CN109970936B - Cross-linked lignin sulfonic cation exchange resin and preparation method and application thereof - Google Patents
Cross-linked lignin sulfonic cation exchange resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of cation exchange resin, and discloses a cross-linking lignin sulfonic cation exchange resin, and a preparation method and application thereof. According to the method, sulfite, ketone, lignosulfonate and aldehyde are subjected to aldol condensation reaction to obtain a reactive condensation polymer; adding a cross-linking agent, preserving heat, curing and carrying out cross-linking reaction to obtain cross-linked lignin sulfonic cation exchange resin; the dosage of each component is calculated by mass portion: 3-8 parts of sulfite, 4-10 parts of ketone, 5-15 parts of lignosulfonate, 5-15 parts of aldehyde and 2-5 parts of a crosslinking agent. The resin of the invention not only introduces a large amount of sulfonic acid groups by sulfonation of ketone units, but also contains a large amount of sulfonic acid groups in lignosulfonate, so that the sulfonated group content of the product is high, the product can be used as a biomass-based strong-acid cation exchange resin, has the characteristics of high exchange equivalent weight and lower cost, can be used in the field of industrial water treatment, and particularly can be used as a strong-acid cation exchange resin in the removal of hard water calcium and magnesium ions.
Description
Technical Field
The invention belongs to the technical field of cation exchange resin, and particularly relates to cross-linked lignin sulfonic cation exchange resin and a preparation method and application thereof.
Background
The ion exchange resin as a cross-linked high polymer loaded with active groups has the functions of exchange, absorption, catalysis and the like, and is mainly used in the fields of water treatment, food, electric power, medicine and health, metallurgy and the like. In China, the dosage of the strong acid type cation exchange resin is large, and occupies 80 percent of the total yield of the ion exchange resin. Most of the currently commercially available cation exchange resins are prepared by using styrene and acrylic acid (ester) as raw materials, performing crosslinking polymerization reaction with a crosslinking agent of divinylbenzene to prepare a three-dimensional polymer with a network skeleton structure, and sulfonating with fuming sulfuric acid to prepare the sulfonated polystyrene cation exchange resin. Sulfonated polystyrene cation exchange resin is sulfonated by fuming sulfuric acid, so that the danger of sulfonation reaction is high, the sulfonation reaction is insufficient, and the actual exchange equivalent of the resin is low. In addition, with the depletion of petroleum and natural gas resources, the raw materials for preparing ion exchange resins (mainly monomers such as styrene and acrylic acid) are in shortage.
There are two main directions for the current development of new cation exchange resins: a composite polystyrene cation exchange resin is prepared from fossil raw material and biomass raw material through cross-linking reaction. Patent CN107519947A (a preparation method of polystyrene cation exchange resin for sewage treatment) discloses a method for preparing composite polystyrene cation exchange resin by reacting calcined cotton stalk, zeolite powder, ethyl styrene, methylene bisacrylamide and the like, which has low raw material cost, good adsorption effect and low exchange equivalent when applied to sewage treatment; patent CN107652406A (a preparation method of strong acid polystyrene cation exchange resin) discloses a strong acid polystyrene cation exchange resin prepared by reacting methyl styrene, methylene bisacrylamide, pretreated rice hull, gelatin and the like, which solves the problems of compact structure and low degree of crosslinking of the traditional polystyrene cation exchange resin.
The other method is to prepare the bio-based cation exchange resin by taking biomass resources as raw materials. Patent CN108325568A (a preparation method of lignin-based strong acid cation exchange resin) synthesizes lignin-based strong acid cation exchange resin with high cation exchange capacity by using lignin, phenol, a sulfonation reagent, formaldehyde and the like as raw materials through a one-step method. Yasuda et al (JWood Sci,2000,46: 477-; however, the degree of activity of the prepared resin is low and the exchange equivalent is small. Feng Juan et al (ion exchange and adsorption, 2006,22(3): 231-. Wartelle et al (J Environ management, 2006,78(2):157-162) adopt 12 agricultural and sideline products as raw materials to perform quaternization modification to synthesize ion exchange resin, and the obtained quaternization resin has stronger adsorption capacity to phosphate ions in solution.
In summary, most of the existing strong acid cation exchange resins are sulfonated crosslinked polystyrene cation exchange resins, or copolymers or composites of styrene with other monomers and fillers. Although the application of the sulfonated crosslinked polystyrene type cation exchange resin is common, such as #732 type cation exchange resin, the danger of fuming sulfuric acid sulfonation reaction is large; and the sulfonation is carried out after the polymerization, so that the sulfonation efficiency is low, and the actual exchange equivalent of the resin is far lower than the theoretical exchange equivalent. The actual exchange equivalent of the composite polystyrene type cation exchange resin is not ideal. Based on the method, the lignosulfonate cation exchange resin with high performance and low cost is prepared by using lignosulfonate, which is a pulping and papermaking byproduct, as a raw material and adopting a sulfonation and polymerization technology, so that not only are the reaction conditions mild and controllable, but also the sulfonate in the molecule can be used as an effective exchange functional group after the lignosulfonate is crosslinked, and the ion exchange equivalent is high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method with mild sulfonation reaction and low cost for the cross-linked lignin sulfonic cation exchange resin.
The preparation method has mild reaction conditions, and the crosslinking lignin sulfonic cation exchange resin is prepared by carrying out aldol condensation reaction on sulfite, ketone, lignosulfonate and aldehyde to obtain active polycondensate, and then carrying out heat preservation curing crosslinking reaction under alkaline.
The invention also aims to provide the cross-linking lignin sulfonic cation exchange resin with high exchange equivalent weight prepared by the method.
The cross-linking lignin sulfonic cation exchange resin prepared by the invention is a strong acid type cation exchange resin with a novel structure, and has high exchange equivalent weight for calcium and magnesium ions in hard water. The reason for its high exchange equivalent is as follows:
(1) the traditional production process of sulfonated polystyrene cation exchange resin is that a polystyrene framework is prepared firstly, then the framework resin is sulfonated, and much styrene in the polystyrene framework is not fully sulfonated, so that the sulfonation efficiency is low, and the actual exchange equivalent is far lower than the theoretical exchange equivalent;
(2) in the method, the ketone unit is subjected to sulfonation grafting reaction firstly, and then polycondensation crosslinking reaction is carried out, so that the ketone unit in the obtained crosslinked resin is fully sulfonated, the sulfonation efficiency is high, and the actual exchange equivalent is high.
The invention further aims to provide the application of the cross-linked lignin sulfonic cation exchange resin in the field of industrial water treatment, in particular to the application of the cross-linked lignin sulfonic cation exchange resin as a strong acid cation exchange resin in removing hard water calcium and magnesium ions.
The purpose of the invention is realized by the following scheme:
a preparation method of cross-linking type lignosulfonic acid group cation exchange resin with mild sulfonation reaction and low cost comprises carrying out aldol condensation reaction on sulfite, ketone, lignosulfonate and aldehyde to obtain active polycondensate; adding a cross-linking agent, preserving heat, curing and carrying out cross-linking reaction to obtain the cross-linked lignin sulfonic cation exchange resin.
In the preparation method, the dosage of each component is calculated by mass parts as follows: 3-8 parts of sulfite, 4-10 parts of ketone, 5-15 parts of lignosulfonate, 5-15 parts of aldehyde and 2-5 parts of a crosslinking agent.
In the preparation method, the aldol condensation reaction preferably comprises the steps of mixing sulfite, ketone and lignosulfonate, heating for reaction, adding aldehyde, and heating for reaction; more specifically, the sulfite, the ketone and the lignosulfonate are mixed and heated to 40-60 ℃ for reaction for 10-20min, and then the aldehyde is added, the temperature is raised to 85-95 ℃ for reaction for 1-3 h.
The aldehyde is preferably added dropwise to the reaction system, more preferably completed within 0.5 to 1 hour.
In the preparation method of the present invention, the aldol condensation reaction is preferably carried out in water, and the amount of the water may be 30 to 60 parts by mass.
In the preparation method, the temperature of the crosslinking reaction is preferably 90-100 ℃; the reaction time is preferably 12 to 24 hours.
In the production method of the present invention, the crosslinking reaction is preferably carried out in a closed vessel.
In the preparation method of the present invention, the sulfite may include at least one of sodium sulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite, and ammonium sulfite.
In the preparation method of the invention, the ketone can comprise at least one of acetone, butanone, 2-pentanone and cyclohexanone.
In the preparation method of the invention, the lignosulfonate may include at least one of sodium lignosulfonate, potassium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate, calcium lignosulfonate and sulfonated alkali lignin.
In the preparation method of the invention, the aldehyde can comprise at least one of formaldehyde, acetaldehyde, propionaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and furfural.
In the preparation method of the invention, the cross-linking agent can comprise at least one of epichlorohydrin, ethylene dibromide and propylene dibromide.
In the preparation method of the invention, the obtained product is crushed to obtain solid resin particles with the particle size of 1-3 mm.
The preparation method comprises the following specific steps: dissolving 3-8 parts of sulfite, 4-10 parts of ketone and 5-15 parts of lignosulfonate in 30-60 parts of water by mass, heating to 40-60 ℃ for reaction, then dropwise adding 5-15 parts of aldehyde, heating to 85-95 ℃ for heat preservation reaction to obtain a liquid active polycondensate; placing the mixture into a closed container, adding 2-5 parts of cross-linking agent, uniformly mixing, and carrying out heat preservation reaction at 90-100 ℃ to obtain the cross-linked lignin sulfonic cation exchange resin.
The invention also provides the cross-linking lignin sulfonic cation exchange resin with high exchange equivalent weight prepared by the method.
The cross-linking lignin sulfonic cation exchange resin prepared by the invention is a strong acid type cation exchange resin with a novel structure, and has high exchange equivalent weight for calcium and magnesium ions in hard water. The reason for its high exchange equivalent is as follows:
(1) the traditional production process of sulfonated polystyrene cation exchange resin is that a polystyrene framework is prepared firstly, then the framework resin is sulfonated, and much styrene in the polystyrene framework is not fully sulfonated, so that the sulfonation efficiency is low, and the actual exchange equivalent is far lower than the theoretical exchange equivalent;
(2) in the method, the ketone unit is subjected to sulfonation grafting reaction firstly, and then polycondensation crosslinking reaction is carried out, so that the ketone unit in the obtained crosslinked resin is fully sulfonated, the sulfonation efficiency is high, and the actual exchange equivalent is high.
The resin of the invention not only introduces a large amount of sulfonic acid groups by sulfonation of ketone units, but also contains a large amount of sulfonic acid groups in the raw material lignosulfonate, so that the sulfonated group content of the product resin is high, the product resin can be used as a biomass-based strong-acid cation exchange resin, has the characteristics of high exchange equivalent weight and low cost, and can be used in the field of industrial water treatment.
The invention also provides application of the cross-linked lignin sulfonic cation exchange resin in the field of industrial water treatment, in particular application of the cross-linked lignin sulfonic cation exchange resin as a strong acid type cation exchange resin in removing hard water calcium and magnesium ions.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the method has the advantages of mild sulfonation reaction, simple and controllable synthesis process and low raw material cost.
2. The cation exchange resin is sulfonated and then crosslinked, the traditional production process of first crosslinking and then sulfonation is overturned, ketone units in the prepared crosslinked resin are fully sulfonated, the sulfonation efficiency is high, the sulfonated group content is high, and the actual exchange equivalent is high.
3. The cation exchange resin of the invention adopts lignosulfonate which is a raw material containing a large number of sulfonic acid groups, and the sulfonic acid groups in lignosulfonate molecules after being crosslinked can be used as effective exchange functional groups.
Drawings
FIG. 1 is an infrared spectrum of a crosslinked lignin sulfonate cation exchange resin obtained in examples 1 to 3.
FIG. 2 is a graph showing the regeneration exchange performance of the crosslinked lignin sulfonate cation exchange resin obtained in examples 1 to 3 and a commercial resin # 732.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The materials referred to in the following examples are commercially available.
Example 1
Dissolving 5 parts by mass of sodium sulfite, 8 parts by mass of sodium lignin sulfonate and 6 parts by mass of acetone in 30 parts by mass of water, then heating to 40 ℃ for reaction for 10 minutes, and then dropwise adding 5 parts by mass of formaldehyde within 0.5 hour; after the dropwise addition, heating to 85 ℃, and carrying out heat preservation reaction for 1 hour to obtain a liquid active condensation polymer; and putting the liquid product in a closed container, adding 2 parts by mass of epoxy chloropropane, uniformly mixing, then carrying out heat preservation reaction at 90 ℃ for 12 hours to obtain crosslinked solid resin, and crushing the product to obtain 2mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.501 mmol/g.
Example 2
Dissolving 5 parts by mass of potassium sulfite, 10 parts by mass of ammonium lignosulfonate and 8 parts by mass of acetone in 40 parts by mass of water, heating to 50 ℃, reacting for 15 minutes, and dripping 12 parts by mass of formaldehyde within 0.5 hour; after the dropwise addition, heating to 90 ℃, and carrying out heat preservation reaction for 1 hour to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, adding 3 parts by mass of epoxy chloropropane, uniformly mixing, then carrying out heat preservation reaction at 95 ℃ for 24 hours to obtain crosslinked solid resin, and crushing the product to obtain 3mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.625 mmol/g.
Example 3
Dissolving 5 parts by mass of sodium bisulfite, 15 parts by mass of potassium lignosulfonate and 10 parts by mass of acetone in 50 parts by mass of water, heating to 60 ℃, reacting for 20 minutes, and dripping 10 parts by mass of formaldehyde in 0.5 hour; after the dropwise addition, heating to 95 ℃ and carrying out heat preservation reaction for 1 hour to obtain a liquid active condensation polymer; and putting the liquid product in a closed container, adding 4 parts by mass of epoxy chloropropane, uniformly mixing, then carrying out heat preservation reaction at 100 ℃ for 24 hours to obtain crosslinked solid resin, and crushing the product to obtain 1mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.891 mmol/g.
Example 4
Dissolving 3 parts by mass of sodium sulfite, 10 parts by mass of magnesium lignosulfonate and 10 parts by mass of acetone in 45 parts by mass of water, heating to 45 ℃, reacting for 10 minutes, and dripping 13 parts by mass of formaldehyde within 0.5 hour; after the dropwise addition, heating to 93 ℃ and carrying out heat preservation reaction for 1 hour to obtain a liquid active condensation polymer; and putting the liquid product in a closed container, adding 5 parts by mass of dibromoethane, uniformly mixing, then carrying out heat preservation reaction at 95 ℃ for 18 hours to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 1.5 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.307 mmol/g.
Example 5
Dissolving 8 parts by mass of sodium sulfite, 5 parts by mass of sodium lignin sulfonate and 8 parts by mass of acetone in 55 parts by mass of water, heating to 55 ℃, reacting for 10 minutes, and dripping 14 parts by mass of furfural within 0.5 hour; after the dropwise addition, heating to 90 ℃ and carrying out heat preservation reaction for 2 hours to obtain a liquid active condensation polymer; putting the liquid product in a closed container, adding 4.5 parts by mass of dibromoethane, uniformly mixing, then carrying out heat preservation reaction at 95 ℃ for 24 hours to obtain crosslinked solid resin, and crushing the product to obtain 2mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.789 mmol/g.
Example 6
Dissolving 4 parts by mass of potassium sulfite, 7 parts by mass of calcium lignosulfonate and 8 parts by mass of butanone in 40 parts by mass of water, heating to 52 ℃, reacting for 20 minutes, and dripping 10 parts by mass of acetaldehyde in 45 minutes; after the dropwise addition, heating to 88 ℃ and carrying out heat preservation reaction for 2 hours to obtain a liquid active condensation polymer; putting the liquid product in a closed container, adding 2.5 parts by mass of dibromopropane, uniformly mixing, then carrying out heat preservation reaction at 95 ℃ for 15 hours to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 3 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.457 mmol/g.
Example 7
Dissolving 6 parts by mass of potassium bisulfite, 15 parts by mass of ammonium lignosulfonate and 6 parts by mass of butanone in 56 parts by mass of water, heating to 54 ℃, reacting for 20 minutes, and then dropwise adding 8 parts by mass of propionaldehyde in 45 minutes; after the dropwise addition, heating to 92 ℃ and carrying out heat preservation reaction for 3 hours to obtain a liquid active condensation polymer; putting the liquid product in a closed container, adding 3 parts by mass of dibromopropane, uniformly mixing, then carrying out heat preservation reaction at 90 ℃ for 15 hours to obtain crosslinked solid resin, and crushing the product to obtain 1.8mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.692 mmol/g.
Example 8
Dissolving 8 parts by mass of sodium metabisulfite, 5 parts by mass of sulfonated alkali lignin and 9 parts by mass of 2-pentanone in 50 parts by mass of water, heating to 52 ℃, reacting for 10 minutes, and then dropwise adding 13 parts by mass of malondialdehyde within 1 hour; after the dropwise addition, heating to 90 ℃ and carrying out heat preservation reaction for 2 hours to obtain a liquid active condensation polymer; and putting the liquid product in a closed container, adding 2.5 parts by mass of epoxy chloropropane, uniformly mixing, then carrying out heat preservation reaction at 90 ℃ for 20 hours to obtain crosslinked solid resin, and crushing the product to obtain 2.4mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.214 mmol/g.
Example 9
Dissolving 5 parts by mass of potassium metabisulfite, 12 parts by mass of sodium lignin sulfonate and 10 parts by mass of acetone in 48 parts by mass of water, heating to 55 ℃, reacting for 15 minutes, and dropwise adding 14 parts by mass of succinaldehyde within 1 hour; after the dropwise addition, heating to 89 ℃, and carrying out heat preservation reaction for 3 hours to obtain a liquid active condensation polymer; putting the liquid product in a closed container, adding 4 parts by mass of dibromopropane, uniformly mixing, then carrying out heat preservation reaction at 100 ℃ for 15 hours to obtain crosslinked solid resin, and crushing the product to obtain 1.4mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.635 mmol/g.
Example 10
Dissolving 8 parts by mass of ammonium sulfite, 5 parts by mass of magnesium lignosulfonate and 10 parts by mass of cyclohexanone in 55 parts by mass of water, heating to 35 ℃ for reaction for 15 minutes, and then dropwise adding 11 parts by mass of glutaraldehyde within 1 hour; after the dropwise addition, heating to 90 ℃, and carrying out heat preservation reaction for 1 hour to obtain a liquid active condensation polymer; and putting the liquid product in a closed container, adding 2 parts by mass of epoxy chloropropane, uniformly mixing, then carrying out heat preservation reaction at 95 ℃ for 24 hours to obtain crosslinked solid resin, and crushing the product to obtain 1.6mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.707 mmol/g.
Example 11
Dissolving 4 parts by mass of potassium sulfite, 9 parts by mass of calcium lignosulfonate and 10 parts by mass of 2-pentanone in 40 parts by mass of water, heating to 60 ℃, reacting for 10 minutes, and then dropwise adding 10 parts by mass of formaldehyde in 45 minutes; after the dropwise addition, heating to 87 ℃ and carrying out heat preservation reaction for 2 hours to obtain a liquid active condensation polymer; putting the liquid product in a closed container, adding 3.5 parts by mass of dibromoethane, uniformly mixing, then carrying out heat preservation reaction at 90 ℃ for 20 hours to obtain crosslinked solid resin, and crushing the product to obtain cation exchange resin particles with the particle size of 2.3 mm.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.543 mmol/g.
Example 12
Dissolving 6 parts by mass of sodium sulfite, 12 parts by mass of sodium lignin sulfonate and 9 parts by mass of acetone in 35 parts by mass of water, heating to 40 ℃, reacting for 15 minutes, and dripping 13 parts by mass of furfural within 1 hour; after the dropwise addition, heating to 95 ℃ and carrying out heat preservation reaction for 3 hours to obtain a liquid active condensation polymer; and (3) putting the liquid product in a closed container, adding 3 parts by mass of epoxy chloropropane, uniformly mixing, then carrying out heat preservation reaction at 90 ℃ for 24 hours to obtain crosslinked solid resin, and crushing the product to obtain 3mm cation exchange resin particles.
The sulfonic acid group content of the exchange resin product obtained in this example was 2.871 mmol/g.
Description of the effects of the embodiments
Table 1 is a table of data of elemental analysis of resins of examples 1 to 3, and the results of the elemental analysis were calculated to obtain theoretical sulfonic acid group capacities (mmol/g) of the samples
Table 1 elemental analysis results for the resins of examples 1-3
As can be seen from the elemental analysis data in Table 1, as the ratio of sulfite to lignosulfonate increased, the sulfur content of the product increased, and the sulfonic acid group content of the product calculated from the sulfur content also increased, so the theoretical exchange equivalent of the product also increased. FIG. 1 is an infrared spectrum of a crosslinked lignin sulfonate cation exchange resin obtained in examples 1 to 3.
The above 3 samples of examples were used to perform a homogeneously mixed ion exchange experiment with calcium and magnesium ion solutions (molar ratio of calcium ions to magnesium ions 1:1) at a concentration of 25 mmol/L, 50 mmol/L, 100 mmol/L, respectively, in a mass ratio of 1:5, and after 24h exchange in a vibrating shaker at 25 ℃ and 200r/min, the dry base exchange equivalents of the samples of examples 1-3 were measured and compared with the exchange performance of a commercial cation exchange resin of type #732 (crosslinked polystyrene sulfonic acid type cation exchange resin), and the results are shown in Table 2:
TABLE 2 Dry base exchange equivalents (in mmol/g) of samples from example 1-example 3 with #732 resin
As can be seen from the results of the exchange experiments in Table 2, the cation exchange resins synthesized in examples 1-3 all have larger dry-basis exchange equivalent in three solutions of 25 mmol/L, 50 mmol/L and 100 mmol/L of Ca and Mg ions than the commercial strong-acid cation exchange resin #732, and the dry-basis exchange equivalent in the working solution of 100 mmol/L of the 3 resins is very close to the theoretical exchange equivalent calculated in Table 1, which shows that the ion exchange resin synthesized by the invention not only shows better dry-basis exchange equivalent than the commercial resin, but also has high utilization rate of effective groups in the resin and better performance of the resin.
The cation exchange resins synthesized in examples 1 to 3 were subjected to a regeneration test in a working solution of calcium and magnesium ions of 50 mmol/L, and the regeneration performance of the resins of examples 1 to 3 and the type #732 resin was compared, the regeneration test was conducted by washing and filtering the resin after the first exchange with water, mixing and regenerating the filtered wet-based resin with a 10% by mass sodium chloride solution at a mass ratio of 1:1, washing the regenerated resin after 24 hours in a shaking table at 25 ℃ and 200r/min, and filtering to obtain a wet-based resin, mixing and exchanging the obtained regenerated resin with a working solution of calcium and magnesium ions of 50 mmol/L at a mass ratio of 1:5, and then measuring the dry-based exchange equivalent of the resin, i.e., completing the first regeneration test, repeating seven times, measuring the regeneration performance of the resin synthesized in examples and the commercial resin seven times, the test results are shown in FIG. 2, and after seven times of regeneration, the dry-based exchange equivalent ratio of the synthetic resins of examples 1 to 3 was close to that of the cation exchange resin prepared in the other examples # resin, and showing that the strong acid exchange performance of the resin prepared in examples # 1 was higher than that of the other examples # resin prepared, and No. L.
The crosslinked lignosulfonate cation exchange resin prepared in the embodiment of the invention takes sulfite, lignosulfonate, ketone and aldehyde as raw materials, lignin-based polycondensate is synthesized through a hydroxyketone condensation reaction, and then the lignin sulfonate cation exchange resin is obtained through high-temperature crosslinking and resinification. The cation exchange resin is sulfonated and then crosslinked, the traditional production process of crosslinking first and then sulfonating is overturned, not only ketone units are sulfonated and introduced into a large number of sulfonic groups in the prepared crosslinked resin, but also raw material lignosulfonate contains a large number of sulfonic groups, so that the sulfonated group content of the product resin is high, and the actual exchange equivalent is high; and the sulfonation reaction is mild, the synthesis process is simple and controllable, and the cost of raw materials is low. The dry-base exchange equivalent of the cation exchange resin is higher than that of the #732 polystyrene cation exchange resin, can be directly used for exchanging calcium and magnesium ions in hard water, can be widely applied to the fields of industrial water treatment, metallurgy and the like, and has wide application value.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A preparation method of cross-linking type lignosulfonic acid cation exchange resin is characterized in that sulfite, ketone, lignosulfonate and aldehyde are subjected to aldol condensation reaction to obtain active polycondensate; adding a cross-linking agent, preserving heat, curing and carrying out cross-linking reaction to obtain cross-linked lignin sulfonic cation exchange resin; the dosage of each component is calculated by mass portion: 3-8 parts of sulfite, 4-10 parts of ketone, 5-15 parts of lignosulfonate, 5-15 parts of aldehyde and 2-5 parts of cross-linking agent;
wherein, the aldol condensation reaction firstly mixes and heats sulfite, ketone and lignosulfonate for reaction, and then adds aldehyde for heating reaction.
2. The method for preparing a crosslinked lignin sulfonic acid cation exchange resin according to claim 1, wherein: the temperature of the crosslinking reaction is 90-100 ℃; the reaction time is 12-24 h.
3. The method for preparing a crosslinked lignin sulfonic acid cation exchange resin according to claim 1, wherein: the sulfite comprises at least one of sodium sulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite and ammonium sulfite.
4. The method for preparing a crosslinked lignin sulfonic acid cation exchange resin according to claim 1, wherein: the ketone comprises at least one of acetone, butanone, 2-pentanone and cyclohexanone.
5. The method for preparing a crosslinked lignin sulfonic acid cation exchange resin according to claim 1, wherein: the lignosulfonate comprises at least one of sodium lignosulfonate, potassium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate, calcium lignosulfonate and sulfonated alkali lignin.
6. The method for preparing a crosslinked lignin sulfonic acid cation exchange resin according to claim 1, wherein: the aldehyde comprises at least one of formaldehyde, acetaldehyde, propionaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and furfural; the cross-linking agent comprises at least one of epichlorohydrin, dibromoethane and dibromopropane.
7. The method for preparing the cross-linked lignin sulfonic cation exchange resin according to claim 1, characterized by comprising the following specific steps: dissolving 3-8 parts of sulfite, 4-10 parts of ketone and 5-15 parts of lignosulfonate in 30-60 parts of water by mass, heating to 40-60 ℃ for reaction, then dropwise adding 5-15 parts of aldehyde, heating to 85-95 ℃ for heat preservation reaction to obtain a liquid active polycondensate; placing the mixture into a closed container, adding 2-5 parts of cross-linking agent, uniformly mixing, and carrying out heat preservation reaction at 90-100 ℃ to obtain the cross-linked lignin sulfonic cation exchange resin.
8. A cross-linked lignin sulfonate cation exchange resin characterized by being prepared according to the method of any one of claims 1 to 7.
9. Use of the cross-linked lignin sulfonate cation exchange resin of claim 8 in the field of industrial water treatment.
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