CN116554375A - Nuclear-grade polyacrylic acid and preparation method and application thereof - Google Patents
Nuclear-grade polyacrylic acid and preparation method and application thereof Download PDFInfo
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- CN116554375A CN116554375A CN202310417071.0A CN202310417071A CN116554375A CN 116554375 A CN116554375 A CN 116554375A CN 202310417071 A CN202310417071 A CN 202310417071A CN 116554375 A CN116554375 A CN 116554375A
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- polyacrylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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 application discloses nuclear polyacrylic acid and a preparation method and application thereof. A core-grade polyacrylic acid, the molecular weight of the core-grade polyacrylic acid is 10 ten thousand to 20 ten thousand, and the sulfur content in the core-grade polyacrylic acid is 500ppb to 1000ppb. The nuclear polyacrylic acid has controllable molecular weight, good polydispersity, excellent scale inhibition performance, excellent decomposition half-life, controllable molecular weight of 10-20 ten thousand and polydispersity of 1.0-3.5; the preparation method has the advantages of short period and simple operation flow; the preparation equipment is simple, the preparation efficiency is high, the volume of the synthesis reaction kettle used for preparation can be adjusted according to the yield, and the preparation efficiency is greatly improved; the invention has the advantages of lower preparation cost, green, clean and no pollution. The raw materials are cheap and easy to obtain in the preparation process, the related reaction kettle only needs to consume a small amount of electric energy, and the sulfur-free initiator is added, so that the related solvents of alcohols and ethers have small environmental pollution.
Description
Technical Field
The application relates to nuclear polyacrylic acid and a preparation method and application thereof, and belongs to the technical field of scale inhibitor preparation.
Background
The scale inhibitor has chelating, dispersing, lattice distortion and other functions on scale matters, and can inhibit scale formation effectively, so that the scale inhibitor is widely applied to the fields of sea water desalination, water circulation systems and the like. Currently, scale inhibitors of the type represented by natural polymer scale inhibitors, inorganic phosphate scale inhibitors, organic phosphonate scale inhibitors and environment-friendly scale inhibitors are widely popularized and applied in actual industrial production. Among the above scale inhibitors, the natural polymer scale inhibitor and the environment-friendly scale inhibitor become ideal scale inhibitor materials because of relatively small pollution to the environment under the current deepening of the environment-friendly concept.
Among the environmentally friendly scale inhibitor materials, polyaspartic Acid (PASP), polyepoxysuccinic acid (PESA), and Acrylic Acid (AA) and derivatives thereof have become hot spots of research in recent years. Wherein, when the concentration of PASP is 3mg/L, the concentration of PASP is equal to that of Ca 2+ The scale inhibition rate of the catalyst reaches 80%; the scale inhibition rate of calcium carbonate when the concentration of PESP of hyperbranched structure is 15mg/LUp to 90%; the inhibition rate of calcium carbonate is 80% at the concentration of AA of 8 mg/L. The polyacrylic acid polymerized by taking AA as a monomer has regular molecular chains and economic and efficient characteristics, and is widely focused in the application field of industrial circulating cooling water systems. In particular, many components in a secondary loop system of a pressurized water reactor nuclear power station, such as a condenser, a feedwater heater, a steam-water separation reheater and the like, are mainly made of carbon steel, and are easy to corrode in the operation process. Corrosion products from corrosion of carbon steel equipment are transported with the feedwater and subsequently deposited in the steam generator, which can lead to a number of serious, detrimental consequences such as heat energy loss, corrosion of heat transfer tubes, thermal hydraulic instability, reduced power output, and the like. Thus, controlling the deposition of corrosion products is a critical issue in ensuring the performance and integrity of the steam generator. In order to alleviate the scaling phenomenon of the steam generator caused by the deposition of corrosion products, various strategies have been adopted in nuclear power plants at home and abroad, wherein polyacrylic acid dispersing agents have been tested under the conditions of shutdown and startup of twenty or more pressurized water reactor units in multiple countries such as the United states, and the like, and have obvious descaling effects.
Currently, among the polyacrylic acid materials that have been reported in China, there are mainly two main categories:
(1) Polyacrylic acid is used as a matrix to carry out relevant improvement and application expansion on the synthesis process. The method for preparing polyacrylic acid, as described in patent CN1324057C, uses the recovered heat medium to purify polyacrylic acid from acrylic acid aqueous solution or acrylic acid, and the method effectively uses and recovers latent heat, thus providing a new idea for low-carbon production; as described in patent CN102858815B, a polyacrylic acid (salt) -based water-absorbent resin, and a method for producing the same, as well as a method for identifying and tracking a water-absorbent resin, which can trace various problems occurring in a production process, a consumer use process, and a disposal process by checking the tracer; further, as described in patent CN104212105B, the method for producing the polyacrylic acid (salt) -based water-absorbent resin powder and the polyacrylic acid (salt) -based water-absorbent resin powder provide a resin powder having both liquid permeability and water absorption rate, and have good application prospects; the method for preparing the polyacrylic acid or the copolymer thereof and the polyacrylate or the copolymer salt thereof, which are described in the patent CN101921359B, utilizes carbon-carbon unsaturated bonds and inorganic ingredients as raw materials to prepare the organic polymer, has the characteristics of low energy consumption, high equipment utilization rate, excellent product performance, safety and environmental protection, and has good application prospect in the aspects of dispersing agents, scale inhibitors, thickening agents and flocculating agents.
(2) And (3) carrying out surface modification on polyacrylic acid to prepare a composite material and related applications. The thermal interface material has excellent heat conducting performance, can be tightly attached to the surfaces of various heat dissipation elements, and has attractive application prospects in the heat dissipation and conduction fields of a CPU and a relay. The preparation method of the polypyrrole/polyacrylic acid composite gel electrolyte is also described in patent CN101714460B, and the composite material has higher stability and higher conductivity and has good application prospect in the fields of dye-sensitized solar cells, lithium ion batteries, supercapacitors and the like; the wet polyurethane grafted polyacrylic acid copolymer resin for embossed leather as described in patent CN101440151B and the preparation method thereof, the synthetic leather prepared by the invention is easy to be embossed, and has clear, full and strong stereoscopic impression. The MWCNTs@polyacrylic acid@MOF-5 composite material and the preparation method thereof are also described in patent CN104689801B, and the synthesized composite material has the characteristics of high specific surface area, good adsorption performance and the like, and has good application prospect on cigarette filters.
Meanwhile, the problems of longer preparation period, low yield, complex preparation process, severe preparation conditions, sulfur-containing initiator and the like exist in the traditional polyacrylic acid synthesis method inevitably. However, in an actual secondary water environment of a nuclear power station, the content of elements such as sulfur is strictly controlled. At present, related reports of the preparation of sulfur-free or low-sulfur polyacrylic acid and the application of the sulfur-free or low-sulfur polyacrylic acid in the nuclear power field are almost absent in China. In addition, the molecular weight of polyacrylic acid has a remarkable influence on the scale inhibition effect, and related reports about the influence of polyacrylic acid with different molecular weight grades on the scale inhibition performance are fewer. In particular, the preparation of low-sulfur high-molecular-weight polyacrylic acid scale inhibitor and the application thereof in the secondary loop of a nuclear power plant are more recently reported.
Disclosure of Invention
According to one aspect of the present application, a core grade polyacrylic acid is provided.
The nuclear polyacrylic acid has controllable molecular weight, good polydispersity, excellent scale inhibition performance and excellent decomposition half-life, has potential for industrial production, and has potential application and development value in the field of secondary loop corrosion and scale inhibition of nuclear power plants.
A core-grade polyacrylic acid, the molecular weight of the core-grade polyacrylic acid is 10 ten thousand to 20 ten thousand, and the sulfur content in the core-grade polyacrylic acid is 500ppb to 1000ppb.
Alternatively, the molecular weight of the core-grade polyacrylic acid is independently selected from any of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or a range of values between any two.
Alternatively, the sulfur content in the core-grade polyacrylic acid is independently selected from any value of 500ppb, 600ppb, 700ppb, 800ppb, 900ppb, 1000ppb, or a range value between any two.
Optionally, the molecular weight of the nuclear-grade polyacrylic acid is 12 ten thousand to 20 ten thousand.
Optionally, the core-grade polyacrylic acid has a polydispersity of 1.0 to 3.5.
Alternatively, the polydispersity of the core-grade polyacrylic acid is independently selected from any value or range between any two values of 1.00, 1.50, 2.00, 2.10, 2.20, 2.30, 2.40, 2.48, 2.50, 2.60, 2.70, 2.80, 2.90, 3.00, 3.10, 3.20, 3.27, 3.30, 3.31, 3.40, 3.43, 3.50.
According to yet another aspect of the present application, a method of preparing a nuclear grade polyacrylic acid is provided.
The preparation period is shorter, the operation flow is simple, the required preparation period is basically controlled within 24 hours, and the operation flow only comprises the steps of weighing materials, dissolving, mixing, heating, preserving heat, reacting, separating out, drying and the like, so that the preparation method is simple and easy to implement; the preparation equipment is simple, the preparation efficiency is high, the required equipment is glassware and a reaction kettle which are commonly used in a laboratory, and the volume of the synthesis reaction kettle used for preparation can be adjusted according to the yield, so that the preparation efficiency is greatly improved; the preparation cost is lower, the method is green, clean and pollution-free, the raw materials are cheap and easy to obtain in the preparation process, the related reaction kettle only needs to consume a small amount of electric energy, and the sulfur-free initiator is added, so that the related solvents of alcohols and ethers have less pollution to the environment.
The preparation method of the nuclear-grade polyacrylic acid comprises the following steps:
and mixing and reacting a mixture containing acrylic acid monomers, an initiator and an organic solvent to obtain the nuclear polyacrylic acid.
Optionally, the initiator is at least one selected from dicumyl peroxide and hydrogen peroxide.
Optionally, the organic solvent is at least one selected from ethylene glycol and isopropanol.
Optionally, the mass ratio of the organic solvent, the acrylic acid monomer and the initiator is 100-600: 100:1.
alternatively, the mass ratio of the organic solvent, the acrylic monomer, the initiator is independently selected from 100:100: 1. 200:100: 1. 300:100: 1. 350:100: 1. 400:100: 1. 450:100: 1. 500:100: 1. 550). 100:1. 600:100:1 or a range value between any two.
Optionally, the mixing time before the reaction is 0.5h to 2.5h.
Alternatively, the reaction conditions are as follows:
the temperature is 60-100 ℃;
the time is 4-10 hours.
Alternatively, the temperature is independently selected from any value or range of values between any two of 60 ℃, 65 ℃, 70 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 100 ℃.
Alternatively, the time is independently selected from any value or range of values between any two of 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h.
Alternatively, the reaction is carried out under an inert gas.
Optionally, after the reaction, the product is mixed with ethylene glycol methyl ether.
Optionally, the mass ratio of the product to the ethylene glycol methyl ether is 1:3 to 5.
According to a third aspect of the present application there is provided the use of a nuclear grade polyacrylic acid as a scale inhibitor.
The scale inhibitor prepared from the nuclear-grade polyacrylic acid has excellent scale inhibition performance and excellent decomposition half-life.
A nuclear polyacrylic acid scale inhibitor is obtained by mashing nuclear polyacrylic acid; the above-mentioned nuclear-grade polyacrylic acid is selected from the above-mentioned nuclear-grade polyacrylic acid and/or the nuclear-grade polyacrylic acid obtained by the above-mentioned preparation method.
The beneficial effects that this application can produce include:
1) The nuclear-grade polyacrylic acid provided by the application has the advantages of controllable molecular weight, good polydispersity, excellent scale inhibition performance, excellent decomposition half-life, controllable molecular weight of 10 ten thousand to 20 ten thousand and polydispersity of 1.0 to 3.5.
2) The preparation period is short, and the operation flow is simple. The required preparation period is basically controlled within 24 hours, and the operation flow only comprises the steps of weighing, dissolving, mixing, heating, preserving heat, reacting, separating out, drying and the like, so that the preparation method is simple and easy to implement; the preparation equipment is simple, and the preparation efficiency is higher. The required equipment is glassware and reaction kettle commonly used in laboratory, and the volume of the synthesis reaction kettle used for preparation can be adjusted according to the yield, so that the preparation efficiency is greatly improved.
3) The invention has the advantages of lower preparation cost, green, clean and no pollution. The raw materials are cheap and easy to obtain in the preparation process, the related reaction kettle only needs to consume a small amount of electric energy, and the sulfur-free initiator is added, so that the related solvents of alcohols and ethers have small environmental pollution.
Drawings
FIG. 1 is an infrared spectrum of polyacrylic acid of example 1 of the present invention.
FIG. 2 is a drawing of a polyacrylic acid scanning electron microscope of example 1 of the present invention.
FIG. 3 is a graph showing the scale inhibition performance of the polyacrylic acid of example 1 of the present invention.
FIG. 4 is a graph showing the summary of the molecular weight and dispersity of polyacrylic acid of examples 1 to 5 of the present invention.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analytical method in the examples of the present application is as follows:
spectral analysis was performed using fourier infrared spectroscopy.
And performing electron microscope analysis by using a field emission scanning electron microscope.
And (5) performing scale inhibition performance analysis by using a spectrophotometer.
Example 1
200g of isopropanol, 100g of acrylic acid monomer and 1g of dicumyl peroxide are weighed, slowly added into a reaction kettle and uniformly mixed for 0.5 hour. Under the protection of high-purity argon, the mixture is slowly heated to 65 ℃ and kept at constant temperature for 4 hours. Then, 50g of the resultant product was weighed and poured into 50g of ethylene glycol methyl ether solvent, and polyacrylic acid solid was precipitated. Then, the precipitated polyacrylic acid was dried at 70℃for 4 hours, then taken out and mashed, followed by further drying for 8 hours. Finally, the formed polyacrylic acid solid powder is the nuclear polyacrylic acid scale inhibitor.
FIG. 1 is an infrared spectrum of the polyacrylic acid of example 1, wherein the positions of characteristic peaks in the spectrum correspond to the characteristic peaks of the polyacrylic acid one by one, which indicates that pure polyacrylic acid has been successfully prepared. Fig. 2 is an optical micrograph of this embodiment. FIG. 3 is a graph showing the scale inhibition performance of example 1, wherein the scale inhibition test uses the corrosion product oxide Fe in a conventional two-circuit system of a PWR nuclear power plant 3 O 4 For example, the dispersing effect of polyacrylic acid prepared by the research and development of the patent is examined.
Example 2
300g of isopropanol, 100g of acrylic acid monomer and 1g of dicumyl peroxide are weighed, slowly added into a reaction kettle and uniformly mixed for 1 hour. Under the protection of high-purity argon, the mixture is slowly heated to 75 ℃ and kept at constant temperature for 6 hours. Then, 50g of the resultant product was weighed and poured into 100g of ethylene glycol methyl ether solvent, and polyacrylic acid solid was precipitated. Then, the precipitated polyacrylic acid was dried at 75℃for 5 hours, then taken out and mashed, followed by further drying for 7 hours. Finally, the formed polyacrylic acid solid powder is the nuclear polyacrylic acid scale inhibitor.
Example 3
400g of isopropanol, 100g of acrylic acid monomer and 1g of hydrogen peroxide are weighed, slowly added into a reaction kettle and uniformly mixed for 1.5 hours. Under the protection of high-purity argon, the mixture is slowly heated to 80 ℃ and kept at constant temperature for 8 hours. Then, 50g of the resultant product was weighed and poured into 150g of ethylene glycol methyl ether solvent, and polyacrylic acid solid was precipitated. Then, the precipitated polyacrylic acid was dried at 80℃for 6 hours, and then taken out and mashed, followed by further drying for 6 hours. Finally, the formed polyacrylic acid solid powder is the nuclear polyacrylic acid scale inhibitor.
Example 4
500g of isopropanol, 100g of acrylic acid monomer and 1g of dicumyl peroxide are weighed, slowly added into a reaction kettle and uniformly mixed for 2 hours. Under the protection of high-purity argon, the mixture is slowly heated to 85 ℃ and kept at the constant temperature for 9 hours. Then, 50g of the resultant product was weighed and poured into 200g of a glycol methyl ether solvent, and a polyacrylic acid solid was precipitated. Then, the precipitated polyacrylic acid was dried at 85℃for 7 hours, then taken out and mashed, followed by further drying for 5 hours. Finally, the formed polyacrylic acid solid powder is the nuclear polyacrylic acid scale inhibitor.
Example 5
600g of isopropanol, 100g of acrylic acid monomer and 1g of hydrogen peroxide are weighed, slowly added into a reaction kettle and uniformly mixed for 2.5 hours. Under the protection of high-purity argon, the mixture is slowly heated to 90 ℃ and kept at constant temperature for 10 hours. Then, 50g of the resultant product was weighed and poured into 250g of ethylene glycol methyl ether solvent, and polyacrylic acid solid was precipitated. Then, the precipitated polyacrylic acid was dried at 90℃for 8 hours, then taken out and mashed, followed by further drying for 4 hours. Finally, the formed polyacrylic acid solid powder is the nuclear polyacrylic acid scale inhibitor.
FIG. 4 is a summary of the molecular weights and the dispersities of the polyacrylic acids of examples 1 to 5, and it can be seen from the figure that the molecular weight distribution is 10 to 20 tens of thousands and the polydispersity is 1.0 to 3.5.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (10)
1. The nuclear polyacrylic acid is characterized in that the molecular weight of the nuclear polyacrylic acid is 10 ten thousand to 20 ten thousand, and the sulfur content in the nuclear polyacrylic acid is 500ppb to 1000ppb.
2. The nuclear grade polyacrylic acid of claim 1, wherein the molecular weight of the nuclear grade polyacrylic acid is 12-20 tens of thousands.
3. The core-grade polyacrylic acid of claim 1, wherein the core-grade polyacrylic acid has a polydispersity of 1.0 to 3.5.
4. The preparation method of the nuclear-grade polyacrylic acid is characterized by comprising the following steps of:
and (3) reacting the mixed solution containing the acrylic acid monomer, the initiator and the organic solvent to obtain the nuclear polyacrylic acid.
5. The method according to claim 4, wherein the initiator is at least one selected from the group consisting of hydrogen peroxide and dicumyl peroxide.
6. The method according to claim 4, wherein the organic solvent is at least one selected from the group consisting of ethylene glycol and isopropyl alcohol.
7. The preparation method according to claim 4, wherein the mass ratio of the organic solvent, the acrylic monomer and the initiator is 100-600: 100:1.
8. the process of claim 4, wherein the reaction conditions are as follows:
the temperature is 60-100 ℃;
the time is 4-10 hours.
9. The process according to claim 4, wherein the reaction is carried out under an inert gas.
10. The nuclear polyacrylic acid scale inhibitor is characterized in that the nuclear polyacrylic acid is smashed to obtain the nuclear polyacrylic acid scale inhibitor;
the above-mentioned nuclear polyacrylic acid is selected from the group consisting of the nuclear polyacrylic acid according to any one of claims 1 to 3 and/or the nuclear polyacrylic acid obtained by the production method according to any one of claims 4 to 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210420411.0A CN114671965A (en) | 2022-04-20 | 2022-04-20 | Nuclear-grade polyacrylic acid and preparation method and application thereof |
| CN2022104204110 | 2022-04-20 |
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| CN116554375A true CN116554375A (en) | 2023-08-08 |
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| CN202210420411.0A Withdrawn CN114671965A (en) | 2022-04-20 | 2022-04-20 | Nuclear-grade polyacrylic acid and preparation method and application thereof |
| CN202310417071.0A Pending CN116554375A (en) | 2022-04-20 | 2023-04-18 | Nuclear-grade polyacrylic acid and preparation method and application thereof |
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| CN115124640A (en) * | 2022-07-01 | 2022-09-30 | 济源市清源水处理有限公司 | Method for preparing polyacrylic acid solid |
| CN115448472A (en) * | 2022-08-17 | 2022-12-09 | 中核武汉核电运行技术股份有限公司 | Nuclear-grade polyacrylic acid high-temperature high-pressure optimal online adding process |
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