CN102600863A - Palladium-copper-based catalyst used for synthesizing oxalate, and preparation method thereof - Google Patents
Palladium-copper-based catalyst used for synthesizing oxalate, and preparation method thereof Download PDFInfo
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- CN102600863A CN102600863A CN2012100489413A CN201210048941A CN102600863A CN 102600863 A CN102600863 A CN 102600863A CN 2012100489413 A CN2012100489413 A CN 2012100489413A CN 201210048941 A CN201210048941 A CN 201210048941A CN 102600863 A CN102600863 A CN 102600863A
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Abstract
The invention relates to a load-type palladium-copper-based catalyst used in gas-phase synthesis of oxalate. Alpha-Al2O3 is adopted as a carrier. The catalyst comprises components of, by weight: 0.01-0.5% of palladium, 0.01-2.0% of copper, 0.01-2.0% of zinc, and 0.01-2.0% of a metal M. The catalyst is prepared with a consecutive impregnation method. The catalyst is advantaged in high activity, high selectivity, and good catalyst reaction performance reproducibility. The preparation method of the catalyst is simple, and is easy to operate. With the method, industrial amplification can easily be realized.
Description
Technical field
The invention belongs to the oxalate preparing technical field, relate to a kind of Catalysts and its preparation method and application that is used for carbon monoxide and nitrites carbonylation synthesis of oxalate.
Background technology
Oxalate is important Organic Chemicals, can be used for preparing oxalic acid, ethylene glycol, carbonic ester, oxamides, oxalyl chloride etc.Nineteen sixty-five, the people such as D.M. Fenton of the U.S. found, with α-Al
2O
3Be carrier, Metal Palladium is an active component, and carbon monoxide carries out coupling reaction and synthesizes oxalate diester in pure medium, has opened up the important channel of C1 chemical synthesis oxalate.Its reaction principle is following:
Wherein: R is an alkyl.
The required nitrites of this reaction can use nitrous acid with the alcohol reaction or by NO, O
2Reaction generates with alcohol, and wherein, alcohol can be selected any saturated fatty alcohol that comprises 1 ~ 8 carbon atom for use, and methyl alcohol, ethanol are the most commonly used.Unstripped gas is used N usually
2Or CO
2Deng as inert gas dilution.
Since the eighties in last century, reported the new development of C1 chemical synthesis oxalate research both at home and abroad successively.Japanese documentation JP8242.656 public reported adopt support type platinum family metallic catalyst to carry out the technological process of CO and methyl nitrite synthesizing dimethyl oxalate, the space-time yield of catalyst is 432g/L/h.
There are many patents to report subsequently again and in catalytic component, add auxiliary agents such as Mo, Ni, Fe, Ti, Si, Zr and Ce respectively; Be applied in the technology of CO and methyl nitrite gas-phase dimethyloxalate synthesis, diethy-aceto oxalate and oxalic acid diisopropyl ester, but space-time yield is still lower or the Pd tenor high.Pd-Ti/Al like the US4507494 report
2O
3Its space-time yield was 429 ~ 462g/L when catalyst was used for CO and methyl nitrite synthesizing dimethyl oxalate
Cat/ h.The ZL1066070 report adopts the Pd-Zr/Al of immersion process for preparing
2O
3Catalyst is at normal pressure, 140 ℃, reaction gas composition: N
2: CO:CH
3ONO=5:3:2 and air speed 3000h
-1Under the condition, the space-time yield of dimethyl oxalate reaches 999g/L
Cat/ h, the selectivity of dimethyl oxalate is greater than 95%.Pd-Ce/ α-the Al of the employing step impregnation method preparation of ZL1141179 report
2O
3Catalyst (wherein Pd content is 1%) is that the conversion per pass of CO reaches 78% under 1.3/1 the condition in the mol ratio of normal pressure, 140 ℃, CO and nitrites, and the space-time yield of dimethyl oxalate is 821 g/L
Cat/ h.Pd content is generally higher in these catalyst, and Pd is a kind of noble metal, costs an arm and a leg, and high load capacity makes the catalyst cost high, influences its use in industry.
Summary of the invention
The present invention aims to provide catalyst that is used for the carbon monoxide gas-phase synthesis of oxalate and the preparation method that a kind of activity, selectivity are high, cost is low.
The load type palladium copper-based catalysts that is used for carbon monoxide and nitrites carbonylation synthesis of oxalate provided by the invention is with α-Al
2O
3Be carrier, each ingredients constitute vehicle weight percentage is: palladium: 0.01-0.5%, and copper: 0.01-2.0%, zinc: 0.01-2.0%, metal M: 0.01-2.0%, wherein metal M is any one in iron, cobalt or the nickel.
Described α-Al
2O
3The specific area of carrier is 3 ~ 20m
- 2/ g, average pore size is 10 ~ 30nm.
Preparation of catalysts method provided by the invention is following:
(1) soluble-salt with copper, zinc and metal M is mixed with maceration extract by metering, soaks α-Al
2O
3Carrier left standstill 2 ~ 24 hours;
(2) filtration is back following dry 4 ~ 24 hours at 40 ~ 140 ℃; 300 ~ 600 ℃ of roastings 2 ~ 12 hours, obtain solid precursor then, be designated as Cu/Zn/M/ α-Al
2O
3
(3) soluble-salt with Metal Palladium is mixed with maceration extract, adds an amount of acid identical with the anion of palladium metal salt palladium salt is all dissolved; The solid precursor that soaking step (2) obtains left standstill 2 ~ 24 hours;
(4) filtration is back following dry 4 ~ 24 hours at 40 ~ 140 ℃;
(5) dried solids in the step (4) is put into reactor, add suitable quantity of water, dripping its pH value of alkaline solution accent is 8 ~ 11, adds 2 ~ 20 times of reducing agents to (Pd+Cu+Zn+M) amount of substance then; Under 40 ~ 90 ℃ of water bath condition, liquid-phase reduction 0.5 ~ 4 hour;
(6) promptly get catalyst after filtration, washing, the drying.
The soluble-salt of copper, zinc, metal M and the palladium of above-mentioned steps (1) and (3) can be in nitrate, sulfate, halides or the acetate any one.
Alkaline solution in the above-mentioned steps (5) can be NaOH, KOH, K
2CO
3, Na
2CO
3Or in the ammoniacal liquor any one.
Reducing agent in the above-mentioned steps (5) can be in hydrazine hydrate, sodium borohydride, potassium borohydride, formic acid or the formaldehyde any one.
Need carry out activation processing before the catalyst that is used for carbon monoxide and nitrites carbonylation synthesis of oxalate of the present invention uses, activation method is with hydrogen-nitrogen mixed gas (H
2Volume content is 10% ~ 100%) or carbon monoxide-nitrogen mixed gas (the CO volume content is 10% ~ 100%) handled 2 ~ 24 hours in 150 ~ 450 ℃ of reduction, air speed is 2000 ~ 4000h
-1Be used for the reaction of carbon monoxide and nitrites carbonylation synthesis of oxalic acid diester behind the catalyst activation, the catalyst service condition is: reaction temperature is 90 ~ 150 ℃, and reaction pressure is normal pressure ~ 1MPa, and air speed is 1000 ~ 9000h
-1
The present invention and prior art relatively have following characteristics:
1. catalyst of the present invention is with α-Al
2O
3Be carrier, palladium is main active component, and copper, zinc and metal M are auxiliary agent, and metal M is any one in iron, cobalt or the nickel.
2. catalyst precious metal palladium content of the present invention is low, is merely less than 0.5% of carrier quality, and the catalyst cost is low; And method for preparing catalyst of the present invention is simple, easy operating, easy realization of industrial production.
3. the space-time yield of catalyst oxalate of the present invention can reach 1400g/L
Cat/ h, the selectivity of oxalate is greater than 94%.
The specific embodiment:
Through embodiment Catalysts and its preparation method of the present invention is described further below.
Auxiliary agent and palladium metal salt are made into the volume of the aqueous solution among the following embodiment, are not strict with, and the aqueous solution that is made into is can the submergence carrier just passable.
Embodiment 1
Press 0.5wt%Cu+0.5wt%Zn+0.5wt%Co+0.5wt%Pd/ α-Al
2O
3Form the preparation catalyst, its step is following: taking by weighing Schweinfurt green, zinc acetate and the cobalt acetate wiring solution-forming soluble in water of amount of calculation, is 10.0m with 10 gram specific areas
2α-Al of/g
2O
3Carrier is put into above-mentioned solution and was soaked 4 hours, filters, 40 ℃ of oven dry 24 hours, in 500 ℃ of roastings 4 hours, obtains Cu/Zn/Co/ α-Al then
2O
3Presoma; Take by weighing the palladium wiring solution-forming of amount of calculation, drip little acetic acid palladium is all dissolved, soak Cu/Zn/Co/ α-Al
2O
3Presoma left standstill 6 hours; Filtration, 60 ℃ of dryings were put into reactor after 20 hours, added suitable quantity of water, and dripping KOH solution adjusting pH value is about 9, adds 4 times of hydrazine hydrates to (Pd+Cu+Zn+Co) amount of substance then, and liquid-phase reduction is 0.5 hour under 90 ℃ of water bath condition; Filtration, washing, drying promptly make Cu/Zn/Co/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content is that hydrogen-nitrogen mixed gas of 30% is in 200 ℃, air speed 4000h
-1Following reductase 12 hour cools to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 10%CH
3ONO+15%CO+75%N
2Unstripped gas, air speed 3000h
-1, reaction result is listed in the table 1.
Embodiment 2
Press 2.0wt%Cu+0.5wt%Zn+0.1wt%Ni+0.2wt%Pd/ α-Al
2O
3Form the preparation catalyst, its step is following: taking by weighing copper chloride, zinc nitrate and the nickel nitrate wiring solution-forming soluble in water of amount of calculation, is 15.0m with 10 gram specific areas
2α-Al of/g
2O
3Carrier is put into above-mentioned solution and was soaked 12 hours, filters, 140 ℃ of oven dry 4 hours, in 300 ℃ of roastings 12 hours, obtains Cu/Zn/Ni/ α-Al then
2O
3Presoma; Take by weighing the palladium bichloride wiring solution-forming of amount of calculation, drip small amount of hydrochloric acid palladium bichloride is all dissolved, soak Cu/Zn/Ni/ α-Al
2O
3Presoma left standstill 24 hours; Filtration, 100 ℃ of dryings were put into reactor after 10 hours, added suitable quantity of water, and dripping NaOH solution adjusting pH value is about 9, adds 6 times of formaldehyde to (Pd+Cu+Zn+Ni) amount of substance then, and liquid-phase reduction is 1 hour under 90 ℃ of water bath condition; Filtration, washing, drying promptly make Cu/Zn/Ni/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content is that hydrogen-nitrogen mixed gas of 10% is in 180 ℃, air speed 3000h
-1Under reduced 3 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 12%CH
3ONO+20%CO+68%N
2Unstripped gas, air speed 2000h
-1, reaction result is listed in the table 1.
Embodiment 3
Press 1.5wt%Cu+0.5wt%Zn+0.01wt%Fe+0.01wt%Pd/ α-Al
2O
3Form the preparation catalyst, its step is following: taking by weighing copper nitrate, zinc nitrate and the ferric nitrate wiring solution-forming soluble in water of amount of calculation, is 20.0m with 10 gram specific areas
2α-Al of/g
2O
3Carrier is put into above-mentioned solution and was soaked 24 hours, filters, 100 ℃ of oven dry 20 hours, in 600 ℃ of roastings 2 hours, obtains Cu/Zn/Fe/ α-Al then
2O
3Presoma; Take by weighing the palladium nitrate wiring solution-forming of amount of calculation, drip a small amount of nitric acid palladium nitrate is all dissolved, soak Cu/Zn/Fe/ α-Al
2O
3Presoma left standstill 24 hours; Filtration, 100 ℃ of dryings were put into reactor after 15 hours, added suitable quantity of water, and it is 11 that dropping ammonia is regulated the pH value, adds 20 times of formic acid to (Pd+Cu+Zn+Fe) amount of substance then, and liquid-phase reduction is 4 hours under 90 ℃ of water bath condition; Filtration, washing, drying promptly make Cu/Zn/Fe/Pd/ α-Al
2O
3Catalyst.
This catalyst is used pure H
2In 150 ℃, air speed is 2000h
-1Under reduced 12 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 15%CH
3ONO+30%CO+55%N
2Unstripped gas, air speed 1000h
-1, reaction result is listed in the table 1.
Embodiment 4
Press 0.8wt%Cu+0.6wt%Zn+0.1wt%Fe+0.2wt%Pd/ α-Al
2O
3Form the preparation catalyst, its step is following: taking by weighing copper sulphate, zinc sulfate and the ferric sulfate wiring solution-forming soluble in water of amount of calculation, is 13.0m with 10 gram specific areas
2α-Al of/g
2O
3Carrier is put into above-mentioned solution and was soaked 19 hours, filters, 120 ℃ of oven dry 15 hours, in 550 ℃ of roastings 5 hours, obtains Cu/Zn/Fe/ α-Al then
2O
3Presoma; Take by weighing the palladium sulfate wiring solution-forming of amount of calculation, drip a small amount of sulfuric acid palladium sulfate is all dissolved, soak Cu/Zn/Fe/ α-Al
2O
3Presoma left standstill 18 hours; Filtration, 130 ℃ of dryings were put into reactor after 12 hours, added suitable quantity of water, dripped Na
2CO
3It is about 9.5 that solution is regulated the pH value, adds 15 times of potassium borohydrides to (Pd+Cu+Zn+Fe) amount of substance then, and liquid-phase reduction is 3 hours under 75 ℃ of water bath condition; Filtration, washing, drying promptly make Cu/Zn/Fe/Pd/ α-Al
2O
3Catalyst.
It is that carbon monoxide-nitrogen mixed gas of 15% is in 450 ℃, air speed 3000h that this catalyst uses CO content
-1Under reduced 8 hours, cool to reaction temperature then, with nitrogen CO is purged clean back and feeds volume and consist of 15%CH
3ONO+15%CO+70%N
2Unstripped gas, air speed 7000h
-1, reaction result is listed in the table 1.
Embodiment 5
Press 0.3wt%Cu+0.3wt%Zn+2.0wt%Co+0.1wt%Pd/ α-Al
2O
3Form the preparation catalyst, its step is following: taking by weighing copper nitrate, zinc nitrate and the cobalt nitrate wiring solution-forming soluble in water of amount of calculation, is 16.0m with 10 gram specific areas
2α-Al of/g
2O
3Carrier is put into above-mentioned solution and was soaked 10 hours, filters, 130 ℃ of oven dry 9 hours, in 450 ℃ of roastings 9 hours, obtains Cu/Zn/Co/ α-Al then
2O
3Presoma; Take by weighing the palladium bichloride wiring solution-forming of amount of calculation, drip small amount of hydrochloric acid palladium bichloride is all dissolved, soak Cu/Zn/Co/ α-Al
2O
3Presoma left standstill 10 hours; Filtration, 90 ℃ of dryings were put into reaction vessel after 14 hours, added suitable quantity of water, dripped K
2CO
3It is about 10 that solution is regulated the pH value, adds 12 times of hydrazine hydrates to (Pd+Cu+Zn+Co) amount of substance then, and liquid-phase reduction is 2.5 hours under 70 ℃ of water bath condition; Filtration, washing, drying promptly make Cu/Zn/Co/Pd/ α-Al
2O
3Catalyst.
This catalyst with pure CO gas in 450 ℃, air speed 2500h
-1Under reduced 6 hours, cool to reaction temperature then, with nitrogen CO is purged clean back and feeds volume and consist of 20%CH
3ONO+20%CO+60%N
2Unstripped gas, air speed 5000h
-1, reaction result is listed in the table 1.
Embodiment 6
Press 0.5wt%Cu+0.5wt%Zn+0.5wt%Ni+0.5wt%Pd/ α-Al
2O
3Form the preparation catalyst, its step is following: taking by weighing chlorination, zinc nitrate and the nickel chloride wiring solution-forming soluble in water of amount of calculation, is 9.0m with 10 gram specific areas
2α-Al of/g
2O
3Carrier is put into above-mentioned solution and was soaked 22 hours, filters, 65 ℃ of oven dry 16 hours, in 550 ℃ of roastings 10 hours, obtains Cu/Zn/Ni/ α-Al then
2O
3Presoma; Take by weighing the palladium bichloride wiring solution-forming of amount of calculation, drip small amount of hydrochloric acid palladium bichloride is all dissolved, soak Cu/Zn/Ni/ α-Al
2O
3Presoma left standstill 20 hours; Filtration, 55 ℃ of dryings were put into reaction vessel after 17 hours, added suitable quantity of water, and dripping KOH solution adjusting pH value is about 9, adds 8 times of formaldehyde to (Pd+Cu+Zn+Ni) amount of substance then, and liquid-phase reduction is 1.5 hours under 85 ℃ of water bath condition; Filtration, washing, drying promptly make Cu/Zn/Ni/Pd/ α-Al
2O
3Catalyst.
It is that hydrogen-nitrogen mixed gas of 80% is in 350 ℃, air speed 3500h that this catalyst uses H2 content
-1Under reduced 8 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 15%CH
3ONO+18%CO+67%N
2Unstripped gas, air speed 4000h
-1, reaction result is listed in the table 1.
Embodiment 7
Press 1.2wt%Cu+1.2wt%Zn+0.9wt%Ni+0.3wt%Pd/ α-Al
2O
3Form the preparation catalyst, its step is following: taking by weighing copper chloride, zinc chloride and the nickel chloride wiring solution-forming soluble in water of amount of calculation, is 17.0m with 10 gram specific areas
2α-Al of/g
2O
3Carrier is put into above-mentioned solution and was soaked 20 hours, filters, 100 ℃ of oven dry 14 hours, in 350 ℃ of roastings 11 hours, obtains Cu/Zn/Ni/ α-Al then
2O
3Presoma; Take by weighing the palladium nitrate wiring solution-forming of amount of calculation, drip a small amount of nitric acid palladium nitrate is all dissolved, soak Cu/Zn/Ni/ α-Al
2O
3Presoma left standstill 6 hours; Filtration, 95 ℃ of dryings were put into reaction vessel after 17 hours, added suitable quantity of water, and dripping NaOH solution adjusting pH value is about 9.5, adds 7 times of potassium borohydrides to (Pd+Cu+Zn+Ni) amount of substance then, and liquid-phase reduction is 3.5 hours under 50 ℃ of water bath condition; Filtration, washing, drying promptly make Cu/Zn/Ni/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content is that hydrogen-nitrogen mixed gas of 10% is in 450 ℃, air speed 3000h
-1Following reductase 12 4 hours cools to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 16%CH
3ONO+20%CO+64%N
2Unstripped gas, air speed 8000h
-1, reaction result is listed in the table 1.
Embodiment 8
Press 1.8wt%Cu+1.2wt%Zn+1.0wt%Fe+0.03wt%Pd/ α-Al
2O
3Form the preparation catalyst, its step is following: taking by weighing copper nitrate, zinc nitrate and the iron chloride wiring solution-forming soluble in water of amount of calculation, is 10.0m with 10 gram specific areas
2α-Al of/g
2O
3Carrier is put into above-mentioned solution and was soaked 24 hours, filters, 70 ℃ of oven dry 22 hours, in 480 ℃ of roastings 8 hours, obtains Cu/Zn/Fe/ α-Al then
2O
3Presoma; Take by weighing the palladium bichloride wiring solution-forming of amount of calculation, drip small amount of hydrochloric acid palladium bichloride is all dissolved, soak Cu/Zn/Fe/ α-Al
2O
3Presoma left standstill 24 hours; Filtration, 70 ℃ of dryings were put into reaction vessel after 20 hours, added suitable quantity of water, and it is about 9 that dropping ammonia is regulated the pH value, adds 2 times of hydrazine hydrates to (Pd+Cu+Zn+Fe) amount of substance then, and liquid-phase reduction is 1 hour under 60 ℃ of water bath condition; Filtration, washing, drying promptly make Cu/Zn/Fe/Pd/ α-Al
2O
3Catalyst.
It is that carbon monoxide-nitrogen mixed gas of 60% is in 250 ℃, air speed 4000h that this catalyst uses CO content
-1Under reduced 7 hours, cool to reaction temperature then, with nitrogen CO is purged clean back and feeds volume and consist of 15%CH
3ONO+15%CO+70%N
2Unstripped gas, air speed 9000h
-1, reaction result is listed in the table 1.
Claims (8)
1. the load type palladium copper-based catalysts of a gas-phase synthesis of oxalate, it is characterized in that: this catalyst is with α-Al
2O
3Be carrier, each ingredients constitute vehicle weight percentage is: palladium: 0.01-0.5%, and copper: 0.01-2.0%, zinc: 0.01-2.0%, metal M: 0.01-2.0%, wherein metal M is any one in iron, cobalt or the nickel.
2. the load type palladium copper-based catalysts of gas-phase synthesis of oxalate according to claim 1 is characterized in that: described α-Al
2O
3The specific area of carrier is 3 ~ 20m
- 2/ g, average pore size is 10 ~ 30nm.
3. the preparation method of the load type palladium copper-based catalysts of each described gas-phase synthesis of oxalate of claim 1-2, it is characterized in that: Preparation of Catalyst comprises the steps:
The soluble-salt of copper, zinc and metal M is mixed with maceration extract by metering, soaks α-Al
2O
3Carrier left standstill 2 ~ 24 hours;
Filter back following dry 4 ~ 24 hours at 40 ~ 140 ℃; 300 ~ 600 ℃ of roastings 2 ~ 12 hours, obtain solid precursor then, be designated as Cu/Zn/M/ α-Al
2O
3
The soluble-salt of Metal Palladium is mixed with maceration extract, adds the acid identical palladium salt is all dissolved with the anion of palladium metal salt; The solid precursor that soaking step (2) obtains left standstill 2 ~ 24 hours;
Filter back following dry 4 ~ 24 hours at 40 ~ 140 ℃;
Dried solids in the step (4) is put into reactor, add entry, dripping its pH value of alkaline solution accent is 8 ~ 11, adds 2 ~ 20 times of reducing agents to (Pd+Cu+Zn+M) amount of substance then; Under 40 ~ 90 ℃ of water bath condition, liquid-phase reduction 0.5 ~ 4 hour;
Promptly get catalyst after filtration, washing, the drying.
4. the preparation method of the load type palladium copper-based catalysts of gas-phase synthesis of oxalate according to claim 3, it is characterized in that: the soluble-salt of copper, zinc, metal M and palladium in step (1) and the step (3) is any one in nitrate, sulfate, halides or the acetate.
5. the preparation method of the load type palladium copper-based catalysts of gas-phase synthesis of oxalate according to claim 3, it is characterized in that: the alkaline solution in the step (5) is NaOH, KOH, K
2CO
3, Na
2CO
3Or in the ammoniacal liquor any one.
6. the preparation method of the load type palladium copper-based catalysts of gas-phase synthesis of oxalate according to claim 3 is characterized in that, the reducing agent in the step (5) is any one in hydrazine hydrate, sodium borohydride, potassium borohydride, formic acid or the formaldehyde.
7. the application of the load type palladium copper-based catalysts of each described gas-phase synthesis of oxalate of claim 1-2; It is characterized in that: this catalyst applications is in the reaction of carbon monoxide and nitrites carbonylation synthesis of oxalate; Catalyst carries out activation processing before using, and activation method is with H
2Volume content is that 10% ~ 100% hydrogen-nitrogen mixed gas or CO volume content are that carbon monoxide-nitrogen mixed gas of 10% ~ 100% was handled 2 ~ 24 hours in 150 ~ 450 ℃ of reduction, and air speed is 2000 ~ 4000h
-1, be used for the reaction of carbon monoxide and nitrites carbonylation synthesis of oxalate behind the catalyst activation.
8. according to the application process of the load type palladium copper-based catalysts of each described gas-phase synthesis of oxalate of claim 1-2; It is characterized in that: this catalyst is used for carbon monoxide and the reaction of nitrites carbonylation synthesis of oxalate; The catalyst service condition is: reaction temperature is 90 ~ 150 ℃; Reaction pressure is normal pressure ~ 1MPa, and air speed is 1000 ~ 9000h
-1
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114160125A (en) * | 2021-12-14 | 2022-03-11 | 河南能源化工集团研究总院有限公司 | Ultralow palladium catalyst for catalytically synthesizing dimethyl oxalate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410722A (en) * | 1981-01-23 | 1983-10-18 | Ube Industries, Ltd. | Process for preparing oxalic acid diesters using platinum group metals supported on alumina |
| CN101543784A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN101993365A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing oxalic ester by CO coupling |
| CN102218320A (en) * | 2011-04-15 | 2011-10-19 | 上海浦景化工技术有限公司 | Catalyst for hydrogenation, preparation method and application thereof |
-
2012
- 2012-02-29 CN CN201210048941.3A patent/CN102600863B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410722A (en) * | 1981-01-23 | 1983-10-18 | Ube Industries, Ltd. | Process for preparing oxalic acid diesters using platinum group metals supported on alumina |
| CN101543784A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Preparation method for catalyst for synthesizing oxalic ester by gas-phase |
| CN101993365A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing oxalic ester by CO coupling |
| CN102218320A (en) * | 2011-04-15 | 2011-10-19 | 上海浦景化工技术有限公司 | Catalyst for hydrogenation, preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114160125A (en) * | 2021-12-14 | 2022-03-11 | 河南能源化工集团研究总院有限公司 | Ultralow palladium catalyst for catalytically synthesizing dimethyl oxalate and preparation method thereof |
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