CN1141179C - Catalyst for gas-phase synthesis of oxalate and its preparing process - Google Patents
Catalyst for gas-phase synthesis of oxalate and its preparing process Download PDFInfo
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- CN1141179C CN1141179C CNB021116245A CN02111624A CN1141179C CN 1141179 C CN1141179 C CN 1141179C CN B021116245 A CNB021116245 A CN B021116245A CN 02111624 A CN02111624 A CN 02111624A CN 1141179 C CN1141179 C CN 1141179C
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Abstract
The present invention discloses a catalyst for the gas phase synthesis of oxalic ester and a method for preparing the catalyst. The catalyst is prepared by that alpha-Al2O3 is used as a catalyst carrier, cerium metal and palladium metal are used as active constituents, and an immersion method is adopted. The catalyst has favorable effects in the reaction that carbon monoxide and nitrite ester are synthesized into dimethyl oxalate and diethyl oxalate. Experiments indicate that Pd-Ce/alpha-Al2O3 not only has high reaction activity and selectivity, but also has the advantages of long service life, stable reaction and easy control.
Description
Technical Field
The invention relates to a catalyst and a preparation method thereof, in particular to a catalyst for gas-phase synthesis of oxalate and a preparation method thereof.
Background
Oxalate is an important chemical raw material and can be used for preparing oxalic acid, glycol, oxamide and intermediates of certain medicaments and dyes.
At present, the method of esterification and dehydration of oxalic acid and alkyl alcohol and toluene is adopted domestically to produce dialkyl oxalate. One of the main raw materials of oxalic acid is produced by sodium formate method, carbon monoxide and sodium hydroxide are put at 160 deg.C, 16-20kgf/cm2Under the pressure, sodium formate is synthesized, then sodium oxalate is generated by concentration and dehydrogenation under 400 ℃, lead oxalate is generated by the action of the sodium formate and lead sulfate, a crude oxalic acid product is obtained by further acidification with sulfuric acid, and finally barium carbonate and one percent of polyacrylamide are used for coagulation and sedimentation to generate refined oxalic acid. The gas phase catalytic synthesis of oxalate from carbon monoxide and nitrite opens up a new important way for producing oxalate by carbon-chemistry. A new development of oxalate synthesis has been reported in succession at home and abroad since the eighties. JP8242.656 patent application first reports a process for synthesizing dimethyl oxalate from carbon monoxide and methyl nitrite using a platinum group metal-supported catalyst, whereinthe space-time yield of the catalyst is 432g/L.h, and the yield is not decreased by 480 hours of continuous reaction. Subsequently, there are many patents which successively report addition of Mo, Ni, Ti, Fe, Ga, Cu, Na, respectively, to the catalyst component2O, and SiO2The catalyst composed of the auxiliary agents is applied to the process for synthesizing dimethyl oxalate, diethyl oxalate and diisopropyl oxalate by using carbon monoxide and nitrite in a gas phase, but the space-time yield is still lower. Pd-Ti/Al as reported in U.S. Pat. No. 4, 4,507,4942O3Catalyst under a pressure of 2.5kg/cm3115-120 ℃ and space velocity of 3000h-1Initial feed gas composition: CH (CH)3ONO：10％ CO：20％ CH3OH：4％ NO：3％ N2: 63% equal conditionThen, the reaction was continued for 950 hours, the space-time yield of dimethyl oxalate was 429-462g/L.h, and the selectivity of dimethyl oxalate from CO reached 95%.
Disclosure of Invention
The invention aims to solve the technical problem of developing a high-efficiency catalyst for synthesizing oxalate.
The technical scheme is as follows:
the active components of the catalyst are metal palladium (Pd) and metal cerium (Ce), and the carrier is α -Al2O3Wherein the content of metal palladium is preferably 0.2-2.0%, most preferably 0.8-1.3% by weight of the carrier, the content of metal cerium is preferably 0.05-1%, most preferably 0.1-0.6% by weight of the carrier, and the carrier is preferably α -Al having porous structure2O3The specific surface area thereof is preferably 3 to 30m2A ratio of 8 to 12 m/g is preferred2/g。
The method for preparing the catalyst comprises the following steps:
(1) preparing aqueous solution of halide, nitrate, acetate or oxalate of cerium (Ce) and water with concentration of 0.003-0.07M, and mixing with carrier α -Al2O3Soaking in the water solution for 4-15 hr, drying, and roasting for 3-8 hr to obtain solid;
(2) preparing an aqueous solution of halide, nitrate, acetate or oxalate of metal palladium (Pd) and water, wherein the concentration of the aqueous solution is 0.03-0.2M, soaking the solid obtained in the step (1) in the aqueous solution for 4-15 hours, taking out and drying to obtain the catalyst.
In order to prevent the metal cerium ions from hydrolyzing to generate hydroxide or oxide precipitates, the same acid as the anion of the metal salt can be added into the aqueous solution of the halide, nitrate, acetate or oxalate of the metal cerium, so that the pH value of the aqueous solution is 5-7.
The use method of the catalyst comprises the following steps:
the catalyst needs to be reduced before use, the reducing gas is hydrogen or carbon oxide, the flow rate is 30-70ml/min. g.cat, the reducing temperature is 250-350 ℃, and the reducing time is 2-5 hours until the water content at the outlet is constant.
The reaction formula for synthesizing oxalate by gas phase catalysis of carbon monoxide and nitrite is as follows:
wherein: r is alkyl.
The nitrite required for the reaction is formed by reacting sodium nitrite, sulfuric acid and alcohol or nitric oxide, oxygen and alcohol, wherein the alcohol can be any saturated aliphatic alcohol containing 1-8 carbon atoms, and methanol, ethanol and butanol are preferred. The reaction not only generates the main product of oxalate, but also generates byproduct of nitric oxide, and the nitric oxide can be recycled by reacting with oxygen and alcohol to generate nitrite, and the reaction formula is as follows:
two reaction cycles were carried out, the overall reaction formula of which is as follows:
the oxalate gas-phase synthesis reaction adopts a fixed bed reactor, the contact time of raw material gas, namely carbon monoxide and nitrite, diluted by nitrogen and a catalyst is 0.2-4 seconds, the reaction temperature is controlled at 90-160 ℃, the contents of CO and RONO in the raw material gas can be changed within a wide range, the content of CO is 10-60%, and the content of RONO is 5-25%.
The specific implementation method comprises the following steps:
the nitrate of metal cerium (Ce) and water are prepared into an aqueous solution, the concentration of the aqueous solution is 0.003M-0.07M, and nitric acid is added into the aqueous solution to ensure that the pH value of the aqueous solution is 5-7 in order to prevent the metal ions from hydrolyzing to generate hydroxide or oxide precipitates. The porous structure has a specific surface area of 3-30m2Support α -Al/g2O3Soaking in the soaking solution for 4-15 hr, drying in water bath to obtain solid, drying at 120 deg.C for 10-15 hr, calcining at 650 deg.C for 3-8 hr, and mixingSoaking the solid in 0.03-0.2M aqueous solution of halide of palladium (Pd) for 4-15 hr, and drying at 120 deg.C for 10-15 hr to obtain Pd-Ce/α -Al2O3A catalyst.
The catalyst of the invention adopts α -Al2O3As a catalyst carrier, metal cerium and metal palladium are used as active components, the catalyst is prepared by an impregnation method, and the catalyst has good effect in the reaction of synthesizing dimethyl oxalate and diethyl oxalate by using carbon monoxide and nitrite, experiments prove that Pd-Ce/α -Al2O3Not only has higher reactivity and selectivity, but also has long service life, stable reaction and easy control.
The invention is further illustrated by the following examples:
in the case of the example 1, the following examples are given,
weighing 10g of α -Al2O31 wt% Pd +0.3 wt% Ce/α -Al2O3Preparing a catalyst by content, which comprises the following steps: selecting Ce (NO)3)3An impregnation solution was prepared according to the amount of Ce supported, and in order to prevent the metal ions from hydrolyzing to form hydroxides or oxides, a small amount of nitric acid was added to the impregnation solution so that the PH of the impregnation solution became 5, and then the specific surface area was set to 3m2Support α -Al/g2O3Soaking in the soaking solution for 12 hr, absorbing completely, drying in water bath to obtain solid, drying at 120 deg.C for 12 hr, calcining at 300 deg.C and 650 deg.C for 6 hr, and loading Pd in the solid2Soaking in the prepared soaking solution for 12 hours, and drying at 120 deg.C for 12 hours to obtain Pd-Ce/α -Al2O3A catalyst.
In the case of the example 2, the following examples are given,
weighing 10g of α -Al2O31 wt% Pd +0.1 wt% Ce/α -Al2O3Preparing a catalyst by content, which comprises the following steps: selecting Ce (NO)3)3The impregnation liquid is prepared according to the Ce loading amount, and is used for preventing the metal ions from hydrolyzing to generate oxyhydrogenPrecipitating the compound or oxide, adding small amount of nitric acid to the solution to adjust pH to 7, and adding waterThe specific surface area is 30m2Support α -Al/g2O3Soaking in the soaking solution for 12 hr, absorbing thoroughly, drying in water bath to obtain solid, drying at 120 deg.C for 12 hr, calcining at 300 deg.C and 650 deg.C for 6 hr, and loading Pd (NO) in the solid according to Pd loading3)2Soaking in the prepared soaking solution for 12 hours, and drying at 120 deg.C for 12 hours to obtain Pd-Ce/α -Al2O3A catalyst.
Example 3, testing of catalyst activity:
the catalyst is placed in a quartz glass reactor, the inner diameter of the reactor is 20mm, a thermowell is arranged in the reactor, the loading amount of the catalyst is 2ml, the raw material gas passes through a catalyst bed layer from top to bottom, and a product dimethyl oxalate is led out from the bottom of the reactor. Before the catalyst takes part in the reaction, the catalyst is subjected to hydrogen reduction treatment at the reduction temperature of 350 ℃, the reduction time of 3 hours and the hydrogen flow of 50ml/min, and the temperature of the catalyst subjected to the reduction treatment is reduced to 140 ℃ in a reaction temperature zone under the protection of the hydrogen flow. The optimal flow ratio of reaction gases of carbon monoxide and nitrous acid ester is 1.3, the reaction is carried out under normal pressure, the reaction temperature is 140 ℃, the per-pass conversion rate of the carbon monoxide reaches 78%, the space-time yield of dimethyl oxalate is 821g/L.h, and dimethyl oxalate and formaldehyde are not detected in the product.
Claims (5)
1. The catalyst for synthesizing oxalate in gas phase is characterized in that active components of the catalyst are metal palladium and metal cerium, and a carrier of the catalyst is α -Al2O3Wherein: the active component contains 0.2-2.0% of metal palladium and 0.05-1% of metal cerium.
2. The catalyst of claim 1, wherein the support is α -Al having a porous structure2O3。
3. The catalyst of claim 2, wherein the support α -Al2O3The specific surface area is 3-30m2/g。
4. The method for preparing any one of the catalysts according to claims 1 to 3, comprising the steps of:
(1) preparing aqueous solution of halide, nitrate, acetate or oxalate of cerium metal and water with the concentration of 0.003-0.07M, and mixing the carrier α -Al2O3Soaking in the aqueous solution for 4-15 hours, taking out, drying at 120 ℃ for 10-15 hours, and roasting at 300-650 ℃ for 3-8 hours to obtain a solid;
(2) preparing an aqueous solution of halide, nitrate, acetate or oxalate of metallic palladium and water, wherein the concentration of the aqueous solution is 0.03-0.2M, soaking the solid obtained in the step (1) in the aqueous solution for 4-15 hours, taking out the solid, and drying the solid at 120 ℃ for 10-15 hours to obtain the catalyst.
5. The method according to claim 4, wherein the same acid as an anion of the metal salt is added to an aqueous solution of a halide, nitrate, acetate or oxalate of cerium metal to adjust the pH of theaqueous solution to 5 to 7.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105396584A (en) * | 2014-08-27 | 2016-03-16 | 中国石油化工股份有限公司 | Oxalate catalyst synthesized through CO coupling, preparation method and purpose of oxalate catalyst |
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| CN101279257B (en) * | 2008-03-27 | 2012-05-30 | 上海焦化有限公司 | Catalyst for synthesizing oxalic ester and preparation method and application thereof |
| CN101596455B (en) * | 2008-06-04 | 2011-09-07 | 中国石油天然气股份有限公司 | Catalyst for synthesizing oxalate and preparation method thereof |
| CN102001938B (en) * | 2009-08-28 | 2014-04-30 | 上海焦化有限公司 | Process and production system for synthesizing dimethyl oxalate or diethyl oxalate and coproducing oxalic acid |
| CN101993363B (en) * | 2009-08-31 | 2013-06-05 | 中国石油化工股份有限公司 | Method for preparing oxalic ester by CO coupling |
| CN101653731B (en) * | 2009-09-23 | 2012-04-25 | 西南化工研究设计院 | Catalyst for synthesizing diethyl oxalate with carbon monoxide, preparation method and application thereof |
| CN101791555B (en) * | 2010-03-19 | 2011-08-24 | 丹阳市丹化金煤化工有限公司 | Catalyst for gas-phase dimethyloxalate synthesis by CO and preparation method thereof |
| CN102442901A (en) * | 2010-10-15 | 2012-05-09 | 安徽淮化股份有限公司 | Method for producing dimethyloxalate |
| CN102649727A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing oxalate through CO gas-phase coupling |
| CN102649056B (en) * | 2011-02-25 | 2016-01-13 | 中国石油化工股份有限公司 | The catalyst of CO preparing oxalate coupling reaction |
| CN102513101B (en) * | 2011-12-14 | 2014-12-10 | 中国科学院福建物质结构研究所 | Nano Pd catalyst used for preparing oxalic ester by CO gas phase oxidation coupling and its preparation method |
| WO2013086691A1 (en) | 2011-12-14 | 2013-06-20 | 中国科学院福建物质结构研究所 | Nano pd catalyst for preparation of oxalate by gas phase co oxidative coupling, and preparation process thereof |
| CN102698748A (en) * | 2012-05-22 | 2012-10-03 | 山东华鲁恒升化工股份有限公司 | Catalyst for synthesizing oxalic ester from CO by gas phase coupling and method for preparing same |
| CN105435779B (en) * | 2014-08-27 | 2018-07-17 | 中国石油化工股份有限公司 | Carbon monoxide vapor- phase synthesis oxalate catalyst |
| CN106799229A (en) * | 2017-01-22 | 2017-06-06 | 南昌大学 | A kind of core shell structure Pd Ce@SiO2Catalyst and preparation method |
| WO2020082200A1 (en) * | 2018-10-22 | 2020-04-30 | Pujing Chemical Industry Co., Ltd | Carbonylation catalyst and preparation thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105396584A (en) * | 2014-08-27 | 2016-03-16 | 中国石油化工股份有限公司 | Oxalate catalyst synthesized through CO coupling, preparation method and purpose of oxalate catalyst |
| CN105396584B (en) * | 2014-08-27 | 2018-04-06 | 中国石油化工股份有限公司 | CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage |
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