CN100469707C - Treatment method of high turbidity high iron circulation cooling water - Google Patents
Treatment method of high turbidity high iron circulation cooling water Download PDFInfo
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Abstract
A process for treating the circulated high-turbidity high-Fe cooling water features that the composite bactericide prepared from polychlorinated-2-hydroxyproply-1, 1-N-dimethylammonium and at least one quaternary ammonium salt is added to said cooling water, which is acting in conjunction with the polymer disperser in the cooling water and the by-pass filter for killing bacteria, flocculating suspended substances and filtering out them.
Description
Technical field
The present invention relates to a kind of treatment process of high turbidity high iron circulation cooling water, particularly turbidity is that 10-30mg/L, iron level are the treatment process of 0.5-1.5mg/L recirculated cooling water.
Background technology
Circulating water treatment technology mainly is divided into two kinds: a kind of is not add sour natural pH operation process, and a kind of is to add acid to transfer pH technology.
For not adding sour natural pH operation process, system does not add acid for adjusting pH value in operational process, the pH value Balance of nature of recirculated water about 9, soft in general being fit to, in low basicity water quality, control calcium hardness and total alkalinity sum are less than 950mgL in the recirculated water
-1The corrosion of the basic ideas of this technology for assisting some inhibiter to come suppression equipment by the high pH value alkaline state under, again suppresses the fouling of system by adding dirt dispersion agent efficiently.The advantage of this technology is that corrosion is easier to control, and shortcoming is that cycles of concentration can not be too high, and the calcium hardness total alkalinity sum that present level both domestic and external is a recirculated water is generally less than 950mgL
-1, otherwise system's fouling will exceed standard, so just very water wasting for the higher make up water of calcium ion and basicity.The corrosion-mitigation scale-inhibition agent prescription is mainly organic phospho acid, zinc salt and contains multipolymer of carboxylic acid group etc. under this processing condition, is referred to as the alkaline operation prescription.
Transfer pH technology for adding acid, system adds acid for adjusting pH value in operational process, and this technology is fit to high rigidity, high basicity water quality, and according to our understanding to domestic circulating water treatment situation, this technology is to moisturizing Ca
2+Greater than 250mgL
-1Condition of water quality, cycles of concentration is generally at 3～5 times.The basic ideas of this technology are with adding H
2SO
4The method pH value of coming Control Circulation water, reduce the basicity in the recirculated water, and then anti-locking system fouling; The inhibiter during increase is filled a prescription simultaneously and the consumption of dispersion agent, the etching problem of emphasis resolution system.The advantage of this technology is that fouling is easier to control, and cycles of concentration is higher, the Ca of recirculated water
2+Can reach 1400mgL
-1, water-saving result is good, and shortcoming is the difficult control of corrosion, and the calcium ion in the recirculated water can not be too low, need to use inhibiter such as inorganic phosphorus, zinc salt, otherwise system's corrosion will exceed standard.Be mainly organic phospho acid, inorganic phosphate, zinc salt and suppress phosphoric acid salt and the zinc salt deposition effect is good contains carboxylic acid group and sulfonic multipolymer at the corrosion-mitigation scale-inhibition agent prescription of processing condition, be referred to as to add acid operation prescription.
At present, domestic each circulating water system is perhaps used not add sour natural pH operation process and corresponding reagent combination according to the characteristics of water quality separately, perhaps uses to add acid and transfer pH technology and corresponding prescription.After circulating water system operation for some time, as turbidity taking place with total iron when higher, circulating water system is taked the method for large excretion and large complement usually, promptly adds adhesive mud remover earlier, and after peeling off, a large amount of drainings add corrosion inhibiting and descaling agent again.This method not only needs a large amount of drainings, also need consume a large amount of corrosion inhibiting and descaling agents again, and needs several days even tens days.
Chinese patent application CN1193609A discloses the cleaning prefilming agent that is used for dirts such as cleaning system microorganism dirt in a kind of circulating water system and has cleaned prefilming method, clean prefilming agent and constitute by biological enzyme scavenging agent, biostats, inorganic salt complex agent with by the conventional water quality stabilizer that inhibiter and dispersion agent are formed, wherein inorganic salt complex agent is made up of silicate, manganate, carbonate, orthophosphoric acid salt.Cleaning prefilming method is under the normal operating condition of circulating water regiment commander thermal load, biological enzyme scavenging agent, biostats, inorganic salt complex agent and conventional water quality stabilizer are joined in the recirculated water by the specific concentrations of always possessing the water yield respectively, and kept this concentration 15-60 days.This method can realize that circulation system at hot does not stop and clean pre-film and once finish.This method is different with the treatment process of high turbidity high iron circulation cooling water of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of treatment process of high turbidity high iron circulation cooling water, use method of the present invention that the recirculated cooling water of high turbidity high iron is handled the effectively turbidity and the iron level of Control Circulation water coolant.
For achieving the above object, the invention provides a kind of treatment process of high turbidity high iron circulation cooling water, its characteristics are to add in high turbidity high iron circulation cooling water by polychlorostyreneization-2-hydroxypropyl-1, the compound disinfectant that 1-N-dimethylammonium (abbreviation polyquaternium) and at least a quaternary ammonium salt are formed.Described quaternary ammonium salt has sterilization and peels off effect, polychlorostyreneization-2-hydroxypropyl-1, the 1-N-dimethylammonium has sterilization and throwing out concurrently, the compound disinfectant that is added cooperates existing polymeric dispersant in the recirculated cooling water, and the by-pass flow of recirculated water is handled, can make sterilization and the throwing out of suspended substance by compound disinfectant in the water, the dissemination that cooperates multipolymer simultaneously, form big floc sedimentation but do not adhere to water cooler, the bypass strainer that floc sedimentation is handled by by-pass flow subsequently filters and can reach the turbidity that reduces recirculated cooling water and the purpose of iron level.Method of the present invention not only can make high turbidity high iron circulation cooling water obtain fast processing, and need not big water gaging the water in the system is replaced, and this method erosion rate is little, and is safe and reliable, is fit to the processing of the recirculated cooling water of high turbidity high iron circulating water system.
Polychlorostyreneization of the present invention-2-hydroxypropyl-1,1-N-dimethylammonium and quaternary ammonium salt weight ratio are 50-95:5-40.Be preferably 80-95:5-20.
Quaternary ammonium salt preferred formula of the present invention is R
1(R
3)
2NR
2The quaternary ammonium salt of X, wherein R
1With R
2Identical or different, R
1Be dodecyl, tetradecyl or hexadecyl, R
2Be octyl or decyl or benzyl, R
3For carbonatoms is the alkyl of 1-4, X is a chlorine or bromine.More preferably chlorination tetradecyl dimethyl benzyl ammonium, dodecyl dimethyl benzyl ammonium chloride, chlorination dodecyl octyldimethyl ammonium or chlorination tetradecyl octyldimethyl ammonium.
Polychlorostyreneization of the present invention-2-hydroxypropyl-1,1-N-dimethylammonium concentration in the time of 25 ℃ is that the viscosity of 40 weight % is at least 10mpa/s.It can be raw material by dimethylamine and epoxy chloropropane, be that solvent carries out solution polymerization and obtains with water.
The add-on of compound disinfectant of the present invention is 20-80mg compound disinfectant/L water.Be preferably 30-40mg compound disinfectant/L water.
With method of the present invention effectively turbidity, the iron level of Control Circulation water coolant, method of the present invention not only can make high turbidity high iron circulation cooling water obtain fast processing, and need not big water gaging replaces the water in the system, this method erosion rate is little, safe and reliable, suitable height is turbid, the processing of the recirculated cooling water of high ferro circulating water system.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
The water quality analysis of the following examples and monitoring heat exchanger adhere to " water coolant analysis and test method " (1993, general petrochemical works, Anqing information center publishes) that the rate determination experimental technique is all write according to production department of China PetroChemical Corporation and development division
Embodiment 1
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 527mg/L, basicity 123mg/L, total iron 0.61mg/L, turbidity 15mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA (vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid/Propylene glycol monoacrylate) multipolymer.
Add compound disinfectant 520kg, the polyquaternium 468kg of 40 weight % (25 ℃ time viscosity be 120mpa/s) wherein, the chlorination tetradecyl dimethyl benzyl ammonium sterilant 52kg of 40 weight %, the ratio of the two effective content (is the weight ratio of the two effective constituent, be 90:10 down together), total add-on is 32mg/L, and change of water quality is as follows:
Table 1
The adhesion speed of bypass monitoring water cooler is 7.0mcm.
Embodiment 2
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH9.0, calcium hardness 327mg/L, basicity 423mg/L, total iron 0.83mg/L, turbidity 23mg/L, recirculated cooling water adopts the nature operation process, the water treatment prescription adopts 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), AA/AMPS/HPA multipolymer.
Add compound disinfectant 650kg, the polyquaternium of 40 weight % (25 ℃ time viscosity be 120mpa/s) 520kg wherein, the chlorination tetradecyl octyldimethyl ammonium sterilant 130kg of 40 weight %, the ratio of the two effective content is 80:20, total add-on is 40mg/L, and change of water quality is as follows:
Table 2
The adhesion speed 11.0mcm of bypass monitoring water cooler does not have obvious variation with 11.5mcm under the normal circumstances.
Embodiment 3
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 627mg/L, basicity 113mg/L, total iron 0.71mg/L, turbidity 25mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add compound disinfectant 520kg, the polyquaternium of 40 weight % (25 ℃ time viscosity be 120mpa/s) 494kg wherein, the chlorination dodecyl octyldimethyl ammonium sterilant 26kg of 40 weight %, the ratio of the two effective content is 95:5, total add-on is 32mg/L, and change of water quality is as follows:
Table 3
The adhesion speed of bypass monitoring water cooler is 9.7mcm.
Embodiment 4
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 527mg/L, basicity 123mg/L, total iron 0.61mg/L, turbidity 18mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add polyquaternium compound disinfectant 520kg, the polyquaternium of 40 weight % (25 ℃ time viscosity be 120mpa/s) 468kg wherein, the chlorination tetradecyl octyldimethyl ammonium sterilant 52kg of 40 weight %, the ratio of the two effective content is 90:10, total add-on is 32mg/L, and change of water quality is as follows:
Table 4
The adhesion speed of bypass monitoring water cooler is 11.7mcm.
Embodiment 5
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 572mg/L, basicity 114mg/L, total iron 0.69mg/L, turbidity 18mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add polyquaternium compound disinfectant 520kg, the polyquaternium of 40 weight % (25 ℃ time viscosity be 120mpa/s) 364kg wherein, the dodecyl dimethyl benzyl ammonium chloride sterilant 156kg of 40 weight %, the ratio of the two effective content is 70:30, total add-on is 32mg/L, and change of water quality is as follows:
Table 5
The adhesion speed of bypass monitoring water cooler is 12.7mcm.
Embodiment 6
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 537mg/L, basicity 132mg/L, total iron 0.71mg/L, turbidity 28mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add polyquaternium compound disinfectant 406kg, the polyquaternium 284kg of 40 weight % wherein, the dodecyl dimethyl benzyl ammonium chloride sterilant 122kg of 40 weight %, the ratio of the two effective content is 70:30, total add-on is 25mg/L, and change of water quality is as follows:
Table 6
The adhesion speed of bypass monitoring water cooler is 13.4mcm.
Embodiment 7
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 534mg/L, basicity 122mg/L, total iron 0.70mg/L, turbidity 28mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add polyquaternium compound disinfectant 975kg, the polyquaternium 682kg of 40 weight % wherein, the dodecyl dimethyl benzyl ammonium chloride sterilant 293kg of 40 weight %, the ratio of the two effective content is 70:30, total add-on is 60mg/L, and change of water quality is as follows:
Table 7
The adhesion speed of bypass monitoring water cooler is 14.1mcm.
Comparative Examples 1
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 527mg/L, basicity 123mg/L, total iron 0.64mg/L, turbidity 15mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add the chlorination tetradecyl dimethyl benzyl ammonium sterilant 520kg of 40 weight %, add-on is 32mg/L, and change of water quality is as follows:
Table 8
The adhesion speed 6.9mcm of bypass monitoring water cooler does not have obvious variation with the adhesion speed of embodiment 2.
Comparative Examples 2
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH9.0, calcium hardness 327mg/L, basicity 423mg/L, total iron 0.81mg/L, turbidity 23mg/L, recirculated cooling water adopts the nature operation process, the water treatment prescription adopts 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), AA/AMPS/HPA multipolymer.
Add the chlorination tetradecyl octyldimethyl ammonium sterilant 650kg of 40 weight %, add-on is 40mg/L, and change of water quality is as follows:
Table 9
The adhesion speed 11.4mcm of bypass monitoring water cooler.
Comparative Examples 3
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 627mg/L, basicity 113mg/L, total iron 0.69mg/L, turbidity 25mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add the chlorination dodecyl octyldimethyl ammonium 520kg of 40 weight %, add-on is 32mg/L, and change of water quality is as follows:
Table 10
The adhesion speed of bypass monitoring water cooler is 9.9mcm
Comparative Examples 4
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, circulating water quality pH8.0, calcium hardness 527mg/L, basicity 123mg/L, total iron 0.61mg/L, turbidity 18mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add the chlorination tetradecyl octyldimethyl ammonium sterilant 520kg of 40 weight %, add-on is 32mg/L, and change of water quality is as follows:
Table 11
The adhesion speed of bypass monitoring water cooler is 12.0mcm
Comparative Examples 5
The internal circulating load 13000m of circulating water system
3/ hr, power system capacity 6500m
3/ hr, the water quality pH8.0 of recirculated water, calcium hardness 527mg/L, basicity 123mg/L, total iron 0.63mg/L, turbidity 18mg/L, recirculated cooling water adopt and add sulfuric acid control pH value technology, and the water treatment prescription adopts Sodium hexametaphosphate 99, zinc chloride, 2-phosphonate group-1,2,4-butane tricarboxylate (PBTCA), AA/AMPS/HPA multipolymer.
Add polyquaternium (the 25 ℃ of viscosity 120mpa/s) 520kg of 40 weight %, add-on is 32mg/L, and change of water quality is as follows:
Table 12
The adhesion speed of bypass monitoring water cooler is 15.3mcm.
In sum, the treatment effect of embodiment is as follows:
Table 13
By the data of the foregoing description and Comparative Examples as can be seen: adopt method of the present invention can reduce the turbidity of water and the content of iron simultaneously, and adhere to suitable, the adhesion speed standard that meets monitoring heat exchanger of speed and Comparative Examples.
Claims (7)
1. the treatment process of a high turbidity high iron circulation cooling water is characterized in that adding by polychlorostyreneization-2-hydroxypropyl-1 compound disinfectant that 1-N-dimethylammonium and at least a quaternary ammonium salt are formed in high turbidity high iron circulation cooling water.
2. the treatment process of high turbidity high iron circulation cooling water according to claim 1 is characterized in that described polychlorostyreneization-2-hydroxypropyl-1, and the weight ratio of 1-N-dimethylammonium and quaternary ammonium salt is 50-95:5-40.
3. the treatment process of high turbidity high iron circulation cooling water according to claim 2 is characterized in that described polychlorostyreneization-2-hydroxypropyl-1, and 1-N-dimethylammonium and quaternary ammonium salt weight ratio are 80-95:5-20.
4. the treatment process of high turbidity high iron circulation cooling water according to claim 1 is characterized in that it is R that described quaternary ammonium salt is selected from general formula
1(R
3)
2NR
2The quaternary ammonium salt of X, wherein R
1With R
2Identical or different, R
1Be dodecyl, tetradecyl or hexadecyl, R
2Be octyl, decyl or benzyl, R
3For carbonatoms is the alkyl of 1-4, X is a chlorine or bromine.
5. the treatment process of high turbidity high iron circulation cooling water according to claim 4 is characterized in that described quaternary ammonium salt is chlorination tetradecyl dimethyl benzyl ammonium, dodecyl dimethyl benzyl ammonium chloride, chlorination dodecyl octyldimethyl ammonium or chlorination tetradecyl octyldimethyl ammonium.
6. the treatment process of high turbidity high iron circulation cooling water according to claim 1, the add-on that it is characterized in that described compound disinfectant is 20-80mg compound disinfectant/L water.
7. the treatment process of high turbidity high iron circulation cooling water according to claim 6, the add-on that it is characterized in that described compound disinfectant is 30-40mg compound disinfectant/L water.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002076207A1 (en) * | 2001-03-27 | 2002-10-03 | The Dial Corporation | Antibacterial compositions |
| CN1425286A (en) * | 2001-12-19 | 2003-06-25 | 王兴元 | Disinfectant |
| CN1426681A (en) * | 2001-12-17 | 2003-07-02 | 北京燕山石油化工公司研究院 | Composite bactericide containing dialkyl quaternary ammonium salt and its application |
| WO2003057227A1 (en) * | 2002-01-10 | 2003-07-17 | Wolff Cellulosics Gmbh & Co. Kg | Use of polysaccharide derivatives as anti-infective substances |
| CN1504087A (en) * | 2002-11-29 | 2004-06-16 | 中国石油天然气股份有限公司 | Compound bactericide |
-
2005
- 2005-03-11 CN CNB2005100534688A patent/CN100469707C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002076207A1 (en) * | 2001-03-27 | 2002-10-03 | The Dial Corporation | Antibacterial compositions |
| CN1426681A (en) * | 2001-12-17 | 2003-07-02 | 北京燕山石油化工公司研究院 | Composite bactericide containing dialkyl quaternary ammonium salt and its application |
| CN1425286A (en) * | 2001-12-19 | 2003-06-25 | 王兴元 | Disinfectant |
| WO2003057227A1 (en) * | 2002-01-10 | 2003-07-17 | Wolff Cellulosics Gmbh & Co. Kg | Use of polysaccharide derivatives as anti-infective substances |
| CN1504087A (en) * | 2002-11-29 | 2004-06-16 | 中国石油天然气股份有限公司 | Compound bactericide |
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