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Oxalate production method of catalyst combination packing

A production method and catalyst technology, applied in the direction of carbon monoxide or formate reaction preparation, organic chemistry, etc., can solve the problems of low selectivity of the target product oxalate, low single-pass conversion rate of raw materials, etc.

Active Publication Date: 2016-04-13
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The technical problem to be solved by the present invention is the low conversion rate of raw materials in the prior art and the low selectivity of the target product oxalate. A new method for producing oxalate with catalyst combination packing is provided. The method has the advantages of raw material High conversion rate and good oxalate selectivity

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] The reactor for CO coupling production of dimethyl oxalate is a fixed-bed reactor with tubes, the catalyst is installed inside the tubes, and the cooling medium is outside the tubes. The molar ratio of CO and methyl nitrite entering the reactor is 1.2:1, the feed temperature is 100°C, and the pressure is 0.3MPa. There are two catalyst beds in the column tube, and the height of the upper and lower catalyst beds is H 2 / H 1 =2:1, the catalyst in the upper catalyst bed is Pd / Al 2 o 3 Catalyst, only supported palladium, by the weight of elemental palladium, the consumption of oxides selected from palladium is 0.5% by weight, and the catalyst in the lower catalyst bed is Pd-Ni / Al 2 o 3 Catalyst, based on the weight of elemental palladium, the amount of oxides selected from metal palladium and palladium is 0.3% by weight, the additive Ni is based on the weight of elemental nickel, and the amount of oxides selected from nickel is 1% by weight. %. Under the above condition...

Embodiment 2

[0017] The reactor for CO coupling to produce dimethyl oxalate is a tubular fixed-bed reactor with a catalyst outside the tube and a cooling medium inside the tube. The form of the reactor is the same as that in Chinese patent 200910057857.6. The molar ratio of CO and methyl nitrite entering the reactor is 3:1, the feed temperature is 70°C, and the pressure is 0.1MPa. The tubes contain three catalyst beds, and the height ratio of the three catalyst beds is H 3 / H 2 / H 1 =3:1.5:1, the catalyst in the first catalyst bed is Pd-Ni / Al 2 o 3 Catalyst, based on the weight of elemental palladium, the amount of oxides selected from metal palladium and palladium is 2% by weight, the additive Ni is based on the weight of elemental nickel, and the amount of oxides selected from nickel is 0.5% by weight %, the catalyst in the second catalyst bed is Pd-Ce / Al 2 o 3 Catalyst, based on the weight of elemental palladium, the amount of oxides selected from metal palladium and palladium is 1...

Embodiment 3

[0019] The reactor for CO coupling to produce diethyl oxalate is a fixed-bed reactor with tubes, the catalyst is installed inside the tubes, and the cooling medium is outside the tubes. The molar ratio of CO and ethyl nitrite entering the reactor is 5:1, the feed temperature is 140°C, and the pressure is 1.0MPa. The tubes contain three catalyst beds, and the height ratio of the three catalyst beds is H 3 / H 2 / H 1 =5:3:1, the catalyst in the first catalyst bed is Pd-Ti / (Al 2 o 3 +SiO2 2 ) catalyst, based on the weight of elemental palladium, the amount of oxides selected from palladium is 0.45% by weight, the auxiliary agent Ti is based on the weight of elemental titanium, and the amount selected from metal titanium is 0.5% by weight, the second The catalyst in the stage catalyst bed is Pd-Co / Al 2 o 3 Catalyst, based on the weight of elemental palladium, the amount of oxides selected from metal palladium and palladium is 0.3%, and the auxiliary agent Co is based on the w...

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Abstract

The invention relates to a production method of catalyst combined loading oxalate, which mainly solves the problems of low raw material per-pass conversion and low selectivity of a target product oxalate in the prior art. With the adoption of the technical scheme that CO and nitrite at a mole ratio of (1-5):1 are introduced to a fixed bed reactor as raw materials at the feed temperature of 60-160 DEG C, and perform contact reaction with a palladium-bearing catalyst to generate oxalate at the pressure of 0-1.5MPa, heat generated by the reaction is removed by heat exchange timely, the reactor comprises at least two catalyst bed layers, the height of each catalyst bed layer is Hn, Hn / H1 is equal to (1-5):1 by taking the height H1 of the first bed layer at the upper part as a reference, and a weight ratio of a catalyst activity ingredient in (n-1)th bed layer to a catalyst activity ingredient in the nth bed layer is (1.2-5):1, the problems are better solved, and the method can be used for industrial production of oxalate.

Description

technical field [0001] The present invention relates to a kind of oxalate ester production method of catalyst combination packing, more specifically, relate to a kind of gas phase method CO and methyl nitrite or ethyl nitrite in the tubular fixed-bed reactor of catalyst combination packing reaction production Dimethyl oxalate or diethyl oxalate method. Background technique [0002] Oxalate is an important chemical raw material, which can be used to prepare oxalic acid, ethylene glycol, carbonate, oxamide, intermediates of drugs and dyes, plastic accelerators and solvents, etc. [0003] The traditional production route of oxalate is the method of esterification and dehydration of oxalic acid and alcohol with toluene as the dehydrating agent. The production process is long, the energy consumption is high, the pollution is serious, and the cost is high. It is urgent to find a new process route. The gas-phase catalyzed synthesis of oxalate from CO and nitrite opens up a new and...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/36C07C67/36
CPCC07C67/36C07C69/36
Inventor 孙凤侠蒯骏赵焱张琳娜
Owner CHINA PETROLEUM & CHEM CORP