CN1122567C - Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture - Google Patents
Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture Download PDFInfo
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- CN1122567C CN1122567C CN98113865A CN98113865A CN1122567C CN 1122567 C CN1122567 C CN 1122567C CN 98113865 A CN98113865 A CN 98113865A CN 98113865 A CN98113865 A CN 98113865A CN 1122567 C CN1122567 C CN 1122567C
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- Prior art keywords
- synthetic gas
- acetaldehyde
- ethanol
- catalyzer
- ethyl acetate
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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
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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Abstract
The present invention relates to a hydrogenation catalysts used for separate acetaldehyde, ethyl acetate, acetic acid or a mixture thereof. The catalyst composed of CuO which is the main constituent, a supporter Al2 O3 and an assistant which is an alkaline earth, such as CaO, MgO, Bao or a transition metal oxide, such as FeO, CoO, WO, MoO, ZnO, or the combination of the oxide. The content of the chemistry constituent of the catalyst is 10 to 70W% of CuO, 1 to 50W% of supporter Al2 O3 and 1 to 55W% of assistant. The present invention can form a composite catalyst together with an Rh/SiO[2] catalyst, and the composite catalyst is used for synthetizing gaseous alcohol. The alcohol selectivity reaches more than 90%.
Description
Technical field
The present invention relates to a kind of synthesis gas preparation alcoholic acid method, relate in particular to and a kind ofly prepare the alcoholic acid method from acetaldehyde, ethyl ester ethyl ester, acetate and composition thereof gas phase hydrogenation, its hydrogen derives from synthetic gas.
Background technology
Ethanol is basic Organic Chemicals, also is a kind of free of contamination high-octane gasoline dope.At present, the alcoholic acid production method mainly is that grain fermentation method and the hydration method of ethene on the phosphoric acid/kieselguhr catalyzer are produced.Also use Sweet natural gas to be raw material system alcoholic acid report, promptly the natural gas via steam reforming makes synthetic gas (CO+H
2), synthetic gas is at Rh/SiO
2On the catalyzer at 6.0MPa～8.0MPa, it is main carbon two oxygenatedchemicalss that 300 ℃ condition can obtain acetaldehyde, ethanol, ethyl acetate and acetate, above carbon two oxygenatedchemicalss pass through catalyzer again, can be ethanol with wherein acetaldehyde, ethyl acetate and acetic acid hydrogenation with synthetic gas.Realization is from coal or Sweet natural gas, through synthetic gas system ethanol.Narrated as the open 62-59232 of 1. Japan special permissions and to have used the copper catalyst of pickling process oxygenerating silicon as carrier.Synthetic gas is passed through Rh/SiO
2Catalyzer, and then the copper catalyst by the silicon oxide carrier are through the selectivity ethanol 61.1% in carbon two oxygenatedchemicalss that generated behind two catalyzer, acetaldehyde 0.7%, acetate 7.0%.2. Japan's special permission discloses 61178942 and uses dipping SiO
2The Pd-Fe catalyzer, realize that compound such as acetaldehyde is hydrogenated to ethanol.3. Japan's special permission public 61178940 is used at SiO
2The Pd-Fe catalyzer and the Rh/SiO that flood on the carrier
2Catalyzer uses together, will be at Rh/SiO
2Go up by the acetaldehyde in mixing carbon two oxygenatedchemicalss (acetaldehyde, ethanol, ethyl acetate, acetate etc.) of synthesis gas reaction generation, acetate etc. and be hydrogenated to ethanol.Be suitable for acetaldehyde, ethyl acetate, acetate or their hydrogenation mixtures as can be seen from the patent documentation of being looked into, be included under the synthetic gas atmosphere, with Rh/SiO
2The compound use of catalyzer is with Rh/SiO
2Acetaldehyde, ethyl acetate, acetate in mixing carbon two oxygenatedchemicalss that catalyzer generated, being hydrogenated to the alcoholic acid catalyzer under synthetic atmosphere all is with SiO
2Be the copper catalyst of carrier, perhaps Cu-Cr/SiO
2, Cu-Zn/SiO
2, Pd-Fe/SiO
2Catalyzer.And the hydrogenation degree to acetate is lower.
Summary of the invention
The object of the present invention is to provide a kind of method of synthetic gas synthesizing alcohol, promptly a kind of acetaldehyde, ethyl acetate, acetate or its mixture method of synthetic gas preparation of ethanol by hydrogenating.
A kind of method of synthetic gas synthesizing alcohol, that is co hydrogenation system alcoholic acid method,
(1) synthetic gas (CO+H
2, H
2/ CO=2) earlier by Rh/SiO is housed
2The reactor of catalyzer, from reactor outlet come out product be carbon two oxygenatedchemicalss and unreacted synthetic gas, carbon two oxygenatedchemicalss mainly are acetaldehyde, ethanol, ethyl acetate and acetate;
(2) product that comes out from (1) enters second reactor that copper catalyst is housed again, and the hydrogen reduction in the synthetic gas that acetaldehyde, acetate and the ethyl acetate in carbon two oxygenatedchemicalss do not transformed is an ethanol;
The underlying condition of above-mentioned (1), (2) step hydrogenation reaction is: reaction pressure 1～15Mpa, 150～400 ℃ of temperature, volume space velocity 5000～30000h-1, hydrogenation can be at H
2Under the atmosphere, also can under synthetic gas atmosphere, carry out.
Reaction pressure in above-mentioned (1), (2) step, preferred 3.0～6.0Mpa.
Preferred 320～330 ℃ of temperature of reaction in the above-mentioned steps (1); (2) temperature of reaction in the step is preferred 150～200 ℃.
The major ingredient of the copper catalyst described in the above-mentioned steps (2) is CuO, and carrier is Al
2O
3, auxiliary agent is a kind of alkaline earth metal oxide such as CaO, MgO, BaO or transition metal oxide such as FeO, CoO, WO, MoO, ZnO, the perhaps combination of above-mentioned oxide compound; Catalyst chemical is formed, main ingredient CuO:10～70W%, carrier Al
2O
3: 1～50W%, auxiliary agent: 1～55W%.
Above-mentioned copper catalyst its preparation method can adopt dipping method, comprising the step impregnation method, promptly elder generation is with the aqueous solution of the salt of above-mentioned metal, perhaps ethanolic soln floods carrier, also can adopt coprecipitation method to prepare catalyzer, 10～200 ℃ of catalyzer drying temperatures, 300～600 ℃ of maturing temperatures, roasting time 1～10 hour.
Use the copper catalyst of method for preparing, under 200～400 ℃ of temperature, with H2 or H
2After reducing 1～50 hour under the rare gas element mixed atmosphere, be used further to the hydrogenation reaction of independent acetaldehyde, ethyl acetate, acetate or their mixture arbitrarily.
The present invention proposes a method from the synthetic gas synthesizing alcohol.Its first step is used Rh/SiO
2Catalyzer, the ethanol of generation accounts for 30～40%; The catalyzer that passes through when the second step reaction adopts when being the copper catalyst of precipitator method preparation, and ethanol accounts for more than 90% in its final product.
Embodiment
Further specify the present invention by the following examples.
Embodiment 1
With 65.5 gram cupric nitrates, 25.3 gram zinc nitrates, but 16.5 aluminum nitrates are dissolved in 280 ml distilled waters, under heated and stirred, with yellow soda ash neutralize PH=7, washing of precipitate then, in 110 ℃ of baking ovens dry 6 hours, the sheet moulding was played catalyzer in 400 ℃ of calcinations 4 hours at last.
Embodiment 2
With 17.5 gram cupric nitrates, 33.3 gram zinc nitrate, 16.5 but aluminum nitrate and 10.4 gram magnesium nitrates are dissolved in 280 ml distilled waters, under heated and stirred, with the yellow soda ash PH=7 that neutralizes, washing of precipitate then, in 110 ℃ of baking ovens dry 6 hours, the sheet moulding is played catalyzer in 400 ℃ of calcinations 4 hours at last.
Embodiment 3
With 29.4 gram cupric nitrates, 34.3 gram zinc nitrate, but 16.5 aluminum nitrate and 10.4 gram magnesium nitrates, be dissolved in 300 ml distilled waters with 5.2 gram nitric acid molybdenums, under heated and stirred, with the yellow soda ash PH=7 that neutralizes, washing of precipitate then, in 110 ℃ of baking ovens dry 6 hours, the sheet moulding was played catalyzer in 400 ℃ of calcinations 4 hours at last.
Embodiment 4
On the small stationary bed reaction device, two reactors of connecting are adorned 0.3 gram Rh/SiO in first reactor
2Catalyzer, second reactor is not put catalyzer.Reacting system pressure is 3.0Mpa, 320 ℃ of first temperature of reaction, and 150～200 ℃ of second temperature of reactor are by synthetic gas (CO+H
2, H
2/ CO=2) 7 liters per hour.The reaction product water absorbs, exhaust emissions, and aqueous solution chromatographically is made composition.Composed as follows in the product carbon two above oxygenatedchemicalss:
Acetaldehyde ethanol propanol ethyl acetate butanols acetate W% 24.7 41.3 3.0 6.3 3.0 21.7
The prepared catalyzer of dress 1.0g embodiment 1 in second reactor.By synthetic gas (CO+H
2, H
2/ CO=2) 7 liters per hour.The reaction product water absorbs, exhaust emissions, and aqueous solution chromatographically is made composition.Composed as follows in the product carbon two above oxygenatedchemicalss:
Acetaldehyde ethanol propanol ethyl acetate butanols acetate W% 1.1 88.3 4.9 1.3 1.3 3.1
Embodiment 5
On the small stationary bed reaction device, two reactors of connecting are adorned 0.3 gram Rh/SiO in first reactor
2Catalyzer, the catalyzer that second reactor dress 1.0g example 2 is prepared.Reaction pressure 3.0Mpa, 320 ℃ of first temperature of reactor, 150～200 ℃ of second temperature of reactor are by synthetic gas (CO+H
2, H
2/ CO=2) 7 liters per hour.The reaction product water absorbs, exhaust emissions, and aqueous solution chromatographically is made composition.Product carbon two above oxygenatedchemicalss are composed as follows:
Acetaldehyde ethanol propanol ethyl acetate butanols acetate W% 0.1 91.4 4.9 0 1.3 2.1
Embodiment 6
On the small stationary bed reaction device, two reactors of connecting are adorned 0.3 gram Rh/SiO in first reactor
2Catalyzer, the catalyzer that second reactor dress 1.0g example 3 is prepared.Reaction pressure is 3.0Mpa, 320 ℃ of first temperature of reactor, and 150～200 ℃ of second temperature of reactor are by synthetic gas (CO+H
2, H
2/ CO=2) 7 liters per hour.The reaction product water absorbs, exhaust emissions, and aqueous solution chromatographically is made composition.Product carbon two above oxygenatedchemicalss are composed as follows:
Acetaldehyde ethanol propanol ethyl acetate butanols acetate W% 0 92.7 5.1 0 1.2 0.89
Embodiment 7
On the single tube simulation test device, two reactors of connecting, first reactor charge 64g Rh/SiO
2Catalyzer, the catalyzer 213g that second reactor charge embodiment 3 is prepared, reaction pressure 6.0Mpa, first temperature of reactor T
1=330 ℃, second temperature of reactor T
2=150～200 ℃, unstripped gas is formed CO+H
2, H
2/ CO=2.Unstripped gas speed 200 liters/hour, the reactant gases circulation, recycle ratio is 20.Reaction product is collected through condensation separation, its composition of chromatographically.Its result, product carbon two above oxygenatedchemicalss are composed as follows:
Acetaldehyde ethanol propanol ethyl acetate butanols acetate W% 0 93.5 4.9 0 1.3 0.7
Comparative example 1
On the single tube simulation test device, two reactors of connecting, first reactor charge 64g Rh/SiO
2Catalyzer, second reactor do not put catalyzer, reaction pressure 6.0Mpa, first temperature of reactor T
1=330 ℃, second temperature of reactor T
2=150～200 ℃, unstripped gas is formed CO+H
2, H
2/ CO=2.Unstripped gas speed 200 liters/hour, the reactant gases circulation, recycle ratio is 20.Reaction product is collected through condensation separation, its composition of chromatographically.Its result, product carbon two above oxygenatedchemicalss are composed as follows:
Acetaldehyde ethanol propanol ethyl acetate butanols acetate W% 21.3 34.3 2.5 7.6 0.4 23.6
Comparative example 2
Catalyzer ethanol selectivity % acetaldehyde selectivity % acetic acid selectivity %
J62592?Rh-Mg-Li/SiO
2//Cu-Zn-Cr?61.1 0.7 7.0
32
Rh-Mg-Li/SiO of the present invention
2//Cu-Zn-Mg 92.7 0 0.9
-Mo-Al
2O
3
Claims (7)
1. the method for a synthetic gas synthesizing alcohol, that is co hydrogenation system alcoholic acid method is characterized in that carrying out as follows:
(1) synthetic gas is earlier by being equipped with Rh/SiO
2The reactor of catalyzer, the product that comes out from reactor outlet is carbon two oxygenatedchemicalss and unreacted synthetic gas, carbon two oxygenatedchemicalss mainly are acetaldehyde, ethanol, ethyl acetate and acetate;
(2) product that comes out from (1) enters second reactor that copper catalyst is housed again, and the hydrogen reduction in the synthetic gas that acetaldehyde, acetate and the ethyl acetate in carbon two oxygenatedchemicalss do not transformed is an ethanol; Described copper catalyst chemical constitution is: main ingredient CuO:10～70W%, carrier Al
2O
3: 1～50W%, auxiliary agent: 1～55W%;
The underlying condition of above-mentioned (1), (2) step hydrogenation reaction is: 150～400 ℃ of reaction pressure 1～15Mpa, temperature
2. the method for synthetic gas synthesizing alcohol as claimed in claim 1 is characterized in that the reaction pressure in step (1), (2) is 3.0～6.0Mpa.
3. the method for synthetic gas synthesizing alcohol as claimed in claim 1 is characterized in that the temperature of reaction in the step (1) is 320～330 ℃.
4. the method for synthetic gas synthesizing alcohol as claimed in claim 1 is characterized in that the temperature of reaction in the step (2) is 150～200 ℃.
5. the method for synthetic gas synthesizing alcohol as claimed in claim 1 is characterized in that the major ingredient of the copper catalyst described in the step (2) is CuO, and carrier is Al
2O
3, auxiliary agent is a kind of among a kind of alkaline earth metal oxide CaO, MgO, the BaO, or transition metal oxide FeO, CoO, WO, MoO, ZnO's is a kind of, the perhaps combination of above-mentioned oxide compound; Catalyst chemical is formed, main ingredient CuO:10～70W%, carrier Al
2O
3: 1～50W%, auxiliary agent: 1～55W%.
6. the method for synthetic gas synthesizing alcohol as claimed in claim 5, copper catalyst adopt the coprecipitation method preparation, it is characterized in that: 10～200 ℃ of catalyzer drying temperatures, 300～600 ℃ of maturing temperatures, roasting time 1～10 hour.
7. the method for synthetic gas synthesizing alcohol as claimed in claim 5 is characterized in that copper catalyst, under 200～400 ℃ of temperature, uses H
2Or H
2Be used further to the synthetic gas hydrogenation reaction with reduction under the rare gas element mixed atmosphere after 1～50 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113865A CN1122567C (en) | 1998-03-26 | 1998-03-26 | Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113865A CN1122567C (en) | 1998-03-26 | 1998-03-26 | Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1230458A CN1230458A (en) | 1999-10-06 |
| CN1122567C true CN1122567C (en) | 2003-10-01 |
Family
ID=5223562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113865A Expired - Lifetime CN1122567C (en) | 1998-03-26 | 1998-03-26 | Catalyst for preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1122567C (en) |
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| CN1095400C (en) * | 1999-12-08 | 2002-12-04 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing gamma-butyrolactone from cis-aldehyde by ordinary-pressure gas-phase hydrogenation and its use |
| US20100197486A1 (en) * | 2008-07-31 | 2010-08-05 | Celanese International Corporation | Catalysts for making ethyl acetate from acetic acid |
| CA2787419A1 (en) * | 2010-02-02 | 2011-08-11 | Celanese International Corporation | Preparation and use of a catalyst for producing ethanol comprising a crystalline support modifier |
| MX2012008928A (en) * | 2010-02-02 | 2012-08-15 | Celanese Int Corp | Process for purifying ethanol. |
| US8552224B2 (en) | 2010-05-07 | 2013-10-08 | Celanese International Corporation | Processes for maximizing ethanol formation in the hydrogenation of acetic acid |
| US9272970B2 (en) | 2010-07-09 | 2016-03-01 | Celanese International Corporation | Hydrogenolysis of ethyl acetate in alcohol separation processes |
| CN101934228A (en) * | 2010-09-30 | 2011-01-05 | 江苏丹化煤制化学品工程技术有限公司 | Catalyst for preparing alcohol by acetic ester hydrogenation as well as preparation method and application thereof |
| CN102020532A (en) * | 2010-11-11 | 2011-04-20 | 江苏索普（集团）有限公司 | Hydrogenation method for preparing alcohol by using water-solution mixture of alcohol, aldehyde, acid and ester as raw material |
| CN102093162B (en) * | 2010-12-13 | 2012-04-18 | 西南化工研究设计院 | Method for preparing ethanol by hydrogenation of acetic ester |
| US8575406B2 (en) | 2011-12-22 | 2013-11-05 | Celanese International Corporation | Catalysts having promoter metals and process for producing ethanol |
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| CN102775299B (en) * | 2012-08-03 | 2015-09-02 | 兖矿国泰化工有限公司 | A kind of acetic acid hydrogenation prepares the method for vinyl acetic monomer indirectly |
| US8957262B2 (en) | 2012-11-20 | 2015-02-17 | Celanese International Corporation | Olefin hydration for hydrogenation processes |
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| CN103894206B (en) * | 2012-12-27 | 2016-09-07 | 中国石油化工股份有限公司 | High activity copper-based catalysts, preparation method and its usage |
| US8975450B2 (en) | 2013-03-15 | 2015-03-10 | Celanese International Corporation | Ethanol and ethyl acetate production using an acetic acid and acetic anhydride mixed feed |
| US8926718B2 (en) | 2013-03-15 | 2015-01-06 | Celanese International Corporation | Thermochemically produced ethanol compositions |
| CN104148086B (en) * | 2013-05-16 | 2017-10-27 | 中国石油化工股份有限公司 | Prepare the catalyst and method of ethanol |
| CN104710280B (en) * | 2013-12-16 | 2017-10-17 | 中国科学院大连化学物理研究所 | Method for producing methanol co-production C2 C4 alcohol |
| WO2015089703A1 (en) * | 2013-12-16 | 2015-06-25 | 中国科学院大连化学物理研究所 | Method for use in production of methanol and coproduction of c2-c4 alcohols |
| CN103920502B (en) * | 2014-04-15 | 2016-04-27 | 北京化工大学 | The Catalysts and its preparation method of ethyl acetate gas phase hydrogenation ethanol and application under a kind of temperate condition |
| WO2018198072A1 (en) | 2017-04-27 | 2018-11-01 | Sabic Global Technologies B.V. | Removal of alkyne impurities from diolefin containing mixtures through cracking over cuo/al2o3 based materials |
| EA202090650A1 (en) * | 2017-09-29 | 2020-06-10 | Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайенсез | METHOD FOR DIRECT OBTAINING ETHANOL FROM SYNTHESIS GAS |
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|---|---|---|---|---|
| DE3042686A1 (en) * | 1979-11-12 | 1981-05-27 | Mitsubishi Gas Chemical Co., Inc., Tokyo | METHOD FOR PRODUCING A CATALYST |
| EP0424069A1 (en) * | 1989-10-17 | 1991-04-24 | Engelhard Corporation | Hydrogenation catalys and process of using said catalyst |
| EP0604792A1 (en) * | 1992-12-28 | 1994-07-06 | Hoechst Aktiengesellschaft | Copper catalyst |
| CN1120975A (en) * | 1995-06-28 | 1996-04-24 | 中国科学院大连化学物理研究所 | Aldose hydrogenating process and catalyst for producing sugar alcohol |
-
1998
- 1998-03-26 CN CN98113865A patent/CN1122567C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3042686A1 (en) * | 1979-11-12 | 1981-05-27 | Mitsubishi Gas Chemical Co., Inc., Tokyo | METHOD FOR PRODUCING A CATALYST |
| EP0424069A1 (en) * | 1989-10-17 | 1991-04-24 | Engelhard Corporation | Hydrogenation catalys and process of using said catalyst |
| EP0604792A1 (en) * | 1992-12-28 | 1994-07-06 | Hoechst Aktiengesellschaft | Copper catalyst |
| CN1120975A (en) * | 1995-06-28 | 1996-04-24 | 中国科学院大连化学物理研究所 | Aldose hydrogenating process and catalyst for producing sugar alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1230458A (en) | 1999-10-06 |
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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 preparation of ethanol by hydrogenating acetaldehyde, ethyl acetate, acetic acid or their mixture Granted publication date: 20031001 License type: Exclusive License Open date: 19991006 Record date: 20120405 |
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Granted publication date: 20031001 |