Method of preparation of ion exchangers molded catalyst

 

The invention relates to the production of ion exchangers molded catalysts used in organic synthesis. Describes the method of preparation of ion exchangers molded catalyst by mixing the copolymer based on styrene and divinylbenzene, and a thermoplastic material, molding the mixture by extrusion with subsequent sulfonation, washing and drying, in which the copolymer based on styrene and divinylbenzene using dual macroporous copolymer of styrene with divinylbenzene in a mixture with a triple gel copolymer of styrene, divinylbenzene and a polar monomer in a mass ratio of from 1:4 to 4:1. The copolymers preferred for use with a particle size of 30-160 mm. Technical result: the catalyst has a higher activity. 1 C.p. f-crystals, 1 table.

The invention relates to the production of ion exchangers molded catalysts used in the processes of hydration of olefins, esterification, dehydration of alcohols, the decomposition of esters and other processes catalyzed by ion exchange.

A known method of preparation of ion exchangers molded catalyst using crushed synthetic resin is a copolymer of styrene with diphenylpyrrolidine material by extrusion and the resulting granules with a diameter of 4-5 mm and a length of 5-10 mm sulfurous sulfuric acid.

This method involves the mandatory pre-swelling molded copolymer in ethylene dichloride at the stage of sulfonation, which complicates the manufacture of the catalyst.

Closest to the claimed method is a method of cooking ionite molded catalyst for organic synthesis by mixing a copolymer of styrene and divinylbenzene with a thermoplastic material [RF patent 1804003, 01 J 31/10, 1995, bull. 8]. The method includes mixing a copolymer of styrene and divinylbenzene with a thermoplastic material; extruding the resulting mixture at a temperature of 70-160oWith subsequent sulfonation of the resulting product, washing and drying. As the copolymer can be used ternary copolymer of styrene, divinylbenzene and a monomer containing a functional group such as nitrile of acrylic acid (EAA) or methyl methacrylate. In this case, the sulfonation is carried out without prior swelling in dichloroethane, and the resulting catalyst has a full static exchange capacity (PSOY) 3,6-3,9 mg-EQ/g and active in the process of decomposition of the butyl alcohol (TBS) - azeotrope 75%.

The present invention is directed to increasing the activity of a catalyst is ravelo, significantly higher activity gel sulfonic cation [N. He Polanski "Catalysis by ion, M, Chemistry, 1973, pp. 54-56].

To increase the activity of the catalyst could be using instead of a ternary copolymer of styrene, divinylbenzene and a polar monomer having a gel structure, double copolymer of styrene with divinylbenzene having a macroporous structure. This sulfonation molded copolymer could also be carried out without preliminary soaking in solvent. It is known that the specific surface area of gel copolymers of styrene with divinylbenzene and ion exchangers based on them varies depending on the size of the particles is from 0.1 to 0.5 m2/g, while the specific surface area of macroporous copolymers of styrene with divinylbenzene and ion exchangers based on them depending on the composition and method of cooking in the ground state (the grain size of 0.6-1 mm) is 5 to 40 m2. When grinding, the specific surface increases (N. Dist. Asporin, A. I. He, L. A. Shooters. Porous ion-exchange resin in proceedings of the Synthesis and properties of ion-exchange materials "Nauka", M., 1968, S. 34-38). Due to the developed internal surface of the ground macroporous copolymer is impossible to obtain a molded product is prohibited in [1] and [2]. To facilitate molding is necessary to increase the amount of thermoplastic in the mixture for molding, which inevitably affects the quality of the obtained catalyst, i.e., to obtain a catalyst with increased activity in this way is not possible.

To achieve the specified result, it is proposed a method of preparation of ion exchangers molded catalyst for organic synthesis by mixing the copolymer based on styrene and divinylbenzene with a thermoplastic polymeric material, molding the mixture by extrusion with subsequent sulfonation, washing and drying, namely, that as a copolymer based on styrene and divinylbenzene using dual macroporous copolymer of styrene with divinylbenzene in a mixture with a triple gel copolymer of styrene, divinylbenzene and a polar monomer in a mass ratio of from 1:4 to 4:1.

It is most preferable to use the resin with a particle size of 30-160 mm.

In the present invention is used of double macroporous copolymers of styrene with divinylbenzene Purolite company with a specific surface area in the unground state from 2.5 m2/g to 30 m2/g and a triple gel copolymers of styrene, divinylbenzene sup>2/,

Mixture of dual and macroporous ternary copolymer with a thermoplastic successfully formed when the mass ratio of copolymer:thermoplastic 70:30.

After sulfonation with concentrated sulfuric acid molded pellets (diameter 5-6 mm, length 5-10 mm) are catalyst having the PSOY of 3.8 to 4.0 mEq/g and catalytic activity in dehydration TBS - azeotrope 80-85%.

Often for the implementation of catalytic processes in tubular reactors requires a catalyst with a particle size of2 mm or less. The proposed method allows to obtain a catalyst with particles of this size, while the activity of the catalyst is greatly increased, for example, in the process of dehydration TBS-azeotrope is 90-93%. The same activity in this process and have the macroporous sulfonic cation, such as KU-23 with a particle size of from 0.3 to 1.25 mm Molded ionite catalysts with small grain size (diameter of 1.5-3 mm, length 2-5 mm) with equal catalytic activity superior to the standard specifications-usability, namely: - have less hydrodynamic resistance; is not subject to cracking, abrasion and destruction in the process; - does not require special is

Example 1 a Mixture of 14 wt. including ternary copolymer of styrene, divinylbenzene and NAC in the form of balls with a particle size of 50 μm, 56 wt. h milled dual macroporous copolymer with a particle size of 30-160 μm (specific surface area of 30 m2/g), 30 wt. including powdered high density polyethylene (HDPE) and 5 wt. including water formed by extrusion. The obtained cylindrical granules of size d=5 mm and 1=10 mm sulfurous sulfuric acid, to which 15 g molded copolymer poured 75 ml of 95% sulfuric acid and stirred at 96-100oWith over 7 hours the Acid is drained, the catalyst is washed with distilled water and dried. The PSOY catalyst of 0.1 N. the NaOH solution is of 3.9 mEq/g

Example 2 a Mixture of 56 wt. including triple milled copolymer of styrene, divinylbenzene and methyl methacrylate, with a particle size of 30-160 μm, 14 wt. h milled dual macroporous copolymer composition as in example 1 with a particle size of 30-160 μm, 30 wt. including HDPE pellets (d=3 mm and 5 wt. including water formed by extrusion. The obtained cylindrical pellets (d = 5 mm and l = 10 mm sulfurous as described in example 1. The PSOY catalyst of 0.1 N. the NaOH solution is 4.0 mEq/g

Example 3 a Mixture of 35 wt. including ternary copolymer composition as in example 1, in the form of Sha is km (specific surface area of 25 m2/g), 30 wt. including HDPE pellets (d=3 mm and 5 wt. including water formed by extrusion. The obtained granules with a diameter of 2 mm and a length of 2-3 mm sulfurous as described in example 1. The PSOY catalyst of 0.1 N. the NaOH solution is 4.1 mEq/g

Example 4 a Mixture of 60 wt. h milled dual macroporous copolymer with a particle size of 30-160 μm (specific surface area of 20 m2/g), 40 wt. including powdered HDPE and 5 wt. including water formed by extrusion. The obtained granules d = 5 mm and l=10 mm sulfurous as described in example 1. The PSOY catalyst of 0.1 n NaOH solution is 3.5 mEq/g

Example 5 Using the prepared catalysts in the process of dehydration TBS-azeotrope.

10 g of catalyst and 50 ml of azeotrope TBS water is placed in a flask equipped with reflux condenser with gas outlet tube and cooled vial for condensation of producing isobutylene. The flask is placed in a boiling water bath. After 2 h measured amount of liquid isobutylene. Calculate the activity of the catalyst as the ratio of the spin-off of isobutylene to theoretically possible, expressed as a percentage.

The table presents the results of the experiment.

As can be seen from example 5, the activity of the catalysts obtained by salelocation, which can be obtained on the basis of each of the copolymers.

Claims

1. The method of obtaining ionite molded catalyst for organic synthesis by mixing the copolymer based on styrene and divinylbenzene, and a thermoplastic material, molding the mixture by extrusion with subsequent sulfonation, washing and drying, characterized in that as a copolymer based on styrene and divinylbenzene using dual macroporous copolymer of styrene with divinylbenzene in a mixture with a triple gel copolymer of styrene, divinylbenzene and a polar monomer in a mass ratio of from 1:4 to 4:1.

2. The method according to p. 1, characterized in that the use of these copolymers with a particle size of 30-160 mm.

 

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