Low-mercury catalyst for acetylene hydrochlorination

A low-mercury catalyst, acetylene hydrochlorination technology, applied in physical/chemical process catalysts, organic chemistry, hydrogen halide addition preparation, etc., can solve the problems of loss of active components, poorer stability than high-mercury catalysts, and high cost

Inactive Publication Date: 2012-03-21
CHENGDU HUIEN FINE CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the industrial acetylene hydrochlorination reaction mainly uses high-mercury catalysts with a loading of mercuric chloride of 12% to 15%. serious health hazard
[0004] For the hydrochlorination of acetylene, there have been reports at home and abroad using precious metals such as platinum, palladium, and gold as the main catalytic component. Although the activity is high, the stability is not as good as that of high mercury catalysts, and the cost is too high to achieve industrial production.
However, when tin, bismuth, copper, zinc and other base metal compounds are used as the main catalyst components, the loss of active components is more serious.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Activated carbon pretreatment (the following examples are the same): commercially available activated carbon (with a specific surface area of ​​500-1500 m 2 / g, the average pore volume is 0.25~0.9 ml / g, the pore diameter is ≤50 nm), the preferred particle size is 20~50 mesh, and the specific surface area is 850~1100 m 2 / g, an average pore volume of 0.48~0.88 ml / g and an average pore diameter of 2~3nm, especially amorphous coconut shell activated carbon of 2.2~2.3 nm, placed in a concentration of 3~5 times the volume (preferably 4 times) is 1.5 mol / L~2.5mol / L (preferably 2mol / L) nitric acid, heat and stir until reflux for 2.5~3.5 hours, wash the activated carbon with distilled water to pH=6~7, and dry it at 45℃~55℃ surface moisture, and then vacuum-dry at 75~85°C to constant weight. Place the activated carbon in a urea solution with a concentration of 2% to 4wt% that is 3.5 to 4.5 times its volume, heat and stir until refluxed for 2.5 to 3.5 hours, then suction filter ...

Embodiment 2

[0034] 0.65g of mercuric chloride, 0.52g of bismuth chloride, 0.13g of cerium chloride, 0.26g of barium chloride and 0.45g of copper chloride are simultaneously dissolved in a hydrochloric acid solution with a concentration of 2mol / L, wherein the concentration of mercuric chloride is 0.009mol / L; add the prepared impregnating solution to 13g of pretreated activated carbon, impregnate at room temperature for 12 hours with equal volume, and add ultrasonic auxiliary load for the initial 0.5 hour; evaporate to dryness in a water bath at 80°C for 2 hours , and then dry the surface moisture in an oven at room temperature at 80°C for 2 hours; wash the activated carbon with a hydrochloric acid solution with a concentration of 0.02mol / L to remove the salt deposited on the outer surface of the activated carbon, and then filter it and place it at a temperature of Dry in an oven at 80°C until constant weight, and cool for later use.

[0035] When the catalyst is used in the reaction of ace...

Embodiment 3

[0037] 0.52g mercuric chloride, 0.65g bismuth chloride, 0.39g cerium chloride, 0.26g barium chloride and 0.26g cupric chloride are simultaneously dissolved in the hydrochloric acid solution whose concentration is 2.5mol / L, wherein the concentration of mercuric chloride 0.007mol / L; add the prepared impregnating solution to 13g of pretreated activated carbon, impregnate at room temperature for 10 hours, and add ultrasonic auxiliary load for the initial 0.5 hour; evaporate to dryness in a water bath at a temperature of 80°C for 2 hours, Then dry the surface moisture in a normal temperature oven at a temperature of 70°C for 2 hours; wash the activated carbon with a hydrochloric acid solution with a concentration of 0.02mol / L to remove the salt deposited on the outer surface of the activated carbon, and then filter it and place it at a temperature of 80 Dry in an oven at ~85°C to constant weight, and cool down for later use.

[0038] In the reaction of acetylene hydrochlorination t...

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Abstract

Disclosed is a low-mercury catalyst for acetylene hydrochlorination. Mercuric chloride is carried on activated carbon. Raw materials comprise, by weight, 100 parts of activated carbon, 4-5 parts of mercuric chloride, 8-10 parts of total essential assistant, 1-5 parts of total non-essential assistant, wherein the essential assistant comprises 2-5 parts of bismuth chloride, 1-5 parts of cerium chloride, 1-5 parts of barium chloride and 2-5 parts of copper chloride; and the non-essential assistant comprises at least one of potassium chloride, phosphoric acid, zinc chloride and cuprous chloride. After being subjected to surface subtraction and drying on acid and oxidizing conditions, activated carbon is in reflux treatment with urea solution; and the catalyst can be prepared by soaking the treated activated carbon with HgC12 dissolved in hydrochloric acid and assistant solution sufficiently after urea is removed by steps of heating, washing the activated carbon with hydrochloric acid and finally drying the same. The carrying capacity of mercuric chloride in the catalyst is lower so that cost for the catalyst is reduced and consumption of mercury resources is decreased. Furthermore, activity and stability of the low-mercury catalyst are much higher than those of the existing high-mercury catalyst, and reforming rate and selectivity of reaction of vinyl chloride can be 99.7% and be higher than 99.8%. Accordingly, the low-mercury catalyst for acetylene hydrochlorination is suitable for industry production and is environment-friendly.

Description

technical field [0001] The invention relates to a low-mercury catalyst for the preparation of vinyl chloride from acetylene through hydrochlorination, and a method for preparing the catalyst. Background technique [0002] Polyvinyl chloride (PVC), which is synthesized from vinyl chloride monomer, is one of the raw materials for thermoplastic resin products with the largest output in the world. It is widely used in plastic building materials, packaging materials, electronic and electrical products, pharmaceutical industry, coatings and adhesives, etc. . [0003] At present, the industrial production of vinyl chloride monomer in the world is mainly based on the ethylene method. Affected by the large fluctuations in crude oil prices, the production of PVC from acetylene through hydrochlorination occupies an important position in China. At present, the industrial acetylene hydrochlorination reaction mainly uses high-mercury catalysts with a loading of mercuric chloride of 12%...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/138C07C21/06C07C17/08
Inventor 蒋文伟周莹杨琴罗芩李晶晶
Owner CHENGDU HUIEN FINE CHEM
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