CN101424672A - Tracer and its use method - Google Patents
Tracer and its use method Download PDFInfo
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- CN101424672A CN101424672A CNA2007101765797A CN200710176579A CN101424672A CN 101424672 A CN101424672 A CN 101424672A CN A2007101765797 A CNA2007101765797 A CN A2007101765797A CN 200710176579 A CN200710176579 A CN 200710176579A CN 101424672 A CN101424672 A CN 101424672A
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- tracer
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- naphthol
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Abstract
The invention provides a fluorescent tracer and a using method thereof. The tracer is the univalence, bivalence or trivalence sulphonation of naphtha substituted by amino and the potassium and sodium salt thereof. The tracer in water has good linear relativity, high sensitivity and low checking limit. The fluorescent strength of the Fe<3+>, Ca< 2+>, Mg2+ and Zn<2+> in water on the tracer is low, and thus, the tracer is suitable for industrial water. When the tracer is used for tracking the water processing medical agent in the industrial water system, the medical agent density in the system can be continuously monitored, medical adding control can be realized, and the functions of saving the medical agent amount and the fresh water using amount and increasing the concentration time can be obtained.
Description
Technical field
The present invention relates to a kind of tracer agent, relate in particular to a kind of tracer agent and using method thereof that is used for monitoring industrial water system water treatment agent concentration.
Background technology
In order to solve the problem of surperficial fouling easily of the watering equipment that exists in the process water and corrosion, various water treatment agents are used widely.In the use of water treatment agent, drug concentration is an important parameter, and drug concentration is low excessively, can not bring into play the effect of water treatment agent; Drug concentration is too high, can cause the waste of medicament and increase water and pollute.
In order better to control the dosage of water treatment agent in the industrial water system, guarantee treatment effect, save pharmaceutical quantities, reduce the workload that test job and water treatment agent add.People have developed the circulation automatic dosing control system, and the drug concentration in the circulation is monitored, and realize the Automatic Dosing of system.
At present, the automatic medicament feeding system in recirculated water field, the mode difference according to medicine system control medicament is divided into following several:
The one, by the rate of water make-up of monitoring recirculated cooling water, the ratio of recirculated water and the conductivity of moisturizing, perhaps three kinds of modes of the temperature difference of recirculated water realize adding automatically continuously, in proportion medicament; The 2nd, measure the amount control dosing of medicament by total phosphine in-line analyzer.
The amount of medicament in the industrial water system can accurately not measured and control to above dual mode, especially at present because the needs of environmental protection are developed a lot of without phosphorus medicaments, the quantitative test of its polymkeric substance does not also have simple and easy to do method at present, and the chamber is analyzed and determined its wear rate by experiment.
The 3rd, the amount of spike medicament is measured and controlled to fluorescent tracer technique by adding the spike medicament,, thus the amount of control water treatment agent.The method has that system is stable, dosing is economized, record data and save advantage such as manpower automatically.
In the prior art, foreign patent " Method of monitoring membrane cleaning processes " (US7060136) and " METHOD OF TRACING DRAINS " (WO03029794), introduced the method and system of monitoring and/or control film piece-rate system cleaning course.This method is used a kind of inert fluorescent tracer, comprises 1,5 naphthalene disulfonic acid disodium salt, 2-amino-1-naphthalene sulfonic aicd, 7-amino-1, the naphthalene of various similar single, two or three sulfonation such as 3-naphthalene sulfonic acids sylvite, 1-amino-7-naphthalene sulfonic acids and potassium thereof, sodium salt.
Foreign patent " Naphthalimide diester fluorescent tracers having improved solubilityand fluorescence " (US6248890) has been introduced naphthalene diformazan imide diester fluorescent tracer, is used for the liquid system leak detection.The tracer agent that foreign patent " Rapid method for detecting leaks of hydraulic fluids inproduction plants " (US2005160795) is introduced comprises 4-amino naphthalenes-1-sulfonate sodium, 4-amino-3-hydroxyl-1-naphthalene sulfonic aicd etc.
The water quality stabilizer that domestic patent " a kind of spike type water quality stabilizer " (CN1506325) is introduced uses acrylic acid-acrylate-phosphonic acids-azole multipolymer to cook fluorescent tracer.The spike water treatment agent that domestic patent " a kind of polymkeric substance and synthetic method thereof that contains tracer group " (CN1229091) is introduced is containing 0-3 sulfonic group and amino aromatic ring acylate is made fluorescent material, as 1-amino-6-naphthalene sulfonic acids etc.
The fluorescent tracer technique technology can be measured the tracer agent of 0.01 μ g/L concentration exactly, in order can in industrial water system, effectively to be used, must not loss in this system as the compound of tracer agent, and promptly be inertia for this system.At present, this compounds is not a lot, needs the new water treatment trace medicament of exploitation, to satisfy the needs of various process waters.
Summary of the invention
The invention provides a kind of novel tracer agent and using method thereof.This probe material can be measured simply, fast and accurately by instrument, and the linear dependence of tracer agent in water body be good, highly sensitive, it is low to detect lower limit, to the Fe in the industrial water system
3+, Ca
2+, Mg
2+, Zn
2+Insensitive, and under conditions such as oxygenant, illumination and higher temperature stable chemical performance, can be used as the spike medicament and in industrial water system, use.
Tracer agent of the present invention is achieved in that
A kind of tracer agent, described tracer agent is: the naphthols that amino and sulfonic group replace.
When concrete facility, described sulfonic group substituting group number is: 1,2 or 3; Its sulfonic group substituting group can be sulfonic group sylvite or sodium salt.Preferred tracer agent is: 1-amino-2-naphthol-4-sulfonic acid, 1-amino-8-naphthol 2-sulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid, 1-amino-8-naphthol-4,6-sodium disulfonate, 2-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-3,4-disulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 2-amido-8-naphthol-6-sulfonic acid or 3-amino naphthalenes-8-hydroxyl-4, the 6-disulfonic acid.
Tracer agent of the present invention is single, two or three sulfonated acids of the amino naphthols that replaces and potassium thereof, sodium salt, and this compounds is a fluorescent chemicals, has fluorescence property preferably, and its concentration can utilize its fluorescence intensity of fluorescent spectrophotometer assay to obtain.
The maximum excitation wavelength and the maximum emission wavelength that use fluorescence spectrophotometry to record this compounds are respectively in 270～300nm and the 400～430nm scope, has very wide spectral range, strengthened the effectiveness of these compounds as the spike medicament, huge difference between maximum excitation wavelength and the maximum emission wavelength has reduced the interference that hydrocarbon compound causes its mensuration.
Tracer agent of the present invention can use in industrial water system, and these systems comprise recirculating cooling water system (comprising open, closed type and single flow), air-conditioning refrigeration system, boiler and boiler feed water system, oil drilling system, water recovery and cleaning system, membrane filtration system and various sewage disposal systems etc.Tracer agent of the present invention stable performance in the industrial water system environment is not subjected to the influence of other compounds, bacterial micro-organism, operational factor etc. in the system.
Temperature has certain influence to the tracer agent fluorescence intensity of solution usually, along with temperature reduces, the fluorescence quantum yield of tracer agent solution and fluorescence intensity have certain increase, and (this is because temperature reduces, the viscosity of medium increases, fluorescence molecule and solvent molecule collision cancellation chance is reduced), the tracer agent solution of the present invention under the normal temperature is heated to 100 ℃ gradually, along with temperature raises, fluorescence intensity slightly descends, but fluorescence intensity changes≤10%.In addition, at 0～1mg/L Fe
3+, 0～1500mg/L Ca
2+, 0～500mg/L Mg
2+, 0～25mg/L Zn
2 +In the concentration range, several metal ion species do not have influence substantially for spike type water treatment agent; The recirculated water common fungicide does not influence substantially to tracer agent under the medicament working concentration yet.
The using method of tracer agent of the present invention is achieved in that
With putting in the industrial water system after tracer agent of the present invention and the water treatment agent mixing,, obtain the concentration of water treatment agent by measuring tracer concentration; The concentration of tracer agent in industrial water system is 0.01～10.0mg/L, and preferred concentration is 0.1～1.0mg/L.
Adopt the fluorescence intensity of fluorescence spectrophotometer measurement water system, because the concentration of tracer agent and water treatment agent has correlativity, can obtain the concentration of water treatment agent quickly and accurately by measuring tracer concentration, obtain the concentration of water treatment agent in the water system on this basis.
When tracer agent of the present invention is used in industrial water system, needed pharmaceutical quantities is very little, generally speaking, making dosage is 0.01～5mg/L, maximum medicament use amount is no more than 10mg/L, the too much spike medicament that adds then causes unnecessary waste, and best use drug concentration is 0.1～1.0mg/L, to the not influence of performance of the employed water treatment agent of industrial water system.
Description of drawings
Fig. 1 tracer agent 3-amino naphthalenes-8-hydroxyl-4, the typical curve of 6-disulfonic acid
Fig. 2 underwater gold belongs to the influence of ion pair tracer agent
The typical curve of Fig. 3 tracer agent 1-amino-8-naphthol 2-sulfonic acid
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to following embodiment.
Tracer agent is 3-amino naphthalenes-8-hydroxyl-4, the 6-disulfonic acid.
1, detection curve
Get an amount of tracer agent and separate with 100ml is water-soluble in beaker, examine or check its dissolubility, test records its solubleness 〉=1g.
The standard solution of water preparation tracer concentration 0.4～10mg/L, fixedly the excitation wavelength of fluorospectrophotometer and emission wavelength are in 275nm and 421nm, with fluorescent spectrophotometer assay 3-amino naphthalenes-8-hydroxyl-4,6-disulfonic acid aqueous solution fluorescence intensity, experimental result is seen Fig. 1.
Experiment shows, 3-amino naphthalenes-8-hydroxyl-4, and the 6-disulfonic acid is good, highly sensitive in water body neutral line correlativity, the detection lower limit is low, and is suitable suitable as tracer agent.
2, the service water intermediate ion is to the influence of tracer agent
Examined or check the Fe in the process water by experiment
3+, Ca
2+, Mg
2+, Zn
2+To tracer agent 3-amino naphthalenes-8-hydroxyl-4, the influence of 6-disulfonic acid solution fluorescence intensity.Tracer concentration is 8mg/L, and fixedly the excitation wavelength of fluorospectrophotometer and emission wavelength are in 275nm and 421nm, and experimental result is seen Fig. 2.
Experiment shows, the Fe in the process water
3+, Ca
2+, Mg
2+, Zn
2+To tracer agent 3-amino naphthalenes-8-hydroxyl-4, the influence of 6-disulfonic acid solution fluorescence intensity is very little, and this tracer agent is adapted at using in the process water.
Tracer agent is 1-amino-8-naphthol-2-sulfonic acid.
Detection curve:
The standard solution of water preparation tracer concentration 0.4～12mg/L, fixedly the excitation wavelength of fluorospectrophotometer and emission wavelength are measured 1-amino-8-naphthol 2-sulfonic acid aqueous solution fluorescence intensity in 275nm and 421nm, and experimental result is seen Fig. 3.
Experiment shows that the corresponding light intensity with it of 1-amino-8-naphthol-2-sulfonic acid concentrations presents good linear relationship, and is suitable suitable as tracer agent.
Claims (6)
1, a kind of tracer agent, described tracer agent are naphthols amino and that sulfonic group replaces.
2, tracer agent according to claim 1 is characterized in that: described sulfonic group substituting group number is: 1,2 or 3.
3, tracer agent according to claim 2 is characterized in that: described sulfonic group substituting group is sulfonic group sylvite or sodium salt
4, tracer agent according to claim 1 is characterized in that:
Described tracer agent is: 1-amino-2-naphthol-4-sulfonic acid, 1-amino-8-naphthol 2-sulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid, 1-amino-8-naphthol-4,6-sodium disulfonate, 2-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-3,4-disulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 2-amido-8-naphthol-6-sulfonic acid or 3-amino naphthalenes-8-hydroxyl-4, the 6-disulfonic acid.
5, a kind of using method of tracer agent,
With putting in the industrial water system after described tracer agent of claim 1～4 and the water treatment agent mixing,, obtain the concentration of water treatment agent by measuring tracer concentration; The concentration of tracer agent in industrial water system is 0.01～10.0mg/L.
6, tracer agent using method according to claim 5 is characterized in that:
The concentration of described tracer agent in industrial water system is 0.1～1.0mg/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101765797A CN101424672A (en) | 2007-10-31 | 2007-10-31 | Tracer and its use method |
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|---|---|---|---|
| CNA2007101765797A CN101424672A (en) | 2007-10-31 | 2007-10-31 | Tracer and its use method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104136377A (en) * | 2012-03-06 | 2014-11-05 | 纳尔科公司 | Treatment of industrial water systems |
| CN104237189A (en) * | 2014-09-28 | 2014-12-24 | 南京大学 | Method for quickly identifying and quantitatively analyzing wastewater pollution in printing and dyeing industry |
| CN107843688A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of tracer and its application for aqueous solution of urea |
| CN109973084A (en) * | 2017-12-28 | 2019-07-05 | 江苏长江地质勘查院 | A kind of new type high temperature geothermal well groundwater tracer and its application |
| CN109983339A (en) * | 2016-11-14 | 2019-07-05 | 株式会社竹中工务店 | Ground injectant concentration deduction system |
| CN111749650A (en) * | 2020-06-09 | 2020-10-09 | 中国石油化工股份有限公司 | Oil well scale inhibitor dosing period determination method |
| CN116106282A (en) * | 2023-02-13 | 2023-05-12 | 上海淼清水处理有限公司 | Method for detecting concentration of scale and corrosion inhibitor in circulating water by fluorescence |
-
2007
- 2007-10-31 CN CNA2007101765797A patent/CN101424672A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104136377A (en) * | 2012-03-06 | 2014-11-05 | 纳尔科公司 | Treatment of industrial water systems |
| US10765999B2 (en) | 2012-03-06 | 2020-09-08 | Ecolab Usa Inc. | Treatment of industrial water systems |
| CN104237189A (en) * | 2014-09-28 | 2014-12-24 | 南京大学 | Method for quickly identifying and quantitatively analyzing wastewater pollution in printing and dyeing industry |
| CN104237189B (en) * | 2014-09-28 | 2016-07-13 | 南京大学 | A kind of method quickly identified with quantitative analysis that dyeing waste water pollutes |
| CN107843688A (en) * | 2016-09-19 | 2018-03-27 | 中国石油化工股份有限公司 | A kind of tracer and its application for aqueous solution of urea |
| CN109983339A (en) * | 2016-11-14 | 2019-07-05 | 株式会社竹中工务店 | Ground injectant concentration deduction system |
| US11231406B2 (en) | 2016-11-14 | 2022-01-25 | Takenaka Corporation | Ground injection agent concentration estimation method |
| CN109983339B (en) * | 2016-11-14 | 2022-08-05 | 株式会社竹中工务店 | Method for estimating concentration of foundation injection agent |
| CN109973084A (en) * | 2017-12-28 | 2019-07-05 | 江苏长江地质勘查院 | A kind of new type high temperature geothermal well groundwater tracer and its application |
| CN111749650A (en) * | 2020-06-09 | 2020-10-09 | 中国石油化工股份有限公司 | Oil well scale inhibitor dosing period determination method |
| CN116106282A (en) * | 2023-02-13 | 2023-05-12 | 上海淼清水处理有限公司 | Method for detecting concentration of scale and corrosion inhibitor in circulating water by fluorescence |
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Open date: 20090506 |