certain density rhodium chloride, cerous nitrate, titanium tetrachloride, palladium chloride aqueous solution, add the silica-gel carrier of requirement then, make 0.1% Rh-0.3% Ce-0.1% Ti-0.3% Pd/SiO by embodiment 1 program
2Catalyst.
Embodiment 7, and certain density rhodium chloride, samaric nitrate, dichloro vanadyl, nickel nitrate aqueous solution are mixed in proportion, add the silica-gel carrier of requirement then, make 1% Rh/SiO by embodiment 1 program
2, 1% Rh-0.3%Ce-0.3% Sm-0.5% V-0.5% Ni/SiO
21% catalyst.
Comparative example 1～3 with rhodium chloride, samaric nitrate and silica-gel carrier raw material, makes 1% Rh/SiO respectively by embodiment 1 program
2, 1% Rh-0.3% Sm/SiO
2With 1% Rh-0.3% Sm-0.1% Ti/SiO
2Catalyst.
Use above-mentioned catalyst, utilize H
2/ CO=2 (molecular proportion) unstripped gas, 310 ℃ of reaction temperatures, pressure 3.0MPa, air speed 13000 hr
-1Under the condition, reaction evaluating the results are shown in Table 1.
The catalyst of table 1 embodiment and comparative example and performance thereof
| Catalyst | Catalyst is formed (weight %, all the other SiO 2) | CO conversion ratio (%) | Space-time yield (gram/kilogram. hour) | Selectivity (C%) |
| Example 1 | 1％ Rh-0.3％ Sm-0.5％ V-0.5％ Co | 4.5 | 270 | 67.6 |
| 1 | 2％ Rh-0.05％ Sm-1.0％ V-1％ Co | 5.3 | 326 | 69.2 |
| 1 | 0.5％ Rh-0.5％Sm-2％ V-3％ Co | 3.8 | 218 | 64.5 |
| 2 | 1％ Rh-0.3％ Sm-0.1％ Ti-0.5％ Co-0.07％Na | 5.0 | 290 | 65.2 |
| 3 | 1％ Rh-0.3％ La-0.5％ V-0.6％ Ni | 4.3 | 256 | 66.7 |
| 4 | 1％ Rh-0.5％ Y-0.1％ Ti-0.6％ Ni-0.01％Li | 4.7 | 284.2 | 68.1 |
| 5 | 0.1％ Rh-0.3％ Nd-0.5％ V-0.5％Ru | 4.6 | 267.2 | 65.4 |
| 6 | 0.3％ Rh-0.3％ Ce-0.1％ Ti-1.3％ Pd | 3.5 | 188 | 60.5 |
| 7 | 1％ Rh-0.3％ Ce-0.3％ Sm-0.5％ V-2％Ni | 5.3 | 250.8 | 50.5 |
| Comparative example | ||||
| 1 | 1％ Rh | 1.72 | 37.4 | 22.3 |
| 2 | 1％ Rh-0.3％ Sm | 3.38 | 176.1 | 53.9 |
| 3 | 1％ Rh-0.3％ Sm-0.1％ Ti | 4.9 | 254.0 | 56.0 |
By the result of last embodiment and comparative example as can be seen, but utilize catalyst high activity of the present invention and height selectively from CO and H
2C_2-oxygen compounds such as reaction ethanol production, acetate, acetaldehyde.
Claims (4)
1. catalyst that consists of rhodium and rare earth metal and transition metal of making c_2-oxygen compound ethanol, acetate and acetaldehyde from synthesis gas reaction, it is characterized in that expression with Rh-(a)-(b)-(c)-(d), wherein (a) is a kind of of element V, Ti, (b) be one or more of La, Ce, Y, Sm or Nd rare earth element, (c) being a kind of of transition metal Ru, Ni, Co, Pd, (d) is a kind of of alkali metal Li, Na or K element or two kinds; The content of rhodium is 0.01～4.0w% of vehicle weight; The element (a) and (b) and (c) carrying capacity be respectively 0.01～10% of vehicle weight, (d) content of element is 0～5% of vehicle weight, all the other are SiO
2, Al
2O
3, molecular sieve or absorbent charcoal carrier.
2. one kind according to the described Preparation of catalysts method of claim 1, the compound that is the element of rhodium and other promotion is dissolved in water or the organic solvent, carrier is added in the solution floods, evaporation removes and desolvates, drying and roasting, dipping process can once be finished, and also can be impregnated into some component earlier earlier and flood other component on the carrier after the drying roasting again, it is characterized in that baking temperature is 10～200 ℃, 1～24 hour time; Roasting is at 200～600 ℃, and the time is 1～100 hour.
3. according to the described Preparation of catalysts method of claim 2, it is characterized in that before carrying out the synthetic c_2-oxygen compound reaction of CO hydrogenation, using pure H
2Or contain H
2Gaseous mixture, or hydrazine reductant reduction is handled; Temperature during with hydrogen or the reduction of hydrogeneous gaseous mixture is 100～600 ℃, 1～80 hour recovery time.
4. the purposes according to the described catalyst of claim 3 is characterized in that being used for making c_2-oxygen compound ethanol, acetate and acetaldehyde from synthesis gas reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113757A CN1088402C (en) | 1998-02-12 | 1998-02-12 | Dicarbonic oxygen-contained compound catalyst such as alcohols, acetic acid, acetaldehyde etc. made from synthetic gas and process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113757A CN1088402C (en) | 1998-02-12 | 1998-02-12 | Dicarbonic oxygen-contained compound catalyst such as alcohols, acetic acid, acetaldehyde etc. made from synthetic gas and process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1225852A CN1225852A (en) | 1999-08-18 |
| CN1088402C true CN1088402C (en) | 2002-07-31 |
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| CN98113757A Expired - Fee Related CN1088402C (en) | 1998-02-12 | 1998-02-12 | Dicarbonic oxygen-contained compound catalyst such as alcohols, acetic acid, acetaldehyde etc. made from synthetic gas and process thereof |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100234477A1 (en) * | 2006-02-16 | 2010-09-16 | Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian China BP P.L.C. | Catalyst and Process for Syngas Conversion |
| CN101116816B (en) * | 2007-07-03 | 2010-08-18 | 中国石油大学(华东) | Method for preparing load type rhodium catalyst for making high-carbon aldehyde using hydroformylation of higher olefins |
| CN102218329A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing C2 and oxygenated chemicals thereof by using synthesis gas |
| CN102218313B (en) * | 2010-04-15 | 2013-12-04 | 中国石油化工股份有限公司 | Synthesis gas reforming catalyst and preparation method thereof |
| CN103301849A (en) * | 2012-03-14 | 2013-09-18 | 中国矿业大学(北京) | Catalyst for preparing dicarbon oxygen compounds by utilizing synthesis gas and preparation method of catalyst |
| CN104772150A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院上海高等研究院 | Cobalt-based catalyst for synthesis gas one-step preparation of mixed alcohol and aldehyde, and preparation method and application thereof |
| CN108816275B (en) * | 2018-04-19 | 2021-02-05 | 南京红太阳生物化学有限责任公司 | Catalyst for preparing pyridine base from synthesis gas, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57109730A (en) * | 1980-12-26 | 1982-07-08 | Showa Denko Kk | Preparation of oxgen-containing hydrocarbon compound from synthetic gas |
| JPS57126432A (en) * | 1981-01-27 | 1982-08-06 | Showa Denko Kk | Preparation of oxygen-containing hydrocarbon compound from synthetic gas |
| JPS61178942A (en) * | 1985-02-02 | 1986-08-11 | Agency Of Ind Science & Technol | Production of ethanol |
| JPS61178936A (en) * | 1985-02-02 | 1986-08-11 | Agency Of Ind Science & Technol | Production of ethanol |
| JPS62248328A (en) * | 1986-04-22 | 1987-10-29 | Fujitsu Ltd | Generation circuit for pass monitoring signal |
| JPS6333342A (en) * | 1986-07-29 | 1988-02-13 | Agency Of Ind Science & Technol | Production of ethylene from synthesis gas |
-
1998
- 1998-02-12 CN CN98113757A patent/CN1088402C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57109730A (en) * | 1980-12-26 | 1982-07-08 | Showa Denko Kk | Preparation of oxgen-containing hydrocarbon compound from synthetic gas |
| JPS57126432A (en) * | 1981-01-27 | 1982-08-06 | Showa Denko Kk | Preparation of oxygen-containing hydrocarbon compound from synthetic gas |
| JPS61178942A (en) * | 1985-02-02 | 1986-08-11 | Agency Of Ind Science & Technol | Production of ethanol |
| JPS61178936A (en) * | 1985-02-02 | 1986-08-11 | Agency Of Ind Science & Technol | Production of ethanol |
| JPS62248328A (en) * | 1986-04-22 | 1987-10-29 | Fujitsu Ltd | Generation circuit for pass monitoring signal |
| JPS6333342A (en) * | 1986-07-29 | 1988-02-13 | Agency Of Ind Science & Technol | Production of ethylene from synthesis gas |
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|---|---|
| CN1225852A (en) | 1999-08-18 |
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