CN101612580A - A kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling and preparation method thereof - Google Patents
A kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling and preparation method thereof Download PDFInfo
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- CN101612580A CN101612580A CN 200910060087 CN200910060087A CN101612580A CN 101612580 A CN101612580 A CN 101612580A CN 200910060087 CN200910060087 CN 200910060087 CN 200910060087 A CN200910060087 A CN 200910060087A CN 101612580 A CN101612580 A CN 101612580A
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Abstract
The invention discloses a kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling, is active component with the Metal Palladium, with α-Al
2O
3Be carrier, with the transition metal copper is co-catalyst, wherein Metal Palladium content is 0.1～5.0% of vehicle weight, transition metal copper content is 0.05～3.0% of vehicle weight, and this catalyst shows high reaction activity and high and higher diethy-aceto oxalate space-time yield in carbon monoxide and the reaction of nitrous ether (ethyl nitrite) synthesis of diethyl oxalate employing.The invention also discloses a kind of above-mentioned Preparation of catalysts method.
Description
Technical field
The invention belongs to the diethy-aceto oxalate preparing technical field, relate in particular to a kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling and preparation method thereof.
Background technology
Diethy-aceto oxalate has another name called diethyl oxalate (Diethyl Oxalate), and molecular formula is C
6H
10O
4It is an important chemical material, is used to prepare various dyestuffs, medicine, important solvent, extractant and multiple intermediate in a large number.Enter 21 century, oxalate is subjected to paying attention to widely in the world as degradable environment-friendly engineering plastics monomer.The oxalate low-voltage hydrogenation can prepare important chemical material ethylene glycol, and ordinary-pressure hydrolysis can make oxalic acid, and normal pressure ammonia is separated and can be got high quality capim gordura acid amides.
Traditional diethy-aceto oxalate production is to be raw material with oxalic acid and ethanol, is dehydrating agent with toluene, adopts the esterification dehydration method to prepare.This production technology operation is long, cost is high, energy consumption is big, seriously polluted, prepared using is unreasonable.The Fenton D.M. of U.S. Union Oil company has at first reported method by the synthetic oxalate of carbon monoxide and alcohols direct oxidation carbonylation the sixties in 20 century, and [C-1 chemistry is meant that compound from a carbon atom is (as CH to have opened up C-1 chemistry
4, CO, CO
2, CH
3OH, HCHO etc.) technology of the synthetic various chemicals that set out] new way of producing oxalate.This method technological process is short, energy consumption is low, product quality is high, but Fenton D.M. adopts liquid phase method, need pressurization in the reaction, and loss is bigger in catalyst and the liquid reactants separation process, therefore company of Ube Industries Ltd. improves this technology subsequently, (USP 4229591,1980 to have reported the method for vapor phase method carbon monoxide coupling producing oxalic ester; USP 4461909,1984), carbon monoxide and methyl nitrite generation coupling reaction generate dimethyl oxalate and nitric oxide under the normal pressure, then the nitric oxide that generates is separated back and the reaction of first alcohol and water and produce methyl nitrite again and return coupling reaction and recycle, whole technical process in fact only consumes carbon monoxide, oxygen and alcohol.
The coal in China reserves are abundanter, and petroleum resources are deficient relatively, and therefore development is the feedstock production organic oxygen-containing compound with the carbon monoxide, and for alleviating the present oil pressure of China, the reasonable development coal resources have the important strategic meaning.
Reported the new development of catalyst for synthesizing oxalic ester in recent years both at home and abroad again successively.Many in the catalyst of being reported at present is active constituent with Metal Palladium (Pd), α-Al
2O
3Be carrier, and with SiO
2With active carbon be that carrier all shows relatively poor catalytic performance (USP 4229591,1980).Be reported in Pd/ α-Al subsequently again
2O
3Add Mo, Ni, Ti, Fe, Ga, Ce, Na in the catalyst
2Auxiliary agents such as O be applied in the technology of catalytic synthesis of oxalic acid from carbon monoxide, coupling process dimethyl ester, diethy-aceto oxalate and oxalic acid diisopropyl ester, but the space-time yield of oxalate are lower.Reported Pd-Fe/ α-Al as Chinese patent CN 1149047A
2O
3Catalyzing carbon monoxide synthesis of diethyl oxalate employing on the catalyst, and passed through 1000 hours study on the stability, the average space-time yield of catalyst is 780g L
-1h
-1Chinese patent CN 1055492A has reported Pd-Ga/ α-Al
2O
3Catalyst, this catalyst is 35～55% to the conversion per pass of carbon monoxide, diethy-aceto oxalate content only is 85%.Chinese patent CN 1148589A has reported a kind of Pd-Zr/ α-Al of immersion process for preparing
2O
3Catalyst, catalyst move 435 hours continuously, and the diethy-aceto oxalate space-time yield is 800g L
-1h
-1About.
Summary of the invention
Main purpose of the present invention is: in coupling-synthesizing diethyl oxalate by catalyzing carbon monoxide technology, deficiency such as the low or oxalate space-time yield of carbon monoxide conversion ratio is low on the catalyst of the prior art, provide a kind of new catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling, active high, the diethy-aceto oxalate space-time yield height of this catalyst.
Another object of the present invention provides a kind of above-mentioned Preparation of catalysts method.
In order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
A kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling is an active component with the Metal Palladium, with α-Al
2O
3Be carrier, and be co-catalyst with the transition metal copper, wherein Metal Palladium content is 0.1～5.0% of vehicle weight, and transition metal copper content is 0.05～3.0% of vehicle weight.
The content of the active component Metal Palladium in the above-mentioned catalyst more preferably vehicle weight 0.3～1.0%.The content of co-catalyst transition metal copper more preferably vehicle weight 0.1～1.0%.
The above-mentioned catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling of the present invention can get by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, earlier, remove the moisture content on surface, nitrogen flow rate 20～60mL min with its in 250～450 ℃ of flowing nitrogen atmosphere dry 4～6 hours
-1
(2) preparation copper salt solution: get soluble copper salt and be dissolved in deionized water or the chloroform and be made into copper salt solution, the concentration of copper ion is 0.0010～0.10M in the solution;
Preferred any one in copper nitrate, Schweinfurt green, copper chloride or acetylacetone copper etc. of used soluble copper salt in the step (2);
(3) preparation mixing salt solution: soluble palladium salt is joined in the copper salt solution of above-mentioned steps (2) gained, fully stir and make the dissolving of palladium salt, palladium ion concentration is 0.0012～0.10M in the solution, obtains mixing salt solution;
Preferred any one in palladium bichloride, palladium nitrate, palladium or palladium acetylacetonate etc. of used soluble palladium salt in the step (3);
(4) preparation solids: the α-Al after taking by weighing that step (1) is dry and handle according to the load capacity of metal ion in the preparation catalyst
2O
3Join in the mixing salt solution of above-mentioned steps (3) gained, stir and obtain suspension, suspension is left standstill 4～24 hours then; Evaporate to dryness while stirring in 50～80 ℃ of water-baths obtains solids then, with the roasting 3～6 hours in 200～500 ℃ of air atmospheres of this solids;
(5) reduction: with the solids of above-mentioned steps (4) gained with reducing gases 200～500 ℃ of reductase 12～8 hour, gas space velocity is 500～5000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly get described catalyst;
Reducing gases in the step (5) can be selected from pure gas H
2, CO, or mist H
2-N
2, CO-N
2
Compared with prior art, the invention has the beneficial effects as follows:
Show that by testing repeatedly catalyst of the present invention shows high reaction activity and high in carbon monoxide and the reaction of nitrous ether (ethyl nitrite) synthesis of diethyl oxalate employing, products obtained therefrom mesoxalic acid diethylester content can reach more than 90%; Also has simultaneously higher diethy-aceto oxalate space-time yield.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.
Embodiment 1
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst A) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 5 hours in 300 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 40mL min
-1
(2) preparation copper salt solution: with copper nitrate (Cu (NO
3)
23H
2O) be dissolved in deionized water, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.010M;
(3) preparation mixing salt solution: get the copper salt solution 100mL of above-mentioned steps (2) gained, add palladium bichloride (PdCl
2), fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.020M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
321.0g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 12 hours; Evaporate to dryness while stirring in 70 ℃ of water-baths obtains solids then, with the roasting 4 hours in 300 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids reducing gases (H of above-mentioned steps (4) gained
2) 300 ℃ of reduction 3 hours, gas space velocity was 1000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst A, and wherein: the content of Pd is 1.0% of vehicle weight, and the content of Cu is 0.30% of vehicle weight.
Embodiment 2
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst B) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 5 hours in 300 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 40mL min
-1
(2) preparation copper salt solution: with copper nitrate (Cu (NO
3)
23H
2O) be dissolved in deionized water, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.010M;
(3) preparation mixing salt solution: get the copper salt solution 100mL of above-mentioned steps (2) gained, add palladium bichloride (PdCl
2), fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.020M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
321.0g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 12 hours; Evaporate to dryness while stirring in 70 ℃ of water-baths obtains solids then, with the roasting 4 hours in 400 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids reducing gases (H of above-mentioned steps (4) gained
2) 300 ℃ of reduction 3 hours, gas space velocity was 1000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst B, and wherein: the content of Pd is 1.0% of vehicle weight, and the content of Cu is 0.30% of vehicle weight.
Embodiment 3
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst C) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 5 hours in 300 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 40mL min
-1
(2) preparation copper salt solution: with copper nitrate (Cu (NO
3)
23H
2O) be dissolved in deionized water, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.010M;
(3) preparation mixing salt solution: get the copper salt solution 100mL of above-mentioned steps (2) gained, add palladium bichloride (PdCl
2), fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.020M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
321.0g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 12 hours; Evaporate to dryness while stirring in 70 ℃ of water-baths obtains solids then, with the roasting 3 hours in 500 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids reducing gases (H of above-mentioned steps (4) gained
2) 300 ℃ of reduction 3 hours, gas space velocity was 1000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst C, and wherein: the content of Pd is 1.0% of vehicle weight, and the content of Cu is 0.30% of vehicle weight.
Embodiment 4
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst D) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 5 hours in 300 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 40mL min
-1
(2) preparation copper salt solution: with copper nitrate (Cu (NO
3)
23H
2O) be dissolved in deionized water, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.020M;
(3) preparation mixing salt solution: get the copper salt solution 100mL of above-mentioned steps (2) gained, add palladium bichloride (PdCl
2), fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.020M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
321.0g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 12 hours; Evaporate to dryness while stirring in 70 ℃ of water-baths obtains solids then, with the roasting 4 hours in 300 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids reducing gases (H of above-mentioned steps (4) gained
2) 300 ℃ of reduction 3 hours, gas space velocity was 4000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst D, and wherein: the content of Pd is 1.0% of vehicle weight, and the content of Cu is 0.61% of vehicle weight.
Embodiment 5
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst E) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 6 hours in 250 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 20mL min
-1
(2) preparation copper salt solution: with Schweinfurt green (Cu (CH
3COO)
2H
2O) be dissolved in the chloroform, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.033M;
(3) preparation mixing salt solution: get the copper salt solution 100mL of above-mentioned steps (2) gained, add palladium (Pd (CH
3COO)
2), fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.020M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
321.0g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 12 hours; Evaporate to dryness while stirring in 70 ℃ of water-baths obtains solids then, with the roasting 4 hours in 300 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids reducing gases (H of above-mentioned steps (4) gained
2) 300 ℃ of reduction 3 hours, gas space velocity was 5000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst E, and wherein: the content of Pd is 1.0% of vehicle weight, and the content of Cu is 1.0% of vehicle weight.
Embodiment 6
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst F) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 5 hours in 400 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 30mL min
-1
(2) preparation copper salt solution: with copper chloride (CuCl
22H
2O) be dissolved in deionized water, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.0010M;
(3) preparation mixing salt solution: get the copper salt solution 200mL of above-mentioned steps (2) gained, add palladium nitrate (Pd (NO
3)
2) solution, fully mix, obtain mixing salt solution, palladium ion concentration is 0.0012M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
325.4g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 24 hours; Evaporate to dryness while stirring in 50 ℃ of water-baths obtains solids then, with the roasting 3 hours in 500 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids of above-mentioned steps (4) gained with reducing gases (CO) at 500 ℃ of reductase 12s hour, gas space velocity is 1000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst F, and wherein: the content of Pd is 0.1% of vehicle weight, and the content of Cu is 0.05% of vehicle weight.
Embodiment 7
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst G) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 4 hours in 450 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 60mL min
-1
(2) preparation copper salt solution: with acetylacetone copper (Cu (C
5H
7O
2)
2) be dissolved in the chloroform, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.0060M;
(3) preparation mixing salt solution: get the copper salt solution 100mL of above-mentioned steps (2) gained, add palladium acetylacetonate (Pd (C
5H
7O
2)
2), fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.010M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
335.5g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 4 hours; Evaporate to dryness while stirring in 70 ℃ of water-baths obtains solids then, with the roasting 3 hours in 500 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids reducing gases (H of above-mentioned steps (4) gained
2) 500 ℃ of reduction 8 hours, gas space velocity was 500h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst G, and wherein: the content of Pd is 0.3% of vehicle weight, and the content of Cu is 0.11% of vehicle weight.
Embodiment 8
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst H) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 5 hours in 300 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 40mL min
-1
(2) preparation copper salt solution: with copper nitrate (Cu (NO
3)
23H
2O) be dissolved in deionized water, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.010M;
(3) preparation mixing salt solution: get the copper salt solution 100mL of above-mentioned steps (2) gained, add palladium bichloride (PdCl
2), fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.020M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
342.5g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 8 hours; Evaporate to dryness while stirring in 80 ℃ of water-baths obtains solids then, with the roasting 3 hours in 500 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids reducing gases (H of above-mentioned steps (4) gained
2-N
2Gaseous mixture) 300 ℃ of reduction 5 hours, gas space velocity was 3000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst H, and wherein: the content of Pd is 0.5% of vehicle weight, and the content of Cu is 0.15% of vehicle weight.
Embodiment 9
The catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling (catalyst I) of present embodiment for getting by the immersion process for preparing that may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, be placed on earlier in the tube furnace, drying is 5 hours in 350 ℃ of flowing nitrogen atmosphere, removes the moisture content on surface, nitrogen flow rate 50mL min
-1
(2) preparation copper salt solution: with copper nitrate (Cu (NO
3)
23H
2O) be dissolved in deionized water, stirring and dissolving is made into the copper salt solution that copper ions concentration is 0.10M;
(3) preparation mixing salt solution: get the copper salt solution 100mL of above-mentioned steps (2) gained, add palladium bichloride (PdCl
2), fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.10M in the solution;
(4) preparation solids: get the α-Al after step (1) drying is handled
2O
321.0g, join in the mixing salt solution of above-mentioned steps (3) gained, resulting suspension was left standstill 24 hours; Evaporate to dryness while stirring in 60 ℃ of water-baths obtains solids then, with the roasting 6 hours in 200 ℃ of left and right sides air atmospheres of this solids;
(5) reduction: with the solids reducing gases (CO-N of above-mentioned steps (4) gained
2Gaseous mixture) 200 ℃ of reduction 8 hours, gas space velocity was 2000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly.
The catalyst of gained is designated as catalyst I, and wherein: the content of Pd is 5.0% of vehicle weight, and the content of Cu is 3.0% of vehicle weight.
Embodiment 10
Present embodiment is the catalyst performance test, tests the correlated performance of catalyst A-I of the foregoing description 1-9 according to following method:
Adopt atmospheric fixed bed reactor, dress thermocouple sheath in the reactor inside diameter 20mm, reactor, catalyst amount is 6mL, by beds, through condensation after collect from top to bottom by the product diethy-aceto oxalate for unstripped gas.The mol ratio of reaction gas carbon monoxide and nitrous ether (ethyl nitrite) is 1.3, and nitrogen is carrier gas, 140 ℃ of catalysts bed temperatures.Shown in the following tabulation 1 of reaction result.
Table 1 catalyst performance test result
| Catalyst | CO conversion per pass/% | Diethy-aceto oxalate selectivity/% | Diethy-aceto oxalate space-time yield/g L -1h -1 |
| ??A | ??68.7 | ??＞95 | ??1076.4 |
| ??B | ??66.0 | ??＞95 | ??1046.1 |
| ??C | ??49.2 | ??＞95 | ??783.7 |
| ??D | ??52.7 | ??＞95 | ??895.4 |
| ??E | ??48.3 | ??＞95 | ??831.5 |
| ??F | ??41.4 | ??＞95 | ??733.7 |
| ??G | ??46.1 | ??＞95 | ??822.7 |
| ??H | ??55.3 | ??＞95 | ??917.5 |
| ??I | ??69.1 | ??＞90 | ??723.2 |
Can find that by above examples comparative by the catalyst of the method preparation, diethy-aceto oxalate selectivity (being product mesoxalic acid diethylester content) is all greater than 90%, than disclosed Pd-Ga/ α-Al among the Chinese patent CN 1055492A
2O
3Catalyst (85%) obviously improves; Also have simultaneously higher CO conversion per pass and diethy-aceto oxalate space-time yield.
Claims (8)
1, a kind of catalyst for synthesis of diethyl oxalate employing carbon monoxide gas-phase catalytic coupling is an active component with the Metal Palladium, with α-Al
2O
3Be carrier, it is characterized in that: be co-catalyst with the transition metal copper, and wherein Metal Palladium content is 0.1～5.0% of vehicle weight, transition metal copper content is 0.05～3.0% of vehicle weight.
2, catalyst according to claim 1 is characterized in that: the content of described active component Metal Palladium is 0.3～1.0% of vehicle weight.
3, catalyst according to claim 1 is characterized in that: the content of described co-catalyst transition metal copper is 0.1～1.0% of vehicle weight.
4, each described Preparation of catalysts method among a kind of claim 1-3 may further comprise the steps:
(1) carrier drying: carrier α-Al
2O
3Before use, earlier, remove the moisture content on surface, nitrogen flow rate 20～60mL min with its in 250～450 ℃ of flowing nitrogen atmosphere dry 4～6 hours
-1
(2) preparation copper salt solution: get soluble copper salt and be dissolved in deionized water or the chloroform and be made into copper salt solution, the concentration of copper ion is 0.0010～0.10M in the solution;
(3) preparation mixing salt solution: soluble palladium salt is joined in the copper salt solution of above-mentioned steps (2) gained, fully stir and make the dissolving of palladium salt, obtain mixing salt solution, palladium ion concentration is 0.0012～0.10M in the solution;
(4) preparation solids: the load capacity according to metal ion in the preparation catalyst takes by weighing the dried α-Al of step (1)
2O
3, join in the mixing salt solution of above-mentioned steps (3) gained, stir and obtain suspension, suspension is left standstill 4～24 hours then; Evaporate to dryness while stirring in 50～80 ℃ of water-baths obtains solids then, with the roasting 3～6 hours in 200～500 ℃ of air atmospheres of this solids;
(5) reduction: with the solids of above-mentioned steps (4) gained with reducing gases 200～500 ℃ of reductase 12～8 hour, gas space velocity is 500～5000h during reduction
-1In reducing gases atmosphere, be cooled to room temperature then, promptly get described catalyst.
5, preparation method according to claim 4 is characterized in that: used soluble copper salt is selected from any one in copper nitrate, Schweinfurt green, copper chloride or the acetylacetone copper in the described step (2).
6, preparation method according to claim 4 is characterized in that: used soluble palladium salt is selected from any one in palladium bichloride, palladium nitrate, palladium or the palladium acetylacetonate in the described step (3).
7, preparation method according to claim 4 is characterized in that: the temperature in the described step (4) during the baked solid thing is 300～500 ℃.
8, preparation method according to claim 4 is characterized in that: the reducing gases in the described step (5) is selected from pure gas H
2, CO, or be selected from mist H
2-N
2, CO-N
2
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964248A (en) * | 2012-12-15 | 2013-03-13 | 久泰能源科技有限公司 | Method for producing nitric oxide and synthesizing dimethyl oxalate through carbonylation |
| CN103041826A (en) * | 2013-01-14 | 2013-04-17 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
| CN103100384A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103357422A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Carbon monoxide catalytic oxidation catalyst and preparation method thereof |
| CN104148088A (en) * | 2014-06-27 | 2014-11-19 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing dimethyl oxalate from CO and ultrasonic dispersion preparation method of catalyst |
| CN104190415A (en) * | 2014-08-29 | 2014-12-10 | 中国科学院福建物质结构研究所 | Anion regulation and control adopted method for preparing Pd/alpha-Al2O3 catalyst |
| CN105688934A (en) * | 2014-11-27 | 2016-06-22 | 上海华谊能源化工有限公司 | Catalyst for carbon monoxide gas-phase catalytic synthesis of dimethyl oxalate and preparation method and application thereof |
| US9463444B2 (en) | 2011-12-14 | 2016-10-11 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Preparation process of nanocatalysts with (111) crystal facet exposed and process for vapour-phase CO oxidative coupling to oxalate |
| CN111495388A (en) * | 2020-05-19 | 2020-08-07 | 天津大学 | Catalyst for synthesizing diethyl oxalate by CO gas-phase coupling of ethyl nitrite and preparation method thereof |
| CN111495389A (en) * | 2020-05-19 | 2020-08-07 | 天津大学 | Catalyst for synthesizing diethyl oxalate by carbon monoxide gas-phase coupling ethyl nitrite and preparation method and application thereof |
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2009
- 2009-07-22 CN CN 200910060087 patent/CN101612580A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103100384A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN103100384B (en) * | 2011-11-09 | 2015-07-22 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| US9463444B2 (en) | 2011-12-14 | 2016-10-11 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Preparation process of nanocatalysts with (111) crystal facet exposed and process for vapour-phase CO oxidative coupling to oxalate |
| CN102964248A (en) * | 2012-12-15 | 2013-03-13 | 久泰能源科技有限公司 | Method for producing nitric oxide and synthesizing dimethyl oxalate through carbonylation |
| CN103041826B (en) * | 2013-01-14 | 2015-04-15 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
| CN103041826A (en) * | 2013-01-14 | 2013-04-17 | 中国科学院福建物质结构研究所 | Bimetal nanometer catalyst as well as preparation and application method thereof |
| CN103357422A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Carbon monoxide catalytic oxidation catalyst and preparation method thereof |
| CN104148088A (en) * | 2014-06-27 | 2014-11-19 | 中国科学院福建物质结构研究所 | Catalyst for synthesizing dimethyl oxalate from CO and ultrasonic dispersion preparation method of catalyst |
| CN104190415A (en) * | 2014-08-29 | 2014-12-10 | 中国科学院福建物质结构研究所 | Anion regulation and control adopted method for preparing Pd/alpha-Al2O3 catalyst |
| CN105688934A (en) * | 2014-11-27 | 2016-06-22 | 上海华谊能源化工有限公司 | Catalyst for carbon monoxide gas-phase catalytic synthesis of dimethyl oxalate and preparation method and application thereof |
| CN111495388A (en) * | 2020-05-19 | 2020-08-07 | 天津大学 | Catalyst for synthesizing diethyl oxalate by CO gas-phase coupling of ethyl nitrite and preparation method thereof |
| CN111495389A (en) * | 2020-05-19 | 2020-08-07 | 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 |
| 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 |
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