CN118908292B

CN118908292B - A production and processing technology of polyferric sulfate

Info

Publication number: CN118908292B
Application number: CN202410939284.4A
Authority: CN
Inventors: 何朝晖; 何青峰; 高力
Original assignee: Hengyang Jianheng Industry Development Co ltd
Current assignee: Hengyang Jianheng Industry Development Co ltd
Priority date: 2024-07-12
Filing date: 2024-07-12
Publication date: 2025-05-09
Anticipated expiration: 2044-07-12
Also published as: CN118908292A

Abstract

The invention discloses a production and processing technology of polymeric ferric sulfate, and belongs to the technical field of polymeric ferric sulfate production. Mixing Melanteritum and water thoroughly, adding concentrated sulfuric acid slowly, heating in water bath, introducing air for oxidation, adding oxidant for oxidation, hydrolyzing and polymerizing to obtain A, preparing modified polyacrylamide solution, and stirring the A and modified polyacrylamide solution thoroughly to obtain polymeric ferric sulfate. The polyacrylamide in the modified polyacrylamide can effectively remove suspended matters, organic matters, heavy metals and other harmful substances in wastewater, and a plurality of hydroxyl groups in the modified polyacrylamide can improve the adsorption and net capturing capacity of the modified polyacrylamide, so that the modified polyacrylamide containing dimethyl hydantoin and quaternary ammonium salt structures is added into the preparation process of the polymeric ferric sulfate, and the polymeric ferric sulfate has the dual functions of flocculation and antibiosis.

Description

Production and processing technology of polymeric ferric sulfate

Technical Field

The invention belongs to the technical field of production of polymeric ferric sulfate, and particularly relates to a production and processing technology of polymeric ferric sulfate.

Background

The inorganic coagulants commonly used at present are mainly divided into two main categories, namely aluminum salts and ferric salts. The aluminum salt is mainly polyaluminum chloride, aluminum sulfate and aluminum chloride. And ferric salt is mainly polymeric ferric sulfate. The polymeric ferric sulfate is an inorganic polymeric flocculant, has the characteristics of wide PH applicability, high impurity removal rate, rapid alum blossom settlement and the like, and is widely used for treating industrial wastewater, urban sewage, industrial water and domestic drinking water.

Contaminants such as suspended matters, organic matters, heavy metal ions, pathogenic bacteria and the like in various kinds of water can cause great harm to human health. Among them, public health problems caused by pathogenic bacterial infection are particularly serious, and various pathogenic bacteria and intestinal bacteria seriously endanger the physical health of humans and animals. Although the polymeric ferric sulfate can partially separate and remove bacteria in water, the polymeric ferric sulfate cannot effectively inhibit or kill the bacteria, so that the antibacterial performance of the polymeric ferric sulfate is enhanced, harmful microorganisms such as algae, bacteria, pathogens and the like are efficiently removed, and the development of the polymeric ferric sulfate with flocculation-antibacterial dual functions is very important.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a production and processing technology of polymeric ferric sulfate.

The aim of the invention can be achieved by the following technical scheme:

A production and processing technology of polymeric ferric sulfate comprises the following steps:

(1) Mixing Melanteritum and water thoroughly, adding concentrated sulfuric acid slowly, heating in water bath, introducing air for oxidation, adding oxidant for oxidation, and hydrolyzing and polymerizing to obtain A;

(2) Preparing a modified polyacrylamide solution;

(3) And (3) fully stirring the modified polyacrylamide solution obtained in the step (1) and the modified polyacrylamide solution obtained in the step (2) to be uniformly mixed to obtain the polymeric ferric sulfate.

Further, the dosage ratio of copperas, concentrated sulfuric acid and water in the step (1) is 55g:5-5.5mL:80-120mL.

Further, the water bath temperature in the step (1) is 40-65 ℃.

Further, the air oxidation time in the step (1) is 6-8h.

Further, the oxidant in the step (1) is any one of hydrogen peroxide and sodium chlorate.

Further, the amount of the oxidant in the step (1) is 120% -150% of the stoichiometric number of the ferrous ions remained after the air oxidation.

Further, the oxidizing time of the oxidizing agent in the step (1) is 1.5-2h.

Further, the mass concentration of the modified polyacrylamide in the step (2) is 0.1-1%.

Further, the modified polyacrylamide in the step (2) is prepared by the following steps:

S1, adding 1, 3-dimethylol-5, 5-dimethylhydantoin, anhydrous aluminum trichloride and DMSO (dimethyl sulfoxide) into a fully dried four-neck flask under the protection of nitrogen, stirring until the materials are uniformly mixed, slowly adding epichlorohydrin while stirring, heating to 60 ℃ after the addition is finished, stirring and reacting for 6 hours, cooling to room temperature after the reaction is finished, and distilling under reduced pressure, wherein the whole process is carried out under the protection of nitrogen to obtain an intermediate 1, 3-dimethylol-5, 5-dimethylhydantoin, epichlorohydrin, anhydrous aluminum trichloride and DMF, wherein the dosage ratio of 0.069mol:0.06mol:1.6g:130mL;

The hydroxyl of the 1, 3-dihydroxymethyl-5, 5-dimethylhydantoin and the epoxy of the epichlorohydrin react under the condition of heating and aluminum trichloride catalysis, and the reaction process is as follows:

S2, blowing nitrogen into a dry three-neck flask for 30min to remove air in the flask, then adding 2-amino-1, 3-propanediol, pyridine and DMSO into the flask under the protection of nitrogen, stirring and dissolving, slowly adding chlorotetradecane, heating to 75 ℃ after the addition is finished for reacting for 2h, cooling to room temperature after the reaction is finished, and distilling under reduced pressure to obtain an intermediate 2, wherein the dosage ratio of 2-amino-1, 3-propanediol, chlorotetradecane, pyridine and DMSO is 0.063mol:0.06mol:7.3mL:100mL;

In the presence of heat and pyridine, the nucleophilic substitution reaction of-Cl of chlorotetradecane and-NH ₂ of 2-amino-1, 3-propanediol occurs, and the reaction process is as follows:

S3, adding the intermediate 2, pyridine and DMSO into a dry three-neck flask under the protection of nitrogen, stirring and dissolving, slowly adding the 4-chloro-1-butene in a constant pressure dropping funnel into the flask, heating to 80 ℃ after the addition is finished, carrying out heat preservation reaction for 3 hours, cooling to room temperature after the reaction is finished, and carrying out reduced pressure distillation to obtain an intermediate 3, wherein the dosage ratio of the intermediate 2, the 4-chloro-1-butene, the pyridine and the DMSO is 0.055mol:0.05mol:6.1mL:180mL;

in the presence of heat and pyridine, the nucleophilic substitution reaction of-NH-of the intermediate 2 and-Cl of 4-chloro-1-butene occurs, and the reaction process is as follows:

S4, adding the intermediate 1, triethylamine and DMF (N, N-dimethylformamide) into a dry three-neck flask under the protection of nitrogen, stirring and dissolving, slowly adding a mixed solution of the intermediate 3 and DMF, heating to 80 ℃ for reaction for 3 hours after the addition, cooling to room temperature after the reaction is finished, and distilling under reduced pressure to obtain an intermediate 4, wherein the dosage ratio of the intermediate 1 to the intermediate 3 to the triethylamine to the DMF is 0.056mol:0.05mol:10.4mL:200mL;

under the heating condition, triethylamine is used as an acid binding agent, and the-Cl of the intermediate 1 and the tertiary amine of the intermediate 3 undergo nucleophilic substitution reaction, wherein the reaction process is as follows:

S5, adding the intermediate 4, acrylamide, disodium ethylenediamine tetraacetate and DMF into a dry four-necked round bottom flask, stirring to form a uniform solution, adjusting the pH to 4 by using 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide, passing nitrogen through a reaction system for 30min to discharge air in the system, adding ammonium persulfate and azodiisobutyronitrile, heating to 60 ℃ and stirring for 3h, washing 5 times by using absolute ethyl alcohol after the reaction is finished, and drying at 60 ℃ for 24h to obtain the modified polyacrylamide. The dosage ratio of acrylamide, intermediate 4, disodium ethylenediamine tetraacetate, ammonium persulfate, azobisisobutyronitrile and DMF was 5g:18.7g:0.3g:0.015 g:0.0120 g:180mL.

Under the action of initiator ammonium persulfate and azodiisobutyronitrile, the carbon-carbon double bond energy at the tail end of the intermediate 4 and the carbon-carbon double bond of acrylamide generate chemical action, and the intermediate 4 is grafted onto a polyacrylamide macromolecular chain to obtain the modified polyacrylamide.

The modified polyacrylamide contains a quaternary ammonium salt structure with a long carbon chain (14 carbons), the quaternary ammonium salt structure is a broad-spectrum bactericide, quaternary ammonium salt cations with positive charges can be dissociated from the quaternary ammonium salt structure, N ⁺ ions of the quaternary ammonium salt structure can be adsorbed on cell walls of bacteria with negative charges, cell membranes are damaged, proteins are denatured, reproduction of DNA is hindered, and therefore an antibacterial effect is achieved. The modified polyacrylamide also contains dimethyl hydantoin, is a broad-spectrum and efficient antibacterial preservative, can effectively resist gram-positive bacteria, gram-negative bacteria, mold and the like, and can be kept stable in a wider pH value and temperature range. Because the dimethyl hydantoin and the quaternary ammonium salt structure are grafted on the polyacrylamide macromolecular chain, the dimethyl hydantoin and the quaternary ammonium salt structure are not easy to migrate and deviate from, can stably exist in the polyacrylamide, and meanwhile, the two antibacterial components have synergistic effect, so that the modified polyacrylamide has excellent antibacterial and antiseptic properties.

The polyacrylamide can effectively remove suspended matters, organic matters, heavy metals and other harmful substances in the wastewater, and the plurality of hydroxyl groups in the modified polyacrylamide can improve the adsorption and net capturing capacity of the modified polyacrylamide to a certain extent. Therefore, the modified polyacrylamide not only has excellent and stable antibacterial and antiseptic capabilities, but also has high and durable wastewater treatment capability. The modified polyacrylamide is added into the preparation of the polymeric ferric sulfate, so that the polymeric ferric sulfate has higher wastewater treatment capacity and has excellent and stable antibacterial and antiseptic performances.

Further, the mass ratio of the A to the modified polyacrylamide solution in the step (3) is (100-1000): 1.

The invention has the beneficial effects that the polyacrylamide in the modified polyacrylamide can effectively remove suspended matters, organic matters, heavy metals and other harmful substances in the wastewater, and a plurality of hydroxyl groups in the modified polyacrylamide can improve the adsorption and net capturing capacity of the modified polyacrylamide, so that the modified polyacrylamide containing dimethyl hydantoin and quaternary ammonium salt structures is added into the preparation process of the polymeric ferric sulfate, and the polymeric ferric sulfate has the dual functions of flocculation and antibiosis.

Detailed Description

The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.

Example 1

The preparation method of the modified polyacrylamide comprises the following specific steps:

S1, under the protection of nitrogen, adding 13g of 1, 3-dimethylol-5, 5-dimethylhydantoin, 1.6g of anhydrous aluminum trichloride and 130 mM LDMSO into a fully dried 250mL four-neck flask, stirring until the mixture is uniform, slowly adding 4.7mL of epichlorohydrin while stirring, heating to 60 ℃ after the addition is finished, stirring and reacting for 6 hours, cooling to room temperature after the reaction is finished, and distilling under reduced pressure, wherein the whole process is performed under the protection of nitrogen to obtain an intermediate 1;

S2, blowing nitrogen into a dry 250mL three-neck flask for 30min to remove air in the flask, then adding 5.7g of 2-amino-1, 3-propanediol, 7.3mL of pyridine and 100mL of LDMSO into the flask under the protection of nitrogen, stirring and dissolving, slowly adding 16.2mL of chlorotetradecane, heating to 75 ℃ after the addition is finished for reaction for 2h, cooling to room temperature after the reaction is finished, and distilling under reduced pressure to obtain an intermediate 2;

S3, adding 15.8g of intermediate 2, 6.1mL of pyridine and 180mL of LDMSO into a dry 250mL three-neck flask under the protection of nitrogen, stirring and dissolving, slowly adding 5.1mL of 4-chloro-1-butene in a constant pressure dropping funnel into the flask, heating to 80 ℃ after the addition, preserving heat for 3h, cooling to room temperature after the reaction is finished, and distilling under reduced pressure to obtain an intermediate 3;

S4, adding 15.7g of intermediate 1, 10.4mL of triethylamine and 140mL of LDMF into a dry 250mL three-neck flask under the protection of nitrogen, stirring and dissolving, slowly adding 17.1g of mixed solution of intermediate 3 and 60mL of LDMF, heating to 80 ℃ after the addition is finished, reacting for 3 hours, cooling to room temperature after the reaction is finished, and distilling under reduced pressure to obtain an intermediate 4;

S5, adding 18.7g of intermediate 4, 5g of acrylamide, 0.3g of disodium ethylenediamine tetraacetate and 180mL of LDMF into a dry 500mL four-necked round bottom flask, stirring to form a uniform solution, regulating the pH to 4 by using 0.1mol/L hydrochloric acid and 0.1mol/L sodium hydroxide, passing nitrogen into a reaction system for 30min to discharge air in the system, adding 0.015g of ammonium persulfate and 0.012g of azobisisobutyronitrile, heating to 60 ℃ and stirring for 3h, washing 5 times by using absolute ethyl alcohol after the reaction is finished, and drying at 60 ℃ for 24h to obtain the modified polyacrylamide.

Example 2

The preparation method of the polymeric ferric sulfate comprises the following specific steps:

(1) Mixing and dissolving 55g copperas and 80mL of water thoroughly, then slowly adding 5mL of concentrated sulfuric acid, heating in a water bath at 40 ℃, introducing air for oxidation for 6 hours, adding 5g of sodium chlorate for oxidation for 1.5 hours, and finally hydrolyzing and polymerizing to obtain A;

(2) Preparing a modified polyacrylamide solution with the mass concentration of 0.1%;

(3) And (3) fully stirring the A in the step (1) and the 0.1% modified polyacrylamide solution in the step (2) to uniformly mix, wherein the mass ratio of the A to the modified polyacrylamide solution is 1000:1, and thus the polymeric ferric sulfate is prepared.

Example 3

(1) Mixing and dissolving 55g copperas and 120mL of water, then slowly adding 5.5mL of concentrated sulfuric acid, heating in a 65 ℃ water bath, introducing air for oxidation for 8 hours, adding 2.7g of hydrogen peroxide for oxidation for 1.8 hours, and finally hydrolyzing and polymerizing to obtain A;

(2) Preparing a modified polyacrylamide solution with the mass concentration of 0.4%;

(3) And (3) fully stirring the A and the 0.4% modified polyacrylamide solution in the step (1) and the step (2) to uniformly mix, wherein the mass ratio of the A to the modified polyacrylamide solution is 200:1, and thus the polymeric ferric sulfate is prepared.

Example 4

(1) Mixing and dissolving 55g copperas and 100mL of water thoroughly, then slowly adding 5.2mL of concentrated sulfuric acid, heating in a 60 ℃ water bath, introducing air for oxidation for 7h, adding 7.3g of sodium chlorate for oxidation for 2h, and finally hydrolyzing and polymerizing to obtain A;

(2) Preparing a modified polyacrylamide solution with the mass concentration of 0.5%;

(3) And (3) fully stirring the A in the step (1) and the 0.5% modified polyacrylamide solution in the step (2) to uniformly mix, wherein the mass ratio of the A to the modified polyacrylamide solution is 100:1, and thus the polymeric ferric sulfate is prepared.

Comparative example 1

the rest steps are unchanged, and the modified polyacrylamide in the example 4 is replaced by polyacrylamide without any modification treatment, so that the polymeric ferric sulfate is prepared.

Comparative example 2

The remaining steps were unchanged, and the modified polyacrylamide of example 4 was replaced with polyacrylamide without any modification treatment, and bitetradecyl dimethyl ammonium bromide was added at the same time, to thereby prepare polymeric ferric sulfate.

Performance testing

Taking 1000mL of 5 groups of wastewater of the same batch in a beaker, respectively adding 2.0mL of polymeric ferric sulfate of the examples 2-4 and 2.0mL of polymeric ferric sulfate of the comparative examples 1-2, stirring, standing, taking supernatant, respectively measuring water quality parameters before and after treatment, and calculating the removal rate, wherein the results are shown in Table 1:

TABLE 1

As is clear from the results of Table 1, the polymeric ferric sulfate prepared in examples 2 to 4 of the present invention has more excellent wastewater treatment ability.

Then, taking 1000mL of 4 groups of wastewater of the same batch in a beaker, respectively adding 15% of polymeric ferric sulfate of examples 2-4 and comparative examples 1-2, uniformly stirring, and testing the antibacterial rate of escherichia coli and staphylococcus aureus, wherein the test results are shown in the following table 2:

TABLE 2

As can be seen from Table 2, the polymeric ferric sulfate prepared in examples 2 to 4 of the present invention has excellent and stable antibacterial effect.

In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.

Claims

1. A production and processing technology of polyferric sulfate, characterized in that it comprises the following steps:

(1) Fully mix green vitriol and water to dissolve, then slowly add concentrated sulfuric acid, heat in a water bath, first introduce air for oxidation, then add an oxidant for oxidation, and finally hydrolyze and polymerize to obtain A;

(2) preparing modified polyacrylamide solution;

(3) fully stirring the A in step (1) and the modified polyacrylamide solution in step (2) to mix them uniformly to obtain polyferric sulfate;

Wherein, the modified polyacrylamide in step (2) is prepared by the following steps:

S1. Add 1,3-dihydroxymethyl-5,5-dimethylhydantoin, anhydrous aluminum chloride and DMSO into a flask under nitrogen protection, stir, add epichlorohydrin, react at 60°C for 6h, cool, and distill under reduced pressure to obtain intermediate 1;

S2, after nitrogen blowing into the flask, add 2-amino-1,3-propanediol, pyridine and DMSO, stir, add tetradecane chloride, react at 75°C for 2h, cool, and distill under reduced pressure to obtain intermediate 2;

S3, under nitrogen protection, add intermediate 2, pyridine and DMSO into a flask, stir, add 4-chloro-1-butene, react at 80°C for 3h, cool, and distill under reduced pressure to obtain intermediate 3;

S4, under nitrogen protection, add intermediate 1, triethylamine and DMF into a flask, stir, add intermediate 3 and DMF, react at 80°C for 3h, cool, and distill under reduced pressure to obtain intermediate 4;

S5. Add intermediate 4, acrylamide, disodium ethylenediaminetetraacetate and DMF into a flask, stir, adjust the pH to 4, add ammonium persulfate and azobisisobutyronitrile, stir at 60° C. for 3 h, wash, and dry to obtain modified polyacrylamide.

2. A production and processing technology for polymerized ferric sulfate according to claim 1, characterized in that the usage ratio of 1,3-dihydroxymethyl-5,5-dimethylhydantoin, epichlorohydrin, anhydrous aluminum chloride and DMSO in step S1 is 0.069mol:0.06mol:1.6g:130mL; the usage ratio of 2-amino-1,3-propylene glycol, tetradecane chloride, pyridine and DMSO in step S2 is 0.063mol:0.06mol:7.3mL:100mL; the usage ratio of intermediate 2, 4 The usage ratio of -1-chloro-butene, pyridine and DMSO is 0.055 mol: 0.05 mol: 6.1 mL: 180 mL; the usage ratio of intermediate 1, intermediate 3, triethylamine and DMF in step S4 is 0.056 mol: 0.05 mol: 10.4 mL: 200 mL; the usage ratio of acrylamide, intermediate 4, disodium ethylenediaminetetraacetate, ammonium persulfate, azobisisobutyronitrile and DMF in step S5 is 5 g: 18.7 g: 0.3 g: 0.015 g: 0.012 g: 180 mL.

3. A production and processing technology for polyferric sulfate according to claim 1, characterized in that the usage ratio of green vitriol, concentrated sulfuric acid and water in the step (1) is 55g:5-5.5mL:80-120mL.

4. The production and processing process of polyferric sulfate according to claim 1, characterized in that the water bath temperature in step (1) is 40-65°C.

5. The production and processing technology of a polyferric sulfate according to claim 1, characterized in that the air oxidation time in step (1) is 6-8h.

6. The production and processing technology of a polyferric sulfate according to claim 1, characterized in that the oxidant in step (1) is any one of hydrogen peroxide and sodium chlorate.

7. The production and processing process of polyferric sulfate according to claim 1, characterized in that the amount of the oxidant used in step (1) is 120%-150% of the stoichiometric amount of ferrous ions remaining after air oxidation.

8. The production and processing technology of polyferric sulfate according to claim 1, characterized in that the oxidation time of the oxidant in step (1) is 1.5-2h.

9. The production and processing process of polyferric sulfate according to claim 1, characterized in that the mass concentration of modified polyacrylamide in step (2) is 0.1-1%.

10. The production and processing process of polyferric sulfate according to claim 1, characterized in that the mass ratio of A to the modified polyacrylamide solution in step (3) is (100-1000):1.