Supported Catalyst, Its Activated Form, and their Preparation and Use

Abstract

A supported catalyst and preparation method thereof, the catalyst comprising an organic polymer material carrier and Raney alloy particles supported on the organic polymer material carrier, wherein substantially all of the Raney alloy particles are partially embedded in the organic polymer material carrier. The catalyst can be used in hydrogenation, dehydrogenation, amination, dehalogenation or desulfuration reactions.

What is claimed is: 
     
         1 . A supported catalyst, comprising: an organic polymer material support and Raney alloy particles supported on the organic polymer material support, wherein substantially all of the Raney alloy particles are partially embedded into the organic polymer material support. 
     
     
         2 . The catalyst of  claim 1 , wherein the Raney alloy comprises at least one Raney metal and at least one leachable element. 
     
     
         3 . The catalyst of  claim 2 , wherein the at least one Raney metal is chosen from nickel, cobalt, copper, and iron, and the at least one leachable element is chosen from aluminum, zinc, and silicon. 
     
     
         4 . The catalyst of  claim 2 , wherein the weight ratio of the Raney metal to the leachable element in the Raney alloy is from 1:99 to 10:1. 
     
     
         5 . The catalyst of  claim 4 , wherein the weight ratio of the Raney metal to the leachable element in the Raney alloy is from 1:10 to 4:1. 
     
     
         6 . The catalyst of  claim 2 , wherein the Raney alloy further comprises at least one promoter chosen from Mo, Cr, Ti, and Ru in an amount of from 0.01 wt. % to 5 wt. %, based on the total weight of the Raney alloy. 
     
     
         7 . The catalyst of any one of  claims 1  to  6 , wherein the organic polymer material is a plastic or a modified plastic. 
     
     
         8 . The catalyst of any one of  claims 1  to  6 , wherein the organic polymer material is chosen from polyolefins, polyamides, polystyrenes, epoxy resins, phenolic resins, and mixtures and blends thereof. 
     
     
         9 . The catalyst of any one of  claims 1  to  6 , wherein the organic polymer material is chosen from polypropylenes, Nylon-6, Nylon-66, polystyrenes, phenolic resins, epoxy resins, and mixtures and blends thereof. 
     
     
         10 . The catalyst of any one of  claims 1  to  9 , wherein in the catalyst, the Raney alloy particles are distributed unevenly, with the concentration of the Raney alloy particles in the surface portion of the support being greater than the concentration of the Raney alloy particles in the core portion of the support. 
     
     
         11 . A process for preparing the catalyst of any one of  claims 1  to  10 , comprising: mould pressing an organic polymer material support surrounded by Raney alloy particles at the mould processing temperature of the organic polymer material for a thermoplastic organic polymer material or under conditions of uncure for a thermoset organic polymer material. 
     
     
         12 . The process of  claim 11 , which is one of:
 process (i) comprising the steps of:   (1) providing thermoplastic organic polymer material particles having desired size and shape;   (2) placing the organic polymer material particles in Raney alloy particles so as to make the organic polymer material particles completely surrounded by the Raney alloy particles;   (3) pressing the mixture of the Raney alloy particles and the thermoplastic organic polymer material particles at the mould processing temperature of the thermoplastic organic polymer material so as to push a certain amount of the Raney alloy particles at least partially into the thermoplastic organic polymer material support particles; and   (4) cooling, then sieving, to obtain particulate supported catalyst,   process (ii) comprising the steps of:   (1) providing a thermoplastic organic polymer material sheet having a desired thickness;   (2) uniformly spreading Raney alloy particles on one or both of the upper and lower surfaces of the sheet;   (3) pressing the sheet having the Raney alloy particles spread thereon at the mould processing temperature of the thermoplastic organic polymer material so as to push a certain amount of the Raney alloy particles at least partially into the sheet, to obtain a support sheet carrying the Raney alloy particles in its surface layer; and   (4) optionally after cooling, forming the support sheet carrying the Raney alloy particles on its surface into particles having desired shape and size, to obtain particulate supported catalyst,   process (iii) comprising the steps of:   (1) formulating a curable composition, which is curable to a thermoset organic polymer material, and which may be a liquid system or a powdery solid system;   (2) to a mould having a desired particle size and cavity shape suitable for fixed bed catalysts or fluidized bed catalysts, adding first Raney alloy particles, then the curable composition formulated in step (1), and then the Raney alloy particles, and then subjecting the thermoset organic polymer material to partially curing treatment, to provide a partially cured particulate support surrounded by the Raney alloy particles;   (3) then, pressing the partially cured particulate support surrounded by the Raney alloy particles to push a certain amount of the Raney alloy particles at least partially into the particulate support and, at the same time or thereafter, completely curing the thermoset organic polymer material; and   (4) sieving, to obtain particulate supported catalyst,   process (iv) comprising the steps of:   (1) formulating a curable composition, which is curable to a thermoset organic polymer material, and which may be a liquid system or a powdery solid system;   (2) partially curing the curable composition in a suitable mould to provide a partially cured organic polymer material sheet, wherein the curing degree is such that the partially cured organic polymer material allows Raney alloy particles to be pressed thereinto in a sequent step;   (3) uniformly spreading Raney alloy particles on one or both of the upper and lower surfaces of the sheet;   (4) pressing the sheet having the Raney alloy particles spread thereon so as to push a certain amount of the Raney alloy particles at least partially into the sheet and, at the same time or thereafter, completely curing the thermoset organic polymer material; and   (5) forming the sheet from step (4) into particles having desired shape and size, to obtain particulate supported catalyst, and   process (v) comprising the steps of:   (1) preparing partially cured thermoset organic polymer material particles having desired shape and size from a curable composition which is curable to the thermoset organic polymer material, with the curing degree of the partially cured thermoset organic polymer material particles being such that it allows Raney alloy particles to be pressed thereinto in a sequent step;   (2) placing the partially cured thermoset organic polymer material particles in the Raney alloy particles so as to make them completely surrounded by the Raney alloy particles;   (3) pressing the mixture of the Raney alloy particles and the partially cured thermoset organic polymer material particles to push a certain amount of the Raney alloy particles at least partially into the organic polymer material support particles and, at the same time or thereafter, completely curing the partially cured thermoset organic polymer material; and   (4) sieving, to obtain the particulate supported catalyst.   
     
     
         13 . An activated, supported catalyst, which comprises an organic polymer material support and activated Raney alloy particles supported on the organic polymer material support, wherein substantially all of the activated Raney alloy particles are partially embedded into the organic polymer material support. 
     
     
         14 . The catalyst of  claim 13 , which is prepared by activating the supported catalyst according to any one of  claims 1  to  10  with a caustic aqueous solution. 
     
     
         15 . A process for preparing the activated, supported catalyst of  claim 13 , comprising:
 (1) mould pressing an organic polymer material support surrounded by Raney alloy particles at the mould processing temperature of the organic polymer material for a thermoplastic organic polymer material or under conditions of uncure for a thermoset organic polymer material, to provide a supported catalyst with Raney alloy particles supported on the organic polymer material;   (2) activating the supported catalyst from step (1) by treating it with a caustic aqueous solution, to form the activated, supported catalyst.   
     
     
         16 . The process of  claim 15 , wherein the caustic aqueous solution is an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration of from 0.5 to 50 wt. %. 
     
     
         17 . Use of the catalyst of  claim 13  in hydrogenation, dehydrogenation, amination, dehalogenation, or desulfuration reaction. 
     
     
         18 . The use of  claim 13 , wherein the reaction is olefin hydrogenation reaction, alkyne hydrogenation reaction, arene hydrogenation reaction, carbonyl hydrogenation reaction, or nitrile hydrogenation reaction. 
     
     
         19 . The use of  claim 17  or  18 , wherein the reaction is carried out in a fixed bed or fluidized bed process.