CN105037601B - A kind of anti-pollution moldeed depth degree softens the synthetic method of chelating resin - Google Patents

Abstract

The invention discloses a method for synthesizing a pollution-resistant deep softening chelating resin, which comprises the following steps: using styrene monomer, divinylbenzene crosslinking agent, porogen, and initiator to prepare an oil phase; using water, dispersing The water phase is formulated with NaCl and NaCl; the oil phase is put into the water phase, the temperature is lowered after the heating process, and the material is discharged, washed, extracted, dried, and sieved to obtain the polystyrene system of pollution-resistant deep softening chelating resin. Then carry out chloromethylation reaction, transformation obtains polystyrene chlorine ball; Stir and expand polystyrene chlorine ball with dichloroethane, throw N-hydroxymethylphthalimide and acetic anhydride, and drop Add catalyst, then heat up, keep warm, cool down, drain the mother liquor, add water, distill under reduced pressure, and clean; add 25% liquid caustic soda, heat up, stabilize, wash with water, then add chloroacetic acid solution for chelation reaction, heat up, keep warm , water washing, acid adjustment, water washing, alkali adjustment, and then water washing to neutral discharge packaging, that is, pollution-resistant deep softening chelating resin.

Description

A kind of synthesis method of anti-pollution deep softening chelating resin

technical field

The invention relates to the technical field of polymer material synthesis in the sewage treatment industry, in particular to a method for synthesizing a pollution-resistant deep softening chelating resin.

Background technique

Chelating resins are a class of cross-linked functional polymer materials that can form multi-coordination complexes with metal ions . The mechanism of chelating resin to adsorb metal ions is that the functional atoms on the resin undergo a coordination reaction with metal ions to form a stable structure similar to small molecular chelates. Chelating resins have a stronger binding force with metal ions than ordinary ion exchange resins. During the deep softening process, the chelating resin can stably keep the concentration of calcium and magnesium ions in the effluent down to ppb level, which is the best choice for deep softening. However, when dealing with sewage containing a large amount of background substances such as humic acid and soluble animal and vegetable oils, ordinary chelating resins are used for deep softening. The chelating resins are easily blocked by dissolved organic matter and cannot leach heavy metal ions in a complex state. The working exchange capacity of the chelating resin is greatly weakened, causing irreversible pollution to the resin.

Contents of the invention

The technical problem to be solved by the present invention is to provide a simple production process, strong anti-pollution performance, good sewage treatment effect, large total exchange capacity, and efficient removal of metal ions in water in sewage with high organic content, aiming at the current state of the prior art. A method for synthesizing a pollution-resistant deep softening chelating resin.

The technical solution adopted by the present invention to solve the above-mentioned technical problems is: a kind of synthetic method of anti-pollution type deep softening chelating resin, and this synthetic method comprises the following steps:

a) Prepare the oil phase in the oil phase preparation kettle. The oil phase is composed of reactants, porogens and initiators; add the reactants and porogens into the oil phase preparation kettle at a mass ratio of 1:0.5 Mix, and add the initiator according to the proportion of 1%-1.5% of the total mass of the oil phase to make it fully dissolved, and then stabilize it in the oil phase preparation kettle for 30 minutes to form the oil phase; the above-mentioned reactants include styrene monomer and divinylbenzene crosslinking agent;

b), prepare a water phase in the polymerization kettle, the water phase is an aqueous solution containing a dispersant and NaCl, based on the total mass of the water phase, the concentration of the dispersant is 3wt%, and the concentration of NaCl is 15 wt%-17wt%; Put water, dispersant and NaCl into the polymerization tank, and raise the temperature to 60°C while stirring, and stabilize for 10 minutes to form a water phase;

c) In the polymerization kettle, the oil phase formed in step a is added to the water phase under stirring according to the ratio of the water phase to the mass of styrene monomer in a ratio of 3:1-1:1 to carry out suspension polymerization to form Multi-phase polymerization system, in which a small amount of methylene blue is added, the stirring speed is changed from slow to fast, and the stirring speed is controlled at 150-250rpm; after the addition, the temperature is raised to 75°C and kept for 3 hours, and the resin skeleton is basically finalized;

d), raise the temperature in the polymerization kettle to 85°C and keep it warm for 2 hours; then raise the temperature to 95°C and keep it warm for 5 hours; cool down, discharge, and wash; drain free water, and extract with acetone; extract to no oil , wash with water until there is no acetone smell, and discharge; dry and sieve into feed granules with appropriate particle size; then further dry the feed granules, screen and cool to obtain polystyrene-based white balls of pollution-resistant deep softening chelating resin ;

e) Mix the dried polystyrene-based white ball and methyl chloride ether at a temperature of 100°C-120°C, and mix the ratio of polystyrene-based white ball to methyl chloride ether 1:0.5-1:2 by mass ratio , carry out chloromethylation reaction, then gradually dilute the product, transform it with hydrochloric acid and sodium hydroxide, and wash it with water to obtain polystyrene-based chlorine balls;

f) Stir and expand polystyrene chlorine balls with dichloroethane for 1 hour, throw N-methylolphthalimide and acetic anhydride, after throwing, start adding catalyst dropwise, and control the exothermic temperature of the reaction not to exceed 60°C; After the catalyst drops, stabilize for half an hour, then raise the temperature to 75°C-80°C, and keep it warm for 12 hours; Wash with water for more than 5 times, until the water is colorless;

g), then add 25% liquid caustic soda, slowly raise the temperature to 80°C, stabilize for 1 hour, close the vent; then raise the temperature to 120°C, slowly open the vent after stabilizing for 2 hours, and close the vent after evacuating the pressure; then raise the temperature to 160 ℃, keep warm for 14 hours; lower the temperature, take a sample and analyze if the weak base ≥ 5.0mmol/g is qualified; after passing the test, drain the mother liquor and wash 5 times with water, and it is required to wash to PH ≤ 10;

h), finally add pre-dissolved chloroacetic acid solution for chelation reaction, heat up to 65-70°C, keep warm for 14 hours, during which the pH value of the reaction solution is constantly controlled, and it is required to be between 8-9; after the heat preservation is completed, take a sample for analysis , to detect the amount of copper ion adsorption; after passing the test, wash 5 times with water, adjust the acid to PH = 1, and stabilize for 1 hour; wash with water until nearly neutral, then adjust the alkali to PH = 12, and stabilize for 1 hour; Packaging, that is, pollution-resistant deep softening chelating resin.

Measures taken to optimize the above technical solutions also include:

The dispersant in the above water phase is one or more of polyvinyl alcohol, starch, methyl cellulose and derivatives thereof, and insoluble inorganic substances sodium chloride, anhydrous magnesium sulfate and sodium carbonate.

The above initiator is one or more of benzoyl peroxide, 2-ethylhexanoic acid and azobisisobutyronitrile.

The porogen mentioned above is one or more of 4-methyl-2-pentanol, liquid paraffin, isobutanol, 200# gasoline, hexamethyldisiloxane and normal oil.

In the above step f, the input amount of N-methylolphthalimide is calculated by mass ratio, and the ratio of expanded polystyrene chlorine balls to N-methylolphthalimide is 1: 2-1:4 , The mass ratio of N-methylolphthalimide to acetic anhydride is 1:1, and the catalyst is acetic acid or sulfuric acid.

25% liquid caustic soda in above-mentioned step g is the sodium hydroxide solution that liquid caustic soda concentration is 25wt%.

The pre-dissolved chloroacetic acid solution in the above h is chloroacetic acid and liquid caustic soda; said liquid caustic soda is a sodium hydroxide solution with a concentration of 20wt%-30wt%, wherein liquid caustic soda and chloroacetic acid are calculated as 1:1- 1:1.5.

The particle size of the above-mentioned pollution-resistant deep softening chelating resin is 0.500-1.000mm.

The above-mentioned pollution-resistant deep softening chelating resin has a water content of 45%-55%; mass total exchange capacity ≥ 5mmol/g; volume total exchange capacity ≥ 2mmol/ml, copper ion adsorption ≥ 45g/L; wet apparent density in 0.73-0.80g/ml; Wet true density is 1.150-1.210g/ml; Uniformity coefficient ≤1.45; Percolation ball rate ≥90%; Expansion rate H+→Na+≤45%.

In the above step a, the mass ratio of p-styrene monomer to divinylbenzene crosslinking agent is 1:0.18-1:0.22, and the crosslinking degree is 8.1.

Compared with the prior art, the synthesis method provided by the present invention is to design the resin synthesis method from the two aspects of the resin's wrapping and adsorption of organic matter and the blocking of organic matter in the resin internal pores. The chelating resin synthesized by this method has good anti- Oil, anti-organic pollution performance, improve the total exchange capacity and working exchange capacity of the resin, and improve the high temperature resistance of the resin according to the characteristics of heavy oil sewage. The invention can more firmly fix the calcium and magnesium ions on the functional groups in the resin pores, and can make the concentration of the calcium and magnesium ions in the effluent less than 20ppb. It is suitable for deep softening of water quality containing more dissolved organic matter and humus-like background substances, and can be used as a secondary softener to absorb most of the calcium and magnesium ions.

detailed description

The present invention is aimed at the prior art, when the sewage containing a large amount of background substances such as humic acid and soluble animal and vegetable oil is deeply softened with common chelating resin, the chelating resin will be blocked by soluble organic matter and cannot be leached out. The heavy metal ions in the complex state greatly weaken the working exchange capacity of the chelating resin and cause irreversible pollution to the technical problem of the resin. It provides a kind of deep softening treatment for water containing more dissolved organic matter and humus background substances. A method for synthesizing a pollution-resistant deep softening chelating resin. The method includes the following steps:

a) Prepare the oil phase in the oil phase preparation kettle. The oil phase is composed of reactants, porogens and initiators; add the reactants and porogens into the oil phase preparation kettle at a mass ratio of 1:0.5 Mix, and add the initiator according to the proportion of 1%-1.5% of the total mass of the oil phase to make it fully dissolved, and then stabilize it in the oil phase preparation kettle for 30 minutes to form the oil phase; the above-mentioned reactants include styrene monomer and divinylbenzene crosslinking agent;

b), prepare a water phase in the polymerization kettle, the water phase is an aqueous solution containing a dispersant and NaCl, based on the total mass of the water phase, the concentration of the dispersant is 3wt%, and the concentration of NaCl is 15 wt%-17wt%; Put water, dispersant and NaCl into the polymerization tank, and raise the temperature to 60°C while stirring, and stabilize for 10 minutes to form a water phase;

c) In the polymerization kettle, the oil phase formed in step a is added to the water phase under stirring according to the ratio of the water phase to the mass of p-styrene monomer of 3:1-1:1 to carry out suspension polymerization A multi-phase polymerization system is formed, in which a small amount of methylene blue is added, the stirring speed is changed from slow to fast, and the stirring speed is controlled at 150-250rpm; after the addition, the temperature is raised to 75°C and kept for 3 hours, and the resin skeleton is basically finalized;

d), raise the temperature in the polymerization kettle to 85°C and keep it warm for 2 hours; then raise the temperature to 95°C and keep it warm for 5 hours; cool down, discharge, and wash; drain free water, and extract with acetone; extract to no oil , wash with water until there is no acetone smell, and discharge; dry and sieve into feed granules with appropriate particle size; then further dry the feed granules, screen and cool to obtain polystyrene-based white balls of pollution-resistant deep softening chelating resin ;

e) Mix the dried polystyrene-based white ball and methyl chloride ether at a temperature of 100°C-120°C, and mix the ratio of polystyrene-based white ball to methyl chloride ether 1:0.5-1:2 by mass ratio , carry out chloromethylation reaction, then gradually dilute the product, transform it with hydrochloric acid and sodium hydroxide, and wash it with water to obtain polystyrene-based chlorine balls;

f) Stir and expand polystyrene chlorine balls with dichloroethane for 1 hour, throw N-methylolphthalimide and acetic anhydride, after throwing, start adding catalyst dropwise, and control the exothermic temperature of the reaction not to exceed 60°C; After the catalyst drops, stabilize for half an hour, then raise the temperature to 75°C-80°C, and keep it warm for 12 hours; Wash with water for more than 5 times, until the water is colorless;

g), then add 25% liquid caustic soda, slowly raise the temperature to 80°C, stabilize for 1 hour, close the vent; then raise the temperature to 120°C, slowly open the vent after stabilizing for 2 hours, and close the vent after evacuating the pressure; then raise the temperature to 160 ℃, keep warm for 14 hours; lower the temperature, take a sample and analyze if the weak base ≥ 5.0mmol/g is qualified; after passing the test, drain the mother liquor and wash 5 times with water, and it is required to wash to PH ≤ 10;

h), finally add pre-dissolved chloroacetic acid solution for chelation reaction, heat up to 65-70°C, keep warm for 14 hours, during which the pH value of the reaction solution is constantly controlled, and it is required to be between 8-9; after the heat preservation is completed, take a sample for analysis , to detect the amount of copper ion adsorption; after passing the test, wash 5 times with water, adjust the acid to PH = 1, and stabilize for 1 hour; wash with water until nearly neutral, then adjust the alkali to PH = 12, and stabilize for 1 hour; Packaging, that is, pollution-resistant deep softening chelating resin.

The dispersant in the above water phase is one or more of polyvinyl alcohol, starch, methyl cellulose and derivatives thereof, and insoluble inorganic substances sodium chloride, anhydrous magnesium sulfate and sodium carbonate.

The above initiator is one or more of benzoyl peroxide, 2-ethylhexanoic acid and azobisisobutyronitrile.

The porogen mentioned above is one or more of 4-methyl-2-pentanol, liquid paraffin, isobutanol, 200# gasoline, hexamethyldisiloxane and normal oil.

In the above step f, the input amount of N-methylolphthalimide is calculated by mass ratio, and the ratio of polystyrene chlorine balls to N-methylolphthalimide after expansion is 1:2-1:4 , The mass ratio of N-methylolphthalimide to acetic anhydride is 1:1, and the catalyst is acetic acid or sulfuric acid.

25% liquid caustic soda in above-mentioned step g is the sodium hydroxide solution that liquid caustic soda concentration is 25wt%.

The pre-dissolved chloroacetic acid solution in the above h is chloroacetic acid and liquid caustic soda; the liquid caustic soda is a sodium hydroxide solution with a concentration of 20 wt%-30wt%, wherein the liquid caustic soda and chloroacetic acid are 1:1 by mass ratio -1: 1.5.

The particle size of the above-mentioned pollution-resistant deep softening chelating resin is 0.500-1.000mm.

The above-mentioned pollution-resistant deep softening chelating resin has a water content of 45%-55%; mass total exchange capacity ≥ 5mmol/g; volume total exchange capacity ≥ 2mmol/ml, copper ion adsorption ≥ 45g/L; wet apparent density in 0.73-0.80g/ml; wet true density 1.150-1.210g/ml; range particle size (0.500mm-1.000mm) ≥ 90.0, lower limit particle size (< 0.450mm) ≤ 1.0; uniformity coefficient ≤ 1.45; osmosis ball rate ≥90%; expansion rate H+→Na+≤45%.

In the above step a, the mass ratio of p-styrene monomer to divinylbenzene crosslinking agent is 1:0.18-1:0.22, and the crosslinking degree is 8.1.

The synthesis method provided by the present invention is to design the resin synthesis method from two aspects: the wrapping and adsorption of the organic matter by the resin and the blocking of the organic matter in the internal pores of the resin. , to improve the hydrophilic and oleophobic properties of the resin, and improve the oil pollution resistance of the resin by changing the synthesis parameters of the resin, thereby improving the working exchange capacity and reaction rate of the resin in heavy oil sewage and the selective adsorption performance of divalent calcium and magnesium ions , suitable for secondary softening with complex backgrounds to prevent ion leakage.

The synthetic method of the anti-pollution type deep softening chelating resin provided by the invention and the anti-pollution type chelating resin have the following advantages:

1. The synthesis method provided by the present invention is similar to the synthesis method of traditional chelating resins. After a large number of research and development experiments, the synthetic formula has successfully synthesized a pollution-resistant deep softening chelating resin for water with high dissolved organic matter and complex water quality. It solves the problem that the traditional resin has a high attenuation rate and cannot be applied. Its main advantages lie in its strong pollution resistance and strong ability to prevent ion leakage. The concentration of calcium and magnesium ions in the final effluent can reach below 20ppb, which is easy to achieve large-scale production;

2. The synthesis method provided by the present invention changes the synthesis parameters for the performances such as the reaction rate and working exchange capacity of resin adsorption of divalent calcium and magnesium ions after determining the synthetic material, which can improve the work of the chelating adsorption resin on divalent calcium and magnesium ions. Exchange capacity, low organic matter adsorption rate and high organic matter elution rate, can reduce the final concentration of calcium and magnesium in the effluent to less than 20ppb;

3. The oil pollution resistance of the resin was investigated through the surface tension, organic matter adsorption rate and organic matter elution rate of the synthetic resin. The infiltration of oil and resin surface is investigated by surface tension, the smaller the surface tension is, the better the oleophobicity of the resin is. The instantaneous adsorption rate of the resin to oil is examined by the organic matter adsorption rate. The smaller the adsorption rate is, the better the oleophobicity of the resin is; the oil elution performance of regeneration is investigated by the organic matter elution rate, and the higher the elution rate is, the better the oleophobicity of the resin is. it is good. Therefore, the monomer selected during the synthesis of this pollution-resistant type depth softening chelating resin is styrene.

4. The synthetic method provided by the present invention selects divinylbenzene as the crosslinking agent and isobutanol as the porogen. Isobutanol has a large molecular weight, and the volume occupied by a single molecule is also large, which can obtain a larger pore size and specific surface area. Therefore, the pore size obtained by using isobutanol as a porogen is also larger. The pore size can improve the elution rate of organic matter by the resin. The larger the pore size, the greater the elution rate of organic matter, that is, the better the anti-pollution performance of the resin. On the other hand, a larger pore size will reduce the specific surface area of the resin, thereby reducing the working exchange capacity of the resin, but it can improve the working exchange capacity by changing the degree of cross-linking through the cross-linking agent divinylbenzene, and the cross-linking capacity of the synthesized white balls The joint degree is 8.1. Therefore, divinylbenzene was selected as a crosslinker and isobutanol as a porogen to improve the antifouling properties of the resin.

5. For the adsorption performance of ions and the working exchange capacity of the resin, the smaller the particle size, the greater the ion removal rate and cycle of the resin. However, in the sewage with high content of dissolved organic matter, a chelating resin with a small particle size is used. The interception effect of organic matter increases, so the more COD it adsorbs and the lower the COD elution rate. Therefore, the selected particle size range is 0.500~1.000mm. Particle size range (0.500mm~1.000mm)≥90%, lower limit particle size (<0.450mm)≤1.0%

6. Compared with the traditional chelating resin, the regeneration after adsorption and saturation of this pollution-resistant and deeply softened chelating resin is more complete, and the attenuation rate is lower, because the internal pores of the resin are larger, and the organic matter trapped in the resin is easier to regenerate During operation, it is purged from the pores of the resin.

7. The ball rate of penetration and grinding is ≥90%, which reflects the anti-wear and anti-seepage ability of the resin to a certain extent. The mechanical strength of ion exchange resin is its ability to withstand various external forces in actual use and maintain the integrity of its particles. The common mechanical strength index is the ball rate of infiltration grinding. This kind of pollution-resistant resin is treated with a certain concentration of acid and alkali to exert the penetration force on the resin, and the pressure and friction force exerted on the resin by the rolling of ceramic balls. The ball penetration rate is still greater than or equal to 90%.

8. The main function of pollution-resistant deep softening chelating resin is deep softening in polluted water, and it is often used as a secondary softening unit, which can make the concentration of calcium and magnesium ions in the softened water reach within 20ppb. The mass total exchange capacity (H+) of this resin is ≥5.00mmol/g, and the volume total exchange capacity (H+) is ≥2.00mmol/ml, which is higher than the total exchange capacity of traditional chelating resins.

9. The water content of the resin is between 45% and 55%. The lower the degree of cross-linking and the larger the pore size of the resin, the higher the water content, so the water content should be within a certain range, so that the resin has better physical and chemical properties.

10. Other performance parameters of the resin, copper ion adsorption ≥ 45g/L, wet apparent density between 0.73-0.80g/ml, wet true density between 1.150-1.210g/ml, uniformity coefficient ≤ 1.45, transformation Expansion rate ≤ 45%.

11. The water inlet standard of the resin: the oil content in the water ≤ 10mg/L; the organic matter content (COD) in the water ≤ 500mg/L. The concentration of calcium and magnesium ions in the effluent is ≤20ppb.

12. The operating temperature is ≤90°C, and its high temperature resistance is considered during the synthesis process.

Embodiment one:

A kind of synthetic method of anti-pollution type depth softening chelating resin, this synthetic method comprises the following steps:

a) Prepare the oil phase in the oil phase preparation kettle, the oil phase is composed of the reactant, isobutanol and benzoyl peroxide; add the reactant and isobutanol to the oil phase at a mass ratio of 1:0.5 for preparation Mix in the kettle, and add benzoyl peroxide to make it fully dissolved in a proportion of 1% of the total mass of the oil phase, and then stabilize it in the oil phase preparation kettle for 30 minutes to form an oil phase; wherein: the reactant is styrene mono Body and by divinylbenzene crosslinking agent; and the mass ratio between styrene monomer and divinylbenzene crosslinking agent is 1:0.2, in the crosslinking agent of 0.2 mass ratio, can be completely divinylbenzene crosslinking agent, It can also be based on divinylbenzene crosslinking agent, with other auxiliary crosslinking agents added;

b), prepare the water phase in the polymerization kettle, the water phase is an aqueous solution containing polyvinyl alcohol and NaCl, based on the total mass of the water phase, the concentration of polyvinyl alcohol is 3wt%, and the concentration of NaCl is 15 wt%; , polyvinyl alcohol and NaCl are put into the polymerization kettle, and the temperature is raised to 60°C under stirring, and stabilized for 10 minutes to form a water phase;

c) In the polymerization kettle, add the oil phase formed in step a to the water phase under stirring according to the ratio of water phase to styrene monomer mass ratio of 3:1, and carry out suspension polymerization to form multi-phase polymerization A small amount of methylene blue is added to the system, the stirring speed is changed from slow to fast, and the stirring speed is controlled at 200rpm; after the addition, the temperature is raised to 75°C and kept for 3 hours, and the resin skeleton is basically finalized;

d), raise the temperature in the polymerization kettle to 85°C and keep it warm for 2 hours; then raise the temperature to 95°C and keep it warm for 5 hours; cool down, discharge, and wash; drain free water, and extract with acetone; extract to no oil , wash with water until there is no acetone smell, and discharge; dry and sieve into feed granules with appropriate particle size; then further dry the feed granules, screen and cool to obtain polystyrene-based white balls of pollution-resistant deep softening chelating resin ;

e) Mix the dried polystyrene-based white ball and chloromethyl ether at a temperature of 110°C in a mass ratio of polystyrene-based white ball to chloromethyl ether in a ratio of 1:1 to carry out the chloromethylation reaction , and then gradually dilute the product, transform it with hydrochloric acid and sodium hydroxide, and wash it with water to obtain polystyrene-based chlorine balls;

f) Stir and expand polystyrene chlorine balls with dichloroethane for 1 hour, throw N-methylolphthalimide and acetic anhydride, after throwing, start adding catalyst dropwise, and control the exothermic temperature of the reaction not to exceed 60°C; After the catalyst drops, stabilize for half an hour, then raise the temperature to 75°C, and keep it warm for 12 hours; After the heat preservation is completed, cool down, and drain the mother liquor; add water, and distill dichloroethane under reduced pressure until the resin is odorless; wash with hot water for 5 More than one time, until the effluent is colorless; Among them, polystyrene chlorine balls are added to N-methylolphthalimide in a mass ratio of 1:2 after being expanded with dichloroethane. The mass ratio of N-methylolphthalimide to acetic anhydride is 1:1. Its catalyst is sulfuric acid.

g), then add 25% liquid caustic soda, slowly raise the temperature to 80°C, stabilize for 1 hour, close the vent; then raise the temperature to 120°C, slowly open the vent after stabilizing for 2 hours, and close the vent after evacuating the pressure; then raise the temperature to 160 ℃, keep warm for 14 hours; lower the temperature, take a sample and analyze if the weak base ≥ 5.0mmol/g is qualified; after passing the test, drain the mother liquor and wash it with water for 5 times, and it is required to wash to pH ≤ 10; 25% liquid alkali is liquid alkali with a concentration of 25wt% sodium hydroxide solution.

h), add the pre-dissolved chloroacetic acid solution to carry out the chelation reaction, heat up to 65°C, and keep warm for 14 hours, during which the pH value of the reaction solution is constantly controlled, and it is required to be between 8-9; after the heat preservation is completed, take a sample for analysis and detect copper Ion adsorption capacity; after passing the test, wash 5 times with water, adjust acid to PH = 1, and stabilize for 1 hour; wash with water until nearly neutral, then adjust alkali to PH = 12, and stabilize for 1 hour; wash with water until neutral, discharge and pack, that is Obtain particle diameter and be the anti-pollution type deep softening chelating resin of 0.500-1.000mm, the chloroacetic acid solution of dissolving in advance is chloroacetic acid and liquid caustic soda; Liquid caustic soda is the sodium hydroxide solution that concentration is 20 wt%, wherein liquid caustic soda and chlorine Acetic acid is calculated as 1:1 by mass ratio.

Embodiment two:

A kind of synthetic method of anti-pollution type depth softening chelating resin, this synthetic method comprises the following steps:

a), prepare the oil phase in the oil phase preparation kettle, the oil phase is composed of reactant and 4-methyl-2-pentanol and isobutanol, the mixture of the porogen formed by hexamethyldisiloxane and 2-ethane The composition of the initiator mixture composed of hexanoic acid and toluyl peroxide; the reactant and the mixture constituting the porogen are added to the oil phase preparation kettle in a mass ratio of 1:0.5 and mixed, and the total mass of the oil phase is Add 1% of the proportion of the initiator mixture and make it fully dissolved, and then stabilize it in the oil phase preparation kettle for 30 minutes to form the oil phase; wherein: the reactant is styrene monomer and the crosslinking agent made of divinylbenzene and the mass ratio between styrene monomer and divinylbenzene crosslinking agent is 1:0.2, and in the crosslinking agent with a mass ratio of 0.2, it can be completely divinylbenzene crosslinking agent, or it can be crosslinked with divinylbenzene agent-based, with other auxiliary cross-linking agents added;

b), prepare the water phase in the polymerization kettle, the water phase is an aqueous solution containing magnesium sulfate, sodium carbonate and NaCl, based on the total mass of the water phase, the concentration of magnesium sulfate and sodium carbonate is 3wt%, and the concentration of NaCl is 16 wt%; put water, magnesium sulfate, sodium carbonate and NaCl into the polymerization kettle, and raise the temperature to 60°C under stirring, and stabilize for 10 minutes to form a water phase;

c) In the polymerization kettle, add the oil phase formed in step a to the water phase under stirring according to the ratio of water phase to styrene monomer mass ratio of 2:1, and carry out suspension polymerization to form multi-phase polymerization A small amount of methylene blue is added to the system, the stirring speed is changed from slow to fast, and the stirring speed is controlled at 200rpm; after the addition, the temperature is raised to 75°C and kept for 3 hours, and the resin skeleton is basically finalized;

d), raise the temperature in the polymerization kettle to 85°C and keep it warm for 2 hours; then raise the temperature to 95°C and keep it warm for 5 hours; cool down, discharge, and wash; drain free water, and extract with acetone; extract to no oil , wash with water until there is no acetone smell, and discharge; dry and sieve into feed granules with appropriate particle size; then further dry the feed granules, screen and cool to obtain polystyrene-based white balls of pollution-resistant deep softening chelating resin ;

e) Mix the dried polystyrene-based white ball and chloromethyl ether uniformly at a mass ratio of 1:1.5 for polystyrene-based white ball to chloromethyl ether under the condition of 115°C, and carry out chloromethylation reaction , and then gradually dilute the product, transform it with hydrochloric acid and sodium hydroxide, and wash it with water to obtain polystyrene-based chlorine balls;

f) Stir and expand polystyrene chlorine balls with dichloroethane for 1 hour, throw N-methylolphthalimide and acetic anhydride, after throwing, start adding catalyst dropwise, and control the exothermic temperature of the reaction not to exceed 60°C; After the catalyst drops, stabilize for half an hour, then raise the temperature to 75°C, and keep it warm for 12 hours; After the heat preservation is completed, cool down, and drain the mother liquor; add water, and distill dichloroethane under reduced pressure until the resin is odorless; wash with hot water for 5 More than one time, until the effluent is colorless; Among them, polystyrene chlorine balls are added to N-methylolphthalimide in a mass ratio of 1:2 after being expanded with dichloroethane. The mass ratio of N-methylolphthalimide to acetic anhydride is 1:1. Its catalyst is sulfuric acid.

g), then add 25% liquid caustic soda, slowly raise the temperature to 80°C, stabilize for 1 hour, close the vent; then raise the temperature to 120°C, slowly open the vent after stabilizing for 2 hours, and close the vent after evacuating the pressure; then raise the temperature to 160 ℃, keep warm for 14 hours; lower the temperature, take a sample and analyze if the weak base ≥ 5.0mmol/g is qualified; after passing the test, drain the mother liquor and wash it with water for 5 times, and it is required to wash to pH ≤ 10; 25% liquid alkali is liquid alkali with a concentration of 25wt% sodium hydroxide solution.

h), add the pre-dissolved chloroacetic acid solution to carry out the chelation reaction, heat up to 65°C, and keep warm for 14 hours, during which the pH value of the reaction solution is constantly controlled, and it is required to be between 8-9; after the heat preservation is completed, take a sample for analysis and detect copper Ion adsorption capacity; after passing the test, wash 5 times with water, adjust acid to PH = 1, and stabilize for 1 hour; wash with water until nearly neutral, then adjust alkali to PH = 12, and stabilize for 1 hour; wash with water until neutral, discharge and pack, that is A pollution-resistant deep softening chelating resin with a particle size of 0.500-1.000 mm is obtained. The pre-dissolved chloroacetic acid solution is chloroacetic acid and liquid caustic soda; the liquid caustic soda is a sodium hydroxide solution with a concentration of 25wt%, wherein the mass ratio of liquid caustic soda and chloroacetic acid is 1:1.5.

i) The above-mentioned pollution-resistant deep softening chelating resin has a water content of 45%-55%; mass total exchange capacity ≥ 5mmol/g; volume total exchange capacity ≥ 2mmol/ml, copper ion adsorption ≥ 45g/L; The density is 0.73-0.80g/ml; the wet true density is 1.150-1.210g/ml; the uniformity coefficient is ≤1.45; the osmosis ball rate is ≥90%; the expansion rate H+→Na+≤45%.

The preferred embodiment of the present invention has been illustrated, and various changes or modifications may be made by those skilled in the art without departing from the scope of the present invention.

Claims (1)

1. a synthetic method of pollution-resistant type depth softening chelating resin is characterized in that: the synthetic method may further comprise the steps: a) Prepare the oil phase in the oil phase preparation kettle. The oil phase is composed of reactants, porogens and initiators; add the reactants and porogens into the oil phase preparation kettle at a mass ratio of 1:0.5 Mix, and add the initiator according to the proportion of 1%-1.5% of the total mass of the oil phase to make it fully dissolved, and then stabilize it in the oil phase preparation kettle for 30 minutes to form the oil phase; the above-mentioned reactants include styrene monomer and Divinylbenzene crosslinking agent; the initiator is one or more of benzoyl peroxide and azobisisobutyronitrile; the porogen is 4-methyl-2-pentanol, One or more of liquid paraffin, isobutanol, 200# gasoline, hexamethyldisiloxane and normal oil; the mass ratio of styrene monomer to divinylbenzene crosslinking agent is 1:0.18-1: 0.22; b), prepare the water phase in the polymerization kettle, the water phase is an aqueous solution containing a dispersant and NaCl, based on the total mass of the water phase, the concentration of the dispersant is 3wt%, and the concentration of NaCl is 15wt%-17wt%; Put water, dispersant and NaCl into the polymerization tank, and heat up to 60°C under stirring, and stabilize for 10 minutes to form a water phase; the dispersant in the water phase is polyvinyl alcohol, starch, methyl cellulose and One or more of its derivatives; c) In the polymerization kettle, the oil phase formed in step a is added to the water phase under stirring according to the ratio of the water phase to the mass of styrene monomer in a ratio of 3:1-1:1 to carry out suspension polymerization to form Multi-phase polymerization system, in which a small amount of methylene blue is added, the stirring speed is changed from slow to fast, and the stirring speed is controlled at 150-250rpm; after the addition, the temperature is raised to 75°C and kept for 3 hours, and the resin skeleton is basically finalized; d), raise the temperature in the polymerization kettle to 85°C and keep it warm for 2 hours; then raise the temperature to 95°C and keep it warm for 5 hours; cool down, discharge, and wash; drain free water, and extract with acetone; extract to no oil , wash with water until there is no acetone smell, and discharge; dry and sieve into feed granules with appropriate particle size; then further dry the feed granules, screen and cool to obtain polystyrene-based white balls of pollution-resistant deep softening chelating resin ; e) Mix the dried polystyrene-based white ball and methyl chloride ether at a temperature of 100°C-120°C, and mix the ratio of polystyrene-based white ball to methyl chloride ether 1:0.5-1:2 by mass ratio , carry out chloromethylation reaction, then gradually dilute the product, transform it with hydrochloric acid and sodium hydroxide, and wash it with water to obtain polystyrene-based chlorine balls; f) Stir and expand polystyrene chlorine balls with dichloroethane for 1 hour, throw N-methylolphthalimide and acetic anhydride, after throwing, start to add the catalyst dropwise, and control the exothermic temperature of the reaction not to exceed 60°C; after the catalyst drops, stabilize for half an hour, then raise the temperature to 75°C-80°C, and keep it warm for 12 hours; Wash with water for more than 5 times, until the water is colorless; the input amount of N-methylolphthalimide is calculated according to the mass ratio, and the ratio of polystyrene chlorine balls after expansion to N-methylolphthalimide is 1:2-1:4, the mass ratio of N-methylolphthalimide to acetic anhydride is 1:1, and the catalyst is acetic acid or sulfuric acid; g), then add 25% liquid caustic soda, slowly raise the temperature to 80°C, stabilize for 1 hour, close the vent; then raise the temperature to 120°C, slowly open the vent after stabilizing for 2 hours, and close the vent after evacuating the pressure; then raise the temperature to 160 ℃, keep warm for 14 hours; lower the temperature, take a sample and analyze if the weak base ≥ 5.0mmol/g is qualified; after passing the test, drain the mother liquor and wash it with water for 5 times, and it is required to wash to pH ≤ 10; 25% liquid alkali is liquid alkali with a concentration of 25wt% sodium hydroxide solution; h), finally add the pre-dissolved chloroacetic acid solution for chelation reaction, heat up to 65-70°C, and keep warm for 14 hours, during which the pH value of the reaction solution is constantly controlled, and it is required to be between 8-9; after the heat preservation is completed, take a sample for analysis , to detect the amount of copper ion adsorption; after passing the test, wash 5 times with water, adjust the acid to pH = 1, and stabilize for 1 hour; wash with water until nearly neutral, then adjust the alkali to pH = 12, and stabilize for 1 hour; Packaging, to obtain pollution-resistant deep softening chelating resin; the pre-dissolved chloroacetic acid solution is chloroacetic acid and liquid caustic; According to the mass ratio, it is 1:1-1:1.5; The particle diameter of described anti-pollution type deep softening chelating resin is 0.500-1.000mm; The water content of the pollution-resistant deep softening chelating resin is 45%-55%; the total exchange capacity of mass is ≥5mmol/g; the total exchange capacity of volume is ≥2mmol/ml, and the adsorption capacity of copper ions is ≥45g/L; In 0.73-0.80g/ml; wet true density in 1.150-1.210g/ml; uniformity coefficient ≤ 1.45; seepage ball rate ≥ 90%; expansion rate H + → Na + ≤ 45%.