CN106622283A - Preparation method of catalyst for synthesis of ethyl acetate and co-production of normal butanol by ethanol one-step method - Google Patents
Preparation method of catalyst for synthesis of ethyl acetate and co-production of normal butanol by ethanol one-step method Download PDFInfo
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- CN106622283A CN106622283A CN201611080849.XA CN201611080849A CN106622283A CN 106622283 A CN106622283 A CN 106622283A CN 201611080849 A CN201611080849 A CN 201611080849A CN 106622283 A CN106622283 A CN 106622283A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
Abstract
The invention relates to the field of preparation of catalysts, and particularly discloses a preparation method of a catalyst for synthesis of ethyl acetate and co-production of normal butanol by an ethanol one-step method. The preparation method comprises the steps: (1) preparing a solution A and a solution B; (2) preparing carrier particles and drying the carrier particles; (3) dipping the carrier particles with the solution A and the solution B separately and roasting for many times; (4) reducing the sample in mixed gas consisting of hydrogen and inert gas to obtain the required catalyst. The catalyst provided by the invention is applied to synthesis of the ethyl acetate and co-production of the normal butanol through ethanol, the catalytic efficiency of the catalyst is high, the ethanol feeding airspeed is 15 liters of ethanol per liter of catalyst per hour, the conversion rate of the ethanol is more than 30 percent and the highest conversion rate of the ethanol is 70 percent; the ethyl acetate selectivity ranges between 10 percent and 80 percent, the corresponding normal butanol selectivity ranges between 80 percent and 100 percent, and a good technical effect is achieved.
Description
（One）Technical field
The present invention relates to urge used by the preparation field of catalyst, more particularly to ethanol with one-step method synthesizing ethyl acetate coproduction of normal butanol
Agent preparation method.
（Two）Background technology
Ethyl acetate is a kind of broad-spectrum fine chemical product, of many uses with excellent dissolubility, quick-drying, is
A kind of very important Organic Chemicals and fabulous industrial solvent, are widely used in acetate fiber, ethyl cellulose, chlorination rubber
In the production process of glue, vinyl, acetate fiber resin, synthetic rubber, coating and paint etc..N-butanol mainly for the manufacture of
The N-butyl class plasticizer of phthalic acid, aliphatic dibasic acid and phosphoric acid, they are widely used in various plastics and rubber
In, it is also the raw material of producing butyladehyde in organic synthesis, butyric acid, butylamine and butyl lactate etc..Or grease, medicine（As antibiotic, swash
Element and vitamin）With the extractant of spices, the additive of phthalic resin coating etc., organic dyestuff and printing-ink are can be used as again
Solvent, dewaxing agent.At present, the catalyst generally existing used by synthesizing ethyl acetate coproduction of normal butanol that catalyst efficiency is low, second
The low defect of alcohol conversion.
（Three）The content of the invention
A kind of defect in order to make up prior art of the invention, there is provided the high step of ethanol one of high catalytic efficiency, ethanol conversion
The preparation method of method synthesizing ethyl acetate coproduction of normal butanol used catalyst.
The present invention is achieved through the following technical solutions：
Ethanol with one-step method synthesizing ethyl acetate coproduction of normal butanol used catalyst preparation method, is characterized in that, step is as follows:
（1）Solution A:By the soluble metallic salt of component a, the soluble metallic salt of the soluble in water or molten a of energy is volatile organic
In solvent, the concentration of the soluble metal salt ion of a is 0.005-0.5mol/L；B solution:By the soluble metallic salt of component b
In the volatile organic solvent of soluble metallic salt soluble in water or the molten b of energy, the concentration of the soluble metal salt ion of b is
0.001-0.1mol/L；
（2）Carrier is carried out into compressing tablet, crushing, granulation, the carrier granular of 20～40 mesh is obtained；Then by carrier granular 80～
Dry 4～8 hours at 120 DEG C；
（3）By step（2）In the carrier granular that obtains be put into rotatable heater and carry out multiple incipient impregnation simultaneously with solution A
Drying, until solution A all impregnates finishing, then dries 11～13 hours, in 200～600 DEG C of roastings 1～10 at 80～120 DEG C
Hour；
（4）By step（3）In the sample that obtains be put into again in rotatable heater and carry out multiple incipient impregnation simultaneously with B solution
Drying, until B solution all impregnates finishing, then dries 11～13 hours at 30～100 DEG C, dries 11～13 at 100～150 DEG C little
When, in 300～600 DEG C of roastings 1～10 hour；
（5）By step（4）In the sample that obtains carry out in the gaseous mixture of hydrogen and inert gas, at 200～600 DEG C also
Original, obtains required catalyst；
Wherein, component a is any one in nickel, copper, zinc or two kinds；
Component b is any one in iridium, platinum, palladium, ruthenium；
The carrier is the mixed-powder of any one or two kinds of in basic magnesium carbonate, magnesium carbonate, magnesium hydroxide, magnesia.
In step（3）、（4）In, the metallic of component a, the metallic of b, the mass ratio of carrier are 0.1～20：
0.01～5：100.
In step（5）In, in the gaseous mixture volume content of hydrogen be 30～90%, the inert gas be nitrogen,
Argon gas or helium.
The invention has the beneficial effects as follows：
Ethanol synthesizing ethyl acetate coproduction of normal butanol, the high catalytic efficiency of catalyst, second are applied to using the catalyst of the present invention
Alcohol Feed space velocities are 15 liters of ethanol/liter catalyst * hours, and ethanol conversion is more than 30%, up to 70%；Ethyl acetate is selected
Property between 10%～80%, corresponding n-butanol is selective between 80%～100%, obtains preferable technique effect.
（Four）Specific embodiment
It is below the specific embodiment of the present invention：
The preparation of solution A：
Embodiment 1：
Copper nitrate is dissolved in water the solution for being configured to that copper ion concentration is 0.005 mol/L.
Embodiment 2：
Zinc nitrate is dissolved in water the solution for being configured to that zinc ion concentration is 0.01 mol/L.
Embodiment 3：
Nickel nitrate is dissolved in water the solution for being configured to that nickel ion concentration is 0.1 mol/L.
Embodiment 4：
Cupric sulfate pentahydrate is dissolved in water the solution for being configured to that copper ion concentration is 0.005 mol/L.
Embodiment 5：
Zinc sulfate is dissolved in water the solution for being configured to that zinc ion concentration is 0.01 mol/L.
Embodiment 6：
Nickel sulfate is dissolved in water the solution for being configured to that nickel ion concentration is 0.1 mol/L.
Embodiment 7：
Copper chloride is dissolved in water the solution for being configured to that copper ion concentration is 0.005 mol/L.
Embodiment 8
Acetylacetone copper is dissolved in carbon tetrachloride the solution for being configured to that copper ion concentration is 0.005 mol/L.
Embodiment 9
Nickel acetylacetonate is dissolved in ether the solution for being configured to that nickel ion concentration is 0.005 mol/L.
Embodiment 10：
It is the molten of 0.01 mol/L that zinc chloride and nitrate trihydrate copper dissolution are configured in ethanol into zinc ion and copper ion concentration
Liquid.
Embodiment 11：
It is the molten of 0.005 mol/L cupric sulfate pentahydrate and zinc nitrate to be dissolved in water and is configured to copper ion and zinc ion concentration
Liquid.
Embodiment 12：
Copper nitrate and zinc nitrate are dissolved in water and are configured to copper ion and solution that zinc ion concentration is 0.1 mol/L.
Any one in nickel, copper, zinc or two kinds can be changed in above-mentioned slaine into；
Any solvable nickel, copper, the volatile organic solvent of zinc slaine can be replaced with above-mentioned organic solvent.
The preparation of B solution：
Embodiment 1：
Acid chloride dissolving is configured into acetone the solution that palladium ion concentration is 0.005 mol/L.
Embodiment 2
Ruthenium acetate is dissolved in ether the solution for being configured to that ruthenium ion concentration is 0.01 mol/L.
Embodiment 3：
Palladium nitrate is dissolved in water the solution for being configured to that palladium ion concentration is 0.1 mol/L.
Embodiment 4：
The dissolving of acetylacetone,2,4-pentanedione platinum is configured into acetone the solution that platinum ion concentration is 0.02 mol/L.
Embodiment 5：
The dissolving of acetylacetone,2,4-pentanedione ruthenium is configured into acetone the solution that ruthenium ion concentration is 0.08mol/L.
Embodiment 6：
Palladium bichloride is dissolved in water plus a few drop hydrochloric acid are configured to the solution that palladium ion concentration is 0.05 mol/L.
Embodiment 7：
Platinum tetrachloride dissolving is configured into acetone the solution that platinum ion concentration is 0.01 mol/L.
Embodiment 8：
Iridium chloride hydrate dissolution is configured into the solution that iridium ion concentration is 0.1 mol/L in water.
Embodiment 9：
β-ruthenium trichloride dissolving is configured into ethanol the solution that ruthenium ion concentration is 0.02 mol/L.
Any one in palladium, iridium, platinum, ruthenium can be changed in above-mentioned slaine into；
Any solvable palladium, iridium, platinum, the volatile organic solvent of ruthenium slaine and water can be replaced with above-mentioned solvent.
Embodiment one：
（1）50 grams of basic magnesium carbonates are carried out into compressing tablet, crushing, granulation, the carrier granular of 20～40 mesh is obtained；Then by carrier
Grain dries 4 hours at 80 DEG C；
（2）；By step（1）In the carrier granular that obtains be put into rotatable heater and carried out repeatedly with above-mentioned any one solution A
Incipient impregnation is simultaneously dried, until solution A all impregnates finishing, is then dried 11 hours at 80 DEG C, then little in 200 DEG C of roastings 1
When；
（3）By step（2）In the sample that obtains be put into again in rotatable heater carried out with above-mentioned any one B solution it is how inferior
Volume impregnation is simultaneously dried, until whole B solutions all impregnate and finish, is then dried 11 hours at 30 DEG C, is dried 11 hours at 100 DEG C,
In 300 DEG C of roastings 1 hour；
In step（2）（3）In, a metallics, b metallics, the mass ratio of carrier are 0.1：0.01：100；
（4）By step（3）In the sample that obtains in the gaseous mixture being made up of hydrogen and nitrogen, reduced at 200 DEG C, obtain
Required catalyst；Wherein, the volume content of hydrogen is 30% in gaseous mixture.
Embodiment two：
（1）50 grams of magnesium carbonate are carried out into compressing tablet, crushing, granulation, the carrier granular of 20～40 mesh is obtained；Then carrier granular is existed
Dry 8 hours at 120 DEG C；
（2）；By step（1）In the carrier granular that obtains be put into rotatable heater and carried out repeatedly with above-mentioned any one solution A
Incipient impregnation is simultaneously dried, until solution A all impregnates finishing, is then dried 13 hours at 120 DEG C, then in 600 DEG C of roastings 10
Hour；
（3）By step（2）In the sample that obtains be put into again in rotatable heater and carry out multiple incipient impregnation simultaneously with B solution
Drying, until whole B solutions all impregnate and finish, then dries 13 hours at 100 DEG C, dries 13 hours at 150 DEG C, in 600 DEG C of roastings
Burn 1 hour；
In step（2）（3）In, a metallics, b metallics, the mass ratio of carrier are 20：5：100；
（4）By step（3）In the sample that obtains in the gaseous mixture being made up of hydrogen and argon gas, reduced at 600 DEG C, obtain
Required catalyst；Wherein, the volume content of hydrogen is 90% in gaseous mixture.
Embodiment three：
（1）50 grams of magnesium hydroxides are carried out into compressing tablet, crushing, granulation, the carrier granular of 20～40 mesh is obtained；Then by carrier granular
Dry 6 hours at 100 DEG C；
（2）；By step（1）In the carrier granular that obtains be put into rotatable heater and carried out repeatedly with above-mentioned any one solution A
Incipient impregnation is simultaneously dried, until solution A all impregnates finishing, is then dried 12 hours at 100 DEG C, then little in 400 DEG C of roastings 5
When；
（3）By step（2）In the sample that obtains be put into again in rotatable heater and carry out multiple incipient impregnation simultaneously with B solution
Drying, until whole B solutions all impregnate and finish, then dries 12 hours at 60 DEG C, dries 12 hours at 120 DEG C, in 500 DEG C of roastings
5 hours；
In step（2）（3）In, a metallics, b metallics, the mass ratio of carrier are 10：0.1：100；
（4）By step（3）In the sample that obtains reduced in the gaseous mixture being made up of hydrogen and helium, at 400 DEG C, obtain
Required catalyst；Wherein, the volume content of hydrogen is 60% in gaseous mixture.
Example IV：
（1）50 grams of magnesia are carried out into compressing tablet, crushing, granulation, the carrier granular of 20～40 mesh is obtained；Then carrier granular is existed
Dry 8 hours at 80 DEG C；
（2）；By step（1）In the carrier granular that obtains be put into rotatable heater and carried out repeatedly with above-mentioned any one solution A
Incipient impregnation is simultaneously dried, until solution A all impregnates finishing, is then dried 13 hours at 80 DEG C, then little in 200 DEG C of roastings 10
When；
（3）By step（2）In the sample that obtains be put into again in rotatable heater and carry out multiple incipient impregnation simultaneously with B solution
Drying, until whole B solutions all impregnate and finish, then dries 13 hours at 30 DEG C, dries 13 hours at 100 DEG C, in 300 DEG C of roastings
10 hours；
In step（2）（3）In, a metallics, b metallics, the mass ratio of carrier are 0.1：5：100；
（4）By step（3）In the sample that obtains reduced in the gaseous mixture being made up of hydrogen and helium, at 200 DEG C, obtain
Required catalyst；Wherein, the volume content of hydrogen is 90% in gaseous mixture.
Embodiment five：
（1）By 50 grams of magnesia and the mixture of basic magnesium carbonate（With arbitrary proportion mixing）Compressing tablet, crushing, granulation are carried out, is obtained
To the carrier granular of 20～40 mesh；Then carrier granular is dried 4 hours at 120 DEG C；
（2）；By step（1）In the carrier granular that obtains be put into rotatable heater and carried out repeatedly with above-mentioned any one solution A
Incipient impregnation is simultaneously dried, until solution A all impregnates finishing, is then dried 11 hours at 120 DEG C, then little in 600 DEG C of roastings 1
When；
（3）By step（2）In the sample that obtains be put into again in rotatable heater and carry out multiple incipient impregnation simultaneously with B solution
Drying, until whole B solutions all impregnate and finish, then dries 11 hours at 100 DEG C, dries 11 hours at 150 DEG C, in 600 DEG C of roastings
Burn 1 hour；
In step（2）（3）In, a metallics, b metallics, the mass ratio of carrier are 20：0.01：100；
（4）By step（3）In the sample that obtains reduced in the gaseous mixture being made up of hydrogen and nitrogen, at 600 DEG C, obtain
Required catalyst；Wherein, the volume content of hydrogen is 30% in gaseous mixture.
Embodiment six：
（1）By 50 grams of magnesium carbonate and the mixture of basic magnesium carbonate（With arbitrary proportion mixing）Compressing tablet, crushing, granulation are carried out, is obtained
To the carrier granular of 20～40 mesh；Then carrier granular is dried 6 hours at 100 DEG C；
（2）；By step（1）In the carrier granular that obtains be put into rotatable heater and carried out repeatedly with above-mentioned any one solution A
Incipient impregnation is simultaneously dried, until solution A all impregnates finishing, is then dried 11 hours at 90 DEG C, then little in 500 DEG C of roastings 8
When；
（3）By step（2）In the sample that obtains be put into again in rotatable heater and carry out multiple incipient impregnation simultaneously with B solution
Drying, until whole B solutions all impregnate and finish, then dries 12 hours at 80 DEG C, dries 11 hours at 120 DEG C, in 500 DEG C of roastings
3 hours；
In step（2）（3）In, a metallics, b metallics, the mass ratio of carrier are 1：1：100；
（4）By step（3）In the sample that obtains reduced in the gaseous mixture being made up of hydrogen and nitrogen, at 300 DEG C, obtain
Required catalyst；Wherein, the volume content of hydrogen is 50% in gaseous mixture.
Embodiment seven：
Carrier granular used is the basic magnesium carbonate and magnesium hydroxide mixed with arbitrary proportion, and remaining is identical with embodiment one.
Embodiment eight：
Carrier granular used is the magnesium carbonate and magnesium hydroxide mixed with arbitrary proportion, and remaining is identical with embodiment two.
Embodiment nine：
Carrier granular used is the basic magnesium carbonate and magnesia mixed with arbitrary proportion, and remaining is identical with embodiment three.
Embodiment ten：
Carrier granular used is the magnesia and magnesium hydroxide mixed with arbitrary proportion, and remaining is identical with example IV.
In addition to technical characteristic described in specification, remaining technical characteristic is technology known to those skilled in the art.
Claims (3)
1. ethanol with one-step method synthesizing ethyl acetate coproduction of normal butanol used catalyst preparation method, is characterized in that, step is as follows:
（1）Solution A:By the soluble metallic salt of component a, the soluble metallic salt of the soluble in water or molten a of energy is volatile organic
In solvent, the concentration of the soluble metal salt ion of a is 0.005-0.5mol/L；B solution:By the soluble metallic salt of component b
In the volatile organic solvent of soluble metallic salt soluble in water or the molten b of energy, the concentration of the soluble metal salt ion of b is
0.001-0.1mol/L；
（2）Carrier is carried out into compressing tablet, crushing, granulation, the carrier granular of 20～40 mesh is obtained；Then by carrier granular 80～
Dry 4～8 hours at 120 DEG C；
（3）By step（2）In the carrier granular that obtains be put into rotatable heater and carry out multiple incipient impregnation simultaneously with solution A
Drying, until solution A all impregnates finishing, then dries 11～13 hours, in 200～600 DEG C of roastings 1～10 at 80～120 DEG C
Hour；
（4）By step（3）In the sample that obtains be put into again in rotatable heater and carry out multiple incipient impregnation simultaneously with B solution
Drying, until B solution all impregnates finishing, then dries 11～13 hours at 30～100 DEG C, dries 11～13 at 100～150 DEG C little
When, in 300～600 DEG C of roastings 1～10 hour；
（5）By step（4）In the sample that obtains carry out in the gaseous mixture of hydrogen and inert gas, at 200～600 DEG C also
Original, obtains required catalyst；
Wherein, component a is any one in nickel, copper, zinc or two kinds；
Component b is any one in iridium, platinum, palladium, ruthenium；
The carrier is the mixed-powder of any one or two kinds of in basic magnesium carbonate, magnesium carbonate, magnesium hydroxide, magnesia.
2. ethanol with one-step method synthesizing ethyl acetate coproduction of normal butanol used catalyst preparation method according to claim 1,
It is characterized in that, in step（3）、（4）In, the metallic of component a, the metallic of b, the mass ratio of carrier are 0.1～20：
0.01～5：100.
3. ethanol with one-step method synthesizing ethyl acetate coproduction of normal butanol used catalyst preparation method according to claim 1,
It is characterized in that, in step（5）In, in the gaseous mixture volume content of hydrogen be 30～90%, the inert gas be nitrogen,
Argon gas or helium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201611080849.XA CN106622283A (en) | 2016-11-30 | 2016-11-30 | Preparation method of catalyst for synthesis of ethyl acetate and co-production of normal butanol by ethanol one-step method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611080849.XA CN106622283A (en) | 2016-11-30 | 2016-11-30 | Preparation method of catalyst for synthesis of ethyl acetate and co-production of normal butanol by ethanol one-step method |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100197486A1 (en) * | 2008-07-31 | 2010-08-05 | Celanese International Corporation | Catalysts for making ethyl acetate from acetic acid |
| CN102264686A (en) * | 2008-11-14 | 2011-11-30 | 国际人造丝公司 | Integrated process for the production of vinyl acetate from acetic acid via ethylene |
| CN102271804A (en) * | 2009-10-26 | 2011-12-07 | 国际人造丝公司 | Processes for making ethyl acetate from acetic acid |
| KR20120073998A (en) * | 2010-12-27 | 2012-07-05 | 금호석유화학 주식회사 | Copper-based catalyst for the conversion of ethanol to acetaldehyde by dehydrogenation and preparing method of the same |
| CN105073697A (en) * | 2013-02-19 | 2015-11-18 | 格林尤格有限责任公司 | Production of higher alcohols |
-
2016
- 2016-11-30 CN CN201611080849.XA patent/CN106622283A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100197486A1 (en) * | 2008-07-31 | 2010-08-05 | Celanese International Corporation | Catalysts for making ethyl acetate from acetic acid |
| CN102264686A (en) * | 2008-11-14 | 2011-11-30 | 国际人造丝公司 | Integrated process for the production of vinyl acetate from acetic acid via ethylene |
| CN102271804A (en) * | 2009-10-26 | 2011-12-07 | 国际人造丝公司 | Processes for making ethyl acetate from acetic acid |
| KR20120073998A (en) * | 2010-12-27 | 2012-07-05 | 금호석유화학 주식회사 | Copper-based catalyst for the conversion of ethanol to acetaldehyde by dehydrogenation and preparing method of the same |
| CN105073697A (en) * | 2013-02-19 | 2015-11-18 | 格林尤格有限责任公司 | Production of higher alcohols |
Non-Patent Citations (1)
| Title |
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| 伏再辉等，: ""乙醇在双功能Pd-Cu/分子筛催化剂上气相氧化氧化一步合成乙酸乙醋"", 《催化学报》 * |
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