A production and processing technology of polyferric sulfate

Abstract

The invention discloses a production and processing technology of polyferric sulfate, and belongs to the technical field of production of polyferric sulfate. Green vitriol and water are fully mixed and dissolved, and then concentrated sulfuric acid is slowly added, heated in a water bath, firstly air is introduced for oxidation, and then an oxidant is added for oxidation, and finally hydrolyzed and polymerized to obtain A; a modified polyacrylamide solution is prepared; A and the modified polyacrylamide solution are fully stirred to mix evenly to obtain polyferric sulfate. The polyacrylamide in the modified polyacrylamide can effectively remove harmful substances such as suspended matter, organic matter and heavy metals in wastewater, and the multiple hydroxyl groups therein can enhance its adsorption and netting ability. Therefore, the modified polyacrylamide containing dimethyl hydantoin and quaternary ammonium salt structure is added into the preparation process of polyferric sulfate, so that the polyferric sulfate can have the dual functions of flocculation and antibacterial.

Description

Technical Field

[0001] The invention belongs to the technical field of production of polyferric sulfate, and in particular relates to a production and processing technology of polyferric sulfate. Background Art

[0002] At present, the commonly used inorganic coagulants are mainly divided into two categories: aluminum salts and iron salts. Among the aluminum salts, polyaluminum chloride, aluminum sulfate, and aluminum chloride are the main ones. And among the iron salts, polyferric sulfate is the main one. Polyferric sulfate is an inorganic polymer flocculant with wide pH applicability, high impurity removal rate, and fast alum floc settling. It is widely used in the treatment of industrial wastewater, urban sewage, industrial water, and drinking water.

[0003] Pollutants such as suspended solids, organic matter, heavy metal ions and pathogenic bacteria in various types of water can cause great harm to human health. Among them, the public health problems caused by pathogenic bacterial infections are particularly serious. Various pathogens and intestinal bacteria seriously endanger the health of humans and animals. Although polyferric sulfate can partially separate and remove bacteria in water, it cannot effectively inhibit or kill these bacteria. Therefore, it is extremely important to enhance the antibacterial properties of polyferric sulfate, efficiently remove harmful microorganisms such as algae, bacteria and pathogens, and develop polyferric sulfate with dual functions of flocculation and antibacterial. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a production and processing technology of polyferric sulfate.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A production and processing technology of polyferric sulfate comprises the following steps:

[0007] (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;

[0008] (2) preparing modified polyacrylamide solution;

[0009] (3) A in step (1) and the modified polyacrylamide solution in step (2) are fully stirred to mix them uniformly to obtain polyferric sulfate.

[0010] Furthermore, in the step (1), the dosage ratio of green vitriol, concentrated sulfuric acid and water is 55g:5-5.5mL:80-120mL.

[0011] Furthermore, in step (1), the water bath temperature is 40-65°C.

[0012] Furthermore, the air oxidation time in step (1) is 6-8 hours.

[0013] Furthermore, in step (1), the oxidant is any one of hydrogen peroxide and sodium chlorate.

[0014] Furthermore, the amount of the oxidant used in step (1) is 120%-150% of the stoichiometric amount of ferrous ions remaining after air oxidation.

[0015] Furthermore, in step (1), the oxidation time of the oxidant is 1.5-2h.

[0016] Furthermore, in step (2), the mass concentration of the modified polyacrylamide is 0.1-1%.

[0017] Furthermore, the modified polyacrylamide in step (2) is prepared by the following steps:

[0018] S1. Add 1,3-dihydroxymethyl-5,5-dimethylhydantoin, anhydrous aluminum chloride and DMSO (dimethyl sulfoxide) into a fully dried four-necked flask under nitrogen protection, stir until mixed evenly, slowly add epichlorohydrin while stirring, raise the temperature to 60°C after the addition is complete, stir and react for 6 hours, cool to room temperature after the reaction is complete, and distill under reduced pressure. The entire process is carried out under nitrogen protection to obtain intermediate 1; the amount ratio of 1,3-dihydroxymethyl-5,5-dimethylhydantoin, epichlorohydrin, anhydrous aluminum chloride and DMF is 0.069 mol: 0.06 mol: 1.6 g: 130 mL;

[0019] The hydroxyl group of 1,3-dihydroxymethyl-5,5-dimethylhydantoin and the epoxy group of epichlorohydrin react under heating and aluminum chloride catalysis. The reaction process is as follows:

[0020]

[0021] S2, nitrogen was blown into a dry three-necked flask for 30 minutes to remove the air in the flask, and then 2-amino-1,3-propanediol, pyridine and DMSO were added to the flask under nitrogen protection, and after stirring and dissolving, tetradecane chloride was slowly added. After the addition was completed, the temperature was raised to 75°C for reaction for 2 hours. After the reaction was completed, it was cooled to room temperature and distilled under reduced pressure to obtain intermediate 2; the dosage ratio of 2-amino-1,3-propanediol, tetradecane chloride, pyridine and DMSO was 0.063 mol: 0.06 mol: 7.3 mL: 100 mL;

[0022] Under the conditions of heating and the presence of pyridine, the -Cl of chlorotetradecane and the -NH2 of 2-amino-1,3-propanediol undergo a nucleophilic substitution reaction. The reaction process is as follows:

[0023]

[0024] S3. Add intermediate 2, pyridine and DMSO to a dry three-necked flask under nitrogen protection. After stirring and dissolving, slowly add 4-chloro-1-butene in the constant pressure dropping funnel to the flask. After the addition is completed, heat to 80°C and keep the temperature for 3 hours. After the reaction is completed, cool to room temperature and distill under reduced pressure to obtain intermediate 3; the amount ratio of intermediate 2, 4-chloro-1-butene, pyridine and DMSO is 0.055 mol: 0.05 mol: 6.1 mL: 180 mL;

[0025] Under the conditions of heating and the presence of pyridine, the -NH- of intermediate 2 and the -Cl of 4-chloro-1-butene undergo a nucleophilic substitution reaction. The reaction process is as follows:

[0026]

[0027] S4. Add intermediate 1, triethylamine and DMF (N,N-dimethylformamide) to a dry three-necked flask under nitrogen protection, stir and dissolve, then slowly add a mixed solution of intermediate 3 and DMF, heat to 80°C and react for 3h after the addition is complete, cool to room temperature after the reaction is complete, and distill under reduced pressure to obtain intermediate 4; the amount ratio of intermediate 1, intermediate 3, triethylamine and DMF is 0.056mol:0.05mol:10.4mL:200mL;

[0028] Under heating conditions, triethylamine acts as an acid-binding agent, and the -Cl of intermediate 1 and the tertiary amine group of intermediate 3 undergo a nucleophilic substitution reaction. The reaction process is as follows:

[0029]

[0030] S5. Add intermediate 4, acrylamide, disodium ethylenediaminetetraacetate and DMF to a dry four-necked round-bottom flask, stir to form a uniform solution, adjust the pH to 4 with 0.1 mol / L hydrochloric acid and 0.1 mol / L sodium hydroxide, pass nitrogen into the reaction system for 30 minutes to exhaust the air in the system, add ammonium persulfate and azobisisobutyronitrile, heat to 60°C and stir for 3 hours, wash with anhydrous ethanol 5 times after the reaction, and dry at 60°C for 24 hours to obtain modified polyacrylamide. The amount ratio of acrylamide, intermediate 4, disodium ethylenediaminetetraacetate, ammonium persulfate, azobisisobutyronitrile and DMF is 5g:18.7g:0.3g:0.015g:0.012g:180mL.

[0031] Under the action of initiators ammonium persulfate and azobisisobutyronitrile, the carbon-carbon double bond at the end of intermediate 4 can react chemically with the carbon-carbon double bond of acrylamide, and intermediate 4 is grafted onto the polyacrylamide macromolecular chain to obtain modified polyacrylamide.

[0032] Modified polyacrylamide contains a quaternary ammonium salt structure with a long carbon chain (14 carbons). The quaternary ammonium salt structure is a broad-spectrum fungicide. The quaternary ammonium salt structure can dissociate into a quaternary ammonium salt cation containing a positive charge. + Ions can be adsorbed onto the cell wall of negatively charged bacteria, destroying the cell membrane, denaturing proteins, and hindering the replication and reproduction of DNA, thereby achieving an antibacterial effect. In addition, when the carbon number of the alkyl chain of the quaternary ammonium salt structure is 10-16, the antibacterial effect is better, and when the carbon number of the alkyl chain of the quaternary ammonium salt structure is 14, the antibacterial effect is the best. Modified polyacrylamide also contains dimethyl hydantoin, which is a broad-spectrum, highly effective antibacterial preservative that can effectively resist Gram-positive bacteria, Gram-negative bacteria, molds, etc., and can remain stable when used in a wide pH value and temperature range. Since dimethyl hydantoin and the quaternary ammonium salt structure are grafted onto the polyacrylamide macromolecular chain, dimethyl hydantoin and the quaternary ammonium salt structure are not easy to migrate and escape, and can stably exist in polyacrylamide. At the same time, the two antibacterial components work synergistically, giving the modified polyacrylamide excellent antibacterial and antiseptic properties.

[0033] Polyacrylamide can effectively remove harmful substances such as suspended matter, organic matter and heavy metals in wastewater, and the multiple hydroxyl groups in modified polyacrylamide can improve the adsorption and netting ability of modified polyacrylamide to a certain extent. Therefore, modified polyacrylamide not only has excellent and stable antibacterial and anticorrosive capabilities, but also has efficient and long-lasting wastewater treatment capabilities. Adding modified polyacrylamide to the preparation of polyferric sulfate can make polyferric sulfate have higher wastewater treatment capabilities and make polyferric sulfate have excellent and stable antibacterial and anticorrosive properties.

[0034] Furthermore, in the step (3), the mass ratio of A to the modified polyacrylamide solution is (100-1000):1.

[0035] The beneficial effects of the present invention are as follows: the polyacrylamide in the modified polyacrylamide can effectively remove harmful substances such as suspended matter, organic matter and heavy metals in wastewater, and the multiple hydroxyl groups therein can enhance its adsorption and capture capabilities. Therefore, adding the modified polyacrylamide containing dimethyl hydantoin and quaternary ammonium salt structure into the preparation process of polyferric sulfate can make the polyferric sulfate have the dual functions of flocculation and antibacterial. DETAILED DESCRIPTION

[0036] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Example 1

[0038] The specific steps for preparing modified polyacrylamide are as follows:

[0039] S1. Under nitrogen protection, add 13 g of 1,3-dihydroxymethyl-5,5-dimethylhydantoin, 1.6 g of anhydrous aluminum chloride, and 130 mL of DMSO into a fully dried 250 mL four-necked flask, stir until mixed evenly, slowly add 4.7 mL of epichlorohydrin while stirring, and after the addition is complete, heat to 60 ° C and stir to react for 6 hours. After the reaction is completed, cool to room temperature and distill under reduced pressure. The entire process is carried out under nitrogen protection to obtain intermediate 1;

[0040] S2, nitrogen was blown into a dry 250 mL three-necked flask for 30 min to remove the air in the flask, and then 5.7 g of 2-amino-1,3-propanediol, 7.3 mL of pyridine and 100 mL of DMSO were added to the flask under nitrogen protection, and after stirring and dissolving, 16.2 mL of tetradecyl chloride was slowly added. After the addition was completed, the temperature was raised to 75 ° C for reaction for 2 h. After the reaction was completed, it was cooled to room temperature and distilled under reduced pressure to obtain intermediate 2;

[0041] S3. Under nitrogen protection, add 15.8 g of intermediate 2, 6.1 mL of pyridine and 180 mL of DMSO to a dry 250 mL three-necked flask. After stirring and dissolving, slowly add 5.1 mL of 4-chloro-1-butene in a constant pressure dropping funnel to the flask. After the addition is complete, heat to 80 ° C and keep the temperature for 3 hours. After the reaction is completed, cool to room temperature and distill under reduced pressure to obtain intermediate 3.

[0042] S4, under nitrogen protection, add 15.7 g of intermediate 1, 10.4 mL of triethylamine and 140 mL of DMF to a dry 250 mL three-necked flask, stir and dissolve, then slowly add a mixed solution of 17.1 g of intermediate 3 and 60 mL of DMF, heat to 80 °C and react for 3 h, cool to room temperature after the reaction, and distill under reduced pressure to obtain intermediate 4;

[0043] S5. Add 18.7 g of intermediate 4, 5 g of acrylamide, 0.3 g of disodium ethylenediaminetetraacetate and 180 mL of DMF into a dry 500 mL four-necked round-bottom flask, stir to form a uniform solution, adjust the pH to 4 with 0.1 mol / L hydrochloric acid and 0.1 mol / L sodium hydroxide, pass nitrogen into the reaction system for 30 min to expel the air in the system, add 0.015 g of ammonium persulfate and 0.012 g of azobisisobutyronitrile, heat to 60 ° C and stir for 3 h, wash with anhydrous ethanol 5 times after the reaction, and dry at 60 ° C for 24 h to obtain modified polyacrylamide.

[0044] Example 2

[0045] Preparation of polyferric sulfate, the specific steps are as follows:

[0046] (1) 55 g of green vitriol and 80 mL of water were fully mixed and dissolved, and then 5 mL of concentrated sulfuric acid was slowly added, heated in a water bath at 40°C, and air was first introduced for oxidation for 6 h, and then 5 g of sodium chlorate was added for oxidation for 1.5 h, and finally hydrolyzed and polymerized to obtain A;

[0047] (2) preparing a modified polyacrylamide solution with a mass concentration of 0.1%;

[0048] (3) A in step (1) and the 0.1% modified polyacrylamide solution in step (2) are fully stirred to mix uniformly, with the mass ratio of A to the modified polyacrylamide solution being 1000:1, to obtain polyferric sulfate.

[0049] Example 3

[0050] Preparation of polyferric sulfate, the specific steps are as follows:

[0051] (1) 55 g of green vitriol and 120 mL of water were fully mixed and dissolved, and then 5.5 mL of concentrated sulfuric acid was slowly added, heated in a water bath at 65°C, and air was first introduced for oxidation for 8 h, and then 2.7 g of hydrogen peroxide was added for oxidation for 1.8 h, and finally hydrolyzed and polymerized to obtain A;

[0052] (2) preparing a modified polyacrylamide solution with a mass concentration of 0.4%;

[0053] (3) A in step (1) and the 0.4% modified polyacrylamide solution in step (2) are fully stirred to mix them evenly, with the mass ratio of A to the modified polyacrylamide solution being 200:1, to obtain polyferric sulfate.

[0054] Example 4

[0055] Preparation of polyferric sulfate, the specific steps are as follows:

[0056] (1) 55 g of green vitriol and 100 mL of water were fully mixed and dissolved, and then 5.2 mL of concentrated sulfuric acid was slowly added, heated in a water bath at 60°C, and air was first introduced for oxidation for 7 h, and then 7.3 g of sodium chlorate was added for oxidation for 2 h, and finally hydrolyzed and polymerized to obtain A;

[0057] (2) preparing a modified polyacrylamide solution with a mass concentration of 0.5%;

[0058] (3) A in step (1) and the 0.5% modified polyacrylamide solution in step (2) are fully stirred to mix them evenly, with the mass ratio of A to the modified polyacrylamide solution being 100:1, to obtain polyferric sulfate.

[0059] Comparative Example 1

[0060] Preparation of polyferric sulfate, the specific steps are as follows:

[0061] The remaining steps remain unchanged, and the modified polyacrylamide in Example 4 is replaced by polyacrylamide that has not undergone any modification treatment, thereby preparing polyferric sulfate.

[0062] Comparative Example 2

[0063] Preparation of polyferric sulfate, the specific steps are as follows:

[0064] The remaining steps remain unchanged, the modified polyacrylamide in Example 4 is replaced by polyacrylamide that has not been subjected to any modification treatment, and ditetradecyl dimethyl ammonium bromide is added to prepare polyferric sulfate.

[0065] Performance Testing

[0066] Take 1000 mL of wastewater from 5 groups of the same batch into a beaker, add 2.0 mL of polyferric sulfate of Example 2-4 and 2.0 mL of polyferric sulfate of Comparative Example 1-2 respectively, stir and let stand, take the supernatant, measure the water quality parameters before and after treatment respectively, calculate the removal rate, and the results are shown in Table 1:

[0067] Table 1

[0068]

[0069]

[0070] It can be seen from the results in Table 1 that the polyferric sulfate prepared in Examples 2-4 of the present invention has a more excellent wastewater treatment capacity.

[0071] 1000 mL of wastewater from the same batch of 4 groups was taken into a beaker, and 15% of the polyferric sulfate of Examples 2-4 and Comparative Examples 1-2 was added respectively, and stirred evenly. The antibacterial rates of Escherichia coli and Staphylococcus aureus were tested. The test results are shown in Table 2 below:

[0072] Table 2

[0073]

[0074] It can be seen from Table 2 that the polyferric sulfate prepared in Examples 2-4 of the present invention has an excellent and stable antibacterial effect.

[0075] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0076] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A production and processing technology of polyferric sulfate, characterized in that: The following steps are involved: (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. The production and processing technology of a polyferric 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 0.069 mol: 0.06 mol: 1.6 g: 130 mL; the usage ratio of 2-amino-1,3-propanediol, tetradecane chloride, pyridine and DMSO in step S2 is 0.063 mol: 0.06 mol: 7.3 mL: 100 mL; the usage ratio of intermediate 2, 4-chloro-1-butene, pyridine and DMSO in step S3 is 0.069 mol: 0.06 mol: 1.6 g: 130 mL; The amount ratio is 0.055mol:0.05mol:6.1mL:180mL; the amount ratio of intermediate 1, intermediate 3, triethylamine and DMF in step S4 is 0.056mol:0.05mol:10.4mL:200mL; the amount ratio of acrylamide, intermediate 4, disodium ethylenediaminetetraacetate, ammonium persulfate, azobisisobutyronitrile and DMF in step S5 is 5g:18.7g:0.3g:0.015g:0.012g:180mL.

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

4. The production and processing technology of a 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: In the step (1), the oxidant is any one of hydrogen peroxide and sodium chlorate.

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

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

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