CN105717054B - The detection method of anti-incrustation corrosion inhibitor concentration, detection device and circulating water cooling treatment control system in on-line checking recirculated cooling water - Google Patents
The detection method of anti-incrustation corrosion inhibitor concentration, detection device and circulating water cooling treatment control system in on-line checking recirculated cooling water Download PDFInfo
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- CN105717054B CN105717054B CN201610096311.1A CN201610096311A CN105717054B CN 105717054 B CN105717054 B CN 105717054B CN 201610096311 A CN201610096311 A CN 201610096311A CN 105717054 B CN105717054 B CN 105717054B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/001—Upstream control, i.e. monitoring for predictive control
Abstract
The present invention provides a kind of detection methods of anti-incrustation corrosion inhibitor concentration in on-line checking recirculated cooling water, using cationic polymerization electrolyte as detection reagent, it will test reagent to be added in circulating cooling water sample to be detected, it is sufficiently mixed, react 15~20min, then the circulating cooling water sample after reaction is detected into absorbance value under 400~600nm of wavelength, the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water is determined according to absorbance value；Whether the detection method is applied widely, be not that phosphorous or without phosphorus medicament is limited by anti-incrustation corrosion inhibitor, and detection cycle is short, and accuracy in detection is high, and stability is good.Using the detection device of detection method, online automatic detection can be achieved, substitute manual operation, the influence of various human factors and links response time lag is eliminated, easy to operate, operating cost is cheap, and, the circulating water cooling treatment control system being made of above-mentioned on-line measuring device is, it can be achieved that process management and Automatic Dosing to recirculated cooling water control, suitable for industrial application.
Description
Technical field
The present invention relates to technology on circulating cooling water treatment field, in particular to scale inhibition in a kind of on-line checking recirculated cooling water
The detection method of density of corrosion inhibitor, and using the detection device of the detection method, and the circulating cooling including the detection device
Water treatment controlling system.
Background technique
With increasingly sharpening for shortage of water resources, industrial water total amount is greatly lowered, promotes water-saving production technology,
The inevitable choice of sustainable development is realized as enterprise.Circulating cooling water consumption is larger in industrial application, improves circulating cooling
Water concentration rate becomes the main water-saving means of current enterprise.
Recirculated cooling water operational process usually will constantly add anti-incrustation corrosion inhibitor, to improve cycles of concentration, prevent from recycling cold
But the corrosion and fouling of water system, therefore anti-incrustation corrosion inhibitor concentration appropriate is controlled, it is the key that circulating cooling water running.Tradition
Circulating cooling water management need to by water sampling, detection, calculating, review, instruction convey, personnel operation, again sample detection, examine
A series of links in cycles such as core operating effect, from discovery water quality it is not up to standard to processing qualification generally require a few hours to number
It time in whole process, relies primarily on and is accomplished manually, the shadow lagged by various human factors and links response time
Ring, recirculating cooling water system easily there is a phenomenon where fluctuation of service, operation it is excessive, both caused water resource, human resources and object
Expect the waste of resource, and easily lead in circulating cooling water running and the problems such as fouling, corrosion easily occur, to the normal production band of enterprise
Carry out hidden danger.
Since anti-incrustation corrosion inhibitor used at present is mostly in recent years, to develop using online inspection containing organic phosphorus medicament
The mode for surveying phosphorus carrys out test agents concentration, and to replace artificial detection, but there are problems in practical application, online such as phosphorus is divided
Analysis needs several steps such as organic phosphorus resolution, reaction, colorimetric, and analytical cycle is long, and can not for non-phosphorus scale and corrosion inhibitor
Analysis, with the environmental protection pressure of sewage discharge, phosphorous anti-incrustation corrosion inhibitor is just increasingly used by limitation, and non-phosphorus scale and corrosion inhibitor
Using more and more extensive；Also have using fluorescent tracing mode test agents concentration, but this method needs increase in anti-incrustation corrosion inhibitor
Add fluorescent material or increase fluorophor on anti-incrustation corrosion inhibitor, and increase fluorescence corresponding instrument in detection device, greatly
The cost for increasing medicament and equipment, is unsuitable for industrial application.
Summary of the invention
To solve the deficiencies in the prior art, it is slow that the present invention provides scale inhibitions in a kind of on-line checking recirculated cooling water
The detection method of agent concentration is lost, the detection method is applied widely, is all suitable for phosphorous, non-phosphorus scale and corrosion inhibitor, detection cycle
Short, accuracy is high, is suitable for industrial application.
To achieve the above object, in on-line checking recirculated cooling water of the invention anti-incrustation corrosion inhibitor concentration detection method,
Using cationic polymerization electrolyte as detection reagent, reagent will test so that whole anti-incrustation corrosion inhibitor quilts in recirculated cooling water
The amount of reaction is added in circulating cooling water sample to be detected, is sufficiently mixed, and 15~20min is reacted, then by following after reaction
The cooling water sample of ring detects absorbance value under 400~600nm of wavelength, determines scale inhibitor in recirculated cooling water according to absorbance value
The concentration of agent；The cationic polymerization electrolyte includes alkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt or alkyl three
Methyl ammonium salt, the alkyl are the chain alkyl of C10~C18.
The anti-incrustation corrosion inhibitor that recirculated cooling water uses is substantially to be made of anionic high-molecular polyelectrolyte, these
Polyeletrolyte forms weak acid base (- COOH), strong acid (- SO after ionizing in water3H), phosphonic acid base (- PO3H2) or hydroxyl
(- OH) etc. anionic groups, by the micromeritics of scaling salt (such as calcium carbonate) in anionic group sorption cycle cooling water,
So that micromeritics is had negative electricity, repel one another, big crystal grain cannot be formed, to have the function that scale inhibition.The present invention using yin from
Subtype polyeletrolyte in water can with cationic polymerization electrolyte occur ion association react generation performance it is stable from
Son it is right, i.e., containing charges of different polarity ion it is close to each other arrive a certain critical distance, attracted each other with Coulomb force, when electrostatic energy be greater than heat
Movement energy, just forms the principle of stable, equivalent ion pair, obtains anionic by the ion pair content after detection reaction
The content of polyeletrolyte is correspondingly made available the concentration of anti-incrustation corrosion inhibitor in recirculated cooling water.Because ion pair content is in wavelength 400
Absorbance value under~600nm is in a linear relationship, and therefore, detection method of the invention is using cationic polymerization electrolyte as inspection
Test agent, by the way that excess detector reagent is added into circulating cooling water sample, after anti-incrustation corrosion inhibitor is reacted completely, in wavelength
The absorbance value of circulating cooling water sample under 400~600nm after detection reaction, to obtain anti-incrustation corrosion inhibitor in recirculated cooling water
Concentration.It is complete that the additional amount of detection reagent can accordingly calculate certifiable anti-incrustation corrosion inhibitor by estimating the amount of anti-incrustation corrosion inhibitor
The amount reacted slightly increases dosage on this basis so that detection reagent is excessive, while the principle of waste being avoided to be determined.It should
The applicable anti-incrustation corrosion inhibitor range of detection method is wide, and whether not by being that phosphorous or without phosphorus medicament is limited, detection cycle is short, only needs
Detection reagent, which is added in circulating cooling water sample, reacts 15~20 minutes, and anti-incrustation corrosion inhibitor can be made to react completely with detection reagent
Stable ion pair is obtained, the absorbance value of circulating cooling water sample is then measured, further according to absorbance value and anti-incrustation corrosion inhibitor
The linear corresponding relation of amount obtains the actual concentrations of anti-incrustation corrosion inhibitor in circulating cooling water sample, and whole cycle only needs 30 minutes, inspection
Flow gauge is simple, stability is good, and low operation cost, is suitable for industrial application.
As the restriction to aforesaid way, the cationic polymerization electrolyte includes dodecyl dimethyl Benzylmagnesium chloride
Appointing in ammonium, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride or stearyl dimethyl benzyl ammonium chloride
It anticipates one kind.
It is verified, using dodecyl benzyl dimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl front three
As detection reagent, reaction is obtained for ammonium chloride or stearyl dimethyl benzyl ammonium chloride these cationic polymerization electrolyte
Ion pair optimal stability, it is higher with the precision of the linear corresponding relation of anti-incrustation corrosion inhibitor concentration, detection accuracy can be improved.
As the restriction to aforesaid way, the anti-incrustation corrosion inhibitor include polycarboxylic acid homopolymer, carboxylic acid copolymer,
At least one of phosphine carboxylic acid class homopolymer or phosphine carboxylic acid analog copolymer.
As the restriction to aforesaid way, the anti-incrustation corrosion inhibitor includes poly-aspartate, poly-epoxy succinic acid, polypropylene
Acid, hydrolysis of polymaleic anhydride, polymethylacrylic acid, acrylic acid-acrylate bipolymer, acrylic acid-hydrolysis maleic acid
Acid anhydride bipolymer, acrylic acid-methacrylate-hydroxy propyl methacrylate terpolymer, acrylic acid -2- acryloyl
At least one of amine -2- methyl propane sulfonic acid copolymer, 1-hydroxy ethylidene-1,1-diphosphonic acid or 2- phosphonic acid butane -1,2,4- tricarboxylic acids.
The anti-incrustation corrosion inhibitors such as currently used polycarboxylic acid homopolymer, copolymer and phosphine carboxylic acid class homopolymer, copolymer are equal
Detection method of the invention can be used accurately to detect.
As the restriction to aforesaid way, the temperature for controlling reaction process circulating cooling water sample is 25~40 DEG C, pH value 6
~9.
Meanwhile the present invention also provides a kind of detection device of anti-incrustation corrosion inhibitor concentration in on-line checking recirculated cooling water,
Including the reactor reacted for detection reagent with circulating cooling water sample, the detection reagent being connected respectively with reactor quantitatively adds
Enter system and circulating cooling water sample be quantitatively adding system, further include be connected to reactor downstream for detect reaction after recycle it is cold
But the detection and analysis unit of water sample absorbance value, the detection and analysis unit includes spectrophotometer and data processor.
As the restriction to aforesaid way, it includes for storing depositing for detection reagent that the detection reagent, which is quantitatively adding system,
Storage tank is set between storage tank and the reactor for being quantitatively adding the peristaltic pump of detection reagent to reactor.
As the restriction to aforesaid way, it includes acquisition circulating cooling water sample that the circulating cooling water sample, which is quantitatively adding system,
Collector, be set between collector and the reactor for being quantitatively adding the wriggling of circulating cooling water sample to reactor
Pump.
As the restriction to aforesaid way, filter is added between the collector and reactor.
Online automatic detection to anti-incrustation corrosion inhibitor concentration in recirculated cooling water can be realized using detection device of the invention,
Manual operation is substituted, the influence of various human factors and links response time lag is eliminated, detection cycle is short, and detection is accurate
Degree is high, and detection stability is good, and structure of the detecting device is simple, is conducive to application operating.
Meanwhile the present invention also provides a kind of circulating water cooling treatment control system, for flowing through circulating cooling water pipe
The processing of road and the recirculated cooling water being serially connected in the collecting-tank in recirculated cooling water pipeline is controlled, including center control is single
Member, further includes:
Draining control unit is mended, the benefit draining control unit includes following with joining be set to of the centralized control unit
Electric conductivity detector on ring cooling water pipeline, and be set at collecting-tank and the joining level sensing of centralized control unit
Instrument, further include be set to collecting-tank at and with the joining moisturizing control valve of centralized control unit and draining control valve；
Anti-incrustation corrosion inhibitor adds control unit, and it includes being set to circulating cooling water pipe that the anti-incrustation corrosion inhibitor, which adds control unit,
The inspection with anti-incrustation corrosion inhibitor concentration in the joining on-line checking recirculated cooling water as described above of centralized control unit on road
Device is surveyed, and is connected in recirculated cooling water pipeline and adds pump with the joining anti-incrustation corrosion inhibitor of centralized control unit；
Concentration rate control unit, the concentration rate control unit include be set to recirculated cooling water pipeline on and and center
The joining pH detector of control unit, and be connected in recirculated cooling water pipeline and with centralized control unit it is joining plus
Acid pump；
Fungicide control unit, the fungicide control unit include being set in recirculated cooling water pipeline and controlling with center
The joining ORP detector of unit, and be connected in recirculated cooling water pipeline and with the joining sterilization of centralized control unit
Agent adds pump.
Above-mentioned circulating water cooling treatment control system can realize the real-time detection to recirculated cooling water, and real-time control is to following
Moisturizing in ring cooling water adds the medicaments such as anti-incrustation corrosion inhibitor, fungicide, realizes the whole-course automation management to recirculated cooling water,
Shorten the response time, eliminates the influence of human factor, achieve the purpose that preferably to save water resource.
In conclusion anti-incrustation corrosion inhibitor is dense in the on-line checking recirculated cooling water of acquisition using technical solution of the present invention
Whether the detection method of degree is applied widely, be not that phosphorous or without phosphorus medicament is limited by anti-incrustation corrosion inhibitor, and detection cycle is short, only
It needs that concentration results can be obtained within 30 minutes, accuracy in detection is high, is not affected by human factors, stability is good.It is examined using the present invention
The detection device of survey method is, it can be achieved that online automatic detection, substitution manual operation, eliminate various human factors and links are rung
The influence of time lag is answered, easy to operate, operating cost is cheap, moreover, the circulating cooling being made of above-mentioned on-line measuring device
Water treatment controlling system is, it can be achieved that whole-course automation management and Automatic Dosing to recirculated cooling water control, suitable for industrial application.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the structure configuration diagram of circulating water cooling treatment control system described in the embodiment of the present invention；
Fig. 2 is the detection device knot of anti-incrustation corrosion inhibitor concentration in on-line checking recirculated cooling water described in the embodiment of the present invention
Structure constitutes figure；
Description of symbols:
1- centralized control unit, 2- electric conductivity detector, 3- Level meter, 4- moisturizing control valve, 5- draining control valve,
The detection device of anti-incrustation corrosion inhibitor concentration in 6- on-line checking recirculated cooling water, 7- anti-incrustation corrosion inhibitor add pump, 8-pH detector,
9- acid adding pump, 10-ORP detector, 11- fungicide add pump, 12- reactor, 13- storage tank, 14- peristaltic pump, 15- acquisition
Device, 16- filter, 17- peristaltic pump, 18- spectrophotometer, 19- data processor.
Specific embodiment
The present embodiment is related to a kind of circulating water cooling treatment control system, for flowing through recirculated cooling water pipeline and concatenation
The processing of recirculated cooling water in the collecting-tank in recirculated cooling water pipeline is controlled, as shown in fig. 1, the circulating cooling
Water processing control device includes centralized control unit 1, further includes being separately positioned in recirculated cooling water pipeline or at collecting-tank
Mend draining control unit, anti-incrustation corrosion inhibitor adds control unit, concentration rate control unit and fungicide control unit.
Particularly, it includes recycling with the joining setting of centralized control unit 1 that draining control unit is mended in the present embodiment
Electric conductivity detector 2 on cooling water pipeline, and be arranged at collecting-tank and the joining level sensing of centralized control unit 1
Instrument 3, further include be arranged at collecting-tank and with the joining moisturizing control valve 4 of centralized control unit 1 and draining control valve 5.
In use, centralized control unit 1 can be written in the setting value of conductivity and liquid level, be detected when via electric conductivity detector 2
When the conductivity of recirculated cooling water is higher than setting value, centralized control unit 1 controls the opening of draining control valve 5 and is drained, if
Recirculated cooling water conductivity value is lower than setting value, then controls the closing of draining control valve 5.By the draining for increasing draining control valve 5
Frequency reduces each displacement, conductivity can be made to be maintained in a more stable range, and can subtract to the greatest extent
It is few to cross the generation for draining phenomenon, avoid the waste of water resource.And works as and detect that the liquid level of collecting-tank is lower than via Level meter 3
When setting value, centralized control unit 1 can control moisturizing control valve 4 to open and carry out moisturizing.
It includes that controlling in recirculated cooling water pipeline with center is arranged in that anti-incrustation corrosion inhibitor, which adds control unit, in the present embodiment
The detection device 6 of anti-incrustation corrosion inhibitor concentration in the on-line checking recirculated cooling water that unit 1 processed is connected, and be connected to circulation it is cold
But pump 7 on waterpipe and also is added with the joining anti-incrustation corrosion inhibitor of centralized control unit 1.In on-line checking recirculated cooling water
The specific structure of the detection device 6 of anti-incrustation corrosion inhibitor concentration is as shown in Figure 2, including reactor 12, and the reactor 12 is used for
It is reacted for detection reagent with circulating cooling water sample；12 upstream of reactor is provided with the detection reagent being connected with reactor 12
It is quantitatively adding system, it includes the storage tank 13 for storing detection reagent that the detection reagent, which is quantitatively adding system, is set to and deposits
Peristaltic pump 14 between storage tank 13 and the reactor 12, the peristaltic pump 14 are used to be added quantitative detection examination to reactor
Agent；The circulating cooling water sample being connected with reactor 12 is additionally provided in 12 upstream of reactor and is quantitatively adding system, and the circulation is cold
But it includes the collector 15 for acquiring circulating cooling water sample that water sample, which is quantitatively adding system, is set to collector 15 and the reactor 12
Between peristaltic pump 17, the peristaltic pump 17 is for quantitative circulating cooling water sample to be added to reactor 12；Work as recirculated cooling water
When the turbidity of sample is greater than 10NTU, filter 16 is added between the collector 15 and reactor 12, makes following in collector 15
The cooling water sample of ring enters back into reactor 12 after the filtering of filter 16 and is reacted；It is provided with and reactor in 12 downstream of reactor
12 connected detection and analysis units, the detection and analysis unit includes spectrophotometer 18 and data processor 19.In use
The setup parameter of anti-incrustation corrosion inhibitor concentration value is written in centralized control unit 1, then centralized control unit 1 is followed according to on-line checking
The real-time detection result control anti-incrustation corrosion inhibitor of the detection device 6 of anti-incrustation corrosion inhibitor concentration adds pump 7 to circulation in ring cooling water
Add anti-incrustation corrosion inhibitor in cooling water.
Concentration rate control unit is specifically included in recirculated cooling water pipeline and is controlled with center single in the present embodiment
First 1 joining pH detector 8, and be connected in recirculated cooling water pipeline and with the joining acid adding of centralized control unit 1
Pump 9.The setup parameter of pH value is written in use in centralized control unit 1, then centralized control unit 1 is according to pH detector 8
Real-time detection result control acid adding pump 9 into recirculated cooling water acid adding.
Fungicide control unit includes setting in recirculated cooling water pipeline in the present embodiment, and and centralized control unit
1 joining ORP detector 10, and being connected in recirculated cooling water pipeline, and with centralized control unit 1 is joining kills
Microbial inoculum adds pump 11.Likewise, centralized control unit 1 is according to the real-time detection of ORP detector 10 as a result, control fungicide adds
Pump 11 adds fungicide into recirculated cooling water.
Whole-course automation management is carried out to recirculated cooling water using above-mentioned circulating water cooling treatment control system and is added automatically
Medicine control.
Embodiment one
The present embodiment is related to the detection device using anti-incrustation corrosion inhibitor concentration in above-mentioned on-line checking recirculated cooling water, to containing
There are 1-hydroxy ethylidene-1,1-diphosphonic acid, hydrolysis of polymaleic anhydride and acrylic acid-methacrylate-hydroxy propyl methacrylate ternary total
The recirculated cooling water of the phosphorus system anti-incrustation corrosion inhibitor of polymers carries out the concentration of anti-incrustation corrosion inhibitor in on-line checking recirculated cooling water, inspection
Survey method is as follows:
The circulating cooling water sample of acquisition is quantitatively adding after the PP cotton filtering in filter by peristaltic pump with 125ml
In reactor, to contain the reagent of hexadecyltrimethylammonium chloride 0.8g/L as detection reagent, by peristaltic pump with 175ml
Quantitatively it is also added in reactor；Test agent to be checked reacts after twenty minutes, after reaction in the reactor with circulating cooling water sample
Circulating cooling water sample be input in spectrophotometer and detect absorbance under wavelength 420nm, obtaining absorbance value is 0.138,
According to the linear equation of the amount of the anti-incrustation corrosion inhibitor stored in data processor and absorbance value: the concentration of anti-incrustation corrosion inhibitor
(ppm)=(absorbance value+0.0038)/0.0017, the concentration that anti-incrustation corrosion inhibitor in circulating cooling water sample is calculated are
83.4ppm。
The concentration value of anti-incrustation corrosion inhibitor in circulating cooling water sample is fed back into Water Treatment in Circulating Cooling System, by control system
It determines the amount whether anti-incrustation corrosion inhibitor needs to be added, be added, and executes operation, whole cycle is 30 minutes.
The additional amount of the detection reagent is small by estimating the concentration of anti-incrustation corrosion inhibitor in the present embodiment recirculated cooling water
It is calculated in 100ppm (discreet value of anti-incrustation corrosion inhibitor concentration is determined according to the service requirement of recirculated cooling water in production), with
Contain the reagent of hexadecyltrimethylammonium chloride 0.8g/L as detection reagent, sets additional amount as 175ml, at this moment detection tries
Agent is about 5-6 times excessive, to guarantee that anti-incrustation corrosion inhibitor is sufficiently reacted, while avoiding wasting.Test detection reagent cetyl
The corresponding relationship for adding concentration, additional amount and testing result of trimethyl ammonium chloride is as follows:
As seen from the above table, the concentration that adds of detection reagent hexadecyltrimethylammonium chloride is 0.6-1.0g/L, additional amount
When for 175ml, testing result meets accuracy requirement, thus the present embodiment select hexadecyltrimethylammonium chloride concentration for
0.8g/L, additional amount 175ml.
The amount and suction that the amount of the present embodiment anti-incrustation corrosion inhibitor and the linear equation of absorbance value pass through drafting anti-incrustation corrosion inhibitor
Shading value working curve obtains, and prepares the water sample that anti-incrustation corrosion inhibitor concentration is 20,40,60,80,100ppm respectively, respectively takes
125ml is mixed with 175ml detection reagent respectively, reaction after twenty minutes, measured at 420nm absorbance value be 0.028,
0.064,0.098,0.130,0.162, the amount of anti-incrustation corrosion inhibitor and the linear equation of absorbance value are obtained according to above-mentioned data are as follows:
Concentration (ppm)=(absorbance value+0.0038)/0.0017 of anti-incrustation corrosion inhibitor.
By manually detecting to same circulating cooling water sample, the concentration of obtained anti-incrustation corrosion inhibitor is 83.8ppm,
It from manual sampling, on-site test, determines anti-incrustation corrosion inhibitor additional amount, executes the addition operation of anti-incrustation corrosion inhibitor, whole cycle 2
Hour.
Pass through comparison, it is seen that detection method of the invention, accuracy in detection is high, stability is good, and detection cycle is short, operation letter
It is single, saving of work and time.
Embodiment two
The present embodiment is related to the detection device using anti-incrustation corrosion inhibitor concentration in above-mentioned on-line checking recirculated cooling water, to containing
There is the low-phosphorus antiincrustation of 2- phosphonic acid butane -1,2,4- tricarboxylic acids, acrylic acid-acrylate bipolymer and polyacrylic acid slow
Agent recirculated cooling water is lost, the concentration of anti-incrustation corrosion inhibitor in on-line checking recirculated cooling water is carried out, detection method is as follows:
The circulating cooling water sample of acquisition is quantitatively adding after the PP cotton filtering in filter by peristaltic pump with 125ml
In reactor, to contain the reagent of hexadecyltrimethylammonium chloride 0.8g/L as detection reagent, by peristaltic pump with 175ml
Quantitatively it is also added in reactor；After test agent to be checked reacts 15 minutes with circulating cooling water sample in the reactor, after reaction
Circulating cooling water sample be input in spectrophotometer under wavelength 420nm detection absorbance value 0.178, according to data processor
The amount of the anti-incrustation corrosion inhibitor of middle storage and the linear equation of absorbance value: the concentration (ppm) of anti-incrustation corrosion inhibitor=(absorbance value+
0.0015) concentration that anti-incrustation corrosion inhibitor in circulating cooling water sample/0.0016, is calculated is 112.2ppm.
The concentration value of anti-incrustation corrosion inhibitor in circulating cooling water sample is fed back into Water Treatment in Circulating Cooling System, by control system
It determines the amount whether anti-incrustation corrosion inhibitor needs to be added, be added, and executes operation, whole cycle is 30 minutes.
The additional amount of the detection reagent is small by estimating the concentration of anti-incrustation corrosion inhibitor in the present embodiment recirculated cooling water
It is calculated in 150ppm (discreet value of anti-incrustation corrosion inhibitor concentration is determined according to the service requirement of recirculated cooling water in production), with
Contain the reagent of hexadecyltrimethylammonium chloride 0.8g/L as detection reagent, sets additional amount as 175ml, at this moment detection tries
Agent is about 5-6 times excessive, to guarantee that anti-incrustation corrosion inhibitor is sufficiently reacted, while avoiding wasting.Test detection reagent cetyl
The corresponding relationship for adding concentration, additional amount and testing result of trimethyl ammonium chloride is as follows:
As seen from the above table, the concentration that adds of detection reagent hexadecyltrimethylammonium chloride is 0.6-1.0g/L, additional amount
When for 175ml, testing result meets accuracy requirement, thus the present embodiment select hexadecyltrimethylammonium chloride concentration for
0.8g/L, dosage 175ml.
The amount and suction that the amount of the present embodiment anti-incrustation corrosion inhibitor and the linear equation of absorbance value pass through drafting anti-incrustation corrosion inhibitor
Shading value working curve obtains, and prepares the water sample that anti-incrustation corrosion inhibitor concentration is 60,80,100,120,140ppm respectively, respectively takes
125ml is mixed with 175ml detection reagent respectively, reaction 15 minutes after, measured at 420nm absorbance value be 0.095,
0.126,0.159,0.193,0.222, the amount of anti-incrustation corrosion inhibitor and the linear equation of absorbance value are obtained according to above-mentioned data: resistance
Concentration (ppm)=(absorbance value+0.0015)/0.0016 of dirty corrosion inhibiter.
By manually detecting to same circulating cooling water sample, the concentration of obtained low-phosphorus antiincrustation corrosion inhibitor is
112.6ppm from manual sampling, on-site test, determines anti-incrustation corrosion inhibitor additional amount, executes the addition operation of anti-incrustation corrosion inhibitor, whole
A period is 2 hours.
Pass through comparison, it is seen that detection method of the invention, accuracy in detection is high, stability is good, and detection cycle is short, operation letter
It is single, saving of work and time.
Embodiment three
The present embodiment is related to the detection device using anti-incrustation corrosion inhibitor concentration in above-mentioned on-line checking recirculated cooling water, to containing
Have poly-aspartate, poly-epoxy succinic acid, acrylic acid-methacrylate-hydroxy propyl methacrylate terpolymer and
The recirculated cooling water of the non-phosphorus scale and corrosion inhibitor of hydrolysis of polymaleic anhydride carries out anti-incrustation corrosion inhibitor in on-line checking recirculated cooling water
Concentration, detection method is as follows:
The circulating cooling water sample of acquisition is quantitatively adding after the PP cotton filtering in filter by peristaltic pump with 125ml
In reactor, to contain the reagent of dodecyl benzyl dimethyl ammonium chloride 0.65g/L as detection reagent, by peristaltic pump with
175ml is quantitatively also added in reactor；Test agent to be checked reacts after twenty minutes in the reactor with circulating cooling water sample, will be anti-
It is 0.210 that circulating cooling water sample after answering, which is input in spectrophotometer and detects absorbance value under wavelength 460nm, according to data
The amount of the anti-incrustation corrosion inhibitor stored in processor and the linear equation of absorbance value: concentration (ppm)=(extinction of anti-incrustation corrosion inhibitor
Angle value+0.0004)/0.0016, the concentration that anti-incrustation corrosion inhibitor in circulating cooling water sample is calculated is 131.5ppm.
The concentration value of anti-incrustation corrosion inhibitor in circulating cooling water sample is fed back into Water Treatment in Circulating Cooling System, by control system
It determines the amount whether anti-incrustation corrosion inhibitor needs to be added, be added, and executes operation, whole cycle is 30 minutes.
The additional amount of the detection reagent is small by estimating the concentration of anti-incrustation corrosion inhibitor in the present embodiment recirculated cooling water
It is calculated in 150ppm (discreet value of anti-incrustation corrosion inhibitor concentration is determined according to the service requirement of recirculated cooling water in production), with
Contain the reagent of dodecyl benzyl dimethyl ammonium chloride 0.65g/L as detection reagent, sets additional amount as 175ml, at this moment
Detection reagent is about 5-6 times excessive, to guarantee that anti-incrustation corrosion inhibitor is sufficiently reacted, while avoiding wasting.Test detection reagent ten
The corresponding relationship for adding concentration, additional amount and testing result of dialkyl dimethyl benzyl ammonium chloride is as follows:
As seen from the above table, detection reagent dodecyl benzyl dimethyl ammonium chloride add concentration be 0.55-0.75g/L,
When additional amount is 175ml, testing result meets accuracy requirement, therefore the present embodiment selects dodecyl dimethyl benzyl chloride
Change ammonium concentration is 0.65g/L, dosage 175ml.
The amount and suction that the amount of the present embodiment anti-incrustation corrosion inhibitor and the linear equation of absorbance value pass through drafting anti-incrustation corrosion inhibitor
Shading value working curve obtains, and prepares the water sample that anti-incrustation corrosion inhibitor concentration is 40,60,80,100,120,140ppm respectively, respectively takes
125ml is mixed with 175ml detection reagent respectively, reaction after twenty minutes, measured at 460nm absorbance value be 0.062,
0.096,0.128,0.159,0.193,0.221, according to above-mentioned data obtain anti-incrustation corrosion inhibitor amount and absorbance value it is linear
Equation: concentration (ppm)=(absorbance value+0.0004)/0.0016 of anti-incrustation corrosion inhibitor.
By manually detecting to same circulating cooling water sample, the concentration of obtained anti-incrustation corrosion inhibitor is 132ppm,
It from manual sampling, on-site test, determines anti-incrustation corrosion inhibitor additional amount, executes the addition operation of anti-incrustation corrosion inhibitor, whole cycle 2
Hour.
Pass through comparison, it is seen that detection method of the invention, accuracy in detection is high, stability is good, and detection cycle is short, operation letter
It is single, saving of work and time.
Example IV
The present embodiment is related to the detection device using anti-incrustation corrosion inhibitor concentration in above-mentioned on-line checking recirculated cooling water, to containing
Have polyacrylic acid, polymethylacrylic acid, hydrolysis of polymaleic anhydride non-phosphorus scale and corrosion inhibitor recirculated cooling water, examined online
The concentration of anti-incrustation corrosion inhibitor in recirculated cooling water is surveyed, detection method is as follows:
The circulating cooling water sample of acquisition is quantitatively adding after the PP cotton filtering in filter by peristaltic pump with 125ml
In reactor, to contain the reagent of stearyl dimethyl benzyl ammonium chloride 0.8g/L as detection reagent, by peristaltic pump with
175ml is quantitatively also added in reactor；Test agent to be checked reacts after twenty minutes in the reactor with circulating cooling water sample, will be anti-
It is 0.204 that circulating cooling water sample after answering, which is input in spectrophotometer and detects absorbance value under wavelength 420nm, according to data
The amount of the anti-incrustation corrosion inhibitor stored in processor and the linear equation of absorbance value: concentration (ppm)=(extinction of anti-incrustation corrosion inhibitor
Angle value+0.0027)/0.0016, the concentration that anti-incrustation corrosion inhibitor in circulating cooling water sample is calculated is 129.2ppm.
The concentration value of anti-incrustation corrosion inhibitor in circulating cooling water sample is fed back into Water Treatment in Circulating Cooling System, by control system
It determines the amount whether anti-incrustation corrosion inhibitor needs to be added, be added, and executes operation, whole cycle is 30 minutes.
The additional amount of the detection reagent is small by estimating the concentration of anti-incrustation corrosion inhibitor in the present embodiment recirculated cooling water
It is calculated in 150ppm (discreet value of anti-incrustation corrosion inhibitor concentration is determined according to the service requirement of recirculated cooling water in production), with
Contain the reagent of stearyl dimethyl benzyl ammonium chloride 0.8g/L as detection reagent, sets additional amount as 175ml, at this moment examine
Test agent is about 5-6 times excessive, to guarantee that anti-incrustation corrosion inhibitor is sufficiently reacted, while avoiding wasting.Test detection reagent 18
The corresponding relationship for adding concentration, additional amount and testing result of zephiran is as follows:
As seen from the above table, the concentration that adds of detection reagent stearyl dimethyl benzyl ammonium chloride is 0.6-1.0g/L, adds
When to enter amount be 175ml, testing result meets accuracy requirement, therefore the present embodiment selects octadecyl dimethyl benzyl chlorination
Ammonium concentration is 0.8g/L, additional amount 175ml.
The amount and suction that the amount of the present embodiment anti-incrustation corrosion inhibitor and the linear equation of absorbance value pass through drafting anti-incrustation corrosion inhibitor
Shading value working curve obtains, and prepares the water sample that anti-incrustation corrosion inhibitor concentration is 40,60,80,100,120,140ppm respectively, respectively takes
125ml is mixed with 175ml detection reagent respectively, reaction after twenty minutes, measured at 420nm absorbance value be 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 value are obtained according to above-mentioned data: resistance
Concentration (ppm)=(absorbance value+0.0027)/0.0016 of dirty corrosion inhibiter.
By manually detecting to same circulating cooling water sample, the concentration of obtained anti-incrustation corrosion inhibitor is
129.6ppm from manual sampling, on-site test, determines anti-incrustation corrosion inhibitor additional amount, executes the addition operation of anti-incrustation corrosion inhibitor, whole
A period is 2 hours.
Pass through comparison, it is seen that detection method of the invention, accuracy in detection is high, stability is good, and detection cycle is short, operation letter
It is single, saving of work and time.
Claims (4)
1. the detection method of anti-incrustation corrosion inhibitor concentration in a kind of on-line checking recirculated cooling water, it is characterised in that: the detection method
Using cationic polymerization electrolyte as detection reagent, reagent will test so that whole anti-incrustation corrosion inhibitor quilts in recirculated cooling water
The amount of reaction is added in circulating cooling water sample to be detected, is sufficiently mixed, and 15~20min is reacted, then by following after reaction
The cooling water sample of ring detects absorbance value under 400~600nm of wavelength, determines scale inhibitor in recirculated cooling water according to absorbance value
The concentration of agent；
The anti-incrustation corrosion inhibitor includes phosphorus anti-incrustation corrosion inhibitor, non-phosphorus scale and corrosion inhibitor；
The cationic polymerization electrolyte include dodecyl benzyl dimethyl ammonium chloride, hexadecyltrimethylammonium chloride,
Any one in octadecyltrimethylammonium chloride or stearyl dimethyl benzyl ammonium chloride；
The detection method carries out in on-Line Monitor Device, and the on-Line Monitor Device includes: for detection reagent and circulating cooling
The reactor that water sample is reacted, the detection reagent being connected respectively with reactor is quantitatively adding system and circulating cooling water sample is quantitative
Addition system, further include be connected to reactor downstream for detect react after circulating cooling water sample absorbance value detection and analysis
Unit, the detection and analysis unit includes spectrophotometer and data processor.
2. the detection method of anti-incrustation corrosion inhibitor concentration, feature in on-line checking recirculated cooling water according to claim 1
Be: the anti-incrustation corrosion inhibitor includes polycarboxylic acid homopolymer, carboxylic acid copolymer, phosphine carboxylic acid class homopolymer or phosphine carboxylic acid class
At least one of copolymer.
3. the detection method of anti-incrustation corrosion inhibitor concentration, feature in on-line checking recirculated cooling water according to claim 2
Be: the anti-incrustation corrosion inhibitor includes poly-aspartate, poly-epoxy succinic acid, polyacrylic acid, hydrolysis of polymaleic anhydride, poly- methyl
Acrylic acid, acrylic acid-acrylate bipolymer, acrylic acid-hydrolyzed maleic anhydride bipolymer, acrylic acid-methyl
Acrylate-hydroxy propyl methacrylate terpolymer, acrylic acid -2- acrylamide-2-methyl propane sulfonic copolymer, hydroxyl
At least one of base ethylene-diphosphonic acid or 2- phosphonic acid butane -1,2,4- tricarboxylic acids.
4. the detection method of anti-incrustation corrosion inhibitor concentration, feature in on-line checking recirculated cooling water according to claim 1
Be: the temperature of control reaction process circulating cooling water sample is 25~40 DEG C, and pH value is 6~9.
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| CN107907496B (en) * | 2017-10-26 | 2020-03-27 | 西南石油大学 | Corrosion inhibitor concentration distribution test field test device and method |
| CN107870154A (en) * | 2017-11-08 | 2018-04-03 | 西安石油大学 | A kind of method of spectrophotometer detection density of corrosion inhibitor |
| CN110261335A (en) * | 2019-06-24 | 2019-09-20 | 陕西省石油化工研究设计院 | A method of measurement poly-epoxy succinic acid content |
| CN114236068B (en) * | 2021-11-24 | 2024-03-01 | 中冶赛迪信息技术(重庆)有限公司 | Chloride ion concentration analysis method and system based on circulating water system |
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