CN103803739A - Method for recycling of reclaimed water in circulating cooling water system - Google Patents
Method for recycling of reclaimed water in circulating cooling water system Download PDFInfo
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- CN103803739A CN103803739A CN201210448004.7A CN201210448004A CN103803739A CN 103803739 A CN103803739 A CN 103803739A CN 201210448004 A CN201210448004 A CN 201210448004A CN 103803739 A CN103803739 A CN 103803739A
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Abstract
The invention relates to a method for recycling of reclaimed water in a circulating cooling water system. The method comprises the steps of: (1) adding lime into reclaimed water to undergo partial softening, and then performing solid-liquid separation; (2) adding a hydroxycarboxylic acid salt and/or a transition metal acid salt corrosion inhibitor into the reclaimed water obtained after solid-liquid separation in step (1); (3) taking the reclaimed water added with the hydroxycarboxylic acid salt and/or the transition metal acid salt in step (2) as the make-up water of circulating cooling water, and adding the reclaimed water into the circulating cooling water of the circulating cooling water system; and (4) adding a polymer antiscale dispersant into the circulating cooling water added with the reclaimed water in step (3). According to the method provided by the invention, the whole operation process of delivering the reclaimed water to the circulating cooling water system realizes ''non-phosphorus'' operation, the water eutrophication risk caused by circulating water pollution discharge is avoided, and corrosion of reclaimed water to delivery pipelines can be effectively reduced.
Description
Technical field
The present invention relates to a kind of method that middle water is back to recirculating cooling water system.
Background technology
Current water resources worsening shortages, in order to realize the sustainable use of water resources, middle water more and more receives publicity as a kind of second water source reliable, that can reuse.Middle water mainly refers to that municipal effluent or sanitary sewage reach certain water quality standard after treatment, reusable undrinkable water within the specific limits, and its water-quality guideline, lower than drinking water standard, allows to enter the emission standard of surface water body higher than sewage.Middle water reuse has been implemented for a long time abroad, and reuse is on a grand scale, and has shown obvious economic benefit.
China's industrial water consumption is huge, and wherein with circulating cooling water consumption proportion maximum, and recirculating cooling water system is lower slightly compared with other production processes to the water quality requirement of its make up water.If middle water can be back to industrial circulating cooling water, not only can save a large amount of fresh waters, and can effectively alleviate the imbalance between supply and demand of town water.But middle water is back to recirculated cooling water and also has some problems in its course of conveying and follow-up recirculated cooling water operational process.
First, middle water and fresh water have certain gap in water quality, and therefore, in course of conveying, middle water is also serious than fresh water to corrosive pipeline.Corrosive pipeline not only can cause that tube wall attenuation and perforation leak, and shortens pipeline work-ing life, reduces pipeline water delivery ability and increases water delivery energy consumption etc., and can cause middle water water quality variation, increases it and enters the use difficulty after recirculated water.At present, domestic centering water course of conveying is not yet taked effective safeguard procedures.
Secondly, in recirculating cooling water system, applying now maximum treatment processs is chemical method, suppresses the corrosion of system by adding inhibiter, and domestic most widely used in circulating cooling water treatment, the most successful inhibiter is containing phosphor corrosion inhibitor.Due to the harm of well-known phosphoric acid salt to environment, be restricted gradually containing the use of phosphor corrosion inhibitor, circulating cooling water treatment is " without phosphatization " urgently.
CN1887749A discloses a kind of environmental protection composite scale inhibiter and application thereof.By weight percentage, this anti-incrustation corrosion inhibitor comprises the Sodium salts humic acids of 40-45%, polyepoxy sodium succinate, the borax of 20-25% and the soda ash of 10-15% of 25-30%.The present invention by organic and inorganic corrosion inhibiting and descaling agent, disperse sequestrant, auxiliary is composite forms, formula composition has obvious synergy, good with sterilant compatibility, to iron ion and halogen better tolerance.But this invention does not relate to the processing of centering water.
CN101125713A discloses a kind of liquid-type inhibiter that is exclusively used in closed circulation water system, and relates to its application and preparation method.This inhibiter contains following component and weight percent content: borax 5.5-10%, caustic alkali 1.0-3.0%, silicate 3.5-4.2%, nitrite 6.4-12.4%, 2-mercaptobenzothiazole 0.1-1.0%, remain as water.
CN101412565A discloses a kind of efficient scale corrosion inhibitor for carbon steel system, is grouped into by the one-tenth of following weight percent: organic phospho acid salt material 5%-15%; Polycarboxylic acid material 30%-40%; (methyl) acrylic acid or the like material 15%-40%; Multi-hydroxy carboxy acid or its sodium salt 6%-12%; Borax 1%-4%; Zinc salt 2%-8%; Water surplus.This invention is different with the anti-incrustation corrosion inhibitor that the present invention uses.
CN101438185A discloses a kind of green scale and corrosion inhibitor, this anti-incrustation corrosion inhibitor mainly comprises poly-epoxy succinic acid, sodium wolframate, Sodium Benzoate, benzotriazole, this invention is different with the anti-incrustation corrosion inhibitor that the present invention uses, and this anti-incrustation corrosion inhibitor neither be applied in middle water.
CN101565241A discloses a kind of non-phosphorus scale and corrosion inhibitor, and this anti-incrustation corrosion inhibitor mainly comprises the components such as poly-epoxy succinic acid, sodium wolframate, Sodium Benzoate, Methylbenzotriazole, Sunmorl N 60S, and this invention is different with the anti-incrustation corrosion inhibitor that the present invention uses.
Although investigator once carried out research to the corrosion inhibition of hydroxycarboxylate, transition metal mixtures at present, also with patent, hydroxycarboxylate, transition metal mixtures are formed together with other medicaments to the corrosion inhibitor formula of recirculating cooling water system by part document both at home and abroad.But the hydroxyl carboxylate salt of reporting in current document, the corrosion inhibitor formula of transition metal mixtures all exist different from the formula of the inhibiter that the present invention adopts.In addition, current technology is not all by hydroxycarboxylate, the corrosion inhibition of transition metal mixtures is applied in alleviation the etching problem of pipeline in water course of conveying, more do not have technology to add hydroxycarboxylate and/or transition metal mixtures by the middle water after lime treatment, to introduce in recirculating cooling water system through above-mentioned middle water after treatment again, on the low side by the middle water hardness after lime treatment, pH value meta-alkalescence, in addition the corrosion inhibition of hydroxycarboxylate and/or transition metal mixtures, exempt containing phosphor corrosion inhibitor at middle water as the application in the recirculating cooling water system of recirculated cooling water moisturizing.
Summary of the invention
While being back in recirculating cooling water system at present middle water, in existence, water needs to add the problem containing phosphor corrosion inhibitor in the etching problem to pipeline and recirculated cooling water in course of conveying, the object of this invention is to provide a kind of method that can effectively suppress the burn into of centering water transport pipe and recirculating cooling water system and need not be back to containing the middle water of phosphor corrosion inhibitor recirculated cooling water.
The present inventor finds through research, adopts the softening middle water of lime to be alkalescence, and higher pH value is conducive to inhibition.Meanwhile, in water, add hydroxycarboxylate and/or the transition metal mixtures with corrosion inhibition.Therefore method provided by the invention can suppress the etching problem of the middle water line of pipes existing in current technology effectively.
The invention provides a kind of method that middle water is back to recirculating cooling water system, the method comprises the following steps:
(1) in Xiang Zhongshui, add lime to soften and process rear solid-liquid separation;
(2) in the middle water obtaining, add hydroxycarboxylate and/or transition metal mixtures inhibiter after step (1) solid-liquid separation;
(3) will in step (2), add the middle water after hydroxycarboxylate and/or transition metal mixtures to join in the recirculated cooling water of recirculating cooling water system as the moisturizing of recirculated cooling water;
(4) in the recirculated cooling water after middle water, add polymeric scale inhibitor dispersion agent to adding in step (3).
Adopt middle water provided by the invention to be back to the method for recirculated cooling water, the phosphorus in can removing on the one hand in water; Can soften on the other hand middle water, reduce it and enter the fouling risk after recirculating cooling water system, reduce the difficulty of circulating cooling water treatment; In can also improving the pH value of water and suppress in the corrosion of heat exchanger to pipeline and after entering recirculated cooling water in water course of conveying, reduce the difficulty of circulating cooling water treatment.Generally, therefrom water is transported to the whole process of recirculating cooling water system operation, can realize " without phosphorus " operation, produces thereby significantly reduced recirculating cooling water system blowdown the risk of polluting.
Embodiment
The invention provides a kind of method that middle water is back to recirculating cooling water system, wherein, the method comprises the following steps:
(1) in Xiang Zhongshui, add lime to soften and process rear solid-liquid separation;
(2) in the middle water obtaining, add hydroxycarboxylate and/or transition metal mixtures inhibiter after step (1) solid-liquid separation;
(3) will in step (2), add the middle water after hydroxycarboxylate and/or transition metal mixtures to join in the recirculated cooling water of recirculating cooling water system as the moisturizing of recirculated cooling water;
(4) in the recirculated cooling water after middle water, add polymeric scale inhibitor dispersion agent to adding in step (3).
According to the present invention, " middle water " refers to the sanitary sewage of discharge, trade effluent to reclaim, and the water that can recycle after treatment, also claims reuse water.The treated facility deep purifying of municipal effluent water after treatment (comprise bath water, vegetable washing water etc. that sewage work deepens water after treatment and building, living community again through second-stage treatment concentrate water after treatment) is referred to as " middle water ".Its water quality is between tap water (upper water) and enter between sewage in pipeline (lower water), and also therefore named is " middle water ".It mainly refers to that municipal effluent or sanitary sewage reach certain water quality standard after treatment, reusable undrinkable water within the specific limits.The COD value of described middle water generally, below 100mg/L, is generally 15-100mg/L.According to reclaimed water reuse in industrial cycle cooling water standard, middle water COD of the present invention should≤60mg/L.
Described in the present invention, " Limiting Viscosity " is called again intrinsic viscosity, refers to the size of polymer shared volume in solution of unit mass.In the present invention, Limiting Viscosity adopts the water conditioner Limiting Viscosity measuring method in GB/T 22593-2008 to measure.
According to method of the present invention, step (1), the present invention is unslaked lime or white lime to the lime adding in middle water.While adding, can directly add solid, also can first be made into milk of lime and add again.The dosage of lime can according in water hardness and processing requirements regulate.Under normal circumstances, the dosage of lime is less than 100mg/L with the middle water hardness after softening and is as the criterion.Because the phosphatic content in middle water is lower, conventionally, adopt after lime treatment, phosphoric acid salt can all be removed.
According to method of the present invention, the present invention does not have particular requirement to the solid-liquid separating method in step (1), can be for prior art is for the various solid-liquid separating methods of water treatment.
According to method of the present invention, kind and the consumption of the present invention to described hydroxycarboxylate's inhibiter do not have special restriction, preferably, the an alkali metal salt that described hydroxycarboxylate's inhibiter is hydroxycarboxylic acid, further preferred described hydroxycarboxylic acid be in gluconic acid, tartrate, citric acid, lactic acid and oxysuccinic acid one or more, described basic metal is sodium and/or potassium; Further preferred described hydroxycarboxylic acid is gluconic acid and/or tartrate; Preferably, in step (2), take middle water every liter described as benchmark, described hydroxycarboxylate's add-on 2-25mg, is preferably 5-20mg.
According to method of the present invention, kind and the consumption of the present invention to described transition metal mixtures inhibiter do not have special restriction, preferably, anhydride and/or the hydrate of an alkali metal salt that described transition metal mixtures inhibiter is transition metal acid, described transition metal is the metal in VB family in the periodic table of elements, group vib and VIIB family; Further preferred described transition metal acid be in molybdic acid, wolframic acid, metavanadic acid and vanadic acid one or more, described basic metal is sodium and/or potassium; The anhydride that further preferred described transition metal mixtures is Sodium orthomolybdate and/or potassium molybdate and/or hydrate (when hydrate, the amount of water is deducted in the time calculating consumption); Preferably, in step (2), take middle water every liter described as benchmark, the add-on of described transition metal mixtures is 2-25mg, is preferably 5-20mg.
According to method of the present invention, kind and the consumption of the present invention to described polymeric scale inhibitor dispersion agent do not have special restriction, preferably, wherein, described polymeric scale inhibitor dispersion agent is selected from poly-(methyl) vinylformic acid, polymaleic acid, poly-methylene-succinic acid, poly-epoxy succinic acid, poly aspartic acid, (methyl) vinylformic acid-polymerization of itaconic acid thing, (methyl) vinylformic acid-(methyl) Propylene glycol monoacrylate polymkeric substance, (methyl) vinylformic acid-2-acrylamide-2-methyl-propyl sulfonic acid polymer, one or more in (methyl) vinylformic acid-(methyl) Propylene glycol monoacrylate-2-acrylamide-2-methyl-propyl sulfonic acid polymer.
According to the present invention, in the embodiment that is copolymer anti-scale disperser at described polymeric scale inhibitor dispersion agent, the present invention does not have special requirement for kind and the weight ratio thereof of various monomers in described copolymer anti-scale disperser, described copolymer anti-scale disperser can be the conventional various copolymer anti-scale dispersers in this area, as long as this multipolymer can play the effect of scale inhibition and antiscale.Preferably, described in while controlling 30 ℃, the Limiting Viscosity of copolymer anti-scale disperser is 0.06-0.1dl/g, more preferably 0.065-0.095dl/g.Be in the embodiment of homopolymer dirt dispersion agent at described polymeric scale inhibitor dispersion agent, described homopolymer dirt dispersion agent can be the conventional various homopolymer dirt dispersion agents in this area, as long as this homopolymer can play the effect of scale inhibition and antiscale.Preferably, described in while controlling 30 ℃, the Limiting Viscosity of homopolymer dirt dispersion agent is 0.06-0.1dl/g, more preferably 0.065-0.095dl/g.Preferably, in step (4), take recirculated cooling water every liter described as benchmark, the add-on of described polymeric scale inhibitor dispersion agent is 4-25mg, is preferably 5-20mg.
Polymeric scale inhibitor dispersion agent of the present invention all can be commercially available, and also laboratory is synthetic as required obtains.Synthetic method is those skilled in the art's common practise, does not repeat them here.
According to method of the present invention, the method is also included in step (4), adds in the recirculated cooling water after middle water and adds Azole Corrosion Inhibitors to step (3).Kind and the consumption of the present invention to described Azole Corrosion Inhibitors do not have special restriction, and preferably, described Azole Corrosion Inhibitors is selected from one or more in benzotriazole, methyl benzotriazazole and mercaptobenzothiazole; Take recirculated cooling water every liter described as benchmark, the add-on of described Azole Corrosion Inhibitors is 0.25-4.5mg, is preferably 0.5-4mg.Add Azole Corrosion Inhibitors, can more effectively suppress the corrosion to copper.
Described Azole Corrosion Inhibitors can add with polymeric scale inhibitor dispersion agent simultaneously, for example, can after Azole Corrosion Inhibitors is together with after polymeric scale inhibitor dispersant, add simultaneously again; Described Azole Corrosion Inhibitors also can add before or after adding polymeric scale inhibitor dispersion agent, and in such cases, the joining day interval of described polymeric scale inhibitor dispersion agent and Azole Corrosion Inhibitors is preferably no more than 3-30 minute.
To be further described in detail the present invention by specific embodiment below.
The present invention adopts GB/T 22593-2008 water conditioner Limiting Viscosity measuring method to measure the Limiting Viscosity of polymeric scale inhibitor dispersion agent.
The present invention carries out corrosion mitigating effect evaluation test with reference to State Standard of the People's Republic of China GB/T 18175-2000 " mensuration-rotary hanging plate method of water conditioner corrosion inhibition " to following embodiment and comparative example.In to the evaluation test of intermediate water pipeline conveying corrosion mitigating effect: test temperature is 30 ± 1 ℃; Test piece rotating speed is 120rpm; Test period is 72h; Test piece material is 20# carbon steel.
In to the evaluation test of recirculating cooling water system corrosion mitigating effect: the test piece of 20# carbon steel or the test piece of H62 brass are fixed on lacing film instrument, put into respectively the test water of embodiment or comparative example, 45 ± 1 ℃ of steady temperatures, keep rotating speed 75rpm rotation 72h, before and after record test, the weight of test piece, calculates average corrosion rate.
Average corrosion rate calculation formula is:
C: computational constant, take mm/a (millimeter/year) during as unit, C=8.76 × 10
7
△ W: the corrosion weight loss (g) of test specimen; A: the area (cm of test specimen
2); T: corrosion test time (h)
ρ: the density (kg/m of material for test
3)
Test with in water and fresh water water quality in table 1.
Table 1 test water water quality
| Project | Detection method | Middle water 1 | Middle water 2 | Middle water 3 | Fresh water |
| COD/(mg/L) | GB?11914-1989 | 11 | 23 | 18 | 0 |
| Ca 2+/(mg/L) | GB/T6910-1986 | 87.9 | 156.2. | 246.6 | 188.5 |
| Total hardness/(mg/L) | GB/T?15452-2009 | 102.3 | 188.4 | 315.5 | 223.2 |
| Total alkalinity/(mg/L) | GB/T15451-2006 | 93.4 | 145.5 | 241.7 | 217.4 |
| Cl -/(mg/L) | GB/T6905.3-1986 | 23.3 | 35.4 | 77.8 | 31.5 |
| SO 4 2-/(mg/L) | Q/SH3155.S08.008-2006 | 32.5 | 28.7 | 92.1 | 58.7 |
| Specific conductivity/(μ S/cm) | GB/T6908-1986 | 298 | 592 | 1115 | 874 |
| pH | GB/T6904.1-1986 | 7.54 | 7.67 | 7.84 | 7.64 |
| Total phosphorus/(mg/L) | HG/T3540-1990 | 0.68 | 1.27 | 1.41 | 0 |
| Positive phosphorus/(mg/L) | HG/T3540-1990 | 0.64 | 1.23 | 1.38 | 0 |
Note: Ca
2+, total alkalinity, total hardness be all with CaCO
3meter; Total phosphorus, positive phosphorus are all with PO
4 3-meter.
In following examples, the concentration of all water treatment agents all refers to effective concentration, i.e. the concentration of the effective constituent in every kind of water treatment agent.
Embodiment 1
Take middle water 1 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 120mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds Sunmorl N 60S 15mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.By concentrated 6.0 times of above-mentioned middle water, simulation adds the middle water of aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add polymaleic acid (Nanjing Chemical Engineering College's Changzhou Wujin water quality stabilizer factory, Limiting Viscosity 30 ℃ time is 0.077dL/g) 8mg/L and methyl phenylpropyl alcohol triazole 3.0mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 2
Take middle water 2 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 220mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds Sodium orthomolybdate, makes Sodium orthomolybdate in the middle water after softening (with MoO
4 2-meter) concentration be 8mg/L, carry out intermediate water pipeline with this and carry corrosion evaluation test.By concentrated 4 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add poly-methylene-succinic acid (Nanjing Chemical Engineering College's Changzhou Wujin water quality stabilizer factory, the Limiting Viscosity 30 ℃ time is 0.071dL/g) 15mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 3
Take middle water 3 as test water, add wherein unslaked lime, take water in every liter as benchmark, unslaked lime is (with CaCO
3meter) add-on be 390mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds potassium molybdate and soluble tartrate, makes potassium molybdate in the middle water after softening (with MoO
4 2-meter) concentration be 4mg/L, the concentration of soluble tartrate is 6mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.By concentrated 3.5 times of above-mentioned middle water, simulation joins the state in the recirculated cooling water in recirculating cooling water system using the middle water of aforementioned inhibiter as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add polyacrylic acid (Limiting Viscosity 30 ℃ time is 0.068dL/g for Changzhou whole world Chemical Co., Ltd., trade mark LN-107) 12mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 4
Take middle water 2 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 180mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds sodium tartrate and Potassium Gluconate, and making the concentration of the sodium tartrate in the middle water after softening is 6mg/L, and the concentration of Potassium Gluconate is 6mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.By concentrated 4 times of above-mentioned middle water, the middle water in simulation production scene after aforementioned inhibiter joins the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water, obtains simulation loop water coolant.In simulation loop water coolant, add vinylformic acid/Propylene glycol monoacrylate polymkeric substance (Changzhou whole world Chemical Co., Ltd., trade mark LN-108, in polymkeric substance, the weight ratio of acrylic acid structure unit and Propylene glycol monoacrylate is 4:1, Limiting Viscosity 30 ℃ time is 0.077dL/g) 17mg/L and benzotriazole 2.0mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 5
Take middle water 3 as test water, add wherein unslaked lime, take water in every liter as benchmark, unslaked lime is (with CaCO
3meter) add-on be 90mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds sodium malate, and making the concentration of the oxysuccinic acid in the middle water after softening is 13mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.By concentrated 4.5 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add (the Changjiang river, the Shandong Chemical Co., Ltd. production of vinylformic acid/2-acrylamide-2-methyl propane sulfonic polymkeric substance, weight ratio is vinylformic acid and 2 '-acrylamide-2-methyl propane sulfonic copolymerization products therefrom of 3:1, Limiting Viscosity 30 ℃ time is 0.073dL/g) 9mg/L, carries out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 6
Take middle water 3 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 280mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds potassium vanadate, makes in the middle water after softening potassium vanadate (with VO
4 3-meter) concentration be 18mg/L, carry out intermediate water pipeline with this and carry corrosion evaluation test.By concentrated 3 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add vinylformic acid/Propylene glycol monoacrylate/2-acrylamide-2-methyl propane sulfonic polymkeric substance (Changzhou whole world Chemical Co., Ltd., trade mark LN-104B, weight is vinylformic acid, Propylene glycol monoacrylate and the 2-acrylamide-2-methyl propane sulfonic copolymerization products therefrom of 4:1:1, Limiting Viscosity 30 ℃ time is 0.083dL/g) 13mg/L, carries out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 7
Take middle water 2 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 140mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds Trisodium Citrate, and making the concentration of the Trisodium Citrate in the middle water after softening is 20mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.By concentrated 5 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add hydrolytic polymaleic anhydride (Changzhou whole world Chemical Co., Ltd., trade mark LN-106, Limiting Viscosity 30 ℃ time is 0.082dL/g) 20mg/L and methyl benzotriazazole 0.5mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 8
Take middle water 3 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 320mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds vanadic acid sodium, makes vanadic acid sodium in the middle water after softening (with VO
4 3-meter) concentration be 16mg/L, carry out intermediate water pipeline with this and carry corrosion evaluation test.By concentrated 2.5 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add vinylformic acid/polymerization of itaconic acid thing (Nanjing Chemical Engineering College's Changzhou Wujin water quality stabilizer factory, weight is vinylformic acid and the polymerization of itaconic acid products therefrom of 3:1, Limiting Viscosity 30 ℃ time is 0.073dL/g) 11mg/L, carries out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 9
Take middle water 1 as test water, add wherein unslaked lime, take water in every liter as benchmark, unslaked lime is (with CaCO
3meter) add-on be 100mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds sodium metavanadate, and the concentration that makes the sodium metavanadate in the middle water after softening is (with VO
3 -meter) 5mg/L, carries out intermediate water pipeline with this and carries corrosion evaluation test.By concentrated 3.5 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add poly aspartic acid (Jin Long Chemical Co., Ltd. of Heng Tai county of Shandong Province, the Limiting Viscosity 30 ℃ time is 0.042dL/g) 5mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 10
Take middle water 3 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 350mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds Seignette salt and Sodium.alpha.-hydroxypropionate, and making the concentration of the middle water unresolvable tartaric acid potassium sodium after softening is 4mg/L, and the concentration of Sodium.alpha.-hydroxypropionate is 5mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.By concentrated 4.0 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add vinylformic acid/Propylene glycol monoacrylate polymkeric substance (Changzhou whole world Chemical Co., Ltd., trade mark LN-108, weight ratio is 4:1 vinylformic acid and Propylene glycol monoacrylate polymerization products therefrom, Limiting Viscosity 30 ℃ time is 0.077dL/g) 14mg/L and mercaptobenzothiazole 1.0mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 11
Take middle water 2 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 160mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds potassium lactate and potassium malate, and making the concentration of potassium lactate in the middle water after softening is 6mg/L, and the concentration of potassium malate is 5mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.By concentrated 4.5 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add poly-epoxy succinic acid (Limiting Viscosity 30 ℃ time is 0.082dL/g for Changzhou whole world Chemical Co., Ltd., trade mark LN-110) 10mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 12
Take middle water 1 as test water, add wherein unslaked lime, take water in every liter as benchmark, unslaked lime is (with CaCO
3meter) add-on be 110mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds sodium wolframate and Tripotassium Citrate, makes sodium wolframate in the middle water after softening (with WO
4 2-meter) concentration be 9mg/L, the concentration of Tripotassium Citrate is 7mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.By concentrated 5 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add hydrolytic polymaleic anhydride (Limiting Viscosity 30 ℃ time is 0.082dL/g for Changzhou whole world Chemical Co., Ltd., trade mark LN-106) 18mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Embodiment 13
Take middle water 2 as test water, add wherein white lime, take water in every liter as benchmark, white lime is (with CaCO
3meter) add-on be 200mg/L, the middle water after solid-liquid separation is softened.Middle water after softening adds potassium wolframate and potassium metavanadate, makes potassium wolframate in the middle water after softening (with WO
4 2-meter) concentration be 8mg/L, potassium metavanadate is (with VO
3 -meter) concentration be 6mg/L, carry out intermediate water pipeline with this and carry corrosion evaluation test.By concentrated 6.0 times of above-mentioned middle water, simulation adds the middle water after aforementioned inhibiter to join the state in the recirculated cooling water in recirculating cooling water system as the moisturizing of recirculated cooling water in production scene, obtains simulation loop water coolant.In simulation loop water coolant, add vinylformic acid-Propylene glycol monoacrylate polymkeric substance (Changzhou whole world Chemical Co., Ltd., trade mark LN-108, weight ratio is vinylformic acid and the Propylene glycol monoacrylate polymerization products therefrom of 4:1, Limiting Viscosity 30 ℃ time is 0.077dL/g) 8mg/L, poly aspartic acid (Jin Long Chemical Co., Ltd. of Heng Tai county of Shandong Province, Limiting Viscosity 30 ℃ time is 0.042dL/g) 8mg/L and benzotriazole 4.0mg/L, carry out the test of recirculating cooling water system corrosion evaluation with this.Twice test-results is in table 2.
Comparative example 1
Not carrying out the softening processing of lime, do not add under the condition of hydroxycarboxylate and/or transition metal mixtures yet, carry out pipeline with middle water 1 and carry corrosion evaluation test, the results are shown in Table 2.
Comparative example 2
Not carrying out the softening processing of lime, do not add under the condition of hydroxycarboxylate and/or transition metal mixtures yet, carry out pipeline with middle water 2 and carry corrosion evaluation test, the results are shown in Table 2.
Comparative example 3
Not carrying out the softening processing of lime, do not add under the condition of hydroxycarboxylate and/or transition metal mixtures yet, carry out pipeline with middle water 3 and carry corrosion evaluation test, the results are shown in Table 2.
Comparative example 4
Not carrying out the softening processing of lime, do not add under the condition of hydroxycarboxylate and/or transition metal mixtures yet, carry out pipeline with fresh water and carry corrosion evaluation test, the results are shown in Table 2.
Comparative example 5
Take middle water 1 as test water, add wherein unslaked lime, take water in every liter as benchmark, unslaked lime is (with CaCO
3meter) add-on be 120mg/L, the middle water after solid-liquid separation soften, carry out pipeline carry corrosion evaluation test.
Comparative example 6
Take middle water 2 as test water, add wherein Sunmorl N 60S, take water in every liter as benchmark, the concentration of Sunmorl N 60S is 20mg/L, carries out intermediate water pipeline carry corrosion evaluation test with this.
Comparative example 7
Take middle water 3 as test water, add wherein potassium molybdate, take water in every liter as benchmark, potassium molybdate is (with MoO
4 2-meter) concentration be 20mg/L, carry out intermediate water pipeline with this and carry corrosion evaluation test.
Table 2 corrosion evaluation test-results
Table 2 result shows, in comparative example 1-3, in three kinds of different qualities, the erosion rate of water will be apparently higher than the erosion rate of fresh water in comparative example 4.By method provided by the invention, embodiment 1-13 has added lime, hydroxycarboxylate and/or transition metal mixtures in middle water, significantly reduced the erosion rate of middle water, illustrate method provided by the invention can effectively alleviate in the corrosion of water to its transport pipe.Meanwhile, effect of the present invention also will significantly be better than the Corrosion results take fresh water as subjects in comparative example 4.Comparative example 5-7 is the test-results that in three kinds, water has added separately respectively lime, hydroxycarboxylate or transition metal mixtures, can find out and in comparative example 5, add separately lime to have comparatively obviously corrosion mitigating effect, but also there is a big difference with the corrosion mitigating effect of embodiment; In comparative example 6-7, add separately hydroxycarboxylate or transition metal mixtures, do not have obvious corrosion mitigating effect.
In addition, table 2 result also shows, according to the middle water of the method for the invention processing as a supplement water be back to after recirculating cooling water system, only need add polymeric scale inhibitor dispersion agent and optionally add copper inhibitor, system can keep lower erosion rate under certain cycles of concentration, meets the requirement of circulating cooling water treatment completely.
Embodiment 14
For simulated field, carry out dynamic analog test.Dynamic analog test method is undertaken by the chemical industry standard HG/T2160-91 of the People's Republic of China (PRC), and test piece material is 20# carbon steel; Test tube material is H62 brass.Control parameter is as follows.
Water quality: the middle water 2 in table 1, through white lime (with CaCO
3meter) 220mg/L is softening, and the clear liquid after filtration adds Sodium orthomolybdate (with MoO
4 2-meter) 8mg/L
Cycles of concentration (ratio of the saltiness of recirculated cooling water and make up water saltiness): 4.0 ± 0.2
PH: nature
Flow velocity: 1.0m/s
Medicament: poly-methylene-succinic acid (30 ℃ time Limiting Viscosity be 0.071dL/g) 15mg/L
Recirculated water is in the temperature at heat exchanger entrance place: 32 ± 1 ℃
Recirculated water is imported and exported the temperature difference: 8-10 ℃
Working time: 16 days
Dynamic analog test the results are shown in Table 3.
Table 3 dynamic analog test result
| Lacing film erosion rate (mm/a) | Test tube adheres to speed (mcm) |
| 0.015 | 3.5 |
Table 3 result shows, apply method of the present invention, middle water is back to recirculated cooling water, the erosion rate of lacing film is 0.015mm/a, is better than " the small-sized experimental analogic method of testing laboratory " " fine level " standard in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment; Adhere to speed 3.5mcm, reach " fine level " standard in " the small-sized experimental analogic method of testing laboratory " in " water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment.
By comprehensive treating process of the present invention, can guarantee that therefrom water is transported to the security of recirculating cooling water system operation whole process, and can realize whole process " without phosphorus " operation, produce thereby significantly reduced recirculating cooling water system blowdown the risk of polluting.
Claims (10)
1. in, water is back to a method for recirculating cooling water system, it is characterized in that, the method comprises the following steps:
(1) in Xiang Zhongshui, add lime to soften and process rear solid-liquid separation;
(2) in the middle water obtaining, add hydroxycarboxylate and/or transition metal mixtures inhibiter after step (1) solid-liquid separation;
(3) will in step (2), add the middle water after hydroxycarboxylate and/or transition metal mixtures to join in the recirculated cooling water of recirculating cooling water system as the moisturizing of recirculated cooling water;
(4) in the recirculated cooling water after middle water, add polymeric scale inhibitor dispersion agent to adding in step (3).
2. method according to claim 1, wherein, the an alkali metal salt that described hydroxycarboxylate's inhibiter is hydroxycarboxylic acid, preferred described hydroxycarboxylic acid is one or more in gluconic acid, tartrate, citric acid, lactic acid and oxysuccinic acid, described basic metal is sodium and/or potassium; Further preferred described hydroxycarboxylate's inhibiter is one or more in Sunmorl N 60S, Potassium Gluconate, sodium tartrate and soluble tartrate.
3. method according to claim 1 and 2, wherein, in step (2), take middle water every liter described as benchmark, the add-on of described hydroxycarboxylate's inhibiter is 2-25mg, is preferably 5-20mg.
4. method according to claim 1, wherein, described transition metal mixtures inhibiter is an alkali metal salt of transition metal acid, described transition metal is the metal in VB family in the periodic table of elements, group vib and VIIB family; Preferred described transition metal acid be in molybdic acid, wolframic acid, metavanadic acid and vanadic acid one or more, described basic metal is sodium or potassium; Further preferred described transition metal mixtures is Sodium orthomolybdate and/or potassium molybdate.
5. according to the method described in claim 1 or 4, wherein, in step (2), take middle water every liter described as benchmark, the add-on of described transition metal mixtures inhibiter is 2-25mg, is preferably 5-20mg.
6. method according to claim 1, wherein, described polymeric scale inhibitor dispersion agent is selected from one or more in poly-(methyl) vinylformic acid, polymaleic acid, poly-methylene-succinic acid, poly-epoxy succinic acid, poly aspartic acid, (methyl) vinylformic acid-polymerization of itaconic acid thing, (methyl) vinylformic acid-(methyl) Propylene glycol monoacrylate polymkeric substance, (methyl) vinylformic acid-2-acrylamide-2-methyl-propyl sulfonic acid polymer, (methyl) vinylformic acid-(methyl) Propylene glycol monoacrylate-2-acrylamide-2-methyl-propyl sulfonic acid polymer.
7. according to the method described in claim 1 or 6, wherein, in step (4), take recirculated cooling water every liter described as benchmark, the add-on of described polymeric scale inhibitor dispersion agent is 4-25mg, is preferably 5-20mg.
8. according to the method described in claim 1 or 6, wherein, Limiting Viscosity when 30 ℃ of described polymeric scale inhibitor dispersion agents is 0.060-0.1dl/g.
9. method according to claim 1, wherein, the method is also included in step (4), adds in the recirculated cooling water after middle water and adds Azole Corrosion Inhibitors to step (3).
10. method according to claim 9, wherein, described Azole Corrosion Inhibitors is selected from one or more in benzotriazole, methyl benzotriazazole and mercaptobenzothiazole; In step (4), take recirculated cooling water every liter described as benchmark, the add-on of described Azole Corrosion Inhibitors is 0.25-4.5mg, is preferably 0.5-4mg.
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| CN104355419A (en) * | 2014-12-03 | 2015-02-18 | 天津天和环能科技有限公司 | Multifunctional scale and corrosion inhibitor and preparation method thereof |
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| CN115584506B (en) * | 2021-07-05 | 2024-04-16 | 天津科技大学 | Preparation method of green efficient compound gas phase corrosion inhibitor for carbon steel |
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