CN117566925A - Concentrated solution scale inhibitor - Google Patents
Concentrated solution scale inhibitor Download PDFInfo
- Publication number
- CN117566925A CN117566925A CN202311701450.9A CN202311701450A CN117566925A CN 117566925 A CN117566925 A CN 117566925A CN 202311701450 A CN202311701450 A CN 202311701450A CN 117566925 A CN117566925 A CN 117566925A
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- CN
- China
- Prior art keywords
- scale inhibitor
- acid
- polyacrylic acid
- carboxymethyl cellulose
- corrosion
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- 239000002455 scale inhibitor Substances 0.000 title claims abstract description 79
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 63
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 63
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 62
- 230000005764 inhibitory process Effects 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000005260 corrosion Methods 0.000 claims abstract description 41
- 230000007797 corrosion Effects 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 32
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 29
- BMOKHTQIBPRXSL-UHFFFAOYSA-N 2h-benzotriazole;sodium Chemical compound [Na].C1=CC=CC2=NNN=C21 BMOKHTQIBPRXSL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229920001577 copolymer Polymers 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 10
- 239000003899 bactericide agent Substances 0.000 claims abstract description 10
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims abstract description 9
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 25
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 23
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 23
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 23
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- -1 sodium alkyl sulfonate Chemical class 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 8
- 229940102253 isopropanolamine Drugs 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 6
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 6
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 6
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 4
- 229940106681 chloroacetic acid Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical class [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000001508 potassium citrate Substances 0.000 claims description 3
- 229960002635 potassium citrate Drugs 0.000 claims description 3
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 3
- 235000011082 potassium citrates Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 235000011087 fumaric acid Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Chemical class 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Chemical class 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims 8
- 230000000694 effects Effects 0.000 abstract description 18
- 230000000052 comparative effect Effects 0.000 description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 26
- 229910000019 calcium carbonate Inorganic materials 0.000 description 13
- 229920000578 graft copolymer Polymers 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- 239000008235 industrial water Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GOLXRNDWAUTYKT-UHFFFAOYSA-N 3-(1H-indol-3-yl)propanoic acid Chemical compound C1=CC=C2C(CCC(=O)O)=CNC2=C1 GOLXRNDWAUTYKT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002699 waste material Substances 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The application relates to a concentrated solution scale inhibitor, which comprises the following components in percentage by weight: 40-50% of polyacrylic acid, 7-9% of carboxymethyl cellulose-polyacrylic acid grafted product, 7-9% of corrosion and scale inhibitor reinforcing agent, 3-5% of maleic acid-acrylic acid copolymer, 1-3% of dispersing auxiliary agent, 1-2% of acid regulator, 1-2% of bactericide, 0.5-1% of stabilizer and the balance of water; wherein the molecular weight of the polyacrylic acid is 500-5000; wherein the corrosion and scale inhibitor reinforcing agent comprises carboxymethyl starch-polyacrylamide grafted copolymer and sodium benzotriazole. The method can improve the corrosion and scale inhibition effect of the scale inhibitor while realizing the phosphorus-free scale inhibition water treatment.
Description
Technical Field
The application relates to the field of water treatment scale inhibitors, in particular to a concentrated solution scale inhibitor.
Background
China is an industrial large country, and a large amount of water resources are consumed each year for industrial water. In industrial water use, in order to protect the environment and save the cost, a water circulation system is generally required to be arranged for recycling the industrial water. However, when industrial water is recycled in the system, the problems of scaling, corrosion and the like of pipelines and equipment are often accompanied, and the normal operation of the equipment is affected, so that certain economic loss and potential safety hazard are caused. In order to solve the problems of scaling and corrosion of water treatment equipment, corrosion and scale inhibitors are mainly used for treating water at present.
The corrosion and scale inhibitor commonly used in industry is mainly made of phosphorus, and the main varieties are as follows: polyphosphates, phosphoric acid vinegar, organic polyphosphonic acids, etc., but without dispersing. The polymer scale inhibition and dispersion agent is divided into natural and synthetic types, wherein the natural polymer scale inhibition and dispersion agent mainly comprises starch, tannin, lignin and the like, but is rarely used at present due to unstable products and high impurity content; the synthetic polymer scale inhibition and dispersion agent mainly comprises carboxylic acid, sulfonic acid and phosphorus, wherein the phosphorus-containing carboxylic acid polymer has good scale inhibition and dispersion performance, and the polymer has low phosphorus content, thereby being relatively beneficial to environmental protection.
However, at present, the annual phosphorus products used for producing corrosion and scale inhibitors are about 10 ten thousand tons, and the phosphorus-containing compounds are finally discharged as waste, so that serious pollution is caused to water environment, and therefore, aiming at the existing scale inhibitors, the development of novel corrosion and scale inhibitors with no phosphorus or lower phosphorus content and high efficiency is a direction of urgent development.
Disclosure of Invention
In order to achieve the effect of corrosion and scale inhibition of the scale inhibitor while achieving the phosphorus-free scale inhibition water treatment, the application provides a concentrated solution scale inhibitor.
The application provides a concentrated solution scale inhibitor which adopts the following technical scheme:
the concentrated solution scale inhibitor comprises the following components in parts by weight:
40-50% of polyacrylic acid, 7-9% of carboxymethyl cellulose-polyacrylic acid grafted product, 7-9% of corrosion and scale inhibitor reinforcing agent, 3-5% of maleic acid-acrylic acid copolymer, 1-3% of dispersing auxiliary agent, 1-2% of acid regulator, 1-2% of bactericide, 0.5-1% of stabilizer and the balance of water;
wherein the molecular weight of the polyacrylic acid is 500-5000;
wherein the corrosion and scale inhibitor reinforcing agent comprises carboxymethyl starch-polyacrylamide grafted copolymer and sodium benzotriazole.
By adopting the technical scheme, firstly, the polyacrylic acid contains a large amount of carboxyl functional groups, and the carboxyl functional groups can be combined with metal ions such as Ca which are easy to form scale in water 2+ 、Mg 2+ Bind to thereby hinder the binding of the scale forming anions (e.g. CO 3 2- ，SO 4 2- Etc.) to form scale forming particles to act as scale inhibitors; and the interaction force and cohesion between polymer molecules of polyacrylic acid with molecular weight of 500-5000The force is weaker than that of the polyacrylic acid with relatively high molecular weight, so that the polyacrylic acid can be better dissolved and dispersed in water, and the scale inhibition effect is further improved by more fully preventing scale formation particles from being contacted and aggregated with each other to form enlargement and deposition. The carboxymethyl cellulose also has a large number of carboxyl functional groups, more carboxyl functional groups can be introduced into the scale inhibitor through forming a carboxymethyl cellulose-polyacrylic acid grafted product, and the carboxymethyl cellulose-polyacrylic acid grafted product and polyacrylic acid cooperate to perform a structure with metal ions which are easy to form scale, so that the scale inhibition effect is further improved.
The maleic acid-acrylic acid copolymer also has the functions of corrosion inhibition and scale inhibition, has good high temperature resistance, and is compounded with polyacrylic acid and carboxymethyl cellulose-polyacrylic acid grafted products for use, so that the scale inhibitor has good scale inhibition effect in a higher-temperature water environment. The acidic regulator can regulate and neutralize the pH value of water to be treated, and other scale inhibition components can better inhibit scale of water with high alkalinity and high pH value.
The carboxymethyl starch-polyacrylamide graft copolymer and the benzotriazole sodium in the corrosion and scale inhibition reinforcing agent have film forming property, and a layer of film is formed on the surface of metal equipment, wherein the film formed on the surface of the equipment by the benzotriazole sodium can protect the surface of the metal and is not easy to corrode, so that the corrosion inhibition effect is achieved; meanwhile, because the carboxymethyl starch in the carboxymethyl starch-polyacrylamide graft copolymer also contains more carboxyl functional groups, after the carboxymethyl starch-polyacrylamide graft copolymer and the benzotriazole sodium form a film on the surface of the metal, the carboxymethyl starch-polyacrylamide graft copolymer can be combined with metal ions which are easy to form scale in water, and the formation of scale particles in a water area close to the metal of the equipment is further hindered, so that the scale inhibition effect is further improved.
All the components do not contain phosphorus, so that the formed scale inhibitor has more excellent corrosion and scale inhibition effects while being free of phosphorus.
Optionally, the preparation method of the carboxymethyl cellulose-polyacrylic acid grafted product comprises the following steps:
mixing hydroxypropyl methyl cellulose with alkaline solution with a certain concentration, adding isopropanol, heating in water bath and stirring for 1-2h, dropwise adding a certain amount of chloroacetic acid fully dissolved in the isopropanol into a reaction system, reacting for 2-4h, adjusting the pH of the product to be neutral, washing, filtering and drying to obtain carboxymethyl cellulose;
dissolving the obtained carboxymethyl cellulose in water, introducing inert gas, stirring for 1-2h in a water bath at 50-60 ℃, adding ammonium persulfate aqueous solution, dropwise adding acrylic acid solution according to a certain proportion after the mixed solution reacts for 15-18min, reacting for 2-3h, extracting and drying the reaction product, and crushing to obtain the carboxymethyl cellulose-polyacrylic acid grafted product.
By adopting the technical scheme, the hydroxypropyl methylcellulose is firstly heated in a water bath, so that the hydroxypropyl methylcellulose is fully swelled and alkalized, chloroacetic acid is used as a modifier to make the hydroxypropyl methylcellulose carry out carboxylation reaction to obtain carboxymethyl cellulose, and then the carboxymethyl cellulose and a certain proportion of acrylic acid are subjected to copolymerization grafting reaction to obtain a carboxymethyl cellulose-polyacrylic acid grafted product with a certain grafting rate.
Optionally, the molar ratio of the carboxymethyl cellulose to the acrylic acid is 1 (0.4-0.7).
By adopting the technical scheme, the grafting rate of the carboxymethyl cellulose-polyacrylic acid grafted product generated by copolymerization grafting of the carboxymethyl cellulose and the acrylic acid according to the molar ratio is 7.15-18.30 percent, and the film forming performance and the scale inhibition performance of the carboxymethyl cellulose-polyacrylic acid grafted product with the grafting rate are relatively better.
Optionally, the mass ratio of the carboxymethyl starch-polyacrylamide grafted copolymer and the sodium benzotriazole in the corrosion and scale inhibition reinforcing agent is 1: (0.7-0.9).
By adopting the technical scheme, the carboxymethyl starch-polyacrylamide grafted copolymer and the benzotriazole sodium are compounded according to the proportion range, so that the corrosion inhibition performance and the scale inhibition effect of the film formed by the carboxymethyl starch-polyacrylamide grafted copolymer and the benzotriazole sodium on the surface of metal equipment are relatively better.
Optionally, the dispersing auxiliary comprises the components with the mass ratio of 1: (0.4-0.6): (2.0-2.8): (2.5-3.5) isopropanolamine, sulfonic polycarboxylic acid, octylphenol polyoxyethylene ether and sodium alkyl sulfonate.
By adopting the technical scheme, the components have better dispersibility and lubricity, and the components are compounded according to the mass ratio, so that isopropanolamine, sulfonic polycarboxylic acid, octyl phenol polyoxyethylene ether and sodium alkyl sulfonate have synergistic effect, and scale forming particles can be better prevented from being contacted with each other and aggregated to form a scale, and the scale inhibition effect is further improved.
Optionally, the acidity regulator is selected from at least one of citric acid, potassium citrate, tartaric acid and fumaric acid.
Optionally, the bactericide is at least one selected from calcium hypochlorite, polyvinylpyrrolidone derivatives and polyurethane.
By adopting the technical scheme, the components can be used for efficiently killing bacteria, fungi and algae generated by depending on the fungi in water, so that the condition that the algae in the circulating water are bred to destroy a circulating water system is reduced.
Optionally, the stabilizer is at least one selected from sodium alginate, dibutyl tin dimaleate and dibutyl tin dilaurate.
By adopting the technical scheme, the components are synergistic, so that the scale inhibitor is reduced in the production and use processes, the possibility of denaturation of other components in the scale inhibitor due to the influence of temperature and pH is reduced, and the product stability of the scale inhibitor is improved.
In a second aspect, the preparation method of the concentrated solution scale inhibitor provided by the application adopts the following technical scheme:
the preparation method of the concentrated solution scale inhibitor comprises the following steps:
mixing and stirring polyacrylic acid, a carboxymethyl cellulose-polyacrylic acid grafted product, a maleic acid-acrylic acid copolymer, an acid regulator, a bactericide, a stabilizer and water, and stirring until the mixture is dissolved to obtain a first solution; and adding a corrosion and scale inhibitor and a dispersing aid into the first solution, and homogenizing to obtain the concentrated solution scale inhibitor.
By adopting the technical scheme, each component in the scale inhibitor can be more fully dissolved and dispersed, so that the product stability of the scale inhibitor is improved.
Optionally, the stirring speed of the mixing and stirring is 150-200r/min, and the stirring time is 3-6min; the homogenizing speed is 700-780r/min, and the homogenizing time is 20-30min.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the carboxymethyl cellulose-polyacrylic acid grafted product and polyacrylic acid cooperate to more fully carry out structure with metal ions which are easy to form scale, and have excellent scale inhibition effect; the carboxymethyl starch-polyacrylamide grafted copolymer and the benzotriazole sodium in the corrosion and scale inhibition reinforcing agent can be adsorbed on the surface of metal equipment to form a layer of film, and the film formed on the surface of the equipment by the benzotriazole sodium can protect the surface of the metal and is not easy to corrode, so that a corrosion inhibition effect is achieved; meanwhile, the carboxymethyl starch-polyacrylamide grafted copolymer can be combined with metal ions which are easy to form scale in water, so that the formation of scale particles in water close to equipment metal is further hindered, and the scale inhibition effect is further improved;
2. the maleic acid-acrylic acid copolymer is compounded with polyacrylic acid and carboxymethyl cellulose-polyacrylic acid grafted products, so that the scale inhibitor has a good scale inhibition effect in a high-temperature water environment; the acidic regulator can regulate and neutralize the pH value of water to be treated, and other scale inhibition components can better inhibit the scale of water with high alkalinity and high pH value;
3. the grafting rate of the carboxymethyl cellulose-polyacrylic acid grafted product generated by the copolymerization grafting of the carboxymethyl cellulose and the acrylic acid according to the molar ratio is 7.15-18.30 percent, and the film forming property and the scale inhibition property of the carboxymethyl cellulose-polyacrylic acid grafted product with the grafting amount are relatively better.
Detailed Description
1. Examples
Example 1:
the concentrated solution scale inhibitor comprises the following components in parts by weight:
40% of polyacrylic acid, 7% of carboxymethyl cellulose-polyacrylic acid grafted product, 7% of corrosion and scale inhibitor reinforcing agent, 3% of maleic acid-acrylic acid copolymer, 1% of dispersing aid, 1% of acidity regulator, 1% of bactericide, 0.5% of stabilizer and the balance of water;
wherein the polyacrylic acid has a molecular weight of 500-5000, preferably a molecular weight of 1000-2000;
wherein the corrosion and scale inhibition reinforcing agent comprises carboxymethyl starch-polyacrylamide grafted copolymer and benzotriazole sodium in a mass ratio of 1:0.8;
wherein the dispersing auxiliary comprises the following components in percentage by mass: 0.5:2.4:3 isopropanolamine, sulfonic polycarboxylic acid, octyl phenol polyoxyethylene ether and sodium alkyl sulfonate;
wherein the bactericide is calcium hypochlorite, the acid regulator is potassium citrate, and the stabilizer is sodium alginate.
Preparing a carboxymethyl cellulose-polyacrylic acid grafted product:
mixing 20g of hydroxypropyl methylcellulose (purchased from Hebei purple gold chemical industry Co., ltd.) with 10mg/L NaOH aqueous solution, adding 150mL of isopropanol, heating in a water bath at 50 ℃, mechanically stirring for 2 hours, dropwise adding 10g of chloroacetic acid fully dissolved in the isopropanol into a reaction system, reacting for 4 hours, adding 2mol/L hydrochloric acid solution (mass fraction is 25%) to adjust the pH of the product to be neutral, washing and filtering with ethanol, and fully drying the obtained product in an oven for 48 hours to obtain carboxymethyl cellulose;
10g of the obtained carboxymethyl cellulose is dissolved in water, nitrogen is introduced, the mixture is stirred for 1h in a water bath at 60 ℃, then ammonium persulfate aqueous solution is added, after the mixed solution reacts for 15min, acrylic acid solution (2 mol/L) is continuously added dropwise according to a certain proportion in a nitrogen environment, and the reaction is carried out for 3h at 50 ℃. After the reaction is finished, settling the reaction product in ethanol, placing the reaction product in a vacuum oven at 50 ℃ for drying for 48 hours, taking out the reaction product after drying, and crushing the reaction product by a high-speed stirring crusher to obtain a carboxymethyl cellulose-polyacrylic acid grafted product after crushing;
wherein the molar ratio of the carboxymethyl cellulose to the acrylic acid is 1:0.5, and the amount of the substance added to the carboxymethyl cellulose is 0.038mol, so that the amount of the substance added to the acrylic acid is 0.019, namely 9.5ML of acrylic acid solution is added dropwise;
preparing carboxymethyl starch-polyacrylamide graft copolymer:
10g of water-soluble acrylamide (purchased from Shandong Hao forward chemical Co., ltd.) and 12g of carboxymethyl starch (purchased from Yingchu Jinyu chemical Co., ltd.) are added into 25g of water and alkyl glycoside emulsifier, 4g of sodium dodecyl benzene sulfonate is added, so that an emulsifying system is formed by acrylamide monomer and starch in a dispersion system, emulsion polymerization is carried out under the action of an initiator permanganate to form carboxymethyl starch-polyacrylamide graft copolymer, and the powdery carboxymethyl starch-polyacrylamide graft copolymer is obtained after azeotropic distillation and dehydration.
And (3) preparing concrete:
mixing and stirring 40g of polyacrylic acid, 7g of carboxymethyl cellulose-polyacrylic acid grafted product, 3g of maleic acid-acrylic acid copolymer, 1g of acid regulator, 1g of bactericide, 0.5g of stabilizer and 39.5g of water, wherein the stirring speed is 180r/min, the stirring time is 5min, and stirring until the mixture is dissolved to obtain a first solution; and adding 7g of corrosion and scale inhibitor and 1g of dispersing aid into the first solution, homogenizing at 740r/min for 26min to obtain the concentrated solution scale inhibitor.
Examples 2-3:
a concentrated scale inhibitor was different from example 1 in the following point as shown in Table 1.
Table 1:
example 4:
a concentrated scale inhibitor which is different from example 2 in that: in the process of preparing the carboxymethyl cellulose-polyacrylic acid grafted product, the molar ratio of the carboxymethyl cellulose to the acrylic acid is 1:0.4.
Example 5:
a concentrated scale inhibitor which is different from example 2 in that: in the process of preparing the carboxymethyl cellulose-polyacrylic acid grafted product, the molar ratio of the carboxymethyl cellulose to the acrylic acid is 1:0.7.
Example 6:
a concentrated scale inhibitor which is different from example 2 in that: polyacrylic acid with molecular weight of 500-1000 is selected.
Example 7:
a concentrated scale inhibitor which is different from example 2 in that: polyacrylic acid with molecular weight of 2000-5000 is selected.
Example 8:
a concentrated scale inhibitor which is different from example 2 in that: the mass ratio of the carboxymethyl starch-polyacrylamide grafted copolymer and the benzotriazole sodium in the corrosion and scale inhibitor reinforcing agent is 1:0.7.
Example 9:
a concentrated scale inhibitor which is different from example 2 in that: the mass ratio of the carboxymethyl starch-polyacrylamide grafted copolymer and the benzotriazole sodium in the corrosion and scale inhibitor reinforcing agent is 1:0.9.
Example 10:
a concentrated scale inhibitor which is different from example 2 in that: the mass ratio of isopropanolamine, sulfonic polycarboxylic acid, octyl phenol polyoxyethylene ether and sodium alkyl sulfonate in the dispersing auxiliary is 1:0.4:2.0:2.5.
example 11:
a concentrated scale inhibitor which is different from example 2 in that: the mass ratio of isopropanolamine, sulfonic polycarboxylic acid, octyl phenol polyoxyethylene ether and sodium alkyl sulfonate in the dispersing auxiliary is 1:0.6:2.8:3.5.
example 12:
a concentrated scale inhibitor which is different from example 2 in that: the acidity regulator is citric acid.
Example 13:
a concentrated scale inhibitor which is different from example 2 in that: the acidity regulator is tartaric acid.
Example 14:
a concentrated scale inhibitor which is different from example 2 in that: the stabilizer is dibutyl tin dimaleate.
Example 15:
a concentrated scale inhibitor which is different from example 2 in that: the stabilizer is dibutyl tin dilaurate.
2. Comparative example
Comparative example 1:
the difference from example 2 is that: the carboxymethyl cellulose-polyacrylic acid grafted product was equally replaced with polyacrylic acid.
Comparative example 2:
the difference from example 2 is that: the corrosion and scale inhibitor reinforcing agent is replaced by polyacrylic acid in an equivalent way.
Comparative example 3:
the difference from example 2 is that: the molar ratio of carboxymethyl cellulose to acrylic acid is 1:0.9.
Comparative example 4:
the difference from example 2 is that: the molar ratio of carboxymethyl cellulose to acrylic acid is 1:0.2.
Comparative example 5:
the difference from example 2 is that: the molecular weight of the polyacrylic acid was 7000.
Comparative example 6:
the difference from example 2 is that: the carboxymethyl starch-polyacrylamide grafted copolymer in the corrosion and scale inhibitor is replaced by sodium benzotriazole in an equivalent amount.
Comparative example 7:
the difference from example 2 is that: and the sodium benzotriazole in the corrosion and scale inhibition reinforcing agent is replaced by carboxymethyl starch-polyacrylamide grafted copolymer in an equivalent way.
Comparative example 8:
the difference from example 2 is that: the mass ratio of the carboxymethyl starch-polyacrylamide graft copolymer and the benzotriazole sodium in the corrosion and scale inhibition reinforcing agent is 1:0.5.
comparative example 9:
the difference from example 2 is that: the mass ratio of the carboxymethyl starch-polyacrylamide graft copolymer and the benzotriazole sodium in the corrosion and scale inhibition reinforcing agent is 1:1.1.
3. performance test
The scale inhibitor prepared in examples 1 to 15 and comparative examples 1 to 9 was diluted 11 times with water to obtain a reference liquid for the test; preparing a test solution containing a certain amount of calcium ions, adding the same dose of the reference solutions of examples 1-15 and comparative examples 1-9 into the test solution, setting a blank control group, and dripping bicarbonate solution into the test solutions of examples 1-15 and comparative examples 1-9 and the blank control group to continuously increase the supersaturation degree of calcium carbonate until calcium carbonate is formed.
1) And detecting the scale inhibition performance by a pH method:
the final point of precipitation of calcium carbonate was determined by the pH values of the test solutions of examples 1 to 15 and comparative examples 1 to 9 and the blank solutions, and the supersaturation degree value of calcium carbonate was calculated.
The test results are expressed as supersaturation degree S of calcium carbonate. The calculation formula is as follows:
wherein:
-the concentration of calcium ions, bicarbonate ions, carbonate ions, hydrogen ions in the pH before the decrease;
C 1 、C 2 -preparing reagent concentrations of CaCl2 and NaHCO3, C 1 ＝0.009mol/L，C 2 ＝0.30mol/L；
V 1 CaCl was added prior to the assay 2 V of (2) 1 ＝150mL
V 2 -NaHCO is added before the pH value decreases 3 Volume, mL of (2)
pHc-maximum pH in solution;
K 2 -secondary ionization equilibrium constant of carbonic acid, K at 25 DEG C 2 ＝10-10.33；
Ksp-solubility product constant of calcium carbonate, ksp=4.8X10-9 at 25 ℃;
evaluation principle: taking the supersaturation degree S of calcium carbonate as a judgment basis, the larger the S is, the better the scale inhibitor has the performance of inhibiting calcium carbonate scale.
2) And detecting the scale inhibition performance by a conductivity method:
the end point of precipitation of calcium carbonate was determined by measuring the conductivities of the test solutions of examples 1 to 15 and comparative examples 1 to 9 and the blank solutions, and the supersaturation degree value of calcium carbonate was calculated. The test results are expressed as supersaturation degree S of calcium carbonate.
The calculation formula is as follows:
wherein:
C 3 、C 4 -configured CaCl configuration 2 And NaCO 3 Concentration of reagent C 3 ＝0.003mol/L，C 4 ＝0.10mol/L；
V 3 CaCl was added prior to the assay 2 V of (2) 1 ＝100mL；
V 4 NaCO is added before the conductivity decreases 3 Is defined as volume in ml.
Evaluation principle: taking the supersaturation degree S of calcium carbonate as a judgment basis, the larger the S is, the better the scale inhibitor has the performance of inhibiting calcium carbonate scale.
The above test results are shown in table 2.
Table 2:
4. analysis and summary of results
As can be seen from a combination of examples 1 to 3 and Table 2, the contents of the respective components in examples 1 to 3 are different, and as can be seen from Table 2, the supersaturation degree by the pH method and the conductivity method in example 2 is higher than that in examples 1 and 3. And in combination with comparative examples 1-2, the carboxymethyl cellulose-polyacrylic acid grafted product in comparative example 1 was replaced with polyacrylic acid in equal amount, and the corrosion and scale inhibitor in comparative example 2 was replaced with polyacrylic acid in equal amount, as can be seen from Table 2, the supersaturation degree of comparative examples 1-2, as measured by the pH method and the conductivity method, was significantly lower than that of examples 1-3.
The scale inhibitor can be prepared by compounding the components such as polyacrylic acid, carboxymethyl cellulose-polyacrylic acid grafted product, corrosion and scale inhibitor reinforcing agent and the like, and can remarkably improve the scale inhibition performance of the scale inhibitor in the water treatment process; and the scale inhibitor has relatively better scale inhibition performance by proportioning according to the content of each component in the embodiment 2.
As can be seen from a combination of examples 2, examples 4 to 5 and Table 2, in the preparation of the carboxymethyl cellulose-polyacrylic acid graft product of examples 4 to 5, the molar ratio of carboxymethyl cellulose to acrylic acid was different from that of example 2, i.e., the grafting ratio of the produced carboxymethyl cellulose-polyacrylic acid graft product was different from that of example 2, and as can be seen from Table 2, the supersaturation degree of examples 4 to 5 as measured by the pH method and the conductivity method was significantly lower than that of example 2.
And in combination with comparative examples 3 to 4, the molar ratio of carboxymethyl cellulose and acrylic acid of comparative examples 3 to 4 was outside the range of the present application, and as can be seen from Table 2, the supersaturation degree of comparative examples 3 to 4, as measured by the pH method and the conductivity method, was significantly lower than that of examples 2 and examples 4 to 5.
From the above, in the process of preparing the carboxymethyl cellulose-polyacrylic acid grafted product, the molar ratio of the carboxymethyl cellulose to the acrylic acid is within the range of the application, so that the effect of improving the scale inhibition performance of the carboxymethyl cellulose-polyacrylic acid grafted product is better, and the molar ratio of the carboxymethyl cellulose to the acrylic acid is 1: at 0.5, the scale inhibition performance is improved relatively better.
As can be seen from a combination of examples 6 to 7 and Table 2, the molecular weights of the polyacrylic acids selected in examples 6 to 7 were different from those in example 2, and it can be seen from Table 2 that the supersaturation degree of examples 6 to 7 as measured by the pH method and the conductivity method was significantly lower than that of example 2. In addition, in combination with comparative example 5, the molecular weight of polyacrylic acid selected in comparative example 5 was outside the range of the present application, and as can be seen from Table 2, the supersaturation degree of comparative example 5 was significantly lower than that of examples 2 and examples 6 to 7 by the pH method and the conductivity method.
From the above, the polyacrylic acid with the molecular weight of 500-5000 can have remarkable improvement effect on the scale inhibition performance, and further, the polyacrylic acid with the molecular weight of 1000-2000 has relatively better improvement effect on the scale inhibition performance.
As can be seen from the combination of examples 8 to 9 and Table 2, the mass ratio of carboxymethyl starch-polyacrylamide graft copolymer and sodium benzotriazole in the corrosion and scale inhibitor in examples 8 to 9 was different from that in example 2, and it can be seen from Table 2 that the supersaturation degree of examples 8 to 9 was lower than that in example 2 by the pH method and the conductivity method.
And in combination with comparative examples 6 to 9, the equivalent substitution of carboxymethyl starch-polyacrylamide graft copolymer in the corrosion and scale inhibitor of comparative example 6 with sodium benzotriazole and the equivalent substitution of sodium benzotriazole in the corrosion and scale inhibitor of comparative example 7 with carboxymethyl starch-polyacrylamide graft copolymer, as can be seen from Table 2, the supersaturation degree of comparative examples 6 to 7, as measured by the pH method and the conductivity method, is significantly lower than that of examples 2 and examples 8 to 9; and the mass ratio of the carboxymethyl starch-polyacrylamide grafted copolymer and the sodium benzotriazole in the corrosion and scale inhibition reinforcing agents of the comparative examples 8-9 is outside the application range, and as can be seen from the table 2, the supersaturation degree of the comparative examples 8-9 measured by a pH method and a conductivity method is obviously lower than that of the examples 2 and 8-9.
From the above, the carboxymethyl starch-polyacrylamide graft copolymer and the sodium benzotriazole are prepared according to the mass ratio of 1: (0.7-0.9) can obviously improve the scale inhibition performance by compounding; and the mass ratio of the carboxymethyl starch-polyacrylamide grafted copolymer to the sodium benzotriazole is 1:0.8, so that the scale inhibition performance is improved relatively better.
As is clear from the combination of examples 10 to 11 and Table 2, the mass ratios of isopropanolamine, sulfonic polycarboxylic acid, octylphenol polyoxyethylene ether and sodium alkylsulfonate in the dispersion auxiliaries of examples 10 to 11 are different from those of example 2, and as is clear from Table 2, the supersaturation degree of examples 10 to 11 as measured by the pH method and the conductivity method is lower than that of example 2. From the above, the mass ratio of isopropanolamine, sulfonic polycarboxylic acid, octyl phenol polyoxyethylene ether and sodium alkyl sulfonate in the dispersion auxiliary agent is 1:0.5:2.4: and 3, the scale inhibition performance is improved relatively better.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes of products, methods and principles of this application are intended to be covered by the scope of this application.
Claims (10)
1. The concentrated solution scale inhibitor is characterized by comprising the following components in parts by weight:
40-50% of polyacrylic acid, 7-9% of carboxymethyl cellulose-polyacrylic acid grafted product, 7-9% of corrosion and scale inhibitor reinforcing agent, 3-5% of maleic acid-acrylic acid copolymer, 1-3% of dispersing auxiliary agent, 1-2% of acid regulator, 1-2% of bactericide, 0.5-1% of stabilizer and the balance of water;
wherein the molecular weight of the polyacrylic acid is 500-5000;
wherein the corrosion and scale inhibitor reinforcing agent comprises carboxymethyl starch-polyacrylamide grafted copolymer and sodium benzotriazole.
2. The concentrate scale inhibitor of claim 1, wherein the method of preparing the carboxymethyl cellulose-polyacrylic acid grafted product comprises the steps of:
mixing hydroxypropyl methyl cellulose with alkaline solution with a certain concentration, adding isopropanol, heating in water bath and stirring for 1-2h, dropwise adding a certain amount of chloroacetic acid fully dissolved in the isopropanol into a reaction system, reacting for 2-4h, adjusting the pH of the product to be neutral, washing, filtering and drying to obtain carboxymethyl cellulose;
dissolving the obtained carboxymethyl cellulose in water, introducing inert gas, stirring for 1-2h in a water bath at 50-60 ℃, adding ammonium persulfate aqueous solution, dropwise adding acrylic acid solution according to a certain proportion after the mixed solution reacts for 15-18min, reacting for 2-3h, extracting and drying the reaction product, and crushing to obtain the carboxymethyl cellulose-polyacrylic acid grafted product.
3. The concentrate scale inhibitor of claim 2, wherein: the molar ratio of the carboxymethyl cellulose to the acrylic acid is 1 (0.4-0.7).
4. The concentrate scale inhibitor of claim 1, wherein: the mass ratio of the carboxymethyl starch-polyacrylamide grafted copolymer to the sodium benzotriazole in the corrosion and scale inhibition reinforcing agent is 1: (0.7-0.9).
5. The concentrate scale inhibitor of claim 1, wherein: the dispersing auxiliary comprises the following components in percentage by mass: (0.4-0.6): (2.0-2.8): (2.5-3.5) isopropanolamine, sulfonic polycarboxylic acid, octylphenol polyoxyethylene ether and sodium alkyl sulfonate.
6. The concentrate scale inhibitor of claim 1, wherein: the acidity regulator is at least one selected from citric acid, potassium citrate, tartaric acid and fumaric acid.
7. The concentrate scale inhibitor of claim 1, wherein: the bactericide is at least one selected from calcium hypochlorite, polyvinylpyrrolidone derivatives and polyurethane.
8. The concentrate scale inhibitor of claim 1, wherein: the stabilizer is at least one selected from sodium alginate, dibutyl tin dimaleate and dibutyl tin dilaurate.
9. A process for preparing a concentrate scale inhibitor according to any one of claims 1 to 8, comprising the steps of:
mixing and stirring polyacrylic acid, a carboxymethyl cellulose-polyacrylic acid grafted product, a maleic acid-acrylic acid copolymer, an acid regulator, a bactericide, a stabilizer and water, and stirring until the mixture is dissolved to obtain a first solution; and adding a corrosion and scale inhibitor and a dispersing aid into the first solution, and homogenizing to obtain the concentrated solution scale inhibitor.
10. The method for preparing the concentrated scale inhibitor according to claim 9, wherein the method comprises the following steps: the stirring speed of the mixing and stirring is 150-200r/min, and the stirring time is 3-6min; the homogenizing speed is 700-780r/min, and the homogenizing time is 20-30min.
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| US20130005639A1 (en) * | 2011-06-28 | 2013-01-03 | Ecolab Usa Inc. | Methods and compositions using sodium carboxymethyl cellulose as scale control agent |
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| US20180094185A1 (en) * | 2015-04-22 | 2018-04-05 | Halliburton Energy Services, Inc. | Cellulose or Cellulose Derivative Including Grafted Acrylamide or Acrylic Acid Groups for Treatment of Subterranean Formations |
| CN108751446A (en) * | 2018-06-20 | 2018-11-06 | 陕西省石油化工研究设计院 | A kind of environment protection type multifunctional antisludging agent and the preparation method and application thereof |
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| US20130005639A1 (en) * | 2011-06-28 | 2013-01-03 | Ecolab Usa Inc. | Methods and compositions using sodium carboxymethyl cellulose as scale control agent |
| US20180094185A1 (en) * | 2015-04-22 | 2018-04-05 | Halliburton Energy Services, Inc. | Cellulose or Cellulose Derivative Including Grafted Acrylamide or Acrylic Acid Groups for Treatment of Subterranean Formations |
| CN105314743A (en) * | 2015-12-04 | 2016-02-10 | 中国海洋石油总公司 | Non-phosphorus corrosion and scale inhibitor applicable to negative hard water quality and preparation method of non-phosphorus corrosion and scale inhibitor |
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