CN116835781A - Degradable efficient sulfate scale inhibitor and preparation method thereof - Google Patents
Degradable efficient sulfate scale inhibitor and preparation method thereof Download PDFInfo
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- CN116835781A CN116835781A CN202310930408.8A CN202310930408A CN116835781A CN 116835781 A CN116835781 A CN 116835781A CN 202310930408 A CN202310930408 A CN 202310930408A CN 116835781 A CN116835781 A CN 116835781A
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 61
- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 230000005764 inhibitory process Effects 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- -1 polypropylene Polymers 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims description 10
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 9
- 108010064470 polyaspartate Proteins 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 3
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 abstract description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910001422 barium ion Inorganic materials 0.000 abstract description 3
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 3
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- 239000011575 calcium Substances 0.000 abstract 1
- 238000001223 reverse osmosis Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 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 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F21/00—Dissolving
- B01F21/02—Methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F21/00—Dissolving
- B01F21/10—Dissolving using driven stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/405—Methods of mixing liquids with liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/43—Mixing liquids with liquids; Emulsifying using driven stirrers
-
- 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
- C02F5/12—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 containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a degradable efficient sulfate scale inhibitor and a preparation method thereof. The degradable efficient sulfate scale preventing and inhibiting agent comprises, by weight, 100% of total weight, 20-40% of degradable macromolecular scale inhibiting synergist, 10-20% of sulfate scale inhibiting polymer and the balance of deionized water; the structural formula of the sulfate scale inhibition polymer is shown as a formula I, wherein a, b and c are positive integers, and a: b: c=10-20: 20-40:1-5; the total molecular weight Mw is less than or equal to 20000. The sulfate scale inhibition polymer introduces sulfonic acid groups, can complex calcium and barium ions in a water system, and effectively prevents the formation of calcium sulfate and barium sulfate; the polymerized monomer also contains hydroxyethyl acrylate, and the adjustment is carried outThe dissolubility of the scale inhibiting polymer is improved, so that the scale inhibiting polymer is easier to remove from the water system; the degradable macromolecular scale inhibition synergist not only can improve the effect of removing sulfate scale, but also can separate scale deposit, avoid the problem of adsorbing excessive scale deposit scale, and effectively prevent the formation of scale.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a degradable efficient sulfate scale inhibitor and a preparation method thereof.
Background
As a resource, water is becoming increasingly scarce in most parts of the world. Water is the basis of our industry, agriculture and life, but as industrialization progresses, the contradiction between the rapid development of industry and the relative shortage of water resources is increasingly prominent. The reverse osmosis technology is widely applied to purification and concentration of various liquids, wherein the most common application example is to remove inorganic ions, bacteria, viruses, organic matters, colloid and other impurities in raw water by using the reverse osmosis technology in the water treatment process so as to obtain high-quality purified water. In recent years, the quality of reverse osmosis inflow water is becoming more and more popular, especially the inflow water with high sulfate is becoming more and more common, and under the condition of the quality of water, the reverse osmosis membrane is easy to generate the phenomenon of fouling.
Along with the continuous increase of 'near zero emission' projects and mine water recycling projects, the water quality of the water inlet of the reverse osmosis system is more and more complex, and particularly, the salt content of the high-salt reverse osmosis system is very high, the most outstanding characteristics are that the sulfate radical content is high, sometimes the sulfate radical content is higher than 30000mg/L, sulfate scale is very easy to occur under the condition, the water yield and the water quality of the produced water are seriously influenced, the operation energy consumption is increased, and even the production is not stopped due to insufficient water supply, so that huge loss is caused. On the other hand, sulfate is insoluble in acid and alkali, the chelating agent has an unobvious cleaning effect, once the scale is seriously formed, the cleaning is very difficult, and a reverse osmosis membrane needs to be replaced when necessary, so that great economic loss is caused.
At present, reverse osmosis scale inhibitors in the technical field of domestic and foreign water treatment are various in variety, and the product quality and technical water quality are uneven. Most market products can only be applied to common water quality, but no good special product is available for high sulfate radical water quality. The ceramic product Acumer4200 is known to have good scale inhibition performance on sulfate, but good scale inhibition effect cannot be achieved even in the face of too high sulfate radical. Chinese patent grant publication No.: CN107261855B discloses a reverse osmosis scale inhibitor for water quality with high hardness and high sulfate radical concentration and a preparation method thereof, and Chinese patent publication No.: CN110975634a discloses a reverse osmosis scale inhibitor for inhibiting deposition of calcium carbonate, calcium sulfate, barium sulfate, strontium sulfate, calcium phosphate, iron oxide, silica scale and suspended matters, and compared with the conventional reverse osmosis scale inhibitor, the disclosed reverse osmosis scale inhibitor has relatively good sulfate scale inhibition performance for sulfate, but still cannot achieve good scale inhibition performance when facing too high sulfate, and especially cannot meet the operation and use of a 'zero emission' high-salt water reverse osmosis system and a mine water comprehensive utilization high-salt reverse osmosis system, and meanwhile, the formed scale cannot be effectively treated, and can continue to be deposited on a reverse osmosis membrane to cause loss.
Disclosure of Invention
The invention aims to: the invention aims to provide a degradable efficient scale inhibitor for preventing sulfate scale formation and a preparation method thereof, so as to solve the problems that under the condition of high sulfate concentration, the scale inhibition effect of the scale inhibitor is not ideal, a formed scale body cannot be effectively treated, and the scale is easy to block and difficult to clean.
The technical scheme of the invention is as follows:
a degradable highly effective sulfate scale inhibitor comprising, based on 100% total mass:
20-40% of degradable macromolecular scale inhibition synergist;
10-20% of sulfate scale inhibition polymer;
the balance of deionized water;
the degradable macromolecular scale inhibition synergist is a water-soluble modified macromolecular polymer formed by polymerizing monomers with carboxylic acid groups and carbon-carbon double bonds and grafting long-chain amino groups;
the structural formula of the sulfate scale inhibition polymer is shown as formula I:
wherein a, b and c are positive integers, a: b: c=10-20: 20-40:1-5; the total molecular weight Mw of the scale inhibiting polymer is less than or equal to 20000.
In some embodiments, the sulfate scale inhibiting polymer sum process comprises: adding p-hydroxystyrene, p-sulfostyrene and hydroxyethyl acrylate into a solvent, and then adding an initiator and uniformly mixing to obtain a mixed solution; adding the same solvent into a reaction bottle, heating to 60-80 ℃, dripping the obtained mixed solution for reaction, and distilling off the solvent after the reaction is finished to obtain the sulfate scale inhibition polymer.
In some embodiments, the degradable macromolecular scale inhibitor has a molecular weight mw=2-6 ten thousand. Through the characteristics of large molecular weight and complete water solubility, the scale remover can be fully unfolded in water, can separate small molecular sediments, avoid scale aggregation to form sediment, and can remove dirt better; the carboxyl on the molecule can complex metal ions in water, thereby forming metal element deposition and facilitating removal.
In some embodiments, the long chain amine groups are compounds having 6 to 14 carbon atoms in the backbone and at least one amine group at one end of the backbone; preferably, the long chain amine group is selected from one or more of dodecylamine, undecylamine.
In some embodiments, the degradable macromolecular scale inhibiting potentiator is selected from one or more of modified polyaspartic acid, modified polypropylene tricarboxylic acid, and modified polyitaconic acid.
In some embodiments, the method of preparing the modified polyaspartic acid comprises:
mixing maleic acid and a solvent, heating to 70-90 ℃, dropwise adding ammonia water, heating to 100-115 ℃ again, taking an organic phase, adding triethylene tetramine, and continuing to react; cooling to 40-60 ℃ after the reaction is finished, adding a triethylamine water solution, stirring until a milky turbid liquid is formed, continuously stirring, standing for layering, and collecting a water phase. Adding long-chain amino into the water phase, and stirring at 70-90 ℃ for reaction to obtain the modified polyaspartic acid.
In some embodiments, the method of preparing the modified polypropylene tricarboxylic acid comprises:
adding propylene tricarboxylic acid into an organic solvent, adding a catalyst, and uniformly mixing to obtain a mixed solution; heating the same solvent, and dripping the mixed solution into the solvent for reaction; and after the reaction is finished, adding long-chain amino into the system, and stirring at 70-90 ℃ to obtain the modified polypropylene tricarboxylic acid.
In some embodiments, the method of preparing the modified polyitaconic acid comprises:
adding itaconic acid into a solvent, adding a catalyst, and uniformly mixing to obtain a mixed solution; heating the same solvent, and dripping the mixed solution into the solvent for reaction; and after the reaction is finished, adding long-chain amino into the system, and stirring at 70-90 ℃ to obtain the modified polypropylene tricarboxylic acid.
In another aspect, the invention also provides a preparation method of the degradable efficient sulfate scale inhibitor, which specifically comprises the following steps:
and mixing and stirring the degradable macromolecular scale inhibition synergist, the sulfate scale inhibition polymer and deionized water according to the formula, and heating the mixed solution to 40-50 ℃ until the mixed solution is completely dissolved to obtain the degradable efficient sulfate scale inhibition agent.
The beneficial effects are that:
the degradable efficient sulfate scale inhibitor provided by the invention comprises a degradable macromolecular scale inhibition synergist and a sulfate scale inhibition polymer. The sulfate scale inhibition polymer introduces sulfonic acid groups, can well complex calcium ions and barium ions in a water system, and effectively prevents scale formation of calcium sulfate, barium sulfate and the like, thereby fundamentally preventing the generation of sulfuric acid scale; the polymeric monomer also contains hydroxyethyl acrylate, so that the dissolubility of the scale inhibiting polymer in the water system is adjusted, and the scale inhibiting polymer is easier to remove from the water system; and because of the synergistic effect of the degradable macromolecular scale inhibition synergist, the effect of removing sulfate scale can be improved, and long chains of macromolecules can separate sediment of the scale inhibition polymer, so that the problem of self-deposition scaling caused by re-adsorption of excessive scale is avoided, and the formation of scale on equipment is effectively prevented.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
The chemical reagents used in the invention are all common commercial analytical pure unless specified. The polyaspartic acid is purchased from Zhengzhou Guandao chemical products Co., ltd, and the product number is 011; the propylene tricarboxylic acid is purchased from Shanghai to Xin chemical industry Co., ltd, and is polymerized to obtain polypropylene tricarboxylic acid with molecular weight of 4W; itaconic acid was obtained from Shandong Hongyun chemical Co., ltd and polymerized to give polyitaconic acid having a molecular weight of 4W. GR-946 was purchased from Gansu Gerui technology Co.
Preparation of modified polyaspartic acid
11.6g of maleic acid was charged into the reactor, 100g of toluene was added as a solvent, the temperature was raised to 70℃and 5.44g of 25% aqueous ammonia was added dropwise to the system for 60 minutes. After the completion of the dropwise addition, the temperature was raised to 100℃and distilled water was separated by a water separator.
When no newly separated water was observed in the water separator, 2.92g of triethylenetetramine was added to the system, and the reaction was continued for 2 hours. After the reaction was completed, the temperature was lowered to 40 ℃. 200g of 0.5% triethylamine aqueous solution was added thereto to increase the stirring speed to form a milky turbid liquid, and the hydrolysis was continued for 20 hours with stirring.
After the hydrolysis is finished, standing and layering are carried out, and the water phase is collected. Adding 0.02mol of dodecyl amine into the water phase, heating to 70 ℃, continuously stirring and reacting for 24 hours, and distilling to remove water after the reaction is finished to obtain the modified polyaspartic acid.
Preparation of modified Polypropylene tricarboxylic acids
17.4g of propylene tricarboxylic acid, 1.12g of allyl acrylate were added to 100g of 4-methyl-2-pentanone, and 0.018g of benzoyl peroxide was added thereto and mixed uniformly to obtain a mixed solution.
To the reaction flask was added 100g of 4-methyl-2-pentanone and the temperature was raised to 80 ℃. The obtained mixed solution was added dropwise over a period of 3 hours.
And after the dripping is finished, adding 0.04mol of dodecyl amine into the system, heating to 90 ℃, continuously stirring and reacting for 24 hours, and distilling to remove the solvent after the reaction is finished, thereby obtaining the modified polypropylene tricarboxylic acid.
Preparation of modified polyitaconic acid
13g of itaconic acid and 1.12g of allyl acrylate are added into 100g of 4-methyl-2-pentanone, and 0.018g of benzoyl peroxide is added, and the mixture is uniformly mixed to obtain a mixed solution.
To the reaction flask was added 100g of 4-methyl-2-pentanone and the temperature was raised to 80 ℃. The obtained mixed solution was added dropwise over a period of 3 hours.
And after the dripping is finished, adding 0.03mol of dodecyl amine into the system, heating to 90 ℃, continuously stirring and reacting for 24 hours, and distilling to remove the solvent for later use after the reaction is finished, thereby obtaining the modified polyitaconic acid.
Preparation of sulfate scale inhibiting polymers
120g of p-hydroxystyrene, 549g of p-sulfostyrene and 11.6g of hydroxyethyl acrylate are added to 500g of 4-methyl-2-pentanone, and 6.8g of azobisisobutyronitrile are added and mixed to obtain a mixed solution.
500g of 4-methyl-2-pentanone were added to the reaction flask and the temperature was raised to 80 ℃. The obtained mixed solution was added dropwise for a reaction time of 5 hours. And distilling off the solvent after the reaction is finished to obtain the sulfate scale inhibition polymer. The molecular formula of the sulfate scale inhibiting polymer is shown as follows:
the infrared absorption spectrum test is carried out on the product, and the test result is as follows: at-822 cm -1 Characteristic peaks of benzene rings appear at the positions; at-1187 cm -1 、-1064cm -1 Characteristic peaks of sulfonate groups appear at the positions; at-1730 cm -1 Characteristic peaks of ester groups appear at the positions; it was confirmed that the compound represented by the formula I-1 was obtained.
Examples 1 to 4
And mixing and stirring different degradable macromolecular scale inhibition synergists, sulfate scale inhibition polymers and deionized water, and heating the mixed solution to 40 ℃ until the mixed solution is completely dissolved to obtain different degradable efficient sulfate scale inhibition agents. In the degradable efficient sulfate scale prevention and inhibition agent, the formulas of the types and the addition amounts of the scale inhibition polymer and the degradable macromolecule are shown in a table 1, and the balance is deionized water.
TABLE 1 formulation of various sulfate scale inhibitors
Comparative examples 1 to 4
And mixing and stirring different degradable macromolecular scale inhibition synergists, sulfate scale inhibition polymers and deionized water, and heating the mixed solution to 40 ℃ until the mixed solution is completely dissolved to obtain different sulfate scale inhibition agents. In the formula of the sulfate scale inhibitor, the types and the addition amounts of the scale inhibition polymer and other macromolecules are shown in table 2, and the balance is deionized water.
TABLE 1 formulation of different sulfate scale inhibitors
The experimental method comprises the following steps: the degradable efficient sulfate scale inhibitor prepared by the embodiment of the invention is subjected to a comparison test (calcium carbonate scale inhibition, calcium sulfate scale inhibition and barium sulfate scale inhibition) with the sulfate scale inhibitor of the comparative example, and the test method is referred to GB/T16632-2020 and Q/SY 126-2014, and the dosing concentration is modified to 10mg/L. The test results for 48 hours are shown in Table 3.
TABLE 3 test results
| Calcium carbonate scale inhibition (%) | Calcium sulfate scale inhibition (%) | Barium sulfate scale inhibition (%) | |
| Example 1 | 94.1 | 99.1 | 99.3 |
| Example 2 | 93.1 | 99.5 | 99.6 |
| Example 3 | 94.6 | 99.4 | 99.4 |
| Example 4 | 92.7 | 99.3 | 99.5 |
| Comparative example 1 | 76.1 | 83.4 | 81.4 |
| Comparative example 2 | 80.3 | 87.6 | 80.2 |
| Comparative example 3 | 79.4 | 81.0 | 83.3 |
| Comparative example 4 | 37.4 | 36.9 | 40.1 |
| Comparative example 5 | 41.4 | 56.9 | 51.7 |
| Comparative example 6 | 84.7 | 83.6 | 84.3 |
As shown in the test experiment results of Table 3, the degradable macromolecular scale inhibition synergist and the sulfate scale inhibition polymer provided by the invention have better silica scale inhibition effect when being matched. As can be seen from examples and comparative examples 4 to 5, the sulfate scale inhibiting polymer has excellent ability to adsorb calcium ions and barium ions, and has high scale inhibiting efficiency in a short period of time. And the added degradable macromolecular scale inhibition synergist is a comb polymer with a large molecular weight, long chains of the comb polymer are fully stretched in water, so that small molecular sulfate scale inhibition polymers can be separated, and as can be seen from examples and comparative examples 1-3, the addition of the degradable macromolecular scale inhibition synergist is beneficial to improving scale inhibition effect and avoiding redeposition agglomeration of dirt.
The present invention is capable of other and further embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A degradable highly effective sulfate scale inhibitor, characterized by comprising, based on 100% total mass:
20-40% of degradable macromolecular scale inhibition synergist;
10-20% of sulfate scale inhibition polymer;
the balance of deionized water;
the degradable macromolecular scale inhibition synergist is a water-soluble modified macromolecular polymer formed by polymerizing monomers with carboxylic acid groups and carbon-carbon double bonds and grafting long-chain amino groups;
the structural formula of the sulfate scale inhibition polymer is shown as formula I:
wherein a, b and c are positive integers, a: b: c=10-20: 20-40:1-5; the total molecular weight Mw of the scale inhibiting polymer is less than or equal to 20000.
2. The degradable high efficiency sulfate scale inhibitor of claim 1, wherein the method of combining the sulfate scale inhibiting polymers comprises: adding p-hydroxystyrene, p-sulfostyrene and hydroxyethyl acrylate into a solvent, and then adding an initiator and uniformly mixing to obtain a mixed solution; adding the same solvent into a reaction bottle, heating to 60-80 ℃, dripping the obtained mixed solution for reaction, and distilling off the solvent after the reaction is finished to obtain the sulfate scale inhibition polymer.
3. The degradable high efficiency sulfate scale inhibitor of claim 1, wherein the molecular weight Mw of the degradable macromolecular scale inhibitor is from 2 to 6 tens of thousands.
4. The degradable, highly effective sulfate scale inhibitor according to claim 1 wherein the long chain amine groups are compounds having 6-14 carbon atoms in the backbone and at least one amine group at one end of the backbone; preferably, the long chain amine group is selected from one or more of dodecylamine, undecylamine.
5. The degradable high efficiency sulfate scale preventing scale inhibitor of claim 1, wherein the degradable macromolecular scale inhibiting synergist is selected from one or more of modified polyaspartic acid, modified polypropylene tricarboxylic acid, and modified polyitaconic acid.
6. The degradable efficient sulfate scale inhibitor according to claim 5, wherein the preparation method of the modified polyaspartic acid comprises the following steps:
mixing maleic acid and a solvent, heating to 70-90 ℃, dropwise adding ammonia water, heating to 100-115 ℃ again, taking an organic phase, adding triethylene tetramine, and continuing to react; cooling to 40-60 ℃ after the reaction is finished, adding a triethylamine aqueous solution, stirring until a milky turbid liquid is formed, continuously stirring, standing for layering, collecting a water phase, adding long-chain amino groups into the water phase, and stirring at 70-90 ℃ for reaction to obtain the modified polyaspartic acid.
7. The degradable high-efficiency sulfate scale inhibitor according to claim 5, wherein the preparation method of the modified polypropylene tricarboxylic acid comprises the following steps: adding propylene tricarboxylic acid into an organic solvent, adding a catalyst, and uniformly mixing to obtain a mixed solution; heating the same solvent, dripping the mixed solution into the solvent for reaction, adding long-chain amino into the system after the reaction is completed, and stirring for reaction at 70-90 ℃ to obtain the modified polypropylene tricarboxylic acid.
8. The degradable efficient sulfate scale inhibitor according to claim 5, wherein the preparation method of the modified polyitaconic acid comprises the following steps: adding itaconic acid into a solvent, adding a catalyst, and uniformly mixing to obtain a mixed solution; heating the same solvent, dripping the mixed solution into the solvent for reaction, adding long-chain amino into the system after the reaction is completed, and stirring for reaction at 70-90 ℃ to obtain the modified polypropylene tricarboxylic acid.
9. The method for preparing the degradable efficient sulfate scale preventing scale inhibitor according to any one of claims 1 to 8, which is characterized by comprising the following steps:
and mixing and stirring the degradable macromolecular scale inhibition synergist, the sulfate scale inhibition polymer and deionized water according to the formula, and heating the mixed solution to 40-50 ℃ until the mixed solution is completely dissolved to obtain the degradable efficient sulfate scale inhibition agent.
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