CN109365009B - Preparation method of ion exchange resin for sulfolane purification - Google Patents
Preparation method of ion exchange resin for sulfolane purification Download PDFInfo
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- CN109365009B CN109365009B CN201811383473.9A CN201811383473A CN109365009B CN 109365009 B CN109365009 B CN 109365009B CN 201811383473 A CN201811383473 A CN 201811383473A CN 109365009 B CN109365009 B CN 109365009B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
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Abstract
The invention discloses a preparation method of ion exchange resin for purifying sulfolane, which adopts macroporous chloromethylated polystyrene resin as a raw material to react with pyridine functional groups and substituted derivatives thereof to obtain chlorine type anion exchange resin, and then uses hydroxyl to replace chloride ions in the resin to obtain the anion exchange resin for purifying sulfolane. Compared with the conventional anion exchange resin, the ion exchange resin prepared by the method has excellent heat-resistant stability, is more effective in deionization when being used for sulfolane purification equipment, and has longer service life.
Description
Technical Field
The invention relates to a synthesis method of ion exchange resin, in particular to a preparation method of anion exchange resin for sulfolane purification.
Background
The strong-base anion exchange resin can be used for water treatment, purification, concentration, separation, transformation of material ion composition, decolorization of material, catalyst and the like. However, strong base anion exchange resins are generally less thermally stable and can only be used at temperatures below 60 ℃, which limits the range of applications for strong base anion exchange resins. The thermal stability of anion exchange resins is related to factors such as the structure of the functional groups, the spacer arms of the resin, etc.
Sulfolane is one of ideal solvents for extracting aromatic hydrocarbons from gasoline, and is widely applied in the field of petrochemical industry. However, a great deal of basic research work shows that sulfolane can generate sulfonic organic acidic substances, which causes equipment corrosion. With the prolonging of the running time of the device, the sulfolane is gradually degraded, the pH value of the sulfolane is continuously reduced, the corrosion rate of the solvent to the device is increased, and the thermal stability is reduced. At present, the domestic technology adopts an ion exchange technology to carry out ion exchange on sulfolane and remove sulfonic acid in a system.
Chinese patent CN1230545A discloses a sulfolane purification method, which adopts macroporous weak-base anion exchange resin ion exchange technology to purify sulfolane, but the resin selected by the technology has poor temperature resistance, short operation time, easy damage of the resin and needs to be replaced regularly.
The pyridine functional group and the substituted derivatives thereof are relatively stable due to the structural characteristics of the pyridine functional group and the substituted derivatives thereof. The carbon-carbon bond in the pyridine molecule is between the C-N single bond and the C ═ N double bond, and the bond length values of the carbon-carbon bond and the carbon-nitrogen bond are also similar, and the average degree of the bond on the pyridine ring is higher, so that the molecule has good stability. According to the invention, macroporous chloromethylated polystyrene resin is used as a raw material, and reacts with pyridine functional groups and substituted derivatives thereof to obtain anion exchange resin with good stability, so that the purification effect of sulfolane is better.
Disclosure of Invention
Aiming at the defects of the prior art, the invention develops the temperature-resistant anion exchange resin for purifying sulfolane by introducing pyridine functional groups and substituted derivatives thereof into the resin.
1. An anion exchange resin for sulfolane purification, having the following general structural formula:
wherein PS is polystyrene copolymer resin skeleton crosslinked with 5-20% divinylbenzene, A is pyridine functional group and its derivative, and has the following structural formula:
wherein R may be: H. CH (CH)3、N(CH3)2(ii) a B is an anion selected from a pair with resin: chloride ion, hydroxide ion, and the like.
2. The preparation method of the anion exchange resin for purifying sulfolane comprises the following steps:
(1) quaternization reaction: putting a part of macroporous chloromethylated polystyrene resin in an organic solvent for swelling reaction at 25-35 ℃ for 10-30 hours, wherein the mass ratio of the chloromethylated polystyrene resin to the organic solvent is 1: 10-30, adding 1.8-3.0 parts of pyridine functional groups or substituted derivatives thereof, heating to 80-100 ℃, stirring for reaction for 10-30h, placing the reacted resin in a glass ion resin exchange column, leaching the resin with absolute ethyl alcohol until effluent liquid does not flow out, and finally leaching the resin with a large amount of deionized water until the effluent liquid is detected to be neutral by a pH test paper to obtain chlorine type strongly basic anion exchange resin;
(2) transformation treatment of resin: and (2) filling the chlorine type strongly basic anion exchange resin obtained in the last step into an ion exchange column, preparing 4% -6% sodium hydroxide or potassium hydroxide solution with the mass 3-10 times of that of the resin according to the total exchange capacity of the resin, adding the solution into the ion exchange column, controlling the volume space velocity to be not more than 5h < -1 >, until effluent liquid is not turbid when being detected by nitric acid-silver nitrate solution, and washing the effluent liquid by deionized water until the effluent liquid is neutral when being detected by a pH test paper, thus obtaining the hydroxide type strongly basic anion exchange resin.
Preferably, the organic solvent is n-butanol, DMF or toluene.
Preferably, the swelling reaction time in the step (1) is 12 to 15 hours, the mixture is heated to 90 ℃ after the pyridine functional group or the substituted derivative thereof is added, and the stirring reaction time is 24 hours.
Preferably, the swelling reaction in step (1) is carried out under the conditions of swelling at 25 ℃ for 15 hours, adding the pyridine functional group or the substituted derivative thereof, heating to 90 ℃, and stirring for 24 hours.
Preferably, the swelling reaction in step (1) is carried out under the conditions of swelling at 30 ℃ for 10 hours, adding the pyridine functional group or the substituted derivative thereof, heating to 90 ℃, and stirring for 24 hours.
Preferably, the mass concentration of the sodium hydroxide or potassium hydroxide solution in the step (2) is 5%.
Preferably, the volume space velocity in the step (2) is controlled to be 4 h-1.
3. The stability evaluation method was performed on the hydroxide-type strongly basic anion exchange resin prepared through the above steps: putting the synthesized hydroxide type strong-base anion exchange resin into a pressure tank with tetrafluoroethylene, adding quantitative deionized water, placing the pressure tank in an oven at 90 ℃ for 100 hours, measuring the reduction condition of the strong-base exchange capacity, and judging the thermal stability of the resin according to the reduction condition.
4. Resin used for sulfolane purification equipment evaluation
Putting the resin into a solid bed in sulfolane purification equipment, starting the equipment and operating the equipment for three months at 60 ℃, opening the equipment to take out the resin, and measuring the exchange capacity.
The invention has the beneficial effects that:
the macroporous anion resin prepared by the invention has the advantages of high selectivity, high exchange capacity, stable product performance, high synthesis yield and environment-friendly production process.
According to the invention, macroporous chloromethylated polystyrene resin is used as a raw material, and reacts with pyridine functional groups and substituted derivatives thereof to obtain anion exchange resin with good stability, and the anion exchange resin has a better purifying effect when used for sulfolane: compared with the conventional anion exchange resin, the loss rate (%) of the exchange capacity is reduced by more than 2 times, the heat-resistant stability is excellent, the method is more effective when being used for deionizing sulfolane purification equipment, the loss rate of the resin exchange is reduced by 3 times, and the service life is longer.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention will be described in further detail with reference to examples and specific embodiments.
Example 1
20g of chlorine balls (namely macroporous chloromethylated polystyrene resin) and 200mL of DMF are added into a 500mL four-neck flask provided with a stirrer, a condenser and a thermometer, and the mixture is swelled at 30 ℃ for 12 hours; and then adding 50g of 4-dimethylaminopyridine into the mixed solution, heating the mixed solution to 90 ℃, stirring the mixed solution for reaction for 30 hours, placing the resin into a glass ion exchange column after the reaction is finished, leaching the resin by using absolute ethyl alcohol until no oil exists in an effluent, and leaching the resin by using a large amount of deionized water to obtain the chlorine type strongly basic anion exchange resin.
And (2) loading the obtained chlorine type strongly basic anion exchange resin into an ion exchange column, adding 200ml of sodium hydroxide solution with the mass fraction of 4% into the ion exchange column, controlling the volume space velocity to be not more than 4h < -1 >, until the effluent liquid is not turbid when being detected by nitric acid-silver nitrate solution, and then washing the resin by using a large amount of deionized water until the effluent liquid is neutral when being detected by pH test paper, thus obtaining the hydrogen-oxygen type strongly basic anion exchange resin PEN-1. The structural formula is as follows:
example 2
Adding 20g of chlorine balls into a 500mL four-neck flask provided with a stirrer, a condenser pipe and a thermometer, swelling for 10 hours at 30 ℃ by using 250mL of n-butyl alcohol, adding 45g of 4-methylpyridine, stirring and reacting for 36 hours at 80 ℃, placing the resin into a glass ion exchange column after the reaction is finished, leaching by using absolute ethyl alcohol until no oil flows out, leaching by using a large amount of deionized water until the effluent is detected to be neutral by using a pH test paper, and obtaining the chlorine type strongly-alkaline anion exchange resin.
And (2) loading the obtained anion exchange resin into an ion exchange column, adding 200ml of sodium hydroxide solution with the mass fraction of 4% into the ion exchange column, controlling the volume space velocity to be not more than 4h < -1 >, checking the effluent liquid by using nitric acid-silver nitrate solution until the effluent liquid is not turbid, and washing the resin by using a large amount of deionized water until the effluent liquid is detected to be neutral by using pH test paper to obtain the hydrogen-oxygen type strongly-alkaline anion exchange resin PEN-2. The structural formula is as follows:
example 3
Adding 20g of chlorine balls into a 500mL four-neck flask provided with a stirrer, a condenser pipe and a thermometer, swelling for 15 hours at 25 ℃ by using 250mL of toluene, adding 40g of pyridine, stirring and reacting for 24 hours at 90 ℃, placing the resin into a glass ion exchange column after the reaction is finished, leaching by using absolute ethyl alcohol until no oil flows out, and leaching by using a large amount of deionized water until the effluent liquid is neutral by using pH test paper to obtain the chlorine type strongly-alkaline anion exchange resin.
Loading the obtained anion exchange resin into an ion exchange column, adding 200ml of 5% sodium hydroxide solution into the ion exchange column, controlling the volume space velocity to be not more than 4h-1 until the effluent liquid is not turbid by using a nitric acid-silver nitrate solution, and washing the resin by using a large amount of deionized water until the effluent liquid is neutral by using a pH test paper. Obtaining the hydrogen-oxygen type strong-alkaline anion exchange resin PEN-3. The structural formula is as follows:
example 4
The resins obtained according to examples 1 to 3 were subjected to evaluation of thermal stability: taking 1kg of synthesized hydroxyl type strongly basic anion exchange resins PEN-1, PEN-2 and PEN-3 and commercially available macroporous weakly basic anion exchange resin D301, putting the resins into a pressure tank with tetrafluoroethylene inside, adding quantitative deionized water, placing the resins in an oven for 100h at 90 ℃, measuring the respective exchange capacities after taking out, and after the resins are heated for 100h at 90 ℃, the loss rates of the exchange capacities of the PEN-1, PEN-2, PEN-3 and D301 are respectively 8.6%, 12.0%, 14.2% and 36.8%.
TABLE 1 exchange amount and thermal stability of the resins
Example 5
The resins obtained according to examples 1 to 3 were used in a sulfolane purification plant for evaluation of the resin exchange efficiency: taking 10kg of synthesized hydrogen-oxygen type strongly basic anion exchange resins PEN-1, PEN-2 and PEN-3 and 10kg of commercially available macroporous weakly basic anion exchange resin ion exchange resin D301 respectively, putting the resins into sulfolane purification equipment, starting the equipment and operating the equipment for three months at 60 ℃, opening the equipment to take out the resins, and measuring the exchange capacity. The loss rates of the exchange capacity of the PEN-1, the PEN-2, the PEN-3 and the D301 ion exchange resins are 5.3 percent, 7.1 percent, 11.7 percent and 29.9 percent in sequence. It is found that the resin synthesized in this example is more effective, and the PEN-1 obtained in the example is most effective.
TABLE 2 exchange amount and thermal stability of the resins
Example 6
After the resin obtained in example 1 was applied to a sulfolane purification plant to purify deteriorated sulfolane, the parameters of the performance tests of regenerated sulfolane and fresh sulfolane and deteriorated sulfolane were compared:
TABLE 3 regenerated sulfolane and fresh sulfolane Performance test
From this, it was confirmed that the resin synthesized in this example has an excellent function of purifying sulfolane, and the recovery rate of 98% was almost achieved without a large change in the parameters of regenerated sulfolane and fresh sulfolane after purification.
Claims (7)
1. A method for preparing anion exchange resin for purifying sulfolane comprises the following steps:
(1) quaternization reaction: putting a part of macroporous chloromethylated polystyrene resin into an organic solvent for swelling reaction at 25-35 ℃ for 10-30 hours, wherein the mass ratio of the chloromethylated polystyrene resin to the organic solvent is 1: 10-30, then adding 1.8-3.0 parts of pyridine functional groups or substituted derivatives thereof into the macroporous chloromethylated polystyrene resin, heating the mixture to 80-100 ℃, stirring the mixture for reaction for 10-30 hours, putting the reacted resin into a glass ion resin exchange column, leaching the reacted resin with absolute ethyl alcohol until effluent flows out without oil, and finally leaching the resin with a large amount of deionized water until the effluent is detected to be neutral by a pH test paper to obtain chlorine type strongly basic anion exchange resin;
the pyridine functional group and the derivative thereof have the following structural general formula:
(2) Transformation treatment of resin: loading the chlorine type strongly basic anion exchange resin obtained in the last step into an ion exchange column, preparing 4-6% sodium hydroxide or potassium hydroxide solution with the mass 3-10 times of that of the resin according to the total exchange capacity of the resin, adding the solution into the ion exchange column, and controlling the volume space velocity not to be more than 5h-1 And (4) until the effluent liquid is not turbid by using a nitric acid-silver nitrate solution, washing the effluent liquid by using deionized water until the pH test paper is neutral, and thus obtaining the hydroxide type strong-base anion exchange resin.
2. The method of claim 1, wherein the organic solvent is n-butanol, DMF or toluene.
3. The method for preparing anion exchange resin for purifying sulfolane according to claim 1, wherein the swelling reaction time in step (1) is 12-15 hours, the temperature is raised to 90 ℃ after the pyridine functional group or the substituted derivative thereof is added, and the stirring reaction time is 24 hours.
4. The method for preparing an anion exchange resin for purifying sulfolane according to claim 1, wherein the swelling reaction in step (1) is performed under conditions of swelling at 25 ℃ for 15 hours, heating to 90 ℃ after adding the pyridine functional group or the substituted derivative thereof, and stirring for 24 hours.
5. The method for preparing an anion exchange resin for purifying sulfolane according to claim 1, wherein the swelling reaction in step (1) is performed under conditions of swelling at 30 ℃ for 10 hours, heating to 90 ℃ after adding the pyridine functional group or the substituted derivative thereof, and stirring for 24 hours.
6. The method for preparing an anion exchange resin for purifying sulfolane according to any one of claims 1 to 5, wherein the mass concentration of the sodium hydroxide or potassium hydroxide solution in the step (2) is 5%.
7. The method for preparing anion exchange resin for purifying sulfolane according to claim 6, wherein the volume space velocity in the step (2) is controlled to be 4h-1。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU751809A1 (en) * | 1978-05-24 | 1980-07-30 | Предприятие П/Я А-1997 | Method of producing anion exchange resins |
| CN1861594A (en) * | 2005-05-13 | 2006-11-15 | 北京思践通科技发展有限公司 | Purifying process of poor quality cyclo butyl sulfone |
| CN101703945A (en) * | 2009-11-13 | 2010-05-12 | 江苏工业学院 | Temperature resistant quaternary ammonium type anion exchange resin phase transfer catalyst and preparation method thereof |
| CN104788599A (en) * | 2015-03-27 | 2015-07-22 | 徐州浩通新材料科技股份有限公司 | Preparation method for macroporous weak-base anion exchange resin |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU751809A1 (en) * | 1978-05-24 | 1980-07-30 | Предприятие П/Я А-1997 | Method of producing anion exchange resins |
| CN1861594A (en) * | 2005-05-13 | 2006-11-15 | 北京思践通科技发展有限公司 | Purifying process of poor quality cyclo butyl sulfone |
| CN101703945A (en) * | 2009-11-13 | 2010-05-12 | 江苏工业学院 | Temperature resistant quaternary ammonium type anion exchange resin phase transfer catalyst and preparation method thereof |
| CN104788599A (en) * | 2015-03-27 | 2015-07-22 | 徐州浩通新材料科技股份有限公司 | Preparation method for macroporous weak-base anion exchange resin |
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