CN113956381A - Method for reducing residual monomer of polyacrylamide dry powder - Google Patents

Method for reducing residual monomer of polyacrylamide dry powder Download PDF

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Publication number
CN113956381A
CN113956381A CN202111432729.2A CN202111432729A CN113956381A CN 113956381 A CN113956381 A CN 113956381A CN 202111432729 A CN202111432729 A CN 202111432729A CN 113956381 A CN113956381 A CN 113956381A
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polymerization
initiator
production
dry powder
emulsifying
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胡奎玲
任建军
蒋永军
吕宁
闫亮杉
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Dongying Baomo Environmental Engineering Co ltd
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Dongying Baomo Environmental Engineering Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52Amides or imides
    • C08F20/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56Acrylamide; Methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/04Azo-compounds

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a method for reducing residual monomer of polyacrylamide dry powder, adding emulsifier, solvent oil and deionized water in sequence, stirring and emulsifying for 5-10 minutes by an emulsifying machine, adding initiator E, emulsifying for 5-10 minutes again to obtain an emulsion type initiation system, in polymerization production, completing the adjustment of liquid preparation according to production requirements, pumping into a polymerization kettle, adding the emulsion type initiation system accounting for 0.3-0.5% of the mass of the emulsion system to obtain the polymerization system; introducing nitrogen into the polymerization system to drive oxygen, and adding a conventional initiator system for polymerization; curing for 1-2 hours after polymerization, starting the post-treatment processes of granulation, drying and grinding, weighing and packaging to finish production. After the emulsion type initiation system is adopted, the content of AM residual monomer in the product is obviously reduced from 0.1-0.2% to 0.01-0.05%, the product quality is improved on the original production period, and the production cost is reduced.

Description

Method for reducing residual monomer of polyacrylamide dry powder
Technical Field
The invention belongs to the technical field of production of polyacrylamide and derivatives, and particularly relates to a method for reducing residual monomers of polyacrylamide dry powder.
Background
The polyacrylamide flocculant is a water-soluble high-molecular polymer, is insoluble in most organic solvents, has good flocculation property, can reduce the friction resistance between liquids, and can be divided into four types of nonionic, anionic, cationic and amphoteric according to the ionic characteristics. The polyacrylamide flocculant is widely applied to thickening, colloid stabilization, drag reduction, adhesion, film formation, biomedical materials and other aspects. The water treatment is used as coagulant aid, flocculant and sludge dewatering agent, and the petroleum drilling and production is used as dewatering agent and oil-displacing agent; used as retention aid and strengthening agent in the paper making process.
Many researches show that acrylamide has obvious toxic and side effects, and the main symptoms and signs are skin desquamation erythema, numbness of limbs, hyperhidrosis of hands and feet, weight loss, distal hypoalgesia, deep reflex hypofunction and other symptoms of impaired nerve functions; experimental animals such as cats, rats, mice, guinea pigs, rabbits, and monkeys, when exposed to AM, show ataxia, splayed hind limb feet, and skeletal muscle weakness, which ultimately leads to dyskinesia. With the continuous improvement of the environmental protection requirement, the requirement on the content of residual monomer acrylamide (AM for short) in the polyacrylamide polymer is higher and higher. The limit value of the residual amount of acrylamide in polyacrylamide industrial products is generally regulated to be 0.5-0.05% by various national health departments, the residual amount of acrylamide is generally allowed to be below 0.2% when the polyacrylamide is used for the purification treatment of industrial and urban sewage, and the residual amount of acrylamide is required to be below 0.05% when the polyacrylamide is used for the direct drinking water treatment.
Generally, the residual AM monomer concentration in industrial production of polyacrylamide is below 0.1%, especially in non-ionic and cationic production, because the polymerization speed is high and the time is short, the residual monomer concentration content sometimes even exceeds 0.1%, and in order to better meet the requirements of production and environmental protection, the residual monomer content in the production of polyacrylamide and derivatives is urgently needed to be reduced.
The traditional method for reducing the residual monomer content of polyacrylamide and derivatives comprises the following steps: firstly, the molecular weight and viscosity of the product can be reduced by increasing the amount of the initiator and the amount of the initiator, and the residual monomer content can be increased rather than 0.1 percent above the content specified in the national standard (GB/T31246-. And secondly, the curing and heat-preserving time is prolonged, so that the production period is increased, the unit yield is reduced, the production cost is increased, and crosslinking possibly occurs to influence the solubility and the quality of the product, thereby causing greater cost loss.
Disclosure of Invention
The invention aims to provide a method for reducing residual monomers of polyacrylamide dry powder.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for reducing residual monomers of polyacrylamide dry powder comprises the following steps:
1) preparing an emulsion type initiation system, wherein the components in percentage by mass are A, B and C, and the mass percentage is 30-70%: 0.3-0.5 percent to 29.5-69.7 percent, wherein A is one of 110-200 solvent oil, B is one of span 20, span 60 and other emulsifiers, and C is deionized water;
2) adding A, B, C raw materials in a certain order, stirring and emulsifying for 5-10 minutes by an emulsifying machine, adding an initiator E, re-emulsifying for 5-10 minutes to obtain an emulsion type initiating system, and standing for later use;
3) in the polymerization production, the liquid preparation adjustment process is completed according to the production requirements, the mixture is pumped into a polymerization kettle, and an emulsion type initiation system accounting for 0.3-0.5 percent of the mass of the emulsification system is added to obtain a polymerization system;
4) introducing nitrogen into the polymerization system to drive oxygen, and adding a conventional initiator system for polymerization;
5) curing for 1-2 hours after polymerization, starting the post-treatment processes of granulation, drying and grinding, weighing and packaging to finish production.
Further, the adding sequence of the raw materials in the step 2) is that B is added firstly, then A is added, and finally C is added.
Further, the initiator E in the step 2) is an azo initiator, the addition amount of the initiator E is 0.3-1% of the mass of the emulsifying system, and specifically is one or more of Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (ABVN) and dimethyl Azobisisobutyrate (AIBME).
Further, the adding amount and the step of the conventional initiator system in the step 4) adopt the conventional amount of the existing polymerization system.
Furthermore, the processes of granulation, drying and grinding in the step 5) all adopt the existing polymerization process parameters.
Generally, in aqueous solution polymerization of polyacrylamide and derivatives, azo initiators are used in a relatively large amount, but the amount of water-soluble azo initiators added is not so large that the molecular weight of the product is reduced, but the amount added is so small that the initiator is consumed up to a high temperature and the content of residual monomer AM in the polymer cannot be effectively reduced. The oil-soluble azo initiator is insoluble in water, is easy to delaminate and float on the surface layer of a polymerization system in the process of introducing nitrogen and removing oxygen in production, has low dissolution of the system, cannot be uniformly distributed in the system, and cannot really realize the effect of reducing residual monomers.
The implementation principle of the invention is as follows: the oil-soluble azo initiator is prepared into an oil-in-water emulsion type initiating system in an emulsifying mode, the initiating system is uniformly dispersed in a polymerization reaction liquid system, the temperature of the system rises after the polymerization reaction liquid system reacts in cooperation with other initiators in the polymerization process, the demulsification of the emulsifying system is initiated, the oil-soluble azo initiator starts to release free radicals to continue to initiate the polymerization reaction, and finally the uniform and stable polymerization of the reaction liquid system is realized, and the purpose of reducing the residual monomer content of the polyacrylamide dry powder product is realized.
The invention has the following beneficial effects: after the emulsion type initiation system is adopted, the content of AM residual monomer in the product is obviously reduced from 0.1-0.2% to 0.01-0.05%, the product quality is improved on the original production period, and the production cost is reduced.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the scope of the present invention is not limited to these examples. All changes, modifications and equivalents that do not depart from the spirit of the invention are intended to be included within the scope thereof.
Example 1: taking 200.03kg of span and 3kg of No. 110 solvent oil, fully dissolving, adding 6.97kg of deionized water, stirring for 10 minutes by using a high-speed stirring motor, then adding 1kg of azodiisobutyronitrile, stirring for 5 minutes to obtain an emulsion type initiating system, completing the batching in the production process, cooling the reaction liquid to 4.5 ℃, then transferring the reaction liquid into a polymerization reactor, adding the emulsion type initiating system accounting for 0.3 percent of the mass of the emulsion system, polymerizing, granulating, drying, grinding, packaging, analyzing and inspecting according to the conventional polyacrylamide production process. The product analysis results are shown in Table 1.
Example 2: 600.05kg of span and 7kg of No. 200 solvent oil are taken and fully dissolved, 2.95kg of deionized water is added, the mixture is stirred for 8 minutes by a high-speed stirring motor, then 1kg of dimethyl azodiisobutyrate is added, the mixture is stirred for 10 minutes to obtain an emulsion type initiation system, the batching is completed in the production process, the reaction liquid is moved into a polymerization reactor after being cooled to 4.5 ℃, the emulsion type initiation system accounting for 0.4 percent of the mass of the emulsion system is added, and then the polymerization, the granulation, the drying and grinding, the packaging, the analysis and the inspection are carried out according to the conventional polyacrylamide production process. The product analysis results are shown in Table 1.
Example 3: 600.04kg of span and 5.5kg of No. 150 solvent oil are taken, fully dissolved, 4.46kg of deionized water is added, stirred for 5 minutes by a high-speed stirring motor, then 1kg of azobisisoheptonitrile is added, stirred for 7 minutes to obtain an emulsion type initiation system, the batching is completed in the production process, the reaction liquid is moved into a polymerization reactor after being cooled to 4.5 ℃, the emulsion type initiation system accounting for 0.5 percent of the mass of the emulsion system is added, and then the polymerization, granulation, drying, grinding, packaging, analysis and inspection are carried out according to the conventional polyacrylamide production process. The product analysis results are shown in Table 1.
Example 4: taking 200.03kg of span and 3kg of No. 180 solvent oil, fully dissolving, adding 5.96kg of deionized water, stirring for 10 minutes by using a high-speed stirring motor, then adding 1kg of a mixture of azobisisobutyronitrile and azobisisoheptonitrile, stirring for 8 minutes to obtain an emulsion type initiation system, completing the batching in the production process, cooling the reaction liquid to 4.5 ℃, then transferring into a polymerization reactor, adding the emulsion type initiation system accounting for 0.5 percent of the mass of the emulsion system, polymerizing, granulating, drying, grinding, packaging, analyzing and inspecting according to the conventional polyacrylamide production process. The product analysis results are shown in Table 1.
Comparative example 1: the production of cationic polyacrylamide products is carried out according to the same proportion, the reaction liquid is moved into a polymerization reactor after being cooled to 4.5 ℃, and then the polymerization, granulation, drying, grinding, packaging, analysis and inspection are carried out according to the conventional polyacrylamide production process.
Comparative example 2: the production of cationic polyacrylamide products is carried out according to the same proportion, the reaction liquid is moved into a polymerization reactor after being cooled to 4.5 ℃, and then the polymerization, granulation, drying, grinding, packaging, analysis and inspection are carried out according to the conventional polyacrylamide production process.
TABLE 1 analysis results of product indices of examples 1, 2, 3 and 4 and comparative examples 1 and 2
Figure BDA0003380865050000031
Figure BDA0003380865050000041
From the comparative data, the content of the residual monomer AM in the polyacrylamide product is obviously reduced, and the residual monomer content reaches below 0.1 percent of the national standard of cationic polyacrylamide.
The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the scope of the present invention, which is similar or similar to the technical solutions of the present invention.
The techniques, shapes, and configurations not described in detail in the present invention are all known techniques.

Claims (5)

1. A method for reducing residual monomers of polyacrylamide dry powder is characterized by comprising the following steps:
1) preparing an emulsion type initiation system, wherein the components in percentage by mass are A, B and C, and the mass percentage is 30-70%: 0.3-0.5 percent to 29.5-69.7 percent, wherein A is one of 110-200 solvent oil, B is one of span 20, span 60 and other emulsifiers, and C is deionized water;
2) adding A, B, C raw materials in a certain order, stirring and emulsifying for 5-10 minutes by an emulsifying machine, adding an initiator E, re-emulsifying for 5-10 minutes to obtain an emulsion type initiating system, and standing for later use;
3) in the polymerization production, the liquid preparation adjustment process is completed according to the production requirements, the mixture is pumped into a polymerization kettle, and an emulsion type initiation system accounting for 0.3-0.5 percent of the mass of the emulsification system is added to obtain a polymerization system;
4) introducing nitrogen into the polymerization system to drive oxygen, and adding a conventional initiator system for polymerization;
5) curing for 1-2 hours after polymerization, starting the post-treatment processes of granulation, drying and grinding, weighing and packaging to finish production.
2. The method for reducing residual monomers in polyacrylamide dry powder according to claim 1, wherein the raw materials in step 2) are added in the order of adding B, then adding A, and finally adding C.
3. The method for reducing the residual monomer content of the polyacrylamide dry powder as claimed in claim 1, wherein the initiator E in the step 2) is an azo initiator, and the addition amount of the initiator E is 0.3-1% by mass of the emulsifying system, and specifically is one or more of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
4. The method for reducing residual monomers in polyacrylamide dry powder according to claim 1, wherein the conventional initiator system is added in an amount and the conventional polymerization system is used in an amount conventional for the conventional polymerization system in the step 4).
5. The method for reducing residual monomers in polyacrylamide dry powder according to claim 1, wherein the processes of granulation, drying and grinding in step 5) all adopt the existing polymerization process parameters.
CN202111432729.2A 2021-11-29 2021-11-29 Method for reducing residual monomer of polyacrylamide dry powder Pending CN113956381A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4739008A (en) * 1986-11-18 1988-04-19 Exxon Chemical Patents Inc. Bi-phase initiator system for water-in-oil emulsion polymers
CN101186672A (en) * 2006-11-15 2008-05-28 南京理工大学 Water solution polymerization preparation method for dimethyl diallyl ammonium chloride and acrylamide copolymers
CN103864986A (en) * 2012-12-07 2014-06-18 中国石油化工股份有限公司 Acrylamide polymer, its preparation method and its application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4739008A (en) * 1986-11-18 1988-04-19 Exxon Chemical Patents Inc. Bi-phase initiator system for water-in-oil emulsion polymers
CN101186672A (en) * 2006-11-15 2008-05-28 南京理工大学 Water solution polymerization preparation method for dimethyl diallyl ammonium chloride and acrylamide copolymers
CN103864986A (en) * 2012-12-07 2014-06-18 中国石油化工股份有限公司 Acrylamide polymer, its preparation method and its application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
地木拉提等: "丙烯酰胺反相乳液聚合的研究", 《新疆石油学院学报》 *
崔传生等主编: "《精细化工工艺学实验教程》", 31 July 2008, 中国海洋大学出版社 *
林浩等: "丙烯酰胺系反相乳液聚合研究进展", 《新疆石油学院学报》 *
赵国玺等著: "《表面活性剂作用原理》", 31 January 2003, 中国轻工业出版社 *

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