Catalyst for preparing vinyl chloride, methods of preparation and application thereof

• US 9,056,305 B2
• Filed: 10/26/2011
• Issued: 06/16/2015
• Est. Priority Date: 10/26/2011
• Status: Active Grant

• Current Assignee: Shanghai Advanced Research Institute,Chinese Academy of Sciences
• Original Assignee: Shanghai Advanced Research Institute, CAS, Zhongke Yigong (Xiamen) Chemical Technology Co., Ltd.
• Inventors: Jiang, Biao, Zhong, Jinguang
• Primary Examiner(s): Hailey, Patricia L
• Application Number:
  US13/806,726
• Publication Number:
  US 20130204052A1
• Time in Patent Office: 1,329 Days
• Field of Search: 502/5, 502/183, 502/208, 570/227
• US Class Current: 1/1
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/02 of the alkali- or alkaline earth metals or beryllium
• CPC Class Codes: B01J 27/138 with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
• CPC Class Codes: B01J 27/1806 with alkaline or alkaline earth metals
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: B01J 37/0201 Impregnation
• CPC Class Codes: B01J 37/0203 the impregnation liquid containing organic compounds
• CPC Class Codes: B01J 37/0223 by rotation
• CPC Class Codes: B01J 37/084 Decomposition of carbon-containing compounds into carbon
• CPC Class Codes: C07C 17/08 to unsaturated hydrocarbons
• CPC Class Codes: C07C 17/25 by splitting-off hydrogen halides from halogenated hydrocarbons
• CPC Class Codes: C07C 21/06 Vinyl chloride

Abstract

The present invention discloses a catalyst used in preparing vinyl chloride, its method of preparation, and its applications. Said catalyst used in making vinyl chloride comprises activated carbon as a support, a barium compound and a phosphorus compound supported thereon. The barium compound accounts for 0.2% to 20% of the total mass of the catalyst and the phosphorus compound accounts for 0% to 10% of the total mass of the catalyst based on the mass percentage. A water-soluble barium compound, a water-soluble phosphorus compound, an aqueous polymer monomer, and water are mixed to form a solution or emulsion A. The activated carbon is added into the solution or emulsion A. The activated carbon is removed from water after impregnation, spin-dried, and then the monomers are polymerized. The activated carbon, after polymerization step, is heated to remove water and to decompose and carbonize the polymer. The catalyst after carbonization was activated to obtain a catalyst used in making vinyl chloride.

Claims

1. A catalyst for the preparation of vinyl chloride, characterized in that:

said catalyst comprises activated carbon as a carrier, a barium compound and a phosphorus compound supported on the carrier, wherein said barium compound has a mass percentage of 0.2% to 20% and said phosphorous compound has a mass percentage of less than 10% based on the total mass of the catalyst,

wherein said phosphorus compound is phosphoric acid.

2. The catalyst of claim 1, wherein said barium compound is barium chloride.

3. A method for preparing a catalyst used in preparing vinyl chloride, comprising the steps of:

(1) mixing a water-soluble barium compound, a water-soluble phosphorus compound, an aqueous polymer monomer, and water to obtain a solution or an emulsion;

(2) impregnating the activated carbon in the solution or the emulsion;

(3) polymerizing the aqueous polymer monomer on the activated carbon after spin-drying to form an aqueous polymer;

(4) heating the aqueous polymer supported on the activated carbon to form a carbonized polymer;

(5) activating the activated carbon having the carbonized polymer supported thereon.

4. The preparation method according to claim 3, wherein, in the Step (1), said water-soluble barium compound is barium chloride and a concentration of an aqueous solution of said water-soluble barium compound is 0.3% to 30%;

said water-soluble phosphorus compound is phosphoric acid and a concentration of an aqueous solution of a water-soluble compound of the said phosphorus is less than 10%.

5. The preparation method according to claim 3, wherein, in step (1), the aqueous polymer monomer is capable of polymerization into a gel that is water soluble or is capable of forming an emulsion with water, said aqueous polymer monomer is chosen from at least one among acrylic compounds, vinyl ester compounds, acrylamide, a mixture of urea and formaldehyde, a mixture of phenol and formaldehyde, a mixture of melamine and formaldehyde, and aqueous polyurethane monomer, wherein a concentration of the aqueous polymer monomer in the solution or the emulsion is 0.1% to 30%.

6. The method according to claim 3, wherein, in Step (2), said impregnation is carried out under vacuum at a temperature ranging from room temperature to 100°

C. for 1 hours to 48 hours.

7. The method according to claim 3, wherein, in Step (3), the aqueous polymer monomer polymerizes using heating, light initiation, or by spraying an initiator.

8. The method according to claim 3, wherein, in Step (4), the heating is carried out in an inert gas at a temperature ranging from 200°

C. to 800°

C. until the aqueous polymer decomposes and carbonizes.

9. The method according to claim 3, wherein, in Step (5), the activation is carried out in an inert gas or a weakly oxidizing gas, wherein said inert gas is nitrogen and said weak oxidizing gas is carbon dioxide or steam, wherein said activation temperature ranges from 400°

C. to 1000°

C. and said activation time ranges from 0.5 hours to 24 hours.

10. A method of preparing vinyl chloride, comprising the step of:

obtaining a catalyst;

reacting acetylene and dichloroethane in the presence of said catalyst,

wherein said catalyst comprises activated carbon as a carrier, a barium compound and a phosphorus compound supported on the carrier, wherein said barium compound has a mass percentage of 0.2% to 20% and said phosphorous compound has a mass percentage of less than 10% based on the total mass of the catalyst,

wherein said phosphorus compound is phosphoric acid.

11. The method of preparing vinyl chloride of claim 10, wherein said barium compound is barium chloride.