CN101244869B - Water treatment scale corrosion inhibitor, preparation method and application thereof - Google Patents

Water treatment scale corrosion inhibitor, preparation method and application thereof Download PDF

Info

Publication number
CN101244869B
CN101244869B CN2008100245944A CN200810024594A CN101244869B CN 101244869 B CN101244869 B CN 101244869B CN 2008100245944 A CN2008100245944 A CN 2008100245944A CN 200810024594 A CN200810024594 A CN 200810024594A CN 101244869 B CN101244869 B CN 101244869B
Authority
CN
China
Prior art keywords
corrosion inhibitor
vinylformic acid
scale
carboxylic acid
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2008100245944A
Other languages
Chinese (zh)
Other versions
CN101244869A (en
Inventor
陈洪龄
蒋银峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN2008100245944A priority Critical patent/CN101244869B/en
Publication of CN101244869A publication Critical patent/CN101244869A/en
Application granted granted Critical
Publication of CN101244869B publication Critical patent/CN101244869B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention relates to a novel water treatment scale and corrosion inhibitor made of fluoro containing cationic carboxylic acid polymer solution and the preparation method as well as the application. The scale and corrosion inhibitor comprises the fluoro containing cationic carboxylic acid polymer and water, wherein the polymer has weight percentage of 20 to 50 percent of the total amount of the solution. Compared with the prior corrosion inhibitor and scale inhibitor, the scale and corrosion inhibitor has double effects, thus being suitable for circulation water treatment of the thermal equipment scale and corrosion. The novel water treatment scale and corrosion inhibitor made of fluoro containing cationic carboxylic acid polymer solution has an advantage of marked scale and corrosion inhibiting effect.

Description

A kind of water treatment scale and corrosion inhibitor and its production and application
Technical field
The present invention relates to a kind of novel water treatment scale and corrosion inhibitor and its production and application, relate in particular to novel water treatment scale and corrosion inhibitor of a kind of fluorine-containing positively charged ion carboxylic acid polyalcohol aqueous solution and its production and application.
Background technology
Along with China's rapid economy development, the rapid increase of social water consumption, water saving, the utilization ratio that improves water resources has been that the Freshwater resources of the task of top priority, particularly China are relatively deficienter, makes task arduous more.A lot of heavy industry large-lot producer, thermal power generation corporations are rich anies influential family of process water, strengthen the management of water resources, improve recirculated water management level, the water saving development trend that is inevitable.Yet, the recycle of water resources, the raising of cycles of concentration requires to adopt suitable water technology, to solve the fouling and the corrosion damage of heat power equipment, the more important thing is that it can cause the equipment can't normal operation, directly restricting unit safety, economical operation, seriously will bring heavy losses to enterprise.At present existing the most frequently used anti-incrustation corrosion inhibitor is the organophosphorus acid type, and the phosphorus discharging will cause the nutrient laden in waters on every side and may cause red tide.In some countries such as America and Europe, Japan, proposed to prohibit the phosphorus measure, require phosphorus discharging≤1mgL as Germany -1Reappraise the effect and the performance of existing anti-incrustation corrosion inhibitor with green concept, their use will be restricted, will be replaced with without phosphorus, biodegradable new high-efficiency green scale and corrosion inhibitor in the near future, this also is the developing direction of 21 world's water conditioners.
Polyacrylic acid has good scale-inhibiting properties, and organic cation also has good corrosion mitigating effect, and the organic fluoride-containing polymkeric substance has " three height " " two hate ", i.e. high surface, high heat-resistant stability and high chemical stability; Its fluorine-containing alkyl is hydrophobic but also hate oil not only.Utilize the chemisorption of organic cation, utilize the characteristic of C-F key effectively to reduce the interior deposition of dirty class on pipeline of pipeline, form three layers of effective protective layer, the ducted corrosion of good restraining at pipe surface at pipe surface; Carboxylic acid is to the Ca in the recirculated water simultaneously 2+, Mg 2+The ionic chelation reduces the formation of calcium dirt, magne-scale effectively, has improved scale inhibition effect.
Summary of the invention
The objective of the invention is to provide a kind of novel water treatment scale and corrosion inhibitor of the fluorine-containing positively charged ion carboxylic acid polyalcohol aqueous solution for the deficiency of improving existing water treatment scale and corrosion inhibitor existence.Another object of the present invention provides the preparation method of the anti-incrustation corrosion inhibitor of above-mentioned novel texture, and the present invention also has a purpose to provide the application of above-mentioned novel water treatment scale and corrosion inhibitor in heat power equipment fouling and corrosive circulating water treatment.
The technical solution adopted for the present invention to solve the technical problems is: a kind of water treatment scale and corrosion inhibitor, it is characterized in that the aqueous solution for fluorine-containing positively charged ion carboxylic acid polyalcohol, and the general structure of wherein fluorine-containing positively charged ion carboxylic acid polyalcohol is:
Figure S2008100245944D00021
Wherein: R 1: H or CH 3R 2: COOH, CONH 2R 3: C 1～C 2Alkyl or C 2Hydramine;
Rf: the fluoro-alkyl of carbonatoms 1～6; N:100～1000; X:Cl
Above-mentioned anti-incrustation corrosion inhibitor is the aqueous solution of fluorine-containing positively charged ion carboxylic acid polyalcohol, and wherein to account for the weight percent of solution total amount be 20-50% to polymkeric substance, and the weight percent that water accounts for the solution total amount is 50-80%.
The present invention also provides the preparation method of above-mentioned anti-incrustation corrosion inhibitor, the steps include:
A. organic addition reaction: vinylformic acid fluorinated ester, propenyl chloride and vinylformic acid or acrylamide are joined in the reactor that contains solvent, add catalyzer and initiator then, reacting by heating stirs, and condensing reflux makes fluoropolymer;
B. quaterisation: the fluoropolymer that makes in above-mentioned steps, control reaction temperature adds quaternizing agent and carries out quaterisation, makes the fluorine-containing positively charged ion carboxylic acid polyalcohol of transparent red-brown solution.
The two-step reaction equation is:
1. organic addition reaction
Figure S2008100245944D00022
2. quaterisation
Wherein: R 1: H or CH 3R 2: COOH, CONH 2R 3: C 1～C 2Alkyl or C 2Hydramine
Rf: the fluoro-alkyl of carbonatoms 1～6; N:100～1000; X:Cl
Preferred vinylformic acid fluorinated ester is trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester or methacrylic acid ten difluoro heptyl esters in the steps A; Described catalyzer is NaOH, KOH or CH 3CH 2ONa; Described initiator is H 2O 2Or (CH 3) 2CNCN=NCCN (CH 3) 2Described quaternizing agent is Trimethylamine 99, trolamine or triethylamine; Described solvent is a distilled water.
Wherein the mol ratio between vinylformic acid fluorinated ester, propenyl chloride, vinylformic acid or the acrylamide was generally 1: 1: 1, but can change to some extent, the quality that catalyzer adds is 0.1%～0.3% of a vinylformic acid fluorinated ester massfraction, and the adding quality of initiator is 0.8～1.2% of a vinylformic acid fluorinated ester massfraction.The add-on of solvent is 50-80% control by the weight percent that water in the aqueous solution of fluorine-containing positively charged ion carboxylic acid polyalcohol accounts for the solution total amount; Be benchmark with the vinylformic acid fluorinated ester generally, every mole adds about the 310-1220 milliliter.
Heating temperature among the preferred steps A is 50～90 ℃, 5～10 hours reaction times; 40～70 ℃ of temperature of reaction among the step B, 4～8 hours reaction times.
The invention allows for above-mentioned fluorine-containing positively charged ion carboxylic acid polyalcohol solution as the application in Treatment of Industrial Water of inhibiter, Scale inhibitors.The scale inhibition performance of fluorine-containing positively charged ion carboxylic acid polyalcohol resistance calcium carbonate scale can reach more than 95% (20mg/L), and the scale inhibition performance of resistance calcium phosphate scale can reach more than 90% (20mg/L), and the corrosion inhibition rate of steel is reached more than 95% (30mg/L).
The fluorine-containing positively charged ion carboxylic acid polyalcohol that the present invention is prepared, its IR collection of illustrative plates as shown in Figure 1, from figure as can be seen at 1000cm -1～1250cm -1The place is the eigen vibration bands of a spectrum of C-F key in the polymkeric substance.In addition, at 500～700cm -1Near obvious absorption peaks has also appearred, this is the characteristic peak of quaternary ammonium salt, simultaneously 1600cm -1The characteristic peak of the C=C at place disappears.1600cm -1～1731cm -1The carbonyl C=O stretching vibration absorption peak at place, 2927cm -1～3198cm -1Wide and diffusing stretching vibration absorption peak is the charateristic avsorption band of less water; 3050cm -1～3300cm -1The place is the stretching vibration absorption peak of c h bond.
Corrosion inhibiting and descaling agent effect evaluation method of the present invention:
(1) corrosion inhibition
Experiment condition: closed environment, 42 ℃ of envrionment temperatures, simulate alkaline industrial circulate water
The lacing film time: 72h
Experimental technique: weight-loss method.Test result sees Table 1.
(2) scale-inhibiting properties
1.CaCO 3The antisludging test condition is: [Ca 2+]=250mg/L, [HCO3 -]=250mg/L is (all with CaCO 3Meter, down together), concentrate 2 times, T=80 ℃, t=10h.Test result sees Table 2.
2.Ca 3(PO 4) 2The antisludging test condition is: [Ca 2+]=250mg/L, [PO 4 3-]=5mg/L, pH=9.0, T=80 ℃, t=10h.Test result sees Table 3.
Beneficial effect:
The fluorine-containing positively charged ion carboxylic acid polyalcohol of novel water conditioner of the present invention has very significant advantage:
1) prepared product also has hydroxy-acid group, ammonium cation salt group and carbon-fluorine bond group simultaneously in structure, not phosphorous, is a kind of green water conditioner of novel texture.
2) utilize " synergistic effect " between these groups simultaneously, make its inhibition, scale-inhibiting properties better.The scale inhibition performance of fluorine-containing positively charged ion carboxylic acid polyalcohol resistance calcium carbonate scale can reach more than 95% (20mg/L), and the scale inhibition performance of resistance calcium phosphate scale can reach more than 90% (20mg/L), and the corrosion inhibition rate of steel is reached more than 95% (30mg/L).Can in industrial circulating cooling water, be extensive use of.
3) this product synthetic route is simple, is easy to control, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the IR collection of illustrative plates of embodiment 1 prepared trifluoroalkyl carboxylic acid polyquaternium.
Embodiment
Embodiment 1:
In the reactor that thermometer, reflux condensing tube are housed, add trifluoroethyl methacrylate 16.812g (0.1mol), propenyl chloride 7.653g (0.1mol), vinylformic acid 7.206g (0.1mol), 122ml distilled water; Add catalyst n aOH0.032g, initiator H then 2O 20.253g under 50 ℃ of whipped states, in 5 hours reaction times, copolymerization product trifluoroalkyl polyacrylic acid is total to 28.503g in the middle of obtaining.
Disposable adding Trimethylamine 99 8.911g (0.1mol) slowly falls and is warming up to 40 ℃, stirs 4 hours.Can make anti-incrustation corrosion inhibitor trifluoroalkyl carboxylic acid polyquaternium 30.441g of the present invention.
Embodiment 2:
In the reactor that thermometer, reflux condensing tube are housed, add vinylformic acid hexafluoro butyl ester 23.611g (0.1mol), propenyl chloride 7.653g (0.1mol), acrylamide 7.108g (0.1mol), 31ml distilled water; Add catalyzer KOH0.095g, initiator (CH then 3) 2CNCN=NCCN (CH 3) 20.380g, under 90 ℃ of whipped states, 10 hours reaction times, copolymerization product hexafluoro alkyl polyacrylamide 28.503g in the middle of obtaining.
Disposable adding Trimethylamine 99 8.911g (0.1mol) slowly is cooled to 70 ℃, stirs 8 hours.Can make anti-incrustation corrosion inhibitor hexafluoro alkylamide polyquaternium 30.362g of the present invention.
Embodiment 3:
In the reactor that thermometer, reflux condensing tube are housed, add methacrylic acid ten difluoro heptyl ester 40.00g (0.1mol), propenyl chloride 7.653g (0.1mol), vinylformic acid 7.206g (0.1mol), 63ml distilled water; Add catalyzer KOH0.095g, initiator (CH then 3) 2CNCN=NCCN (CH 3) 20.253g, under 90 ℃ of whipped states, 10 hours reaction times, copolymerization product ten fluoroalkyl polyacrylic acid 28.415g in the middle of obtaining.
Disposable adding trolamine 14.911g (0.1mol) slowly falls and is warming up to 40 ℃, stirs 4 hours.Can make anti-incrustation corrosion inhibitor ten fluoroalkyl carboxylic acid polyquaternium 37.731g of the present invention.
Embodiment 4:
In the reactor that thermometer, reflux condensing tube are housed, add trifluoroethyl methacrylate 16.812g (0.1mol), propenyl chloride 7.653g (0.1mol), acrylamide 7.108g (0.1mol), 39ml distilled water; Add catalyzer CH then 3CH 2ONa0.095g, initiator H 2O 20.253g, under 50 ℃ of whipped states, 5 hours reaction times, copolymerization product trifluoroalkyl polyacrylamide 28.503g in the middle of obtaining.
Disposable adding trolamine 14.911g (0.1mol) slowly is cooled to 70 ℃, stirs 8 hours.Can make anti-incrustation corrosion inhibitor trifluoroalkyl acid amides polyquaternium 37.652g of the present invention.
Corrosion inhibiting and descaling agent corrosion mitigating effect evaluation method of the present invention:
(1) corrosion inhibition
Experiment condition: closed environment, 42 ℃ of envrionment temperatures, simulate alkaline industrial circulate water
The lacing film time: 72h
Experimental technique: weight-loss method.
Table 1 agent for preventing scale, corrosion-resistance and disinfection corrosion mitigating effect
Figure S2008100245944D00051
(2) scale-inhibiting properties
1.CaCO 3The antisludging test condition is: [Ca 2+]=250mg/L, [HCO3 -]=250mg/L is (all with CaCO 3Meter, down together), concentrate 2 times, T=80 ℃, t=10h.
Table 2 agent for preventing scale, corrosion-resistance and disinfection scale inhibition effect-CaCO 3Antisludging test
Figure S2008100245944D00052
2.Ca 3(PO 4) 2The antisludging test condition is: [Ca 2+]=250mg/L, [PO 4 3-]=5mg/L, pH=9.0, T=80 ℃, t=10h.
Table 3 agent for preventing scale, corrosion-resistance and disinfection scale inhibition effect-Ca 3(PO 4) 2Antisludging test
Figure S2008100245944D00053
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, every foundation technical spirit of the present invention all still belongs in the scope of technical solution of the present invention any simple modification, equivalent variations and modification that above embodiment did.

Claims (7)

1. a water treatment scale and corrosion inhibitor is characterized in that the aqueous solution for fluorine-containing positively charged ion carboxylic acid polyalcohol, and the general structure of wherein fluorine-containing positively charged ion carboxylic acid polyalcohol is:
Wherein: R 1: H or CH 3R 2: COOH, CONH 2R 3: C 1～C 2Alkyl or C 2Hydramine Rf: the fluoro-alkyl of carbonatoms 1～6; N:100～1000; X:Cl
2. anti-incrustation corrosion inhibitor according to claim 1 is characterized in that the weight percent that polymkeric substance in the aqueous solution of fluorine-containing positively charged ion carboxylic acid polyalcohol accounts for the solution total amount is 20-50%, and all the other are water.
3. the preparation method of anti-incrustation corrosion inhibitor according to claim 1 the steps include:
A. organic addition reaction: join in the reactor that contains solvent vinylformic acid fluorinated ester, propenyl chloride and vinylformic acid or vinylformic acid fluorinated ester, propenyl chloride and acrylamide, add catalyzer and initiator then, reacting by heating stirs, condensing reflux makes fluoropolymer;
B. quaterisation: the fluoropolymer that makes in above-mentioned steps, control reaction temperature adds quaternizing agent and carries out quaterisation, makes the fluorine-containing positively charged ion carboxylic acid polyalcohol of transparent red-brown solution.
4. preparation method according to claim 3 is characterized in that the vinylformic acid fluorinated ester described in the steps A is trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester or methacrylic acid ten difluoro heptyl esters; Described solvent is a distilled water; Described catalyzer is NaOH, KOH or CH 3CH 2ONa; Described initiator is H 2O 2Or (CH 3) 2CNCN=NCCN (CH 3) 2Described quaternizing agent is Trimethylamine 99, trolamine or triethylamine.
5. preparation method according to claim 3, it is characterized in that the mol ratio between vinylformic acid fluorinated ester, propenyl chloride and vinylformic acid or vinylformic acid fluorinated ester, propenyl chloride and the acrylamide is 1: 1: 1, the quality that catalyzer adds is 0.1%～0.3% of a vinylformic acid fluorinated ester quality, and the adding quality of initiator is 0.8～1.2% of a vinylformic acid fluorinated ester quality.
6. the preparation method of anti-incrustation corrosion inhibitor according to claim 3 is characterized in that the Heating temperature in the steps A is 50～90 ℃, 5～10 hours reaction times; 40～70 ℃ of temperature of reaction among the step B, 4～8 hours reaction times.
7. the described anti-incrustation corrosion inhibitor of claim 1 is as the application in Treatment of Industrial Water of inhibiter, Scale inhibitors.
CN2008100245944A 2008-03-28 2008-03-28 Water treatment scale corrosion inhibitor, preparation method and application thereof Expired - Fee Related CN101244869B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008100245944A CN101244869B (en) 2008-03-28 2008-03-28 Water treatment scale corrosion inhibitor, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008100245944A CN101244869B (en) 2008-03-28 2008-03-28 Water treatment scale corrosion inhibitor, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN101244869A CN101244869A (en) 2008-08-20
CN101244869B true CN101244869B (en) 2010-09-29

Family

ID=39945594

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008100245944A Expired - Fee Related CN101244869B (en) 2008-03-28 2008-03-28 Water treatment scale corrosion inhibitor, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN101244869B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102491541B (en) * 2011-11-25 2013-06-05 东南大学 Green environment-friendly corrosion and scale inhibiting dispersant and its preparation method
CN105198098B (en) * 2014-11-06 2017-09-15 马鞍山市鸿伟环化有限公司 A kind of preparation method of environmental type corrosion inhibiting and descaling agent
CN105016496A (en) * 2015-08-02 2015-11-04 宁波保税区维迪克环保科技有限公司 Composite water treating agent and preparation method thereof
CN105110490A (en) * 2015-09-02 2015-12-02 江苏绿科生物技术有限公司 Scale and corrosion inhibitor
CN105130020A (en) * 2015-09-02 2015-12-09 江苏绿科生物技术有限公司 Preparing method for scale and corrosion inhibitor
CN108641695B (en) * 2018-06-13 2020-07-07 中国石油工程建设有限公司 Corrosion inhibition bactericide for shale gas field
CN111662496B (en) * 2020-07-10 2022-02-18 西南交通大学 Anti-scaling high-concentration organic wastewater transport modified pipe and preparation method thereof

Also Published As

Publication number Publication date
CN101244869A (en) 2008-08-20

Similar Documents

Publication Publication Date Title
CN101244869B (en) Water treatment scale corrosion inhibitor, preparation method and application thereof
CN100579637C (en) Scale inhibitor and preparation for reverse osmosis membrane
CN102732892A (en) Metal corrosion inhibitor composition, metal corrosion inhibitor thereof and application thereof
CN105366823A (en) Non-phosphorus corrosion and scale inhibitor composition, non-phosphorus corrosion and scale inhibitor, application of non-phosphorus corrosion and scale inhibitor and application of copolymer to corrosion inhibition
CN101412565A (en) Efficient scale corrosion inhibitor for carbon steel system
CN103508568B (en) A kind of boiler scale dispersion agent
CN105461085A (en) Non-phosphorus environmentally-friendly corrosion-inhibition scale-inhibition dispersion agent and preparation method and application thereof
CN102689992A (en) Terpolymer antisludging agent and preparation process thereof
CN103570145A (en) Preparation method of olefin ether and unsaturated carboxylic acid copolymer anti-sludging agent
CN103265125B (en) Quaternary non-phosphorus aggregate type corrosion and scale inhibitor PIAAM and preparation method thereof
CN104211194A (en) Corrosion and scale inhibitor for high hardness circulation cooling water with high concentration multiple
CN105036370A (en) Ultra-temperature circulating water scale inhibitor and preparation method thereof
CN104528966B (en) A kind of corrosion-proofing and antisludging method of aluminium heat-exchange device
CN104140162B (en) With the non-phosphorus scale and corrosion inhibitor and preparation method thereof of seawater as recirculated cooling water
CN103242476B (en) A kind of preparation method with the acrylic polymers of fluorescent characteristic
CN104528960B (en) A kind of high efficiency corrosion inhibiting scale retardant
CN102515372A (en) Composite scale inhibitor using recycled water in circulating cooling water system and preparation method of composite scale inhibitor
CN104528964B (en) A kind of without phosphorus compound corrosion inhibiting and descaling agent
CN104556426B (en) The preparation method of without phosphorus compound corrosion inhibiting and descaling agent
CN105038855A (en) Antisludging agent of catalytic cracking oil slurry system and preparation method of antisludging agent
CN104556419B (en) A kind of preparation method of high efficiency corrosion inhibiting scale retardant
CN107586361A (en) A kind of environment-friendly type can fluorescent tracing water treatment agent and preparation method thereof
CN102515369A (en) Environment-friendly phosphorus-free scale and corrosion inhibitor and manufacturing method for same
CN107381840B (en) Environment-friendly scale and corrosion inhibitor and preparation method thereof
CN108658262B (en) Preparation of environment-friendly water quality stabilizer RG-10

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100929

Termination date: 20130328