CN102441405A - Catalyst used for gas-phase synthesis of oxalate ester and its preparation method - Google Patents
Catalyst used for gas-phase synthesis of oxalate ester and its preparation method Download PDFInfo
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- CN102441405A CN102441405A CN2011103367432A CN201110336743A CN102441405A CN 102441405 A CN102441405 A CN 102441405A CN 2011103367432 A CN2011103367432 A CN 2011103367432A CN 201110336743 A CN201110336743 A CN 201110336743A CN 102441405 A CN102441405 A CN 102441405A
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Abstract
Belonging to the technical field of oxalate ester preparation, the invention aims to provide a catalyst which has high activity and high selectivity and is used in a reaction between carbon monoxide and nitrous acid ester for gas-phase synthesis of oxalate ester as well as its preparation method. The catalyst takes alpha-Al2O3 as a carrier, adopts palladium as a main active component, and employs copper as a first auxiliary agent and M as a second auxiliary agent, wherein, M can be ferrum, nickel, zinc, cobalt, titanium, cerium, molybdenum or tungsten. In terms of the carrier mass, the catalyst is composed of: 0.01-0.5 wt% of palladium, 0.01-1.0 wt% of copper, and 0.01-1.0 wt% of M. Prepared by a deposition-precipitation method, the catalyst of the invention can be used for carbonylation of CO and nitrous acid ester so as to synthesize oxalate ester. And the catalyst is used at a reaction temperature of 80-140DEG C, a reaction pressure of normal pressure to 1.0Mpa, and a reaction space velocity of 500-9000h<-1>. The catalyst provided in the invention has high reaction activity and selectivity, good repeatability of reaction performance, low cost, and simple preparation method, thus being easy for large-scale production.
Description
Technical field
The invention belongs to the oxalate preparing technical field, relate to a kind of Catalysts and its preparation method 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 made catalyst, 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.
From having attend the world since the eighties, 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; Successive reaction 480 hours, significant change does not take place in catalyst activity.
Many bibliographical informations different carriers, like γ-Al
2O
3, molecular sieve, active carbon and silica gel etc. is to the influence of performance of Pd catalyst, result of study shows α-Al
2O
3It is a kind of better carrier that is used for CO and nitrites reaction system oxalate diester.Reported by many patents again subsequently and in catalyst, added the catalyst that auxiliary agents such as Mo, Ni, Fe, Ti, Cu, Zr and Si are formed 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 Pd-Mo/Al of US4384433 report
2O
3And Pd-Ni/Al
2O
3Catalyst is at normal pressure, 110 ℃ and air speed 2000h
-1, unstripped gas is formed: CH
3ONO/CO/CH
3OH/NO/N
2React under=15/20/15/3/47 condition, the space-time yield of dimethyl oxalate is about 400g/L
Cat/ h is by CH
3The selectivity that ONO generates dimethyl oxalate is 95%.The Pd-Ce/Al of the employing immersion process for preparing of CN1381310A report
2O
3Catalyst, Pd content are about 0.8 ~ 1.3wt%.The Pd-Ga/Al of the employing immersion process for preparing of CN1055492A report
2O
3Catalyst, Pd content are 0.5 ~ 1.5%.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 a kind of cost low and active high catalyst that is used for gas-phase synthesis of oxalate and Preparation of catalysts method.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is following:
The catalyst of gas-phase synthesis of oxalate of the present invention, this catalyst is with α-Al
2O
3Be carrier, palladium is an active component, and copper is first auxiliary agent; Metal M is second auxiliary agent, and M is any one in iron, nickel, zinc, cobalt, titanium, molybdenum or the tungsten, and the composition of catalyst is counted with the carrier quality: palladium 0.01 ~ 0.5wt%; Copper 0.01 ~ 1.0wt%, metal M 0.01 ~ 1.0wt%.
Described α-Al
2O
3The specific area of carrier is 5 ~ 30m
2/ g, profile is spherical.
The Preparation of catalysts method of gas-phase synthesis of oxalate of the present invention adopts deposition-precipitation method to prepare catalyst, is undertaken by following steps in sequence:
(1) soluble-salt with metal M and Cu is made into mixed solution;
(2) with the solution impregnation α-Al of step (1)
2O
3Carrier left standstill 2 ~ 6 hours;
(3) filter, room temperature puts into reaction vessel after drying, and adds suitable quantity of water, drips precipitating reagent down in 40 ~ 90 ℃ of water-baths, stirring condition, regulate rate of addition with the pH value that guarantees mixed system in the reaction vessel between 7 ~ 12;
(4) dropwise after, aging 2 ~ 6 hours;
(5) after filtration, washing, the drying,, make Cu/M/ α-Al 300 ~ 500 ℃ of roastings 2 ~ 5 hours
2O
3Presoma;
(6) with the salt wiring solution-forming of Metal Palladium;
(7) the Cu/M/ α-Al that makes in the solution impregnation step (5) with step (6)
2O
3Presoma left standstill 2 ~ 6 hours;
(8) filter, room temperature puts into reaction vessel after drying, and adds suitable quantity of water, drips precipitating reagent down in 40 ~ 90 ℃ of water-baths, stirring condition, regulate rate of addition with the pH value that guarantees mixed system in the reaction vessel between 8 ~ 12;
(9) dropwise after, aging 2 ~ 6 hours;
(10) with 2 ~ 20 times to the reducing agent liquid-phase reduction of (M+Pd+Cu) amount of substance 0.5 ~ 4 hour;
(11) dry under filtration, washing, the inert gas shielding condition, promptly make catalyst.
Metal M in the described step (1) and the soluble-salt of Cu can be nitrate, halide, acetate or sulfate, and when metal M was molybdenum and tungsten, soluble-salt can also be ammonium molybdate and ammonium tungstate.
Precipitating reagent in described step (3) and the step (8) can be KOH, NaOH, K
2CO
3, Na
2CO
3, NaHCO
3Or KHCO
3In any one.
Palladium metal salt in the described step (6) can be palladium nitrate, palladium bichloride, palladium, oxalic acid palladium or palladium sulfate.
Reducing agent described in the described step (10) can be hydrazine hydrate, formaldehyde, formic acid, sodium borohydride and potassium borohydride.
Being used for of the present invention preparation need be carried out activation processing before carbon monoxide uses with nitrites carbonylation synthesis of oxalate catalyst for reaction, and activation method is feeding 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 the reaction of carbon monoxide and nitrites carbonylation synthesis of oxalate behind the catalyst activation; The catalyst service condition is: reaction temperature is 80 ~ 140 ℃, preferred 90 ~ 130 ℃; Reaction pressure is normal pressure ~ 1.0MPa, and air speed is 500 ~ 9000h
-1, preferred 2000 ~ 5000h
-1
The present invention and prior art relatively have following characteristics:
1, catalyst of the present invention is main reactive metal with Pd, and Cu is first auxiliary agent, and M is second auxiliary agent, and M is iron, nickel, zinc, cobalt, titanium, cerium, molybdenum or tungsten.
2, catalyst space-time yield of the present invention can reach 1200g/L
Cat/ h, the oxalate selectivity is greater than 96%.
3, catalyst of the present invention is few with noble metal amount, is merely below 0.5% of carrier quality, and the catalyst cost is low.
The specific embodiment
Through embodiment Catalysts and its preparation method of the present invention is described further below.
The volume of the solution that promoter metal salt is made among the following embodiment, palladium are made into the volume of the aqueous solution, are not strict with, and the aqueous solution that is made into is can the submergence carrier just passable.
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 (like 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, and 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 through 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 0.01wt%Cu+1.0wt%Mo+0.5wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: taking by weighing the copper nitrate and the ammonium molybdate wiring solution-forming soluble in water of amount of calculation, is 5.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 4 hours, and filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 40 ℃ of water-baths, stirring condition, dripping concentration is the K of 1mol/L
2CO
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 9; After dropwising, aging 6 hours; Filtration, washing, drying 500 ℃ of roastings 2 hours, make Cu/Mo/ α-Al
2O
3Presoma; Take by weighing the palladium bichloride wiring solution-forming of amount of calculation, dipping Cu/Mo/ α-Al
2O
3Presoma left standstill 6 hours; Filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 60 ℃ of water-baths, stirring condition, dripping concentration is the K of 1mol/L
2CO
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 8; After dropwising, aging 2 hours; Add 4 times then to the hydrazine hydrate reduction of (Cu+Mo+Pd) amount of substance 0.5 hour; Filtration, washing, drying promptly make Cu/Mo/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content be hydrogen-nitrogen mixed gas of 30% in 150 ℃ of reduction 4 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 3000h
-1, reaction result is listed in the table 1.
Embodiment 2
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 1.0wt%Cu+0.01wt%Fe+0.3wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: taking by weighing the copper nitrate and the ferric nitrate wiring solution-forming soluble in water of amount of calculation, is 10.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 5 hours; Filtration, room temperature are put into reaction vessel after drying, and add an amount of water, under 50 ℃ of water-baths, stirring condition; Dripping concentration is the KOH aqueous solution of 1mol/L, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 9; After dropwising, aging 2 hours; Filtration, washing, drying 300 ℃ of roastings 5 hours, make Cu/Fe/ α-Al
2O
3Presoma; Take by weighing the palladium nitrate wiring solution-forming of amount of calculation, dipping Cu/Fe/ α-Al
2O
3Presoma left standstill 4 hours; Filter, room temperature puts into reaction vessel after drying, and adds an amount of water, under 60 ℃ of water-baths, stirring condition, dripping concentration is the KOH aqueous solution of 1mol/L, regulate rate of addition with the pH value of solution in the assurance reaction vessel about 9; After dropwising, aging 3 hours; Add 3 times then to the formalin reductase 12 of (Cu+Fe+Pd) amount of substance hour; Filtration, washing, drying promptly make Cu/Fe/Pd/ α-Al
2O
3Catalyst.
This catalyst in 180 ℃ of reductase 12s hour, cools to reaction temperature with pure hydrogen then, with nitrogen with H
2Purge clean back feeding volume and consist of 10%CH
3ONO+15%CO+75%N
2Unstripped gas, air speed 6000h
-1, reaction result is listed in the table 1.
Embodiment 3
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.3wt%Cu+0.9wt%Zn+0.4wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: taking by weighing the copper nitrate and the zinc nitrate wiring solution-forming soluble in water of amount of calculation, is 30.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 6 hours, and filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 70 ℃ of water-baths, stirring condition, dripping concentration is the Na of 1mol/L
2CO
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 10; After dropwising, aging 6 hours; Filtration, washing, drying 400 ℃ of roastings 4 hours, make Cu/Zn/ α-Al
2O
3Presoma; Take by weighing the palladium wiring solution-forming of amount of calculation, dipping Cu/Zn/ α-Al
2O
3Presoma left standstill 2 hours; Filter, room temperature puts into reaction vessel after drying, and adds an amount of water, under 60 ℃ of water-baths, stirring condition, dripping concentration is the NaOH aqueous solution of 1mol/L, regulate rate of addition with the pH value of solution in the assurance reaction vessel about 12; After dropwising, aging 5 hours; Adding 3 times of sodium borohydride solutions to (Cu+Zn+Pd) amount of substance then reduced 1 hour; Filtration, washing, drying promptly make Cu/Zn/Pd/ α-Al
2O
3Catalyst.
It is carbon monoxide-nitrogen mixed gas of 10% in 450 ℃ of reductase 12s hour that this catalyst uses CO content, cools to reaction temperature then, with nitrogen carbon monoxide is purged clean back and feeds volume and consist of 15%CH
3ONO+25%CO+60%N
2Unstripped gas, air speed 4000h
-1, reaction result is listed in the table 1.
Embodiment 4
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.9wt%Cu+0.2wt%Ni+0.1wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: taking by weighing the copper chloride and the nickel chloride wiring solution-forming soluble in water of amount of calculation, is 15.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 3 hours, and filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 60 ℃ of water-baths, stirring condition, dripping concentration is the NaHCO of 1mol/L
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 8; After dropwising, aging 5 hours; Filtration, washing, drying 500 ℃ of roastings 4 hours, make Cu/Ni/ α-Al
2O
3Presoma; Take by weighing the palladium bichloride wiring solution-forming of amount of calculation, dipping Cu/Ni/ α-Al
2O
3Presoma left standstill 3 hours; Filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 60 ℃ of water-baths, stirring condition, dripping concentration is the NaHCO of 1mol/L
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 8; After dropwising, aging 5 hours; Add 10 times then to the formic acid solution reductase 12 of (Cu+Ni+Pd) amount of substance hour; Filtration, washing, drying promptly make Cu/Ni/Pd/ α-Al
2O
3Catalyst.
This catalyst use CO content be carbon monoxide-nitrogen mixed gas of 50% in 400 ℃ of reduction 3 hours, cool to reaction temperature then, feed volume and consist of 10%CH
3ONO+15%CO+70%N
2Unstripped gas, air speed 9000h
-1, reaction result is listed in the table 1.
Embodiment 5
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.01wt%Cu+0.5wt%Co+0.05wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: taking by weighing the copper sulphate and the cobalt nitrate wiring solution-forming soluble in water of amount of calculation, is 20.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 6 hours, and filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 80 ℃ of water-baths, stirring condition, dripping concentration is the KHCO of 1mol/L
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 8; After dropwising, aging 3 hours; Filtration, washing, drying 400 ℃ of roastings 3 hours, make Cu/Co/ α-Al
2O
3Presoma; Take by weighing the palladium bichloride wiring solution-forming of amount of calculation, dipping Cu/Co/ α-Al
2O
3Presoma left standstill 5 hours; Filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 90 ℃ of water-baths, stirring condition, dripping concentration is the KHCO of 1mol/L
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 8; After dropwising, aging 2 hours; Adding 3 times of formalins to (Cu+Co+Pd) amount of substance then reduced 4 hours; Filtration, washing, drying promptly make Cu/Co/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content be hydrogen-nitrogen mixed gas of 50% in 300 ℃ of reductase 12 .5 hours, cool to reaction temperature then, feed volume and consist of 20%CH
3ONO+30%CO+50%N
2Unstripped gas, air speed 500h
-1, reaction result is listed in the table 1.
Embodiment 6
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.05wt%Cu+0.3wt%Ti+0.01wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: taking by weighing the copper sulphate and the cobalt nitrate wiring solution-forming soluble in water of amount of calculation, is 13.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 3 hours, and filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 60 ℃ of water-baths, stirring condition, dripping concentration is the K of 1mol/L
2CO
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 12; After dropwising, aging 4 hours; Filtration, washing, drying 500 ℃ of roastings 3 hours, make Cu/Ti/ α-Al
2O
3Presoma; Take by weighing the palladium nitrate wiring solution-forming of amount of calculation, dipping Cu/Ti/ α-Al
2O
3Presoma left standstill 5 hours; Filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 80 ℃ of water-baths, stirring condition, dripping concentration is the K of 1mol/L
2CO
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 11; After dropwising, aging 2.5 hours; Dropwise 5 doubly reduced 4 hours to the hydrazine hydrate solution of (Cu+Ti+Pd) amount of substance; Filtration, washing, drying promptly make Cu/Ti/Pd/ α-Al
2O
3Catalyst.
This catalyst in 240 ℃ of reduction 3.5 hours, cools to reaction temperature with pure carbon monoxide gas then, with nitrogen carbon monoxide is purged clean back feeding volume and consists of 18%CH
3ONO+25%CO+57%N
2Unstripped gas, air speed 2000h
-1, reaction result is listed in the table 1.
Embodiment 7
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.4wt%Cu+0.8wt%W+0.4wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: taking by weighing the copper chloride and the ammonium tungstate wiring solution-forming soluble in water of amount of calculation, is 18.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 6 hours, and filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 70 ℃ of water-baths, stirring condition, dripping concentration is the Na of 1mol/L
2CO
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 7; After dropwising, aging 3 hours; Filtration, washing, drying 500 ℃ of roastings 4 hours, make Cu/W/ α-Al
2O
3Presoma; Take by weighing the palladium bichloride wiring solution-forming of amount of calculation, dipping Cu/W/ α-Al
2O
3Presoma left standstill 4.5 hours; Filter, room temperature puts into reaction vessel after drying, and adds an amount of water, under 70 ℃ of water-baths, stirring condition, dripping concentration is the NaOH aqueous solution of 1mol/L, regulate rate of addition with the pH value of solution in the assurance reaction vessel about 10; After dropwising, aging 3.5 hours; Dripping 8 times of sodium borohydride solutions to (Cu+W+Pd) amount of substance reduced 3.5 hours; Filtration, washing, drying promptly make Cu/W/Pd/ α-Al
2O
3Catalyst.
It is carbon monoxide-nitrogen mixed gas of 23% in 350 ℃ of reductase 12s hour that this catalyst uses carbon monoxide content, cools to reaction temperature then, with nitrogen carbon monoxide is purged clean back and feeds volume and consist of 15%CH
3ONO+20%CO+65%N
2Unstripped gas, air speed 6000h
-1, reaction result is listed in the table 1.
Embodiment 8
Take by weighing 10 gram α-Al
2O
3Carrier is pressed 0.2wt%Cu+0.2wt%Ce+0.2wt%Pd/ α-Al
2O
3Content prepares catalyst, and its step is following: taking by weighing the copper chloride and the cerous nitrate wiring solution-forming soluble in water of amount of calculation, is 9.0 m with specific area
2α-Al of/g
2O
3Carrier is put into the maceration extract for preparing and was soaked 5 hours, and filtration, room temperature are put into reaction vessel after drying, and add an amount of water, and under 60 ℃ of water-baths, stirring condition, dripping concentration is the K of 1mol/L
2CO
3The aqueous solution, regulate rate of addition with the pH value that guarantees solution in the reaction vessel about 11; After dropwising, aging 6 hours; After filtration, washing, the drying,, make Cu/Ce/ α-Al 400 ℃ of roastings 3 hours
2O
3Presoma; Take by weighing the palladium wiring solution-forming of amount of calculation, dipping Cu/Ce/ α-Al
2O
3Presoma left standstill 5.5 hours; Filter, room temperature puts into reaction vessel after drying, and adds an amount of water, under 70 ℃ of water-baths, stirring condition, dripping concentration is the NaOH aqueous solution of 1mol/L, regulate rate of addition with the pH value of solution in the assurance reaction vessel about 12; After dropwising, aging 6 hours; Dripping 9 times of formalins to (Cu+Ce+Pd) amount of substance reduced 3 hours; Filtration, washing, drying promptly make Cu/Ce/Pd/ α-Al
2O
3Catalyst.
This catalyst is used H
2Content be hydrogen-nitrogen mixed gas of 60% in 350 ℃ of reduction 3 hours, cool to reaction temperature then, with nitrogen with H
2Purge clean back feeding volume and consist of 15%CH
3ONO+25%CO+60%N
2Unstripped gas, air speed 5000h
-1, reaction result is listed in the table 1.
Table 1 catalyst performance evaluation result
Claims (9)
1. the catalyst of a gas-phase synthesis of oxalate, it is characterized in that: this catalyst is with α-Al
2O
3Be carrier, palladium is an active component, and copper is first auxiliary agent; Metal M is second auxiliary agent, and M is any one in iron, nickel, zinc, cobalt, titanium, cerium, molybdenum or the tungsten, and the composition of catalyst is counted with the carrier quality: palladium 0.01 ~ 0.5wt%; Copper 0.01 ~ 1.0wt%, metal M 0.01 ~ 1.0wt%.
2. the catalyst of gas-phase synthesis of oxalate according to claim 1 is characterized in that: described α-Al
2O
3The specific area of carrier is 5 ~ 30m
2/ g, profile is spherical.
3. according to the Preparation of catalysts method of each the described gas-phase synthesis of oxalate among the claim 1-2, it is characterized in that: adopt deposition-precipitation method to prepare catalyst, undertaken by following steps in sequence:
The soluble-salt of metal M and Cu is made into mixed solution;
Solution impregnation α-Al with step (1)
2O
3Carrier left standstill 2 ~ 6 hours;
Filter, room temperature puts into reaction vessel after drying, and adds suitable quantity of water, drips precipitating reagent down in 40 ~ 90 ℃ of water-baths, stirring condition, regulate rate of addition with the pH value that guarantees mixed system in the reaction vessel between 7 ~ 12;
After dropwising, aging 2 ~ 6 hours;
After filtration, washing, the drying,, make Cu/M/ α-Al 300 ~ 500 ℃ of roastings 2 ~ 5 hours
2O
3Presoma;
Salt wiring solution-forming with Metal Palladium;
Cu/M/ α-the Al that makes in the solution impregnation step (5) with step (6)
2O
3Presoma left standstill 2 ~ 6 hours;
Filter, room temperature puts into reaction vessel after drying, and adds suitable quantity of water, drips precipitating reagent down in 40 ~ 90 ℃ of water-baths, stirring condition, regulate rate of addition with the pH value that guarantees mixed system in the reaction vessel between 8 ~ 12;
After dropwising, aging 2 ~ 6 hours;
With 2 ~ 20 times to the reducing agent liquid-phase reduction of (M+Pd+Cu) amount of substance 0.5 ~ 4 hour;
Dry under filtration, washing, the inert gas shielding condition, promptly make catalyst.
4. the Preparation of catalysts method of gas-phase synthesis of oxalate according to claim 3; It is characterized in that: metal M in the described step (1) and the soluble-salt of Cu can be in nitrate, halide, acetate or the sulfate any one; When metal M was molybdenum and tungsten, soluble-salt can also be ammonium molybdate and ammonium tungstate.
5. the Preparation of catalysts method of synthesis of oxalate according to claim 3, it is characterized in that: the precipitating reagent in described step (3) and the step (8) can be KOH, NaOH, K
2CO
3, Na
2CO
3, NaHCO
3Or KHCO
3In any one.
6. the Preparation of catalysts method of gas-phase synthesis of oxalate according to claim 3 is characterized in that: the salt of the Metal Palladium in the described step (6) can be in palladium nitrate, palladium bichloride, palladium, oxalic acid palladium or the palladium sulfate any one.
7. the Preparation of catalysts method of gas-phase synthesis of oxalate according to claim 3 is characterized in that: the reducing agent described in the described step (10) can be in hydrazine hydrate, formaldehyde, formic acid, sodium borohydride and the potassium borohydride any one.
8. the Application of Catalyst method of gas-phase synthesis of oxalate as claimed in claim 1 is characterized in that: catalyst need carry out activation processing before using, and activation method is feeding 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 ~ 6 hours, be used for the reaction of carbon monoxide and nitrites carbonylation synthesis of oxalate behind the catalyst activation.
9. the Application of Catalyst method of gas-phase synthesis of oxalate as claimed in claim 1; It is characterized in that application conditions is: adopt fixed bed reactors; Unstripped gas carbon monoxide and nitrites are used nitrogen dilution, and the proportion control of nitrites and carbon monoxide is in 10 ~ 20:15 ~ 30 (volume ratio), 80 ~ 140 ℃ of reaction temperatures; Reaction pressure normal pressure ~ 1.0MPa, air speed 500 ~ 9000h-
-1
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| CN 201110336743 CN102441405B (en) | 2011-10-31 | 2011-10-31 | Catalyst used for gas-phase synthesis of oxalate ester and its preparation method |
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| CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
| CN111992209A (en) * | 2020-09-02 | 2020-11-27 | 山东阿斯德科技有限公司 | Catalyst for synthesizing dimethyl oxalate and preparation method and application thereof |
| CN113788524A (en) * | 2021-09-27 | 2021-12-14 | 金风环保有限公司 | Method for treating papermaking wastewater and wastewater treatment apparatus |
| CN114054043A (en) * | 2021-11-29 | 2022-02-18 | 江苏金聚合金材料有限公司 | Dimethyl carbonate synthetic catalyst and preparation method thereof |
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| 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 |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110743544A (en) * | 2019-11-07 | 2020-02-04 | 西安凯立新材料股份有限公司 | Palladium-carbon catalyst for preparing α -phenylethyl alcohol by selective hydrogenation of acetophenone and preparation method and application thereof |
| CN111992209A (en) * | 2020-09-02 | 2020-11-27 | 山东阿斯德科技有限公司 | Catalyst for synthesizing dimethyl oxalate and preparation method and application thereof |
| CN113788524A (en) * | 2021-09-27 | 2021-12-14 | 金风环保有限公司 | Method for treating papermaking wastewater and wastewater treatment apparatus |
| CN113788524B (en) * | 2021-09-27 | 2023-06-02 | 金风环保有限公司 | Method for treating papermaking wastewater and wastewater treatment device |
| CN114054043A (en) * | 2021-11-29 | 2022-02-18 | 江苏金聚合金材料有限公司 | Dimethyl carbonate synthetic catalyst and preparation method thereof |
| CN114054043B (en) * | 2021-11-29 | 2023-11-03 | 江苏金聚合金材料有限公司 | Dimethyl carbonate synthesis catalyst and preparation method thereof |
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| CN102441405B (en) | 2013-07-24 |
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