Ionic liquid-promoted palladium-based catalyst and application thereof to catalytic hydrogenation and halogenation of unsaturated hydrocarbons

A technology of ionic liquid and palladium catalyst, which is applied in the direction of catalyst activation/preparation, catalytic reaction, physical/chemical process catalyst, etc., can solve the problems of active component loss, high cost, low conversion rate of acetylene, etc., and achieve simple preparation and operation Convenient, highly reactive effect

Active Publication Date: 2018-03-23
ZHEJIANG UNIV OF TECH
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Problems solved by technology

[0004] The literature (Catalysis Communications 83 (2016) 9-13) reported that adding KCl to the Pd/NFY catalyst can improve the stability of the catalyst, but at 160 °C, V(HCl)/V(C 2 h 2 )=1.25 After reacting for 10h, there is still 37.8% Pd species loss in the Pd-K/NFY catalyst
[0005] Chinese patent application (CN 101716508 A) discloses that palladium chloride is used as an active component, lanthanum chloride is used as an auxiliary agent, and the raw material gas ratio V(HCl)/V(C 2 h 2 )=1.05, the acetylene hydrochlorination reaction performance test was carried out at 150°C, and the reaction tail gas was analyzed. The acetylene conversion rate of the catalyst was 98.2%, and the vinyl chloride selectivity was 98%. Although the catalyst has high stability and activity, the precious metal High load mass fraction, which makes it expensive and impractical for industrial applications
[0014] Chinese patent application (CN 102357336 A) discloses that molecular sieves such as HZSM-5, NaZSM-5, and zeolite are used as carriers to support PdCl 2 Prepared catalyst, in raw gas ratio V(HCl)/V(C 2 h 2 ) = 1.15 under the condition of 160 ℃ for acetylene hydrochlorination reaction performance test, analysis of the reaction tail gas, the initial conversion rate of acetylene of the catalyst is 89.78%, the selectivity of vinyl chloride is 98.62%, the activity of the catalyst is relatively low, and does not meet the requirements of industrialization
[0018] Chinese patent application (CN 101716528 A) 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 gas liquid reaction system, there are deficiencies such as low mass transfer efficiency of reactants and products, and easy loss of active components of the catalyst due to stirring or pneumatic stirring. bed or fluidized bed
[0019] C...

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0063] Select columnar activated carbon as the carrier, its particle size is 40 mesh, the ash content is 5.0wt%, and the specific surface area is 950m 2 / g, pore volume 0.8mL / g, and treated with 300ml of 10wt% hydrochloric acid at 20°C for 0.5h. Dry at 110°C for 20 hours and set aside. 50ml of H 2 PdCl 4 The solution (wherein the Pd content is 0.001g / ml) is mixed with 2.5g of 1-butyl-3-methylimidazolium chloride salt, and the mixed solution is added dropwise on the 100g activated carbon carrier under the action of ultrasonic waves at 20°C. The immersion time was 6 hours. Then at 30°C, add 10ml of Na to the above system dropwise under the action of ultrasound. 2 S solution (wherein the S content is 0.01g / ml), and 20ml of deionized water, and soaked for 1 hour under the action of ultrasonic waves. The impregnated catalyst was vacuum-dried at 120° C. for 3 hours to obtain catalyst A, wherein the loading of Pd (relative to the mass of the carrier) was 0.05 wt%, the loa...

Embodiment 2

[0066] Select columnar carbon nanotubes as the carrier, the particle size is 60 mesh, the ash content is 3.0wt%, and the specific surface area is 450m 2 / g, the pore volume is 0.62mL / g, and it is treated with 300ml of 10wt% hydrochloric acid at 40°C for 20h. Dry at 200°C for 0.5h for later use. 20ml of Na 2 PdCl 4 The solution (wherein the Pd content is 0.05g / ml) is mixed with 25g of N-hexylpyridinium bromide, and the mixture is added dropwise to 100g of carbon nanotube carrier under the action of ultrasonic waves at 60°C, and the immersion time is 6 hours under the action of ultrasonic waves . Then, at 40° C., 10 ml of KHS solution (in which the S content is 0.5 g / ml) and 32 ml of deionized water were added dropwise to the above system under the action of ultrasonic waves, and immersed for 20 hours under the action of ultrasonic waves. The impregnated catalyst was vacuum-dried at 60° C. for 30 hours to obtain the B catalyst, wherein the Pd load (relative to the ma...

Embodiment 3

[0069] Select columnar graphene as the carrier, its particle size is 80 mesh, the ash content is 2.1wt%, and the specific surface area is 650m 2 / g, pore volume 0.4mL / g. 10ml of (NH 4 ) 2 PdCl 4 The solution (wherein the Pd content is 0.005g / ml) is mixed with the tetrafluoroborate of 20g of N-butyl-N-methylpyrrolidine, and the mixed solution is added dropwise to the 100g graphene carrier under the action of ultrasonic waves at 20°C On, the immersion time is 4 hours under the action of ultrasonic waves. Then at 20°C, add 10ml of (NH 4 ) 2 S 2 o 3 solution (wherein the S content is 0.01g / ml), and 20ml of deionized water, and soaked for 8 hours under the action of ultrasonic waves. The impregnated catalyst was vacuum-dried at 90° C. for 9 hours to obtain catalyst C, in which the Pd load (relative to the mass of the support) was 0.05 wt%, the load of the S element (relative to the mass of the support) was 0.1 wt%, and the load of the ionic liquid (relative carrier...

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Abstract

The invention discloses a porous solid carrier-supported ionic liquid-promoted palladium catalyst. The catalyst is prepared according to the following method: mixing a prepared palladium-containing solution and an ionic liquid to obtain a mixed solution; dropwise adding the mixed solution to a porous solid carrier at a temperature of 20-60 DEG C under action of ultrasonic waves, and performing impregnation under the effect of ultrasonic waves for 0.5-6 hours by employing an equivalent-volume impregnation method; dropwise adding an inorganic salt solution to the porous solid carrier impregnatedwith the mixed solution under the action of ultrasonic waves at a temperature of 20-60 DEG C, and performing impregnation under the action of ultrasonic waves for 1 to 20 hours; and performing vacuumdrying at a temperature of 60-120 DEG C for 3 to 30 hours, so as to obtain the supported type ionic liquid-promoted palladium catalyst. The active components of the catalyst are not easily sublimated. The catalyst has good stability, long running time, high catalytic activity, simple preparation and convenient operation.

Description

Background technique [0001] Polyvinyl chloride (PVC) is an important general-purpose plastic. Due to the energy storage 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 polyvinyl chloride production in my country. Mercury chloride is currently used as a catalyst for the synthesis of vinyl chloride in the industry. Because it causes serious pollution to the environment, and the synthesized polyvinyl chloride contains a small amount of mercury, the application of polyvinyl chloride is limited. Therefore, the mercury chloride catalyst will be gradually eliminated, and the synthesis of vinyl chloride under the condition of mercury-free catalyst will become the main direction for the future sustainable development of calcium carbide method PVC. Mercury-free catalysts mainly use metal chlorides as active components, among which noble metal chlorides exhibit the bes...

Claims

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Application Information

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IPC IPC(8): B01J31/28B01J31/38C07C17/08C07C21/06
CPCB01J31/0292B01J31/28B01J31/38B01J37/0203B01J37/024B01J37/343B01J2231/32C07C17/08C07C21/06
Inventor 李小年赵佳张群峰王柏林卢春山吕井辉
Owner ZHEJIANG UNIV OF TECH
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