CN117585821A - Composite scale and corrosion inhibitor and preparation method and application thereof - Google Patents
Composite scale and corrosion inhibitor and preparation method and application thereof Download PDFInfo
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- CN117585821A CN117585821A CN202311587831.9A CN202311587831A CN117585821A CN 117585821 A CN117585821 A CN 117585821A CN 202311587831 A CN202311587831 A CN 202311587831A CN 117585821 A CN117585821 A CN 117585821A
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- corrosion inhibitor
- scale
- quaternary ammonium
- dispersing agent
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- 230000007797 corrosion Effects 0.000 title claims abstract description 96
- 238000005260 corrosion Methods 0.000 title claims abstract description 96
- 239000003112 inhibitor Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 56
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 51
- 239000002270 dispersing agent Substances 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 21
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 21
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 21
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 20
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 claims abstract description 3
- 150000003852 triazoles Chemical class 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- -1 benzothiazole compound Chemical class 0.000 claims description 18
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 17
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- PCHBMNCFKJKQPA-UHFFFAOYSA-N 5-chlorothiophen-2-amine Chemical compound NC1=CC=C(Cl)S1 PCHBMNCFKJKQPA-UHFFFAOYSA-N 0.000 claims description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- IDXCVQOKCGDSOR-UHFFFAOYSA-N 1-butylbenzotriazole Chemical compound C1=CC=C2N(CCCC)N=NC2=C1 IDXCVQOKCGDSOR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 abstract description 27
- 241000195493 Cryptophyta Species 0.000 abstract description 13
- 230000001954 sterilising effect Effects 0.000 abstract description 12
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 8
- 239000011574 phosphorus Substances 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001580 bacterial effect Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 150000003751 zinc Chemical class 0.000 abstract description 5
- 230000005791 algae growth Effects 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 description 1
- WHCCOSVDXKJRKC-UHFFFAOYSA-N 4-(chloromethyl)-2h-benzotriazole Chemical group ClCC1=CC=CC2=C1N=NN2 WHCCOSVDXKJRKC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 1
- LGSSPYUWAYUJNF-UHFFFAOYSA-N Cl.CC1=CC=CC2=C1N=NN2 Chemical compound Cl.CC1=CC=CC2=C1N=NN2 LGSSPYUWAYUJNF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000295146 Gallionellaceae Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920001529 polyepoxysuccinic acid Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
-
- 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
- C02F5/125—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 combined with inorganic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (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)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention belongs to the technical field of water treatment agents, and particularly relates to a composite scale and corrosion inhibitor, and a preparation method and application thereof. The composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 20-30 parts of polyaspartic acid; 10-15 parts of modified polyacrylamide; 1-5 parts of inorganic metal salt; 5-10 parts of sodium gluconate; 2-4 parts of triazole derivatives; 1-3 parts of quaternary ammonium salt dispersing agent; the composite scale and corrosion inhibitor does not contain phosphorus and zinc salt components, is environment-friendly, has good scale and corrosion inhibition performance, has multiple sterilization and algae removal effects, can effectively prevent the problems of bacterial corrosion and bacterial algae growth of a circulating water system, has small addition amount, has good scale, corrosion inhibition and sterilization and algae removal effects, and can better meet market demands.
Description
Technical Field
The invention belongs to the technical field of water treatment agents, and particularly relates to a composite scale and corrosion inhibitor, and a preparation method and application thereof.
Background
The industrial circulating cooling water accounts for 60-80% of the industrial water, and usually contains particles, organic matters and scaling ions, salt is crystallized and precipitated due to evaporation of water, sediment forms scale on the surfaces of equipment and pipelines to cause scale corrosion, so that the pipelines are completely and partially blocked and damaged, the heat transfer efficiency of the equipment is reduced, potential safety hazards exist, and in order to relieve the shortage of water resources, the aim of saving the industrial water is fulfilled, the recycling rate of the circulating cooling water is improved as much as possible, and meanwhile, pollution discharge is reduced.
The scale and corrosion inhibitor is generally added into the circulating water to reduce the generation of scale, further slow down the corrosion to equipment and ensure the safe operation of the equipment; some phosphorus-containing scale and corrosion inhibitors emit, degrade and release inorganic phosphorus which can cause eutrophication of surrounding water areas, promote the growth of bacteria and algae to form red tide, bring great harm to aquaculture and natural ecology, and in order to prevent secondary pollution to the environment, environment-friendly low-phosphorus or phosphorus-free scale and corrosion inhibitors are attracting more attention; the patent with application number 202011023892.9 discloses a low-temperature scale and corrosion inhibitor and a scale and corrosion inhibition method of circulating cooling water, wherein the low-temperature scale and corrosion inhibitor comprises a condensation reaction product of gluconate and triethanolamine, polyamino polyether methylene phosphoric acid, a sulfonic acid group-containing copolymer and zinc salt and optionally heterocyclic compounds, and can pertinently perform scale and corrosion inhibition treatment on closed low-temperature water, especially closed low-temperature water with groundwater as supplementing water and the temperature between 5 ℃ and 8 ℃, and has excellent scale and corrosion inhibition effect; the patent with application number 20201101101709.X discloses a low-phosphorus scale and corrosion inhibitor and a preparation method thereof, wherein the scale and corrosion inhibitor comprises the following raw materials in parts by weight: 10-20 parts of polyepoxysuccinic acid, 5-10 parts of 2-hydroxyphosphonoacetic acid, 3-8 parts of water-soluble zinc salt, 5-10 parts of sodium gluconate, 20-30 parts of multipolymer and 20-60 parts of water, and the scale and corrosion inhibitor obtained by compounding has the characteristics of excellent corrosion inhibition performance and small quantity and high efficiency.
Although the scale and corrosion inhibitor achieves good corrosion inhibition effect, the components of the scale and corrosion inhibitor contain phosphorus components, and certain pollution to the environment can be caused after the components are discharged and degraded, so that the development of the phosphorus-free and small-amount efficient scale and corrosion inhibitor has important significance.
Disclosure of Invention
In order to solve the problems, the invention provides the composite scale and corrosion inhibitor, and the preparation method and application thereof, wherein the composite scale and corrosion inhibitor does not contain phosphorus and zinc salt components, is environment-friendly, has good scale and corrosion inhibition performance, has multiple sterilization and algae removal effects, can effectively prevent the problems of bacterial corrosion and bacterial algae growth of a circulating water system, has small addition amount, has good scale, corrosion inhibition and algae removal effects, and can better meet market demands.
The technical scheme for solving the problems is as follows:
the composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 20-30 parts of polyaspartic acid; 10-15 parts of modified polyacrylamide; 1-5 parts of inorganic metal salt; 5-10 parts of sodium gluconate; 2-4 parts of triazole derivatives; 1-3 parts of quaternary ammonium salt dispersing agent;
further, the inorganic metal salt is any one or a mixture of several of sodium molybdate, potassium molybdate, ammonium molybdate, sodium tungstate, potassium tungstate and ammonium tungstate; the triazole derivative is any one or a mixture of more of benzotriazole, methylbenzotriazole, chlorinated methylbenzotriazole and 1-n-butylbenzotriazole.
Further, the preparation method of the quaternary ammonium salt dispersing agent comprises the following steps:
(1) Adding 2-amino-5-chlorothiophene, lactic acid and a catalyst into N, N-dimethylformamide, heating to 100-110 ℃ under the protection of nitrogen, and reacting for 4-6 hours to obtain a benzothiazole compound with the structural formula:
the molar ratio of the 2-amino-5-chlorothiophene to the lactic acid to the catalyst is 1:1.1-1.2:0.05-0.1; the catalyst is zinc chloride and anhydrous copper sulfate with a molar ratio of 1:1;
(2) Adding benzothiazole compound and dodecyl dimethyl tertiary amine into dioxane, placing the mixture in a microwave reactor, and carrying out reflux reaction for 2-3h to obtain a quaternary ammonium salt dispersing agent, wherein the structural formula is as follows:
the molar ratio of the benzothiazole compound to the dodecyl dimethyl tertiary amine is 1:1.1-1.2.
Further, the preparation method of the modified polyacrylamide comprises the following steps:
s1, adding a quaternary ammonium salt dispersing agent and pyridine into anhydrous tetrahydrofuran, slowly dropwise adding thionyl chloride, and reacting at room temperature for 1-2 hours after the completion of the dropwise adding to obtain a modifier, wherein the structural formula is as follows:
the molar ratio of the quaternary ammonium salt dispersing agent to the thionyl chloride to the pyridine is 1:1.1-1.2:1.5-2.0;
s2, adding polyacrylamide, a modifier and N, N-diisopropylethylamine into ethylene glycol, heating to 60-70 ℃, and reacting for 4-6 hours to obtain the modified polyacrylamide, wherein the mass ratio of the polyacrylamide to the modifier to the N, N-diisopropylethylamine is 1:0.1-0.2:0.3-0.4.
The invention provides a preparation method of a composite scale and corrosion inhibitor, which comprises the following steps: adding polyaspartic acid, modified polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and quaternary ammonium salt dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the modified polyacrylamide.
The invention provides application of the composite scale and corrosion inhibitor in industrial circulating water treatment, wherein the addition amount of the composite scale and corrosion inhibitor is 20-100mg/L.
The invention has the following beneficial effects:
the invention takes 2-amino-5-chlorothiophene as raw material, and reacts with lactic acid and dodecyl dimethyl tertiary amine in sequence to obtain the quaternary ammonium salt dispersing agent, the structure of the prepared quaternary ammonium salt dispersing agent contains hydroxyl, long-chain quaternary ammonium salt group and benzothiazole group, the quaternary ammonium salt dispersing agent has good surface activity and dispersing effect, and has double antibacterial effect, and the quaternary ammonium salt dispersing agent is added into the composite scale and corrosion inhibitor, so that the raw materials are fully and uniformly dispersed, the full play of the effect is facilitated, and the scale and corrosion inhibition performance and the sterilization and algae removal performance of the composite scale and corrosion inhibitor are improved; meanwhile, the modified polyacrylamide is obtained by modifying the polyacrylamide, wherein the modified polyacrylamide is grafted with a modifier containing long-chain quaternary ammonium salt groups and benzothiazole groups on the surface, so that the chelating capacity, dispersibility and antibacterial performance of the modified polyacrylamide to ions are improved, and the modified polyacrylamide is added into the composite scale and corrosion inhibitor to act synergistically with the quaternary ammonium salt dispersing agent, so that the scale and corrosion inhibition performance and the sterilization and algae removal performance of the composite scale and corrosion inhibitor are further improved.
The composite scale and corrosion inhibitor provided by the invention does not contain phosphorus and zinc salt components, is environment-friendly, has good scale and corrosion inhibition performance, has multiple sterilization and algae removal effects, can effectively prevent the problems of bacterial corrosion and bacterial algae growth of a circulating water system, has small addition amount, has good scale, corrosion inhibition and sterilization algae removal effects, and can more meet market demands.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
The raw materials used in the following examples are all common commercial products. Wherein, the polyaspartic acid CAS number is 25608-40-6; sodium gluconate CAS number 527-07-1; sodium molybdate CAS number 7631-95-0; potassium molybdate CAS number 13446-49-6; sodium tungstate CAS No. 13472-45-2; potassium tungstate CAS No. 7790-60-5; benzotriazole CAS number 95-14-7; methylbenzotriazole CAS number 29385-43-1; methyl benzotriazol chloride CAS number 202420-04-0; 1-n-butylbenzotriazole CAS number 708-43-0; polyacrylamide CAS number 9003-05-8 (molecular weight 200 ten thousand); 2-amino-5-chlorothiophene CAS No. 23474-98-8; lactic acid CAS number 50-21-5; zinc chloride CAS No. 7646-85-7; anhydrous copper sulfate CAS number 7758-98-7; dodecyl dimethyl tertiary amine CAS number 112-18-5; thionyl chloride CAS number 7719-09-7; pyridine CAS number 110-86-1; n, N-diisopropylethylamine CAS number 7087-68-5; ethylene glycol CAS number 107-21-1; tetrahydrofuran CAS number 109-99-9; dioxane CAS No. 123-91-1; n, N-dimethylformamide CAS number 68-12-2; dichloromethane CAS number 75-09-2; acetone CAS number 67-64-1.
Example 1
A composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 30 parts of polyaspartic acid; 15 parts of modified polyacrylamide; 5 parts of inorganic metal salt; 10 parts of sodium gluconate; 4 parts of triazole derivative; 3 parts of quaternary ammonium salt dispersing agent; wherein the inorganic metal salt is sodium molybdate, and the triazole derivative is benzotriazole.
A preparation method of a composite scale and corrosion inhibitor comprises the following steps: adding polyaspartic acid, modified polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and quaternary ammonium salt dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the modified polyacrylamide.
The preparation method of the quaternary ammonium salt dispersing agent comprises the following steps:
(1) 16.0g of 2-amino-5-chlorothiophene, 9.9g of lactic acid and a catalyst (0.7 g of zinc chloride and 0.8g of anhydrous copper sulfate) are added into 500mL of N, N-dimethylformamide, the temperature is raised to 110 ℃ under the protection of nitrogen, the reaction is carried out for 5 hours, after the reaction is finished, insoluble substances are filtered and removed, 500mL of water and 1000mL of methylene dichloride are added into filtrate for extraction, an organic phase is collected, and 18.3g of benzothiazole compound is obtained after drying and decompression concentration; the molar ratio of the 2-amino-5-chlorothiophene to the lactic acid to the catalyst is 1:1.1:0.1; the catalyst is zinc chloride and anhydrous copper sulfate with a molar ratio of 1:1; the reaction process is as follows:
benzothiazole compounds: ESI (m/z): 214.0[ M+H ]] + ， 1 H-NMR(600MHz，DMSO-d 6 ，δppm)：8.13(s，1H)，7.60(d，J＝8.6Hz，1H)，7.56(d，J＝8.6Hz，1H)，5.17(s，1H)，4.95-4.98(m，1H)，1.49(d，J＝7.5Hz，3H)。
(2) 15.0g of benzothiazole compound and 16.5g of dodecyl dimethyl tertiary amine are added into 350mL of dioxane, the mixture is placed in a microwave reactor for reflux reaction for 3h, after the reaction is finished, the dioxane is removed by reduced pressure distillation, 400mL of water and 400mL of dichloromethane are used for extraction, and the aqueous phase is concentrated under reduced pressure to obtain 24.6g of quaternary ammonium salt dispersing agent; the molar ratio of the benzothiazole compound to the dodecyl dimethyl tertiary amine is 1:1.1, and the reaction process is as follows:
quaternary ammonium salt dispersant: ESI (m/z): 427.2[ M+H ]] + ， 1 H-NMR(600MHz，DMSO-d 6 ，δppm)：7.86(s，1H)，7.66(d，J＝8.6Hz，1H)，7.29(d，J＝8.6Hz，1H)，5.20(s，1H)，4.95-4.98(m，1H)，3.72(s，6H)，3.20-3.22(m，2H)，1.54-1.57(m，5H)，1.26-1.29(m，18H)，0.88(t，J＝6.8Hz，3H)。
The preparation method of the modified polyacrylamide comprises the following steps:
s1, adding 10.0g of quaternary ammonium salt dispersing agent and 2.8g of pyridine into 150mL of anhydrous tetrahydrofuran, slowly dropwise adding 3.1g of thionyl chloride, reacting for 2 hours at room temperature after the completion of the dropwise addition, removing the anhydrous tetrahydrofuran, extracting with 100mL of water and 100mL of dichloromethane, and concentrating the water phase under reduced pressure to obtain 9.5g of modifier, wherein the molar ratio of the quaternary ammonium salt dispersing agent to the thionyl chloride to the pyridine is 1:1.1:1.5; the reaction process is as follows:
and (3) a modifier: ESI (m/z): 445.2[ M+H ]] + ， 1 H-NMR(600MHz，DMSO-d 6 ，δppm)：7.86(s，1H)，7.66(d，J＝8.6Hz，1H)，7.29(d，J＝8.6Hz，1H)，4.86-4.88(m，1H)，3.72(s，6H)，3.22-3.23(m，2H)，1.78-1.80(m，5H)，1.26-1.29(m，18H)，0.88(t，J＝6.8Hz，3H)。
S2, adding polyacrylamide, a modifier and N, N-diisopropylethylamine into ethylene glycol, heating to 70 ℃, reacting for 6 hours, naturally cooling to room temperature after the reaction is finished, precipitating and purifying by using acetone (the same volume as the ethylene glycol), and drying the precipitate in a vacuum drying oven at 45 ℃ for 10 hours to obtain modified polyacrylamide, wherein the substitution degree of the modifier is 26.5% measured by an elemental analysis method; the prepared modified polyacrylamide has fluorescence absorption under an ultraviolet lamp (254 nm); wherein the mass ratio of the polyacrylamide to the modifier to the N, N-diisopropylethylamine is 1:0.2:0.4; the mass ratio of the polyacrylamide to the glycol is 1:15; the reaction process is as follows:
example 2
A composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 20 parts of polyaspartic acid; 10 parts of modified polyacrylamide; 1 part of inorganic metal salt; 5 parts of sodium gluconate; 2 parts of triazole derivative; 1 part of quaternary ammonium salt dispersing agent; wherein the inorganic metal salt is sodium tungstate, and the triazole derivative is methylbenzotriazole.
A preparation method of a composite scale and corrosion inhibitor comprises the following steps: adding polyaspartic acid, modified polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and quaternary ammonium salt dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the modified polyacrylamide.
The preparation method of the quaternary ammonium salt dispersing agent and the modified polyacrylamide is the same as that of the example 1.
Example 3
A composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 25 parts of polyaspartic acid; 13 parts of modified polyacrylamide; 3 parts of inorganic metal salt; 8 parts of sodium gluconate; 3 parts of triazole derivative; 2 parts of quaternary ammonium salt dispersing agent; wherein the inorganic metal salt is potassium molybdate, and the triazole derivative is chloromethyl benzotriazol.
A preparation method of a composite scale and corrosion inhibitor comprises the following steps: adding polyaspartic acid, modified polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and quaternary ammonium salt dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the modified polyacrylamide.
The preparation method of the quaternary ammonium salt dispersing agent and the modified polyacrylamide is the same as that of the example 1.
Example 4
A composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 30 parts of polyaspartic acid; 10 parts of modified polyacrylamide; 5 parts of inorganic metal salt; 5 parts of sodium gluconate; 2 parts of triazole derivative; 2 parts of quaternary ammonium salt dispersing agent; wherein the inorganic metal salt is potassium tungstate, and the triazole derivative is 1-n-butyl benzotriazole;
a preparation method of a composite scale and corrosion inhibitor comprises the following steps: adding polyaspartic acid, modified polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and quaternary ammonium salt dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the modified polyacrylamide.
The preparation method of the quaternary ammonium salt dispersing agent and the modified polyacrylamide is the same as that of the example 1.
Comparative example 1
A composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 30 parts of polyaspartic acid; 15 parts of polyacrylamide; 5 parts of inorganic metal salt; 10 parts of sodium gluconate; 4 parts of triazole derivative; 3 parts of quaternary ammonium salt dispersing agent; wherein the inorganic metal salt is sodium molybdate, and the triazole derivative is benzotriazole.
A preparation method of a composite scale and corrosion inhibitor comprises the following steps: adding polyaspartic acid, polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and quaternary ammonium salt dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the finished product.
Wherein the preparation method of the quaternary ammonium salt dispersing agent is the same as that of the example 1.
Comparative example 2
A composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 30 parts of polyaspartic acid; 15 parts of modified polyacrylamide; 5 parts of inorganic metal salt; 10 parts of sodium gluconate; 4 parts of triazole derivative; 3 parts of dispersing agent; wherein the inorganic metal salt is sodium molybdate, and the triazole derivative is benzotriazole; the dispersing agent is sodium dodecyl benzene sulfonate.
A preparation method of a composite scale and corrosion inhibitor comprises the following steps: adding polyaspartic acid, modified polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the finished product.
Comparative example 3
A composite scale and corrosion inhibitor comprises the following raw materials in parts by weight: 30 parts of polyaspartic acid; 15 parts of polyacrylamide; 5 parts of inorganic metal salt; 10 parts of sodium gluconate; 4 parts of triazole derivative; 3 parts of dispersing agent; wherein the inorganic metal salt is sodium molybdate, and the triazole derivative is benzotriazole; the dispersing agent is sodium dodecyl benzene sulfonate.
A preparation method of a composite scale and corrosion inhibitor comprises the following steps: adding polyaspartic acid, polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the finished product.
Correlation testing
1. Test of scale and corrosion inhibition performance of composite scale and corrosion inhibitor
The scale and corrosion inhibition performance test is carried out on the composite scale and corrosion inhibitors prepared in the examples 1-4 and the comparative examples 1-3, wherein the main indexes of the water quality of the test are 756mg/L total hardness (calculated by calcium carbonate), 522mg/L calcium hardness (calculated by calcium carbonate), pH=8.45 and 375mg/L alkalinity (calculated by calcium carbonate); the scale inhibition performance test method is carried out according to the specification of GB/T16632-2008 ' determination of the scale inhibition performance of Water treatment agent ' calcium carbonate deposition method '; the corrosion inhibition performance test method is carried out according to the specification of GB/T18175-2014 rotary hanging method for measuring corrosion inhibition performance of water treatment agent, and the corrosion inhibition performance test sheet is made of 20# carbon steel or red copper; the test results are shown in Table 1.
TABLE 1 scale and corrosion inhibition Properties of the composite Scale and corrosion inhibitor
As shown by the results in Table 1, the composite scale and corrosion inhibitors prepared in examples 1-4 have good scale and corrosion inhibition performance, and when the concentration of the composite scale and corrosion inhibitor is 60mg/L, the scale inhibition rate is over 99.5 percent, and the corrosion inhibition rate is over 98.9 percent; compared with comparative examples 1-3, the modified polyacrylamide and quaternary ammonium salt dispersing agent added in the embodiment 1 can effectively improve the scale and corrosion inhibition performance of the composite scale and corrosion inhibitor, wherein the modified polyacrylamide molecular chain is grafted with the modifying agent containing benzothiazole groups and long-chain quaternary ammonium salt groups, the benzothiazole groups can improve the chelating capacity of the modified polyacrylamide to ions, and the long-chain quaternary ammonium salt groups improve the dispersion performance of the modified polyacrylamide; the benzothiazole group and the hydroxyl long-chain quaternary ammonium salt group contained in the quaternary ammonium salt dispersing agent also have certain chelating ion function and dispersing function, so that the components can be fully mixed and dispersed uniformly, and the performances of the components can be fully exerted; the modified polyacrylamide and the quaternary ammonium salt dispersing agent can be further compounded with other components to realize synergistic effect, so that the scale and corrosion inhibition performance of the composite scale and corrosion inhibitor is improved.
2. Sterilization and algae removal performance test for composite scale and corrosion inhibitor
The composite scale and corrosion inhibitor prepared in the examples 1-4 and the comparative examples 1-3 are added into a water sample, after the water sample is contacted for a certain time at 35+/-2 ℃, the residual heterotrophic bacteria number and the residual fungi number in the water sample are measured by a plate count method according to the methods in HG/T3609-2000 and GB/T14643.5-2009, the sulfate reducing bacteria number and the iron bacteria number are measured by a dilution culture counting method (MPN method), a blank sample is simultaneously made, the sterilization rate is calculated, and the inhibition rate of the composite scale and corrosion inhibitor prepared by the invention to chlorella is measured by spectrophotometry, and the results are shown in the table 2.
Table 2 Sterilization and algae removal Properties of the composite Scale and Corrosion inhibitor
As shown in the results of Table 2, the composite scale and corrosion inhibitor prepared in the examples 1-4 has better sterilization and algae removal performance, and compared with the comparative examples 1-3, the modified polyacrylamide and the quaternary ammonium salt dispersing agent added in the example 1 both contain quaternary ammonium salt and benzothiazole groups, and the quaternary ammonium salt and benzothiazole groups have good antibacterial effect, and the modified polyacrylamide and the quaternary ammonium salt dispersing agent are compounded for use, so that the composite scale and corrosion inhibitor has multiple antibacterial effect, and the sterilization and algae removal performance of the composite scale and corrosion inhibitor can be effectively improved by adding the modified polyacrylamide and the quaternary ammonium salt dispersing agent into the composite scale and corrosion inhibitor.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The composite scale and corrosion inhibitor is characterized by comprising the following raw materials in parts by weight: 20-30 parts of polyaspartic acid; 10-15 parts of modified polyacrylamide; 1-5 parts of inorganic metal salt; 5-10 parts of sodium gluconate; 2-4 parts of triazole derivatives; 1-3 parts of quaternary ammonium salt dispersing agent; the structural formula of the quaternary ammonium salt dispersing agent is as follows:
the preparation method of the modified polyacrylamide comprises the following steps:
s1, adding a quaternary ammonium salt dispersing agent and pyridine into anhydrous tetrahydrofuran, slowly dropwise adding thionyl chloride, and reacting at room temperature for 1-2 hours after the completion of the dropwise adding to obtain a modifier, wherein the structural formula is as follows:
s2, adding polyacrylamide, a modifier and N, N-diisopropylethylamine into ethylene glycol, heating to 60-70 ℃, and reacting for 4-6h to obtain the modified polyacrylamide.
2. The composite scale and corrosion inhibitor according to claim 1, wherein the molar ratio of the quaternary ammonium salt dispersing agent, thionyl chloride and pyridine in the step S1 is 1:1.1-1.2:1.5-2.0.
3. The composite scale and corrosion inhibitor according to claim 1, wherein the mass ratio of the polyacrylamide to the modifier to the N, N-diisopropylethylamine in the step S2 is 1:0.1-0.2:0.3-0.4.
4. The composite scale and corrosion inhibitor according to claim 1, wherein the preparation method of the quaternary ammonium salt dispersing agent is as follows:
(1) Adding 2-amino-5-chlorothiophene, lactic acid and a catalyst into N, N-dimethylformamide, heating to 100-110 ℃ under the protection of nitrogen, and reacting for 4-6 hours to obtain a benzothiazole compound with the structural formula:
(2) Adding benzothiazole compound and dodecyl dimethyl tertiary amine into dioxane, placing the mixture in a microwave reactor, and carrying out reflux reaction for 2-3h to obtain the quaternary ammonium salt dispersing agent.
5. The compound scale and corrosion inhibitor according to claim 4, wherein the molar ratio of the 2-amino-5-chlorothiophene, the lactic acid and the catalyst in the step (1) is 1:1.1-1.2:0.05-0.1; the catalyst is zinc chloride and anhydrous copper sulfate in a molar ratio of 1:1.
6. The composite scale and corrosion inhibitor according to claim 4, wherein the molar ratio of the benzothiazole compound to the dodecyl dimethyl tertiary amine in the step (2) is 1:1.1-1.2.
7. The composite scale and corrosion inhibitor according to claim 1, wherein the inorganic metal salt is any one or a mixture of sodium molybdate, potassium molybdate, ammonium molybdate, sodium tungstate, potassium tungstate and ammonium tungstate.
8. The compound scale and corrosion inhibitor according to claim 1, wherein the triazole derivative is any one or a mixture of a plurality of benzotriazole, methylbenzotriazole, chlorinated methylbenzotriazole and 1-n-butylbenzotriazole.
9. The method for preparing the composite scale and corrosion inhibitor according to any one of claims 1 to 8, comprising the steps of: adding polyaspartic acid, modified polyacrylamide, inorganic metal salt, sodium gluconate, triazole derivative and quaternary ammonium salt dispersing agent into a stirrer according to the weight ratio, and uniformly mixing to obtain the modified polyacrylamide.
10. The use of the composite scale and corrosion inhibitor according to any one of claims 1 to 8 in industrial circulating water treatment, wherein the addition amount of the composite scale and corrosion inhibitor is 20 to 100mg/L.
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