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Palladium compound being stable in acetylene atmosphere at high temperature, and application thereof

A complex and palladium compound technology, applied in chemical/physical processes, physical/chemical process catalysts, catalyst activation/preparation, etc., can solve the problems of active component loss, catalyst activity decline, loss, etc., to achieve convenient operation and preparation simple effect

Active Publication Date: 2018-03-16
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

(3) in PdCl 2 Addition of BiCl to the catalyst system 3 Partially inhibited carbon deposition, but could not effectively inhibit PdCl 2 PdCl formed with acetylene 2 ·C 2 h 2 Sublimation loss of the complex [Sichuan Chemical Industry, 2007,10(5):13-15]
(3) Use Y-type zeolite instead of activated carbon as a carrier, add KCl additive or NH 4 F modified Y zeolite carrier, etc., but still failed to inhibit PdCl 2 PdCl formed with acetylene 2 ·C 2 h 2 Sublimation loss of the complex [Wang et.al., Reaction Kinetics Mechanisms & Catalysis, 2013, 110(1): 187-194;
The point of view of this literature is different from that of most supported gold catalysts, but it is difficult to provide a reference for improving the loss and deactivation of supported palladium catalysts
[0007] In summary, improving the stability of supported palladium-based catalysts in acetylene hydrochlorination is still a major unsolved challenge. Although adding additives and other methods can slow down its loss, the modified method The catalyst stability is still unsatisfactory, which shows that the activity of the catalyst decreases significantly during the long-term evaluation time, and the problem of the loss of active components has not been fundamentally solved, mainly because the structure and composition of the active center have not changed. Adding sulfur-containing compounds as promoters to supported gold catalysts can improve its catalytic performance, but the mechanism of promoters mentioned in the existing literature is not suitable for improving the deactivation of supported palladium catalysts due to sublimation

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] The particle size of activated carbon is 40 mesh, the ash content is 5.0wt%, and the specific surface area is 900m 2 / g, pore volume 1.0mL / g, and treated with 300ml of 10wt% hydrochloric acid at 20°C for 3h, and then dried at 110°C for 12h to obtain the desired carrier.

[0046] 50ml of K 2 PdCl 4 solution (wherein the Pd content is 0.001g / ml) and 10ml of Na 2 The S solution (wherein the S content is 0.00015g / ml) was mixed evenly, and an appropriate amount of deionized water was added to make the volume to 100ml, and was added dropwise to 100g spherical activated carbon carrier at 30°C under the action of ultrasonic waves. Immersed for 5h under the action of ultrasonic waves, and then the catalyst was vacuum dried at 110°C for 5h, and the catalyst was tested to be PdS 0.1 Cl 1.8 / AC, wherein the Pd loading (relative to the mass of the support) is 0.05wt%, and the loading of S element (relative to the mass of the support) is 0.0015wt%.

[0047] Take 2g of this catal...

Embodiment 2

[0049] γ-Al 2 o 3 The particle size is 20 mesh and the specific surface area is 200m 2 / g, pore volume 0.6mL / g. 20ml of Na 2 PdCl 4 solution (in which the Pd content is 0.05g / ml) and 10ml of KHS solution (in which the S content is 0.03g / ml) are mixed evenly, add an appropriate amount of deionized water to make the volume to 60ml, and add it drop by drop under the action of ultrasonic waves at 60°C to 100g columnar γ-Al 2 o 3 Carrier, then the catalyst was dried in vacuum at 90°C for 10h, and the catalyst was detected to be PdS 1.9 Cl 0.1 / γ-Al 2 o 3 , wherein the loading of Pd (relative to the mass of the support) is 1 wt%, and the loading of S element (relative to the mass of the support) is 0.3 wt%.

[0050] Take 2g of this catalyst and apply it to the hydrochlorination of acetylene in a fixed bed reactor. The reaction conditions are: temperature 180°C, pressure 0.2MPa, n(HCl) / n(C 2 h 2 )=1.2 / 1, acetylene space velocity 60h -1 . At the beginning of the reaction...

Embodiment 3

[0052] SiO 2 The particle size is 80 mesh and the specific surface area is 100m 2 / g, pore volume 0.6mL / g. 50ml of (NH 4 ) 2 PdCl 4 solution (wherein the Pd content is 0.008g / ml) and 10ml of (NH 4 ) 2 S 2 o 3 The solution (in which the S content is 0.01g / ml) was mixed evenly, and was added dropwise to 100g columnar SiO 2 Carrier, then the catalyst was dried in vacuum at 80°C for 15h, and the catalyst was detected to be PdS 0.8 Cl 0.4 / SiO 2, wherein the loading of Pd (relative to the mass of the support) is 0.4wt%, and the loading of S element (relative to the mass of the support) is 0.1wt%.

[0053] Take 2g of this catalyst and apply it to the hydrochlorination of acetylene in a fixed bed reactor. The reaction conditions are: temperature 150°C, pressure 0.3MPa, n(HCl) / n(C 2 h 2 ) = 1.05 / 1, acetylene space velocity 10h -1 . At the beginning of the reaction, the conversion rate of acetylene was 99.9%, and the selectivity of vinyl chloride was 99.9%. After 2000 ho...

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Abstract

The invention provides a palladium compound PdSxCl2-2x (wherein x is more than 0 and less than 1) being stable in an acetylene atmosphere at a high temperature and having a catalysis activity on acetylene hydrochlorination for synthesizing vinyl chloride. The palladium compound comprises a porous solid carrier and a PdSxCl2-2x compound supported on the surface of the porous solid carrier, the PdSxCl2-2x compound is a PdSxCl2-2x ionic compound formed through using Pd as the core and bonding S and Cl with Pd through ionic bonds, wherein x is more than 0 and less than 1, the loading quantity of the Pd element is 0.05-1% of the weight of the carrier, and the loading quantity of the S element is 0.1-5% of the weight of the carrier. The ionic bonds between Pd and S and between Pd and Cl in the PdSxCl2-2x compound formed through introducing the S element to the PdSxCl2-2x compound are stronger than ionic bonds of PdCl2 or [PdCl4]<2->, so sublimation induced loss of a complex formed by the PdSxCl2-2x compound used as an active site and C2H2 is difficult, thereby the stability of the supported palladium catalyst in an acetylene hydrochlorination reaction is improved.

Description

technical field [0001] The invention belongs to the technical field of catalyst materials, and in particular relates to a palladium complex which is stable at high temperature in an acetylene atmosphere and has the activity of catalyzing the hydrochlorination of acetylene to synthesize vinyl chloride. Background technique [0002] Vinyl chloride is the monomer of polyvinyl chloride (PVC), one of the five largest synthetic resins in the world, and is mainly produced by the calcium carbide acetylene method and the petroleum ethylene method. China's coal-rich, oil-poor, and gas-poor energy reserves determine that the calcium carbide acetylene method will continue to be the main process for the production of vinyl chloride in my country for a long time to come, that is, mercuric chloride catalyzes the reaction of acetylene and hydrogen chloride to produce vinyl chloride. However, the highly toxic mercuric chloride catalyst seriously pollutes the environment and endangers human h...

Claims

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Application Information

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IPC IPC(8): B01J27/13C07C17/08C07C21/06
CPCB01J27/13B01J37/0207B01J37/343C07C17/08C07C21/06
Inventor 李小年赵佳谷山川张群峰丰枫卢春山吕井辉
Owner ZHEJIANG UNIV OF TECH
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