CN109749031B - A kind of cross-linked sulfonated aldehyde and ketone cation exchange resin and its preparation method and application - Google Patents

Abstract

The invention belongs to the technical field of cation exchange resin, and discloses a cross-linked sulfonated aldehyde and ketone cation exchange resin and a preparation method and application thereof. In the method of the invention, sulfites, ketones and aldehydes are first subjected to aldol condensation reaction to obtain oligomers, and then phenol is added to carry out thermal insulation polycondensation reaction to prepare active polycondensates; resin. The invention also provides the cross-linked sulfonated aldehyde and ketone cation exchange resin obtained by the above method, and its application in the removal of calcium and magnesium ions from hard water. The method of the invention is first sulfonated and then cross-linked, which subverts the traditional production process of first cross-linking and then sulfonated, and the sulfonation reaction is mild, and the process is simple and controllable; the ketone units in the obtained exchange resin are fully sulfonated, and the actual exchange equivalent Higher than #732 polystyrene cation exchange resin, it can be directly used in the exchange of calcium and magnesium ions in hard water, and can be widely used in water treatment, food, metallurgy and other fields, and has a wide range of application value.

Description

A kind of cross-linked sulfonated aldehyde and ketone cation exchange resin and its preparation method and application

technical field

The invention belongs to the technical field of cation exchange resins, and particularly relates to a cross-linked sulfonated aldehyde and ketone cation exchange resin and a preparation method and application thereof.

Background technique

Ion exchange resin, as a cross-linked polymer loaded with active groups, has the functions of exchange, absorption and catalysis, and is mainly used in water treatment, food, electric power, medicine and health and metallurgy and other fields. In my country, the amount of strong acid cation exchange resin is very large, accounting for 80% of the total output of ion exchange resin. At present, most of the commercial cation exchange resins are made of styrene and acrylic acid (ester) as raw materials, and cross-linking polymerization with the cross-linking agent divinyl benzene to prepare a body-shaped polymer with a network skeleton structure, and then sulfonated with fuming sulfuric acid. Preparation of sulfonated polystyrene cation exchange resin. The sulfonated polystyrene cation exchange resin uses fuming sulfuric acid to sulfonate the styrene skeleton, and the sulfonation reaction is dangerous, and the sulfonation reaction is not sufficient, and the actual exchange equivalent of the resin is low.

At present, there are two main directions for the research and development of new cation exchange resins: one is a composite polystyrene cation exchange resin obtained by cross-linking reaction of fossil raw materials and biomass raw materials. Patent CN107519947A (a preparation method of polystyrene cation exchange resin for sewage treatment) discloses a method for preparing composite polystyrene by reacting calcined cotton rod, zeolite powder, ethyl styrene, methylene bisacrylamide, etc. Cation exchange resin has low cost of raw materials, and is used in sewage treatment, with good adsorption effect, but low exchange equivalent; patent CN107652406A (a preparation method of strong acid polystyrene cation exchange resin) discloses a kind of cation exchange resin with methyl Strong acid polystyrene cation exchange resin prepared by reacting styrene, methylene bisacrylamide, pretreated rice husk, gelatin, etc., solves the problem of traditional polystyrene cation exchange resin with compact structure and low degree of crosslinking The problem.

The other is to prepare bio-based cation exchange resins from biomass resources. Patent CN108325568A (a preparation method of lignin-based strong acid cation exchange resin) uses lignin, phenol, sulfonating reagent, formaldehyde, etc. as raw materials to synthesize a lignin-based strong acid cation exchange resin with high cation exchange capacity in one step. Yasuda et al. (JWood Sci (2000) 46:477-479) used acid-hydrolyzed lignin as raw material to synthesize strong acid cation exchange resin through phenolization, sulfonation and acidification. However, the activity of the prepared resin is lower and the exchange equivalent is smaller.

To sum up, most of the existing strong acid type cation exchange resins are sulfonated cross-linked polystyrene type cation exchange resins, or copolymers or composites of styrene and other monomers and fillers. Although the application of sulfonated cross-linked polystyrene type cation exchange resin is common, such as #732 type cation exchange resin, the sulfonation reaction of oleum is very dangerous; and it is first polymerized and then sulfonated, and the sulfonation efficiency is low. The actual exchange equivalent of the resin is much lower than the theoretical exchange equivalent. The actual exchange equivalents of composite polystyrene cation exchange resin and bio-based cation exchange resin are not ideal. How to synthesize strong acid cation exchange resin under mild conditions and effectively increase its actual exchange equivalent is a difficult problem to be solved in the field of strong acid cation exchange resin.

SUMMARY OF THE INVENTION

In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a mild preparation method for the sulfonation reaction of a cross-linked sulfonated aldehyde-ketone cation exchange resin.

The preparation method of the invention firstly performs aldol condensation reaction with sulfite, ketone and aldehyde to obtain an oligomer, then adds phenol to carry out a polycondensation reaction to prepare an active polycondensate, and the cross-linked sulfonated aldehyde is obtained by thermal insulation curing and cross-linking reaction under alkaline condition Ketone cation exchange resin. The preparation method of the invention is sulfonated first and then cross-linked, and the reaction is mild and controllable.

Another object of the present invention is to provide a cross-linked sulfonated aldehyde and ketone cation exchange resin prepared by the above method. The cation exchange resin of the present invention is a strong acid type cation exchange resin with a novel structure, which has high exchange equivalent, especially high exchange equivalent for calcium and magnesium ions in hard water.

Another object of the present invention is to provide the application of the above-mentioned cross-linked sulfonated aldehyde-ketone cation exchange resin in the removal of calcium and magnesium ions from hard water.

The object of the present invention is realized through the following scheme:

A method for preparing a cross-linked sulfonated aldehyde-ketone cation exchange resin with mild sulfonation reaction, firstly performing aldol condensation reaction with sulfite, ketone and aldehyde to obtain oligomer, and then adding phenol to carry out thermal insulation polycondensation reaction to prepare active polycondensation heat preservation curing crosslinking reaction to obtain crosslinked sulfonated aldehyde and ketone cation exchange resin.

In the preparation method of the present invention, the dosage of each component is calculated in parts by mass: 8-12 parts of sulfite, 6-12 parts of ketone, 7-14 parts of aldehyde, and 1-5 parts of phenol.

In the present invention, the sulfite can be, but not limited to, at least one of potassium sulfite, sodium sulfite, potassium hydrogen sulfite, sodium metabisulfite, potassium metabisulfite, and ammonium sulfite.

In the present invention, the ketone may be, but not limited to, at least one of acetone, butanone, 2-pentanone, and cyclohexanone.

In the present invention, the aldehyde can be, but not limited to, at least one of formaldehyde, acetaldehyde, propionaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, and furfural.

In the present invention, the aldol condensation reaction with sulfite, ketone and aldehyde to obtain oligomer first, sulfite and ketone can be added to water for mixing reaction, and then aldehyde is added for heating reaction to obtain oligomer.

The temperature of the mixing reaction is preferably 50-57° C., and the reaction time is preferably 10-20 min.

The temperature of the temperature-raising reaction is preferably 80-90° C., and the reaction time is preferably 1-3 h.

The added amount of the water is preferably 40 to 50 parts by mass.

The aldehyde is preferably added dropwise, more preferably, the dropwise addition is completed within 0.5-1 h.

In the present invention, the temperature of the thermal insulation polycondensation reaction is preferably 85-95° C., and the reaction time is preferably 10-15 min.

In the present invention, the thermal insulation curing crosslinking reaction is preferably carried out in a closed container. The temperature of the heat preservation is preferably 90-95°C; the reaction time is preferably 12-24 h.

More specifically, the preparation method of the present invention comprises the following steps:

In parts by mass, dissolve 8 to 12 parts of sulfite and 6 to 12 parts of ketone in 40 to 50 parts of water, heat up to 50 to 57 °C for reaction; then add 7 to 14 parts of aldehyde dropwise, and heat up to 80 to 90 ℃ heat preservation reaction; then add 1～5 parts of phenol, heat preservation reaction at 85～95 ℃ to obtain active polycondensate; place it in a closed container, heat at 90～95 ℃ for 12～24 hours to obtain cross-linked sulfonated Aldehyde and ketone cation exchange resin.

The present invention also provides the cross-linked sulfonated aldehyde-ketone cation exchange resin prepared by the above method. The cation exchange resin of the present invention is a strong acid type cation exchange resin with a new structure, which has a high exchange equivalent, especially the exchange equivalent of calcium and magnesium ions in hard water, which is much higher than that of the traditional sulfonated polyethylene cation exchange resin. It can be used in the removal of calcium and magnesium ions from hard water.

The cross-linked sulfonated aldehyde ketone cation exchange resin of the present invention has a high exchange equivalent mainly based on:

(1) The traditional production process of sulfonated polystyrene cation exchange resin is to prepare polystyrene skeleton first, and then sulfonate the skeleton resin. Many styrenes in the polystyrene skeleton are not fully sulfonated, so sulfonation The efficiency is low, resulting in the actual exchange equivalent being much lower than the theoretical exchange equivalent;

(2) In the method of the present invention, the ketone unit is firstly sulfonated and grafted, and then the polycondensation crosslinking reaction is performed. The ketone unit in the obtained exchange resin is fully sulfonated, so the sulfonation efficiency is high and the actual exchange equivalent is high.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

1. The sulfonation reaction of the preparation method of the present invention is mild, the synthesis process is simple and controllable, and the cost of raw materials is low.

2. The cation exchange resin of the present invention is first sulfonated and then cross-linked, which subverts the traditional production process of first cross-linking and then sulfonated. The ketone units in the prepared exchange resin are fully sulfonated, the sulfonation efficiency is high, and the content of sulfonated groups is high. high, the actual exchange equivalent is high.

3. The ketosulfonic acid cation exchange resin of the present invention enriches the types of strong acid cation exchange resins and broadens the research scope of strong acid cation exchange resins.

Description of drawings

FIG. 1 is an infrared spectrum diagram of the cross-linked sulfonated aldehyde and ketone cation exchange resins obtained in Examples 1 to 4. FIG.

Figure 2 is a graph showing the regeneration exchange performance of the cross-linked sulfonated aldehyde ketone cation exchange resin obtained in Examples 1 to 4 and the #732 type commercial resin.

Detailed ways

The present invention will be described in further detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.

The materials involved in the following examples can be obtained from commercial sources. The amount of each material is in parts by mass.

Example 1

10 parts of sodium sulfite and 9 parts of acetone were dissolved in 45 parts of water, then the temperature was raised to 55°C for 10 minutes, and then 10.6 parts of formaldehyde were added dropwise within 0.5 hour; 1.5 parts of phenol was incubated and reacted at 90°C for 10 minutes to obtain a liquid reactive polycondensate; the liquid product was placed in a closed container, and the reaction was incubated at 95°C for 12 hours to obtain a cross-linked solid resin. The product was crushed to obtain cations of 2 mm Exchange resin particles.

The sulfonic acid group content of the exchange resin product obtained in this example was 2.619 mmol/g.

Example 2

10 parts of potassium sulfite and 7.5 parts of acetone were dissolved in 40 parts of water, then the temperature was raised to 50°C for 15 minutes, and then 9 parts of formaldehyde were added dropwise within 0.5 hours; Then, 1 part of phenol was added, and the reaction was kept at 95°C for 15 minutes to obtain a liquid reactive polycondensate; the liquid product was placed in a closed container, and the reaction was kept at 95°C for 24 hours to obtain a cross-linked solid resin. The product was crushed to obtain 3mm of cation exchange resin particles.

The sulfonic acid group content of the exchange resin product obtained in this example was 2.988 mmol/g.

Example 3

10 parts of sodium bisulfite and 7.5 parts of acetone were dissolved in 42 parts of water, then the temperature was raised to 57°C for 20 minutes, and 9.6 parts of formaldehyde were added dropwise within 0.5 hour; , then add 1.2 parts of phenol, and react at 95°C for 10 minutes to obtain a liquid reactive polycondensate; put the liquid product in a closed container, and keep the reaction at 95°C for 24 hours to obtain a cross-linked solid resin. The product can be obtained by crushing 1mm cation exchange resin particles.

The sulfonic acid group content of the exchange resin product obtained in this example was 3.030 mmol/g.

Example 4

10 parts of sodium sulfite and 6.4 parts of acetone were dissolved in 45 parts of water, then the temperature was raised to 53°C for 10 minutes, and 7.6 parts of formaldehyde were added dropwise within 0.5 hours; 1 part of phenol was incubated and reacted at 95°C for 10 minutes to obtain a liquid reactive polycondensate; the liquid product was placed in a closed container, and the reaction was kept at 95°C for 18 hours to obtain a cross-linked solid resin. Cation exchange resin particles.

The sulfonic acid group content of the exchange resin product obtained in this example was 3.176 mmol/g.

Example 5

10 parts of sodium sulfite and 6 parts of acetone were dissolved in 45 parts of water, then the temperature was raised to 55°C for 10 minutes, and then 7 parts of formaldehyde were added dropwise within 0.5 hours; 1.2 parts of phenol were incubated at 95°C for 15 minutes to obtain a liquid reactive polycondensate; the liquid product was placed in a closed container, and the reaction was kept at 95°C for 24 hours to obtain a cross-linked solid resin. The product was crushed to obtain 2mm cationic Exchange resin particles.

The sulfonic acid group content of the exchange resin product obtained in this example was 3.252 mmol/g.

Example 6

Dissolve 8 parts of potassium sulfite and 8 parts of butanone in 40 parts of water, then heat up to 52 ° C for 20 minutes, and then add 9 parts of acetaldehyde dropwise within 45 minutes; 2 hours, then add 2 parts of phenol, keep the reaction at 90 °C for 10 minutes to obtain a liquid reactive polycondensate; put the liquid product in a closed container, and keep the reaction at 95 °C for 12 hours to obtain a cross-linked solid resin. 3 mm cation exchange resin particles were obtained.

The sulfonic acid group content of the exchange resin product obtained in this example was 2.668 mmol/g.

Example 7

8 parts of potassium hydrogen sulfite, 2 parts of ammonium sulfite and 10 parts of butanone were dissolved in 48 parts of water, then the temperature was raised to 54°C for 15 minutes, and 9.5 parts of propionaldehyde were added dropwise within 45 minutes; Be warmed up to 85 ℃ of insulation reactions for 3 hours, then add 2.5 parts of phenol, at 85 ℃ of insulation reactions for 15 minutes, to obtain a liquid reactive polycondensate; the liquid product is placed in a closed container, and at 95 ℃ of insulation reactions for 15 hours to obtain cross-linked polycondensates. Solid resin, the product can be crushed to obtain cation exchange resin particles of 1.8mm.

The sulfonic acid group content of the exchange resin product obtained in this example was 2.473 mmol/g.

Example 8

11 parts of sodium metabisulfite and 12 parts of 2-pentanone were dissolved in 50 parts of water, then the temperature was raised to 56 °C for 15 minutes, and then 11 parts of malondialdehyde were added dropwise within 1 hour; after the dropwise addition, the temperature was raised to 90 °C for insulation The reaction was carried out for 2 hours, then 3 parts of phenol were added, and the reaction was kept at 93°C for 10 minutes to obtain a liquid reactive polycondensate; the liquid product was placed in a closed container, and the reaction was kept at 95°C for 20 hours to obtain a cross-linked solid resin. Pulverization yields cation exchange resin particles of 2.4 mm.

The sulfonic acid group content of the exchange resin product obtained in this example was 2.214 mmol/g.

Example 9

10 parts of potassium metabisulfite and 10 parts of acetone were dissolved in 47 parts of water, then the temperature was raised to 50°C for 20 minutes, and then 14 parts of succinaldehyde were added dropwise within 1 hour; after the addition was completed, the temperature was raised to 87°C for reaction After 3 hours, 3.5 parts of phenol were added, and the reaction was kept at 87°C for 10 minutes to obtain a liquid reactive polycondensate; the liquid product was placed in a closed container, and the reaction was kept at 95°C for 15 hours to obtain a cross-linked solid resin, and the product was crushed Cation exchange resin particles of 1.4 mm were obtained.

The sulfonic acid group content of the exchange resin product obtained in this example was 2.618 mmol/g.

Example 10

Dissolve 12 parts of ammonium sulfite and 12 parts of cyclohexanone in 45 parts of water, then heat up to 55°C for 15 minutes, and then add 13 parts of glutaraldehyde dropwise within 1 hour; after the dropwise addition, heat up to 90°C for insulation The reaction was performed for 1 hour, then 5 parts of phenol were added, and the reaction was incubated at 95°C for 15 minutes to obtain a liquid reactive polycondensate; the liquid product was placed in a closed container, and the reaction was incubated at 95°C for 24 hours to obtain a cross-linked solid resin. Pulverization yields cation exchange resin particles of 1.6 mm.

The sulfonic acid group content of the exchange resin product obtained in this example was 2.707 mmol/g.

Example 11

8 parts of potassium sulfite, 3 parts of potassium metabisulfite and 10 parts of 2-pentanone were dissolved in 50 parts of water, then the temperature was raised to 57°C for 10 minutes, and then 10 parts of formaldehyde were added dropwise within 45 minutes; , heat the temperature to 88°C for 2 hours, then add 4 parts of phenol, and keep the reaction at 88°C for 10 minutes to obtain a liquid reactive polycondensate; put the liquid product in a closed container, and keep the reaction at 95°C for 20 hours to obtain cross-linking. 2.3mm cation exchange resin particles can be obtained by crushing the product.

The sulfonic acid group content of the exchange resin product obtained in this example was 2.553 mmol/g.

Example 12

Dissolve 6 parts of sodium sulfite, 2 parts of ammonium sulfite and 9 parts of acetone in 40 parts of water, then heat up to 50°C for 15 minutes, and then add 14 parts of furfural dropwise within 1 hour; after the dropwise addition, heat up to 90°C for insulation The reaction was performed for 3 hours, then 5 parts of phenol were added, and the reaction was incubated at 93°C for 15 minutes to obtain a liquid reactive polycondensate; the liquid product was placed in a closed container, and the reaction was incubated at 95°C for 24 hours to obtain a cross-linked solid resin. Pulverization yields cation exchange resin particles of 3 mm.

The sulfonic acid group content of the exchange resin product obtained in this example was 3.029 mmol/g.

Description of the effect of the embodiment

Table 1 is the elemental analysis data table of Examples 1 to 5, and the elemental analysis results are calculated to obtain the theoretical sulfonate capacity (mmol/g) of the sample.

Table 1 Elemental analysis of samples from Examples 1 to 5

From the elemental analysis data in Table 1, it can be seen that with the increase of the sulfite ratio, the sulfur content in the product continues to increase, and the sulfonic acid group content of the product calculated according to the sulfur content also continues to increase, so the theoretical exchange equivalent of the product is also keep improving. The above-mentioned five embodiment samples are respectively used to mix the calcium and magnesium ion solutions with concentrations of 25mmol/L, 50mmol/L and 100mmol/L (the molar ratio of calcium ions and magnesium ions is 1:1) according to the mass ratio of 1:5. In the ion exchange experiment, after exchanging 24h in a shaking shaker at 25°C and 200r/min, measure the dry basis exchange equivalents of the samples from Examples 1 to 5, and compare them with commercial #732 cation exchange resin (cross-linked polymer The exchange performance of styrene sulfonic acid type cation exchange resin) is compared, and the results are shown in Table 2:

Table 2 Dry basis exchange equivalents of resin samples of Examples 1 to 5 and #732 resin (unit: mmol/g)

As can be seen from the results of the exchange experiments in Table 2, the dry basis exchange equivalents of the cation exchange resins synthesized in Examples 1 to 5 in three different concentrations of calcium and magnesium ion solutions of 25 mmol/L, 50 mmol/L and 100 mmol/L All are larger than the commercial #732 strong acid cation exchange resin. And the dry basis exchange equivalents of the five resins in the 100 mmol/L working solution are very close to the theoretical exchange equivalents calculated in Table 1, which shows that the ion exchange resin synthesized by the method of the present invention not only shows a dry basis that is better than that of commercial resins. Exchange equivalent, and the utilization rate of effective groups in the resin is also high, and the performance of the resin is better.

The cation exchange resins synthesized in Examples 1 to 4 were subjected to regeneration experiments in 50 mmol/L calcium and magnesium ion working solution, and the regeneration performance of the resins of Examples 1 to 4 and #732 exchange resins were compared. The regeneration experiment method is as follows: the resin after the first exchange is washed and filtered with water, and the filtered wet-based resin and the sodium chloride solution with a mass fraction of 10% are mixed and regenerated according to the mass ratio of 1:1. After working for 24h in a vibrating shaker for min, the regenerated resin was washed and filtered to obtain a wet-based resin. The obtained regenerated resin was mixed and exchanged with 50 mmol/L calcium and magnesium ion working solution according to the mass ratio of 1:5, and then the dry basis exchange equivalent of the resin was measured, that is, the first regeneration experiment was completed. This is repeated seven times, and the regeneration capacity of the resin synthesized in the embodiment and the commercial resin is measured seven times. The experimental results are shown in FIG. 2 . It can be seen from Figure 2 that after seven regenerations, the dry basis exchange equivalents of the synthetic resins in Examples 1 to 4 are higher than those of the #732 strongly acidic cation exchange resin, and the ion exchange capacity after regeneration is greater than or equal to 1 mmol/L. FIG. 1 is an infrared spectrum diagram of the cross-linked sulfonated aldehyde and ketone cation exchange resins obtained in Examples 1 to 4. FIG.

The sulfonated aldehyde-ketone resin cation exchange resin prepared in the above embodiment of the present invention uses sulfite, ketone, aldehyde and phenol as raw materials to synthesize sulfonated aldehyde-ketone polycondensate through aldehyde-ketone condensation reaction, and then high-temperature cross-linking resin is obtained to obtain sulfonic acid Acid type cation exchange resin. The cation exchange resin of the invention is first sulfonated and then cross-linked, which subverts the traditional production process of first cross-linking and then sulfonated. The actual exchange equivalent is high. The sulfonation reaction is mild, the synthesis process is simple and controllable, and the cost of raw materials is low. The dry basis exchange equivalent of the cation exchange resin of the invention is higher than that of the #732 type polystyrene type cation exchange resin, and can be directly used for the exchange of calcium and magnesium ions in hard water, and can be widely used in water treatment, food, metallurgy and other fields. Broad application value.

The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, The simplification should be equivalent replacement manners, which are all included in the protection scope of the present invention.

Claims (9)

1. A preparation method of cross-linking sulfonated aldehyde ketone cation exchange resin is characterized in that firstly sulfite, ketone and aldehyde are subjected to aldol condensation reaction to obtain oligomer, and then phenol is added to carry out thermal insulation polycondensation reaction to prepare active polycondensate; carrying out heat preservation, curing and crosslinking reaction to obtain a crosslinking sulfonated aldehyde ketone cation exchange resin;

the dosage of each component is calculated by mass portion: 8-12 parts of sulfite, 6-12 parts of ketone, 7-14 parts of aldehyde and 1-5 parts of phenol.

2. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising: the sulfite comprises at least one of potassium sulfite, sodium sulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite and ammonium sulfite;

the ketone comprises at least one of acetone, butanone, 2-pentanone and cyclohexanone; the aldehyde comprises at least one of formaldehyde, acetaldehyde, propionaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde and furfural.

3. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising: firstly, carrying out aldol condensation reaction on sulfite, ketone and aldehyde to obtain an oligomer, firstly adding the sulfite and the ketone into water for mixing reaction, then adding the aldehyde for heating reaction to obtain the oligomer.

4. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 3, comprising: the temperature of the mixing reaction is 50-57 ℃, and the reaction time is 10-20 min; the temperature of the heating reaction is 80-90 ℃, and the reaction time is 1-3 h.

5. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising: the temperature of the heat preservation polycondensation reaction is 85-95 ℃, and the reaction time is 10-15 min.

6. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising: the heat preservation temperature of the heat preservation curing crosslinking reaction is 90-95 ℃; the reaction time is 12-24 h.

7. The method for preparing a crosslinked sulfonated aldehyde ketone cation exchange resin according to claim 1, comprising the steps of: dissolving 8-12 parts by mass of sulfite and 6-12 parts by mass of ketone in 40-50 parts by mass of water, and heating to 50-57 ℃ for reaction; dropwise adding 7-14 parts of aldehyde, heating to 80-90 ℃, and carrying out heat preservation reaction; then adding 1-5 parts of phenol, and carrying out heat preservation reaction at 85-95 ℃ to obtain a reactive condensation polymer; placing the mixture into a closed container, and preserving the heat for 12-24 hours at the temperature of 90-95 ℃ to obtain the cross-linked sulfonated aldehyde ketone cation exchange resin.

8. A crosslinked sulfonated aldehyde ketone cation exchange resin characterized by being obtained by the production method according to any one of claims 1 to 7.

9. Use of the cross-linked sulfonated aldehyde ketone cation exchange resin of claim 8 for removing calcium and magnesium ions from hard water.

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