CN105498758A - Catalyst for synthesizing diethyl oxalate with carbon monoxide as well as preparation and application thereof - Google Patents

Catalyst for synthesizing diethyl oxalate with carbon monoxide as well as preparation and application thereof Download PDF

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Publication number
CN105498758A
CN105498758A CN201610035644.3A CN201610035644A CN105498758A CN 105498758 A CN105498758 A CN 105498758A CN 201610035644 A CN201610035644 A CN 201610035644A CN 105498758 A CN105498758 A CN 105498758A
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catalyst
preparation
carbon monoxide
carrier
diethyl oxalate
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董玲玉
李扬
王科
范鑫
李文龙
胡玉容
袁小金
夏伟
许红云
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Southwest Research and Desigin Institute of Chemical Industry
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Southwest Research and Desigin Institute of Chemical Industry
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention relates to a catalyst for synthesizing diethyl oxalate with carbon monoxide, belonging to the technical field of catalysts of diethyl oxalate. The catalyst for synthesizing diethyl oxalate with carbon monoxide comprises a carrier alpha-Al2O3, an active ingredient Pd accounting for 0.1-0.5% of the weight of the carrier and a carrier surface coating beta-Al2O3 accounting for 1-10% of the weight of the carrier. The invention also relates to a preparation method and application of the catalyst. The method comprises the following steps: pretreatment of the carrier alpha-Al2O3, preparation of coating pulp, pulp coating of the carrier coating, preparation of Pd solution, preparation of solid substances and preparation of the catalyst. The catalyst has high reactivity and can improve the conversion rate of carbon monoxide and the selectivity and space time yield of diethyl oxalate. Compared with the traditional soaking process, the catalyst prepared by the preparation method has lower Pd capacity under high activity. The catalyst and the preparation method thereof have the advantages that the catalytic activity is good, the conversion rate of carbon monoxide is high, the selectivity and the space time yield of diethyl oxalate are good, the Pd capacity is low, the preparation technique is simple, and the industrial value is high.

Description

A kind of catalyst of synthesizing diethyl oxalate with carbon monoxide and Synthesis and applications thereof
Technical field
The invention belongs to diethy-aceto oxalate catalyst technical field, particularly a kind of catalyst of synthesizing diethyl oxalate with carbon monoxide and Synthesis and applications thereof.
Background technology
Diethy-aceto oxalate (DiethylOxalate), molecular formula is C 6h 10o 4, it is a kind of important industrial chemicals, is widely used in the chemicals such as synthesis medicine, dyestuff, extractant.Oxalate low-voltage hydrogenation can synthesize important industrial chemicals ethylene glycol, and ordinary-pressure hydrolysis can obtain oxalic acid, and normal pressure ammonia solution can obtain high quality capim gordura acid amides.
It is be raw material with oxalic acid and ethanol that traditional diethy-aceto oxalate is produced, and take toluene as dehydrating agent, prepared by the method adopting esterification to dewater.This production technology operation is long, and cost is high, energy consumption is large, seriously polluted, raw material utilizes unreasonable.The sixties in 20th century, U.S. UnionOil company first reported the method by carbon monoxide and alcohols direct oxidation glycosylation synthesis of oxalate, opened the new way that C-1 chemistry produces oxalate.The method technological process is short, energy consumption is low, product quality is high, but Union company adopts liquid phase method, pressurization is needed in reaction, and lose larger in catalyst and liquid reactants separation process, therefore company of Ube Industries Ltd. improves this technique subsequently, report the method for vapor phase method carbon monoxide coupling producing oxalic ester, carbon monoxide and methyl nitrite generation coupling reaction oxalic dimethyl ester and nitric oxide under normal pressure, then after the nitric oxide of generation being separated and first alcohol and water react and produce methyl nitrite again and return coupling reaction and recycle, whole technical process in fact only consumes carbon monoxide, oxygen and alcohol.
In recent years, the new development of catalyst for synthesizing oxalic ester is reported both at home and abroad successively.Be active component mainly with Metal Palladium (Pd) in the catalyst reported at present, α-Al 2o 3for carrier, and with SiO 2be that carrier all shows poor catalytic performance with active carbon.Pd/ α-Al 2o 3catalyst application is high at the space-time yield of oxalate, and possess good stability, but Pd content is still higher on catalyst, the direction of therefore CO coupling catalyst for synthesizing oxalic ester research is on the basis keeping catalyst performance, reduces the load capacity of Pd on catalyst.Researcher has carried out large quantifier elimination, attempt by adding auxiliary agent or improving the Pd load capacity that preparation method reduces catalyst, but no matter be by adding auxiliary agent or controlling catalyst coating Pd active component thickness, method is all more loaded down with trivial details, cost is also relatively high, is unfavorable for industrialized production.
Summary of the invention
The object of the invention is to for existing catalyst for synthesizing diethyl oxalate with carbon monoxide Pd content high, this present situation that catalyst cost is high, develops that a kind of catalytic activity is good, Pd content is low and the catalyst being applicable to synthesizing diethyl oxalate with carbon monoxide that preparation method is simple.The present invention is realized by following technical proposals:
A catalyst for synthesizing diethyl oxalate with carbon monoxide, described catalyst comprises: active component Pd, carrier α-Al 2o 3and carrier surface coating γ-Al 2o 3, wherein, active component Pd content is 0.1% ~ 5.0% of vehicle weight, carrier surface coating γ-Al 2o 3content is 1% ~ 10% of vehicle weight.
An object of the present invention is to provide the preparation method of the catalyst of described synthesizing diethyl oxalate with carbon monoxide, comprise the following steps:
1) carrier α-Al 2o 3pretreatment: by carrier α-Al 2o 3the nitrogen atmosphere being placed in flowing is dry;
2) preparation of coating slurry: by active γ-Al 2o 3fine powder adds water formation slurries;
3) will through step 1) the carrier α-Al that processed 2o 3immerse step 2) in the coating slurry for preparing, and the carrier through coating is taken out, dries;
4) preparation of palladium solution: be dissolved in deionized water by soluble palladium salt, is prepared into soluble palladium saline solution;
5) preparation of solids: by step 4) the palladium solution prepared is added drop-wise to through step 3) on the coating carrier of drying, then flood successively, dry, roasting;
6) preparation of catalyst: by step 5) solid prepared reduces, and is down to room temperature under reducing gases atmosphere, obtains catalyst of the present invention.
Preferred as one of the present invention, described carrier α-Al 2o 3for one or more in the column of compression molding, sphere or Raschig ring shape thing.
Preferred as one of the present invention, step 1) in, the temperature of described nitrogen is 250 ~ 450 DEG C, and drying time is 3 ~ 6 hours.
Preferred as one of the present invention, described soluble palladium salt is one or more in palladium bichloride, palladium nitrate, palladium or palladium acetylacetonate.
Preferred as one of the present invention, in described soluble palladium saline solution, the concentration of palladium ion is 0.005 ~ 0.06mol/L.
Preferred as one of the present invention, step 5) in, described dip time is 10 ~ 24 hours, and bake out temperature is 60 ~ 110 DEG C, and sintering temperature is 300 ~ 500 DEG C, and the time is 3 ~ 6 hours.
Preferred as one of the present invention, the temperature of described reducing gases is 300 ~ 500 DEG C, and air speed is 800 ~ 3000h -1, the recovery time is 3 ~ 5 hours.
Preferred as one of the present invention, described reducing gases is single H 2, CO, N 2or H 2and N 2mist.
Another object of the present invention is to provide the application of described catalyst in carbon monoxide and nitrous ether (ethyl nitrite) synthesis of diethyl oxalate employing.
Preferred as one of the present invention, the mol ratio of described carbon monoxide and nitrous ether (ethyl nitrite) is 1.2 ~ 1.6, and temperature is 110 ~ 140 DEG C, and catalyst contact time is 1 ~ 3s, and product diethy-aceto oxalate is drawn by reactor bottom, collects after condensation.Wherein, the reaction equation of carbon monoxide and nitrites gas-phase catalytic coupling synthesis of diethyl oxalate employing is as follows:
2CO+2C 2H 5ONO→(C 2H 5OCO) 2+2NO
Compared with prior art, the present invention has following beneficial effect:
The invention provides a kind of catalyst of synthesizing diethyl oxalate with carbon monoxide, catalyst of the present invention has higher reactivity, can improve the conversion ratio of carbon monoxide and the selective of diethy-aceto oxalate and space-time yield.The present invention also provides the preparation method of described catalyst, compared with the catalyst prepared with traditional dipping process, the present invention adopts and carries out to carrier surface catalyst prepared by coating treatment method can realize diethy-aceto oxalate high selectivity and space-time yield effect when Pd load capacity is lower, when activity is suitable, on catalyst of the present invention, Pd load capacity is lower, greatly reduce catalyst cost, and this catalyst preparation process is simple, has industrial value.The invention provides the Catalysts and its preparation method that a kind of catalytic reaction activity is good, CO conversion is high, diethy-aceto oxalate is selective and space-time yield is good, Pd load capacity is low, preparation technology is simple, industrial value is high.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Carry out the preparation of catalyst for synthesizing diethyl oxalate with carbon monoxide according to the preparation method of catalyst of the present invention, concrete preparation process is as follows:
1), carrier α-Al 2o 3pretreatment: the α-Al taking 50g 2o 3carrier, is placed in tube furnace, and drying 5 hours in the nitrogen atmosphere of 300 DEG C of flowings, removing carrier surface moisture, wherein, nitrogen flow rate is 40mLmin -1;
2), the preparation of coating slurry: by active γ-Al 2o 3fine powder adds water formation slurries;
3), will through step 1) the carrier α-Al that processed 2o 3immerse step 2) in the coating slurry for preparing, and the carrier through coating is taken out, dry at 100 DEG C;
4), the preparation of palladium solution: by palladium nitrate (Pd (NO 3) 2nH 2o) be dissolved in deionized water, be transferred in volumetric flask the palladium nitrate aqueous solution being configured to 100mL, wherein, palladium ion concentration is 0.006mol/L;
5), the preparation of solids: get step 4) the palladium nitrate aqueous solution 8.33mL for preparing dropwise is added drop-wise to through step 3) on the coating carrier of drying, and to flood 12 hours successively, 100 DEG C of oven dry, more in air atmosphere in 500 DEG C of roastings 3 hours;
6), the preparation of catalyst: by step 5) solids prepared is at H 2reduce 4 hours under atmosphere, wherein reducing gas temperature is 300 DEG C, and air speed is 2000h -1, be then down to room temperature under reducing atmosphere, obtain the present embodiment catalyst A, wherein, the content of Pd is 0.1% of vehicle weight, carrier surface coating γ-Al 2o 3content be 2% of vehicle weight.
Embodiment 2
Carry out the preparation of catalyst for synthesizing diethyl oxalate with carbon monoxide according to the preparation method of catalyst of the present invention, concrete preparation process is as follows:
1), carrier α-Al 2o 3pretreatment: the α-Al taking 50g 2o 3carrier, is placed in tube furnace, and drying 6 hours in the nitrogen atmosphere of 250 DEG C of flowings, removing carrier surface moisture, wherein, nitrogen flow rate is 20mLmin -1;
2), the preparation of coating slurry: by active γ-Al 2o 3fine powder adds water formation slurries;
3), will through step 1) the carrier α-Al that processed 2o 3immerse step 2) in the coating slurry for preparing, and the carrier through coating is taken out, dry at 100 DEG C;
4), the preparation of palladium solution: be dissolved in by palladium bichloride in deionized water, be transferred in volumetric flask the palladium chloride aqueous solution being configured to 100mL, wherein, palladium ion concentration is 0.016mol/L;
5), the preparation of solids: get step 4) the palladium chloride aqueous solution 9.38mL for preparing dropwise is added drop-wise to through step 3) on the coating carrier of drying, and to flood 10 hours successively, 110 DEG C of oven dry, then roasting 6 hours at 300 DEG C in air atmosphere;
6), the preparation of catalyst: by step 5) solids prepared reduces 5 hours under CO atmosphere, wherein reducing gas temperature is 500 DEG C, and air speed is 1000h -1, be then down to room temperature under reducing atmosphere, obtain the present embodiment catalyst B, wherein, the content of Pd is 0.3% of vehicle weight, carrier surface coating γ-Al 2o 3content be 5% of vehicle weight.
Embodiment 3
Carry out the preparation of catalyst for synthesizing diethyl oxalate with carbon monoxide according to the preparation method of catalyst of the present invention, concrete preparation process is as follows:
1), carrier α-Al 2o 3pretreatment: the α-Al taking 50g 2o 3carrier, is placed in tube furnace, and drying 3 hours in the nitrogen atmosphere of 400 DEG C of flowings, removing carrier surface moisture, wherein, nitrogen flow rate is 60mLmin -1;
2), the preparation of coating slurry: by active γ-Al 2o 3fine powder adds water formation slurries;
3), will through step 1) the carrier α-Al that processed 2o 3immerse step 2) in the coating slurry for preparing, and the carrier through coating is taken out, dry at 100 DEG C;
4), the preparation of palladium solution: palladium be dissolved in deionized water, be transferred in volumetric flask the palladium aqueous solution being configured to 100mL, wherein, palladium ion concentration is 0.020mol/L;
5), the preparation of solids: get step 4) the palladium aqueous solution 12.50mL for preparing dropwise is added drop-wise to through step 3) on the coating carrier of drying, and to flood 22 hours successively, 80 DEG C of oven dry, then roasting 4 hours at 400 DEG C in air atmosphere;
6), the preparation of catalyst: by step 5) solids prepared is at H 2and N 2reduce 3 hours under the atmosphere of mist, wherein reducing gas temperature is 400 DEG C, and air speed is 3000h -1, be then down to room temperature under reducing atmosphere, obtain the present embodiment catalyst C, wherein, the content of Pd is 0.5% of vehicle weight, carrier surface coating γ-Al 2o 3content be 8% of vehicle weight.
Embodiment 4
In order to verify that the present invention carries out catalyst prepared by coating processing and tradition to carrier surface and floods the catalyst prepared have the selective and space-time yield of better diethy-aceto oxalate in performance, test for embodiment 1 comparison of design, namely carry out the preparation of catalyst for synthesizing diethyl oxalate with carbon monoxide without coating slurry dipping process, concrete preparation process is as follows:
1), carrier α-Al 2o 3pretreatment: the α-Al taking 50g 2o 3carrier, is placed in tube furnace, and drying 5 hours in the nitrogen atmosphere of 300 DEG C of flowings, removing carrier surface moisture, wherein, nitrogen flow rate is 40mLmin -1;
2), the preparation of palladium solution: by palladium nitrate (Pd (NO 3) 2nH 2o) be dissolved in deionized water, be transferred in volumetric flask the palladium nitrate aqueous solution being configured to 100mL, wherein, palladium ion concentration is 0.006mol/L;
3), the preparation of solids: get step 2) the palladium nitrate aqueous solution 8.33mL for preparing dropwise is added drop-wise to through step 1) on the coating carrier of drying, and to flood 12 hours successively, 100 DEG C of oven dry, more in air atmosphere in 500 DEG C of roastings 3 hours;
4), the preparation of catalyst: by step 3) solids prepared is at H 2reduce 4 hours under atmosphere, wherein reducing gas temperature is 300 DEG C, and air speed is 2000h -1, be then down to room temperature under reducing atmosphere, obtain the present embodiment catalyst D, wherein, the content of Pd is 0.1% of vehicle weight.
Embodiment 5
In order to verify that the present invention carries out catalyst prepared by coating processing and tradition to carrier surface and floods the catalyst prepared have the selective and space-time yield of better diethy-aceto oxalate in performance, test for embodiment 2 comparison of design, namely carry out the preparation of catalyst for synthesizing diethyl oxalate with carbon monoxide without coating slurry dipping process, concrete preparation process is as follows:
1), carrier α-Al 2o 3pretreatment: the α-Al taking 50g 2o 3carrier, is placed in tube furnace, and drying 6 hours in the nitrogen atmosphere of 250 DEG C of flowings, removing carrier surface moisture, wherein, nitrogen flow rate is 20mLmin -1;
2), the preparation of palladium solution: be dissolved in by palladium bichloride in deionized water, be transferred in volumetric flask the palladium chloride aqueous solution being configured to 100mL, wherein, palladium ion concentration is 0.016mol/L;
3), the preparation of solids: get step 2) the palladium chloride aqueous solution 9.38mL for preparing dropwise is added drop-wise to through step 3) on the coating carrier of drying, and to flood 10 hours successively, 110 DEG C of oven dry, then roasting 6 hours at 300 DEG C in air atmosphere;
4), the preparation of catalyst: by step 3) solids prepared reduces 5 hours under CO atmosphere, wherein reducing gas temperature is 500 DEG C, and air speed is 1000h -1, be then down to room temperature under reducing atmosphere, obtain the present embodiment catalyst E, wherein, the content of Pd is 0.3% of vehicle weight.
Embodiment 6
In order to verify that the present invention carries out catalyst prepared by coating processing and tradition to carrier surface and floods the catalyst prepared have the selective and space-time yield of better diethy-aceto oxalate in performance, test for embodiment 3 comparison of design, namely carry out the preparation of catalyst for synthesizing diethyl oxalate with carbon monoxide without coating slurry dipping process, concrete preparation process is as follows:
1), carrier α-Al 2o 3pretreatment: the α-Al taking 50g 2o 3carrier, is placed in tube furnace, and drying 3 hours in the nitrogen atmosphere of 400 DEG C of flowings, removing carrier surface moisture, wherein, nitrogen flow rate is 60mLmin -1;
2), the preparation of palladium solution: palladium be dissolved in deionized water, be transferred in volumetric flask the palladium aqueous solution being configured to 100mL, wherein, palladium ion concentration is 0.020mol/L;
3), the preparation of solids: get step 2) the palladium aqueous solution 12.50mL for preparing dropwise is added drop-wise to through step 3) on the coating carrier of drying, and to flood 22 hours successively, 80 DEG C of oven dry, then roasting 4 hours at 400 DEG C in air atmosphere;
4), the preparation of catalyst: by step 3) solids prepared is at H 2and N 2reduce 3 hours under mixed-gas atmosphere, wherein reducing gas temperature is 400 DEG C, and air speed is 3000h -1, be then down to room temperature under reducing atmosphere, obtain the present embodiment catalyst F, wherein, the content of Pd is 0.5% of vehicle weight.
Embodiment 7
In order to verify the impact of above-described embodiment 1 ~ 6 prepared catalyst correlated performance such as selective and space-time yield on CO conversion ratio, diethy-aceto oxalate, utilize catalyst A ~ F to carry out synthesizing diethyl oxalate with carbon monoxide respectively, concrete synthesis and reaction process as follows:
The present embodiment adopts atmospheric fixed bed reactor, and wherein, reactor inside diameter is 20mm, the in-built thermocouple sheath of reactor, and catalyst amount is 10mL, and unstripped gas passes through beds, and product diethy-aceto oxalate is collected after condensation.The mol ratio of reaction gas carbon monoxide and nitrous ether (ethyl nitrite) is 1.3, and carrier gas is nitrogen, and catalysts bed temperature is 120 DEG C, and catalyst contact time is 3s.The performance test results that catalyst A ~ F carries out synthesizing diethyl oxalate with carbon monoxide is as shown in table 1 below:
Table 1 catalyst A ~ F carries out the performance test results of synthesizing diethyl oxalate with carbon monoxide
Catalyst CO conversion ratio/% Diethy-aceto oxalate selective (%) Diethy-aceto oxalate space-time yield (gL -1·h -1)
A 31.7 90.6 640.9
B 32.9 91.5 767.8
C 37.2 93.4 866.2
D 22.7 84.5 443.5
E 29.6 85.3 658.6
F 33.8 85.9 760.7
As can be seen from Table 1, adopt catalyst A prepared by the inventive method, B, C with apply without coating slurry the catalyst D prepared, E, F compares, the conversion ratio of carbon monoxide can be significantly improved, and catalyst A, B, the ethyl oxalate selective (i.e. product mesoxalic acid diethylester content) of C catalyst can reach more than 90%, and catalyst D, E, the ethyl oxalate of F is selective only has about 85%, simultaneously, catalyst A is compared to catalyst D, catalyst B is compared to catalyst E, catalyst C has better diethy-aceto oxalate space-time yield compared to catalyst F.Shown by above catalyst performance test result data, the present invention is flooded by the catalyst A of carrier surface being carried out to coating processing and preparing, B, C and tradition compared with catalyst D, E, F of preparing, shows the selective and space-time yield of higher CO conversion, diethy-aceto oxalate when identical Pd load capacity.
Meanwhile, the catalyst A that the present invention is prepared by carrying out coating processing to carrier surface, even if its Pd content is only 0.1% of vehicle weight, but the space-time yield of its diethy-aceto oxalate when carbon monoxide coupling synthesis of diethyl oxalate employing can reach 640.9gL -1h -1, this and the Pd content adopting typical impregnation method to prepare are the diethy-aceto oxalate space-time yield 658.6gL of the catalyst E of carrier quality 0.3% -1h -1almost suitable, illustrate that the present invention adopts the method for preparing catalyst carrying out coating processing to carrier surface can realize the effect of diethy-aceto oxalate height space-time yield when Pd load capacity is lower, can effectively reduce Pd load capacity, save catalyst cost, there is high industrial application value.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. a catalyst for synthesizing diethyl oxalate with carbon monoxide, is characterized in that, described catalyst comprises: active component Pd, carrier α-Al 2o 3, carrier surface coating γ-Al 2o 3, active component Pd content is 0.1% ~ 5.0% of vehicle weight, carrier surface coating γ-Al 2o 3content is 1% ~ 10% of vehicle weight.
2. the preparation method of a kind of catalyst of synthesizing diethyl oxalate with carbon monoxide as claimed in claim 1, is characterized in that, comprise the following steps:
1) carrier α-Al 2o 3pretreatment: by carrier α-Al 2o 3the nitrogen atmosphere being placed in flowing is dry;
2) preparation of coating slurry: by active γ-Al 2o 3fine powder adds water formation slurries;
3) will through step 1) the carrier α-Al that processed 2o 3immerse step 2) in the coating slurry for preparing, and the carrier through coating is taken out, dries;
4) preparation of palladium solution: be dissolved in deionized water by soluble palladium salt, is prepared into soluble palladium saline solution;
5) preparation of solids: by step 4) the palladium solution prepared is added drop-wise to through step 3) on the coating carrier of drying, then flood successively, dry, roasting;
6) preparation of catalyst: by step 5) solid prepared reduces, and is down to room temperature under reducing gases atmosphere, obtains catalyst of the present invention.
3. the preparation method of a kind of catalyst of synthesizing diethyl oxalate with carbon monoxide as claimed in claim 2, is characterized in that, described carrier α-Al 2o 3for one or more in the column of compression molding, sphere or Raschig ring shape thing.
4. the preparation method of a kind of catalyst of synthesizing diethyl oxalate with carbon monoxide as claimed in claim 2, is characterized in that, step 1) in, the temperature of described nitrogen is 250 ~ 450 DEG C, and drying time is 3 ~ 6 hours.
5. the preparation method of a kind of catalyst of an oxidative synthesis diethy-aceto oxalate as claimed in claim 2, it is characterized in that, described soluble palladium salt is one or more in palladium bichloride, palladium nitrate, palladium or palladium acetylacetonate.
6. the preparation method of a kind of catalyst of synthesizing diethyl oxalate with carbon monoxide as claimed in claim 2, it is characterized in that, in described soluble palladium saline solution, the concentration of palladium ion is 0.005 ~ 0.06mol/L.
7. the preparation method of a kind of catalyst of synthesizing diethyl oxalate with carbon monoxide as claimed in claim 2, is characterized in that, step 5) in, described dip time is 10 ~ 24 hours, bake out temperature is 60 ~ 110 DEG C, and sintering temperature is 300 ~ 500 DEG C, and the time is 3 ~ 6 hours.
8. the preparation method of a kind of catalyst of synthesizing diethyl oxalate with carbon monoxide as claimed in claim 2, it is characterized in that, the temperature of described reducing gases is 300 ~ 500 DEG C, and air speed is 800 ~ 3000h -1, the recovery time is 3 ~ 5 hours.
9. the catalyst of a kind of synthesizing diethyl oxalate with carbon monoxide as claimed in claim 1, is characterized in that, the application of described catalyst in carbon monoxide and nitrous ether (ethyl nitrite) preparing diethyl oxalate by coupling.
10. the application of catalyst in carbon monoxide and nitrous ether (ethyl nitrite) preparing diethyl oxalate by coupling as claimed in claim 9, it is characterized in that, the mol ratio of described carbon monoxide and nitrous ether (ethyl nitrite) is 1.2 ~ 1.6, temperature is 110 ~ 140 DEG C, catalyst contact time is 1 ~ 3s, product diethy-aceto oxalate is drawn by reactor bottom, collects after condensation.
CN201610035644.3A 2016-01-20 2016-01-20 Catalyst for synthesizing diethyl oxalate with carbon monoxide as well as preparation and application thereof Pending CN105498758A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115996792A (en) * 2020-06-26 2023-04-21 巴斯夫欧洲公司 Tabletting alpha-alumina catalyst carrier

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993362A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for producing oxalic ester through coupling CO

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993362A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for producing oxalic ester through coupling CO

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115996792A (en) * 2020-06-26 2023-04-21 巴斯夫欧洲公司 Tabletting alpha-alumina catalyst carrier

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