CN101353191A - Recirculated cooling water nanofiltration ion exchange softening micro-basification method - Google Patents

Recirculated cooling water nanofiltration ion exchange softening micro-basification method Download PDF

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Publication number
CN101353191A
CN101353191A CNA2008101968781A CN200810196878A CN101353191A CN 101353191 A CN101353191 A CN 101353191A CN A2008101968781 A CNA2008101968781 A CN A2008101968781A CN 200810196878 A CN200810196878 A CN 200810196878A CN 101353191 A CN101353191 A CN 101353191A
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water
type
cooling water
ion
hco
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CN101353191B (en
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叶春松
王世杰
曾惠明
林久养
佟立辉
钱勤
余菲
肖兴
叶金华
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BEIJING JIEMING ZHICHEN Corp
Wuhan University WHU
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BEIJING JIEMING ZHICHEN Corp
Wuhan University WHU
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Abstract

The invention discloses a method which is suitable for softening and dealing with industrial circulating cooling water by micro-basification. Nanofiltration process equipment is adopted for removing the multivalent ions such as Ca<2+>, Mg<2+>, SO4<2+>, and the like, in the water and some Na<+> ions are preserved, or the combination of cation-exchange resin weak-acid and nanofiltration is adopted for removing the multivalent ions such as Ca<2+>, Mg<2+>, SO4<2+>, and the like, in the water and some Na<+> ions are preserved; anion resin of OH-type/CO3-type/HCO3-type is adopted for removing the left superacid anions in the water, and the superacid anions are exchanged by OH<->/CO3<2->/HCO3<->, and the producing water is alkaline. The alkaline producing water reacts with the CO2 in the air to realize chemical equilibrium, and dilute solution with buffering is formed, the pH value of the circulating cooling water is adjusted to alkalescency ranging from 8.3 to 9.2, and softening and micro-basification treatment of the circulating cooling water is realized. The method of the invention can realize that various additionally added chemical agents such as antiseptic, corrosion inhibitor, scale inhibitor, water stabilizer, bactericidal algicide, and the like, are avoided for use in the circulating cooling water system, and has the technical effects of corrosion prevention, scaling prevention and microbial contamination prevention as well as comprehensive economic benefit that discharge of enriched water and chemical substance is reduced.

Description

A kind of method of recirculated cooling water nanofiltration ion exchange softening micro-basification
Technical field
The present invention is specifically related to the treatment process of a kind of industrial circulating cooling water nanofiltration ion exchange softening and little alkalization, belongs to field of environment engineering technology, also belongs to technical field of chemical engineering.
Background technology
The recirculating cooling water system of industrial water consumption maximum, modal problem are burn into fouling, microbial contamination, and concentrated water discharge contaminate environment water resource waste.The harm of modal three big problems is: corrosion, cause metal pipe material mechanical properties decrease even function to destroy corrosion product deposition affects water cooler heat exchange property; Fouling causes thermal resistance increase, heat transfer property decline, flow area to reduce, fail the increase of stream energy consumption, underdeposit corrosion etc.; Microbial growth causes heat transfer property to descend, also can produce corrosive pipeline, quickens pipeline scale.At this three big problem, traditional corrosion prevention measure mainly is plated film and adds inhibiter; Control fouling method is normally added Scale inhibitors; The controlling microbial growth method is to add Biocidal algae-killing agent.But, these technical measures need continuous dosing, keep doses, can obtain protection against corrosion preferably, good antiscale property and prevent the effect of microbial contamination, and, the thickening problem that also has aggressiveness ionic state material, deposition property impurity and inefficacy medicament needs the dense water of discharging, replenishes new water.There are problems such as water resource waste and environmental pollution in the dense water of discharging; The organic compound of bio-refractory in the dense water that effluxes can cause the severe contamination of water body and soil.
Aspect cooling system metallic corrosion protection, current the most frequently used method is that the pre-film of chemistry is handled earlier, adds inhibiter control corrosion then.Research about inorganic inhibitor has more report (HU Xian-qi, LIANG Cheng-hao, HUANG Nai-bao.Anticorrosion Performance of Carbon Steel in 55% LiBr SolutionContaining PMA/SbBr3 Inhibitor[J] .Journal of Iron and Steel Reserch, 2006,13 (4): 56-60; M.Saremi, C.Dehghanian, M.Mohammadi Sabet, The effect of molybdate concentration andhydrodynamic effect on mild steel corrosion inhibition in simulated cooling water[J] .Corrosion Science, 2006, (48): 1404-1412; Li Jianghua, Hu Yuehua. the research of caprolactam production apparatus recirculated cooling water corrosion inhibiting and descaling agent and application [J]. chemical industry progress, 2005,24 (3): 314-318).The research of novel organic inhibitor is based on azole material (S.Ramesha.S.Rajeswaria, S.Maruthamuthu.Corrosion inhibition ofcopper by new triazole phosphonate derivatives[J] .Applied Surface Science, 2004, (229): 214-225; M.Benmessaoud, K.Es-salah, N.Hajjaji, H.Takenouti, A.Srhiri and M.Ebentouhami.Inhibiting effect of 2-mercaptobenzimidazole on the corrosion of Cu-30Ni alloyin aerated 3%NaCl in presence of ammonia[J] .Corrosion Science, 2007, (49): 3880-3888).Obtained aspect the research of natural organic matter inhibiter certain progress (Lou Hongming, Qiu Xueqing, Yang Dongjie. the development of green corrosion inhibiting and descaling agent GCL2 and performance study [J]. Sichuan University's journal (engineering science version), 2002,34 (5): 93-97; A.Bouyanzer, B.Hammouti, L.Majidi.Pennyroyal oil from Mentha pulegium as corrosioninhibitor for steel in 1M HCl[J] .Materials Letters, 2006, (60): 2840-2843).But in any case, the inhibiter of interpolation has increased the salt content and the refractory organic of recirculated water, and after concentrating, necessary blowdown causes medicament loss and environmental pollution.
Industrial circulating cooling water system prevents the method for fouling, mainly is to add Scale inhibitors.Phosphorus is that the application of Scale inhibitors is comparatively general, and its subject matter is the nutrition source that dissolved phosphoric acid salt becomes microorganism.Be head it off, new prescription at research and development acrylic acid series Scale inhibitors has research report (P.Shakkthivel, T.Vasudevan, Acrylicacid-diphenylamine sulphonic acid copolymer threshold inhibitor for sulphate and carbonatescales in cooling water systems[J] .Desalination 2006 (197): 179-189; Yunxia ZHANG, JihuaiWU, Sancun HAO and Minghua LIU, Synthesis and Inhibition Efficiency of a NovelQuadripolymer Inhibitor[J] .Chinese Journal of Chemical Engineering 2007,15 (4): 600-605), with acrylic acid derivative is lime carbonate and the calcium sulfate scaling that main synthetic multiple copolymer is used for preventing recirculated cooling water, has effect preferably, but acrylic acid derivative is difficult to biological degradation.Carry out in addition composite reagent research report (Li Jianghua, Hu Yuehua etc. the research of caprolactam production apparatus recirculated cooling water corrosion inhibiting and descaling agent and application [J]. chemical industry makes progress, 2005,24 (3): 314-318; Dong-Jin Choi, Seung-Jae You and Jung-Gu Kim.Development of an environmentally safe corrosion, scale, and microorganism inhibitor foropen recirculating cooling systems[J] .Materials Science and Engineering 2002 (A335): 228-236), by combinational antisludging agent and inhibiter, utilize synergistic effect to improve powder performance, reduce consumption, but phosphorus and organic problem still exist.
Prevent recirculating cooling water system microbial contamination, main method is to add Biocidal algae-killing agent.Chlorine is a kind of medicament commonly used, but chlorination is not suitable for shellfish growth (Sanjeevi Rajagopal in the Control Circulation cooling water system, Gerard Van derVeldea, Marinus Van der Gaaga, Henk A.Jenner.How effective is intermittent chlorination tocontrol adult mussel fouling in cooling water systems[J] .Water Research 2003, (37): 329-338); Control for pathogenic agent (legionella), can adopt three water chloramine-T (Nazmiye OzlemSanli-Yurudu, Ayten Kimiran-Erdem, Aysin Cotuk.Studies on the efficacy of Chloramine Ttrihydrate (N-chloro-p-toluene sulfonamide) against planktonic and sessile populations ofdifferent Legionella pneumophila strains[J] .Int.J.Hyg.Environ.-Health 2007, (210), 147-153), but must consider microbiological manipulation dosage that swim and set simultaneously; Also there is report to be used for sulfate radical in the controlled chilling system and reduces (Susana SilvaMart ì nez such as bacterium and intestinal bacteria with electrolytic silver, copper and a certain amount of chlorine root proportioning, Alberto Alvarez Gallegos, Esteban Mart ì nez, Electrolytically generated silver andcopper ions to treat cooling water:an environmentally friendly novel alternative[J] .International Journal of Hydrogen Energy, 2004, (29): 921-93).Excessive oxidisability biocide, influential to the corrosion prevention of system; Various biocides all have certain toxicity in varying degrees.
The existing method of polluting based on anticorrosion, the antiscale and the preventing microorganism of the industrial cycle water system that adds chemical agent can not fundamentally solve problem of adding chemical agent itself and water resource waste and the problem of environmental pollution that is produced.The organism of the spissated salt in the sewer, heavy metal ion, difficult for biological degradation etc. causes the problem of irreversible breaking still to exist to environment.
Little alkalization theory of ion-exchange and technology thereof, Ye Chunsong etc. go up in the international water meeting (IWC) of calendar year 2001 first and propose (Chun-song YE, Jin-chu FAN.Controlling Corrosion of Copper Within a Turbine Generatorby Conditioning Inner Cooling Water Quality.2001 International Water Conference, Oct.21-25,2001, Pittsburgh, Pennsylvania, USA.IWC-01-28,205～211), and be applied to generator unit stator circulate the hollow copper conductor corrosion prevention of cold water system (Ye Chunsong. trace copper corrosion control principle and application technical research in the pure water. Tongji University's doctorate paper, 2002.4; Ye Chunsong, Zhang Jin, money duty, Fan Shengping. the accurate dynamic analog test research of generator copper conductor corrosion control [J]. corrosion science and guard technology, 2004, (01), 17-19; Ye Chunsong, Zhang Jin, money duty, Fan Shengping. the little alkalinisation treatment electric generator inner cooling water of ion-exchange experimental study [J]. Treatment of Industrial Water, 2004, (06), 17-19; Ye Chunsong, Liu Kaipei, the money duty, Chen Yongqiang, Luo Zhihong. the pure water cooling system leak testing research of Three Gorges power plant. the outstanding academic paper first prize, Hubei Province Electrical Engineering Society, 2006.12), the patent of invention of being declared obtained in 2003 country authorize (leaf spring pine .ZL01138300.3 inner-cooling water microcirculation slowly-releasing regulation and control method and supervisory system thereof. authorize time 2003.10.29).Through further investigation, development and application practice in a few years, the fairly perfect theoretical system and the application art of comparative maturity have been formed, formed technical specifications, write " electric generator inner cooling water treatment guide rule " technological standard (Ye Chunsong, Su Yao, Li Shaojie, the money duty. the power industry standard DL/T1039-2007 of the People's Republic of China (PRC) " electric generator inner cooling water treatment guide rule ". China Electric Power Publishing House, 2007.12).
Summary of the invention
The objective of the invention is, the problems referred to above at the recirculating cooling water system existence, according to the reason of burn into fouling and microbial contamination and the ultimate principle that tackles the problem at its root, take to remove the technical measures of detrimental impurity and water quality regulation, a kind of New Method for Processing of recirculated cooling water nanofiltration ion exchange softening micro-basification is provided, realizes that not needing to add chemical agent can work in coordination with antiscale, anticorrosion and preventing microorganism pollution; And when obtaining " three is anti-" technology effect, obtain the economy and the environmental benefit of water saving and pollution reduction naturally.
Technical thought of the present invention is to adopt nanofiltration membrane to remove Ca in the recirculated cooling water 2+, Mg 2+And SO 4 2+Deng polyvalent ion, retained part Na +Ion is realized water softening and partial deionization; Utilize OH type, CO 3Type or HCO 3Type anionite-exchange resin is with remaining NO in the water 3 -, Cl -Be exchanged for OH Deng strong acid anion -, CO 3 2-Or HCO 3 -, improve and produce alkalinity of water; Its produce water again with airborne CO 2Reach the dynamic chemical balance, obtain surge capability, and its pH value is adjusted to the slight alkalinity scope of 8.3-9.2.Through handling, recirculated cooling water by modified for having softening and little alkalization water of resiliency.
In the modified process of above-mentioned softening micro-basification, main chemical reactions is as follows:
NO 3 -+ROH→RNO 3+OH - (1)
Cl -+ROH→RCl+OH - (2)
OH -+CO 2→HCO 3 - (3)
Or: 2NO 3 -+ R 2CO 3→ 2RNO 3+ CO 3 2-(4)
2Cl -+R 2CO 3→2RCl+CO 3 2- (5)
CO 3 2-+H 2O+CO 2→2HCO 3 - (6)
Or: NO 3 -+ RHCO 3→ RNO 3+ HCO 3 -(7)
Cl -+RHCO 3→RCl+HCO 3 - (8)
2HCO 3 -→CO 3 2-+H 2O+CO 2 (9)
Reaction formula (1)～(2) are NO residual in the nanofiltration softening water 3 -, Cl -Deng the alkalization ion exchange reaction of strong acid anion and the generation of OH type resin, reaction generates OH -Softening alkalization water is again according to CO in reaction formula (3) and the air 2React and generate HCO 3 -Final recirculated water by modified for having the softening micro-basification water of resiliency.If adopt CO 3Type anionite-exchange resin carries out alkalinisation treatment, and then the strong acid anion in the recirculated water carries out according to reaction formula (4)～(5), the CO in the softening alkalization water 3 2-Again according to CO in reaction formula (6) and the air 2React and generate HCO 3 -Final recirculated water by modified for having the softening micro-basification water of resiliency.If adopt HCO 3Type anionite-exchange resin carries out alkalinisation treatment, and then the strong acid anion in the recirculated water carries out according to reaction formula (7)～(8), produces water again according to CO in reaction formula (9) and the air 2Reach hydrolysising balance, the pH value is increased to little alkalization scope; Final recirculated water by modified for having the softening micro-basification water of resiliency.
The technical scheme that the present invention proposes is: a kind of method of recirculated cooling water nanofiltration ion exchange softening micro-basification is characterized in that: adopt nanofiltration equipment to remove Ca in the water 2+, Mg 2+And SO 4 2+Polyvalent ion, retained part Na +Ion; Adopt OH type/CO 3Type/HCO 3Type anionite-exchange resin is removed and is remained strong acid anion in the water and it is exchanged for OH -/ CO 3 2-/ HCO 3 -Negatively charged ion.
The present invention adopts nanofiltration equipment to remove Ca in the water 2+, Mg 2+Ion, retained part Na +Ion has been removed fouling composition-hardness in the water; Adopt OH type/CO 3Type/HCO 3Type anionite-exchange resin is removed in the water strong acid anion and it is exchanged for OH -/ CO 3 2-/ HCO 3 -Negatively charged ion has been removed the Cl that strong acid anion in the water particularly has erosion action to passive film and the stainless steel of metals such as copper and carbon steel -Ion; CO in ion-exchanger water outlet or recirculated cooling water and the air 2Balance forms buffered soln, and recirculated cooling water pH value is adjusted to the slight alkalinity scope of 8.3-9.2.
Perhaps, recirculated cooling water by weakly acidic cationic exchanger resin and nanofiltration devices in series combined system, is removed Ca in the water 2+And Mg 2+Ion, and retained part Na +Ion; Then the water after the nanofiltration device processes is passed through OH type, CO 3Type or HCO 3Type anionite-exchange resin is removed strong acid anion in the water, and it is exchanged for OH -, CO 3 2-Or HCO 3 -Negatively charged ion.
Above-mentioned ion-exchanger water outlet or recirculated cooling water are through spray column and airborne CO 2Chemical reaction running balance, solution has resiliency.
The present invention adopts technique scheme, removes hardness in the water and metal passivation film and stainless steel pipe is had the Cl of erosion action -Ion can improve more than the recirculated water concentration rate to 10, thereby reduces concentrated water discharge, has water-saving benefit.Therefore, the recirculated water behind the softening micro-basification need not add pharmaceutical chemicalss such as Scale inhibitors, inhibiter and Biocidal algae-killing agent, has economic benefit of saving the chemical agent expense and the environmental benefit that reduces pollutant emission.
The technology that the present invention forms, be expected to obtain widespread use, have substantial economics and environmental benefit at power station recirculating cooling water system, petrochemical complex and ferrous metallurgy interchanger cooling water system, central air-conditioning cooling water system, semi-conductor industry cooling water system etc.
Embodiment
Embodiment 1: with recirculated water successively by nanofiltration equipment, OH type strong base anion exchange column, spray column.Nanofiltration equipment goes out water hardness 0.02mmol/L, cloudy post water outlet pH8.8, and after concentrating through circulating, pH is between 8.5-9.2.
Embodiment 2: with recirculated water successively by nanofiltration equipment, CO 3Type strong base anion exchange column, spray column.Nanofiltration equipment goes out water hardness 0.02mmol/L, cloudy post water outlet pH8.3, and after concentrating through circulating, pH is between 8.5-9.2.
Embodiment 3: with recirculated water successively by nanofiltration equipment, HCO 3Type strong base anion exchange column, spray column.Nanofiltration equipment goes out water hardness 0.02mmol/L, cloudy post water outlet pH5.6, and after the spray circulation concentrated, pH was between 8.5-9.2.
Embodiment 4: circulating water system is passed through Weak-acid cation exchange column, nanofiltration equipment and HCO successively 3Type strong base anion exchange column.Nanofiltration equipment goes out water hardness 0.02mmol/L, cloudy post water outlet pH5.5, and after the spray circulation concentrated, pH was between 8.3-9.2.

Claims (4)

1. the method for a recirculated cooling water nanofiltration ion exchange softening micro-basification is characterized in that: adopt nanofiltration equipment to remove Ca in the water 2+, Mg 2+And SO 4 2+Polyvalent ion, retained part Na +Ion; Adopt OH type/CO 3Type/HCO 3Type anionite-exchange resin is removed and is remained strong acid anion in the water and it is exchanged for OH -/ CO 3 2-/ HCO 3 -Negatively charged ion.
2. method according to claim 1 is characterized in that: also comprise and will pass through OH type, CO 3Type or HCO 3Water behind the type anionite-exchange resin is through CO in spray column and the air 2Chemical equilibrium is reached in reaction.
3. the method that recirculated cooling water ion exchange softening micro-basification is handled is characterized in that: comprise the steps: recirculated cooling water is passed through Weak-acid cation exchange column and nanofiltration devices in series combined system, remove Ca in the water 2+, Mg 2+And SO 4 2+Polyvalent ion, retained part Na +Ion; Adopt OH type, CO then 3Type or HCO 3Type anionite-exchange resin is removed in the water remaining strong acid anion and it is exchanged for OH -, CO 3 2-Or HCO 3 -Negatively charged ion.
4. method according to claim 3 is characterized in that: also comprise and will pass through OH type, CO 3Type or HCO 3Water behind the type anionite-exchange resin is through CO in spray column and the air 2Chemical equilibrium is reached in reaction.
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Cited By (5)

* Cited by examiner, † Cited by third party
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CN102583820A (en) * 2012-02-03 2012-07-18 美的集团有限公司 Filtering device of water purifier
CN104591437A (en) * 2015-01-05 2015-05-06 广东电网有限责任公司电力科学研究院 Inner cold water nanofiltration micro-basification treatment system and method of electric generator
CN105597512A (en) * 2016-01-20 2016-05-25 西北大学 Regenerating method of flue gas desulfurization agent
CN105498539B (en) * 2016-01-20 2017-06-16 西北大学 A kind of method for recycling of fume desulfurizing agent
CN111170497A (en) * 2019-11-29 2020-05-19 南京大学 Method for promoting Fenton oxidation efficiency by resin regulation and control

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN2601248Y (en) * 2003-03-10 2004-01-28 北京洁明天地环保设备有限公司 Small domestic water purifier
CN100999338A (en) * 2006-12-29 2007-07-18 哈尔滨双龙水处理技术开发有限公司 Power generator internal cooling water oxygen removal or electrolemma microalkalination treatment device and its treatment method
CN101234799A (en) * 2007-11-09 2008-08-06 武汉大学 Separating and regeneration method adapted for electric generator inner cooling water mixture iron exchange resin

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102583820A (en) * 2012-02-03 2012-07-18 美的集团有限公司 Filtering device of water purifier
CN104591437A (en) * 2015-01-05 2015-05-06 广东电网有限责任公司电力科学研究院 Inner cold water nanofiltration micro-basification treatment system and method of electric generator
CN105597512A (en) * 2016-01-20 2016-05-25 西北大学 Regenerating method of flue gas desulfurization agent
CN105498539B (en) * 2016-01-20 2017-06-16 西北大学 A kind of method for recycling of fume desulfurizing agent
CN105597512B (en) * 2016-01-20 2017-06-16 西北大学 A kind of renovation process of fume desulfurizing agent
CN111170497A (en) * 2019-11-29 2020-05-19 南京大学 Method for promoting Fenton oxidation efficiency by resin regulation and control

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