CN106423156A - Catalyst for catalytically synthesizing dimethyl oxalate by CO gas phase and preparation method and application of catalyst - Google Patents
Catalyst for catalytically synthesizing dimethyl oxalate by CO gas phase and preparation method and application of catalyst Download PDFInfo
- Publication number
- CN106423156A CN106423156A CN201610748007.0A CN201610748007A CN106423156A CN 106423156 A CN106423156 A CN 106423156A CN 201610748007 A CN201610748007 A CN 201610748007A CN 106423156 A CN106423156 A CN 106423156A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- alkali metal
- preparation
- air speed
- dimethyl oxalate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for catalytically synthesizing dimethyl oxalate by a CO gas phase and a preparation method and application of the catalyst. The catalyst is a Pd-loaded theta-Al2O3 catalyst which contains a trace amount of alkali metal, wherein the content of Pd accounts for 0.1-1% of the weight of the catalyst; the content of the alkali metal accounts for 0.1-5% of the weight of the catalyst; and the specific surface area of a catalyst vector theta-Al2O3 is 20-200 m<2>/g. The invention further provides the preparation method and application of the catalyst. The catalyst for catalytically synthesizing dimethyl oxalate by the CO gas phase has the advantages that Cl- is not introduced in a preparation process of the catalyst, and element dropping and catalyst loss in a followed-up washing process of the catalyst are avoided; meanwhile, owing to an alkali metal ion solution, a Pd element is uniformly loaded on the surface of the vector, and the alkali metal as an auxiliary can improve the catalytic performance of the catalyst in reaction; and a preparation process of the catalyst is simple and controllable, and the catalyst has high selectivity and space time yield when used at low temperature, and is particularly suitable for industrially catalytically synthesizing the dimethyl oxalate by the CO gas phase.
Description
Technical field
The present invention relates to a kind of catalyst, especially a kind of catalyst for CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method and
Its preparation method and its application.
Background technology
Dimethyl oxalate is a kind of important Organic Chemicals, is mainly used in organic synthesis, pharmacy, agricultural chemicals etc..Oxalic acid
Dimethyl ester hydrolysis can prepare oxalic acid, and hydrogenation can prepare ethylene glycol, and amination can prepare oxamides.At present, used carbon monoxide gas
Catalyze and synthesize the intermediate materials as hydrogeneration processes synthesizing glycol for the dimethyl oxalate mutually, be dimethyl oxalate most attraction
Application.Since the eighties, China also expands the application study of synthesis of oxalate, urging especially for this synthetic reaction
Agent has carried out numerous studies.Patent CN201210028850.3 proposes a kind of Pd-M/Al2O3Catalyst, wherein M be Mg, Ce,
Co or Ni, uses M auxiliary agent to improve the catalytic performance of catalyst, and uses the method repeatedly washed to wash away catalyst system in this patent
Cl during Bei-So that this catalyst obtains higher catalysis activity and selectivity in catalytic reaction.Patent
CN201010128732.0 proposes and mixes palladium bichloride, perrhenic acid, lanthanum chloride, hydrochloric acid and deionized water, impregnates α-Al2O3Carry
Body, then catalyst roasting are cleaned multiple times by deionized water, use hydrazine hydrate soaking and reducing after roasting, thus prepare doping
Lanthanum, the Pd/ α-Al of rhenium2O3Catalyst, this catalyst has very high activity and selectivity.But these methods are drawn in preparation process
Enter Cl-And add water-washing process, cause preparation process complicated, and cause the loss of catalyst.
Content of the invention
To be solved by this invention first technical problem is that provide one to have height lives for above-mentioned prior art present situation
Property and be optionally used for CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method reaction catalyst.
The technical scheme that the present invention solves that above-mentioned first technical problem used is:This is for CO gas phase catalytic synthesis grass
The catalyst of dimethyl phthalate, it is characterised in that:Described catalyst is the Pd load θ-Al containing trace alkali metal2O3Catalysis
Agent, wherein the content of Pd accounts for the 0.1%~1% of catalyst weight, wherein alkali metal content account for catalyst weight 0.1%~
5%, described percentage is weight percentage.
As improvement, described catalyst carrier θ-Al2O3Specific surface area be preferably 20~200m2/ g, pore volume is 0.5
~1.5m2/ g, aperture is 3~20nm.
Improving, described alkali metal is preferably Na or K or Rb again.
To be solved by this invention second technical problem is that provide for above-mentioned prior art present situation a kind of for CO gas
Catalyzing and synthesizing the preparation method of the catalyst of dimethyl oxalate reaction mutually, this preparation method technique is simple, it is not necessary to water-washing step, system
Standby catalyst has high activity and selectivity.
The technical scheme that the present invention solves that above-mentioned second technical problem used is:The preparation method of above-mentioned catalyst,
It is characterized in that:Comprise the steps of,
First, by Pd compound and alkali metal salt and water mixing wiring solution-forming;Wherein the solution concentration of Pd compound be 20~
500mmol/L, alkali metal ion solution concentration is 20~1000mmol/L;
2nd, by carrier θ-Al2O3Join in the solution of step one and impregnate, carrier θ-Al2O3Addition quality and step one
Middle Pd mass ratio is 100~1000: 1, then by the carrier θ-Al after dipping2O3Moisture evaporation drying, then roasting, i.e. make for
The catalyst of CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method.
As in improvement, step one, described Pd compound may be selected to be palladium nitrate or palladium acetylacetonate.
As in improvement, step one, described alkali metal salt may be selected to be sodium nitrate, sodium carbonate, potassium nitrate, potassium carbonate, nitre
One or more in acid rubidium, rubidium carbonate.
As in improvement, step one, Pd compound solution concentration is preferably 20~500mmol/L, in alkali metal salt
Alkali metal ion solution concentration is 20~1000mmol/L, adds carrier θ-Al2O3Quality with Pd mass ratio in step one be
100~1000: 1.
As improvement, in step 2, moisture evaporation drying be may be selected to be ultrasonic wave or heating, when moisture evaporation drying is
During heating, carrier θ-Al2O3Being dried in drying box, the temperature of described roasting is 300~600 DEG C, and roasting time is 2~10 little
When.
To be solved by this invention 3rd technical problem is that provide for above-mentioned prior art present situation a kind of for CO gas
Catalyze and synthesize the application of the catalyst of dimethyl oxalate reaction mutually.
The present invention solves above-mentioned 3rd technical scheme that technical problem is used:The application of above-mentioned catalyst, it is special
Levy and be:Catalyst is before application through H2Reduction, the H of reduction2Air speed is 100~1000h-1, reduction temperature is 150~250 DEG C,
Recovery time is 5~72 hours, is then placed in the catalyst after reduction in reactor.
As improvement, described dimethyl oxalate synthetic reaction can use fixed bed reactors, raw material carbon monoxide and nitrous
Acid methyl esters is diluted by nitrogen, and CO air speed is 200~2000h-1, the air speed of methyl nitrite is 1~2: 2~1 with CO air speed ratio, N2
Air speed is 2~10 with CO air speed ratio: 1, and reaction temperature controls at 110~130 DEG C, and reaction pressure controls at normal pressure~1MPa.
Compared with prior art, it is an advantage of the current invention that:
First, the catalyst providing does not introduces Cl in preparation process-, eliminate unit in follow-up water-washing process for the catalyst
Element comes off and catalyst loss.The existence of alkali metal ion solution simultaneously make Pd element homogeneous be supported on carrier surface, and
Alkali metal can improve the catalytic performance of catalyst in the reaction as auxiliary agent.
2nd, the catalyst preparation process providing is simply controlled, when using at low temperatures, has higher selectivity and space-time
Productivity, is particularly suitable for industrializing CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
One aspect of the embodiment of the present invention provides a kind of urging for the reaction of CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method
Agent, the Pd load θ-Al that this catalyst is doping trace alkali metal2O3Catalyst.In alkali metal preferred Na, K, Rb one
Kind;Described carrier θ-Al2O3, its specific surface area is 20-200m2/ g, pore volume is 0.5-1.5m2/ g, aperture is 3-20nm;Catalysis
In agent, the content of Pd is 0.1wt%-1.0wt%, and the content of alkali metal is 0.1wt%-5wt%.
The method step that the present invention prepares catalyst is:
(1) by Pd presoma, alkali metal ionic compounds, water mixing wiring solution-forming;
(2) by carrier θ-Al2O3Ball joins the solution in step 1, in normal temperature dipping a period of time, then steams its moisture content
Dry dry, roasting.
In step (1) Pd presoma be palladium nitrate, one or more in palladium acetylacetonate, but be not limited to this;
Alkali metal ionic compounds be sodium nitrate, sodium carbonate, potassium nitrate, potassium carbonate, rubidium nitrate, the one in rubidium carbonate or
Multiple, but it is not limited to this;Pd presoma (i.e. referring to Pd compound, as follows) solution concentration is 20~500mmol/L, alkali metal from
Sub-solution concentration is 20~1000mmol/L;Described carrier θ~Al2O3, its specific surface area is 20~200m2/ g, pore volume is 0.5
~1.5m2/ g, aperture is 3~20nm;Add carrier θ-Al2O3Quality and step 1 in Pd mass ratio be 100: 1~1000: 1;
Method by moisture evaporation drying is ultrasonic, heating or the method being dried at drying box;Sintering temperature is 300~600 DEG C, roasting
Time is 2~10 hours;Catalyst before use, uses H2Reduction, H2Air speed is 100~1000h-1, reduction temperature is 150~
250 DEG C, the recovery time is 5~72 hours.
The embodiment of the present invention also provides described catalyst for the use in the reaction of CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method
On the way.
The embodiment of the present invention additionally provides the synthetic method of a kind of synthesizing dimethyl oxalate, and it includes:Use described urging
Agent participates in the reaction of CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method, and particularly CO and methyl nitrite are under the diluting effect of nitrogen
The reaction of synthesizing dimethyl oxalate.
The method of the synthesis of dimethyl oxalate specifically includes:Reaction unit uses fixed bed reactors, raw material carbon monoxide
Diluting with nitrogen with methyl nitrite, CO air speed is 200~2000h-1, the air speed of methyl nitrite is 1~2 with CO air speed ratio: 2
~1, N2Air speed is 2~10 with CO air speed ratio: 1, and reaction temperature controls at 110~130 DEG C, reaction pressure control normal pressure~
1MPa.
For detecting this catalyst reaction activity, the synthetic reaction of dimethyl oxalate continues 4 hours, weighs product quality, adopts
By means detection assay products such as gas-chromatographies, calculate selectivity and the space-time yield of catalyst.The method is also used for
The active testing of described catalyst.
In order to be further appreciated by the present invention, below in conjunction with some embodiments, the preferred embodiments of the invention are retouched
State, but it is to be understood that these describe simply for further illustrating the features and advantages of the present invention, rather than to right of the present invention
The restriction requiring.
The preparation technology of a kind of catalyst that embodiment 1 the present embodiment relates to comprises the steps:
By 2.3mmol palladium nitrate, 2.3mmol potassium nitrate, 50g water mixing wiring solution-forming.By 100g carrier θ-Al2O3Ball adds
Enter in above-mentioned solution, normal temperature dipping 48 hours, 120 DEG C of evaporation dryings in drying box, then 500 DEG C of roastings 3 hours.In catalysis
Agent uses H before using2Reduction, H2Air speed is 500h-1, reduction temperature is 200 DEG C, and the recovery time is 24 hours.Obtain catalyst sample
Product 1, wherein the load factor of Pd is 0.25wt%.
The preparation technology of a kind of catalyst that embodiment 2 the present embodiment relates to comprises the steps:
By 2.3mmol palladium nitrate, 1.2mmol potassium nitrate, 50g water mixing wiring solution-forming.By 100g carrier θ-Al2O3Ball adds
Enter in above-mentioned solution, normal temperature dipping 24 hours, 120 DEG C of evaporation dryings in drying box, then 500 roastings 3 hours.At catalyst
H is used before using2Reduction, H2Air speed is 500h-1, reduction temperature is 200 DEG C, and the recovery time is 24 hours.Obtain catalyst sample 2
Number, wherein the load factor of Pd is 0.25wt%.
The preparation technology (i.e. method, as follows) of a kind of catalyst that embodiment 3 the present embodiment relates to comprises the steps:
By 2.3mmol palladium nitrate, 9.2mmol potassium nitrate, 50g water mixing wiring solution-forming.By 100g carrier θ-Al2O3Ball adds
Enter in above-mentioned solution, normal temperature dipping 48 hours, 120 DEG C of evaporation dryings in drying box, then 500 DEG C of roastings 3 hours.In catalysis
Agent uses H before using2Reduction, H2Air speed is 500h-1, reduction temperature is 200 DEG C, and the recovery time is 24 hours.Obtain catalyst sample
Product 3, wherein the load factor of Pd is 0.25wt%.
The preparation technology of a kind of catalyst that embodiment 4 the present embodiment relates to comprises the steps:
By 2.3mmol palladium acetylacetonate, 2.3mmol sodium nitrate, 50g water mixing wiring solution-forming.By 100g carrier θ-Al2O3
Ball adds in above-mentioned solution, normal temperature dipping 12 hours, and 120 DEG C of evaporation dryings in drying box, then 500 DEG C of roastings 3 hours.?
Catalyst uses H before using2Reduction, H2Air speed is 500h-1, reduction temperature is 200 DEG C, and the recovery time is 24 hours.Obtain catalysis
Agent sample 4, wherein the load factor of Pd is 0.25wt%.
The preparation technology of a kind of catalyst that embodiment 5 the present embodiment relates to comprises the steps:
By 2.3mmol palladium acetylacetonate, 2.3mmol rubidium nitrate, 50g water mixing wiring solution-forming.By 100g carrier θ-Al2O3
Ball adds in above-mentioned solution, normal temperature dipping 48 hours, and 120 DEG C of evaporation dryings in drying box, then 500 DEG C of roastings 3 hours.?
Catalyst uses H before using2Reduction, H2Air speed is 500h-1, reduction temperature is 200 DEG C, and the recovery time is 24 hours.Obtain catalysis
Agent sample 5, wherein the load factor of Pd is 0.5wt%.
The preparation technology of a kind of catalyst that embodiment 6 the present embodiment relates to comprises the steps:
By 4.6mmol palladium acetylacetonate, 4.6mmol rubidium carbonate, 50g water mixing wiring solution-forming.By 100g carrier θ-Al2O3
Ball adds in above-mentioned solution, normal temperature dipping 48 hours, and 120 DEG C of evaporation dryings in drying box, then 500 DEG C of roastings 5 hours.?
Catalyst uses H before using2Reduction, H2Air speed is 500h-1, reduction temperature is 200 DEG C, and the recovery time is 24 hours.Obtain catalysis
Agent sample 6, wherein the load factor of Pd is 0.5wt%.
The preparation technology of a kind of catalyst that embodiment 7 the present embodiment relates to comprises the steps:
By 4.6mmol palladium acetylacetonate, 2.3mmol sodium carbonate, 50g water mixing wiring solution-forming.By 100g carrier θ-Al2O3
Ball adds in above-mentioned solution, normal temperature dipping 48 hours, and 120 DEG C of evaporation dryings in drying box, then 500 DEG C of roastings 5 hours.?
Catalyst uses H before using2Reduction, H2Air speed is 500h-1, reduction temperature is 200 DEG C, and the recovery time is 24 hours.Obtain catalysis
Agent sample 7, wherein the load factor of Pd is 0.5wt%.
The preparation technology of a kind of catalyst that embodiment 8 the present embodiment relates to comprises the steps:
By 2.3mmol palladium nitrate, 50g water mixing wiring solution-forming.By 100g carrier θ-Al2O3Ball adds in above-mentioned solution,
Normal temperature dipping 48 hours, 120 DEG C of evaporation dryings in drying box, then 500 DEG C of roastings 3 hours.H is used before catalyst uses2
Reduction, H2Air speed is 500h-1, reduction temperature is 200 DEG C, and the recovery time is 24 hours.Obtain catalyst blank sample 8, wherein
The load factor of Pd is 0.25wt%.
The catalytic performance of its CO synthesizing dimethyl oxalate evaluated in fixed bed reactors by the catalyst preparing, in reactor
Footpath 25mm, loaded catalyst is 100ml, and beds respectively loads 70ml inertia porcelain bead, three sections of temperature controls of reactor up and down.Former
Material is the gaseous mixture of CO, methyl nitrite and nitrogen, and CO air speed is 400h-1, the air speed of methyl nitrite is 1 with CO air speed ratio
: 1, N2Air speed is 4: 1 with CO air speed ratio, and reaction temperature controls at 118 DEG C-122 DEG C, and reaction pressure controls at 0.4MPa.Reaction
Continue 4 hours, use the means detection assay products such as gas-chromatography, and calculate its catalytic performance.
Result is as shown in Table 1.
Table one:Catalyst performance evaluation result
Claims (10)
1. the catalyst for CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method, it is characterised in that:Described catalyst is containing micro-
The Pd load θ-Al of amount alkali metal2O3Catalyst, wherein the content of Pd accounts for the 0.1%~1% of catalyst weight, wherein alkali
Tenor accounts for the 0.1%~5% of catalyst weight, and described percentage is weight percentage.
2. catalyst according to claim 1, it is characterised in that:Described catalyst carrier θ-Al2O3Specific surface area be 20
~200m2/ g, pore volume is 0.5~1.5m2/ g, aperture is 3~20nm.
3. catalyst according to claim 1 and 2, it is characterised in that:Described alkali metal is Na or K or Rb.
4. the preparation method of catalyst described in a claim 1, it is characterised in that:Comprise the steps of,
First, by Pd compound and alkali metal salt and water mixing wiring solution-forming;Wherein the solution concentration of Pd compound be 20~
500mmol/L, alkali metal ion solution concentration is 20~1000mmol/L;
2nd, by carrier θ-Al2O3Join in the solution of step one and impregnate, carrier θ-Al2O3Addition quality and step one in Pd
Mass ratio is 100~1000: 1, then by the carrier θ-Al after dipping2O3Moisture evaporation drying, then roasting, i.e. make for CO gas
Catalyze and synthesize the catalyst of dimethyl oxalate mutually.
5. the preparation method according to claim 4, it is characterised in that:In step one, described Pd compound is palladium nitrate
Or palladium acetylacetonate.
6. the preparation method according to claim 4, it is characterised in that:In step one, described alkali metal salt be sodium nitrate,
One or more in sodium carbonate, potassium nitrate, potassium carbonate, rubidium nitrate, rubidium carbonate.
7. the preparation method according to claim 4, it is characterised in that:In step one, Pd compound solution concentration is 20
~500mmol/L, the alkali metal ion solution concentration in alkali metal salt is 20~1000mmol/L, adds carrier θ-Al2O3Matter
Amount is 100~1000 with Pd mass ratio in step one: 1.
8. the preparation method according to claim 4, it is characterised in that:It in step 2, is ultrasonic by moisture evaporation drying
Ripple or heating, when moisture evaporation drying is for heating, carrier θ-Al2O3Being dried in drying box, the temperature of described roasting is 300
~600 DEG C, roasting time is 2~10 hours.
9. the application of catalyst described in a claim 1, it is characterised in that:Catalyst is before application through H2Reduction, the H of reduction2
Air speed is 100~1000h-1, reduction temperature is 150~250 DEG C, and the recovery time is 5~72 hours, then by the catalysis after reduction
Agent is placed in reactor.
10. the application of catalyst according to claim 9, it is characterised in that:Described dimethyl oxalate synthetic reaction uses
Fixed bed reactors, raw material carbon monoxide and methyl nitrite are diluted by nitrogen, and CO air speed is 200~2000h1, nitrous acid first
The air speed of ester is 1~2: 2~1 with CO air speed ratio, N2Air speed is 2~10 with CO air speed ratio: 1, reaction temperature controls 110~
130 DEG C, reaction pressure controls at normal pressure~1MPa.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610748007.0A CN106423156B (en) | 2016-08-27 | 2016-08-27 | The preparation method of catalyst for CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610748007.0A CN106423156B (en) | 2016-08-27 | 2016-08-27 | The preparation method of catalyst for CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106423156A true CN106423156A (en) | 2017-02-22 |
CN106423156B CN106423156B (en) | 2019-03-05 |
Family
ID=58181672
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610748007.0A Active CN106423156B (en) | 2016-08-27 | 2016-08-27 | The preparation method of catalyst for CO Synthesis of Dimethyl Oxalate with Gaseous Catalyzing Method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106423156B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107376954A (en) * | 2017-08-02 | 2017-11-24 | 宁波中科远东催化工程技术有限公司 | The preparation method and applications of catalyst, the catalyst for CO gas phase coupling Synthesis of dimethyl carbonate |
CN114805070A (en) * | 2022-03-28 | 2022-07-29 | 易高卓新节能技术(上海)有限公司 | Method for synthesizing dimethyl carbonate from CO and methyl nitrite |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102649082A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for enhancing activity of catalyst for preparing oxalic ester from CO |
US20140296564A1 (en) * | 2011-12-14 | 2014-10-02 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Preparation process of nanocatalysts with (111) crystal facet exposed and process for vapour-phase co oxidative coupling to oxalate |
-
2016
- 2016-08-27 CN CN201610748007.0A patent/CN106423156B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102649082A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for enhancing activity of catalyst for preparing oxalic ester from CO |
US20140296564A1 (en) * | 2011-12-14 | 2014-10-02 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Preparation process of nanocatalysts with (111) crystal facet exposed and process for vapour-phase co oxidative coupling to oxalate |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107376954A (en) * | 2017-08-02 | 2017-11-24 | 宁波中科远东催化工程技术有限公司 | The preparation method and applications of catalyst, the catalyst for CO gas phase coupling Synthesis of dimethyl carbonate |
CN114805070A (en) * | 2022-03-28 | 2022-07-29 | 易高卓新节能技术(上海)有限公司 | Method for synthesizing dimethyl carbonate from CO and methyl nitrite |
Also Published As
Publication number | Publication date |
---|---|
CN106423156B (en) | 2019-03-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105363436B (en) | Carbon monoxide gas phase coupling catalyst for synthesizing oxalic ester, preparation method and its usage | |
CN104248968B (en) | A kind of catalyst of propane direct dehydrogenation propylene and preparation method thereof | |
CN105921148A (en) | Catalyst for preparing olefins from saturated alkanes through dehydrogenation and preparing method and application thereof | |
CN109603819B (en) | Graphene-loaded PdRu bimetallic catalyst and preparation method and application thereof | |
CN112169795B (en) | Optimized polyol hydrogenolysis catalyst activation process | |
CN105597743A (en) | Preparation method of catalyst for CO gas-phase catalyzed synthesis of dimethyl oxalate | |
CN107376954B (en) | Catalyst for CO gas phase coupling synthesis of dimethyl carbonate, preparation method and application thereof | |
CN106866589B (en) | A kind of preparation method of gamma-valerolactone | |
CN108067220A (en) | A kind of hydrogen peroxide synthesis loaded catalyst and its preparation method and application | |
CN108117480A (en) | A kind of catalyzed conversion methanol and alcohol mixeding liquid prepare the new method of isobutanol | |
CN106423284A (en) | Vinyl acetate catalyst and preparing method thereof | |
CN101658798B (en) | Method for modifying titanium silicate molecular sieve material | |
CN106423156A (en) | Catalyst for catalytically synthesizing dimethyl oxalate by CO gas phase and preparation method and application of catalyst | |
CN107694572A (en) | A kind of preparation method of hydrogenation of oxalate for preparing ethylene glycol catalyst | |
CN105435779B (en) | Carbon monoxide vapor- phase synthesis oxalate catalyst | |
CN104549254B (en) | Catalyst for preparing 1,6-hexanediol through direct reduction of adipic acid | |
CN109689606A (en) | The method for preparing 1,3- cyclohexanedimethanol | |
CN105903466A (en) | Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis | |
CN108246289A (en) | The catalyst of CO gas phase coupling synthesizing dimethyl oxalates, preparation method and application | |
US20120259132A1 (en) | Process to prepare an ethanol-derivate | |
CN110124682A (en) | A kind of synthetic method of Ce-Co modification manganese oxide | |
CN109529910A (en) | Catalyst, styrene preparation method for the reaction of methylbenzene methanol side chain alkylation | |
CN105032454B (en) | A kind of support type three-dimensional Halogen Bridged Mixed-valence Platinum gold compound catalyst and its preparation and application | |
CN114653378A (en) | Novel catalyst for synthesizing dimethyl carbonate | |
CN107262092A (en) | A kind of catalyst of the butylene of 1,1,1,4,4,4 hexafluoro of synthesizing cis 2 and its production and use |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |