CN114773519A - Water-soluble low-molecular-weight copolymer scale inhibitor and preparation method and application thereof - Google Patents
Water-soluble low-molecular-weight copolymer scale inhibitor and preparation method and application thereof Download PDFInfo
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- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 80
- 229920001577 copolymer Polymers 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 28
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 36
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 18
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 18
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 18
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 30
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 28
- 239000001506 calcium phosphate Substances 0.000 abstract description 16
- 229910000389 calcium phosphate Inorganic materials 0.000 abstract description 16
- 235000011010 calcium phosphates Nutrition 0.000 abstract description 16
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 15
- 239000008367 deionised water Substances 0.000 abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 abstract description 15
- PPRAVOKAIZTTHZ-UHFFFAOYSA-N tert-butyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(C)(C)OC(=O)C=C PPRAVOKAIZTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000498 cooling water Substances 0.000 abstract description 4
- 238000001228 spectrum Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a water-soluble low-molecular-weight copolymer scale inhibitor and a preparation method and application thereof, wherein the water-soluble low-molecular-weight copolymer scale inhibitor is obtained by polymerization reaction by using acrylic acid and tert-butyl acrylate as monomers, and the mass ratio of the acrylic acid to the tert-butyl acrylate is (8-9.5): 0.5 to 2; the preparation method comprises the following steps: heating deionized water to 80-85 ℃, then dropwise adding an acrylic acid-tert-butyl acrylate mixture, an initiator aqueous solution and a reducing agent aqueous solution into the deionized water, carrying out heat preservation reaction for 30-60 min, and cooling to 20-30 ℃ after the reaction is finished, thus obtaining the water-soluble low-molecular-weight copolymer scale inhibitor. The water-soluble low-molecular-weight copolymer scale inhibitor prepared by the invention has good scale inhibition performance on calcium carbonate, calcium sulfate and calcium phosphate, can effectively solve the scaling problem in a circulating cooling water system, and has the advantages of simple preparation method, less monomer residual amount, high conversion rate, low cost, easy popularization and good application prospect.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a water-soluble low-molecular-weight copolymer scale inhibitor, and a preparation method and application thereof.
Background
Water is the source of life, the basis for production and ecology. The method is an irreplaceable foundation support for economic and social development and is an indispensable important condition for modern industrial construction. With the rapid development of economy, the water demand is increasing day by day, and particularly, the water consumption of the industrial industry is obviously increased; especially, in the circulating process of cooling water, salt in water is concentrated due to evaporation, corrosion and scaling of pipelines and heat exchange equipment are easily caused, the heat exchange effect of the equipment is further influenced, and even pipeline leakage and perforation can be caused in serious conditions, so that the industrial production safety is endangered.
In the cooling water treatment technology, adding a water treatment agent is the most common and most economical and effective method at present. The water treatment agents are of various types and can be divided into biocides, corrosion inhibitors, cleaning agents, scale inhibition and dispersion agents, coagulants and flocculants according to the functions. The common scale inhibitor mainly comprises an organic phosphorus scale inhibitor, a polycarboxylic acid scale inhibitor and the like. However, long-term use of the phosphorus-containing scale inhibitor is easy to form water eutrophication, which causes water pollution; in some countries such as Europe and America, Japan, etc., phosphorus inhibition measures have been proposed, such as Germany, which requires that the phosphorus emission is less than or equal to 1 mg/L. Therefore, the application of the phosphorus-free water treatment agent is the development direction of the water treatment industry in future. The carboxylic acid homopolymer scale inhibitor has single performance; for example, the acrylic acid homopolymer has good performance on calcium carbonate resistance and calcium sulfate resistance, but the calcium phosphate resistance is poor, and the application range is limited.
In view of the above, it is needed to develop a green and environment-friendly medicament with small dosage and comprehensive scale inhibition effect.
Disclosure of Invention
The invention provides a water-soluble low-molecular-weight copolymer scale inhibitor and a preparation method and application thereof, aiming at the problems that the phosphorus-containing scale inhibitor pollutes the environment and the acrylic scale inhibitor has poor calcium phosphate resistance and large dosage in the prior art.
The invention is realized by the following technical scheme:
a water-soluble low-molecular-weight copolymer scale inhibitor is prepared by taking acrylic acid and tert-butyl acrylate as monomers and carrying out polymerization reaction, wherein the mass ratio of the acrylic acid to the tert-butyl acrylate is (8-9.5): 0.5 to 2; preferably, the mass ratio of the acrylic acid to the tert-butyl acrylate is 8-8.75: 1.25 to 2.
Further, the viscosity average molecular weight of the water-soluble low molecular weight copolymer scale inhibitor is 3000-4500.
The preparation method of the water-soluble low molecular weight copolymer scale inhibitor takes acrylic acid and tert-butyl acrylate as monomers, and the water-soluble low molecular weight copolymer scale inhibitor is obtained by a method of free radical aqueous solution polymerization reaction under the action of an initiator and a reducing agent.
Further, the preparation method specifically comprises the following steps:
(1) dissolving tert-butyl acrylate in acrylic acid to obtain a monomer solution, dissolving an initiator in water to obtain an initiator aqueous solution, and dissolving a reducing agent in water to obtain a reducing agent aqueous solution;
(2) heating water to 80-85 ℃, adding a monomer solution, an initiator aqueous solution and a reducing agent aqueous solution, carrying out heat preservation reaction for 30-60 min, and cooling after the reaction is finished to obtain a water-soluble low-molecular-weight copolymer scale inhibitor; preferably, the reaction time is 40 min.
Further, the initiator is sodium persulfate, and the mass of the initiator is 1.5-2% of that of the monomer solution; the reducing agent is sodium bisulfite, and the mass of the reducing agent is 9-9.5% of that of the monomer solution.
Further, the mass percentage concentration of the initiator is 10-20 wt%; the mass percentage concentration of the reducing agent is 25-35 wt%.
Further, the monomer solution, the initiator aqueous solution and the reducing agent aqueous solution are added into the reaction container in three drops, the dropping time of the monomer is 50-70 min, the initiator aqueous solution and the reducing agent aqueous solution are dropped in advance 2-3min before the monomer, and after the dropping of the monomer is finished, the initiator aqueous solution and the reducing agent aqueous solution are continuously dropped for 1-3 min.
Furthermore, the mass of the water is 1-1.1 times of that of the monomer solution.
In the invention, the water-soluble low molecular weight copolymer scale inhibitor is applied to water treatment; the water-soluble low-molecular-weight copolymer scale inhibitor is used for scale inhibition of calcium carbonate, calcium sulfate and calcium phosphate, and the adding amount of the water-soluble low-molecular-weight copolymer scale inhibitor is 5-10 mg/L.
Advantageous effects
(1) The water-soluble low-molecular-weight copolymer scale inhibitor disclosed by the invention does not contain any inorganic phosphorus and organic phosphorus compound in the selected raw materials, is excellent in safety and environmental protection performance, and has a wide actual application prospect;
(2) the water-soluble low-molecular-weight copolymer scale inhibitor is an acrylic acid/tert-butyl acrylate copolymer, contains carboxyl and ester groups, has good scale inhibition performance on calcium carbonate, calcium sulfate and calcium phosphate, can effectively solve the scaling problem in a circulating cooling water system, has the advantages of simple preparation method and process, less monomer residual amount, high conversion rate, small addition amount and low use cost, is easy to popularize, can be added according to the required concentration during use, and has good application prospect.
Drawings
FIG. 1 is nuclear magnetic hydrogen spectrum of water-soluble low molecular weight copolymer scale inhibitor prepared in example 1;
FIG. 2 is a carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in example 1;
FIG. 3 is the nuclear magnetic hydrogen spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in example 2;
FIG. 4 is a carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in example 2;
FIG. 5 is the nuclear magnetic hydrogen spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in example 3;
FIG. 6 is a carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in example 3;
FIG. 7 is the nuclear magnetic hydrogen spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in example 4;
FIG. 8 is a carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in example 4;
FIG. 9 is a nuclear magnetic hydrogen spectrum of a copolymer of acrylic acid and tert-butyl acrylate prepared in comparative example 1;
FIG. 10 is a carbon spectrum of a copolymer of acrylic acid and t-butyl acrylate prepared in comparative example 1;
FIG. 11 is a nuclear magnetic hydrogen spectrum of a t-butyl acrylate-acrylic acid copolymer prepared in comparative example 2;
FIG. 12 is a carbon spectrum of a copolymer of acrylic acid and t-butyl acrylate prepared in comparative example 2;
FIG. 13 is a nuclear magnetic hydrogen spectrum of a copolymer of acrylic acid and tert-butyl acrylate prepared in comparative example 3;
FIG. 14 is a carbon spectrum of an acrylic acid-t-butyl acrylate copolymer prepared in comparative example 3.
Detailed Description
The present invention will be described in more detail with reference to examples, which are intended to illustrate only some embodiments of the present invention, but not all embodiments of the present invention. The experimental technical methods and scientific terms used in the examples have the same meanings as commonly understood by a person of ordinary skill in the art without specific descriptions.
Unless otherwise stated, the experimental consumables and reagents related to the invention are generally available in commercial ways without any special remarks.
In the following examples and comparative examples, the calcium carbonate scale inhibition performance of the agent is evaluated by using the calcium carbonate deposition method which is the determination of the scale inhibition performance of a water treatment agent in the national standard GB/T16632-2019; the method for measuring the scale inhibition performance of the calcium sulfate adopts the technical specification of corrosion and scale inhibitor for oilfield water treatment indicated by the trade mark Q/SY 126-; the calcium phosphate scale inhibition performance of the agent is evaluated by adopting the national standard GB/T22626-.
Example 1
(1) Weighing 24.49g of tert-butyl acrylate, dissolving the tert-butyl acrylate in 171.41g of acrylic acid to obtain a monomer solution, dissolving 3.0g of sodium persulfate in water to obtain a sodium persulfate water solution with the mass percentage concentration of 15wt%, and dissolving 18g of sodium bisulfite in water to obtain a sodium bisulfite water solution with the mass percentage concentration of 30 wt%;
(2) weighing 205.0g of deionized water, placing the deionized water in a four-neck flask, heating to 83 ℃, then dropwise adding a monomer solution, a sodium persulfate aqueous solution and a sodium bisulfite aqueous solution into the deionized water through a peristaltic pump, wherein the monomer solution is dropwise added for 60min, the sodium persulfate aqueous solution and the sodium bisulfite aqueous solution are dropwise added for 2min in advance compared with an acrylic acid-tert-butyl acrylate mixture, lagging for 1min, keeping the temperature for reaction for 40min after the dropwise addition is finished, and cooling to 25 ℃ after the reaction is finished to obtain white viscous transparent liquid, namely the water-soluble low-molecular-weight copolymer scale inhibitor, wherein the solid content is 44.70% and the viscosity average molecular weight is 3949.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in the example 1 are shown in figures 1 and 2;
the water-soluble low molecular weight copolymer scale inhibitor prepared in the example 1 is respectively measured according to the adding amount of 5mg/L and 10mg/L in a scale inhibition performance experiment, and when the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 5mg/L, the calcium carbonate scale inhibition rate is 55.27 percent; when the dosage of the water-soluble low molecular weight copolymer scale inhibitor is 10mg/L, the scale inhibition rate of calcium sulfate and calcium phosphate is 99.06 percent and 82.58 percent respectively.
Example 2
(1) Weighing 29.39g of tert-butyl acrylate, dissolving the tert-butyl acrylate in 166.52g of acrylic acid to obtain a monomer solution, dissolving 3.0g of sodium persulfate in water to obtain a sodium persulfate water solution with the mass percentage concentration of 15wt%, and dissolving 18g of sodium bisulfite in water to obtain a sodium bisulfite water solution with the mass percentage concentration of 30 wt%;
(2) weighing 205.0g of deionized water, placing the deionized water in a four-neck flask, heating the flask to 83 ℃, then dropwise adding a monomer solution, a sodium persulfate aqueous solution and a sodium bisulfite aqueous solution into the deionized water by a peristaltic pump, wherein the monomer solution is dropwise added for 60min, the sodium persulfate aqueous solution and the sodium bisulfite aqueous solution are dropwise added for 2min in advance compared with an acrylic acid-tert-butyl acrylate mixture, lagging the solution for 2min, carrying out heat preservation reaction for 45min after the dropwise addition is finished, and cooling the solution to 25 ℃ after the reaction is finished to obtain white viscous transparent liquid, namely the water-soluble low-molecular-weight copolymer scale inhibitor, wherein the solid content is 44.72% and the viscosity average molecular weight is 3411.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in the example 2 are shown in figures 3 and 4;
the water-soluble low molecular weight copolymer scale inhibitor prepared in example 2 was subjected to scale inhibition performance test measurements at 5mg/L and 10mg/L addition levels, respectively. When the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 5mg/L, the calcium carbonate scale inhibition rate is 62.69 percent; when the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 10mg/L, the scale inhibition rate of calcium sulfate and calcium phosphate is 100 percent and 91.76 percent respectively.
Example 3
(1) Weighing 34.28g of tert-butyl acrylate, dissolving the tert-butyl acrylate in 161.62g of acrylic acid to obtain a monomer solution, dissolving 3.0g of sodium persulfate in water to obtain a sodium persulfate water solution with the mass percentage concentration of 15wt%, and dissolving 18g of sodium bisulfite in water to obtain a sodium bisulfite water solution with the mass percentage concentration of 30 wt%;
(2) weighing 205.0g of deionized water, placing the deionized water in a four-neck flask, heating the deionized water to 82 ℃, then dropwise adding a monomer solution, a sodium persulfate aqueous solution and a sodium bisulfite aqueous solution into the deionized water through a peristaltic pump, wherein the monomer solution is dropwise added for 60min, the sodium persulfate aqueous solution and the sodium bisulfite aqueous solution are dropwise added in advance for 3min and lagged for 1min compared with an acrylic acid-tert-butyl acrylate mixture, after the dropwise adding is finished, the temperature is kept for 45min, and after the reaction is finished, the temperature is reduced to 25 ℃ to obtain white viscous transparent liquid, namely the water-soluble low-molecular-weight copolymer scale inhibitor, the solid content is 44.72%, and the viscosity average molecular weight is 3927.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in the example 3 are shown in fig. 5 and 6;
the water-soluble low molecular weight copolymer scale inhibitor prepared in example 3 was subjected to scale inhibition performance test measurements at 5mg/L and 10mg/L addition levels, respectively. When the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 5mg/L, the calcium carbonate scale inhibition rate is 62.26 percent; when the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 10mg/L, the scale inhibition rate of calcium sulfate and calcium phosphate is 97.06% and 86.2% respectively.
Example 4
(1) Weighing 39.18g of tert-butyl acrylate, dissolving the tert-butyl acrylate in 156.72g of acrylic acid to obtain a monomer solution, dissolving 3.0g of sodium persulfate in water to obtain a sodium persulfate water solution with the mass percentage concentration of 15wt%, and dissolving 18g of sodium bisulfite in water to obtain a sodium bisulfite water solution with the mass percentage concentration of 30 wt%;
(2) weighing 205.0g of deionized water, placing the deionized water in a four-neck flask, heating the flask to 84 ℃, then dropwise adding a monomer solution, a sodium persulfate aqueous solution and a sodium bisulfite aqueous solution into the deionized water by a peristaltic pump, wherein the monomer solution is dropwise added for 60min, the sodium persulfate aqueous solution and the sodium bisulfite aqueous solution are dropwise added for 2min in advance compared with an acrylic acid-tert-butyl acrylate mixture, lagging the solution for 3min, after the dropwise adding is finished, carrying out heat preservation reaction for 35min, and after the reaction is finished, cooling the solution to 25 ℃ to obtain white viscous transparent liquid, namely the water-soluble low-molecular-weight copolymer scale inhibitor, wherein the solid content is 44.72%, and the viscosity average molecular weight is 3829.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in the example 4 are shown in figures 7 and 8;
the water-soluble low molecular weight copolymer scale inhibitor prepared in example 4 was subjected to scale inhibition performance test measurements at 5mg/L and 10mg/L addition levels, respectively. When the adding amount of the water-soluble low-molecular-weight copolymer scale inhibitor is 5mg/L, the calcium carbonate scale inhibition rate is 53.14%; when the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 10mg/L, the scale inhibition rates of the calcium sulfate and the calcium phosphate are respectively 100 percent and 86.33 percent.
Comparative example 1
A water-soluble low-molecular-weight copolymer scale inhibitor was prepared as described in example 1, except that in step (1), the mass of t-butyl acrylate was 9.75g and the mass of acrylic acid was 186.11 g.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in the comparative example 1 are shown in FIGS. 9 and 10;
the water-soluble low molecular weight copolymer scale inhibitor prepared in comparative example 1 was subjected to scale inhibition performance test at 5mg/L and 10mg/L, respectively. When the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 5mg/L, the calcium carbonate scale inhibition rate is 58.23 percent; when the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 10mg/L, the scale inhibition rate of calcium sulfate and calcium phosphate is 99.79 percent and 9.93 percent respectively.
Comparative example 2
A water-soluble low-molecular-weight copolymer scale inhibitor was prepared as described in example 1, except that in step (1), the mass of t-butyl acrylate was 14.69g, and the mass of acrylic acid was 181.21 g.
The nuclear magnetic hydrogen spectrogram and the carbon spectrogram of the water-soluble low molecular weight copolymer scale inhibitor prepared in the comparative example 2 are shown in figures 11 and 12;
the water-soluble low molecular weight copolymer scale inhibitor prepared in comparative example 2 was subjected to scale inhibition performance test at 5mg/L and 10mg/L, respectively. When the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 5mg/L, the calcium carbonate scale inhibition rate is 56.46 percent; when the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 10mg/L, the scale inhibition rate of calcium sulfate and calcium phosphate is 100 percent and 10.94 percent respectively.
Comparative example 3
An acrylic acid-t-butyl acrylate copolymer scale inhibitor was prepared as described in example 1, except that in step (1), the mass of t-butyl acrylate was 19.59g and the mass of acrylic acid was 176.31 g.
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the water-soluble low molecular weight copolymer scale inhibitor prepared in the comparative example 3 are shown in FIGS. 13 and 14;
the water-soluble low molecular weight copolymer scale inhibitor prepared in comparative example 3 was subjected to scale inhibition performance test at 5mg/L and 10mg/L, respectively. When the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 5mg/L, the calcium carbonate scale inhibition rate is 59.81 percent; when the adding amount of the water-soluble low molecular weight copolymer scale inhibitor is 10mg/L, the scale inhibition rates of the calcium sulfate and the calcium phosphate are respectively 99.15 percent and 63.97 percent.
As can be seen from the above examples 1-4 and comparative examples 1-3, the water-soluble low molecular weight copolymer scale inhibitor provided by the invention has a calcium carbonate scale inhibition rate of 62.69%, a calcium sulfate scale inhibition rate of 100%, and a calcium phosphate scale inhibition rate of 91.76%, has good hydrophobic effect and calcium carbonate, calcium sulfate and calcium phosphate blocking capability, and is small in addition amount, low in use cost and simple and convenient to operate. However, when the acrylic acid is excessive, the scale inhibition rate of the water-soluble low-molecular-weight copolymer scale inhibitor to calcium phosphate is linearly reduced and is only about 10 percent; when the tert-butyl acrylate is too much, the obtained product cannot be dissolved in water and cannot be used as a water-soluble scale inhibitor.
Claims (10)
1. The water-soluble low-molecular-weight copolymer scale inhibitor is characterized by being prepared by taking acrylic acid and tert-butyl acrylate as monomers and carrying out polymerization reaction, wherein the mass ratio of the acrylic acid to the tert-butyl acrylate is (8-9.5): 0.5 to 2.
2. The water-soluble low-molecular-weight copolymer scale inhibitor according to claim 1, wherein the viscosity average molecular weight of the water-soluble low-molecular-weight copolymer scale inhibitor is 3000 to 4500.
3. The water-soluble low-molecular-weight copolymer scale inhibitor according to claim 1, wherein the mass ratio of acrylic acid to tert-butyl acrylate is 8-8.75: 1.25 to 2.
4. A preparation method of the water-soluble low-molecular-weight copolymer scale inhibitor as claimed in any one of claims 1 to 3, characterized in that acrylic acid and tert-butyl acrylate are used as monomers, and a free radical aqueous solution polymerization reaction method is carried out under the action of an initiator and a reducing agent to obtain the water-soluble low-molecular-weight copolymer scale inhibitor.
5. The preparation method according to claim 4, wherein the preparation method specifically comprises the following steps:
(1) dissolving tert-butyl acrylate in acrylic acid to obtain a monomer solution, dissolving an initiator in water to obtain an initiator aqueous solution, and dissolving a reducing agent in water to obtain a reducing agent aqueous solution;
(2) heating water to 80-85 ℃, adding the monomer solution, the initiator aqueous solution and the reducing agent aqueous solution, carrying out heat preservation reaction for 30-60 min, and cooling after the reaction is finished to obtain the water-soluble low-molecular-weight copolymer scale inhibitor.
6. The preparation method according to claim 5, characterized in that the initiator is sodium persulfate, and the mass of the initiator is 1.5-2% of that of the monomer solution; the reducing agent is sodium bisulfite, and the mass of the reducing agent is 9-9.5% of that of the monomer solution.
7. The preparation method according to claim 5, wherein the mass percentage concentration of the initiator is 10-20 wt%; the mass percentage concentration of the reducing agent is 25-35 wt%.
8. The preparation method of claim 5, wherein the monomer solution, the initiator aqueous solution and the reducing agent aqueous solution are added into the reaction vessel in three drops, the dropping time of the monomer is 50-70 min, the initiator aqueous solution and the reducing agent aqueous solution are dropped 2-3min in advance of the monomer, and after the dropping of the monomer is finished, the initiator aqueous solution and the reducing agent aqueous solution are continuously dropped for 1-3 min.
9. The method according to claim 5, wherein the mass of the water is 1 to 1.1 times of the mass of the monomer solution.
10. The use of the water-soluble low molecular weight copolymer scale inhibitor of any one of claims 1 to 3 in water treatment.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115594805A (en) * | 2022-12-14 | 2023-01-13 | 山东泰和科技股份有限公司（Cn） | Calcium sulfate scale inhibitor, preparation method thereof and application thereof in water treatment |
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| WO2002070411A1 (en) * | 2001-02-09 | 2002-09-12 | Ciba Specialty Chemicals Water Treatments Limited | Scale removal or prevention |
| CN107001744A (en) * | 2014-10-06 | 2017-08-01 | 赫尔克里士有限公司 | Low molecule amount graft polymers for antisludging agent |
| CN107849185A (en) * | 2015-08-18 | 2018-03-27 | 东亚合成株式会社 | Water-soluble polymer composition and its manufacture method and its utilization |
| CN107935207A (en) * | 2017-11-29 | 2018-04-20 | 无锡昊瑜节能环保设备有限公司 | A kind of preparation method of without phosphorus nitrogen-free environmental protection dirt dispersion agent |
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| WO2002070411A1 (en) * | 2001-02-09 | 2002-09-12 | Ciba Specialty Chemicals Water Treatments Limited | Scale removal or prevention |
| CN107001744A (en) * | 2014-10-06 | 2017-08-01 | 赫尔克里士有限公司 | Low molecule amount graft polymers for antisludging agent |
| CN107849185A (en) * | 2015-08-18 | 2018-03-27 | 东亚合成株式会社 | Water-soluble polymer composition and its manufacture method and its utilization |
| CN107935207A (en) * | 2017-11-29 | 2018-04-20 | 无锡昊瑜节能环保设备有限公司 | A kind of preparation method of without phosphorus nitrogen-free environmental protection dirt dispersion agent |
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Application publication date: 20220722 |