CN107175104A - A kind of catalyst of gas-phase dimethyloxalate synthesis and its preparation method and application - Google Patents
A kind of catalyst of gas-phase dimethyloxalate synthesis and its preparation method and application Download PDFInfo
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- CN107175104A CN107175104A CN201610140636.5A CN201610140636A CN107175104A CN 107175104 A CN107175104 A CN 107175104A CN 201610140636 A CN201610140636 A CN 201610140636A CN 107175104 A CN107175104 A CN 107175104A
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Abstract
The invention belongs to oxalate diester preparing technical field, it is related to a kind of catalyst of gas-phase dimethyloxalate synthesis and preparation method thereof.The combined treatment one or both of heated by ultrasonic disperse and microwave first, then palladium precursor/acetone soak liquid is controlled by photo-irradiation treatment, prepare Pd/ α Al2O3Catalyst.The catalyst for the CO gas-phase dimethyloxalate synthesis that the present invention is provided has the advantages that palladium load capacity is low, preparation process is simple, efficient catalysis CO gas-phase dimethyloxalate synthesis, with the prospect in the industrial production for CO gas-phase dimethyloxalate synthesis.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof, a kind of vapor- phase synthesis oxalic acid is in particulard relate to
Catalyst of dimethyl ester and preparation method thereof.
Background technology
Oxalate is a kind of important Organic Chemicals, available for fine chemistry industry produce various dyestuffs,
Medical, important solvent, extractant and other intermediates, is widely used in synthesizing various chemical products.
For example, oxalic acid can be made in oxalate ordinary-pressure hydrolysis, normal pressure ammonolysis can obtain high-quality chemical fertilizer i.e. slow-release nitrogen fertilizer
Oxamides, such as material that oxalate is synthesized by other approach, dihydroxy acetic acid are used for spices processed and doctor
Medicine, oxalic acid acid hydrazide is used as fibre finish, and pyrazolone is used as dyestuff intermediate etc., is even more important
Application be that a kind of large industrial chemicals can be made in oxalic acid ester through hydrogenation, mainly for the production of polyester resin
(PET) ethylene glycol.
Traditional oxalate production method is depositing in inorganic acid catalyst and dehydrating agent by alcohol and oxalic acid
In lower lactate synthesis, but a large amount of caustic soda and sulfuric acid etc. are consumed in technique, energy consumption and pollution problem are prominent
Go out, and the production cycle is longer, no longer adapts to the development of modernization industry.Therefore, by one
The research and development of carbonoxide coupling synthesis of oxalate is very swift and violent in recent years, for Oxidation of Carbon Monoxide
Coupling method synthesis of oxalate carries out that liquid phase method and vapor phase method can be divided into from development course.Liquid phase method is coupled
Synthesis of oxalate was carried by U.S. Union Oil Company D.M.Fenton in 1966 at first
Go out, still, the process conditions of liquid phase method synthesis of oxalate are harsher, reaction is carried out under high pressure,
Liquid-phase system corrosive equipment, and catalyst is easy to run off in course of reaction, these inevitable shortcomings,
Promote people that research emphasis is turned into vapor phase method by liquid phase method.Company of Ube Industries Ltd., Italy cover
The research that special Edison and UCC companies of the U.S. have carried out normal pressure gas phase catalytic synthesis oxalate diester is ground
Study carefully.CO gas-phase catalytic coupling oxalate diester techniques have that raw material sources are abundant, inexpensive, reaction condition
Gently, the advantages of energy consumption is low, equipment is simple, environment-friendly, selectivity is high, turns into the country at present
One of important topic of outer C1 chemical research, the focus that wherein vapor phase method is particularly studied.
Since last century the eighties, CO gaseous oxidations are reported successively both at home and abroad and have coupled preparation grass
The New research progress of acid diesters.But it is relatively low to there is oxalate diester yield in the patent reported, such as specially
Sharp JP8242.656 discloses Application Publication and reports a kind of space-time yield of platinum group metal loaded catalyst
Only 432g/ (Lh)；Many patents report in succession in the catalyst addition Mo, Ni, Zr, Ce,
Ti、Fe、La、Re、Ga、MOxThe catalyst constituted Deng auxiliary agent, there is also oxalic acid two for some catalyst
Ester space-time yield is relatively low, the Pd-Ti/Al that such as US4507494 is reported2O3Catalyst space-time yield is
The Pd-Mo/Al of 429~462g/ (Lh), US4384433 report2O3And Pd-Ni/Al2O3During catalyst
Empty yield be 400g/ (Lh), or in catalyst precious metals pd load capacity it is generally higher, such as in
The Pd contents of state's patent CN95116136.9 and CN101791555A report are all 1.5% or so, and China is specially
The catalyst of sharp CN1381310A, CN1055492A, CN101138722A, CN101596455A report
Middle Pd content is 1% or so；The method for preparing catalyst of some patent reports is complicated, and such as China is special
In sharp CN102527377A and CN102553579A after carrier impregnation Pd precursor solutions in a heated condition
Ultrasonic disperse, drying, roasting, add reducing agent, structure directing agent and protective agent and are reduced, very
Sky dry etc. a series of processes come prepare Pd precursors in catalyst, CN102513101A, reducing agent,
Structure directing agent and protective agent composition mixed solution are as maceration extract, in CN103041826A preparation process
Use organic complexing agent, surfactant and reducing agent.Therefore develop a kind of preparation method simplify, it is expensive
The catalyst that metal Pd load capacity is low, efficient CO gas phases couple synthesizing dimethyl oxalate has important meaning
Justice.
The content of the invention
To solve the above problems, the present invention provide a kind of gas-phase dimethyloxalate synthesis catalyst and its
Preparation method, its step is：
Palladium precursor is added in acetone solvent, then processing forms palladium precursor/acetone soak liquid；To
The Alpha-alumina of fired processing is added in palladium precursor/acetone soak liquid, sealing dipping first is certain
After time, then it is distilled off after acetone, eventually passes one or both of dry or reduction place
Reason mode prepares Pd/ α-Al2O3Catalyst, is harmonious for methyl nitrite (MN) and carbon monoxide gas
Into oxalate diester reaction.
As described above, the combination of one or both of palladium precursor palladium or palladium acetylacetonate is added
Enter in acetone；By two-step pretreatment, first pass around ultrasonication, its process be 20~50 DEG C,
10~90min of ultrasonication and microwave are heated at reflux one in 10~90s of processing under 10~40KHz of frequency
Kind or two kinds of combination, then by 2~120h of photo-irradiation treatment, form palladium decentralization and polymerization in solution
The controllable palladium precursor/acetone soak liquid of degree, wherein palladium content are 0.003~0.015g/ml；As above institute
State, palladium content is 0.001~0.025g/ml in palladium precursor/acetone soak liquid, preferably palladium content is
0.003~0.015g/ml.
As described above, palladium precursor/acetone soln processing mode is two steps, pass through ultrasonic wave or micro- first
The combination of one or both of Wave heating, then pass through the decentralization of palladium in photo-irradiation treatment control solution
And the degree of polymerization.Wherein ultrasonication mode be at 20~50 DEG C in Ultrasound Instrument 10~40KHz of frequency
With under ultrasonic 50~200W of electrical power under ultrasonically treated 10~90min, preferably ultrasonic electrical power 100~150
W, sonication treatment time is 30~60min；Microwave heating treatment is that microwave power is in microwave instrument
100~1200W, microwave is heated to reflux 10~90s of processing, preferably 200~600W of power, processing time
20~60s；The light source of photo-irradiation treatment be natural light, ultraviolet light, visible ray, ultraviolet-visible light and
Any of infrared light, illumination power is 20~300W, preferably 50~200W of power, irradiation time
For 2~120h, preferably 24~96h.
As described above, alumina support sintering temperature is 1000~1400 DEG C, preferably sintering temperature is
1100~1300 DEG C；Heating rate is 1~20 DEG C/min, and preferably heating rate is 5~15 DEG C/min；Roasting
The burning time is 0.5~24h, and preferably roasting time is 4~12h.
As described above, acetone is distilled off in 40~50 DEG C under vacuo with Rotary Evaporators.
As described above, drying temperature is 100~200 DEG C, preferably drying temperature is 120~150 DEG C；It is dry
The dry time is 1~24h, and preferably drying time is 4~12h.
As described above, reduction temperature is 200~600 DEG C, preferably reduction temperature is 300~500 DEG C；Also
The former time is 1~8h, and the preferably recovery time is 2~4h.
Walked as described above, the alpha-oxidation aluminium ball through 1000~1400 DEG C of 0.5~24h of calcination process is added
Suddenly in the maceration extract obtained by (1), sealing palladium-impregnated solution min is 0.5~24h, when preferably impregnating
Between be 2~12h.
As described above, after the acetone being distilled off in the Alpha-alumina after step (2) is handled, in
1~24h is dried at 100~200 DEG C, after 1~8h is either reduced at 200~600 DEG C or is dried again
Reduction prepares Pd/ α-Al of the present invention2O3In catalyst, wherein catalyst the content of palladium relative to
The ratio of carrier quality is 0.05~0.5wt%.
The invention has the advantages that：
Pd load capacity is low in catalyst, and simplifying the preparation method of catalyst reduces cost, keeps higher
The advantages of oxalate diester space-time yield.
Brief description of the drawings
Fig. 1 is 0.1%Pd/ α-Al prepared by embodiment 1,2 and 32O3Acid chloride/acetone soak of catalyst
Liquid ultraviolet-visible absorption spectroscopy figure, wherein, (a) is the catalyst of embodiment 1；(b) it is embodiment 2
Catalyst；(c) it is the catalyst of embodiment 3.
Embodiment
Embodiment is enumerated below and combination table 1 and Fig. 1 are described in further details to the present invention.To this hair
It is bright to be described in further details, but the scope of the present invention is not limited to lifted embodiment.
The calcination process process of Alpha-alumina：Alumina support is from room temperature using heating rate as 8 DEG C/min
1200 DEG C are warming up to, then roasting time is 8h.
Embodiment 1, catalyst preparation；After acid chloride 0.0851g is added in acetone 10ml, first
Ultrasonication (ultrasonic electrical power 200W, ultrasonic time 0.5h), then natural light irradiation 24h
Processing prepares acid chloride/acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter ball
Acetone is distilled off after shape Alpha-alumina 20g, dipping 6h.Air dry oven is finally putting at 120 DEG C
Lower dry 4h, then the reductase 12 h at 300 DEG C, that is, be made 0.2%Pd/ α-Al2O3Catalyst.From Fig. 1
(a) ultraviolet-visible absorption spectroscopy figure can be seen that in acid chloride/acetone soln without the generation of Pd colloids.
Embodiment 2, after acid chloride 0.0851g is added in acetone 10ml, ultrasonication is (super first
Acoustoelectric power 120W, ultrasonic time 1h), then natural light irradiation 72h processing prepare acid chloride/
Acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after dipping 6h.Be finally putting into air dry oven at 120 DEG C dry 4h, then
Reductase 12 h at 300 DEG C, that is, be made 0.2%Pd/ α-Al2O3Catalyst.From Fig. 1 (b) UV, visible light
Abosrption spectrogram, which can be seen that, the generation of trace P d colloids in acid chloride/acetone soln.
Embodiment 3, after acid chloride 0.0851g is added in acetone 10ml, ultrasonication is (super first
Acoustoelectric power 50W, ultrasonic time 1.5h), then natural light irradiation 120h processing prepare acid chloride/
Acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after dipping 6h.Be finally putting into air dry oven at 120 DEG C dry 4h, then
Hydrogen reducing 2h at 300 DEG C, that is, be made 0.2%Pd/ α-Al2O3Catalyst.From the ultraviolet of Fig. 1 (c)
Visible absorption spectra figure, which can be seen that, has a small amount of Pd colloids to produce in acid chloride/acetone soln.
Embodiment 4, after palladium acetylacetonate 0.1143g is added in acetone 10ml, first at ultrasonic wave
Manage (ultrasonic electrical power 120W, ultrasonic time 1h), then natural light irradiation 72h processing prepares second
Acyl acetone palladium/acetone soak liquid.Then, into the solution sealing dipping diameter 3~5mm globular α-
Acetone is distilled off after aluminum oxide 20g, dipping 6h.Air dry oven is finally putting at 120 DEG C
4h, then the reductase 12 h at 300 DEG C are dried, that is, 0.2%Pd/ α-Al are made2O3Catalyst.
Embodiment 5, after acid chloride 0.0851g is added in acetone 10ml, ultrasonication is (super first
Acoustoelectric power 120W, ultrasonic time 1h), then made with infrared lamp (50W) irradiation 24h processing
Standby acid chloride/acetone soak liquid.Then, into the solution sealing dipping diameter 3~5mm globular α-
Acetone is distilled off after aluminum oxide 20g, dipping 6h.Air dry oven is finally putting at 120 DEG C
4h, then the reductase 12 h at 300 DEG C are dried, that is, 0.2%Pd/ α-Al are made2O3Catalyst.
Embodiment 6, after acid chloride 0.0851g is added in acetone 10ml, ultrasonication is (super first
Acoustoelectric power 120W, ultrasonic time 1h), then natural light irradiation 72h processing prepare acid chloride/
Acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after dipping 6h.It is finally putting into air dry oven and 4h is dried at 120 DEG C, that is, makes
Obtain 0.2%Pd/ α-Al2O3Catalyst.
Embodiment 7, after acid chloride 0.1702g is added in acetone 10ml, ultrasonication is (super first
Acoustoelectric power 120W, ultrasonic time 1h), then natural light irradiation 72h processing prepare acid chloride/
Acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after dipping 6h.It is finally putting into air dry oven and 4h is dried at 120 DEG C, then at
Hydrogen reducing 2h at 300 DEG C, that is, be made 0.4%Pd/ α-Al2O3Catalyst.
Embodiment 8, after acid chloride 0.2128g is added in acetone 8ml, ultrasonication is (super first
Acoustoelectric power 120W, ultrasonic time 1h), then natural light irradiation 72h processing prepare acid chloride/
Acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after dipping 6h.Be finally putting into air dry oven at 120 DEG C dry 4h, then
Reductase 12 h at 300 DEG C, that is, be made 0.5%Pd/ α-Al2O3Catalyst.
Embodiment 9, after acid chloride 0.0851g is added in acetone 10ml, microwave is heated at reflux first
(power 600W, heat time 10s), then natural light irradiation 24h processing prepare acid chloride/
Acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after dipping 8h.Be finally putting into air dry oven at 120 DEG C dry 4h, then
Hydrogen reducing 2h at 300 DEG C, that is, be made 0.2%Pd/ α-Al2O3Catalyst.
Embodiment 10, after acid chloride 0.0851g is added in acetone 10ml, microwave is heated at reflux first
(power 300W, heat time 30s), then natural light irradiation 72h processing prepare acid chloride/
Acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after dipping 8h.It is finally putting into air dry oven and 4h is dried at 120 DEG C, then at
Hydrogen reducing 2h at 300 DEG C, that is, be made 0.2%Pd/ α-Al2O3Catalyst.
Embodiment 11, after acid chloride 0.0851g is added in acetone 10ml, microwave is heated at reflux first
(power 200W, heat time 90s), then natural light irradiation 120h processing prepare acid chloride/
Acetone soak liquid.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after dipping 8h.It is finally putting into air dry oven and 4h is dried at 120 DEG C, then at
Hydrogen reducing 2h at 300 DEG C, that is, be made 0.2%Pd/ α-Al2O3Catalyst.
Embodiment 12, after acid chloride 0.0851g is added in acetone 10ml, ultrasonication is (super first
Acoustoelectric power 120W, ultrasonic time 1h), then microwave be heated at reflux processing (power 300W, plus
Hot time 30s), last natural light irradiation 72h processing prepares acid chloride/acetone soak liquid.Then,
Distill and remove after 3~5mm of sealing dipping diameter spherical Alpha-alumina 20g, dipping 8h into the solution
Remove acetone.It is finally putting into air dry oven and 4h, the hydrogen reducing at 300 DEG C is dried at 120 DEG C
2h, that is, be made 0.2%Pd/ α-Al2O3Catalyst.
Comparing embodiment 1, after acid chloride 0.0851g is added in acetone 10ml, ultrasonication is (super
Acoustoelectric power 120W, ultrasonic time 1h) prepare acid chloride/acetone soak liquid.Then, to the solution
Acetone is distilled off after 6 hours in 3~5mm of middle sealing dipping diameter spherical Alpha-alumina 20g, dipping.
4h is finally dried at 120 DEG C with air dry oven, hydrogen reducing 2h, that is, make at 300 DEG C
Obtain 0.2%Pd/ α-Al2O3Catalyst.
Comparing embodiment 2, after acid chloride 0.0851g is added in acetone 10ml, microwave is heated at reflux
Processing (power 300W, heat time 30s) prepares acid chloride/acetone soak liquid.Then, to this
3~5mm of sealing dipping diameter spherical Alpha-alumina 20g in solution, dipping is distilled off after 6 hours
Acetone.4h, then the hydrogen reducing 2h at 300 DEG C are finally dried at 120 DEG C with air dry oven,
0.2%Pd/ α-Al are made2O3Catalyst.
Comparing embodiment 3, after acid chloride 0.0851g is added in acetone 10ml, at natural light irradiation
Reason 72h prepares acid chloride/acetone soak liquid.Then, 3~5mm of sealing dipping diameter into the solution
Spherical Alpha-alumina 20g, dipping 6 hours after acetone is distilled off.Finally existed with air dry oven
4h, the hydrogen reducing 2h at 300 DEG C are dried at 120 DEG C, that is, 0.2%Pd/ α-Al are made2O3Urge
Agent.
Comparing embodiment 4, acid chloride 0.0851g is added in acetone 10ml, acid chloride/acetone is prepared
Maceration extract.Then, into the solution, sealing impregnates 3~5mm of diameter spherical Alpha-alumina 20g,
Acetone is distilled off after 6 hours in dipping.4h is finally dried at 120 DEG C with air dry oven, then at
Hydrogen reducing 2h at 300 DEG C, that is, be made 0.2%Pd/ α-Al2O3Catalyst.
Comparing embodiment 5, concentrated hydrochloric acid 0.5ml and deionized water 10ml is added by palladium bichloride 0.0672g
In after, ultrasonication (ultrasonic electrical power 120W, ultrasonic time 1h) first, then natural light
Irradiation 72h processing prepares palladium chloride solution.Then, 3~5mm of sealing dipping diameter into the solution
Spherical Alpha-alumina 20g, dipping dries naturally after 6 hours.Finally with air dry oven at 120 DEG C
Lower dry 4h, the hydrogen reducing 2h at 300 DEG C, that is, be made 0.2%Pd/ α-Al2O3Catalyst.
Embodiment 10, reactivity worth evaluation；In internal diameter 12mm, long 600mm fixed bed reactors,
Fill the catalyst 8ml prepared in the embodiment 1~12 and comparing embodiment 1~5, then at an upper portion thereof and
A small amount of quartz sand is loaded in bottom, and unstripped gas composition (volume ratio) is 21%CO, 16%MN, and remaining is
Nitrogen, gas space velocity is 4000h-1, reaction pressure is 0.1MPa, is 110~130 DEG C in bed temperature
The lower reaction 4h that carries out investigates catalyst performance.
Table 1
The catalyst for the CO gas-phase dimethyloxalate synthesis that the present invention is provided have palladium load capacity it is low, prepare
Process is simple, efficient catalysis CO gas-phase dimethyloxalate synthesis the advantages of, with being closed for CO gas phases
Prospect into the industrial production of dimethyl oxalate.
Claims (10)
1. a kind of preparation method of gas-phase dimethyloxalate synthesis catalyst, it is characterised in that：
(1) palladium precursor is added in acetone solvent, two steps then is carried out to precursor/acetone soln
Processing, first step processing mode is the combination by one or both of ultrasonic wave or microwave heating,
Second step processing mode is light irradiation, ultimately forms palladium precursor/acetone soak liquid；
(2) fired processing is added into palladium precursor/acetone soak liquid after above-mentioned two-step pretreatment
After Alpha-alumina, first sealing dipping, redistillation removes acetone, eventually passes in drying or reducing
One or two kinds of processing modes prepare Pd/ α-Al2O3Catalyst.
2. preparation method as claimed in claim 1, it is characterised in that：Palladium precursor uses palladium
Or the combination of one or both of palladium acetylacetonate, palladium content is in palladium precursor/acetone soak liquid
0.001~0.025g/ml, preferably palladium content are 0.003~0.015g/ml.
3. preparation method as claimed in claim 1, it is characterised in that：Wherein ultrasonication mode
For at 20~50 DEG C in Ultrasound Instrument under 10~40KHz of frequency and ultrasonic 50~200W of electrical power at ultrasound
10~90min is managed, preferably 100~150W of ultrasonic electrical power, sonication treatment time is 30~60min；It is micro-
Wave heating is processed as the microwave in microwave instrument and is heated to reflux 10~90s of processing, and microwave power is 100~1200
W, preferably 20~60s of preferred process time, 200~600W of power；The light source of photo-irradiation treatment is nature
Any of light, ultraviolet light, visible ray, ultraviolet-visible light and infrared light, illumination power are 20~300
W, preferably 50~200W of power, irradiation time are 2~120h, preferably 24~96h.
4. preparation method as claimed in claim 1, it is characterised in that：Alumina support sintering temperature
For 1000~1400 DEG C, preferably sintering temperature is 1100~1300 DEG C；Heating rate is 1~20 DEG C/min,
It is preferred that heating rate is 5~15 DEG C/min；Roasting time is 0.5~24h, and preferably roasting time is 4~12h.
5. preparation method as claimed in claim 1, it is characterised in that：Seal palladium-impregnated solution min
For 0.5~24h, preferably dip time is 2~12h.
6. preparation method as claimed in claim 1, it is characterised in that：Still-process is to be steamed with rotation
Acetone is distilled off in 40~50 DEG C under vacuo in hair instrument.
7. preparation method as claimed in claim 1, it is characterised in that：Drying temperature is
100~200 DEG C, preferably drying temperature is 120~150 DEG C；Drying time is 1~24h, is preferably dried
Time is 4~12h；
Reduced under hydrogen, reduction temperature is 200~600 DEG C, preferably reduction temperature is 300~500 DEG C；
Recovery time is 1~8h, and the preferably recovery time is 2~4h.
8. preparation method as claimed in claim 1, it is characterised in that：Palladium contains in the catalyst
Amount is calculated as the 0.05~0.5% of vehicle weight with palladium element.
9. the catalyst obtained by a kind of any described preparation methods of claim 1-8.
10. the application of catalyst described in a kind of claim 9, Pd/ α-Al2O3Catalyst is used for nitrous acid
In methyl esters (MN) and the reaction of carbon monoxide vapor- phase synthesis oxalate diester.
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| CN201610140636.5A CN107175104A (en) | 2016-03-11 | 2016-03-11 | A kind of catalyst of gas-phase dimethyloxalate synthesis and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110508277A (en) * | 2019-08-30 | 2019-11-29 | 浙江工业大学 | A kind of high dispersive palladium nanoparticle catalyst and its preparation method and application |
| CN112642469A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol by hydrogenating oxalate, preparation method and application thereof, and method for preparing ethylene glycol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103962130A (en) * | 2014-04-28 | 2014-08-06 | 河南能源化工集团研究院有限公司 | Catalyst for oxalate ester synthetic reaction and preparation method of catalyst |
| CN105381799A (en) * | 2015-11-30 | 2016-03-09 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Catalyst synthesizing dimethyl oxalate by CO gas phase coupling and preparing method of catalyst |
-
2016
- 2016-03-11 CN CN201610140636.5A patent/CN107175104A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103962130A (en) * | 2014-04-28 | 2014-08-06 | 河南能源化工集团研究院有限公司 | Catalyst for oxalate ester synthetic reaction and preparation method of catalyst |
| CN105381799A (en) * | 2015-11-30 | 2016-03-09 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Catalyst synthesizing dimethyl oxalate by CO gas phase coupling and preparing method of catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110508277A (en) * | 2019-08-30 | 2019-11-29 | 浙江工业大学 | A kind of high dispersive palladium nanoparticle catalyst and its preparation method and application |
| CN112642469A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol by hydrogenating oxalate, preparation method and application thereof, and method for preparing ethylene glycol |
| CN112642469B (en) * | 2019-10-10 | 2023-06-06 | 中国石油化工股份有限公司 | Catalyst for preparing ethylene glycol by oxalate hydrogenation, preparation method and application thereof, and method for preparing ethylene glycol |
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Application publication date: 20170919 |