CN103071547B - Method for regenerating inactivated strongly acidic cation-exchange resin - Google Patents
Method for regenerating inactivated strongly acidic cation-exchange resin Download PDFInfo
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- CN103071547B CN103071547B CN201310043411.4A CN201310043411A CN103071547B CN 103071547 B CN103071547 B CN 103071547B CN 201310043411 A CN201310043411 A CN 201310043411A CN 103071547 B CN103071547 B CN 103071547B
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Abstract
The invention discloses a method for regenerating an inactivated strongly acidic cation-exchange resin. The method comprises the following steps of (1) alkaline cleaning, immersing the waste resin in a strongly alkaline solution with a mass concentration of 5% to 30%, and mixing to enable the resin to realize full contact with the alkaline solution; (2) acid cleaning, immersing the resin in inorganic acid or organic sulfonic acid with a mass concentration of 10% to 20% for multiple times, and replacing alkaline metal ions in sulphonate on the resin into hydrogen ions; (3) water cleaning, rinsing and cleaning the resin with deionized water, and filtering moisture off; and (4) drying, putting the wet resin in an organic solvent which has an azeotropic property with water, and raising temperature to carry out azeotropic distillation, until the moisture content is decreased to the drying degree required by the resin to be used as a catalyst. The method has the advantages that the drying is thorough, the activity of the old resin is effectively restored, the pollution to the environment by the waste resin is reduced, the utilization rate of the resin is improved, and the production cost is reduced.
Description
Technical field
The strongly acidic cation-exchange renovation process that the present invention relates to a kind of inactivation, belongs to ion-exchange resin technique field.
Background technology
Due to the easy etching apparatus of inorganic acid, strongly acidic cation-exchange is commonly used for inorganic acid example hydrochloric acid, the sulfuric acid etc. of solid catalyst to add in surrogate response, is widely used in the reaction of organosilicon industry and petroleum chemical industry.
Wherein a kind of common strongly acidic cation-exchange is to react on the macromolecule cross-linked structure matrix forming through suspension copolymerization with divinylbenzene at styrene, adheres to highly acid sulfonic acid group and prepares.In the catalytic reaction of addressing above, the sulfonic group generation dissociation on resin, discharges hydrogen ion, thereby plays the effect of catalysis.
Resin is after the use of continuous a period of time, some is deposited on outer surface and the duct inner surface of ion exchange resin by the high molecular polymer forming in reaction, the activated centre on resin catalyst surface is covered gradually, and the hydrogen ion on part sulfonic acid group runs off the carrying out along with reaction gradually simultaneously.The acting in conjunction of these two kinds of factors extends in time (being repeatedly used) by the catalytic activity that causes ion exchange resin and declines gradually.To a certain degree cause product quality to decline or running cost when too high when the activity of resin drops to, just this resin abandoned well more must be renewed to resin.If discarded resin does not add processing, will become solid waste to environment, also increase the cost of product simultaneously.
Existing a kind of processing method is directly to use the old resin of strong acid (as sulfuric acid or hydrochloric acid etc.) soaking inactivation, and the temperature that raises, resin is stirred in hot strong acid, can make like this organosilicon macromolecule polymer that is deposited on resin surface under the effect of strong acid, resolve into little molecule, thereby leave resin surface, make the sulfonic acid group exposing surface of resin surface, then carry out pickling, washing and drying process.So also can reach the object of the catalytic activity of recovering resin.But the resin activity after recovering is not equal to before.
Summary of the invention
The invention provides a kind of strongly acidic cation-exchange renovation process of inactivation, after alkali cleaning and pickling, adopt azeotropic distillation to be dried, dehydration thoroughly, does not destroy this body structure of resin, keeps the good catalytic activity of resin.
The present invention realizes by following technical scheme:
A strongly acidic cation-exchange renovation process for inactivation is to realize by following step:
(1) alkali cleaning: soak discarded resin with the strong base solution of 5-30% mass concentration, stir resin is fully contacted with alkali lye;
(2) pickling: use the inorganic or organic sulfonic acid of 10-20% mass concentration to soak resin some times, the alkali metal ion in the sulfonate on resin is replaced as to hydrogen ion;
(3) washing: by deionized water, resin rinsing is clean and be filtered dry moisture, between pH to 6.0-7.0;
(4) dry: wet resin to be put into the azeotropic organic solvent that has azeotropic characteristic with glassware for drinking water, heated and carry out azeotropic distillation, until its moisture content is reduced to it as the needed degree of drying of catalyst.
Wherein the alkali lye in step (1) with cover the organosilicon macromolecule polymer reaction in resin surface and duct thereof and make it resolve into less molecule, thereby leave resin surface and duct inner surface thereof.Meanwhile, the sulfonic acid group being originally attached on resin matrix also will be neutralized, and form alkali-metal salt.
Described alkali lye is preferably NaOH, potassium hydroxide or both mixtures.
The resin soaking in acid solution in step (2) can be replaced as hydrogen ion by alkali metal ion in the sulfonate on resin, makes its exchange capacity return to or approach the level of fresh resin.
In described step (2), inorganic acid is the one in sulfuric acid, hydrochloric acid, and organic sulfonic acid is methanesulfonic acid; Soak resin for soaking 1-3 time.
The solvent that contains moisture in step (4) can be processed in another water knockout drum, remove moisture wherein, the solvent after dewatering continues to recycle, thereby improves the utilization rate of solvent, reduce the running cost of whole technique, the impact of the discharge of minimizing solvent slop on environment.Conventional way is to blow over resin with the gas heating as air or nitrogen to be dried---the shortcoming of this technique is because the moisture on resin particle surface runs off first in a large number, cause porch, duct sharply to be shunk, from but the large quantity of moisture of inside, duct be difficult to by evaporate to dryness, cause dry resin later still to there is higher moisture content.If extend drying time or improve dry temperature, likely cause the structure of resin matrix at high temperature destroyed, thereby make resin ineffective.
In described step (4), azeotropic organic solvent is the one in benzene, toluene and dimethylbenzene.
In described step (4) azeotropic distillation to resin water content lower than 5%.
Beneficial effect of the present invention is:
1. employing azeotropic distillation carries out the dehydration of resin, more thorough than conventional drying means, can not destroy the molecular structure of resin itself.
2. by resin regeneration, reduce the environmental pollution that waste resin is brought, improved the utilization rate of resin simultaneously, reduced the cost of product.
3. recover resin and substantially reach the exchange capacity of fresh resin, and substantially reach the viscosity of fresh resin in the balance telomerisation medium viscosity of catalysis polysiloxanes.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The old resin of inactivation producing in 200 grams of manufacture process is placed in to round-bottomed flask, adds the sodium hydroxide solution of 150 gram of 10% mass concentration, at room temperature fully stir 2 hours.Then alkali lye is filtered and removed, resin after filtration adds in the sulfuric acid solution that the mass concentration of 200 grams is 20%, after rinsing 4-6 hour by resin filter out, with enough deionized water drip washing resins, to wash away sulfuric acid residual in resin surface and duct, until the moisture pH value filtering out reaches 6.0-7.0.Then by resin elimination moisture.Finally, this wet resin and 500 grams of toluene are positioned in the round-bottomed flask of 1 liter, stir, be heated to 85 DEG C of left and right, now toluene and water formation azeotropic distillation, distill out systemic resin moisture gradually.After in resin, most of water is removed, in flask, toluene temperature will continue to rise, until 110 DEG C of left and right, toluene boiling, after the some time, toluene is by evaporate to dryness, and now resin has reached dry object.
The dried resin of regenerating is measured to its exchange capacity, and contrast with fresh resin.Meanwhile, with the balance telomerisation of resin catalysis polysiloxanes of regeneration gained, judge degree that reaction is carried out and the catalytic efficiency of regenerating resin by the variation of finished product viscosity.Acquired results is in table 1.
Embodiment 2
The old resin of inactivation producing in 200 grams of manufacture process is placed in to flask, adds the potassium hydroxide solution of 100 gram of 30% mass concentration, at room temperature fully stir 2 hours.Then alkali lye is filtered and removed, 200-300 gram of sulfuric acid solution rinsing three times for the resin after filtration (each h 2 so 4 concentration used is followed successively by 20%, 10% and 5%), each 2-3 hour.Then by resin filter out, with enough rinsed with deionized water 3-5 hour (band stirs), elimination moisture.Repeat this rinsing operation three times, until the moisture pH value filtering out reaches 6.0-7.0.Then by resin elimination moisture.Finally, this wet resin and 500 grams of benzene are positioned in the round-bottomed flask of 1 liter, stir, be heated to 69 DEG C of left and right, now benzene and water form azeotropic distillation, systemic resin moisture is distilled out gradually, and after in resin, most of water is removed, in flask, benzene temperature will continue to rise, until 80.4 DEG C of left and right, benzene constantly boiling, after the some time, benzene is by evaporate to dryness, and now resin has reached dry object.
The dried resin of regenerating is measured to its exchange capacity, and contrast with fresh resin.Meanwhile, with the balance telomerisation of resin catalysis polysiloxanes of regeneration gained, judge degree that reaction is carried out and the catalytic efficiency of regenerating resin by the variation of finished product viscosity.Acquired results is in table 1.
Embodiment 3
The old resin of inactivation producing in 500 grams of manufacture process is placed in to flask, adds the sodium hydroxide solution of 300 gram of 5% mass concentration, fully stir and make resin be fully immersed in 4-6 hour in alkali lye.Then alkali lye is filtered and removed, the hydrochloric acid solution rinsing of 10% mass concentration of 300 grams 2 hours for the resin after filtration, then use the sulfuric acid rinsing 2 hours of 5% concentration of 300 grams.Then by resin filter, with enough rinsed with deionized water 3-5 hour, elimination moisture.Repeat this rinsing operation three times, until the moisture pH value filtering out reaches 6.0-7.0.Then by resin elimination moisture.Finally, this wet resin and 800 grams of toluene are placed in the round-bottomed flask with 2 liters, stirred, be heated to 85 DEG C of left and right, now toluene and water form azeotropic distillation, systemic resin moisture is distilled out gradually, and after in resin, most of water is removed, in flask, toluene temperature will continue to rise, until 110 DEG C of left and right, toluene constantly boiling, after the some time, benzene is by evaporate to dryness, and now resin has reached dry object.
The dried resin of regenerating is measured to its exchange capacity, and contrast with fresh resin.Meanwhile, with the balance telomerisation of resin catalysis polysiloxanes of regeneration gained, judge degree that reaction is carried out and the catalytic efficiency of regenerating resin by the variation of finished product viscosity.Acquired results is in table 1.
Embodiment 4
The old resin of inactivation producing in 300 grams of manufacture process is placed in to flask, adds the sodium hydroxide solution of 100 gram of 30% mass concentration, fully stir and make resin be fully immersed in alkali lye 2 hours.Then alkali lye is filtered and removed, the methanesulfonic acid solution rinsing of 10% mass concentration of 150 grams three times for the resin after filtration, each 1 hour.Then by resin filter out, with enough deionized water drip washing, elimination moisture, until the moisture pH value filtering out reaches 6.0-7.0.Then by resin elimination moisture.Finally, this wet resin and 400 grams of dimethylbenzene are placed in the round-bottomed flask with 1 liter, stirred, be heated to 92 DEG C, now dimethylbenzene and water form azeotropic distillation, systemic resin moisture is distilled out gradually, and after in resin, most of water is removed, in flask, dimethylbenzene temperature will continue to rise, until 138 DEG C of left and right, dimethylbenzene boiling, after the some time, dimethylbenzene is by evaporate to dryness, and now resin has reached dry object.
The dried resin of regenerating is measured to its exchange capacity, and contrast with fresh resin.Meanwhile, with the balance telomerisation of resin catalysis polysiloxanes of regeneration gained, judge degree that reaction is carried out and the catalytic efficiency of regenerating resin by the variation of finished product viscosity.Acquired results is in table 1.
Table 1
As can be seen from Table 1, adopt the inventive method resin exchange capacity of regenerating to approach fresh resin, and the resin of regeneration while carrying out the balance telomerisation of catalysis polysiloxanes as catalyst the viscosity of product also approach the viscosity while using fresh resin.
Claims (5)
1. a strongly acidic cation-exchange renovation process for inactivation, it is characterized in that realizing by following step:
(1) alkali cleaning: soak discarded resin with the strong base solution of 5-30% mass concentration, stir resin is fully contacted with alkali lye;
(2) pickling: use the inorganic acid of 10-20% mass concentration or organic sulfonic acid to soak resin some times, the alkali metal ion in the sulfonate on resin is replaced as to hydrogen ion;
(3) washing: by deionized water, resin rinsing is clean and be filtered dry moisture, between pH to 6.0-7.0;
(4) dry: wet resin to be put into the azeotropic organic solvent that has azeotropic characteristic with glassware for drinking water, heated and carry out azeotropic distillation, until its moisture content is reduced to it as the needed degree of drying of catalyst.
2. the strongly acidic cation-exchange renovation process of inactivation as claimed in claim 1, is characterized in that the alkali lye in described step (1) is NaOH, potassium hydroxide or both mixtures.
3. the strongly acidic cation-exchange renovation process of inactivation as claimed in claim 1, is characterized in that in described step (2), inorganic acid is the one in sulfuric acid, hydrochloric acid, and organic sulfonic acid is methanesulfonic acid; Soak resin for soaking 1-3 time.
4. the strongly acidic cation-exchange renovation process of inactivation as claimed in claim 1, is characterized in that in described step (4), azeotropic organic solvent is the one in benzene, toluene and dimethylbenzene.
5. the strongly acidic cation-exchange renovation process of inactivation as claimed in claim 1, it is characterized in that in described step (4) azeotropic distillation to resin water content lower than 5%.
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