Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

A high temperature stable palladium complex in an acetylene atmosphere and its application

A composite, palladium compound technology, applied in chemical/physical process, physical/chemical process catalyst, catalyst activation/preparation, etc., can solve the loss of active components, decrease in catalyst activity, and is not suitable for improving the loss of supported palladium catalyst. problems such as living, to achieve the effect of simple preparation and convenient operation

Active Publication Date: 2020-04-24
ZHEJIANG UNIV OF TECH
View PDF6 Cites 0 Cited by
  • 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] The particle size of the 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, treated with 300ml of hydrochloric acid with a concentration of 10wt% at 20°C for 3h, and then dried at 110°C for 12h to obtain the required carrier.

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

[0047] 2g of this catalyst is used in the hydrochlorin...

Embodiment 2

[0049] γ-Al 2 O 3 The particle size is 20 mesh, the specific surface area is 200m 2 / g, pore volume 0.6mL / g. Add 20ml of Na 2 PdCl 4 The solution (with Pd content of 0.05g / ml) and 10ml of KHS solution (with S content of 0.03g / ml) mixed uniformly, add an appropriate amount of deionized water to make the volume up to 60ml, and add dropwise under the action of 60℃ and ultrasonic To 100g columnar γ-Al 2 O 3 On the carrier, the catalyst was vacuum dried at 90°C for 10 hours. The catalyst was tested to be PdS 1.9 Cl 0.1 / γ-Al 2 O 3 , Wherein Pd loading (relative to carrier mass) is 1wt%, and S element loading (relative to carrier mass) is 0.3wt%.

[0050] 2g of this catalyst is used in the acetylene hydrochlorination reaction in a fixed bed reactor. The reaction conditions are: temperature 180℃, pressure 0.2MPa, n(HCl) / n(C 2 H 2 )=1.2 / 1, acetylene space velocity 60h -1 . In the initial stage of the reaction, the acetylene conversion rate was 39.4%, and the vinyl chloride selectivity wa...

Embodiment 3

[0052] SiO 2 The particle size is 80 mesh, the specific surface area is 100m 2 / g, pore volume 0.6mL / g. Add 50ml of (NH 4 ) 2 PdCl 4 Solution (where Pd content is 0.008g / ml) and 10ml (NH 4 ) 2 S 2 O 3 The solution (with S content of 0.01g / ml) is mixed uniformly, and added dropwise to 100g columnar SiO under the action of 50℃ and ultrasonic 2 On the carrier, the catalyst was vacuum dried at 80°C for 15 hours. The catalyst was tested to be PdS 0.8 Cl 0.4 / SiO 2 , Wherein Pd loading (relative to carrier mass) is 0.4wt%, and S element loading (relative to carrier mass) is 0.1wt%.

[0053] 2g of this catalyst is used in the hydrochlorination of acetylene in a fixed bed reactor. The reaction conditions are: temperature 150℃, pressure 0.3MPa, n(HCl) / n(C 2 H 2 ) = 1.05 / 1, acetylene space velocity 10h -1 . In the initial stage of the reaction, the acetylene conversion rate was 99.9%, and the vinyl chloride selectivity was 99.9%; after the reaction for 2000 hours, the acetylene conversion r...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

PropertyMeasurementUnit
specific surface areaaaaaaaaaaa
concentrationaaaaaaaaaa
concentrationaaaaaaaaaa
Login to View More

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 specifically relates to a palladium composite that 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 a monomer of polyvinyl chloride (PVC), one of the world's five largest synthetic resins, and is mainly produced by the calcium carbide acetylene method and the petroleum ethylene method. China's coal-rich, oil-poor, and low-gas energy resources determine that for a long time in the future, the calcium carbide acetylene process will continue to be the main process for the production of vinyl chloride in my country, that is, mercury 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 health...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
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
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products