CN106563480A - Catalyst for synthesis of methyl acetate and ethanol through hydrogenation of dimethyl oxalate, and preparation method and application thereof - Google Patents
Catalyst for synthesis of methyl acetate and ethanol through hydrogenation of dimethyl oxalate, and preparation method and application thereof Download PDFInfo
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- CN106563480A CN106563480A CN201611006285.5A CN201611006285A CN106563480A CN 106563480 A CN106563480 A CN 106563480A CN 201611006285 A CN201611006285 A CN 201611006285A CN 106563480 A CN106563480 A CN 106563480A
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- dimethyl oxalate
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention provides a catalyst for synthesis of methyl acetate and ethanol through hydrogenation of dimethyl oxalate. The catalyst is characterized in that molybdenum carbide is used as an active component; silicon oxide is used as a carrier; and a weight ratio of molybdenum carbide to silicon oxide is 2-85 wt%: 15-98 wt%. The catalyst provided by the invention has the advantages of high stability, high selectivity and high activity.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method thereof, more particularly to a kind of prepared by dimethyl oxalate plus hydrogen takes acetic acid first
Catalyst of ester and ethanol and its preparation method and application.
Background technology
Methyl acetate has been widely used as a kind of excellent solvent.For example, in resin, ink, adhesive, painting
In the production process such as material and leather.Also can be used as important chemical reaction intermediate, downstream product mainly has acetic acid, acetamide, and third
E pioic acid methyl ester, acetic anhydride and vinylacetate etc..At present, industrialized production methyl acetate is mainly urged in sulphuric acid by acetic acid and methanol
Carry out in agent obtained by esterification, CN103265429A discloses one kind using differential pressure thermal coupled process and reactive distillation partition
The technique that tower combines, carries out esterification synthesis of acetic acid methyl ester on sulphuric acid by methanol and acetic acid.Although the method is efficiently steady
It is fixed, but the liquid-phase reaction system is related to acidic liquid, has certain corrosivity to consersion unit, and large-scale production is subject to
Limit.Therefore, seek to produce the environmental protection process route of methyl acetate, have become the direction of industry transition.
Ethanol is one of primary raw material of many chemicals synthesis, is widely used in the fields such as food, medicine and chemical industry.
Also can be applied as the raw material of the additive of gasoline and fuel cell on a large scale simultaneously.At present, industrial production of ethyl alcohol is main
Using ethylene hydration and yeast fermentation method, but it is restricted because the atrophy of petroleum resources and biochemical process are costly.Therefore, open
Send out with biological and ethanol synthetic method of the coal based synthetic gas as raw material and be developed rapidly.
At present, coal gasification preparing synthetic gas have been successfully realized industry with CO gas phases carbonylation dimethyl oxalate. (DMO)
Change, DMO becomes the intermediate compound of a scale supply.In the last few years, it is stable in the process upstream technology maturation of production DMO
Under the conditions of, the product chain for further developing DMO downstreams has become the research emphasis of the technical field.And with DMO as intermediate,
Derive a series of new Non oil-based route chemicals.
The reaction of prepared by dimethyl oxalate plus hydrogen methyl acetate and ethanol is as follows：
H3COOC-COOCH3+H2→H3C-COOCH3+CH3CH2OH+CH3OH+H2O
As can be seen from the above equation, dimethyl oxalate. can generate methyl acetate and ethanol.From the point of view of existing document, in cuprio
On catalyst Hydrogenation of Dimethyl Oxalate product based on ethanol (selectivity up to more than 80%) (CN102350358B,
CN101830776A).Cut-off up till now, does not also have document report to cross the catalysis of dimethyl oxalate. gas phase hydrogenation synthesis of acetic acid methyl ester
Agent.Therefore exploitation is hydrogenation of oxalate for preparing methyl acetate and ethanol with high stability, high selectivity and highly active catalyst
One of key technical problems.
The content of the invention
It is an object of the invention to provide the synthesis of a kind of high stability, high selectivity and highly active Hydrogenation of Dimethyl Oxalate
Catalyst of methyl acetate and ethanol and its preparation method and application.
The present invention is achieved by the following technical programs.
The catalyst of a kind of Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester of the present invention and ethanol is with molybdenum carbide as activearm
Point, silicon oxide is carrier；Catalyst weight ratio is consisted of：Molybdenum carbide is 2-85wt%, and silicon oxide is 15-98wt%.
The catalyst of a kind of above-mentioned Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester and ethanol, catalyst optimum weight ratio group
Become 5-80wt%, silicon oxide 20-95wt%.
The preparation method of the catalyst of a kind of above-mentioned Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester and ethanol, including it is as follows
Step：
(1) it is 5- the ammonia mixed dissolution of ammonium molybdate, urotropine and 25wt% to be formed molybdic acid ammonium concentration
The mixed solution of 30mmol/L, is then stirred at room temperature 1-24h；
(2), under stirring, the solution obtained by step (1) is heated to into 60-120 DEG C and keeps 2-40h to obtain pressed powder；
(3) pressed powder obtained by step (2) is heated to into 500-900 DEG C of holding 1-10h in a hydrogen atmosphere, obtains carbon
Change molybdenum；
(4) silica support is added in the molybdenum carbide obtained by step (3), while adding ethanol, and is stirred at 20-50 DEG C
5-40h is mixed, the 350-600 DEG C of molybdenum carbide sample for keeping 2-10h to obtain silicon oxide load is then heated in a hydrogen atmosphere；
(5) the molybdenum carbide sample Passivation Treatment for carrying silicon oxide, obtains catalyst, prevents oxidation by air destruction catalyst
Structure.
Above-mentioned ammonium molybdate with the mol ratio of urotropine is：1-12：1.
Above-mentioned ethanol is 50-300 with the mass ratio of molybdenum carbide：1.
Above-mentioned catalyst application includes that the method for extruded moulding, rotational forming and compression molding carries out molding.
Include provided by the present invention for the application process of Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester and alcohol catalysis agent
The step of：
The catalyst of molding is put in fixed bed reactors, is reduced in pure hydrogen, reduction pressure is 0.1-
1.0MPa, H2Volume space velocity is 500-10000h-1, with the ramp of 1-5 DEG C/min to 200-600 DEG C, reduce 4-9h, reduction
After end, when methyl acetate is needed, controlling reaction temperature to 130-200 DEG C, control pressure 1.0-3.0MPa, dimethyl oxalate.
Liquid hourly space velocity (LHSV) be 0.1-2.0h-1, H2:The mol ratio of dimethyl oxalate. be 10-300, the methanol of 5-25wt% dimethyl oxalate .s
Solution carries out hydrogenation reaction, and which mainly generates methyl acetate and a small amount of ethanol；When ethanol is needed, controlling reaction temperature to 220-
260 DEG C, control pressure 1.0-3.0MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 0.1-2.0h-1, H2:Dimethyl oxalate. mole
Hydrogenation reaction is carried out than the methanol solution for 10-300,5-25wt% dimethyl oxalate .s, which mainly generates ethanol and a small amount of acetic acid
Methyl ester.
Compared with prior art, catalyst of the present invention is in catalysis Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester and second for the present invention
There is in the reaction of alcohol high reactivity and selectivity.The preparation method of catalyst is simple, and raw material is sufficient, while catalyst
Stability and regenerability are good.Suitable for actual industrialized production, catalytic performance is excellent.
Specific embodiment
Activity rating of catalyst is carried out in fixed bed rustless steel pressurized reactor, and tube inner diameter is 10mm, a length of
1000mm., by front and back's pressure-setting valve control, the scope of reaction temperature fluctuation is at ± 0.5 DEG C for reaction pressure.In reactor load 2 grams into
The catalyst of type, bed insert the inertia quartz sand of 20-40 mesh up and down.By the mixed liquor of dimethyl oxalate. and methanol by dosing pump
Squeeze into.Product is collected after cooling and carries out composition analysis.
Embodiment 1
(1) by 6 grams by the ammonium molybdate and 6 grams of urotropines ammonia solvent of 200 milliliters of 25wt%, then in room
The lower stirring 1h of temperature；(2), under stirring, the solution obtained by step (1) is heated to into 120 DEG C and keeps 2h to obtain pressed powder；(3)
Pressed powder obtained by (2) is heated to into 700 DEG C of holding 2h in a hydrogen atmosphere, the molybdenum component that is carbonized is obtained；(4) 3 grams are aoxidized
During silicon carrier adds the powder obtained by step (3), plus 50mL ethanol, and 10h is stirred at 20 DEG C, then add in a hydrogen atmosphere
Heat to 400 DEG C keeps 4h to obtain the molybdenum carbide catalyst of silicon oxide load；(5) the molybdenum carbide Hydrogenation of Dimethyl Oxalate that silicon oxide is carried
Catalyst structure process, prevents oxidation by air from destroying the structure of catalyst.
2 grams of the molybdenum carbide catalyst that above-mentioned silicon oxide is carried is filled in fixed-bed tube reactor.By catalyst in body
Product air speed 4000h-1, pressure 0.2MPa H2400 DEG C are warming up to 2 DEG C/min under atmosphere, 4h is reduced at this temperature, then will
The temperature of gas phase fixed bed is reduced to temperature required when reaction occurs.(1) Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester is anti-
Answer condition as follows：180 DEG C of reaction temperature, reaction pressure 2.5MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 0.2h-1, H2：Oxalic acid two
Methyl ester mol ratio is 200:1.Under reaction condition as described above, the conversion ratio 100% of dimethyl oxalate., the selection of methyl acetate
Property 71%, the selectivity 23% of ethanol.(2) Hydrogenation of Dimethyl Oxalate synthesizing alcohol reaction condition is as follows：220 DEG C of reaction temperature,
Reaction pressure 2.0MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 0.4h-1, H2：Dimethyl oxalate. mol ratio is 300:1.As above
Under the reaction condition, the conversion ratio 100% of dimethyl oxalate., the selectivity 14% of methyl acetate, the selectivity 82% of ethanol.
Embodiment 2
(1) by 6 grams by the ammonium molybdate and 3 grams of urotropines ammonia solvent of 600 milliliters of 25wt%, then in room
The lower stirring 10h of temperature；(2), under stirring, the solution obtained by step (1) is heated to into 100 DEG C and keeps 12h to obtain pressed powder；
(3) pressed powder obtained by (2) is heated to into 600 DEG C of holding 4h in a hydrogen atmosphere, obtains the molybdenum component that is carbonized；(4) by 0.3 gram
During silica support adds the powder obtained by step (3), plus 70mL ethanol, and 20h is stirred at 30 DEG C, then in hydrogen atmosphere
Under be heated to 500 DEG C keep 6h obtain silicon oxide load molybdenum carbide catalysts；(5) the molybdenum carbide dimethyl oxalate. that silicon oxide is carried
Hydrogenation catalyst Passivation Treatment, prevents oxidation by air from destroying the structure of catalyst.
2 grams of the molybdenum carbide catalyst that above-mentioned silicon oxide is carried is filled in fixed-bed tube reactor.By catalyst in body
Product air speed 500h-1, pressure 0.5MPa H2300 DEG C are warming up to 1 DEG C/min under atmosphere, 5h is reduced at this temperature, then will
The temperature of gas phase fixed bed is reduced to temperature required when reaction occurs.(1) Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester is anti-
Answer condition as follows：200 DEG C of reaction temperature, reaction pressure 1MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 0.1h-1, H2：Oxalic acid diformazan
Ester mol ratio is 150:1.Under reaction condition as described above, the conversion ratio 98% of dimethyl oxalate., the selectivity of methyl acetate
73%, the selectivity 20% of ethanol.(2) Hydrogenation of Dimethyl Oxalate synthesizing alcohol reaction condition is as follows：240 DEG C of reaction temperature, instead
Pressure 2MPa is answered, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 1.2h-1, H2：Dimethyl oxalate. mol ratio is 250:1.As described above
Under reaction condition, the conversion ratio 100% of dimethyl oxalate., the selectivity 16% of methyl acetate, the selectivity 81% of ethanol.
Embodiment 3
(1) by 6 grams by the ammonium molybdate and 4 grams of urotropines ammonia solvent of 500 milliliters of 25wt%, then in room
The lower stirring 15h of temperature；(2), under stirring, the solution obtained by step (1) is heated to into 80 DEG C and keeps 20h to obtain pressed powder；
(3) pressed powder obtained by (2) is heated to into 800 DEG C of holding 5h in a hydrogen atmosphere, obtains the molybdenum component that is carbonized；(4) by 7 grams of oxygen
During SiClx carrier adds the powder obtained by step (3), plus 100mL ethanol, and 40h is stirred at 40 DEG C, then in hydrogen atmosphere
Under be heated to 450 DEG C keep 5h obtain silicon oxide load molybdenum carbide catalysts；(5) the molybdenum carbide dimethyl oxalate. that silicon oxide is carried
Hydrogenation catalyst Passivation Treatment, prevents oxidation by air from destroying the structure of catalyst.
2 grams of the molybdenum carbide catalyst that above-mentioned silicon oxide is carried is filled in fixed-bed tube reactor.By catalyst in body
Product air speed 2000h-1, pressure 0.7MPa H2500 DEG C are warming up to 5 DEG C/min under atmosphere, 7h is reduced at this temperature, then will
The temperature of gas phase fixed bed is reduced to temperature required when reaction occurs.(1) Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester is anti-
Answer condition as follows：160 DEG C of reaction temperature, reaction pressure 1.5MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 1h-1, H2：Oxalic acid diformazan
Ester mol ratio is 100:1.Under reaction condition as described above, the conversion ratio 97% of dimethyl oxalate., the selectivity of methyl acetate
72%, the selectivity 22% of ethanol.(2) Hydrogenation of Dimethyl Oxalate synthesizing alcohol reaction condition is as follows：230 DEG C of reaction temperature, instead
Pressure 3.0MPa is answered, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 2h-1, H2：Dimethyl oxalate. mol ratio is 200:1.As described above
Under reaction condition, the conversion ratio 100% of dimethyl oxalate., the selectivity 15% of methyl acetate, the selectivity 83% of ethanol.
Embodiment 4
(1) by 6 grams by the ammonium molybdate and 5 grams of urotropines ammonia solvent of 300 milliliters of 25wt%, then in room
The lower stirring 5h of temperature；(2), under stirring, the solution obtained by step (1) is heated to into 60 DEG C and keeps 30h to obtain pressed powder；(3)
Pressed powder obtained by (2) is heated to into 900 DEG C of holding 1h in a hydrogen atmosphere, the molybdenum component that is carbonized is obtained；(4) 12 grams are aoxidized
During silicon carrier adds the powder obtained by step (3), plus 150mL ethanol, and 20h is stirred at 50 DEG C, then in a hydrogen atmosphere
It is heated to 350 DEG C of molybdenum carbide catalysts for keeping 10h to obtain silicon oxide load；(5) the molybdenum carbide dimethyl oxalate. that silicon oxide is carried
Hydrogenation catalyst Passivation Treatment, prevents oxidation by air from destroying the structure of catalyst.
2 grams of the molybdenum carbide catalyst that above-mentioned silicon oxide is carried is filled in fixed-bed tube reactor.By catalyst in body
Product air speed 7000h-1, pressure 1MPa H2200 DEG C are warming up to 3 DEG C/min under atmosphere, 9h is reduced at this temperature, then by gas
The temperature of phase fixed bed is reduced to temperature required when reaction occurs.(1) Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester reaction
Condition is as follows：190 DEG C of reaction temperature, reaction pressure 3MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 0.5h-1, H2：Dimethyl oxalate.
Mol ratio is 10:1.Under reaction condition as described above, the conversion ratio 95% of dimethyl oxalate., the selectivity of methyl acetate
70%, the selectivity 21% of ethanol.(2) Hydrogenation of Dimethyl Oxalate synthesizing alcohol reaction condition is as follows：250 DEG C of reaction temperature, instead
Pressure 1MPa is answered, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 1h-1, H2：Dimethyl oxalate. mol ratio is 100:1.Anti- as mentioned above
Under the conditions of answering, the conversion ratio 100% of dimethyl oxalate., the selectivity 18% of methyl acetate, the selectivity 80% of ethanol.
Embodiment 5
(1) by 6 grams by the ammonium molybdate and 7 grams of urotropines ammonia solvent of 400 milliliters of 25wt%, then in room
The lower stirring 40h of temperature；(2), under stirring, the solution obtained by step (1) is heated to into 70 DEG C and keeps 24h to obtain pressed powder；
(3) pressed powder obtained by (2) is heated to into 500 DEG C of holding 10h in a hydrogen atmosphere, obtains the molybdenum component that is carbonized；(4) by 19 grams
During silica support adds the powder obtained by step (3), plus 200mL ethanol, and 5h is stirred at 40 DEG C, then in hydrogen atmosphere
Under be heated to 600 DEG C keep 2h obtain silicon oxide load molybdenum carbide catalysts；(5) the molybdenum carbide dimethyl oxalate. that silicon oxide is carried
Hydrogenation catalyst Passivation Treatment, prevents oxidation by air from destroying the structure of catalyst.
2 grams of the molybdenum carbide catalyst that above-mentioned silicon oxide is carried is filled in fixed-bed tube reactor.By catalyst in body
Product air speed 10000h-1, pressure 0.1MPa H2600 DEG C are warming up to 4 DEG C/min under atmosphere, 6h is reduced at this temperature, then
The temperature of gas phase fixed bed is reduced to into temperature required when reaction occurs.(1) Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester
Reaction condition is as follows：170 DEG C of reaction temperature, reaction pressure 2MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 1.5h-1, H2：Oxalic acid two
Methyl ester mol ratio is 300:1.Under reaction condition as described above, the conversion ratio 96% of dimethyl oxalate., the selection of methyl acetate
Property 71%, the selectivity 24% of ethanol.(2) Hydrogenation of Dimethyl Oxalate synthesizing alcohol reaction condition is as follows：260 DEG C of reaction temperature,
Reaction pressure 2.5MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 2h-1, H2：Dimethyl oxalate. mol ratio is 200:1.In as above institute
State under reaction condition, the conversion ratio 100% of dimethyl oxalate., the selectivity 16% of methyl acetate, the selectivity 81% of ethanol.
Claims (6)
1. the catalyst of a kind of Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester and ethanol, it is characterised in that catalyst is with molybdenum carbide
For active component, silicon oxide is carrier, and it is 2-85wt% that catalyst weight ratio consists of molybdenum carbide, and silicon oxide is 15-98wt%.
2. the catalyst of a kind of Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester as claimed in claim 1 and ethanol, its feature exist
5-80wt%, silicon oxide 20-95wt% are consisted of in catalyst weight ratio.
3. the preparation of the catalyst of a kind of Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester as claimed in claim 1 or 2 and ethanol
Method, it is characterised in that comprise the steps：
（1）It is 5-30mmol/L that the ammonia mixed dissolution of ammonium molybdate, urotropine and 25wt% is formed molybdic acid ammonium concentration
Mixed solution, 1-24h is then stirred at room temperature；
（2）Under stirring, the solution obtained by step (1) is heated to into 60-120 DEG C and keeps 2-40h to obtain pressed powder；
（3）By step (2）The pressed powder of gained is heated to 500-900 DEG C of holding 1-10h in a hydrogen atmosphere, is carbonized
Molybdenum；
（4）Silica support is added into step (3）In the molybdenum carbide of gained, while adding ethanol, and 5- is stirred at 20-50 DEG C
40h, is then heated to the 350-600 DEG C of molybdenum carbide sample for keeping 2-10h to obtain silicon oxide load in a hydrogen atmosphere；
（5）The molybdenum carbide sample Passivation Treatment that silicon oxide is carried, obtains catalyst.
4. the preparation side of the catalyst of a kind of Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester as claimed in claim 3 and ethanol
Method, it is characterised in that ammonium molybdate is 1-12 with the mol ratio of urotropine：1.
5. the preparation side of the catalyst of a kind of Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester as claimed in claim 3 and ethanol
Method, it is characterised in that ethanol is 50-300 with the mass ratio of molybdenum carbide：1.
6. the application of the catalyst of a kind of Hydrogenation of Dimethyl Oxalate synthesis of acetic acid methyl ester as claimed in claim 1 or 2 and ethanol,
It is characterized in that comprising the steps：
The catalyst of molding is put in fixed bed reactors, is reduced in pure hydrogen, reduction pressure is 0.1-1.0MPa,
H2Volume space velocity is 500-10000h-1, with the ramp of 1-5 DEG C/min to 200-600 DEG C, 4-9h is reduced, after reduction terminates,
When methyl acetate is needed, controlling reaction temperature to 130-200 DEG C, control pressure 1.0-3.0MPa, during the liquid of dimethyl oxalate.
Air speed is 0.1-2.0h-1, H2:The mol ratio of dimethyl oxalate. is 10-300, and the methanol solution of 5-25wt% dimethyl oxalate .s carries out
Hydrogenation reaction, which mainly generates methyl acetate and a small amount of ethanol；When ethanol is needed, controlling reaction temperature to 220-260 DEG C, control
Pressing pressure 1.0-3.0MPa, the liquid hourly space velocity (LHSV) of dimethyl oxalate. is 0.1-2.0h-1, H2:The mol ratio of dimethyl oxalate. is 10-
The methanol solution of 300,5-25wt% dimethyl oxalate .s carries out hydrogenation reaction, and which mainly generates ethanol and a small amount of methyl acetate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611006285.5A CN106563480A (en) | 2016-11-16 | 2016-11-16 | Catalyst for synthesis of methyl acetate and ethanol through hydrogenation of dimethyl oxalate, and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611006285.5A CN106563480A (en) | 2016-11-16 | 2016-11-16 | Catalyst for synthesis of methyl acetate and ethanol through hydrogenation of dimethyl oxalate, and preparation method and application thereof |
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| CN106563480A true CN106563480A (en) | 2017-04-19 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688768A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院山西煤炭化学研究所 | Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof |
| CN104368370A (en) * | 2014-09-30 | 2015-02-25 | 西北有色金属研究院 | Preparation method of supported molybdenum carbide catalyst |
| CN105646148A (en) * | 2015-12-31 | 2016-06-08 | 浙江工业大学 | Method for preparing ethanol by hydrogenating acetic acid |
-
2016
- 2016-11-16 CN CN201611006285.5A patent/CN106563480A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688768A (en) * | 2012-06-05 | 2012-09-26 | 中国科学院山西煤炭化学研究所 | Cobalt-based catalyst for synthesizing ethanol, preparation method and application thereof |
| CN104368370A (en) * | 2014-09-30 | 2015-02-25 | 西北有色金属研究院 | Preparation method of supported molybdenum carbide catalyst |
| CN105646148A (en) * | 2015-12-31 | 2016-06-08 | 浙江工业大学 | Method for preparing ethanol by hydrogenating acetic acid |
Non-Patent Citations (1)
| Title |
|---|
| YANTING LIU, ET AL.: "Molybdenum carbide as an efficient catalyst for low-temperature hydrogenation of dimethyl oxalate", 《CHEM. COMMUN.》 * |
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