A continuous method of obtaining a sulfonic cation exchanger

 

(57) Abstract:

The invention relates to the production of sulfonated cation exchange resins based on crosslinked copolymers of styrene and refers in particular to continuous processes of their production. The method provides improved performance of the process of obtaining sulfonic cation exchanger as a whole. This is achieved by the swelling of the copolymer of styrene with divinylbenzene and methyl methacrylate with the original ratio of the components is equal to 88,2 - 89,1 : 6,9-8,2 : 3,6-4,0, accordingly, in dichloroethane at a mass ratio of copolymer: ethylene dichloride is 1 : 0.1 to 0.2 and subsequent sulfonation of the swollen copolymer in the reactor continuous action 94 - 98% sulfuric acid at 95 - 105oC.

The invention relates to the production of sulfonated cation exchange resins based on crosslinked copolymers of styrene and refers in particular to continuous processes of their production.

For industrial use of most interest are the most productive continuous processes.

Known continuous way to obtain a strongly acidic cations, including on the basis of a copolymer of styrene with divinylbenzene, carried out in a cascade of successively soedinenieto) when the mass ratio is 4:1 to 20:1 and spend the swelling of the copolymer at 20oC. the Swollen copolymer continuously served in the following reactor and it goes through all the reactors of the cascade, each of which is continuously injected sulfureuse agent. The process of sulfonation is carried out at 80-100oC. as sulfurous agent using 98% sulfuric acid. After sulfonation, the cation exchanger is fed to the stage of hydration [1]

The disadvantage of this method is the high intensity of instrumentation, the complexity of installation and low productivity. In addition, sulfonation obtained in a known manner, is not a high exchange capacity: the maximum achievable value is only of 4.75 mEq/g

On an industrial scale has been applied method for continuous receipt sulfonic cation exchanger based on a copolymer of styrene with divinylbenzene (KU-2-8) in which stage of sulfonation is carried out in multiple mixing apparatus. The method includes the swelling of the copolymer in ethylene dichloride in their mass ratio equal to 1: 5, respectively, for 0.5 h at narwhale continuous action. Swollen copolymer is continuously fed into sulfonator where introduced simultaneously with 96% sulfuric acid at their bulk P>oC. the Total duration of stay of the copolymer in sulfonator is 6 o'clock At the output of sulfonator sulfonation press from the liquid phase and is directed to a two-step hydration: in the Hydrator 1st stage hydration spend 50-55% sulfuric acid for 2-tier softened water. Washed the cation exchange resin is filtered and Packed [2]

The method allows to obtain sulfonation KU-2-8 exchange capacity at the level of 4.8 to 5.0 mEq/g and osmotic stability 95% with sulfonation contains not more than 5% of damaged granules.

The disadvantage of this method is its low productivity.

An object of the invention is to improve the performance of the process.

This task is solved in that in the method of continuous receipt sulfonic cation exchanger by swelling the crosslinked copolymer based on styrene in dichloroethane, followed by sulfonation of the swollen copolymer 94-98% sulfuric acid at 95-105oC in the reactor of a mixture of continuous action, as a cross-linked copolymer used is a copolymer of styrene with divinylbenzene and methyl methacrylate with a mass ratio of the components is equal to 88,2-89,1:6,9-8,2:3,6-4,0, respectively, and swelling of prazolam and methyl methacrylate get by known techniques suspension copolymerization of styrene cross-linking agents at a ratio of initial components equal 88,2-89,1:6,9-8,2:3,6-4,0, respectively. The copolymerization is carried out in the presence of the initiator benzoyl peroxide and stabilizer starch (Grigoriev A. P. and other Laboratory plastic technology. M High. school, 1986, S. 20, 66-69).

Carrying out the method according to the proposed method allows to reduce the duration of the process up to 1.5-2 hours

During the process of sulfonation reactor mixing of continuous operation with the use of a copolymer of styrene with divinylbenzene and methyl methacrylate with a ratio of initial monomers outside the claimed range, decreases the efficiency of the process (by increasing the time of sulfonation, the necessary dilution sulfatase).

If the swelling of the copolymer to use dichloroethane in the amount of less than 0.1 m H. 1 m H. copolymer, the time of sulfonation increases.

Increased consumption of dichloroethane more than 0.2 m H. 1 m H. copolymer does not lead to further reduction of the time of sulfonation, but reduces the efficiency of the process due to dilution sulfatase.

Example 1. A copolymer of styrene with divinylbenzene and methyl methacrylate obtained when the ratio of initial components equal 89,1:6 avno 1:0,1) continuously served in nebuhaler continuous action. The residence time of the copolymer in narwhale is 30 minutes Swollen copolymer continuously served in sulfator screw type with capacity of 4.5 m3. At the same time in sulfator with the speed of 1320 kg/h serves 94% sulfuric acid (mass ratio of copolymer:sulfuric acid is 1: 6). As the copolymer of the apparatus is sulfonation. The temperature of the sulfonation is 105oC, the residence time of the copolymer in Salvatore is 2 hours Sulfonated copolymer is continuously directed to a two-step hydration, carried out by a known method. Washed from sulfuric acid sulfonation Packed and Packed.

The performance of the process according to the cation exchanger is 370 kg/h

The resulting cation exchange resin has a static exchange capacity of 5.0 mEq/g, the osmotic stability of 95% and the number of destroyed granules 5%

Example 2. The method is carried out according to example 1, but using the copolymer with the original ratio of styrene: divinylbenzene:methyl methacrylate equal 88,2: 8,2:3,6; his swelling is carried out at a mass ratio of copolymer:ethylene dichloride is 1:0,2, carrying a continuous supply of the copolymer at a speed of 250 kg/h and dichloroethane at 50 kg is at 95oC, when the feed speed 98 sulfuric acid equal to 1500 kg/h, the residence time of the copolymer in Salvatore 1.5 hours

The performance of the process according to the cation exchange resin is 400 kg/h of the resulting cation exchange resin has a static exchange capacity of 4.8 mEq/g, the osmotic stability of 95% and 3% destroyed granules.

Example 3. The method is carried out according to example 1, but using the copolymer mass ratio of styrene: divinylbenzene:methyl methacrylate equal 88,5:7,7:3,8; the swelling is carried out at a mass ratio of copolymer:giggleton equal to 1:0,15, for which the filing of a copolymer operate at speeds of 220 kg/h and dichloroethane with a speed of 33 kg/h; for sulfonation using 96% sulfuric acid, through its filing in sulfator with the speed of 1320 kg/h, and the sulfonation is carried out at 100oC, while the average residence time of the copolymer in Salvatore is 2 o'clock

The performance of the process according to the cation exchanger is 370 kg/h of the Obtained copolymer has a static exchange capacity of 5.1 mEq/g, osmotic stability 100 and the number of damaged granules 3

The data show that the proposed method of obtaining a sulfonic cation exchanger has a duration of stage of sulfiram the m smaller dilution sulfatase) the process performance of the proposed method above 4.5-5 times compared to the prototype.

Received sulfonation their properties static exchange capacity, osmotic stability and the number of damaged granules is on par with brand sulfonic cation exchanger KU-2-8 from the prototype.

A continuous method of obtaining a sulfonic cation exchanger by swelling the crosslinked copolymer based on styrene in dichloromethane and subsequent sulfonation of the swollen copolymer in the reactor mixing continuous action 94 98% sulfuric acid at a temperature of 95 to 105o, Characterized in that as the cross-linked copolymer used is a copolymer of styrene with divinylbenzene and methyl methacrylate at a mass ratio of the components is equal to 88 2 89,1 6,9 8,2 3,6 4,0, respectively, and the swelling is carried out at a mass ratio of copolymer: ethylene dichloride, 0.1 to 0.2.

 

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