CN102430421B - Catalytic agent for synthesizing oxalic ester and preparing method thereof - Google Patents
Catalytic agent for synthesizing oxalic ester and preparing method thereof Download PDFInfo
- Publication number
- CN102430421B CN102430421B CN 201110336742 CN201110336742A CN102430421B CN 102430421 B CN102430421 B CN 102430421B CN 201110336742 CN201110336742 CN 201110336742 CN 201110336742 A CN201110336742 A CN 201110336742A CN 102430421 B CN102430421 B CN 102430421B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxalate
- carrier
- molybdenum
- hours
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalytic agent for synthesizing oxalic ester and a preparing method of the catalytic agent. The catalytic agent comprises the following components in percent by weight: 0.01-0.5wt% of active component Pd, 0.01-1.0wt% of addition agent Mo (in the form of beta-Mo2C) and 0.01-1.0wt% of addition agent M (Fe, Co, Ni, Cu or Zn) and is prepared by using a stepwise impregnation method. Carrier alpha-Al2O3 is washed, dried and baked for use and is characterized in that the specific surface of the carrier alpha-Al2O3 is 5-20m<2>/g, the pore volume of the carrier alpha-Al2O3 is 0.03-0.13cm<3/>g, and the average pore size of the carrier alpha-Al2O3 is 10-20nm. The catalytic agent prepared by the method has certain shape and size, high mechanical strength, low noble metal Pd content and low service life. The catalytic agent has good activity and selectivity in the reaction process of synthesizing ethylene glycol through oxalic ester hydrogenation. As Mo and M are adopted for replacing a part of noble metal Pd, the content of the noble metal in the catalytic agent and the production cost are reduced; and therefore, the catalytic agent has better economic efficiency.
Description
Technical field
The present invention relates to the synthetic of oxalate, particularly a kind of synthetic Catalysts and its preparation method of oxalate that is used for.
Background technology
Oxalate can be used for making the intermediate of ethylene glycol, oxalic acid, oxamides and some drugs and dyestuff, is important basic chemical industry raw material, and important effect is arranged in C-1 chemistry.The liquid phase synthesis of oxalate is at first proposed in 1966 by U.S.'s combined oil (Unocal) company, adopts PdCl
2-CuCl
2Catalyst reacts under 125 ℃, 7.0MPa.This method is owing to use chloride catalyst, and equipment corrosion is serious, and for keeping anhydrous state, needs to use a large amount of dehydrating agents, and process economy is poor.After this, U.S. Arco company and company of Ube Industries Ltd. improve catalyst system, but still fail to solve the equipment corrosion problem.Afterwards, emerging product company of space portion has developed the technology of synthesis of oxalic ester by gaseous catalysis, JP8242656 special permission communique is at first reported and is adopted the platinum group metal loaded catalyst to carry out the technological process of carbon monoxide and methyl nitrite synthesizing dimethyl oxalate, and reaction pressure 0.5MPa, temperature are 80 ~ 150 ℃.This process mould examination is operation 480h continuously, and the average space-time yield of dimethyl oxalate is 432g/L
Cat/ h.There are many patents to report in succession subsequently again and in catalytic component, add Ti, Mo, Ni, Fe, Ga, Cu, Ce, Zr, Na respectively
2O and SiO
2Catalyst Deng auxiliary agent is formed is applied in the technology of carbon monoxide and nitrites gas-phase dimethyloxalate synthesis, diethy-aceto oxalate and oxalic acid diisopropyl ester.Pd/Al as the CN1381310A report
2O
3Added the Ce auxiliary agent in the catalyst, Pd content is about 0.8 ~ 1.3wt%.The Pd-Ga/Al of CN1055492A report
2O
3Pd content is 0.5 ~ 1.5% in the catalyst.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 catalyst cost height, influences its use in industry.
Summary of the invention
The purpose of this invention is to provide a kind of new catalyst that is used for synthesis of oxalate and preparation method thereof, shortcomings such as existing catalyst activity is low to overcome, poor stability, precious metals pd load capacity height.
For achieving the above object, the technical solution used in the present invention is as follows:
The synthetic catalyst of oxalate that is used for of the present invention, this catalyst is with α-Al
2O
3Be carrier, palladium is an active component, and molybdenum is first auxiliary agent, and metal M is second auxiliary agent, and M is any one among Fe, Co, Ni, Cu or the Zn, and the composition of catalyst is counted with the carrier quality: palladium 0.01 ~ 0.5wt%, molybdenum 0.01 ~ 1.0wt%, metal M 0.01 ~ 1.0wt%.
Described α-Al
2O
3The specific area of carrier is 5 ~ 20 m
2/ g, pore volume are 0.03 ~ 0.13 cm
3/ g, average pore size is 10 ~ 20 nm.
The synthetic Preparation of catalysts method of oxalate that is used for of the present invention, catalyst adopts the step impregnation method preparation, may further comprise the steps:
(1) be mixed with maceration extract with molybdenum salt and organic complex by metering, wherein organic complex and molybdenum amount of substance are than being (0.4 ~ 2.0): 1;
(2) solution with step (1) soaks α-Al
2O
3Carrier left standstill 3 ~ 20 hours;
(3) after filtration, the drying, carbonization under light hydrocarbon and hydrogen mixed gas atmosphere, light hydrocarbon and hydrogen mol ratio are 1/5 ~ 1/3, wherein light hydrocarbon is CH
4, C
2H
6, C
3H
8, C
2H
4Or C
3H
6In any one; Then at O
2Volume content is 0.2% O
2With promptly get presoma after the passivation under the Ar mixed atmosphere;
(4) salt with palladium, metal M is mixed with maceration extract by metering;
(5) with the presoma in the solution soaking step (3) of step (4), left standstill 2 ~ 12 hours;
(6) filtration, drying add suitable quantity of water, drip precipitating reagent while stirring under 40 ~ 90 ℃ of water bath condition, and the pH value of regulating mixed system is 6 ~ 13, aging 2 ~ 6 hours;
(7) with 2 ~ 20 times to the reducing agent liquid-phase reduction of (M+Pd) amount of substance 0.5 ~ 2 hour; After filtration, washing, the drying, promptly make catalyst.
Palladium salt in described step (1) and (4), molybdenum salt and metal M salt can be in nitrate, halide, oxalates or the acetate any one, and wherein molybdenum salt can also be ammonium molybdate.
Organic complexing agent in the described step (1) can be in citric acid, lactic acid, mandelic acid or the oxalic acid any one, and wherein organic complex and molybdenum amount of substance are than being (0.4 ~ 2.0): 1.
Precipitating reagent in the described step (6) can be K
2CO
3, Na
2CO
3, KOH, NaOH, NaHCO
3Or KHCO
3Any one.
Reducing agent in the described step (7) can be in hydrazine hydrate, formaldehyde, formic acid, sodium borohydride or the potassium borohydride any one.
Catalyst of the present invention carries out activation processing before using, and activation method is to feed hydrogen-nitrogen mixed gas (H
2Volume content 10% ~ 100%) or carbon monoxide-nitrogen mixed gas (CO volume content 10% ~ 100%) in 150 ~ 450 ℃ of activation processing 2 ~ 4 hours, feed unstripped gas after the catalyst activation treatment and react unstripped gas carbon monoxide and nitrites nitrogen dilution; Unstripped gas contacts with above-mentioned catalyst, and be 0.5 ~ 4 second time of contact, and reaction temperature is 90 ~ 140 ℃, and reaction pressure is normal pressure ~ 1.0MPa.
The synthetic Application of Catalyst condition of oxalate that is used for of the present invention is: adopt fixed bed reactors, catalyst need carry out activation processing before using, and activation method is to feed hydrogen-nitrogen mixed gas (H
2Volume content 10% ~ 100%) or carbon monoxide-nitrogen mixed gas (CO volume content 10% ~ 100%) in 150 ~ 450 ℃ of activation processing 2 ~ 4 hours, be used for carbon monoxide and the reaction of nitrites carbonylation synthesis of oxalate after the catalyst activation, unstripped gas carbon monoxide and nitrites nitrogen dilution, the proportion control of carbon monoxide and nitrites is in 15 ~ 30:10 ~ 20(volume ratio), the described catalyst of unstripped gas and claim 1 time of contact is 0.5 ~ 4 second, reaction temperature is 90 ~ 140 ℃, and reaction pressure is normal pressure ~ 1.0MPa.
The reaction equation of carbon monoxide and nitrites synthesis of oxalic ester by gaseous catalysis is as follows:
Wherein: R is an alkyl.
The required nitrites of this reaction can be with 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
2As inert gas dilution.
The present invention compared with prior art has following characteristics:
(1) the novel Mo of the inventive method preparation
2C/M/Pd/ α-Al
2O
3Catalyst, the content of noble metal component Pd reduces greatly, has reduced the cost of catalyst.
(2) the present invention is with the α-Al of moulding
2O
3Be carrier, reduced the forming step of catalyst;
(3) catalyst disclosed by the invention has high reaction activity and high and selectivity, and its reactivity worth repeatability is relatively good; Method for preparing catalyst is simple, and easy operating is realized the industry amplification easily.
The specific embodiment
The volume of the solution that palladium salt and promoter metal salt are made among the following embodiment is not strict with, and the aqueous solution that is made into can get final product by the submergence carrier.
The present invention reacts the performance of evaluate catalysts with carbon monoxide and methyl nitrite synthesizing dimethyl oxalate, should understand the present invention and can be applicable to carbon monoxide and other nitrites (as nitrous ether (ethyl nitrite), propyl nitrite, butyl nitrite, amyl nitrite etc.) prepared in reaction oxalate.Catalyst places stainless steel reactor, reactor inside diameter is 15mm, dress thermocouple sheath in the reactor, loaded catalyst is 3ml, after reduction process finishes, the question response actuator temperature is reduced to reaction and is switched to unstripped gas after temperature required and react, and by beds, by reactor bottom discharged from top to bottom by the product dimethyl oxalate for unstripped gas.
Embodiment 1
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.2wt%Mo+0.1wt%Zn+0.5wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is as follows: selecting ammonium molybdate for use, is 1 to add citric acid in maceration extract by citric acid/molybdenum amount of substance ratio, is 8.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 6 hours, takes out in baking oven dry; After the oven dry, at CH
4/ H
2(1/5) carbonization under the atmosphere, standby after the passivation, be designated as Mo
2C/ α-Al
2O
3Select zinc nitrate and palladium for use, be mixed with maceration extract according to the load capacity of Zn and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 4 hours, filters, dries; Add suitable quantity of water, drip NaOH solution while stirring under 50 ℃ of water bath condition, regulating the pH value is 9.0, aging 2 hours, and add 4 times of hydrazine hydrate solutions then and reduced 1 hour to (Cu+Pd) amount of substance, after filtration, washing, the oven dry, promptly get Mo
2C/Zn/Pd/ α-Al
2O
3Catalyst.
This catalyst is carbon monoxide-nitrogen mixed gas of 60% with CO content in 240 ℃ of reductase 12s hour, cools to reaction temperature then, with nitrogen CO is purged clean back and feeds volume and consist of 20%CH
3ONO+30%CO+50%N
2Unstripped gas, be 1 second time of contact, reaction result is listed in the table 1.
Embodiment 2
Take by weighing 10 gram α-Al
2O
3Carrier is by 0.5 wt%Mo+0.01wt%Fe+0.4 wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is as follows: selecting ammonium molybdate for use, is 0.8 to add mandelic acid in maceration extract by mandelic acid/molybdenum amount of substance ratio, is 8.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 12 hours, takes out in baking oven dry; After the oven dry, at CH
4/ H
2(1/4) carbonization under the atmosphere, standby after the passivation, be designated as Mo
2C/ α-Al
2O
3Select iron chloride and palladium bichloride for use, be mixed with maceration extract according to the load capacity of Fe and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 12 hours; Filter, dry, add suitable quantity of water, under 90 ℃ of water bath condition, drip KOH solution while stirring, the pH value of regulating mixed system is 6.0, wore out 4 hours, with 2 times to the formalin reductase 12 of (Fe+Pd) amount of substance hour, after filtering, wash, drying, promptly get Mo
2C/Fe/Pd/ α-Al
2O
3Catalyst.
This catalyst H
2Content be hydrogen-nitrogen mixed gas of 30% in 180 ℃ of reduction 4 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 18%CH
3ONO+30%CO+52%N
2Unstripped gas, be 1 second time of contact, reaction result is listed in the table 1.
Embodiment 3
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 1.0wt%Mo+0.5wt%Co+0.05wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is as follows: selecting molybdenum chloride for use, is 2.0 to add oxalic acid in maceration extract by oxalic acid/molybdenum amount of substance ratio, is 20.0m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 3 hours, takes out in baking oven dry; After the oven dry, at C
3H
8/ H
2(1/4) carbonization under the atmosphere, standby after the passivation, be designated as Mo
2C/ α-Al
2O
3Select cobalt nitrate and palladium nitrate for use, be mixed with maceration extract according to the load capacity of Co and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 2 hours, filters, dries; Under 40 ℃ of water bath condition, drip Na while stirring
2CO
3Solution, the pH value of regulating mixed system is 13.0, aging 6 hours, use 20 times of sodium borohydride solutions to reduce then 1.5 hours to (Co+Pd), after filtration, washing, the oven dry, promptly get Mo
2C/Co/Pd/ α-Al
2O
3Catalyst.
This catalyst H
2Content be hydrogen-nitrogen mixed gas of 60% in 220 ℃ of reduction 3 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, be 2 seconds time of contact, reaction result is listed in the table 1.
Embodiment 4
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.6wt%Mo+0.5wt%Cu+0.3wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is as follows: selecting the acetic acid molybdenum for use, is 0.8 to add mandelic acid in maceration extract by mandelic acid/molybdenum amount of substance ratio, is 15.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 7 hours, takes out in baking oven dry; After the oven dry, at C
2H
4/ H
2(1/3) carbonization under the atmosphere, standby after the passivation, be designated as Mo
2C/ α-Al
2O
3Select cupric oxalate and palladium nitrate for use, be mixed with maceration extract according to the load capacity of Cu and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 7 hours, filters, dries; Add suitable quantity of water, under 40 ℃ of water bath condition, drip KHCO while stirring
3Solution, the pH value of regulating mixed system is 9.0, aging 5 hours, use 10 times of formalins to reduce then 1 hour to (Cu+Pd) amount of substance, after filtration, washing, the oven dry, promptly get Mo
2C/Cu/Pd/ α-Al
2O
3Catalyst.
This catalyst with CO content be carbon monoxide-nitrogen mixed gas of 10% in 280 ℃ of reductase 12 .5 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, be 1.5 seconds time of contact, reaction result is listed in the table 1.
Embodiment 5
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.2wt%Mo+1.0wt%Co+0.5wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is as follows: selecting molybdenum trisulfate for use, is 1 to add citric acid in maceration extract by citric acid/molybdenum amount of substance ratio, is 8.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 6 hours, takes out in baking oven dry; After the oven dry, at CH
4/ H
2(1/4) carbonization under the atmosphere, standby after the passivation, be designated as Mo
2C/ α-Al
2O
3Select cobalt nitrate and palladium bichloride for use, be mixed with maceration extract according to the load capacity of Co and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 4 hours, filters, dries; Add suitable quantity of water, under 50 ℃ of water bath condition, drip NaHCO while stirring
3Solution, the pH value of regulating mixed system is 9.0, aging 2 hours, reduced 1 hour with 3 times of solution of potassium borohydride to (Co+Pd), after filtration, washing, the oven dry, promptly get Mo
2C/Co/Pd/ α-Al
2O
3Catalyst.
This catalyst H
2Content be hydrogen-nitrogen mixed gas of 10% in 400 ℃ of reduction 5 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 15%CH
3ONO+15%CO+70%N
2Unstripped gas, be 0.5 second time of contact, reaction result is listed in the table 1.
Embodiment 6
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 1.0wt%Mo+0.01wt%Fe+0.01 wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is as follows: selecting ammonium molybdate for use, is 0.5 to add citric acid in maceration extract by citric acid/molybdenum amount of substance ratio, is 10.0m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 8 hours, takes out in baking oven dry; After the oven dry, at C
2H
6/ H
2(1/4) carbonization under the atmosphere, standby after the passivation, be designated as Mo
2C/ α-Al
2O
3Select ferric nitrate and palladium for use, be mixed with maceration extract according to the load capacity of Fe and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 12 hours, filters, dries, and adds suitable quantity of water, drips NaHCO while stirring under 80 ℃ of water bath condition
3Solution, the pH value of regulating mixed system is 11.0, aging 5 hours, reduced 0.5 hour with 15 times of formalins to (Fe+Pd), after filtration, washing, the oven dry, promptly get Mo
2C/Fe/Pd/ α-Al
2O
3Catalyst.
This catalyst H
2Content is hydrogen-nitrogen mixed gas of 50% in 450 ℃ of reductase 12s hour, cools to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 20%CH
3ONO+30%CO+50%N
2Unstripped gas, be 4 seconds time of contact, reaction result is listed in the table 1.
Embodiment 7
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.8wt%Mo+0.3wt%Ni+0.2wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is as follows: selecting the nitric acid molybdenum for use, is 0.4 to add lactic acid in maceration extract by lactic acid/molybdenum amount of substance ratio, is 20.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 20 hours, takes out in baking oven dry; After the oven dry, at C
3H
6/ H
2(1/5) carbonization under the atmosphere, standby after the passivation, be designated as Mo
2C/ α-Al
2O
3Select nickel chloride and palladium bichloride for use, be mixed with maceration extract according to the load capacity of Ni and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 10 hours, filter, dry, add suitable quantity of water, under 40 ℃ of water bath condition, drip KOH solution while stirring, the pH value of regulating mixed system is 13.0, wore out 3 hours, with 6 times to the hydrazine hydrate solution reductase 12 of (Ni+Pd) amount of substance .0 hour, after filtering, wash, drying, promptly get Mo
2C/Ni/Pd/ α-Al
2O
3Catalyst.
This catalyst with CO content be carbon monoxide-nitrogen mixed gas of 30% in 150 ℃ of reduction 4 hours, cool to reaction temperature then, with nitrogen CO is purged clean back and feeds volume and consist of 15%CH
3ONO+20%CO+65%N
2Unstripped gas, be 1.5 seconds time of contact, reaction result is listed in the table 1.
Embodiment 8
Take by weighing 10 gram α-Al
2O
3Carrier is by 0.7 wt%Mo+0.6 wt%Ni+0.1 wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is as follows: selecting ammonium molybdate for use, is 0.4 to add citric acid in maceration extract by citric acid/molybdenum amount of substance ratio, is 12.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 16 hours, takes out in baking oven dry; After the oven dry, at CH
4/ H
2(1/4) carbonization under the atmosphere, standby after the passivation, be designated as Mo
2C/ α-Al
2O
3Select nickel nitrate and palladium nitrate for use, be mixed with maceration extract according to the load capacity of Ni and Pd, Mo
2C/ α-Al
2O
3Presoma is put into maceration extract and was soaked 10 hours, filters, dries, and adds suitable quantity of water, drips K while stirring under 60 ℃ of water bath condition
2CO
3Solution, the pH value of regulating mixed system is 10.0, aging 2 hours, reduced 0.5 hour with 8 times of hydrazine hydrate solutions to (Ni+Pd), after filtration, washing, the oven dry, promptly get Mo
2C/Ni/Pd/ α-Al
2O
3Catalyst.
The pure H of this catalyst
2Gas cools to reaction temperature then in 180 ℃ of reductase 12s hour, with nitrogen with H
2Purge clean back feeding volume and consist of 15%CH
3ONO+25%CO+60%N
2Unstripped gas, be 0.72 second time of contact, reaction result is listed in the table 1.
Claims (6)
1. one kind is used for the synthetic catalyst of oxalate, and it is characterized in that: this catalyst is with α-Al
2O
3Be carrier, palladium is an active component, and molybdenum is first auxiliary agent, and metal M is second auxiliary agent, and M is any one among Fe, Co, Ni, Cu or the Zn, and the composition of catalyst is counted with the carrier quality: palladium 0.01 ~ 0.5wt%, molybdenum 0.01 ~ 1.0wt%, metal M 0.01 ~ 1.0wt%; Catalyst adopts the step impregnation method preparation, may further comprise the steps:
(1) be mixed with maceration extract with molybdenum salt and organic complex by metering, wherein organic complex and molybdenum amount of substance are than being (0.4 ~ 2.0): 1;
(2) solution with step (1) soaks α-Al
2O
3Carrier left standstill 3 ~ 20 hours;
(3) after filtration, the drying, carbonization under light hydrocarbon and hydrogen mixed gas atmosphere, light hydrocarbon and hydrogen mol ratio are 1/5 ~ 1/3, wherein light hydrocarbon is CH
4, C
2H
6, C
3H
8, C
2H
4Or C
3H
6In any one; Then at O
2Volume content is 0.2% O
2With promptly get presoma after the passivation under the Ar mixed atmosphere;
Salt with palladium, metal M is mixed with maceration extract by metering;
Presoma with in the solution soaking step (3) of step (4) left standstill 2 ~ 12 hours;
Filtration, drying add suitable quantity of water, drip precipitating reagent while stirring under 40 ~ 90 ℃ of water bath condition, and the pH value of regulating mixed system is 6 ~ 13, aging 2 ~ 6 hours;
With 2 ~ 20 times to the reducing agent liquid-phase reduction of (M+Pd) amount of substance 0.5 ~ 2 hour; After filtration, washing, the drying, promptly make catalyst.
2. the synthetic catalyst of oxalate that is used for according to claim 1 is characterized in that: described α-Al
2O
3The specific area of carrier is 5 ~ 20 m
2/ g, pore volume are 0.03 ~ 0.13 cm
3/ g, average pore size is 10 ~ 20 nm.
3. the synthetic catalyst of oxalate that is used for according to claim 1, it is characterized in that: the palladium salt in described step (1) and (4), metal M salt are any one in nitrate, halide, oxalates or the acetate, and molybdenum salt is any one in nitrate, halide, oxalates, acetate or the ammonium molybdate.
4. the synthetic catalyst of oxalate that is used for according to claim 1, it is characterized in that: the organic complexing agent in the described step (1) is any one in citric acid, lactic acid, mandelic acid or the oxalic acid, and wherein organic complex and molybdenum amount of substance are than being (0.4 ~ 2.0): 1.
5. the synthetic catalyst of oxalate that is used for according to claim 1, it is characterized in that: the precipitating reagent in the described step (6) is K
2CO
3, Na
2CO
3, KOH, NaOH, NaHCO
3Or KHCO
3Any one.
6. the synthetic catalyst of oxalate that is used for according to claim 1, it is characterized in that: the reducing agent in the described step (7) is any one in hydrazine hydrate, formaldehyde, formic acid, sodium borohydride or the potassium borohydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110336742 CN102430421B (en) | 2011-10-31 | 2011-10-31 | Catalytic agent for synthesizing oxalic ester and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110336742 CN102430421B (en) | 2011-10-31 | 2011-10-31 | Catalytic agent for synthesizing oxalic ester and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102430421A CN102430421A (en) | 2012-05-02 |
| CN102430421B true CN102430421B (en) | 2013-07-24 |
Family
ID=45978985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110336742 Active CN102430421B (en) | 2011-10-31 | 2011-10-31 | Catalytic agent for synthesizing oxalic ester and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102430421B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903466A (en) * | 2016-05-03 | 2016-08-31 | 中国科学院福建物质结构研究所 | Catalyst for dimethyl oxalate synthesis and preparation method of catalyst for dimethyl oxalate synthesis |
| CN111085193A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Impregnation method of supported palladium catalyst |
| CN111495389B (en) * | 2020-05-19 | 2022-12-20 | 天津大学 | Catalyst for synthesizing diethyl oxalate by carbon monoxide gas-phase coupling ethyl nitrite and preparation method and application thereof |
| CN111495388B (en) * | 2020-05-19 | 2022-12-20 | 天津大学 | Catalyst for synthesizing diethyl oxalate by CO gas-phase coupling of ethyl nitrite and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| 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 |
| CN101544539A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate |
-
2011
- 2011-10-31 CN CN 201110336742 patent/CN102430421B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462961A (en) * | 2008-01-28 | 2009-06-24 | 上海戊正工程技术有限公司 | Process flow for producing ethylene glycol with coproduction product dimethyl carbonate |
| 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 |
| CN101544539A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Method for producing polymer grade ethylene glycol and co-producing methyl glycolate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102430421A (en) | 2012-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101954288B (en) | Catalyst for hydrogenation of dimethyl oxalate to prepare methyl glycolate, preparation method and application thereof | |
| CN101596455B (en) | Catalyst for synthesizing oxalic ester and preparation method thereof | |
| CN101347737B (en) | Selective hydrogenation catalyst of aromatic aldehydes for refinement of terephthalic acid | |
| CN106563449B (en) | Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst and preparation method thereof and start-up method | |
| CN110961110B (en) | Catalyst and application thereof in 2,3,6-trichloropyridine hydrodechlorination | |
| CN101279257B (en) | Catalyst for synthesizing oxalic ester and preparation method and application thereof | |
| CN102430421B (en) | Catalytic agent for synthesizing oxalic ester and preparing method thereof | |
| CN111085198B (en) | Hydroformylation catalyst and preparation method and application thereof | |
| CN111774070B9 (en) | Catalyst for preparing methyl formate by catalyzing methanol dehydrogenation and preparation method and application thereof | |
| CN1066070C (en) | oxalate synthesis catalyst | |
| CN103539635A (en) | Method for preparing isopropanol through acetone hydrogenation | |
| CN101844078B (en) | Catalyst for preparing glycol through oxalate hydrogenation and preparation method thereof | |
| CN102441405B (en) | Catalyst used for gas-phase synthesis of oxalate ester and its preparation method | |
| CN112237946B (en) | Terephthalic acid hydrofining reaction and catalyst thereof | |
| CN113058608B (en) | Catalyst for preparing isopropylbenzene by hydrogenolysis of alpha-dimethyl benzyl alcohol and preparation method thereof | |
| CN109772291B (en) | Selective hydrogenation and dealkynization catalyst and preparation method and application thereof | |
| CN115212905B (en) | Alkynol selective hydrogenation catalyst and preparation method and application thereof | |
| CN108997266B (en) | Method for preparing 2, 2-di (2-tetrahydrofuryl) propane by hydrogenating 2, 2-di (2-furyl) propane | |
| CN112138676B (en) | Catalyst for preparing o-phenylphenol and preparation method thereof | |
| CN104478660B (en) | A kind of method of low-temperature growth Virahol | |
| CN110743567B (en) | Iridium-carbon catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde and preparation method and application thereof | |
| CN102218328A (en) | Aromatic aldehyde selective hydrogenating catalyst used for refining terephthalic acid | |
| CN102600863B (en) | Palladium-copper-based catalyst used for synthesizing oxalate, and preparation method thereof | |
| CN113649049A (en) | Maleic anhydride selective hydrogenation catalyst, and preparation method and application method thereof | |
| CN111420657A (en) | Ru-based catalyst for synthesizing 3-pentanone through ethylene conversion and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: The development zone of Kaifeng City in Henan Province Road No. 1 song 475000 Patentee after: HENAN ENERGY CHEMICAL GROUP ADVANCED EQUIPMENT INSTITUTE Co.,Ltd. Address before: The development zone of Kaifeng City in Henan Province Road No. 1 song 475000 Patentee before: HENAN ENERGY AND CHEMICAL INDUSTRY GROUP RESEARCH INSTITUTE CO.,LTD. |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: The development zone of Kaifeng City in Henan Province Road No. 1 song 475000 Patentee after: HENAN ENERGY AND CHEMICAL INDUSTRY GROUP RESEARCH INSTITUTE CO.,LTD. Address before: 450046, Henan province Zhengzhou Zheng Dong New District business circle road 6 country dragon building Patentee before: HENAN COAL CHEMICAL INDUSTRY GROUP INSTITUTE Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190919 Address after: The 12th Floor of Newton International B Block, 97 Xuzhuang Road, Jinshui District, Zhengzhou City, Henan Province, 450000 Patentee after: HENAN ENERGY AND CHEMICAL INDUSTRY GROUP RESEARCH INSTITUTE CO.,LTD. Address before: The development zone of Kaifeng City in Henan Province Road No. 1 song 475000 Patentee before: HENAN ENERGY CHEMICAL GROUP ADVANCED EQUIPMENT INSTITUTE Co.,Ltd. |