CN113200617A - Degradable non-phosphorus scale and corrosion inhibitor and preparation method thereof - Google Patents
Degradable non-phosphorus scale and corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN113200617A CN113200617A CN202110545775.7A CN202110545775A CN113200617A CN 113200617 A CN113200617 A CN 113200617A CN 202110545775 A CN202110545775 A CN 202110545775A CN 113200617 A CN113200617 A CN 113200617A
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- deionized water
- phosphorus
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- 230000007797 corrosion Effects 0.000 title claims abstract description 85
- 238000005260 corrosion Methods 0.000 title claims abstract description 85
- 239000003112 inhibitor Substances 0.000 title claims abstract description 63
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 26
- 239000011574 phosphorus Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 49
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 45
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 45
- 239000000230 xanthan gum Substances 0.000 claims abstract description 44
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 44
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 44
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 44
- 239000000017 hydrogel Substances 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 27
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 27
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 10
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 239000008367 deionised water Substances 0.000 claims description 68
- 229910021641 deionized water Inorganic materials 0.000 claims description 68
- 239000011259 mixed solution Substances 0.000 claims description 56
- 238000010438 heat treatment Methods 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 15
- 235000011152 sodium sulphate Nutrition 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000007605 air drying Methods 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 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
- 238000005406 washing Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000002455 scale inhibitor Substances 0.000 abstract description 15
- 239000007787 solid Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 description 25
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 17
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 description 14
- 229920001529 polyepoxysuccinic acid Polymers 0.000 description 9
- 239000001506 calcium phosphate Substances 0.000 description 8
- 229910000389 calcium phosphate Inorganic materials 0.000 description 8
- 235000011010 calcium phosphates Nutrition 0.000 description 8
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229960001484 edetic acid Drugs 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- -1 alkaline earth metal cations Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 229920005605 branched copolymer Polymers 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process 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
- 239000003292 glue Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 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
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)
- Compositions Of Macromolecular Compounds (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention discloses a degradable non-phosphorus scale and corrosion inhibitor, which comprises the following raw materials in parts by weight: 15-20 parts of modified epoxy succinic acid-sodium p-styrenesulfonate copolymer, 25-30 parts of polyvinyl alcohol/xanthan gum composite hydrogel, 0.5-1 part of graphene oxide, 10-15 parts of zinc sulfate and 1-2 parts of sodium molybdate; the invention also discloses a preparation method of the phosphorus-free scale and corrosion inhibitor. The invention selects the modified epoxysuccinic acid-sodium p-styrenesulfonate copolymer and zinc sulfate as the scale inhibitor and the corrosion inhibitor respectively, compounds the scale inhibitor and the corrosion inhibitor according to a proper compatibility ratio, and loads the scale inhibitor and the corrosion inhibitor on the polyvinyl alcohol/xanthan gum composite hydrogel to form the solid scale and corrosion inhibitor with higher density.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a degradable non-phosphorus scale and corrosion inhibitor and a preparation method thereof.
Background
In a circulating cooling water system in industrial production, alkaline earth metal cations and a small amount of other cations contained in water can generate insoluble inorganic salts such as Ca with anions in water due to the influence of factors such as evaporation of water, change of pH value, rise of temperature, change of water flow speed, impurities in water, pressure of the system and the like in the using process3(PO4)2、CaCO3、CaSO4、Mg(OH)2Etc. deposited on the surfaces of pipes and heat exchangers to cause the heat transfer efficiency of the heat exchangers to be lowered and to cause corrosion under the scale, so that the use of scale and corrosion inhibitors for inhibiting the formation of scales and preventing the corrosion of metals is to maintain the cooling water circulation systemOne of the key technologies for good operation of the system is also an effective means for controlling scale formation and preventing metal corrosion in the treatment of industrial water and wastewater, common scale and corrosion inhibitors are organic phosphines, plant-extracted high molecules, polyaspartic acids and polyepoxysuccinic acids, phosphorus in the organic phosphorus scale inhibitor is a nutrient source for bacteria and algae, and the phosphorus-containing scale inhibitor is easy to cause eutrophication of environmental water areas and promotes the growth of bacteria and algae to form red tide to cause water source pollution.
The polyepoxysuccinic acid is one of the existing environmentally-friendly scale inhibitors, can be biodegraded, does not contain elements such as nitrogen, phosphorus and potassium to enrich water, has a good inhibition effect on inorganic calcium scales such as calcium carbonate and calcium sulfate, has a certain slow release performance on carbon steel, is a multifunctional scale inhibitor, and has the defects at the same time, because the polyepoxysuccinic acid mainly contains carboxyl functional groups in the molecular structure, the polyepoxysuccinic acid has an insignificant effect on the aspects of calcium phosphate scale inhibition, calcium silicate scale inhibition, magnesium silicate scale inhibition and the like and has poor zinc salt stabilization and iron oxide dispersion capacities due to single functional groups, so that the functional groups of the polyepoxysuccinic acid are enriched, and the polyepoxysuccinic acid scale inhibitor has potential significance for compensating the functionality of the polyepoxysuccinic acid scale inhibitor; in addition, the scale and corrosion inhibitor in a liquid state flows away with water or is attached to the pipe wall near the dosing point, and can only play a role in scale and corrosion inhibition in a limited range, so that the overall scale and corrosion inhibition effect is not ideal, and therefore, changing the use state of the scale and corrosion inhibitor is also one of means for improving the performance of the scale and corrosion inhibitor.
Disclosure of Invention
The invention aims to provide a degradable phosphorus-free scale and corrosion inhibitor and a preparation method thereof, wherein a modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and zinc sulfate are respectively selected as a scale inhibitor and a corrosion inhibitor, are compounded according to a proper compatibility ratio, and are loaded on polyvinyl alcohol/xanthan gum composite hydrogel to form a solid scale and corrosion inhibitor with higher density.
The purpose of the invention can be realized by the following technical scheme:
a degradable non-phosphorus scale and corrosion inhibitor comprises the following raw materials in parts by weight:
15-20 parts of modified epoxy succinic acid-sodium p-styrenesulfonate copolymer, 25-30 parts of polyvinyl alcohol/xanthan gum composite hydrogel, 0.5-1 part of graphene oxide, 10-15 parts of zinc sulfate and 1-2 parts of sodium molybdate;
the degradable non-phosphorus scale and corrosion inhibitor is prepared by the following steps:
step A1, soaking the polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 12-16 hours, and then heating and stirring at 80-85 ℃ and 230-;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 30-40 minutes at the frequency of 80-100kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 70-80 ℃ and at the speed of 250-300rpm for 4-5 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a drying box at 70-80 ℃ for drying for 24-48 hours, demolding, air drying and molding to obtain the phosphorus-free degradable scale and corrosion inhibitor.
Further, the amount of the deionized water in the step A1 is 2.8-3 times of the mass of the polyvinyl alcohol/xanthan gum composite hydrogel.
Further, the amount of the deionized water in the step A2 is 0.8-1 time of the total mass of the sodium sulfate and the sodium molybdate.
Further, the modified epoxy succinic acid-sodium p-styrene sulfonate copolymer is prepared by the following steps:
step S1, adding maleic anhydride and deionized water into a three-neck flask, dropwise adding a sodium hydroxide solution after the maleic anhydride is dissolved to prepare an intermediate 1, then heating to 50-60 ℃, adding a composite catalyst, dropwise adding a hydrogen peroxide solution, and reacting at constant temperature for 2-3 hours after the dropwise adding is finished to prepare an intermediate 2;
the reaction process is as follows:
step S2, adding calcium hydroxide into the intermediate 2 prepared in the step S1, heating to 80-90 ℃, reacting for 3-3.5 hours, washing the product with absolute ethyl alcohol for 2-3 times, and drying in an oven at 40-45 ℃ for 3-4 hours to obtain an intermediate 3;
the reaction process is as follows:
and step S3, adding deionized water into the intermediate 3 prepared in the step S2 to dissolve the intermediate, adding glycol amine and sodium p-styrene sulfonate, heating to 80-90 ℃, adding an initiator, and reacting at constant temperature for 2-3 hours to obtain the modified epoxy succinic acid-sodium p-styrene sulfonate copolymer.
The reaction process is as follows:
further, the dosage of the maleic anhydride, the deionized water, the sodium hydroxide solution, the composite catalyst and the hydrogen peroxide solution in the step S1 is 9.2-10 g: 12.5-15 mL: 6-7 g: 0.4-0.5 g: 8-10mL, 50% of sodium hydroxide solution by mass, 30% of hydrogen peroxide solution by mass, and the composite catalyst is prepared by mixing sodium tungstate and sodium molybdate in a mass ratio of 1: 1.
Further, the amount of calcium hydroxide used in step S2 is 0.7-0.9 g.
Further, the mass ratio of the intermediate 3, the glycol amine and the sodium p-styrene sulfonate in the step S3 is 10:7:4, the amount of deionized water is 2-3 times of the mass of the intermediate 3, the initiator is one of sodium persulfate, potassium persulfate and sodium metabisulfite, and the amount of the initiator is 10-20% of the mass of the intermediate 3.
Further, the polyvinyl alcohol/xanthan gum composite hydrogel is prepared by the following steps:
step C1, adding polyvinyl alcohol, xanthan gum and sodium hydroxide into a three-neck flask, adding deionized water, heating and stirring at 90-95 ℃ and 200-;
and step C2, soaking the mixture prepared in the step C1 in deionized water to be neutral, and then placing the mixture in a drying oven at 50-55 ℃ to be dried to constant weight to prepare the polyvinyl alcohol/xanthan gum composite hydrogel.
Further, the dosage ratio of the polyvinyl alcohol, the xanthan gum, the sodium hydroxide and the deionized water in the step C1 is 20-30 g: 4-6 g: 0.2-0.5 g: 150-200mL, the cross-linking agent is epichlorohydrin, and the dosage of the cross-linking agent is 0.5-1 mL.
A preparation method of a degradable non-phosphorus scale and corrosion inhibitor comprises the following preparation steps:
step A1, soaking the polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 12-16 hours, and then heating and stirring at 80-85 ℃ and 230-;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 30-40 minutes at the frequency of 80-100kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 70-80 ℃ and at the speed of 250-300rpm for 4-5 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a drying box at 70-80 ℃ for drying for 24-48 hours, demolding, air drying and molding to obtain the phosphorus-free degradable scale and corrosion inhibitor.
The invention has the beneficial effects that: the invention aims to provide a degradable phosphorus-free scale and corrosion inhibitor and a preparation method thereof, wherein a modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and zinc sulfate are respectively selected as a scale inhibitor and a corrosion inhibitor, are compounded according to a proper compatibility ratio, and are loaded on polyvinyl alcohol/xanthan gum composite hydrogel to form a solid scale and corrosion inhibitor with higher density, compared with a liquid scale and corrosion inhibitor, the effective components of the solid scale and corrosion inhibitor can be slowly released in a carrier, so that the solid scale and corrosion inhibitor has excellent and continuous scale inhibition performance and corrosion inhibition performance, and biodegradable epoxy succinic acid and polyvinyl alcohol are adopted, so that the material has degradable, green and environment-friendly properties; compared with epoxy succinic acid with single function, the epoxy succinic acid is modified, the epoxy succinic acid only has carboxyl functional groups, so that the epoxy succinic acid has poor effects on calcium phosphate scale, calcium sulfate scale and the like, the sulfonic group belongs to a hydrophilic group, is stronger in acidity than carboxylic acid, has better descaling performance on calcium sulfate and calcium phosphate, has good dispersing performance on iron salt and slime, can stabilize metal ions, has lasting drug potency and is not easy to glue, so that the epoxy succinic acid and sodium styrene sulfonate carrying sulfonic acid groups are combined together by a polymer copolymerization method to synthesize a copolymer with two functional groups of strong acid sulfonic acid group and weak acid carboxylic acid group, the advantages are complementary to exert the advantages of the polyepoxysuccinic acid salt and the sulfonic acid salt, the defects are avoided, the multi-scale inhibition performance of the polyepoxysuccinic acid salt is improved, in addition, amide-CONH-is generated by the amino dehydration reaction of the carboxylic acid group of the epoxy succinic acid and glycol amine, and introduce the polyhydroxy, make the multi-branched copolymer containing amide and hydroxy group, have better scale inhibition performance to the calcium phosphate, -COOH has better scale inhibition performance to the calcium carbonate, make the antisludging agent have high-efficient scale inhibition performance, in addition, zinc sulfate is the corrosion inhibitor of cathode type, zinc ion can form zinc hydroxide deposit on the surface of cathode rapidly in water, play a role of protective film, it can accelerate the film forming speed of the corrosion inhibitor with sodium molybdate to compound and use, play a role in inhibiting corrosion and increasing efficiency and preventing producing the cavitation, can keep the durability of the formed film, have excellent slow release effects, through inhibiting calcium phosphate/calcium sulfate and measuring and degrading the rate of the performance measurement, inhibition performance of calcium sulfate, prove that the non-phosphorus antisludging corrosion inhibitor prepared in this invention has excellent calcium phosphate inhibiting, calcium sulfate antisludging effects, and compare with the comparative example, have lower corrosion rate and higher inhibition efficiency, in addition, the degradation rate of 30 days is as high as about 92%, and the biodegradable polyester film has biodegradability, green environmental protection performance and certain application value.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A degradable non-phosphorus scale and corrosion inhibitor comprises the following raw materials in parts by weight: 15 parts of modified epoxy succinic acid-sodium p-styrenesulfonate copolymer, 25 parts of polyvinyl alcohol/xanthan gum composite hydrogel, 0.5 part of graphene oxide, 10 parts of zinc sulfate and 1 part of sodium molybdate;
the degradable non-phosphorus scale and corrosion inhibitor is prepared by the following steps:
step A1, soaking polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 12 hours, and then heating and stirring at 80 ℃ and 230rpm for 2 hours to prepare a mixed solution a;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 30 minutes at the frequency of 80kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 70 ℃ and 250rpm for 4 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a 70 ℃ drying oven for drying for 24 hours, demolding, air-drying and molding to obtain the degradable phosphorus-free scale and corrosion inhibitor.
Wherein the dosage of the deionized water in the step A1 is 2.8 times of the mass of the polyvinyl alcohol/xanthan gum composite hydrogel.
Wherein the dosage of the deionized water in the step A2 is 0.8 time of the total mass of the sodium sulfate and the sodium molybdate.
Wherein, the modified epoxy succinic acid-sodium p-styrene sulfonate copolymer is prepared by the following steps:
step S1, adding maleic anhydride and deionized water into a three-neck flask, dropwise adding a sodium hydroxide solution after the maleic anhydride is dissolved to prepare an intermediate 1, then heating to 50 ℃, adding a composite catalyst, dropwise adding a hydrogen peroxide solution, and reacting at constant temperature for 2 hours after the dropwise adding is finished to prepare an intermediate 2;
step S2, adding calcium hydroxide into the intermediate 2 prepared in the step S1, heating to 80 ℃, reacting for 3 hours, washing the product for 2 times by using absolute ethyl alcohol, and then drying in an oven at 40 ℃ for 3 hours to obtain an intermediate 3;
and step S3, adding deionized water into the intermediate 3 prepared in the step S2 to dissolve the intermediate, adding glycol amine and sodium p-styrene sulfonate, heating to 80 ℃, adding an initiator, and reacting at constant temperature for 2 hours to obtain the modified epoxysuccinic acid-sodium p-styrene sulfonate copolymer.
Wherein the dosage of the maleic anhydride, the deionized water, the sodium hydroxide solution, the composite catalyst and the hydrogen peroxide solution in the step S1 is 9.2 g: 12.5 mL: 6 g: 0.4 g: 8mL, 50 percent of sodium hydroxide solution by mass, 30 percent of hydrogen peroxide solution by mass, and the composite catalyst is prepared by mixing sodium tungstate and sodium molybdate in a mass ratio of 1: 1.
Wherein the dosage of the calcium hydroxide in the step S2 is 0.7 g.
Wherein the mass ratio of the intermediate 3, the glycol amine and the sodium p-styrene sulfonate in the step S3 is 10:7:4, the use amount of the deionized water is 2 times of the mass of the intermediate 3, the initiator is sodium persulfate, and the use amount of the initiator is 10% of the mass of the intermediate 3.
The polyvinyl alcohol/xanthan gum composite hydrogel is prepared by the following steps:
step C1, adding polyvinyl alcohol, xanthan gum and sodium hydroxide into a three-neck flask, adding deionized water, heating and stirring at 90 ℃ and 200rpm until the deionized water is dissolved, adding a cross-linking agent, and standing at room temperature for 2 days to obtain a mixture;
and step C2, soaking the mixture prepared in the step C1 in deionized water to be neutral, and then placing the mixture in a drying oven at 50 ℃ to be dried to be constant in weight to prepare the polyvinyl alcohol/xanthan gum composite hydrogel.
Wherein the dosage ratio of the polyvinyl alcohol, the xanthan gum, the sodium hydroxide and the deionized water in the step C1 is 20 g: 4 g: 0.2 g: 150mL, the crosslinking agent is epichlorohydrin, and the dosage of the crosslinking agent is 0.5 mL.
A preparation method of a degradable non-phosphorus scale and corrosion inhibitor comprises the following preparation steps:
step A1, soaking polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 12 hours, and then heating and stirring at 80 ℃ and 230rpm for 2 hours to prepare a mixed solution a;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 30 minutes at the frequency of 80kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 70 ℃ and 250rpm for 4 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a 70 ℃ drying oven for drying for 24 hours, demolding, air-drying and molding to obtain the degradable phosphorus-free scale and corrosion inhibitor.
Example 2
A degradable non-phosphorus scale and corrosion inhibitor comprises the following raw materials in parts by weight: 17 parts of modified epoxy succinic acid-sodium p-styrenesulfonate copolymer, 27 parts of polyvinyl alcohol/xanthan gum composite hydrogel, 0.7 part of graphene oxide, 12 parts of zinc sulfate and 1.5 parts of sodium molybdate;
the degradable non-phosphorus scale and corrosion inhibitor is prepared by the following steps:
step A1, soaking the polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 12 hours, and then heating and stirring at 80 ℃ and 230rpm for 2.5 hours to prepare a mixed solution a;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 35 minutes at the frequency of 90kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 75 ℃ and 280rpm for 4.5 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a 75 ℃ drying oven for drying for 36 hours, demolding, air-drying and molding to obtain the degradable phosphorus-free scale and corrosion inhibitor.
Wherein the dosage of the deionized water in the step A1 is 2.9 times of the mass of the polyvinyl alcohol/xanthan gum composite hydrogel.
Wherein the dosage of the deionized water in the step A2 is 0.85 times of the total mass of the sodium sulfate and the sodium molybdate.
Wherein, the modified epoxy succinic acid-sodium p-styrene sulfonate copolymer is prepared by the following steps:
step S1, adding maleic anhydride and deionized water into a three-neck flask, dropwise adding a sodium hydroxide solution after the maleic anhydride is dissolved to prepare an intermediate 1, then heating to 55 ℃, adding a composite catalyst, dropwise adding a hydrogen peroxide solution, and reacting at constant temperature for 2.5 hours after the dropwise adding is finished to prepare an intermediate 2;
step S2, adding calcium hydroxide into the intermediate 2 prepared in the step S1, heating to 84 ℃, reacting for 3 hours, washing the product for 2 times by using absolute ethyl alcohol, and then drying in an oven at 42 ℃ for 3.5 hours to obtain an intermediate 3;
and step S3, adding deionized water into the intermediate 3 prepared in the step S2 to dissolve the intermediate, adding glycol amine and sodium p-styrene sulfonate, heating to 83 ℃, adding an initiator, and reacting at constant temperature for 2.5 hours to obtain the modified epoxysuccinic acid-sodium p-styrene sulfonate copolymer.
Wherein the dosage of the maleic anhydride, the deionized water, the sodium hydroxide solution, the composite catalyst and the hydrogen peroxide solution in the step S1 is 9.6 g: 13.5 mL: 6.2 g: 0.45 g: 8.5mL, 50% of sodium hydroxide solution by mass, 30% of hydrogen peroxide solution by mass, and the composite catalyst is prepared by mixing sodium tungstate and sodium molybdate in a mass ratio of 1: 1.
Wherein the dosage of the calcium hydroxide in the step S2 is 0.75g.
Wherein the mass ratio of the intermediate 3, the glycol amine and the sodium p-styrene sulfonate in the step S3 is 10:7:4, the amount of deionized water is 2.5 times of the mass of the intermediate 3, the initiator is potassium persulfate, and the amount of the initiator is 15% of the mass of the intermediate 3.
The polyvinyl alcohol/xanthan gum composite hydrogel is prepared by the following steps:
step C1, adding polyvinyl alcohol, xanthan gum and sodium hydroxide into a three-neck flask, adding deionized water, heating and stirring at the speed of 210rpm at the temperature of 92 ℃ until the deionized water is dissolved, adding a cross-linking agent, and standing at room temperature for 2.5 days to obtain a mixture;
and step C2, soaking the mixture prepared in the step C1 in deionized water to be neutral, and then placing the mixture in a drying oven at 52 ℃ to be dried to be constant in weight to prepare the polyvinyl alcohol/xanthan gum composite hydrogel.
Wherein the dosage ratio of the polyvinyl alcohol, the xanthan gum, the sodium hydroxide and the deionized water in the step C1 is 25 g: 5 g: 0.25 g: 180mL, the crosslinking agent is epichlorohydrin, and the dosage of the crosslinking agent is 0.75mL.
A preparation method of a degradable non-phosphorus scale and corrosion inhibitor comprises the following preparation steps:
step A1, soaking the polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 12 hours, and then heating and stirring at 80 ℃ and 230rpm for 2.5 hours to prepare a mixed solution a;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 35 minutes at the frequency of 90kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 75 ℃ and 280rpm for 4.5 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a 75 ℃ drying oven for drying for 36 hours, demolding, air-drying and molding to obtain the degradable phosphorus-free scale and corrosion inhibitor.
Example 3
A degradable non-phosphorus scale and corrosion inhibitor comprises the following raw materials in parts by weight:
20 parts of modified epoxy succinic acid-sodium p-styrenesulfonate copolymer, 30 parts of polyvinyl alcohol/xanthan gum composite hydrogel, 1 part of graphene oxide, 15 parts of zinc sulfate and 2 parts of sodium molybdate;
the degradable non-phosphorus scale and corrosion inhibitor is prepared by the following steps:
step A1, soaking polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 16 hours, and then heating and stirring at 85 ℃ and 250rpm for 3 hours to prepare a mixed solution a;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 40 minutes at the frequency of 100kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 80 ℃ and 300rpm for 5 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a drying oven at 80 ℃ for drying for 48 hours, demolding, air-drying and molding to obtain the degradable phosphorus-free scale and corrosion inhibitor.
Wherein the amount of the deionized water in the step A1 is 3 times of the mass of the polyvinyl alcohol/xanthan gum composite hydrogel.
Wherein the dosage of the deionized water in the step A2 is 1 time of the total mass of the sodium sulfate and the sodium molybdate.
Wherein, the modified epoxy succinic acid-sodium p-styrene sulfonate copolymer is prepared by the following steps:
step S1, adding maleic anhydride and deionized water into a three-neck flask, dropwise adding a sodium hydroxide solution after the maleic anhydride is dissolved to prepare an intermediate 1, then heating to 60 ℃, adding a composite catalyst, dropwise adding a hydrogen peroxide solution, and reacting at constant temperature for 3 hours after the dropwise adding is finished to prepare an intermediate 2;
step S2, adding calcium hydroxide into the intermediate 2 prepared in the step S1, heating to 90 ℃, reacting for 3.5 hours, washing the product with absolute ethyl alcohol for 3 times, and drying in an oven at 45 ℃ for 4 hours to obtain an intermediate 3;
and step S3, adding deionized water into the intermediate 3 prepared in the step S2 to dissolve the intermediate, adding glycol amine and sodium p-styrene sulfonate, heating to 90 ℃, adding an initiator, and reacting at constant temperature for 3 hours to obtain the modified epoxysuccinic acid-sodium p-styrene sulfonate copolymer.
Wherein the dosage of the maleic anhydride, the deionized water, the sodium hydroxide solution, the composite catalyst and the hydrogen peroxide solution in the step S1 is 10 g: 15mL of: 7 g: 0.5 g: 10mL, 50 percent of sodium hydroxide solution by mass, 30 percent of hydrogen peroxide solution by mass, and the composite catalyst is prepared by mixing sodium tungstate and sodium molybdate in a mass ratio of 1: 1.
Wherein the dosage of the calcium hydroxide in the step S2 is 0.9 g.
Wherein the mass ratio of the intermediate 3, the glycol amine and the sodium p-styrene sulfonate in the step S3 is 10:7:4, the amount of deionized water is 3 times of the mass of the intermediate 3, the initiator is sodium metabisulfite, and the amount of the initiator is 20% of the mass of the intermediate 3.
The polyvinyl alcohol/xanthan gum composite hydrogel is prepared by the following steps:
step C1, adding polyvinyl alcohol, xanthan gum and sodium hydroxide into a three-neck flask, adding deionized water, heating and stirring at 95 ℃ and 220rpm until the deionized water is dissolved, adding a cross-linking agent, and standing at room temperature for 3 days to obtain a mixture;
and step C2, soaking the mixture prepared in the step C1 in deionized water to be neutral, and then placing the mixture in a drying oven at 55 ℃ to be dried to be constant in weight to prepare the polyvinyl alcohol/xanthan gum composite hydrogel.
Wherein the dosage ratio of the polyvinyl alcohol, the xanthan gum, the sodium hydroxide and the deionized water in the step C1 is 30 g: 6 g: 0.5 g: 200mL, the crosslinking agent is epichlorohydrin, and the dosage of the crosslinking agent is 1 mL.
A preparation method of a degradable non-phosphorus scale and corrosion inhibitor comprises the following preparation steps:
step A1, soaking polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 16 hours, and then heating and stirring at 85 ℃ and 250rpm for 3 hours to prepare a mixed solution a;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 40 minutes at the frequency of 100kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 80 ℃ and 300rpm for 5 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a drying oven at 80 ℃ for drying for 48 hours, demolding, air-drying and molding to obtain the degradable phosphorus-free scale and corrosion inhibitor.
Comparative example
A commercially available non-phosphorus scale and corrosion inhibitor.
The following performance tests were performed on the phosphorus-free scale and corrosion inhibitors obtained in examples 1 to 3 and comparative examples: (1) the principle of calcium phosphate scale inhibition performance measurement is that orthophosphate and ammonium molybdate react in an acid environment to generate yellow phosphomolybdic heteropoly acid, the phosphomolybdic heteropoly acid is reduced into phosphomolybdic blue by ascorbic acid, and the phosphomolybdic blue is measured by a spectrophotometer according to GB/T22626-2008, and the experimental condition is C (Ca)2+)＝250mg/L，C(PO4 3-) 5mg/L, and the calculation formula of the scale inhibition rate is eta ═ (A)1-A0)/(A2-A0) X 100%, where eta is the scale inhibition rate, A1Is the absorbance after adding the scale inhibitor and heating, AOAbsorbance after heating without adding scale inhibitor, A2The absorbance is the absorbance without adding scale inhibitor and heating; (2) the calcium sulfate scale inhibition performance is measured, and the experimental conditions are that 25mL CaCl with the concentration of 20mg/mL is measured2Adding 1mg of non-phosphorus scale and corrosion inhibitor into the solution in a 250mL volumetric flask, and then adding 25mL of Na with the concentration of 40mg/mL2SO4Solution prepared to concentration c (Ca)2+)＝c(SO2 -4) 6800mg/L (in CaSO)4Metering) water sample, keeping the temperature of the water sample at 80 ℃ for 10 hours, cooling, taking 25mL of water sample into a conical flask, adding 2mL of 8mo L/L KOH solution to adjust the pH value to 10, adding a small amount of calcium indicator, titrating by using EDTA standard solution until the solution is changed from purple to blue-green, namely the end point, simultaneously carrying out a blank experiment, and calculating the scale inhibition rate (ZG) according to the following formula1-V0)/(V2-V0) X 100% where V1After the scale inhibitor is added and the temperature is kept for 10 hours, the volume of EDTA consumed by the calcium ion concentration is calibrated,V2calibrating the volume of EDTA (ethylene diamine tetraacetic acid) consumed by calcium ions for an unheated blank water sample; (3) the corrosion inhibition performance is measured by adopting a gravimetric static coupon corrosion experiment, the experimental principle is that the corrosion rate is calculated by using the change of the weight of the test piece before and after corrosion, and the experimental conditions are as follows: the experimental water sample tap water, the corrosion test piece A3 carbon steel test piece (50mm multiplied by 25mm multiplied by 2mm), the temperature is 40 ℃, the time is 72h, the chemical industry HG/T2159-91 standard is executed for experimental test, and the corrosion rate and the corrosion inhibition rate of the scale and corrosion inhibition dispersant are calculated as follows: corrosion rate (mm/a) [ < 8760X 10 × (W)0-W)]/A×D×T，W0W is the weight of the corrosion coupon before and after corrosion, g, 8760 is the number of hours corresponding to 1a, h/a, 10 is the number of millimeters corresponding to 1cm, mm/cm, A is the surface area, 20cm2D is density, 7.850g/cm3T is corrosion time, 72 h; (4) according to GB/T15456-95, the degradation rate on day n is (initial net COD-day n net COD)/initial net COD, where initial net COD is day 0 COD with scale inhibitor-blank day 0 COD, day n net COD is day n COD with scale inhibitor-blank day n COD, and the test data are shown in table 1:
TABLE 1
As can be seen from Table 1, the phosphorus-free scale and corrosion inhibitor prepared in the examples has excellent calcium phosphate scale inhibition and calcium sulfate scale inhibition effects, has a lower corrosion rate and a higher corrosion inhibition efficiency compared with the comparative examples, has a degradation rate of about 92% in 30 days, and has biodegradability and green environmental protection performance.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A degradable non-phosphorus scale and corrosion inhibitor is characterized by comprising the following raw materials in parts by weight: 15-20 parts of modified epoxy succinic acid-sodium p-styrenesulfonate copolymer, 25-30 parts of polyvinyl alcohol/xanthan gum composite hydrogel, 0.5-1 part of graphene oxide, 10-15 parts of zinc sulfate and 1-2 parts of sodium molybdate;
the degradable non-phosphorus scale and corrosion inhibitor is prepared by the following steps:
step A1, soaking the polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 12-16 hours, and then heating and stirring at 80-85 ℃ and 230-;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 30-40 minutes at the frequency of 80-100kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 70-80 ℃ and at the speed of 250-300rpm for 4-5 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a drying box at 70-80 ℃ for drying for 24-48 hours, demolding, air drying and molding to obtain the phosphorus-free degradable scale and corrosion inhibitor.
2. The degradable phosphorus-free scale and corrosion inhibitor according to claim 1, which is characterized in that: the dosage of the deionized water in the step A1 is 2.8-3 times of the mass of the polyvinyl alcohol/xanthan gum composite hydrogel.
3. The degradable phosphorus-free scale and corrosion inhibitor according to claim 1, which is characterized in that: the dosage of the deionized water in the step A2 is 0.8-1 time of the total mass of the sodium sulfate and the sodium molybdate.
4. The degradable phosphorus-free scale and corrosion inhibitor according to claim 1, which is characterized in that: the modified epoxy succinic acid-sodium p-styrene sulfonate copolymer is prepared by the following steps:
step S1, adding maleic anhydride and deionized water into a three-neck flask, dropwise adding a sodium hydroxide solution after the maleic anhydride is dissolved to prepare an intermediate 1, then heating to 50-60 ℃, adding a composite catalyst, dropwise adding a hydrogen peroxide solution, and reacting at constant temperature for 2-3 hours after the dropwise adding is finished to prepare an intermediate 2;
step S2, adding calcium hydroxide into the intermediate 2 prepared in the step S1, heating to 80-90 ℃, reacting for 3-3.5 hours, washing the product with absolute ethyl alcohol for 2-3 times, and drying in an oven at 40-45 ℃ for 3-4 hours to obtain an intermediate 3;
and step S3, adding deionized water into the intermediate 3 prepared in the step S2 to dissolve the intermediate, adding glycol amine and sodium p-styrene sulfonate, heating to 80-90 ℃, adding an initiator, and reacting at constant temperature for 2-3 hours to obtain the modified epoxy succinic acid-sodium p-styrene sulfonate copolymer.
5. The degradable phosphorus-free scale and corrosion inhibitor according to claim 1, which is characterized in that: the polyvinyl alcohol/xanthan gum composite hydrogel is prepared by the following steps:
step C1, adding polyvinyl alcohol, xanthan gum and sodium hydroxide into a three-neck flask, adding deionized water, heating and stirring at 90-95 ℃ and 200-;
and step C2, soaking the mixture prepared in the step C1 in deionized water to be neutral, and then placing the mixture in a drying oven at 50-55 ℃ to be dried to constant weight to prepare the polyvinyl alcohol/xanthan gum composite hydrogel.
6. The degradable phosphorus-free scale and corrosion inhibitor according to claim 4, wherein: the dosage of the maleic anhydride, the deionized water, the sodium hydroxide solution, the composite catalyst and the hydrogen peroxide solution in the step S1 is 9.2-10 g: 12.5-15 mL: 6-7 g: 0.4-0.5 g: 8-10mL, 50% of sodium hydroxide solution by mass, 30% of hydrogen peroxide solution by mass, and the composite catalyst is prepared by mixing sodium tungstate and sodium molybdate in a mass ratio of 1: 1.
7. The degradable phosphorus-free scale and corrosion inhibitor according to claim 4, wherein: the dosage of the calcium hydroxide in the step S2 is 0.7-0.9 g.
8. The degradable phosphorus-free scale and corrosion inhibitor according to claim 4, wherein: the mass ratio of the intermediate 3, the glycol amine and the sodium p-styrene sulfonate in the step S3 is 10:7:4, the amount of deionized water is 2-3 times of the mass of the intermediate 3, the initiator is one of sodium persulfate, potassium persulfate and sodium metabisulfite, and the amount of the initiator is 10-20% of the mass of the intermediate 3.
9. The degradable phosphorus-free scale and corrosion inhibitor according to claim 5, wherein: the dosage ratio of the polyvinyl alcohol, the xanthan gum, the sodium hydroxide and the deionized water in the step C1 is 20-30 g: 4-6 g: 0.2-0.5 g: 150-200mL, the cross-linking agent is epichlorohydrin, and the dosage of the cross-linking agent is 0.5-1 mL.
10. A preparation method of a degradable non-phosphorus scale and corrosion inhibitor is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
step A1, soaking the polyvinyl alcohol/xanthan gum composite hydrogel with deionized water for 12-16 hours, and then heating and stirring at 80-85 ℃ and 230-;
step A2, dissolving sodium sulfate and sodium molybdate in deionized water to prepare a mixed solution b, adding graphene oxide into the mixed solution b, and performing ultrasonic dispersion for 30-40 minutes at the frequency of 80-100kHz to prepare a mixed solution c;
and step A3, sequentially adding the modified epoxy succinic acid-sodium p-styrenesulfonate copolymer and the mixed solution c into the mixed solution a, heating and stirring at 70-80 ℃ and at the speed of 250-300rpm for 4-5 hours, pouring into a mold, standing and cooling, after the sample is condensed, putting into a drying box at 70-80 ℃ for drying for 24-48 hours, demolding, air drying and molding to obtain the phosphorus-free degradable scale and corrosion inhibitor.
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