A kind of palladium catalyst complexed with sulfide ionic liquid and its preparation method and application

A technology of ionic liquid and palladium catalyst, which is applied in the direction of organic compound/hydride/coordination complex catalyst, physical/chemical process catalyst, catalytic reaction, etc., can solve the problem that is not suitable for improving the deactivation and large-scale The limitations of the industrial application of production equipment, the unsatisfactory catalyst stability and other problems, to achieve good economy and industrial application value, high stability and low loading effect

Active Publication Date: 2020-07-28
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0014] Chinese patent application (CN 102357336 A) discloses using molecular sieves such as HZSM-5, NaZSM-5, and zeolite as carriers to support PdCl 2 The prepared catalyst, at the feed gas ratio V (HCl) / V (C2H2) Under the condition of =1.15, the acetylene hydrochlorination reaction performance test was carried out at 160 °C, and the reaction tail gas was analyzed. The initial conversion rate of acetylene of the catalyst was 89.78%, and the selectivity of vinyl chloride was 98.62%. The catalyst activity was low and did not meet the requirements of industrialization
Chinese patent CN101716528 discloses an ionic liquid dissolving metal chlorides such as gold, platinum, palladium, tin, mercury, copper or rhodium as a catalyst system, which is applied to acetylene hydrochlorination, but the reaction system belongs to a gas-liquid reaction system, and there is The mass transfer efficiency of reactants and products is low, stirring or pneumatic stirring is easy to cause the loss of catalyst active components, etc., and the industrial application of large-scale production equipment is particularly limited.
[0019] 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 stability of the catalyst 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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  • A kind of palladium catalyst complexed with sulfide ionic liquid and its preparation method and application
  • A kind of palladium catalyst complexed with sulfide ionic liquid and its preparation method and application
  • A kind of palladium catalyst complexed with sulfide ionic liquid and its preparation method and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066] Select columnar activated carbon as the carrier, its particle size is 40 mesh, the ash content is 3.0wt%, and the specific surface area is 950m 2 / g, a pore volume of 0.45 mL / g, and treated with 300 ml of 10 wt% hydrochloric acid at 25° C. for 3 h. The treated carrier was washed with deionized water until neutral, dried at 110 °C for 12 h, and used for later use.

[0067] Synthesis of Sulfide Ionic Liquid A:

[0068] The ionic liquid 1-butyl-3-methylimidazolium chloride and sulfur powder were mixed in a mass ratio of 1:0.5, stirred in a water bath at 40 °C for 10 min, and then added with acetonitrile solution, dissolved, and stirred at 40 °C for 12 hours. The above mixed solution was stirred evenly, then filtered to remove unreacted sulfur powder, and the obtained filtrate was dried at 110 ° C. Subsequently, the sample obtained after drying was dissolved in dichloromethane, and an appropriate amount of desulfurization was added. Ionized water and sodium bicarbonate so...

Embodiment 2

[0072] The main difference between this example and Example 1 is that the type of ionic liquid is different, and its influence on the catalytic performance of the catalyst is studied.

[0073] Synthesis of Sulfide Ionic Liquid B:

[0074] Mix the ionic liquid 1-propyl-3-methylimidazolium tetrafluoroborate with sulfur powder in a mass ratio of 1:0.5, stir in a water bath at 40 °C for 10 min, add acetonitrile solution, dissolve, and stir at 40 °C After 12 hours, the above mixture was stirred evenly, then filtered to remove the unreacted sulfur powder, and the obtained filtrate was dried at 110°C. Appropriate amount of deionized water and sodium bicarbonate solution were used to further remove impurities in the solution. Finally, after drying the above mixture at 110 °C for 16 hours, recrystallized at room temperature to obtain the required sulfide ionic liquid. B.

[0075] Select columnar activated carbon as the carrier, its particle size is 40 mesh, the ash content is 3.0wt%,...

Embodiment 3

[0079] Select columnar activated carbon as the carrier, its particle size is 40 mesh, the ash content is 3.0wt%, and the specific surface area is 950m 2 / g, pore volume 0.6 mL / g, and treated with 300 ml of 10 wt% hydrochloric acid at 25° C. for 3 h. The treated carrier was washed with deionized water until neutral, dried at 110 °C for 12 h, and used for later use.

[0080] Synthesis of Sulfide Ionic Liquid A:

[0081] The ionic liquid 1-butyl-3-methylimidazolium chloride and sulfur powder were mixed in a mass ratio of 1:0.5, stirred in a water bath at 40 °C for 10 min, and then added with acetonitrile solution, dissolved, and stirred at 40 °C for 12 hours. The above mixed solution was stirred evenly, then filtered to remove unreacted sulfur powder, and the obtained filtrate was dried at 110 ° C. Subsequently, the sample obtained after drying was dissolved in dichloromethane, and an appropriate amount of desulfurization was added. Ionized water and sodium bicarbonate solution...

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Abstract

The invention discloses a vulcanized ionic liquid complex palladium catalyst, and a preparation method and applications thereof. According to the preparation method, an ionic liquid is subjected to sulfuration modification to introduce sulfur containing groups, and the treated ionic liquid is loaded with PdCl2 precursor so as to form a Pd-S-IL system with a special structure, and increase both thereaction activity and the stability of the palladium catalyst. The supported ionic liquid promoted palladium catalyst possesses relatively high stability in ethyne hydrochlorination, after 6000h of operation, no palladium loss is detected, the highest ethyne conversion rate is 99.8%, and the highest vinyl chloride selectivity is 99.95%.

Description

Background technique [0001] Polyvinyl chloride (PVC) is an important general-purpose plastic. Due to the characteristics of rich coal, poor oil and little gas in my country, the preparation of vinyl chloride by calcium carbide acetylene method is the mainstream process of PVC production in my country. Mercury chloride is an existing catalyst for industrial synthesis of vinyl chloride, which causes serious pollution to the environment, and the synthesized polyvinyl chloride contains a small amount of mercury, which limits the application of polyvinyl chloride. Therefore, the mercury chloride catalyst will be gradually eliminated, and the synthesis of vinyl chloride without mercury catalyst will become the main direction of the future sustainable development of calcium carbide PVC. Mercury-free catalysts mainly use metal chlorides as active components, among which noble metal chlorides have the best catalytic activity. Gold is considered to be the most promising catalyst for t...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J31/22B01J31/26C07C17/08C07C21/06
CPCB01J31/226B01J31/26B01J2231/32B01J2531/824C07C17/08C07C21/06
Inventor 李小年赵佳张群峰丰枫
Owner ZHEJIANG UNIV OF TECH
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