CN114276493B - Preparation method of composite polyacrylamide - Google Patents
Preparation method of composite polyacrylamide Download PDFInfo
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- CN114276493B CN114276493B CN202210202123.8A CN202210202123A CN114276493B CN 114276493 B CN114276493 B CN 114276493B CN 202210202123 A CN202210202123 A CN 202210202123A CN 114276493 B CN114276493 B CN 114276493B
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention provides a preparation method of composite polyacrylamide, and also provides the composite polyacrylamide prepared by the preparation method and application of the composite polyacrylamide as a sewage treatment agent. According to the preparation method provided by the invention, the natural polymer modified chitosan quaternary ammonium salt is innovatively introduced in the polymerization process of the cationic polyacrylamide, so that the composite polyacrylamide with a monobasic system is formed, and the cationic polyacrylamide and the chitosan quaternary ammonium salt realize higher water treatment efficiency through synergistic action, so that the preparation method is particularly suitable for the treatment of sewage and sludge. In addition, because of the use of the natural polymer, the dependence on petroleum routes is reduced under the same treatment effect, and the low-carbon and environment-friendly requirements are better met. The composite polyacrylamide provided by the invention has excellent performance, the preparation method is simple and convenient, and high cost is not required, so that the composite polyacrylamide has wide application prospect.
Description
Technical Field
The invention relates to the field of polyacrylamide, in particular to a preparation method of composite polyacrylamide, the composite polyacrylamide prepared by the preparation method and application of the composite polyacrylamide as a sewage treatment agent.
Background
The polyacrylamide polymer has the advantages of good water solubility, high molecular weight, easy generation of bridging flocculation on particles in an aqueous solution and the like, so the polyacrylamide polymer is widely applied to sewage treatment and sludge treatment, and is widely researched as a common water treatment agent. The polyacrylamide polymer is classified into cationic type, anionic type and nonionic type, wherein the cationic polyacrylamide is mainly used for treating sewage and sludge containing particles with negative surface charges, such as municipal sludge and the like. However, the monomer acrylamide of polyacrylamide is converted from acrylonitrile, and acrylonitrile is from petroleum route, and at present, the petroleum resource is increasingly tense, and the high dependence on the petroleum route is not beneficial to the wide application of products, and the low-carbon and environment-friendly requirements cannot be met.
Chitosan is a natural polymer derived from chitin, the yield is second to cellulose in nature, and the modified chitosan quaternary ammonium salt is an excellent water-soluble polymer, has better cation adsorbability and biodegradability, so the chitosan quaternary ammonium salt has attracted attention and is widely applied to the aspects of paper treatment, textile printing and dyeing treatment, environment-friendly water treatment and the like. However, chitosan has a rigid cyclic chain structure, so that the flocculation and bridging abilities are weaker than those of polyacrylamide, and the requirements of high-efficiency field application cannot be fully met.
Disclosure of Invention
In order to solve the application defects of a single cationic polyacrylamide product, the invention aims to provide a preparation method of composite polyacrylamide, and a natural high molecular substance chitosan quaternary ammonium salt is introduced in the polymerization process of cationic polyacrylamide, so that a composite system with better flocculation performance, higher water treatment efficiency and more environmental protection can be formed, and the composite system is particularly suitable for the treatment of sludge and sewage.
The preparation method of the composite polyacrylamide provided by the invention comprises the following steps:
s1: according to the parts by weight, 5-20 parts of chitosan quaternary ammonium salt is dissolved in 50-70 parts of water to form a solution;
s2: adding 30-60 parts of acrylamide, 20-50 parts of cationic monomer, 0.0025-0.01 part of tetrasodium ethylenediamine tetraacetate and 0.0001-0.0003 part of organic acid into the solution prepared in the step S1 to prepare a polymerization solution, and adjusting the pH value to be 4-6;
s3: under the protection of inert gas, controlling the temperature of the polymerization liquid prepared in the step S2 to be 0-5 ℃, adding an oxidant and a reducing agent for polymerization reaction, and controlling the temperature of the polymerization liquid to be not more than 20 ℃ in the polymerization process; and
s4: and after the polymerization reaction is finished, preserving the heat for 2 to 4 hours, taking out the obtained colloid, granulating, drying and crushing.
The compound polyacrylamide prepared by the preparation method provided by the invention comprises cationic polyacrylamide and chitosan quaternary ammonium salt. Cationic polyacrylamide is mutually and electrostatically adsorbed with colloid particles with negative charges, and simultaneously bridges the particles to guide the particles to aggregate, flocculate and settle. The chitosan quaternary ammonium salt is derived from rigid-chain chitosan, can effectively adsorb particles with negative charges, and simultaneously keeps molecular chains from collapsing, so as to more effectively realize bridging. However, the molecular weight of the chitosan quaternary ammonium salt is far smaller than that of polyacrylamide, so that the flocculation and bridging capacity is limited. The inventor of the invention finds that the combination of the chitosan and the chitosan can play a very good synergistic effect, and simultaneously, the chitosan with a rigid chain can endow the system with better shear resistance and reduce the viscosity loss of the system in the dissolving and solution preparation processes. In addition, under the same treatment effect, the introduction of the natural polymer system also reduces the dosage of cationic polyacrylamide, thereby reducing the dependence of a water treatment system on an oil route, better meeting the requirements of low carbon and environmental protection and obviously reducing the economic cost.
In the preparation method provided by the invention, the chitosan quaternary ammonium salt is added into a reaction system together with monomers such as acrylamide and the like before cationic polyacrylamide is polymerized, and forms a unitary composite system with the polyacrylamide. The inventor of the present invention also finds that a binary system formed by mixing and compounding two polymers has a significantly poorer effect than the unitary system of the present invention, and supposes that the possible reasons are: the chitosan quaternary ammonium salt exists in a polymerization solution of a reaction system before acrylamide polymerization, so that molecular chains stretch and are easy to form molecular chain entanglement configuration with stable interaction with a product after polymerization. In a binary system compounded after polymerization, because both molecules are macromolecules, the molecules are difficult to move to a stable molecular chain entanglement configuration through chain segments, and a synergistic result cannot be fully reflected, the difference of application performance is obvious. When mixing two polymer solutions having tackifying ability, uniform mixing is often difficult, especially for polymers having ultra-high molecular weight such as polyacrylamide.
In the preparation method provided by the invention, by controlling the polymerization temperature, the phenomenon that the chitosan quaternary ammonium salt and the acrylamide comonomer are subjected to free radical polymerization and then grafted can be avoided, the formation of a cross-linked substance is easily caused by the occurrence of grafting, and the obtained polymer is insoluble, so that the performance of the polymer is reduced. In the composite polyacrylamide prepared by the preparation method provided by the invention, the chitosan quaternary ammonium salt does not participate in the formation of cationic polyacrylamide basically.
In the preparation method provided by the invention, the chitosan quaternary ammonium salt can be any common type. In some preferred embodiments, the degree of substitution of the chitosan quaternary ammonium salt is 92 to 98%, the water-insoluble content is 0.8 to 1.2wt%, the weight loss on drying is 8 to 12wt%, and the ignition residue is 0.8 to 1.2wt%.
In the preparation method provided by the invention, the cationic monomer can be any common kind used in preparation of cationic polyacrylamide products. In some preferred embodiments, the cationic monomer is selected from one or more of dimethylethylallylammonium chloride, dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride.
In the preparation method provided by the invention, the organic acid is selected from one or more of formic acid, acetic acid, propionic acid, butyric acid, valeric acid and caproic acid.
In the preparation method provided by the invention, the oxidizing agent in the step S3 is selected from potassium bromate, and the using amount of the oxidizing agent is 0.00001-0.000025 part by weight.
In the preparation method provided by the invention, the reducing agent in the step S3 is selected from sodium metabisulfite, and the using amount of the reducing agent is 0.00001-0.000025 part by weight.
In the preparation method provided by the invention, the reaction time of the polymerization reaction can be 8-12 hours.
The invention also provides the compound polyacrylamide which is prepared by the preparation method of any one of the technical schemes.
The composite polyacrylamide provided by the invention is a particle or powdery polymer product, and the solid content is more than 89%.
The viscosity average molecular weight of the composite polyacrylamide provided by the invention is 1000-3000 ten thousand. In some preferred embodiments, the viscosity-average molecular weight of the composite polyacrylamide is 1000 to 2000 ten thousand. In some more preferred embodiments, the viscosity average molecular weight of the composite polyacrylamide is 1750 to 1900 ten thousand.
The invention also provides application of the compound polyacrylamide in any technical scheme as a water treatment agent.
In some preferred embodiments, the water treatment agent is a water treatment agent for municipal sludge and sewage.
Compared with the common cationic polyacrylamide product, the composite polyacrylamide provided by the invention can reduce the dosage of polyacrylamide, is low in cost and more environment-friendly, and can achieve higher flocculation efficiency. For example, when the composite polyacrylamide provided by the invention is used as a water treatment agent to treat municipal sludge containing 96% of water, the water content of a mud cake is less than 55%, the dehydration rate of the sludge is more than 93%, and the viscosity retention rate of a polymer mother liquor with the concentration of 0.2% is more than 90% after the polymer mother liquor is sheared for 5 minutes under the high shear of 2000 rpm.
According to the preparation method provided by the invention, natural high-molecular modified chitosan quaternary ammonium salt is innovatively introduced in the polymerization process of cationic polyacrylamide, so that the composite polyacrylamide of a monobasic system is formed. The rigid chitosan quaternary ammonium salt slows down the collapse of the flexible polyacrylamide chains on the surfaces of the colloidal particles, improves the bridging flocculation effect, strengthens the adsorption, agglomeration and sedimentation capabilities of the colloidal particles in the water treatment process, and also improves the anti-shearing capability of a water treatment system. Therefore, the cationic polyacrylamide and the chitosan quaternary ammonium salt realize more efficient water treatment efficiency through synergistic action, and are particularly suitable for the treatment of sewage and sludge. In addition, because of the use of the natural polymer, the dependence on petroleum routes is reduced under the same treatment effect, and the low-carbon and environment-friendly requirements are better met.
The composite polyacrylamide provided by the invention has excellent performance, the preparation method is simple and convenient, and high cost is not required, so that the composite polyacrylamide has wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the action mechanism of the composite polyacrylamide of the present invention;
FIG. 2 is an infrared spectrum of the composite polyacrylamide prepared in examples 1-3 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following specific examples.
The chitosan quaternary ammonium salts used in examples 1-3 of the present invention were purchased from Macklin reagent and were sold under the designations 850124 (degree of substitution 92%, water-insoluble 1%, loss on drying 10.0%, ignition residue 1.0%), 850125 (degree of substitution 95%, water-insoluble 1%, loss on drying 10.0%, ignition residue 1.0%) and 850126 (degree of substitution 98%, water-insoluble 1%, loss on drying 10.0%, ignition residue 1.0%), respectively.
Other raw materials or reagents used in examples of the present invention and comparative examples are commercially available products unless otherwise specified.
The percentages used in the examples of the present invention and comparative examples are mass percentages unless otherwise specified.
Example 1 preparation of composite polyacrylamide
The following raw material components are used in parts by weight:
40 parts of acrylamide;
30 parts of dimethyldiallylammonium chloride;
0.005 part of tetrasodium ethylenediamine tetraacetate;
0.0001 part of oxalic acid;
65 parts of deionized water;
5 parts of chitosan quaternary ammonium salt (the substitution degree is 92%, the water-insoluble substance is 1%, the drying weight loss is 10.0%, and the ignition residue is 1.0%).
Firstly, dissolving chitosan quaternary ammonium salt in deionized water, adding the other raw material components in sequence after uniform dissolution to prepare uniform polymerization liquid, adding the uniform polymerization liquid into a polymerization kettle, and introducing nitrogen to remove oxygen for more than 1 hour. Adjusting the system temperature in a polymerization kettle to 2-3 ℃ through water bath, respectively dissolving 0.00001 part of potassium bromate and 0.000015 part of sodium metabisulfite in 1 part of deionized water, adding into the polymerization kettle, introducing nitrogen until the system temperature rises to start polymerization reaction, and controlling the temperature of the polymerization system to be not more than 20 ℃ in the polymerization process and the polymerization time to be about 9 hours. After polymerization, preserving heat for 2 hours, discharging, granulating, drying at 85-90 ℃ and crushing to obtain the product.
The infrared spectrum of the product obtained in example 1 is shown as # 1 in FIG. 2.
Example 2 preparation of composite type polyacrylamide
The following raw material components are used in parts by weight:
45 parts of acrylamide;
25 parts of dimethylethylallylammonium chloride;
0.0025 parts of tetrasodium ethylenediaminetetraacetate;
0.0002 part of oxalic acid;
70 parts of deionized water;
15 parts of chitosan quaternary ammonium salt (the substitution degree is 95%, the water insoluble matter is 1%, the drying weight loss is 10.0%, and the ignition residue is 1.0%).
Firstly, dissolving chitosan quaternary ammonium salt in deionized water, adding the other raw material components in sequence after uniform dissolution to prepare uniform polymerization liquid, adding the uniform polymerization liquid into a polymerization kettle, and introducing nitrogen to remove oxygen for more than 1 hour. Adjusting the system temperature in a polymerization kettle to 2-3 ℃ through water bath, respectively dissolving 0.000015 parts of potassium bromate and 0.00002 parts of sodium metabisulfite in 1.5 parts of deionized water, adding into the polymerization kettle, introducing nitrogen until the system temperature rises to start polymerization, controlling the temperature of the polymerization system to be not more than 20 ℃ in the polymerization process, and allowing the polymerization time to be about 8 hours. After polymerization, preserving heat for 2 hours, discharging, granulating, drying at 85-90 ℃ and crushing to obtain the product.
The infrared spectrum of the product obtained in example 2 is shown as # 2 in FIG. 2.
EXAMPLE 3 preparation of composite Polyacrylamide
The following raw material components are used in parts by weight:
50 parts of acrylamide;
45 parts of acryloyloxyethyltrimethyl ammonium chloride;
0.01 part of tetrasodium ethylenediamine tetraacetate;
0.0003 part of oxalic acid;
55 parts of deionized water;
20 parts of chitosan quaternary ammonium salt (the substitution degree is 98%, the water insoluble matter is 1%, the drying weight loss is 10.0%, and the ignition residue is 1.0%).
Firstly, dissolving chitosan quaternary ammonium salt in deionized water, adding the other raw material components in sequence after uniform dissolution to prepare uniform polymerization liquid, adding the uniform polymerization liquid into a polymerization kettle, and introducing nitrogen to remove oxygen for more than 1 hour. Adjusting the system temperature in a polymerization kettle to 2-3 ℃ through water bath, respectively dissolving 0.00002 parts of potassium bromate and 0.000025 parts of sodium metabisulfite in 1 part of deionized water, adding into the polymerization kettle, introducing nitrogen until the system temperature rises to start polymerization, and controlling the temperature of the polymerization system to be not more than 20 ℃ in the polymerization process and the polymerization time to be about 10 hours. After polymerization, preserving heat for 2 hours, discharging, granulating, drying at 85-90 ℃ and crushing to obtain the product.
The infrared spectrum of the product obtained in example 3 is shown as # 3 in FIG. 2.
Comparative example 1
The product of comparative example 1 was prepared from chitosan quaternary ammonium salt (degree of substitution 98%, water-insoluble matter 1%, loss on drying 10.0%, residue on ignition 1.0%).
Comparative example 2 preparation of ordinary cationic polyacrylamide
Except that the chitosan quaternary ammonium salt is not added, the components of other raw materials and the operation steps are the same as those of the example 1, and an unmodified cationic polyacrylamide product is prepared.
Comparative example 3 preparation of Mixed Polyacrylamide
The products of comparative example 1 and comparative example 2 were mixed in a weight ratio of 5.
Comparative example 4 preparation of Mixed Polyacrylamide
Except that the chitosan quaternary ammonium salt is not added, the components of other raw materials and the operation steps are the same as those of the example 2, and an unmodified cationic polyacrylamide product is prepared.
The obtained cationic polyacrylamide product was mixed with chitosan quaternary ammonium salt (degree of substitution 95%, water-insoluble content 1%, loss on drying 10.0%, ignition residue 1.0%) at a weight ratio of 85.
The products obtained in the above examples 1 to 3 and comparative examples 1 to 4 were prepared into a polymer solution having a concentration of 0.2% in clear water, the polymer solution thus prepared was sheared for 5 minutes under a high shear of 2000 rpm, and after 10 minutes of recovery, the viscosities before shearing and after shearing and recovery were measured respectively by a haake rheometer at a shear rate of 10 arcseconds at 25 ℃ to calculate the viscosity retention rates, as shown in table 1. Taking sludge 1L containing 96% of water and the polymer solution 2 g, dropwise adding the polymer solution into the sludge under slow stirring, stirring for 10 minutes, and then centrifuging for ten minutes at the speed of 5000 revolutions per minute. Taking out the supernatant and the sludge at the bottom, and testing the dehydration rate of the sludge and the water content of a sludge cake, wherein the test data are shown in table 1.
TABLE 1 results of Performance test of examples 1 to 3 and comparative examples 1 to 4
As can be seen from the results in Table 1, the composite polyacrylamide prepared in examples 1-3 of the present invention has significantly higher shear resistance than the conventional cationic polyacrylamide (such as comparative example 2), while the higher retention of shear viscosity of the quaternary ammonium salt of chitosan in comparative example 1 is due to the lower bulk viscosity. The water content of mud cakes and the sludge dehydration rate can also show that the composite polyacrylamide has superiority, and the synergistic mechanism of the sludge dehydration is shown in figure 1.
Comparative examples 3 and 4 are respectively a binary system corresponding to examples 1 and 2, in which the unitary polymerization system is changed into a unitary compounding system, and the unitary compounding system is compounded with chitosan quaternary ammonium salt after acrylamide polymerization. It can be seen that the performance of the binary system formed by compounding after polymerization is poorer than that of the unitary composite system formed by integral polymerization. The slightly poor performance but the difference is not particularly obvious when the viscosity and the shear resistance are seen alone, mainly because the tackifying capability is mainly embodied by polyacrylamide, and relatively the tackifying capability of the chitosan quaternary ammonium salt is too low, so the contribution is not great, but the tackifying capability and the shear resistance of the unitary system are slightly higher than those of the binary system. The difference is obvious corresponding to the performance parameters of the water content of the mud cake and the dehydration rate of the sludge, and the conjecture is mainly that in a unitary system, the chitosan quaternary ammonium salt exists in the solution of the reaction system before acrylamide polymerization, so that molecular chains stretch and easily form a molecular chain entanglement configuration with stable interaction with the polymerized product. In a binary system compounded after polymerization, because both molecules are macromolecules, the molecules are difficult to move to a stable molecular chain entanglement configuration through chain segments, and a synergistic result cannot be fully reflected, the difference of application performance is obvious.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (6)
1. A preparation method of compound polyacrylamide used as a sewage treatment agent is characterized by comprising the following steps:
s1: according to the parts by weight, 5-20 parts of chitosan quaternary ammonium salt with the substitution degree of 92-98 percent are dissolved in 50-70 parts of water to form a solution;
s2: adding 30-60 parts of acrylamide, 20-50 parts of cationic monomer, 0.0025-0.01 part of tetrasodium ethylenediamine tetraacetate and 0.0001-0.0003 part of organic acid into the solution prepared in the step S1 to prepare a polymerization solution, and adjusting the pH value to be 4-6;
s3: under the protection of inert gas, controlling the temperature of the polymerization liquid prepared in the step S2 to be 0-5 ℃, adding an oxidant and a reducing agent for polymerization reaction, and controlling the temperature of the polymerization liquid to be not more than 20 ℃ in the polymerization process; and
s4: after the polymerization reaction is finished, preserving the heat for 2 to 4 hours, taking out the obtained colloid, granulating, drying and crushing;
wherein the cationic monomer is selected from one or more of dimethyl ethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride and acryloyloxyethyl trimethyl ammonium chloride;
the organic acid is selected from one or more of formic acid, acetic acid, propionic acid, butyric acid, valeric acid and caproic acid;
the oxidant is selected from potassium bromate, and the reducing agent is selected from sodium metabisulfite.
2. The method according to claim 1, wherein the chitosan quaternary ammonium salt has a water-insoluble content of 0.8 to 1.2wt%, a loss on drying of 8 to 12wt%, and a residue on ignition of 0.8 to 1.2wt%.
3. The method according to claim 1, wherein the oxidizing agent is used in an amount of 0.00001 to 0.000025 parts by weight in step S3.
4. The method according to claim 1, wherein the reducing agent in step S3 is used in an amount of 0.00001 to 0.000025 parts by weight.
5. A composite polyacrylamide characterized by being produced by the production method according to any one of claims 1 to 4.
6. Use of the composite polyacrylamide according to claim 5 as a sewage treatment agent.
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