CN112978942A - Preparation method of controllable brush-shaped structure environment-friendly scale inhibitor - Google Patents
Preparation method of controllable brush-shaped structure environment-friendly scale inhibitor Download PDFInfo
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- CN112978942A CN112978942A CN201911298561.3A CN201911298561A CN112978942A CN 112978942 A CN112978942 A CN 112978942A CN 201911298561 A CN201911298561 A CN 201911298561A CN 112978942 A CN112978942 A CN 112978942A
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- scale inhibitor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
Abstract
The invention relates to the field of scale inhibitors, in particular to a preparation method of an environment-friendly scale inhibitor with a controllable brush-shaped structure. The scale inhibitor with a brush-shaped structure is prepared by taking polyvinyl alcohol and an alpha, beta-unsaturated carbonyl compound which are environment-friendly materials with multiple functionality as raw materials through a Michael addition reaction. The controllability of the scale inhibition performance is realized by regulating and controlling the types of the polyvinyl alcohol and the branched chain and the feed ratio of the components. The scale inhibitor has excellent dispersion scale inhibition effect and is environment-friendly.
Description
Technical Field
The invention relates to the field of scale inhibitors, in particular to a preparation method of an environment-friendly scale inhibitor with a controllable brush-shaped structure.
Background
Scaling is a difficult problem that plagues the normal operation of systems in industrial cooling water systems, heat exchangers, reverse osmosis membrane surfaces and oil field industries where water usage is extremely high. The scale will reduce the heat transfer efficiency, block the water flow, cause the scale corrosion and other consequences, which will affect the operation of the cooling water system. According to different water quality conditions, inorganic salt scale is often calcium carbonate, calcium sulfate, calcium silicate, magnesium silicate, calcium phosphate and the like, and the scale is compact in crystallization, relatively hard, strong in adhesive force and not easy to wash away. The prior solutions mainly comprise physical methods and chemical methods, wherein the former has certain application value under certain specific conditions, but the scale inhibition performance of the former cannot be compared with that of the latter. As for the chemical method, the softening treatment method aims at eliminating scaling ions in the water solution, has higher cost and is only suitable for places with higher requirements on water quality; the acidification method and the carbonization method may cause corrosion of equipment in an industrial process, thereby complicating the equipment, so that such methods have been rarely used at present. At present, circulating cooling water systems in domestic and foreign production processes mainly adopt scale inhibitors to prevent and treat scaling on heat exchange surfaces, and the measure is convenient, economic and efficient.
Through research in nearly two centuries, the scale inhibitor goes through the development process from inorganic phosphate to organic phosphonate and then to polymer scale inhibitor. While the development of polymeric scale inhibitors has undergone several major changes: (1) according to the development process and the functional groups playing the main role, the polymer scale inhibitor can be divided into natural polymer scale inhibitors, carboxylic acid polymer scale inhibitors, sulfonic acid polymer scale inhibitors, phosphine polymer scale inhibitors and environment-friendly polymer scale inhibitors. With the enhancement of environmental awareness, the environmentally friendly polymer scale inhibitor which is easily biodegradable gradually becomes a hot point of research, and in recent years, the major researches are polyaspartic acid, polyepoxysuccinic acid and derivatives thereof. (2) According to the research on the structure, the polymer can be divided into straight-chain and dendritic macromolecules, and Neofetistou and Demadis and the like research on the treatment of industrial cooling water by polyamide dendrimers and find that the polymer can effectively inhibit SiO from being used for treating industrial cooling water2And scale resulting from the deposition of metal oxides, Naka et al also studied dendrimer pairs of CaCO3The influence of the crystals indicates that the dendrimer converts the calcium carbonate crystals from stable calcite to vaterite and that the size of CaCO increases with increasing branching3The smaller the crystal size of the crystal, the less likely it is to be deposited.
With the continuous enhancement of the environmental protection consciousness of people, the environment-friendly scale inhibitor is more and more favored by people, and more environment-friendly scale inhibitors are gradually applied to actual life and production.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly scale inhibitor with a controllable brush-shaped structure.
In order to realize the purpose of the invention, the technical scheme is as follows:
the invention relates to a controllable brush-shaped structure environment-friendly scale inhibitor, which is characterized in that the scale inhibitor is based on Michael addition reaction, takes environment-friendly materials with multiple functionality, namely polyvinyl alcohol and alpha, beta-unsaturated carbonyl compound as raw materials, and realizes the controllability of scale inhibition performance through the regulation and control of the types of polyvinyl alcohol and branched chains and the feed ratio of components. The method is characterized by comprising the following steps: uniformly mixing polyvinyl alcohol and a catalyst, adding a certain amount of alpha, beta-unsaturated carbonyl compound, uniformly mixing, and then heating to react for a certain time to obtain a product.
The first preferred technical scheme of the invention is as follows: in the steps, the polyvinyl alcohol has the average molecular weight of 16000 g/mol-200000 g/mol and the alcoholysis degree of 85% -89%.
The second preferred technical scheme of the invention is as follows: in the above step, the catalyst is a basic catalyst such as sodium hydroxide, potassium hydroxide, triethylamine, etc.
The third preferred technical scheme of the invention is as follows: in the above steps, the mass percentage of the catalyst is 5% -20%.
The fourth preferred technical scheme of the invention is as follows: in the above step, the α, β -unsaturated carbonyl compound has a functional group such as a carboxyl group, a hydroxyl group, and a sulfonic acid group.
The fifth preferred technical scheme of the invention is as follows: in the above step, the proportion of the α, β -unsaturated carbonyl compound is 5% to 50%.
The sixth preferred technical scheme of the invention is as follows: in the above step, the reaction temperature is 50 ℃ to 80 ℃.
The seventh preferred technical scheme of the invention is as follows: in the above step, the reaction time is 1 to 24 hours.
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with the benefit of the present disclosure with additional guidance to adapt the invention without departing from the scope of the invention as defined by the appended claims.
Detailed Description
Example 1
Dissolving polyvinyl alcohol with the molecular weight of 47000g/mol and the alcoholysis degree of 88% and triethylamine with the molecular weight of 5% in water, then adding 50% of alpha, beta-unsaturated carbonyl compound with carboxyl groups, uniformly mixing, heating to 50 ℃, and reacting for 10 hours to obtain the product. The scale inhibition rate is 88.1 percent by adopting a static scale inhibition method.
Example 2
Dissolving polyvinyl alcohol with the molecular weight of 16000g/mol and the alcoholysis degree of 85% and 10% of sodium hydroxide in water, then adding 5% of alpha, beta-unsaturated carbonyl compound with sulfonic group, uniformly mixing, heating to 65 ℃, and reacting for 5 hours to obtain the product. The scale inhibition rate is 83.6 percent by adopting a static scale inhibition method.
Example 3
Dissolving polyvinyl alcohol with the molecular weight of 168000g/mol and alcoholysis degree of 86% and 15% of potassium hydroxide in water, then adding 40% of alpha, beta-unsaturated carbonyl compound with hydroxyl groups, uniformly mixing, heating to 75 ℃, and reacting for 1h to obtain the product. The scale inhibition rate is 82.9 percent by adopting a static scale inhibition method.
Example 4
Dissolving polyvinyl alcohol with the molecular weight of 145000g/mol and the alcoholysis degree of 89% and 10% triethylamine in water, then adding 10% of alpha, beta-unsaturated carbonyl compound with sulfonic group, uniformly mixing, heating to 60 ℃, and reacting for 15h to obtain the product. The scale inhibition rate is 85.9 percent by adopting a static scale inhibition method.
Example 5
Dissolving polyvinyl alcohol with the molecular weight of 180000g/mol and the alcoholysis degree of 85% and 20% of sodium hydroxide in water, then adding 20% of alpha, beta-unsaturated carbonyl compound with carboxyl groups, uniformly mixing, heating to 80 ℃, and reacting for 24 hours to obtain the product. The scale inhibition rate is 87.6 percent by adopting a static scale inhibition method.
Example 6
Dissolving polyvinyl alcohol with the molecular weight of 200000g/mol and the alcoholysis degree of 86% and triethylamine with the molecular weight of 15% in water, then adding 30% of alpha, beta-unsaturated carbonyl compound with hydroxyl groups, uniformly mixing, heating to 55 ℃, and reacting for 20 hours to obtain the product. The scale inhibition rate is 85.3 percent by adopting a static scale inhibition method.
Example 7
Dissolving polyvinyl alcohol with the molecular weight of 31000g/mol and the alcoholysis degree of 88 percent and 5 percent potassium hydroxide in water, then adding 15 percent of alpha, beta-unsaturated carbonyl compound with sulfonic group, uniformly mixing, heating to 70 ℃, and reacting for 6 hours to obtain the product. The scale inhibition rate is 85.0 percent by adopting a static scale inhibition method.
Example 8
Dissolving polyvinyl alcohol with molecular weight of 67000g/mol and alcoholysis degree of 87% and triethylamine with molecular weight of 20% in water, adding 25% of alpha, beta-unsaturated carbonyl compound with hydroxyl group, mixing uniformly, heating to 80 ℃, and reacting for 22h to obtain the product. The scale inhibition rate is 83.6 percent by adopting a static scale inhibition method.
Claims (9)
1. The controllable brush-shaped structure environment-friendly scale inhibitor is characterized in that the scale inhibitor is based on Michael addition reaction, takes environment-friendly materials with multiple functionality, namely polyvinyl alcohol and alpha, beta-unsaturated carbonyl compounds, as raw materials, and realizes the controllability of scale inhibition performance through the regulation and control of the types of polyvinyl alcohol and branched chains and the feed ratio of components.
2. The controllable brush-shaped structure environment-friendly scale inhibitor as claimed in claim 1, characterized by comprising the following steps: uniformly mixing polyvinyl alcohol and a catalyst, adding a certain amount of alpha, beta-unsaturated carbonyl compound, uniformly mixing, and then heating to react for a certain time to obtain a product.
3. The controllable brush-shaped structure environment-friendly scale inhibitor according to claim 1, wherein the polyvinyl alcohol has an average molecular weight of 16000 g/mol-200000 g/mol and an alcoholysis degree of 85% -89%.
4. The controllable brush-shaped structure environment-friendly scale inhibitor according to claim 1, wherein the catalyst is a basic catalyst such as sodium hydroxide, potassium hydroxide and triethylamine.
5. The controllable brush-shaped structure environment-friendly scale inhibitor as claimed in claim 1, wherein the catalyst is 5-20% by mass.
6. The controllable brush-shaped structure environment-friendly scale inhibitor as claimed in claim 1, wherein the α, β -unsaturated carbonyl compound has carboxyl, hydroxyl, sulfonic acid group and other functional groups.
7. The controllable brush-shaped structure environment-friendly scale inhibitor as claimed in claim 1, wherein the proportion of the α, β -unsaturated carbonyl compound is 5-50%.
8. The controllable brush-shaped structure environment-friendly scale inhibitor as claimed in claim 1, wherein the reaction temperature is 50-80 ℃.
9. The controllable brush-shaped structure environment-friendly scale inhibitor as claimed in claim 1, wherein the reaction time is 1-24 h.
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Citations (8)
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|---|---|---|---|---|
| US5350801A (en) * | 1993-07-07 | 1994-09-27 | Air Products And Chemicals, Inc. | Solid state process for modification of polyvinyl alcohol using Michael-type addition |
| JPH08127622A (en) * | 1994-09-09 | 1996-05-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Modified polyvinyl alcohol |
| JPH1036757A (en) * | 1996-07-23 | 1998-02-10 | Dai Ichi Kogyo Seiyaku Co Ltd | Hydrophilic surface treatment agent for heat exchanger fin |
| JPH1099670A (en) * | 1996-09-26 | 1998-04-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Dispersant for aqueous emulsion |
| US20050081994A1 (en) * | 2003-01-02 | 2005-04-21 | Beckley Ronald S. | Methods of using Michael addition compositions |
| CN102532560A (en) * | 2012-01-06 | 2012-07-04 | 北京工业大学 | Method for preparing cement dispersing agent based on polyvinyl alcohol Michael addition reaction |
| CN107032509A (en) * | 2017-03-14 | 2017-08-11 | 成都云图控股股份有限公司 | A kind of terpolymer concentration slow-release scale inhibitor and preparation method thereof |
| CN109153866A (en) * | 2016-06-03 | 2019-01-04 | 赛鲁斯股份有限公司 | Water imbibition or water-soluble polymer, intermediate compound and its method |
-
2019
- 2019-12-17 CN CN201911298561.3A patent/CN112978942A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5350801A (en) * | 1993-07-07 | 1994-09-27 | Air Products And Chemicals, Inc. | Solid state process for modification of polyvinyl alcohol using Michael-type addition |
| JPH08127622A (en) * | 1994-09-09 | 1996-05-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Modified polyvinyl alcohol |
| JPH1036757A (en) * | 1996-07-23 | 1998-02-10 | Dai Ichi Kogyo Seiyaku Co Ltd | Hydrophilic surface treatment agent for heat exchanger fin |
| JPH1099670A (en) * | 1996-09-26 | 1998-04-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Dispersant for aqueous emulsion |
| US20050081994A1 (en) * | 2003-01-02 | 2005-04-21 | Beckley Ronald S. | Methods of using Michael addition compositions |
| CN102532560A (en) * | 2012-01-06 | 2012-07-04 | 北京工业大学 | Method for preparing cement dispersing agent based on polyvinyl alcohol Michael addition reaction |
| CN109153866A (en) * | 2016-06-03 | 2019-01-04 | 赛鲁斯股份有限公司 | Water imbibition or water-soluble polymer, intermediate compound and its method |
| CN107032509A (en) * | 2017-03-14 | 2017-08-11 | 成都云图控股股份有限公司 | A kind of terpolymer concentration slow-release scale inhibitor and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王国建: "《功能高分子材料 第2版》", 30 June 2014, 同济大学出版社 * |
| 马自俊: "《油田开发水处理技术问答》", 31 October 2003, 中国石化出版社 * |
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