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Preparation method of oxalate by CO gas phase coupling synthesis using regular catalyst

A production method and catalyst technology, applied in the direction of chemical instruments and methods, physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problems of increasing the production cost of oxalate and achieve improved performance The effect of visual activity, production cost reduction and energy consumption reduction

Active Publication Date: 2013-03-06
TIANJIN UNIV +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In recent years, many scholars at home and abroad have made some progress in the selection of catalysts, activity and carrier effects, and process operating conditions. However, the use of noble metal Pd as the active component of the catalyst increases the production cost of oxalate.

Method used

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Examples

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Comparison scheme
Effect test

preparation example Construction

[0022] The preparation method of above-mentioned regular structure catalyst provided by the present invention, its steps are:

[0023] (1) Preparation of ball milling sol: mixing one or more metal nitrates, hydroxides or oxides, adding concentration is 1-15wt.% dilute nitric acid, controlling pH value to 1-4, through ball mill ( Planetary ball mill XQM-2L, Nanjing Shunco) after ball milling for 1-48 hours at a speed of 200 rpm, the ball mill glue for coating the carrier was obtained;

[0024] (2) Loading of the carrier coat: use the above-mentioned ball mill glue to carry out the carrier coat loading of the cordierite ceramic honeycomb carrier or the metal honeycomb carrier by a known dip coating method, and then dry at 70-130° C. for 2-4 hours, And bake in the muffle furnace at 900-1200 ℃ for 1-12 hours to form a carrier coating. The loading of the coating is 5-50wt.% of the honeycomb carrier. In order to obtain a coating with a high loading, it must be used many times. Dip ...

Embodiment 1

[0029] Catalyst preparation

[0030] Weigh 12.5g γ-Al 2 o 3 , 3.5gAlOOH, 6.5gAl(OH) 3 and 8.0gAl(NO 3 ) 3 And 100ml of dilute HNO with a mass concentration of 10% 3 The solution was ball-milled by a ball mill for 16 hours to obtain an alumina slurry for use.

[0031] Put a 400 hole / square inch cordierite ceramic honeycomb carrier (Φ25mm×25mm) in a muffle furnace and bake it at 700°C for 2 hours to remove organic impurities, then use the conventional dip coating method to load the alumina coating, and the dip coating slurry is the above alumina The slurry was uploaded and dried by microwave and weighed. After 3 times of dip coating, after the loading of alumina reached 20wt.%, the temperature was raised to 1200 °C in the muffle furnace for 4 hours, and then the PdCl 2 -FeCl 3 Immerse in hydrochloric acid solution for 5 minutes, where PdCl 2 and FeCl 3 The molar concentrations were 0.2M and 0.13M, respectively, and after drying, use H 2 Reduction at 500°C for 4 hours y...

Embodiment 2

[0035] Except reaction pressure is controlled at 0.6MPa, all the other are with embodiment 1, and reaction result is shown in Table 1.

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Abstract

The invention relates to a preparation method of oxalate by CO gas phase coupling synthesis using a regular catalyst. In the method, a fixed bed reactor is adopted, a catalyst bed consists of a regular structural catalyst loaded with noble metal; CO and vaporized nitrite are introduced into a reactor for reacting on the regular catalyst so as to generate the oxalate at the conditions that the pressure is 0.1-2MPa, the reaction temperature is 80-200 DEG C, and N2 is taken as a carrier gas, wherein the volume ratio of the materials is as follows: N2:CO:nitrite is 20-80:5-60:10-40, and the retention time is 0.5-10 hours. The method of the invention improves mass transfer efficiency of the reaction materials between the gas phase and the solid phase or among the gas phase, the liquid phase and the solid phase, increases the contact area of the reaction materials and the catalyst and reduces the usage amount of the catalyst in the noble metal, wherein the usage amount of the catalyst noble metal Pd is saved by more than 86%. The method of the invention has the characteristics of high catalyst activity, low cost, convenient and fast replacement and the like, and is beneficial for realizing large-scale engineered application.

Description

technical field [0001] The invention relates to the synthesis of oxalate, in particular to a production method for synthesizing oxalate by CO gas-phase coupling using a regular catalyst. Background technique [0002] In view of the current situation of more coal and less oil in my country, using coal or natural gas instead of petroleum ethylene to synthesize ethylene glycol technology is a major C1 chemical technology with the most scientific raw material route and the most reasonable resource utilization, which is obviously superior to the petroleum route. Oxalate is one of the important intermediate products, and its synthesis is of great significance to the realization of my country's strategic goal of "replacing petroleum ethylene with coal or natural gas to synthesize ethylene glycol". In addition, oxalate is also an important organic chemical raw material, which is widely used in the fine chemical industry to prepare various dyes, medicines, important solvents, extract...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/36C07C67/36B01J35/04B01J23/89
Inventor 马新宾赵玉军王保伟吕静王胜平李振花徐艳
Owner TIANJIN UNIV
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