CN107986462A - A kind of air for air conditioning in textile factories circulation antisludging agent and preparation method thereof - Google Patents
A kind of air for air conditioning in textile factories circulation antisludging agent and preparation method thereof Download PDFInfo
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- CN107986462A CN107986462A CN201711267632.4A CN201711267632A CN107986462A CN 107986462 A CN107986462 A CN 107986462A CN 201711267632 A CN201711267632 A CN 201711267632A CN 107986462 A CN107986462 A CN 107986462A
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- antisludging agent
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- mixed liquor
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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
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of air for air conditioning in textile factories circulation antisludging agent, it by three kinds of itaconic acid, Sodium Allyl Sulfonate, hydroxyethyl methacrylate monomers is raw material that the antisludging agent, which is, by radical solution copolymerization reaction synthesis containing sulfonic group, carboxylic acid group, hydroxyl, ester group terpolymer antisludging agent.The antisludging agent of the present invention solves the problems, such as that antisludging agent scale inhibition efficiency existing in the prior art is low, preparation process is complicated.The invention also discloses a kind of preparation method of air for air conditioning in textile factories circulation antisludging agent.
Description
Technical field
The invention belongs to technical field of water treatment chemical, a kind of air for air conditioning in textile factories circulation antisludging agent, the present invention is also
It is related to the preparation method of above-mentioned antisludging agent.
Background technology
At present, in many industrial productions, recirculated cooling water almost with the overall process of production, plays very important
Effect, good circulation is the premise of enterprise's process units stable operation.At the widely used spray system of textile enterprise
The room air of spinning and weaving workshop is managed, the water of different temperatures is sprayed into droplet and is directly contacted with air by spray chamber, carries out hot and humid area.
Spray chamber is sprayed using two level and evaporates cooling more, using recirculated water, but as the continuous operation of spray air-conditioning system is with timely
Between cumulative function so that recirculated water hardness and basicity under high concentration ratio raise, and cause equipment and pipeline scale so that pipe
Road resistance increase, ultimately results in running efficiency of system decline.Therefore, only will be unable to that incrustation scale will be formed by simple filter method
Chemical substance be adequately filtered out, also need to be aided with some chemical methodes, i.e., using antisludging agent.At present, phosphorous copolymer antisludging agent
Use be limited by very large due to the presence of phosphorus, the organic polymer mitigation and antiscaling technology of without phosphorus formula is just gradually obtaining extensively
General popularization, the good research of non-phosphorus scale inhibitor of development effectiveness have complied with the needs of development.And in the state of the art, add into system
The copolymer of unsaturated carboxylic acid can be carried out certain modification by entering esters of unsaturated carboxylic acids, and can improve the scale inhibition of copolymer
Dispersion performance.
The content of the invention
The object of the present invention is to provide a kind of air for air conditioning in textile factories circulation antisludging agent, solve and exist in the prior art
Antisludging agent scale inhibition efficiency is low, the problem of preparation process is complicated.
Present invention also offers the preparation method of above-mentioned antisludging agent.
The technical solution adopted in the present invention is a kind of air for air conditioning in textile factories circulation antisludging agent, the antisludging agent be by
Three kinds of itaconic acid, Sodium Allyl Sulfonate, hydroxyethyl methacrylate monomers are raw material, are reacted and closed by radical solution copolymerization
Into containing sulfonic group, carboxylic acid group, hydroxyl, ester group terpolymer antisludging agent.
The first of the invention technical solution is further characterized in that,
Terpolymer antisludging agent structural formula is:
Wherein, m, n, y represent mole of itaconic acid in copolymer, Sodium Allyl Sulfonate, hydroxyethyl methacrylate respectively
Quality, m:n:Y=(1.5~4.5):1:(0.4~1.0).
Second of technical solution of the present invention is to prepare a kind of side of air for air conditioning in textile factories circulation antisludging agent
Method, specifically implements according to following steps:
Step 1, following components is weighed respectively by mass percentage:Itaconic acid 2.91%~5.11%, Sodium Allyl Sulfonate
1.26%~1.29%, hydroxyethyl methacrylate 0.45%~0.92%, initiator 0.44%~0.83%, molecular regulation agent
0.51%~0.68%, distilled water 91.69%~93.92%, the sum of said components mass percent is 100%;
Step 2, by the itaconic acid weighed in step 1, Sodium Allyl Sulfonate, hydroxyethyl methacrylate, molecular regulation agent
Mixed with distilled water, carry out magnetic agitation and be heated to certain temperature while solid all dissolvings, magnetic agitation, obtain
Mixed liquor a;
Step 3, initiator step 1 weighed is added dropwise in the mixed liquor a in step 2, and 1.5 are kept the temperature after being added dropwise
~3h, is subsequently cooled to room temperature, then adjusts pH value 5~7 with potassium hydroxide solution, obtains light yellow transparent liquid, that is, mixes
Liquid b;
Step 4, absolute ethyl alcohol is added into the mixed liquor b obtained by step 3 and carries out precipitating, and sediment is subjected to decompression pumping
Filter and be dried in vacuo, obtain antisludging agent.
Second of technical solution of the invention be further characterized in that,
Molecular regulation agent is the tert-butyl alcohol.
Initiator is ammonium persulfate.
Step 2 be step 1 is weighed itaconic acid, Sodium Allyl Sulfonate, hydroxyethyl methacrylate, molecular regulation agent and
Distilled water adds three-necked flask, and three-necked flask is fixed on constant-temperature heating magnetic stirring apparatus, is stirred by magnetic stirring apparatus
Mix and be heated to 75 DEG C~90 DEG C.
Initiator is added dropwise into mixed liquor a using constant pressure funnel in step 3.
The absolute ethyl alcohol that ethanol in step 4 is 95%, its addition are 2~3 times of mixed liquor b cumulative volumes.
The beneficial effects of the invention are as follows:A kind of air for air conditioning in textile factories circulation antisludging agent of the present invention overcomes existing scale inhibition
The problem of agent scale inhibition efficiency is low, preparation process is complicated and environmental pollution is serious, effectively solve textile mills spray air-conditioning system with
And the scale problems of circulating water pipeline, the resistance of ducting is reduced, the service life of equipment is extended, improves running efficiency of system,
The harm to environment is reduced at the same time;Carboxyl in antisludging agent of the present invention has calcium ion stronger sequestering power, increases nothing
The solubility of machine salt, suppresses the formation of calcium carbonate, calcium sulfate scale;Hydroxyl causes crystal structure to be distorted, and reduces crystal and increases
Speed, makes it keep good homogeneously dispersed state;Sulfonic group has stronger hydrophily, makes its tolerance to bivalent cation
Degree improves;Ester group is that unsaturated carboxylic acid analog copolymer is modified, and then improves scale-inhibiting properties.In addition, the scale inhibition of the present invention
Agent is a kind of antisludging agent suitable for high concentration multiple air for air conditioning in textile factories circulation, not only meets the need of water technology
Will, and be economic and environment-friendly type antisludging agent.
Embodiment
With reference to embodiment, the present invention is described in detail.
A kind of air for air conditioning in textile factories circulation antisludging agent of the present invention, the antisludging agent be by itaconic acid, Sodium Allyl Sulfonate,
Three kinds of monomers of hydroxyethyl methacrylate are raw material, contain sulfonic group, carboxylic acid by radical solution copolymerization reaction synthesis
Base, hydroxyl, the terpolymer antisludging agent of ester group;Terpolymer antisludging agent structural formula is:
Wherein, m, n, y represent mole of itaconic acid in copolymer, Sodium Allyl Sulfonate, hydroxyethyl methacrylate respectively
Quality, m:n:Y=(1.5~4.5):1:(0.4~1.0).
The present invention prepares a kind of method of air for air conditioning in textile factories circulation antisludging agent, specifically implements according to following steps:
Step 1, following components is weighed respectively by mass percentage:Itaconic acid 2.91%~5.11%, Sodium Allyl Sulfonate
1.26%~1.29%, hydroxyethyl methacrylate 0.45%~0.92%, ammonium persulfate 0.44%~0.83%, the tert-butyl alcohol
0.51%~0.68%, distilled water 91.69%~93.92%, the sum of said components mass percent is 100%;
Step 2, by the itaconic acid weighed in step 1, Sodium Allyl Sulfonate, hydroxyethyl methacrylate, the tert-butyl alcohol and steaming
Distilled water is added in three-necked flask, and three-necked flask is fixed on constant-temperature heating magnetic stirring apparatus, is stirred by magnetic stirring apparatus
Mix until solid all dissolves and is heated to 75 DEG C~90 DEG C, obtain mixed liquor a;
Step 3, the ammonium persulfate that step 1 weighs is added dropwise in the mixed liquor a in step 2 with constant pressure funnel, treated
1.5~3h is kept the temperature after being added dropwise, is subsequently cooled to room temperature, then pH value 5~7 is adjusted with potassium hydroxide solution, is obtained yellowish
Color transparency liquid, i.e. mixed liquor b;
Step 4, the absolute ethyl alcohol that 95% is added into the mixed liquor b obtained by step 3 carries out precipitating, and sediment is carried out
Decompression is filtered and is dried in vacuo, and obtains antisludging agent, wherein, 95% absolute ethyl alcohol addition is the 2~3 of mixed liquor b cumulative volumes
Times.
The reaction equation of antisludging agent composition principle of the present invention is as follows:
Carboxyl in a kind of air for air conditioning in textile factories circulation antisludging agent of the present invention has stronger chelating energy to calcium ion
Power, increases the solubility of inorganic salts, suppresses the formation of calcium carbonate, calcium sulfate scale;Hydroxyl causes crystal structure to be distorted, and reduces
Crystal rate of rise, makes it keep good homogeneously dispersed state;Sulfonic group has stronger hydrophily, make its to divalence sun from
The tolerance of son improves;Ester group is that unsaturated carboxylic acid analog copolymer is modified, and then improves scale-inhibiting properties.
Embodiment 1:
Step 1, weigh respectively:Itaconic acid (IA) 9.2929g, Sodium Allyl Sulfonate (SAS) 4.12g, hydroxyethyl methacrylate
Ethyl ester (HEMA) 2.97463g, ammonium persulfate 1.4077g, tert-butyl alcohol 1.6385g, distilled water 300g;
Step 2, by the itaconic acid taken in step 1 (IA), Sodium Allyl Sulfonate (SAS), hydroxyethyl methacrylate
(HEMA), the tert-butyl alcohol and distilled water are added in three-necked flask, and three-necked flask is fixed on constant-temperature heating magnetic stirring apparatus, are carried out
90 DEG C are stirred and heated to, until after solid all dissolves, obtains mixed liquor a;
Step 3, by constant pressure funnel in step 2 mixed liquor a be added dropwise ammonium persulfate, wait that insulation is added dropwise
1.5h, postcooling to room temperature, it is 5 to adjust pH value with potassium hydroxide solution, obtains light yellow transparent liquid, i.e. mixed liquor b;
Step 4, into step 3, the mixed liquor b of gained adds 2 times of 95% absolute ethyl alcohol that volume is mixed liquor b volumes
Precipitating is carried out, sediment is subjected to decompression suction filtration and is dried in vacuo, obtains purified product finished product antisludging agent.
Embodiment 2:
Step 1, weigh respectively:Itaconic acid (IA) 13.01g, Sodium Allyl Sulfonate (SAS) 4.12g, hydroxyethyl methacrylate second
Ester (HEMA) 1.48731g, ammonium persulfate 1.7422g, tert-butyl alcohol 1.8614g, distilled water 300g;
Step 2, by the itaconic acid taken in step 1 (IA), Sodium Allyl Sulfonate (SAS), hydroxyethyl methacrylate
(HEMA), the tert-butyl alcohol and distilled water are added in three-necked flask, and three-necked flask is fixed on constant-temperature heating magnetic stirring apparatus, are carried out
Stirring obtains mixed liquor a until solid all dissolves and is heated to 85 DEG C;
Step 3, by constant pressure funnel in step 2 mixed liquor a be added dropwise ammonium persulfate, wait that insulation is added dropwise
3h, postcooling to room temperature, it is 5 to adjust pH value with potassium hydroxide solution, obtains light yellow transparent liquid, i.e. mixed liquor b;
Step 4, into step 3, the mixed liquor b of gained adds 2 times of 95% absolute ethyl alcohol that volume is mixed liquor b volumes
Precipitating is carried out, sediment is subjected to decompression suction filtration and is dried in vacuo, obtains purified product finished product antisludging agent.
Embodiment 3:
Step 1, weigh respectively:Itaconic acid (IA) 13.01g, Sodium Allyl Sulfonate (SAS) 4.12g, hydroxyethyl methacrylate second
Ester (HEMA) 2.97463g, ammonium persulfate 2.7099g, tert-butyl alcohol 2.0102g, distilled water 300g;
Step 2, by the itaconic acid taken in step 1 (IA), Sodium Allyl Sulfonate (SAS), hydroxyethyl methacrylate
(HEMA), the tert-butyl alcohol and distilled water are added in three-necked flask, and three-necked flask is fixed on constant-temperature heating magnetic stirring apparatus, is stirred
Mix until solid all dissolves and is heated to 75 DEG C, obtain mixed liquor a;
Step 3, by constant pressure funnel in step 2 mixed liquor a be added dropwise ammonium persulfate, wait that insulation is added dropwise
2h, postcooling to room temperature, it is 5 to adjust pH value with potassium hydroxide solution, obtains light yellow transparent liquid, i.e. mixed liquor b;
Step 4, into step 3, the mixed liquor b of gained adds 2 times of 95% absolute ethyl alcohol that volume is mixed liquor b volumes
Precipitating is carried out, sediment is subjected to decompression suction filtration and is dried in vacuo, obtains purified product finished product antisludging agent.
Embodiment 4:
Step 1, weigh respectively:Itaconic acid (IA) 16.7271g, Sodium Allyl Sulfonate (SAS) 4.12g, hydroxyethyl methacrylate
Ethyl ester (HEMA) 1.48731g, ammonium persulfate 2.6201g, tert-butyl alcohol 2.2332g, distilled water 300g;
Step 2, by the itaconic acid taken in step 1 (IA), Sodium Allyl Sulfonate (SAS), hydroxyethyl methacrylate
(HEMA), the tert-butyl alcohol and distilled water are added in three-necked flask, and three-necked flask is fixed on constant-temperature heating magnetic stirring apparatus, is stirred
Mix until solid all dissolves and is heated to 90 DEG C, obtain mixed liquor a;
Step 3, by constant pressure funnel in step 2 mixed liquor a be added dropwise ammonium persulfate, wait that insulation is added dropwise
2h, is cooled to room temperature after the completion of reaction, and it is 5 to adjust pH value with potassium hydroxide solution, obtains light yellow transparent liquid, i.e. mixed liquor
b;
Step 4, into step 3, the mixed liquor b of gained adds 2 times of 95% absolute ethyl alcohol that volume is mixed liquor b volumes
Precipitating is carried out, sediment is subjected to decompression suction filtration and is dried in vacuo, obtains purified product finished product antisludging agent.
Embodiment 5:
Step 1, weigh respectively:Itaconic acid (IA) 13.01g, Sodium Allyl Sulfonate (SAS) 4.12g, hydroxyethyl methacrylate second
Ester (HEMA) 2.97463g, ammonium persulfate 2.2112g, tert-butyl alcohol 2.0102g, distilled water 300g;
Step 2, by the itaconic acid taken in step 1 (IA), Sodium Allyl Sulfonate (SAS), hydroxyethyl methacrylate
(HEMA), the tert-butyl alcohol and distilled water are added in three-necked flask, and three-necked flask is fixed on constant-temperature heating magnetic stirring apparatus, is stirred
Mix until solid all dissolves and is heated to 90 DEG C, obtain mixed liquor a;
Step 3, by constant pressure funnel in step 2 mixed liquor a be added dropwise ammonium persulfate, wait that insulation is added dropwise
2h, is cooled to room temperature after the completion of reaction, and it is 5 to adjust pH value with potassium hydroxide solution, obtains light yellow transparent liquid, i.e. mixed liquor
b;
Step 4, into step 3, the mixed liquor b of gained adds 2 times of 95% absolute ethyl alcohol that volume is mixed liquor b volumes
Precipitating is carried out, sediment is subjected to decompression suction filtration and is dried in vacuo, obtains purified product finished product antisludging agent.
Textile mills' two season of winter in summer Air Conditioning Cycle water water temperature system is used to the antisludging agent synthesized in embodiment 1-5, is led to
Percarbonic acid doped calcium method tests its scale inhibition effect to calcium carbonate scale and calcium sulfate scale, while tests scale inhibitor poly-asparagic acid and exist
Scale inhibition effect under the same terms is contrasted:
Calcium carbonate scale scale inhibition effect is tested:Calcium ion concentration 240mg/L, bicarbonate ion concentration 732mg/L, experiment temperature
Spend for 25 DEG C, 35 DEG C;
Calcium sulfate scale scale inhibition effect is tested:Calcium ion concentration 6000mg/L, sulfate ion concentration 7000mg/L, experiment temperature
Spend for 25 DEG C, 35 DEG C;
Test result is as shown in table 1, the dosage of antisludging agent of the dosage prepared by different embodiments in table,
Table 1
As it can be seen from table 1 the antisludging agent of the present invention is substantially better than poly- aspartic acid ammonium to the scale inhibition effect of calcium sulfate, implement
Antisludging agent prepared by example 4 and embodiment 5 is substantially better than poly-aspartate to the scale inhibition effect of calcium carbonate, a kind of weaving of the present invention
Factory's air-conditioner circulating water system antisludging agent overcomes that existing antisludging agent scale inhibition efficiency is low, preparation process is complicated and environmental pollution is serious
The problem of.Textile mills' spray air-conditioning system and the scale problems of circulating water pipeline are effectively solved, the resistance of ducting is reduced, extends
The service life of equipment, improves running efficiency of system, while reduces the harm to environment.
Claims (8)
1. a kind of air for air conditioning in textile factories circulation antisludging agent, it is characterised in that the antisludging agent is by itaconic acid, allyl sulphonic acid
Three kinds of sodium, hydroxyethyl methacrylate monomers are raw material, contain sulfonic group, carboxylic by radical solution copolymerization reaction synthesis
Acidic group, hydroxyl, the terpolymer antisludging agent of ester group.
2. a kind of air for air conditioning in textile factories circulation antisludging agent according to claim 1, it is characterised in that the ternary is total to
Polymers antisludging agent structural formula is:
Wherein, m, n, y represent the molal weight of itaconic acid in copolymer, Sodium Allyl Sulfonate, hydroxyethyl methacrylate respectively,
m:n:Y=(1.5~4.5):1:(0.4~1.0).
3. prepare a kind of method of air for air conditioning in textile factories circulation antisludging agent as claimed in claim 1, it is characterised in that tool
Body is implemented according to following steps:
Step 1, following components is weighed respectively by mass percentage:Itaconic acid 2.91%~5.11%, Sodium Allyl Sulfonate
1.26%~1.29%, hydroxyethyl methacrylate 0.45%~0.92%, initiator 0.44%~0.83%, molecular regulation agent
0.51%~0.68%, distilled water 91.69%~93.92%, the sum of said components mass percent is 100%;
Step 2, by the itaconic acid weighed in step 1, Sodium Allyl Sulfonate, hydroxyethyl methacrylate, molecular regulation agent and steaming
Distilled water mixes, and carries out magnetic agitation and is heated to certain temperature while solid all dissolvings, magnetic agitation, is mixed
Liquid a;
Step 3, initiator step 1 weighed is added dropwise in the mixed liquor a in step 2, after being added dropwise keep the temperature 1.5~
3h, is subsequently cooled to room temperature, then adjusts pH value 5~7 with potassium hydroxide solution, obtains light yellow transparent liquid, i.e. mixed liquor
b;
Step 4, absolute ethyl alcohol is added into the mixed liquor b obtained by step 3 and carries out precipitating, and sediment is subjected to decompression and is filtered simultaneously
Vacuum drying, obtains antisludging agent.
A kind of 4. preparation method of air for air conditioning in textile factories circulation antisludging agent according to claim 3, it is characterised in that
The molecular regulation agent is the tert-butyl alcohol.
A kind of 5. preparation method of air for air conditioning in textile factories circulation antisludging agent according to claim 3, it is characterised in that
The initiator is ammonium persulfate.
A kind of 6. preparation method of air for air conditioning in textile factories circulation antisludging agent according to claim 3, it is characterised in that
The step 2 is itaconic acid, Sodium Allyl Sulfonate, hydroxyethyl methacrylate, molecular regulation agent and the distillation for weighing step 1
Water adds three-necked flask, and three-necked flask is fixed on constant-temperature heating magnetic stirring apparatus, is stirred simultaneously by magnetic stirring apparatus
It is heated to 75 DEG C~90 DEG C.
A kind of 7. preparation method of air for air conditioning in textile factories circulation antisludging agent according to claim 3, it is characterised in that
Initiator is added dropwise into mixed liquor a using constant pressure funnel in the step 3.
A kind of 8. preparation method of air for air conditioning in textile factories circulation antisludging agent according to claim 3, it is characterised in that
The absolute ethyl alcohol that ethanol in the step 4 is 95%, its addition are 2~3 times of the mixed liquor b cumulative volumes.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113045700A (en) * | 2021-03-03 | 2021-06-29 | 东南大学 | Terpolymer and preparation method and application thereof |
CN116041608A (en) * | 2023-02-16 | 2023-05-02 | 天津大学 | Preparation method of scale inhibitor for inhibiting formation of calcium carbonate scale in geothermal well bore in high-temperature geothermal water utilization process |
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CN107010740A (en) * | 2017-06-12 | 2017-08-04 | 西安工程大学 | A kind of sewage disposal antisludging agent and preparation method thereof |
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EP0511850A1 (en) * | 1991-04-30 | 1992-11-04 | Calgon Corporation | Terpolymer of itaconic acid for high PH scale control |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113045700A (en) * | 2021-03-03 | 2021-06-29 | 东南大学 | Terpolymer and preparation method and application thereof |
CN113045700B (en) * | 2021-03-03 | 2022-03-08 | 东南大学 | Terpolymer and preparation method and application thereof |
CN116041608A (en) * | 2023-02-16 | 2023-05-02 | 天津大学 | Preparation method of scale inhibitor for inhibiting formation of calcium carbonate scale in geothermal well bore in high-temperature geothermal water utilization process |
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