CN103420497B - Non-phosphorous corrosion and scale inhibitor containing lignosulfonate and application thereof - Google Patents
Non-phosphorous corrosion and scale inhibitor containing lignosulfonate and application thereof Download PDFInfo
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- CN103420497B CN103420497B CN201310375136.6A CN201310375136A CN103420497B CN 103420497 B CN103420497 B CN 103420497B CN 201310375136 A CN201310375136 A CN 201310375136A CN 103420497 B CN103420497 B CN 103420497B
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Abstract
The invention discloses a non-phosphorous corrosion and scale inhibitor containing lignosulfonate and application of the non-phosphorous corrosion and scale inhibitor containing the lignosulfonate in industrial circulating cooling water. The non-phosphorous corrosion and scale inhibitor containing the lignosulfonate comprises the lignosulfonate, polyepoxysuccinic acid, acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer, zinc salt, azole compounds and water. The non-phosphorous corrosion and scale inhibitor containing the lignosulfonate comprises, by mass, 30%-40% of the lignosulfonate, 15%-20% of the polyepoxysuccinic acid, 10%-15% of the acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer, 5%-15% of the zinc salt, 1%-2% of the azole compounds, and the balance the water. The non-phosphorous corrosion and scale inhibitor containing the lignosulfonate is applied to an industrial circulating cooling water system. Under the water quality shown in the embodiments, when the dosage of the non-phosphorous corrosion and scale inhibitor containing the lignosulfonate is 50-70mg/L, the corrosion rate of carbon steel is smaller than 0.075mm/a, the scale inhibition rate is larger than 98%, the non-phosphorous corrosion and scale inhibitor containing the lignosulfonate is free of phosphorus, biodegradation performance is good, cost of follow-up processing is reduced, and the non-phosphorous corrosion and scale inhibitor containing the lignosulfonate is excellent in performance and protects the environment.
Description
Technical field
The present invention relates to a kind of water treatment agent for industrial circulating cooling water system, particularly a kind of phosphate-free corrosion inhibition antisludging agent containing sulfonated lignin.
Background technology
Water resources in china total amount is 2.8 tcms, accounts for 7% of world water resources total amount, but China per capita water resources only have 2304 m
3/ people, belongs to the country of water scarcity.Water shortage problem is day by day serious, and this has become the large obstacle that restriction China realizes Sustainable development.China city is because of lack of water, and annual financial loss reaches more than 1,200 hundred million yuans, and therefore water saving is very urgent.People, with in water, except agricultural is with the large open air of water, be secondly exactly process water, and industrial cooling water account for about 70% of process water total amount.Therefore, the industrial repeating utilization factor that technology on circulating cooling water treatment will be adopted to improve water, saves a large amount of process water.
Circulating water water system usually faces the problem of equipment corrosion and fouling, brings and has a strong impact on, cause heavy economic losses to enterprise and country to industrial production.People study discovery, use high efficiency corrosion inhibiting scale retardant effectively can prevent the erosion and encrustation of pipeline, can not only reduce enterprise's production cost, maintain the safe operation of circulating water system simultaneously in circulating water system.Due to have chemical stability good, high temperature resistant, have the advantage such as obvious threshold effect and good synergistic effect, organic phosphine system water treatment agent is widely applied in recent years.But the phosphorous meeting of medicament causes the eutrophication of water proximate, causes the excessive multiplication of bacterium algae, thus causes pollution of waterhead.Therefore, the use of organic phosphine system water treatment agent will progressively be restricted, and develops without phosphorus, that biodegradability is good novel corrosion-retarding Scale inhibitors has become water treatment agent instantly developing direction.Chinese patent (application number 201110443255.1) discloses a kind of phosphate-free corrosion inhibition antisludging agent being applicable to industrial circulating cooling water, is made up of the amino soap (sylvite or sodium salt) of N-alkyl-N-fat phthalidyl, light base shuttle hydrochlorate (Sunmorl N 60S, Sodium lactobionate, oxysuccinic acid are received), shuttle acid copolymer (vinylformic acid-AMPS-methyl propane sulfonic acid multipolymer, polymaleic acid, poly aspartic acid, poly-epoxy succinic acid), metal-salt (zinc salt, chromic salt, silicate, molybdate, tungstate) and water.Chinese patent (application number 201110443253.2) provide to be bluffed by Sodium orthomolybdate, zinc salt, Citrate trianion, trolamine, the proud triazole of benzene, poly aspartic acid, polycyclic oxygen clap acid, vinylformic acid sulfonic acid terpolymer, solid base be the phosphate-free corrosion inhibition antisludging agent of main component.Although above-mentioned phosphate-free corrosion inhibition antisludging agent is not phosphorous, environmentally friendly, have excellent corrosion and scale inhibition performance, formula composition is more complicated, and cost is higher, is unfavorable for promoting the use of.
Summary of the invention
The object of the present invention is to provide a kind of phosphate-free corrosion inhibition antisludging agent and the application thereof that are applicable to process industrial circulating cooling water system, can be good at the fouling and the etching problem that suppress system cloud gray model generation, nontoxic cheapness, simultaneously environmentally friendly, avoid pollution of waterhead problem.
The technical solution realizing the object of the invention is:
Containing the without phosphorus composite slow-corrosion scale resistors of sulfonated lignin, described phosphate-free corrosion inhibition antisludging agent is made up of sulfonated lignin, poly-epoxy succinic acid, AA/AMPS multipolymer, zinc salt, azole compounds and water, the mass percent shared by each component respectively:
Sulfonated lignin 30% ~ 40%,
Poly-epoxy succinic acid 15% ~ 20%,
AA/AMPS copolymer 1 0% ~ 15%,
Zinc salt 5% ~ 15%,
Azole compounds 1% ~ 2%,
All the other are water.
Wherein, sulfonated lignin select molecular weight ranges 2000 ~ 3000 sodium lignosulfonate or ammonium lignosulphonate.Zinc salt is selected from zinc chloride or Zinc Sulphate Heptahydrate.Azole compounds is selected from one or several in benzotriazole, methyl benzotriazazole or mercaptobenzothiazole.
Above-mentioned phosphate-free corrosion inhibition antisludging agent is prepared by the following method: sulfonated lignin, poly-epoxy succinic acid, AA/AMPS multipolymer, zinc salt, azole compounds and water are added successively in proportion in container, at room temperature stir 1 ~ 2 hour, liquid to be mixed is clarified and is obtained product without during insoluble impurities.
Described phosphate-free corrosion inhibition antisludging agent is applicable to industrial circulating cooling water, and under embodiment condition of water quality, when added amount of chemical is 50 ~ 70mg/L, corrosion of carbon steel rate is less than the 0.075mm/a of national regulations, and scale inhibition performance reaches more than 98%.
The principle of the invention is as follows:
(1) sulfonated lignin (such as sodium lignosulfonate) in formula and poly-epoxy succinic acid have good scale inhibition and dispersion performance, the two is composite, to causing dirty metal ion, there is very strong sequestering action, by dissemination be suppressed to dirty crystal growth and can prevent the scaling salt class such as calcium carbonate, calcium sulfate, barium sulfate precipitation very well.(2) zinc salt in formula, such as zinc chloride, with Zn (OH) in water
2form forms precipitation membrane thus protection metal on surface, metallic cathode district.Sulfonated lignin and zinc salt composite, there is certain chelating, stablize Zn
2+effect, self can form adsorption film in metallic surface simultaneously, play inhibition synergism.(3) AA/AMPS multipolymer and zinc salt composite, not only can play stable Zn
2+effect, can also play antiscaling dispersion effect.(4) the azole salt in formula, such as benzotriazole (BTA), has good corrosion inhibition to copper and alloy.
Compared with prior art, its remarkable advantage is in the present invention: (1) is not phosphorous, and biodegradability is good, to environment nontoxic pollution-free; (2) anticorrosion-antiscaling effect is better than phosphorus system water conditioner; (3) abundant raw material source, preparation technology is simple, and cost is low; (4) when a kind of without phosphorus composite slow-corrosion scale resistor containing sulfonated lignin of the present invention is applied in industrial circulating cooling water system, under embodiment condition of water quality, when added amount of chemical is 50 ~ 70mg/L, corrosion of carbon steel rate is less than the 0.075mm/a of national regulations, and scale inhibition performance reaches more than 98%.
Embodiment
Respectively organize the moisturizing water quality used in embodiment below as shown in table 1.
The moisturizing water quality of embodiment respectively organized by table 1
embodiment 1
Reagent combination: sodium lignosulfonate accounts for 30%, poly-epoxy succinic acid accounts for 15%, AA/AMPS copolymer 1 0%, and Zinc vitriol accounts for 15%, and benzotriazole accounts for 2%, and water accounts for 28%.
Moisturizing water quality: the moisturizing of Henan Jiaozuo Wanfang power plant, added amount of chemical is 60mg/L.
scale inhibition is tested: measure scale inhibition performance by Bubbling method.Add medicament after concentrated 1.5 times of test water, start experiment at test temperature 60 DEG C, quickening air blasts speed and is concentrated into 5 times and keeps 6h.Measuring scale inhibition performance is 99%.
corrosion experiment: measure corrosion rate by standard rotary hanging plate method.Add medicament toward test water, start experiment at test temperature 50 DEG C, be then concentrated into 5 times and keep 72h.It is 0.023mm/a that measuring obtains A3 carbon steel dosing corrosion rate.
embodiment 2
Reagent combination: sodium lignosulfonate accounts for 30%, poly-epoxy succinic acid accounts for 20%, AA/AMPS copolymer 1 0%, and Zinc vitriol accounts for 12%, and benzotriazole accounts for 1.5%, and water accounts for 26.5%.
Moisturizing water quality: Tengzhou Sheng Long coke-oven plant moisturizing, added amount of chemical is 70mg/L.
scale inhibition is tested: measure scale inhibition performance by Bubbling method.At test temperature 60 DEG C, in test water, add medicament start experiment, quickening air blasts speed and is concentrated into 5 times and keeps 6h.Measuring scale inhibition performance is 98%.
corrosion experiment: measure corrosion rate by standard rotary hanging plate method.Add medicament toward test water, start experiment at test temperature 50 DEG C, be then concentrated into 5 times and keep 72h.It is 0.033mm/a that measuring obtains A3 carbon steel dosing corrosion rate.
embodiment 3
Reagent combination: sodium lignosulfonate accounts for 35%, poly-epoxy succinic acid accounts for 20%, AA/AMPS copolymer 1 0%, and Zinc vitriol accounts for 12%, and benzotriazole accounts for 1.5%, and water accounts for 21.5%.
Moisturizing water quality: the moisturizing of Wuxi Xi Xing Steel Plant, added amount of chemical is 70mg/L.
scale inhibition is tested: measure scale inhibition performance by Bubbling method.Add medicament after concentrated 1.5 times of test water, start experiment at test temperature 60 DEG C, quickening air blasts speed and is concentrated into 5 times and keeps 6h.Measuring scale inhibition performance is 98%.
corrosion experiment: measure corrosion rate by standard rotary hanging plate method.In test water, add medicament, start experiment at test temperature 50 DEG C, be then concentrated into 5 times and keep 72h.It is 0.029mm/a that measuring obtains A3 carbon steel dosing corrosion rate.
embodiment 4
Reagent combination: sodium lignosulfonate accounts for 30%, poly-epoxy succinic acid accounts for 15%, AA/AMPS copolymer 1 0%, and Zinc vitriol accounts for 15%, and benzotriazole accounts for 2%, and water accounts for 28%.
Moisturizing water quality: Nanjing tap water, added amount of chemical is 50mg/L.
scale inhibition is tested: measure scale inhibition performance by Bubbling method.Add medicament after concentrated 1.5 times of test water, start experiment at test temperature 60 DEG C, quickening air blasts speed and is concentrated into 6 times and keeps 6h.Measuring scale inhibition performance is 100%.
corrosion experiment: measure corrosion rate by standard rotary hanging plate method.In test water, add medicament, start experiment at test temperature 50 DEG C, be then concentrated into 6 times and keep 72h.It is 0.021mm/a that measuring obtains A3 carbon steel dosing corrosion rate.
embodiment 5
Reagent combination: sodium lignosulfonate accounts for 30%, poly-epoxy succinic acid accounts for 15%, AA/AMPS copolymer 1 0%, and Zinc vitriol accounts for 15%, and benzotriazole accounts for 1.5%, and water accounts for 28.5%.
Moisturizing water quality: Maanshan Iron and Steel Co., Anhui's moisturizing, added amount of chemical is 60mg/L.
scale inhibition is tested: measure scale inhibition performance by Bubbling method.Add medicament after concentrated 1.5 times of test water, start experiment at test temperature 60 DEG C, quickening air blasts speed and is concentrated into 5 times and keeps 6h.Measuring scale inhibition performance is 99%.
corrosion experiment: measure corrosion rate by standard rotary hanging plate method.In test water, add medicament, start experiment at test temperature 50 DEG C, be then concentrated into 5 times and keep 72h.It is 0.025mm/a that measuring obtains A3 carbon steel dosing corrosion rate.
Claims (4)
1. the without phosphorus composite slow-corrosion scale resistor containing sulfonated lignin, it is characterized in that: described without phosphorus composite slow-corrosion scale resistor by molecular weight ranges be limited to 2000 ~ 3000 sodium lignosulfonate or ammonium lignosulphonate, poly-epoxy succinic acid, AA/AMPS multipolymer, zinc salt, azole compounds and water form, the mass percent shared by each component respectively:
Sulfonated lignin 30% ~ 40%,
Poly-epoxy succinic acid 15% ~ 20%,
AA/AMPS copolymer 1 0% ~ 15%,
Zinc salt 5% ~ 15%,
Azole compounds 1% ~ 2%,
All the other are water
Sulfonated lignin select molecular weight ranges 2000 ~ 3000 sodium lignosulfonate or ammonium lignosulphonate.
2. a kind of without phosphorus composite slow-corrosion scale resistor containing sulfonated lignin according to claim 1, is characterized in that: zinc salt is selected from zinc chloride or Zinc Sulphate Heptahydrate.
3. a kind of without phosphorus composite slow-corrosion scale resistor containing sulfonated lignin according to claim 1, is characterized in that: azole compounds is selected from one or several in benzotriazole, methyl benzotriazazole or mercaptobenzothiazole.
4. a kind of without phosphorus composite slow-corrosion scale resistor containing sulfonated lignin according to claim 1, it is characterized in that preparing by the following method: sulfonated lignin, poly-epoxy succinic acid, AA/AMPS multipolymer, zinc salt, azole compounds and water are added in container in proportion successively, at room temperature stir 1 ~ 2 hour, liquid to be mixed is clarified and is obtained product without during insoluble impurities.
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| CN103964590A (en) * | 2014-05-16 | 2014-08-06 | 山东大学 | Environment-friendly efficient scale inhibitor of bittern |
| CN104058511A (en) * | 2014-06-16 | 2014-09-24 | 淄博海星环保科技有限公司 | Non-phosphorus composite corrosion and scale inhibitor used for circulating water |
| CN105565513B (en) * | 2014-10-10 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of composite slow-corrosion scale resistor and its preparation method and application |
| CN104326577B (en) * | 2014-11-24 | 2016-05-04 | 邢台旭阳煤化工有限公司 | A kind of composite slow-corrosion scale resistor for circulating cooling water treatment |
| CN105000683A (en) * | 2015-07-10 | 2015-10-28 | 杨红微 | Phosphorus-free, green and environment-friendly slow-release scale inhibitor |
| CN105753075A (en) * | 2015-07-31 | 2016-07-13 | 南通德安化工有限公司 | Novel efficient and environment-friendly water treatment agent |
| CN106477737A (en) * | 2015-08-25 | 2017-03-08 | 南京理工大学 | A kind of continuous cast mold fIthy circulating system highly effective corrosion and scale inhibition disperser |
| CN106745856A (en) * | 2017-03-27 | 2017-05-31 | 刘雄杰 | A kind of without phosphorus slow-release scale inhibitor |
| CN110040857A (en) * | 2019-04-12 | 2019-07-23 | 嘉兴沃特泰科环保科技有限公司 | A kind of phosphorus-free green corrosion inhibiting and descaling agent and preparation method thereof |
| CN109928522A (en) * | 2019-04-17 | 2019-06-25 | 南京广全环保技术服务有限公司 | Compound phosphate-free corrosion inhibition antisludging agent and preparation method thereof |
| CN112645457A (en) * | 2019-10-11 | 2021-04-13 | 西南科技大学 | Environment-friendly corrosion and scale inhibitor for chromium salt wastewater evaporation system |
| CN111115856A (en) * | 2019-12-25 | 2020-05-08 | 河南普绿环保科技有限公司 | Green phosphorus-free scale and corrosion inhibition material for circulating cooling water |
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| CN101066811A (en) * | 2007-06-15 | 2007-11-07 | 武汉金坡化工科技有限公司 | No-phosphate corrosion and scale inhibitor and its application |
| CN101525185A (en) * | 2009-04-13 | 2009-09-09 | 李洪社 | Phosphorus-free corrosion and scale inhibitor and preparation method thereof |
| CN102557277A (en) * | 2010-12-21 | 2012-07-11 | 上海洗霸科技股份有限公司 | Phosphorus-free composite water treatment agent and preparation method thereof |
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| EP0541318A1 (en) * | 1991-11-06 | 1993-05-12 | Diversey Corporation | Cooling water treatment composition and method |
| CN101066811A (en) * | 2007-06-15 | 2007-11-07 | 武汉金坡化工科技有限公司 | No-phosphate corrosion and scale inhibitor and its application |
| CN101525185A (en) * | 2009-04-13 | 2009-09-09 | 李洪社 | Phosphorus-free corrosion and scale inhibitor and preparation method thereof |
| CN102557277A (en) * | 2010-12-21 | 2012-07-11 | 上海洗霸科技股份有限公司 | Phosphorus-free composite water treatment agent and preparation method thereof |
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Effective date of registration: 20160929 Address after: 210094 Xiaolingwei, Jiangsu, No. 200, Patentee after: NANJING University OF SCIENCE AND TECHNOLOGY Patentee after: Nanjing elegance Chemical Co.,Ltd. Address before: 210094 Xiaolingwei, Jiangsu, No. 200, Patentee before: Nanjing University of Science and Technology |
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