CN105717054A - Detection method and detection device for online detection of scale and corrosion inhibitor concentration in circulating cooling water and circulating cooling water treatment control system - Google Patents
Detection method and detection device for online detection of scale and corrosion inhibitor concentration in circulating cooling water and circulating cooling water treatment control system Download PDFInfo
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- CN105717054A CN105717054A CN201610096311.1A CN201610096311A CN105717054A CN 105717054 A CN105717054 A CN 105717054A CN 201610096311 A CN201610096311 A CN 201610096311A CN 105717054 A CN105717054 A CN 105717054A
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- G—PHYSICS
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a detection method for online detection of the scale and corrosion inhibitor concentration in circulating cooling water. A cationic polyelectrolyte serves as a detection reagent, the detection reagent is added to a circulating cooling water sample, full mixing is performed, reaction is performed for 15-20 minutes, then an absorbance value of the reacted circulating cooling water sample is detected under the wavelength condition of 400-600 nm, and the scale and corrosion inhibitor concentration in the circulating cooling water is determined according to the absorbance value. The detection method is wide in application range, short in detection period, high in detection accuracy and good in stability and is not limited by the condition whether a scale and corrosion inhibitor is a phosphorus-containing or phosphorus-free agent. The detection device adopting the detection method can achieve online automatic detection, replace manual operation and eliminate various human factors and the influence of response time lag of all links and is simple in operation and low in operation cost. In addition, the circulating cooling water treatment control system composed of the online detection device can achieve whole-process management and automatic dosing control of circulating cooling water and is suitable for industrial application.
Description
Technical field
The present invention relates to technology on circulating cooling water treatment field, particularly to the detection method of scale inhibitor agent concentration in a kind of on-line checking recirculated cooling water, and adopt the detecting device of this detection method, and the circulating water cooling treatment including this detecting device controls system.
Background technology
Along with increasingly sharpening of shortage of water resources, water for industrial use total amount is greatly lowered, promotes water-saving production technology, it has also become enterprise realizes the inevitable choice of sustainable development.Recirculated cooling water large usage quantity in commercial Application, improves concentration rate of circulating cooling water and becomes the main water saving means of current enterprise.
Recirculated cooling water running, generally constantly to add anti-incrustation corrosion inhibitor, to improve cycles of concentration, it is prevented that the corrosion of recirculating cooling water system and fouling, therefore controls suitable scale inhibitor agent concentration, is the key of circulating cooling water running.Traditional circulating cooling water management need to through water sampling, detection, calculate, check, instruction is passed on, human users, again sample detection, a series of links gone round and begun again such as review operations effect, from finding that water quality is not up to standard to processing the qualified time generally requiring a few hours to a couple of days, in whole process, rely primarily on and be accomplished manually, by the impact that various anthropic factors and links response time are delayed, very easily there is fluctuation of service in recirculating cooling water system, operate excessive phenomenon, both water resource had been caused, the waste of human resources and material resource, it is easily caused again in circulating cooling water running and fouling easily occurs, the problems such as corrosion, hidden danger is brought to normal production of enterprise.
Owing to currently used anti-incrustation corrosion inhibitor is mostly the medicament containing organophosphor, in recent years, develop and adopt the mode of on-line checking phosphorus to carry out test agents concentration, to replace manual detection, but practical application exists problems, several steps such as the on-line analysis such as phosphorus needs the clearing up of organophosphor, reacts, colorimetric, analytical cycle is long, and cannot analyze for non-phosphorus scale and corrosion inhibitor, environmental protection pressure along with sewage discharge, phosphorous anti-incrustation corrosion inhibitor is used by restriction just day by day, and the application of non-phosphorus scale and corrosion inhibitor is more and more extensive；Also there is employing fluorescent tracing mode test agents concentration, but the method needs increase fluorescent material in anti-incrustation corrosion inhibitor or increase fluorophor on anti-incrustation corrosion inhibitor, and in detection equipment, increase fluorescence corresponding instrument, greatly add the cost of medicament and equipment, be unsuitable for commercial Application.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides the detection method of scale inhibitor agent concentration in a kind of on-line checking recirculated cooling water, this detection method is applied widely, phosphorous, non-phosphorus scale and corrosion inhibitor are all suitable for, the detection cycle is short, and accuracy is high, is suitable to commercial Application.
For achieving the above object, the detection method of scale inhibitor agent concentration in the on-line checking recirculated cooling water of the present invention, adopt cationic polymerization electrolyte as detectable, by detectable so that the amount that in recirculated cooling water, whole anti-incrustation corrosion inhibitors are reacted joins in circulating cooling water sample to be detected, it is sufficiently mixed, reaction 15～20min, then reacted circulating cooling water sample is detected under wavelength 400～600nm absorbance, determines the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water according to absorbance；Described cationic polymerization electrolyte includes alkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt or alkyl trimethyl ammonium salt, and described alkyl is the chain alkyl of C10～C18.
The anti-incrustation corrosion inhibitor that recirculated cooling water uses is substantially and is made up of anionic high-molecular polyelectrolyte, and these polyeletrolytes form weak acid base (COOH), strong acid (SO after ionizing in water3H), phosphonate group (PO3H2) or the anionic group such as hydroxyl (OH), cool down the microcrystalline grain of scaling salt (such as calcium carbonate etc.) in water by anionic group sorption cycle, make microcrystalline grain all with negative electricity, repel one another, big crystal grain can not be formed, thus reaching the effect of scale inhibition.The present invention utilizes anionic polyelectrolyte can react, with cationic polymerization electrolyte generation ion association, the ion pair generating stable performance in water, namely charges of different polarity ion is contained close to each other to a certain critical distance, attract each other with Coulomb force, when electrostatic energy is more than energy of thermal motion, just principle stable, equivalent ion pair is formed, the content of anionic polyelectrolyte is obtained, the concentration being correspondingly made available in recirculated cooling water anti-incrustation corrosion inhibitor by detecting reacted ion pair content.Because ion pair content absorbance under wavelength 400～600nm is linear, therefore, the detection method of the present invention is using cationic polymerization electrolyte as detectable, by adding excess detector reagent in circulating cooling water sample, after anti-incrustation corrosion inhibitor is reacted completely, the absorbance of reacted circulating cooling water sample is detected, thus obtaining the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water under wavelength 400～600nm.The addition of detectable can be passed through to estimate the amount of anti-incrustation corrosion inhibitor and calculate the amount that can ensure that anti-incrustation corrosion inhibitor is reacted completely accordingly, slightly increases consumption on this basis so that detectable is excessive, avoids the principle of waste to be determined simultaneously.The anti-incrustation corrosion inhibitor scope that this detection method is suitable for is wide, by the restriction being whether phosphorous or without phosphorus medicament, the detection cycle is short, only need detectable to join in circulating cooling water sample to react 15～20 minutes, anti-incrustation corrosion inhibitor and detectable complete reaction can be made to obtain stable ion pair, then the absorbance of circulating cooling water sample is measured, linear corresponding relation further according to absorbance Yu the amount of anti-incrustation corrosion inhibitor, obtain the actual concentrations of anti-incrustation corrosion inhibitor in circulating cooling water sample, the whole cycle only needs 30 minutes, testing process is simple, good stability, and low operation cost, be suitable to commercial Application.
As the restriction to aforesaid way, described cationic polymerization electrolyte includes any one in dodecyl dimethyl benzyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride or stearyl dimethyl benzyl ammonium chloride.
Empirical tests, adopt dodecyl dimethyl benzyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride or these cationic polymerization electrolyte of stearyl dimethyl benzyl ammonium chloride as detectable, the ion pair optimal stability being obtained by reacting, higher with the precision of the linear corresponding relation of scale inhibitor agent concentration, accuracy of detection can be improved.
As the restriction to aforesaid way, described anti-incrustation corrosion inhibitor includes at least one in polycarboxylic acid homopolymer, carboxylic acid copolymer, phosphine carboxylic acids homopolymer or phosphine carboxylic acid copolymer.
As the restriction to aforesaid way, described anti-incrustation corrosion inhibitor includes poly-aspartate, poly-epoxy succinic acid, polyacrylic acid, hydrolytic polymaleic anhydride, polymethylacrylic acid, acrylic acrylate bipolymer, acrylic acid hydrolyzed maleic anhydride bipolymer, acrylate methacrylate Hydroxypropyl methacrylate terpolymer, acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer, 1-hydroxy ethylidene-1,1-diphosphonic acid or 2-phosphonic acid butane-1, at least one in 2,4-tricarboxylic acids.
The anti-incrustation corrosion inhibitors such as polycarboxylic acid homopolymer, copolymer and phosphine carboxylic acids homopolymer, the copolymer commonly used at present all can use the detection method of the present invention accurately to detect.
As the restriction to aforesaid way, the temperature controlling course of reaction circulating cooling water sample is 25～40 DEG C, and pH value is 6～9.
Simultaneously, present invention also offers the detecting device of scale inhibitor agent concentration in a kind of on-line checking recirculated cooling water, including the reactor reacted for detectable and circulating cooling water sample, the detectable being connected with reactor respectively is quantitatively adding system and circulating cooling water sample is quantitatively adding system, also including the detection analytic unit for detecting reaction Posterior circle cooling water sample absorbance being connected to reactor downstream, described detection analytic unit includes spectrophotometer and data processor.
As the restriction to aforesaid way, described detectable is quantitatively adding system and includes the storage tank for depositing detectable, is arranged between storage tank and described reactor for being quantitatively adding the peristaltic pump of detectable to reactor.
As the restriction to aforesaid way, described circulating cooling water sample is quantitatively adding system and includes gathering the harvester of circulating cooling water sample, is arranged between harvester and described reactor for being quantitatively adding the peristaltic pump of circulating cooling water sample to reactor.
As the restriction to aforesaid way, between described harvester and reactor, set up filter.
The detecting device adopting the present invention can realize the online automatic detection of scale inhibitor agent concentration in recirculated cooling water, substitute manual operation, eliminate various anthropic factor and the delayed impact of links response time, the detection cycle is short, accuracy in detection is high, detection good stability, and structure of the detecting device is simple, is beneficial to application operating.
Meanwhile, present invention also offers a kind of circulating water cooling treatment and control system, for the process flowing through circulating cooling water pipe road and the recirculated cooling water that is serially connected with in the collecting-tank on recirculated cooling water pipeline is controlled, including centralized control unit, also include:
Mend draining control unit, described benefit draining control unit includes the electric conductivity detector be located at recirculated cooling water pipeline on joining with described centralized control unit, and be located at collecting-tank place and the joining Level meter of centralized control unit, also include being located at collecting-tank place and with the joining benefit water control valve of centralized control unit and draining control valve；
Anti-incrustation corrosion inhibitor adds control unit, described anti-incrustation corrosion inhibitor adds control unit and includes the detecting device of scale inhibitor agent concentration in the on-line checking recirculated cooling water joining with centralized control unit as above being located on recirculated cooling water pipeline, and is connected on recirculated cooling water pipeline and adds pump with the joining anti-incrustation corrosion inhibitor of centralized control unit；
Concentration rate control unit, described concentration rate control unit includes being located on recirculated cooling water pipeline and pH detector joining with centralized control unit, and is connected on recirculated cooling water pipeline and acid adding pump joining with centralized control unit；
Antibacterial control unit, described antibacterial control unit includes being located on recirculated cooling water pipeline and ORP detector joining with centralized control unit, and is connected on recirculated cooling water pipeline and adds pump with the joining antibacterial of centralized control unit.
Above-mentioned circulating water cooling treatment controls system can realize the real-time detection to recirculated cooling water, and control moisturizing in recirculated cooling water in real time, add the medicament such as anti-incrustation corrosion inhibitor, antibacterial, realize the whole-course automation of recirculated cooling water is managed, shorten response time, eliminate the impact of anthropic factor, reach the purpose of good saving water resource.
In sum, adopt technical scheme, in the on-line checking recirculated cooling water obtained, the detection method of scale inhibitor agent concentration is applied widely, it it is not whether the restriction of phosphorous or without phosphorus medicament by anti-incrustation corrosion inhibitor, the detection cycle is short, only needs just to obtain concentration results in 30 minutes, and accuracy in detection is high, it is not affected by human factors, good stability.Adopt the detecting device of detection method, online automatic detection can be realized, substitute manual operation, eliminating various anthropic factor and the delayed impact of links response time, simple to operate, operating cost is cheap, and, the circulating water cooling treatment being made up of above-mentioned on-line measuring device controls system, it may be achieved the whole-course automation of recirculated cooling water is managed and Automatic Dosing controls, be suitable to commercial Application.
Accompanying drawing explanation
The accompanying drawing constituting the part of the present invention is used for providing a further understanding of the present invention, and the schematic description and description of the present invention is used for explaining the present invention, is not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is the structure configuration diagram that the circulating water cooling treatment described in the embodiment of the present invention controls system；
Fig. 2 is the structure of the detecting device pie graph of scale inhibitor agent concentration in the on-line checking recirculated cooling water described in the embodiment of the present invention；
Description of reference numerals:
1-centralized control unit, 2-electric conductivity detector, 3-Level meter, 4-mends water control valve, 5-draining control valve, the detecting device of scale inhibitor agent concentration in 6-on-line checking recirculated cooling water, 7-anti-incrustation corrosion inhibitor adds pump, 8-pH detector, 9-acid adding pump, 10-ORP detector, 11-antibacterial adds pump, 12-reactor, 13-storage tank, 14-peristaltic pump, 15-harvester, 16-filter, 17-peristaltic pump, 18-spectrophotometer, 19-data processor.
Detailed description of the invention
The present embodiment relates to a kind of circulating water cooling treatment and controls system, for the process flowing through circulating cooling water pipe road and the recirculated cooling water that is serially connected with in the collecting-tank on recirculated cooling water pipeline is controlled, as shown in fig. 1, this circulating water cooling treatment controls device and includes centralized control unit 1, also includes being separately positioned on recirculated cooling water pipeline or the benefit draining control unit at collecting-tank place, anti-incrustation corrosion inhibitor add control unit, concentration rate control unit and antibacterial control unit.
Particularly, the present embodiment is mended draining control unit and includes the electric conductivity detector 2 that be arranged on recirculated cooling water pipeline on joining with centralized control unit 1, and be arranged on collecting-tank place and the joining Level meter 3 of centralized control unit 1, also include being arranged on collecting-tank place and with the joining benefit water control valve 4 of centralized control unit 1 and draining control valve 5.In use, the setting value of electrical conductivity and liquid level can be write centralized control unit 1, when circulating cooling electrical conductivity of water being detected higher than setting value via electric conductivity detector 2, namely centralized control unit 1 controls draining control valve 5 and opens and carry out draining, if recirculated cooling water conductivity value is lower than setting value, then controls draining control valve 5 and close.By increasing the drainage frequency of draining control valve 5, reduce each displacement, electrical conductivity can be made to be maintained in a more stable scope, and can farthest reduce the generation of draining phenomenon, it is to avoid the waste of water resource.And when detecting that via Level meter 3 liquid level of collecting-tank is lower than setting value, centralized control unit 1 can control moisturizing and control valve 4 and open and carry out moisturizing.
In the present embodiment, anti-incrustation corrosion inhibitor adds control unit and includes the detecting device 6 of scale inhibitor agent concentration in the on-line checking recirculated cooling water being connected with centralized control unit 1 being arranged on recirculated cooling water pipeline, and is connected on recirculated cooling water pipeline and also adds pump 7 with the joining anti-incrustation corrosion inhibitor of centralized control unit 1.In on-line checking recirculated cooling water, the concrete structure of the detecting device 6 of scale inhibitor agent concentration is as shown in Figure 2, and including reactor 12, described reactor 12 is for reacting for detectable and circulating cooling water sample；Reactor 12 upstream is provided with the detectable being connected with reactor 12 and is quantitatively adding system, described detectable is quantitatively adding system and includes the storage tank 13 for depositing detectable, being arranged at the peristaltic pump 14 between storage tank 13 and described reactor 12, described peristaltic pump 14 is for adding quantitative detectable to reactor；It is additionally provided with, in reactor 12 upstream, the circulating cooling water sample being connected with reactor 12 and is quantitatively adding system, described circulating cooling water sample is quantitatively adding system and includes gathering the harvester 15 of circulating cooling water sample, being arranged at the peristaltic pump 17 between harvester 15 and described reactor 12, described peristaltic pump 17 is for adding quantitative circulating cooling water sample to reactor 12；When the turbidity of circulating cooling water sample is more than 10NTU, between described harvester 15 and reactor 12, set up filter 16, make the circulating cooling water sample in harvester 15 enter back into reactor 12 after filter 16 filters and react；Be provided with the detection analytic unit being connected with reactor 12 in reactor 12 downstream, described detection analytic unit includes spectrophotometer 18 and data processor 19.Using the setup parameter writing anti-incrustation corrosion inhibitor concentration value in centralized control unit 1, then centralized control unit 1 controls anti-incrustation corrosion inhibitor according to the real-time testing result of the detecting device 6 of scale inhibitor agent concentration in on-line checking recirculated cooling water and adds pump 7 and add anti-incrustation corrosion inhibitor in recirculated cooling water.
In the present embodiment, concentration rate control unit specifically includes and is located on recirculated cooling water pipeline and pH detector 8 joining with centralized control unit 1, and is connected on recirculated cooling water pipeline and acid adding pump 9 joining with centralized control unit 1.Using the setup parameter writing pH value in centralized control unit 1, then centralized control unit 1 controls acid adding pump 9 to acid adding in recirculated cooling water according to the real-time testing result of pH detector 8.
In the present embodiment, antibacterial control unit includes being arranged on recirculated cooling water pipeline, and ORP detector 10 joining with centralized control unit 1, and is connected on recirculated cooling water pipeline, and adds pump 11 with the joining antibacterial of centralized control unit 1.Same, the centralized control unit 1 real-time testing result according to ORP detector 10, control antibacterial adds pump 11 and adds antibacterial in recirculated cooling water.
Adopt above-mentioned circulating water cooling treatment to control system and recirculated cooling water is carried out whole-course automation management and Automatic Dosing control.
Embodiment one
The present embodiment relates to adopting the detecting device of scale inhibitor agent concentration in above-mentioned on-line checking recirculated cooling water, recirculated cooling water to the phosphorus system anti-incrustation corrosion inhibitor containing 1-hydroxy ethylidene-1,1-diphosphonic acid, hydrolytic polymaleic anhydride and acrylate methacrylate Hydroxypropyl methacrylate terpolymer, carrying out the concentration of anti-incrustation corrosion inhibitor in on-line checking recirculated cooling water, detection method is as follows:
After the circulating cooling water sample gathered PP cotton in filter is filtered, it is quantitatively adding in reactor by peristaltic pump with 125ml, using the reagent containing hexadecyltrimethylammonium chloride 0.8g/L as detectable, quantitatively it is also added in reactor with 175ml by peristaltic pump；After reagent to be detected and circulating cooling water sample react 20 minutes in the reactor, reacted circulating cooling water sample input to spectrophotometer will detect absorbance under wavelength 420nm, obtaining absorbance is 0.138, linear equation according to the amount of the anti-incrustation corrosion inhibitor of storage in data processor with absorbance: concentration (ppm)=(absorbance+0.0038)/0.0017 of anti-incrustation corrosion inhibitor, it is 83.4ppm that calculating obtains the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water sample.
The concentration value of anti-incrustation corrosion inhibitor in circulating cooling water sample being fed back to Water Treatment in Circulating Cooling System, control system determines that anti-incrustation corrosion inhibitor is the need of the amount added, add, and perform operation, the whole cycle is 30 minutes.
The addition of described detectable is to be calculated less than 100ppm (discreet value of scale inhibitor agent concentration is determined according to the service requirement of recirculated cooling water in producing) by estimating the concentration of anti-incrustation corrosion inhibitor in the present embodiment recirculated cooling water, using the reagent containing hexadecyltrimethylammonium chloride 0.8g/L as detectable, set addition as 175ml, at this moment about excessive 5-6 times of detectable, to ensure that anti-incrustation corrosion inhibitor is fully reacted, avoid waste simultaneously.The corresponding relation adding concentration, addition and the testing result such as following table of experiment detectable hexadecyltrimethylammonium chloride:
As seen from the above table, detectable hexadecyltrimethylammonium chloride add concentration when be 0.6-1.0g/L, addition being 175ml, testing result all meets accuracy requirement, and therefore the present embodiment selects hexadecyltrimethylammonium chloride concentration to be 0.8g/L, and addition is 175ml.
The amount of the present embodiment anti-incrustation corrosion inhibitor and the linear equation of absorbance obtain with absorbance working curve by drawing the amount of anti-incrustation corrosion inhibitor, preparation scale inhibitor agent concentration is 20 respectively, 40, 60, 80, the water sample of 100ppm, respectively take 125ml, mix with 175ml detectable respectively, after reacting 20 minutes, recording absorbance under 420nm is 0.028, 0.064, 0.098, 0.130, 0.162, the linear equation of the amount and absorbance that obtain anti-incrustation corrosion inhibitor according to above-mentioned data is: concentration (ppm)=(absorbance+0.0038)/0.0017 of anti-incrustation corrosion inhibitor.
By manually same circulating cooling water sample being detected, the concentration of the anti-incrustation corrosion inhibitor obtained is 83.8ppm, from manual sampling, Site Detection, determines anti-incrustation corrosion inhibitor addition, performs the addition operation of anti-incrustation corrosion inhibitor, and the whole cycle is 2 hours.
By contrasting, it is seen that the detection method of the present invention, accuracy in detection is high, good stability, and the detection cycle is short, simple to operate, saving of work and time.
Embodiment two
The present embodiment relates to adopting the detecting device of scale inhibitor agent concentration in above-mentioned on-line checking recirculated cooling water, to containing 2-phosphonic acid butane-1,2,4-tricarboxylic acids, acrylic acrylate bipolymer and polyacrylic low-phosphorus antiincrustation corrosion inhibitor recirculated cooling water, carrying out the concentration of anti-incrustation corrosion inhibitor in on-line checking recirculated cooling water, detection method is as follows:
After the circulating cooling water sample gathered PP cotton in filter is filtered, it is quantitatively adding in reactor by peristaltic pump with 125ml, using the reagent containing hexadecyltrimethylammonium chloride 0.8g/L as detectable, quantitatively it is also added in reactor with 175ml by peristaltic pump；After reagent to be detected and circulating cooling water sample react 15 minutes in the reactor, reacted circulating cooling water sample input to spectrophotometer will detect absorbance 0.178 under wavelength 420nm, linear equation according to the amount of the anti-incrustation corrosion inhibitor of storage in data processor with absorbance: concentration (ppm)=(absorbance+0.0015)/0.0016 of anti-incrustation corrosion inhibitor, it is 112.2ppm that calculating obtains the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water sample.
The concentration value of anti-incrustation corrosion inhibitor in circulating cooling water sample being fed back to Water Treatment in Circulating Cooling System, control system determines that anti-incrustation corrosion inhibitor is the need of the amount added, add, and perform operation, the whole cycle is 30 minutes.
The addition of described detectable is to be calculated less than 150ppm (discreet value of scale inhibitor agent concentration is determined according to the service requirement of recirculated cooling water in producing) by estimating the concentration of anti-incrustation corrosion inhibitor in the present embodiment recirculated cooling water, using the reagent containing hexadecyltrimethylammonium chloride 0.8g/L as detectable, set addition as 175ml, at this moment about excessive 5-6 times of detectable, to ensure that anti-incrustation corrosion inhibitor is fully reacted, avoid waste simultaneously.The corresponding relation adding concentration, addition and the testing result such as following table of experiment detectable hexadecyltrimethylammonium chloride:
As seen from the above table, detectable hexadecyltrimethylammonium chloride add concentration when be 0.6-1.0g/L, addition being 175ml, testing result all meets accuracy requirement, and therefore the present embodiment selects hexadecyltrimethylammonium chloride concentration to be 0.8g/L, and dosage is 175ml.
The amount of the present embodiment anti-incrustation corrosion inhibitor and the linear equation of absorbance obtain with absorbance working curve by drawing the amount of anti-incrustation corrosion inhibitor, preparation scale inhibitor agent concentration is 60 respectively, 80, 100, 120, the water sample of 140ppm, respectively take 125ml, mix with 175ml detectable respectively, after reacting 15 minutes, recording absorbance at 420nm place is 0.095, 0.126, 0.159, 0.193, 0.222, the amount of anti-incrustation corrosion inhibitor and the linear equation of absorbance is obtained: concentration (ppm)=(absorbance+0.0015)/0.0016 of anti-incrustation corrosion inhibitor according to above-mentioned data.
By manually same circulating cooling water sample being detected, the concentration of the low-phosphorus antiincrustation corrosion inhibitor obtained is 112.6ppm, from manual sampling, Site Detection, determines anti-incrustation corrosion inhibitor addition, performs the addition operation of anti-incrustation corrosion inhibitor, and the whole cycle is 2 hours.
By contrasting, it is seen that the detection method of the present invention, accuracy in detection is high, good stability, and the detection cycle is short, simple to operate, saving of work and time.
Embodiment three
The present embodiment relates to adopting the detecting device of scale inhibitor agent concentration in above-mentioned on-line checking recirculated cooling water, recirculated cooling water to the non-phosphorus scale and corrosion inhibitor containing poly-aspartate, poly-epoxy succinic acid, acrylate methacrylate Hydroxypropyl methacrylate terpolymer and hydrolytic polymaleic anhydride, carrying out the concentration of anti-incrustation corrosion inhibitor in on-line checking recirculated cooling water, detection method is as follows:
After the circulating cooling water sample gathered PP cotton in filter is filtered, it is quantitatively adding in reactor by peristaltic pump with 125ml, using the reagent containing dodecyl dimethyl benzyl ammonium chloride 0.65g/L as detectable, quantitatively it is also added in reactor with 175ml by peristaltic pump；After reagent to be detected and circulating cooling water sample react 20 minutes in the reactor, it is 0.210 by reacted circulating cooling water sample input to spectrophotometer detects absorbance under wavelength 460nm, linear equation according to the amount of the anti-incrustation corrosion inhibitor of storage in data processor with absorbance: concentration (ppm)=(absorbance+0.0004)/0.0016 of anti-incrustation corrosion inhibitor, it is 131.5ppm that calculating obtains the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water sample.
The concentration value of anti-incrustation corrosion inhibitor in circulating cooling water sample being fed back to Water Treatment in Circulating Cooling System, control system determines that anti-incrustation corrosion inhibitor is the need of the amount added, add, and perform operation, the whole cycle is 30 minutes.
The addition of described detectable is to be calculated less than 150ppm (discreet value of scale inhibitor agent concentration is determined according to the service requirement of recirculated cooling water in producing) by estimating the concentration of anti-incrustation corrosion inhibitor in the present embodiment recirculated cooling water, using the reagent containing dodecyl dimethyl benzyl ammonium chloride 0.65g/L as detectable, set addition as 175ml, at this moment about excessive 5-6 times of detectable, to ensure that anti-incrustation corrosion inhibitor is fully reacted, avoid waste simultaneously.The corresponding relation adding concentration, addition and the testing result such as following table of experiment detectable dodecyl dimethyl benzyl ammonium chloride:
As seen from the above table, detectable dodecyl dimethyl benzyl ammonium chloride add concentration when be 0.55-0.75g/L, addition being 175ml, testing result all meets accuracy requirement, and therefore the present embodiment selects dodecyl dimethyl benzyl ammonium chloride concentration to be 0.65g/L, and dosage is 175ml.
The amount of the present embodiment anti-incrustation corrosion inhibitor and the linear equation of absorbance obtain with absorbance working curve by drawing the amount of anti-incrustation corrosion inhibitor, preparation scale inhibitor agent concentration is 40 respectively, 60, 80, 100, 120, the water sample of 140ppm, respectively take 125ml, mix with 175ml detectable respectively, after reacting 20 minutes, recording absorbance at 460nm place is 0.062, 0.096, 0.128, 0.159, 0.193, 0.221, the amount of anti-incrustation corrosion inhibitor and the linear equation of absorbance is obtained: concentration (ppm)=(absorbance+0.0004)/0.0016 of anti-incrustation corrosion inhibitor according to above-mentioned data.
By manually same circulating cooling water sample being detected, the concentration of the anti-incrustation corrosion inhibitor obtained is 132ppm, from manual sampling, Site Detection, determines anti-incrustation corrosion inhibitor addition, performs the addition operation of anti-incrustation corrosion inhibitor, and the whole cycle is 2 hours.
By contrasting, it is seen that the detection method of the present invention, accuracy in detection is high, good stability, and the detection cycle is short, simple to operate, saving of work and time.
Embodiment four
The present embodiment relates to adopting the detecting device of scale inhibitor agent concentration in above-mentioned on-line checking recirculated cooling water, to containing polyacrylic acid, polymethylacrylic acid, hydrolytic polymaleic anhydride the recirculated cooling water of non-phosphorus scale and corrosion inhibitor, carrying out the concentration of anti-incrustation corrosion inhibitor in on-line checking recirculated cooling water, detection method is as follows:
After the circulating cooling water sample gathered PP cotton in filter is filtered, it is quantitatively adding in reactor by peristaltic pump with 125ml, using the reagent containing stearyl dimethyl benzyl ammonium chloride 0.8g/L as detectable, quantitatively it is also added in reactor with 175ml by peristaltic pump；After reagent to be detected and circulating cooling water sample react 20 minutes in the reactor, it is 0.204 by reacted circulating cooling water sample input to spectrophotometer detects absorbance under wavelength 420nm, linear equation according to the amount of the anti-incrustation corrosion inhibitor of storage in data processor with absorbance: concentration (ppm)=(absorbance+0.0027)/0.0016 of anti-incrustation corrosion inhibitor, it is 129.2ppm that calculating obtains the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water sample.
The concentration value of anti-incrustation corrosion inhibitor in circulating cooling water sample being fed back to Water Treatment in Circulating Cooling System, control system determines that anti-incrustation corrosion inhibitor is the need of the amount added, add, and perform operation, the whole cycle is 30 minutes.
The addition of described detectable is to be calculated less than 150ppm (discreet value of scale inhibitor agent concentration is determined according to the service requirement of recirculated cooling water in producing) by estimating the concentration of anti-incrustation corrosion inhibitor in the present embodiment recirculated cooling water, using the reagent containing stearyl dimethyl benzyl ammonium chloride 0.8g/L as detectable, set addition as 175ml, at this moment about excessive 5-6 times of detectable, to ensure that anti-incrustation corrosion inhibitor is fully reacted, avoid waste simultaneously.The corresponding relation adding concentration, addition and the testing result such as following table of experiment detectable stearyl dimethyl benzyl ammonium chloride:
As seen from the above table, detectable stearyl dimethyl benzyl ammonium chloride add concentration when be 0.6-1.0g/L, addition being 175ml, testing result all meets accuracy requirement, and therefore the present embodiment selects stearyl dimethyl benzyl ammonium chloride concentration to be 0.8g/L, and addition is 175ml.
The amount of the present embodiment anti-incrustation corrosion inhibitor and the linear equation of absorbance obtain with absorbance working curve by drawing the amount of anti-incrustation corrosion inhibitor, preparation scale inhibitor agent concentration is 40 respectively, 60, 80, 100, 120, the water sample of 140ppm, respectively take 125ml, mix with 175ml detectable respectively, after reacting 20 minutes, recording absorbance at 420nm place is 0.06, 0.094, 0.123, 0.156, 0.19, 0.218, the amount of anti-incrustation corrosion inhibitor and the linear equation of absorbance is obtained: concentration (ppm)=(absorbance+0.0027)/0.0016 of anti-incrustation corrosion inhibitor according to above-mentioned data.
By manually same circulating cooling water sample being detected, the concentration of the anti-incrustation corrosion inhibitor obtained is 129.6ppm, from manual sampling, Site Detection, determines anti-incrustation corrosion inhibitor addition, performs the addition operation of anti-incrustation corrosion inhibitor, and the whole cycle is 2 hours.
By contrasting, it is seen that the detection method of the present invention, accuracy in detection is high, good stability, and the detection cycle is short, simple to operate, saving of work and time.
Claims (10)
1. the detection method of scale inhibitor agent concentration in an on-line checking recirculated cooling water, it is characterized in that: this detection method adopts cationic polymerization electrolyte as detectable, by detectable so that the amount that in recirculated cooling water, whole anti-incrustation corrosion inhibitors are reacted joins in circulating cooling water sample to be detected, it is sufficiently mixed, reaction 15～20min, then reacted circulating cooling water sample is detected under wavelength 400～600nm absorbance, determines the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water according to absorbance；Described cationic polymerization electrolyte includes alkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt or alkyl trimethyl ammonium salt, and described alkyl is the chain alkyl of C10～C18.
2. the detection method of scale inhibitor agent concentration in on-line checking recirculated cooling water according to claim 1, it is characterised in that: described cationic polymerization electrolyte includes any one in dodecyl dimethyl benzyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride or stearyl dimethyl benzyl ammonium chloride.
3. the detection method of scale inhibitor agent concentration in on-line checking recirculated cooling water according to claim 1, it is characterised in that: described anti-incrustation corrosion inhibitor includes at least one in polycarboxylic acid homopolymer, carboxylic acid copolymer, phosphine carboxylic acids homopolymer or phosphine carboxylic acid copolymer.
4. the detection method of scale inhibitor agent concentration in on-line checking recirculated cooling water according to claim 3, it is characterized in that: described anti-incrustation corrosion inhibitor includes poly-aspartate, poly-epoxy succinic acid, polyacrylic acid, hydrolytic polymaleic anhydride, polymethylacrylic acid, acrylic acrylate bipolymer, acrylic acid hydrolyzed maleic anhydride bipolymer, acrylate methacrylate Hydroxypropyl methacrylate terpolymer, acrylic acid-2-acrylamide-2-methyl propane sulfonic copolymer, 1-hydroxy ethylidene-1,1-diphosphonic acid or 2-phosphonic acid butane-1, 2, at least one in 4-tricarboxylic acids.
5. the detection method of scale inhibitor agent concentration in on-line checking recirculated cooling water according to claim 1, it is characterised in that: the temperature controlling course of reaction circulating cooling water sample is 25～40 DEG C, and pH value is 6～9.
6. the detecting device of scale inhibitor agent concentration in an on-line checking recirculated cooling water, it is characterized in that: include the reactor reacted for detectable and circulating cooling water sample, the detectable being connected with reactor respectively is quantitatively adding system and circulating cooling water sample is quantitatively adding system, also including the detection analytic unit for detecting reaction Posterior circle cooling water sample absorbance being connected to reactor downstream, described detection analytic unit includes spectrophotometer and data processor.
7. the detecting device of scale inhibitor agent concentration in on-line checking recirculated cooling water according to claim 6, it is characterized in that: described detectable is quantitatively adding system and includes the storage tank for depositing detectable, be arranged between storage tank and described reactor for being quantitatively adding the peristaltic pump of detectable to reactor.
8. the detecting device of scale inhibitor agent concentration in on-line checking recirculated cooling water according to claim 6, it is characterized in that: described circulating cooling water sample is quantitatively adding system and includes gathering the harvester of circulating cooling water sample, is arranged between harvester and described reactor for being quantitatively adding the peristaltic pump of circulating cooling water sample to reactor.
9. the detecting device of scale inhibitor agent concentration in on-line checking recirculated cooling water according to claim 8, it is characterised in that: between described harvester and reactor, set up filter.
10. circulating water cooling treatment controls a system, for the process flowing through circulating cooling water pipe road and the recirculated cooling water that is serially connected with in the collecting-tank on recirculated cooling water pipeline is controlled, it is characterised in that include centralized control unit, also include:
Mend draining control unit, described benefit draining control unit includes the electric conductivity detector be located at recirculated cooling water pipeline on joining with described centralized control unit, and be located at collecting-tank place and the joining Level meter of centralized control unit, also include being located at collecting-tank place and with the joining benefit water control valve of centralized control unit and draining control valve；
Anti-incrustation corrosion inhibitor adds control unit, described anti-incrustation corrosion inhibitor adds control unit and includes the detecting device of scale inhibitor agent concentration in the on-line checking recirculated cooling water joining with centralized control unit as claimed in claim 6 being located on recirculated cooling water pipeline, and is connected on recirculated cooling water pipeline and adds pump with the joining anti-incrustation corrosion inhibitor of centralized control unit；
Concentration rate control unit, described concentration rate control unit includes being located on recirculated cooling water pipeline and pH detector joining with centralized control unit, and is connected on recirculated cooling water pipeline and acid adding pump joining with centralized control unit；
Antibacterial control unit, described antibacterial control unit includes being located on recirculated cooling water pipeline and ORP detector joining with centralized control unit, and is connected on recirculated cooling water pipeline and adds pump with the joining antibacterial of centralized control unit.
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