JPH0611437B2 - How to monitor an industrial or municipal water system - Google Patents

Description

Description: FIELD OF THE INVENTION This invention relates to the use of compositions containing one or more fluorescent agents, and more particularly to the rate of delivery of processing chemicals to a liquid containing system. A method of utilizing the composition to quantify and control (s). In addition, the one or more fluorescent agents provide a means of measuring composition performance at rest or altering the operating conditions of the system. Furthermore,
One or more fluorescent agents are used to quantify important properties of the system, such as the total volume and amount of liquid entering and leaving the system.

As used herein, the term liquid means any liquid, aqueous, non-aqueous, and mixed aqueous / non-aqueous.

[Conventional technology]

In a system containing a liquid to which the treating agent is added, maintaining an appropriate supply amount of the treating agent is essential for optimum performance. Improper feed rates of treating agents can lead to serious problems. For example, when using unreasonable amounts of treating agent, severe corrosion and / or deposit formation can occur rapidly on the heat exchanger surfaces in cooling and boiler water systems. One common method of calculating treatment agent concentration is to measure the amount of active ingredient (eg, polymeric scale inhibitor, phosphate, or organophosphonate) in the treatment agent formulation. The technique is often unsatisfactory due to one or more of the following problems: (a) Background interference from system liquids or substances contained in the liquid: (b) Use of expensive and expensive analytical methods. (C) time-consuming and labor-intensive analyzes are not compatible with continuous monitoring; (d) inaccurate readings are due to degradation or precipitation of active ingredients in the system.

Another method of measuring treating agent feed rate is, in particular, by adding metal ions (eg Li ⁺ ) to the formulation or system. The method helps avoid degradation / deposition and background interference problems. However, quantification of low tracer levels typically adds to the problems associated with expensive equipment and time consuming test methods. Additional factors that must be considered are tracer cost and environmental acceptability. For example,
Radiotracers are detectable at very low levels but are generally expensive and unacceptable due to environmental and health issues.

[Problems to be Solved by the Invention] An object of the present invention is to avoid all of the above problems.

[Means for solving the problem]

The present invention provides for the determination of whether the concentration of treated components is at an acceptable value under operating conditions, as a whole, while consuming in the system while containing impurities and removing or neutralizing impurities in water bodies. What is claimed is: 1. A method of monitoring an industrial or municipal water system of the type including a device for passing a moving body of water containing a quantified dose of a water treatment component that has the role of being absorbed, the method comprising: An amount of a water-soluble fluorescent tracer proportional to the amount of the treated component of (wherein the fluorescence of the tracer is inert to water and not affected by water, inert to the device and not affected by the device, And (B) it is inert to the treated components and is not affected by the treated components); (B) the system discharges a sample of the water body containing both the component and the tracer, The sample, the essentially tracer concentration was subjected to analysis comprising the step of comparing the standard emissivity basis to determine the concentration of tracer in the sample;
And, if the operating concentration is outside the acceptable operating range, (C) until the acceptable range of concentrations for the treatment components is achieved, the volume of water, the rate of addition or discharge of water or the treatment components Provided is a method of monitoring an industrial or municipal water system characterized by varying doses.

As mentioned above, the present invention incorporates a fluorescent compound as a tracer into the treatment agent formulation to provide quantitative measurement / control of treatment agent delivery rate and performance. By its very nature, fluorescence is a powerful selective trace component analysis technique [J. R. Racowitz, "Principles of Fluorescence Spectroscopy" (19
83)].

Generally, the concentration of fluorescent tracer is measured directly from the tracer concentration vs. emission calibration curve (FIG. 1). The comparison allows measurement of the concentration range where a linear luminescence response is observed. At higher tracer concentrations, a negative deviation from ideal behavior is observed. The concentration of tracer can still be measured directly from the calibration curve, or the sample can simply be diluted until the tracer concentration falls within the linear emission response range. In the case of extremely dilute samples, the technique consists in increasing the concentration of the fluorescent tracer until it is within the desired concentration range (eg liquid-liquid extraction).

By properly selecting the fluorescent reagent, ppt to ppm
Quantitative and in-situ measurements of tracer amounts up to can be routinely achieved on an immediate or continuous basis using inexpensive portable devices. Further, multiple tracers may be used simultaneously by selecting a tracer with the appropriate spectral characteristics. As such, various combinations of fluorescent tracer and treating agent feed can be quantified within the liquid system. For example, four individual treatments containing a single unique fluorescent tracer plus one additional treatment containing two fluorescent tracers could be used in the liquid system. In that case, each fluorescent tracer and 5
The corresponding individual concentrations of the individual treatments can each be quantified.
In addition to being able to quantify complex combinations of treating agent feeds, fluorescent compounds are available that are environmentally acceptable, are not degraded by liquid systems, do not precipitate in liquid systems and are available at low cost.

The present invention is generally applicable in the following ways: a) direct addition of one or more fluorescent tracers to a liquid system; b) 1-6 (or more) to a chemical treating composition containing other ingredients. A fluorescent tracer (wherein the treating agent is applied to a liquid system to maintain proper operation of the system); c) 1 to 6 chemical treating agents (or more) containing one or more fluorescent tracers. ) Is added directly to the liquid system or to the liquid feed leading to the system; d) Individual tracer concentrations of 1 ppt in the liquid system.
(1 part / 1 trillion part) to 100 ppm, preferably 1 ppb
Addition of fluorescent tracer so that -10 ppm, most preferably 10 ppb-2 ppm is achieved.

The present invention is directed to a wide range of aqueous, mixed aqueous / non-aqueous, or non-aqueous liquid systems where the amount of chemical treating agent affects the performance of the system (eg, boiler, clarifier, waste treatment, liquid solids separation, down-hole. (Down-hole) oil field application).

Two systems were evaluated on a large scale: 1) Pilot cooling towers used to simulate industrial systems (second); 2) Field tests in open-recirculating cooling water systems of industrial plants.

An important difference between the pilot cooling tower (PCT) and the industrial cooling water system is that the latter is more complex [multiple water flow passages through heat exchangers, multiple make-up and blow-down water sources and operational control ranges]. Fluctuations (concentration of hardness ions, temperature, water quality, pH, etc.)].

In all systems, energy is extracted by recirculating cooling water from the process side of the system, which is at a higher temperature. In order to maintain the efficiency of heat transfer, energy needs to be removed by evaporative cooling of the recirculated water in the cooling tower and the heat exchanger surfaces must remain clean. Evaporation of cooling water (E) results in concentration of suspended dissolved solids in the cooling system. The term concentration ratio (CR) is a measure of the amount of increase in dissolved suspension in the system (Equation 1).

Solids deposition and heat exchanger surface corrosion are the most commonly encountered problems. Cooling water systems usually contain highly supersaturated amounts of scaling salts, and the precipitation of solids throughout the system (especially in metal heat exchangers) is accompanied by one or more chemical treatments containing scale inhibitors. If the agent is not added, it will occur. To prevent corrosion of the metal heat exchangers and water transfer lines, one or more chemical treating agents typically contain a corrosion inhibitor. If the chemical treating agent feed rate is too high or too low, severe scaling and corrosion can occur throughout the heat exchanger and system.

Amount of dissolved suspended solids, total volume of liquid in the system ( _VT )
It is essential that the chemical treating agent concentration be maintained between certain values in order to provide economical use of water, efficient heat transfer, minimal fouling of the total cooling system, and low operating costs. In order to maintain the concentration ratio (CR) within an acceptable range, water containing "high" concentrations of impurities is removed from the system (collectively defined as "blowdown" (B)). It must be replaced by water containing low'concentrations of impurities (collectively defined as'make-up '(M)). E,
The B, M, and CR values are variable due to changes in weather, industrial plant operating conditions, and makeup water quality. These factors are all correlated (as shown below), and changes in any one of the factors must be balanced by corresponding changes in other operating parameters.

B + M = E (Equation 2) CR = M / B (Equation 3) In addition to the dynamic operating conditions of the cooling water system, other significant variables and unknown factors are commonly encountered. For example, blowdown water (B) can be removed from the cooling system by various methods (Equation 4). This unfortunately tends to be variable and ill-defined. The rate at which water is specifically pumped from a cooling water system is defined as "recirculating water blowdown" ( _BR ), and even that rate due to practical difficulties in measuring large volumes of water. Not always known exactly. In addition, indefinite amounts of recirculated water (un-accounted system losses) are usually removed from the cooling water system to be used in other parts of the industrial plant (“plant blowdown” (B _P ))). Recirculating water leakage ( _BL ) and droplet drift from the cooling tower ( _BD ) also add to the unknown system loss. A similar situation is that the total make-up water speed (M) is the sum of the speed at which make-up water is specifically pumped into the recirculation system (M _R ) and the speed of the liquid originating from other sources (M ′). It may occur in the case of makeup water. The complexity of the situation can be recognized by considering equations 2-5.

B = _BR + _BP + _BL + _BD (Equation 4) M = M _R + M '(Equation 5) The supply rate of the chemical treatment agent to the cooling water system is usually M
Based on the calculation value of the _R or _{B R.} This means that there can be considerable uncertainty regarding the concentration of chemical treating agents. When the operating conditions of the cooling water system change,
The feed rate of the chemical treatment should be adjusted. These adjustments may or may not be made depending on how carefully the cooling water system is monitored and controlled. Even when adjusting the feed rate, the concentration of chemical treating agent in the cooling water system may generally respond slowly to changes (Equation 6).

t = (V _T / B) 1n (2) (Equation 6) (In the equation, t is a response time when a concentration increase of 50% occurs.) For example, one million gallons (3.785 × 10 ³ m ³ ) And a total blowdown rate of 300 gallons (1.136)
Consider a typical system with m ³ ) / min. If the feed rate of the treating agent is increased from 50 ppm to 100 ppm, assuming that no other variation or change has occurred in the system, 38.5 hours is only half of the change (increase in treating agent concentration of 25 ppm). Needed to achieve. For very large values and small values of B of the V _T, the response time may be measured in days or weeks.
In other cases, changes, eg, deliberate (or inadvertent) flushing of the system, can occur rapidly.
Therefore, maintaining good control and accurate monitoring of the system is important.

Another significant operating parameter to be quantified is the retention time index (HTI), a measure of the half-life of the species in the system (Equation 7).

HTI = 0.693 (V _T / B) (Equation 7) Under severe operating conditions, it is possible to optimize the HTI to reduce possible degradation of components in chemical treating agents without significantly increasing operating costs. ,is important.

Due to all operational limitations and uncertainties in cooling water systems, the need to rapidly measure and continuously monitor the concentration of chemical treating agents is clear. The addition of the propensity tracer to the chemical treating agent allows an accurate determination of all the unknown operating conditions, inaccurately known operating conditions and variable operating conditions mentioned above.

FIGS. 3A-3C show the operation of the water treatment program at the molecular level as a function of time. The concentrated chemical treating agent (containing one or more components) is slowly fed to the recirculating cooling water where it rapidly dilutes and is distributed throughout the system. If the operating conditions of the cooling water system remain constant, the addition and removal of treating agent (due to recirculating water blowdown and system loss) will be in equilibrium (A in Figure 3). The concentration of the chemical treating agent and its components should ideally remain unchanged. However, that situation does not arise. As time progressed (FIG. 3B to FIG. 3C), additional amounts of Zn ⁺² , polymer, and phosphorus-containing compounds were deposited and protective film formation and chemical / biological degradation on the metal surface. May be lost from recirculated water due to process. Also, changes in operating conditions (blowdown rate, concentration ratio, product feed rate, etc.) affect the concentration of process components. Without a fluorescent tracer, analysis of recycled water may measure some current concentrations of treatment components (assuming analytical methods exist), but cannot directly indicate the original feed rate of the treatment program. Quantifying and controlling treatment agent feed rates using fluorescent tracers is a valuable (if not essential) addition to current water treatment programs.

In addition, FIGS. 3A to 3C show how the addition of the inert fluorescent tracer enables accurate measurement of the treating agent supply rate and the treating effect in spite of the precipitation of other components in the chemical treating agent. Indicates what can be given to. For example, assume the feed rate of the formulation is 100 ppm. If precipitation occurs on the heat exchanger, 40% of the phosphorus-containing species will be lost from the recycled water, but no fluorescent tracer will be lost.
The total phosphorus concentration would suggest that only 60 ppm product was present. However, the fluorescent tracer would accurately show that the feed rate of the formulation was 100 ppm and that a loss of phosphorus-containing component equivalent to that provided by the 40 ppm feed of the formulation was deposited. The measurement of the rate of loss of one or more active ingredients of the treating agent is
It is a direct measure of treatment efficacy.

In short, important system characteristics of many industrial systems (total capacity, blowdown and replenishment rate, retention time index, feed rate of treating agent, etc.) are inaccurately known in nature, variable, and sometimes predictable. Can not. Lack of knowledge about those factors can lead to significant deposit and corrosion problems throughout the entire cooling water system. In particular, over / under supply of treatment programs or improper operation of cooling water systems can result in significant loss of one or more treatment components and adversely affect heat transfer within the cooling water system. In addition, water treatment programs usually contain modulators or toxic substances such as zinc ions, phosphates, or chromates. Oversupply of treating agent can be dangerous and make industrial values more difficult to meet control off-the-shelf for effluent discharge. The use of fluorescent tracers is a highly desirable means of accurately measuring, continuously monitoring, and controlling cooling water system properties and treating agent feed rates (within the desired range).

The successful use of fluorescent tracers to accomplish the task has been accomplished in several systems. Pilot cooling tower tests (Example 1) demonstrate the concept and feasibility of using fluorescent tracers in treating agent compositions, and field tests have demonstrated the applicability of fluorescent tracers in real world systems (Example 2).

Example 1: Treatment Efficiency and Scaling Rate Measurements (Pilot Cooling Test) The test was carried out in a pilot cooling tower designed to simulate an industrial cooling water system (Figure 2). Processes such as recirculating water, chemical treat feed, deposit formation and corrosion on heat exchangers, blowdown and make-up, and evaporative cooling from column packing are all included. A significant feature of this laboratory system is that fluorescent tracer measurements of system volume and treating agent feed rate can be substantiated by another direct measurement.

The results from the PCT test are summarized in Figure 4. A single water treatment formulation was used which consisted of two fluorescent tracers (sodium salt of 2-naphthalene sulfonic acid and Acid Yellow 7 dye), polymer (scale inhibitor), organophosphorus compound (scale / scale). Corrosion inhibitor), and aryltriazole (corrosion inhibitor for brass).
The concentration of each fluorescent tracer was quantified and compared to the total phosphorus concentration in the system's recycled water. Total phosphorus content was measured by oxidizing organophosphorus species with persulfate to orthophosphate, then forming a blue phosphomolybdate complex and spectrophotometrically quantifying this complex [M. C. Rand, "Standard Methods for Testing Water and Wastewater," 14th Edition (1975)]. Each fluorescent tracer was individually quantified by choosing a widely separated wavelength of light to excite the individual tracer and observing the fluorescence emission for each tracer at the widely separated wavelength of light (5th).
Figure). A dilute solution of treatment (100 ppm) was used as a reference standard and all concentrations of tracer and phosphorus-containing species (total phosphorus content) are expressed as equivalent formulation concentrations.

The aryltriazole corrosion inhibitor in the formulation is a phosphor. However, proper selection of the wavelength of excitation light and observation of fluorescence emission of 2-naphthalene sulfonic acid (2-NSA) and Acid Yellow 7 tracer
Avoided potential interference with aryltriazoles. The basic principle for quantification of individual fluorescent tracers and avoidance of interference from other fluorescent compounds is shown in FIG.

The specific objectives of this pilot cooling tower test are as follows: (a) Demonstrating that the fluorescent tracer can accurately measure total system capacity and treating agent feed rate; (b) more than one fluorescent tracer. Demonstrating that they can be individually quantified; (c) showing that the fluorescent tracer can be quantified in the presence of one or more other fluorescent compounds; (d) the fluorescent tracer can provide a treatment agent feed rate (eg, total phosphorus concentration). Demonstrating superiority over other currently used methods for measuring a); (e) measuring the difference between the fluorescent tracer reading and one or more other active ingredients of the treating agent. And demonstrating that the loss of one or more active ingredients and the overall treatment efficacy can be quantified.

Each of the above goals was successfully achieved in a pilot cooling tower test (see Figure 4). The PCT system was initially dosed with 192 ppm formulation for a total system volume of 52. The initial tracer readings for Acid Yellow 7 and 2-NSA were 190 ppm and 186 pp of treating agent.
m has been injected into the PCT system, which has system capacity values of 52.5 and 53.1, respectively.
Will correspond to. The tracer results were internally consistent and gave an accurate measure of system capacity.

During the first 40 hours of the PCT of operation, the blowdown pump was turned off and the recirculated water was concentrated by evaporation from a concentration ratio of 1 (make-up water) to a value of 4 (see equation 1). At that time, the drift from the cooling tower should be only the loss of recirculated water from the system, which should give rise to a small equal downslope of the amount of each fluorescent tracer, the response of which was exactly observed. Is. Between 40 and 48 hours, a recirculation water blowdown was used to maintain a constant concentration ratio, and 213 pp of treating agent was used whenever blowdown occurred.
The system was supplied at a rate of m. As such, a small, equal increase in the concentration of each fluorescent tracer should be observed in the time period that was the case above. Between 48 hours and the completion of the test, the treating agent was delivered at an average rate of 112 ppm no matter when the system blowdown occurred. At that time,
The amount of each tracer should undergo an equal exponential decrease (see Equation 6) and finally after about 190 hours 112
It should level off at concentrations approaching ppm.
From 190 hours to the end of the test, the concentration of each tracer may undergo small equal increases or decreases in response to small variations in PCT operating conditions (eg, changes in blowdown rate, concentration ratio, etc.). The expected behavior of each fluorescent tracer was exactly what was observed throughout the entire PCT study (Figure 4).

Comparison of treating agent feed rates in recycled water predicted by fluorescent tracer amount vs total phosphorus concentration demonstrates the superior accuracy of fluorescent tracers and the ability to measure treatment efficacy. After 190 hours, the total phosphorus content was 75-86 for the treatment agent concentration.
ppm, while the fluorescent tracer showed that the amount of treating agent was 110 ppm on average. The difference between them is
It originates from the precipitation of the organic phosphorus component of the treating agent on the heat exchange tube. A difference of one or more between the fluorescent tracer amount (s) and the total phosphorus amount quantifies how much active phosphorus-containing component is lost in the system from the deposition and corrosion processes, thus directly affecting the process effectiveness. Is a measure of. In an "ideal" operating system, the total phosphorus amount and fluorescent tracer amount would all exhibit the same treating agent concentration.

Upon completion of the PCT test, solid deposits were removed from the heat exchange tubes and analyzed. A high rate of precipitate formation was measured (54
mg / day), while 35 mg / day was considered to be the maximum acceptable limit. The total phosphorus content of the precipitate was 10.4% by weight (as orthophosphate), which is consistent with the precipitation of the organophosphorus-containing treated components as described above. Despite the high scaling rate, no detectable amount (<0.003% by weight) of Acid Yellow 7 or 2-NSA was observed. This demonstrates the inertness and non-adsorption of these fluorescent tracers.

Example 2: Industrial Cooling Tower (Field Attempt) In a field test, an industrial system was operated under severe conditions as follows: (a) Total system capacity was inaccurately known, blowdown rate was inaccurately measured; (B) long retention time index and large capacity of recirculated water; (c) high skin temperature on the heat exchange tubes; (d) low flow of cooling water experienced in some parts; (e) particulates present. (F) significant variation in concentration ratio; (g) system was not pretreated to minimize the possibility of depositing tracer on the surface and deposits; (h) ) High average flow rate of recirculated water (approximately 100,000
00 gallons (3.785 × 10 ⁵ m ³ ) / day).

The system studied was a complex (but typical) recirculating water system that included a cooling tower used to cool the hot process side fluid. However, the cooling tower and system should have been used in an industrial process where energy is extracted by heat exchange in a moving body of water. There were numerous points for bleed-off or blowdown of recirculated water, as well as several make-up water sources possible.

First, a treatment program consisting of a fixed ratio of corrosion inhibitors (Zn ⁺² and inorganic / organic phosphorus compounds), polymeric scale inhibitors (to prevent corrosion inhibitors and scaling salt precipitation in the system), and cooling water. Supplied to the system. The first treating agent contained no fluorescent tracer and the treating agent feed rate was based on a flow meter reading from a blowdown pump. Analysis of the recycled water showed unexpectedly low amounts of zinc, phosphorus, and polymer. It was not known at that time whether the low treating agent amounts were due to treatment component precipitation / deterioration, poor analytical results, or low treating agent feed rates. It has become essential to quantify the operating characteristics of the system and to determine if the chemical treating agents function properly.

To see why only small amounts of chemically treated components were observed, the inert fluorescent tracer, sodium salt of 2-naphthalene sulfonic acid (2-NSA) was used in the following test: Test A: Known addition to system "Slug-feed and slug-feed using a two-tracer combination with a quantity of lithium chloride and phosphor 2-NSA.
and die-away) ”research (see Figure 6).

Test B: A known amount of 2-NSA was added to the treatment formulation (slowly fed to the system) as described above in Example 1.

The 2-NSA fluorescent tracer is inert to the cooling water system in the sense that it is not reactive with other components in the body of water and cannot be coupled or deposited in any way with the system equipment.

This fluorescent tracer is a true indicator of the treatment feed rate and the properties of the cooling water system as it can penetrate the entire recirculation system while remaining an independent, unchanged substance.

"Slug Feed and Diaway" (Reagent A, Figure 6) is the total amount of recirculated water removed from the system (blowdown + system leak + unknown system loss + cooling tower drift) and total capacity of the cooling water system. Is a classical method of measuring. By adding a known amount of tracer and measuring the concentration after penetrating the system, the total system capacity can be measured quantitatively. Li ⁺ is traditionally used as an inert non-adsorbent tracer in “slug feed and die away” studies. However, lithium is very expensive to use, cannot be continuously monitored, and quantitative analysis requires an automated adsorption or emission spectrophotometer, and a significant existing background for lithium is present in some systems. To do. 2-NSA fluorescent tracer gives results comparable to Li ^+, an amount smaller by far as compared to Li ⁺ (mass 1/6 and cost 1
/ 30) 2-NSA. Furthermore, quantitative analysis of 2-NSA in the cooling water system (fluorescence emission and 2-NSA
(Compared to the reference solution of) is much simpler and faster than the AA analysis of lithium (atomic absorption spectroscopy). Moreover, no significant existing background of 2-NSA was encountered at the industrial application site. A 2-NSA tracer slug feed and "Diaway" study demonstrated the following facts.

a) 2-NSA served as an inert tracer that was not measurable adsorbed by the industrial cooling water system under study, did not precipitate in the industrial cooling water system and was not degraded by the industrial cooling water system; b) The total amount of recirculated water removed from the system was 40% higher than that indicated by the Brodow flowmeter measurements.
This difference traces to previously unknown losses of cooling water to be used in the plant; c) low levels of treatment components result in low treatment agents due to previously unknown losses from the cooling water system. It was the result of the feed rate (no breakage of the treating agent program); d) Total volume of system (1.6 megagallons) (6.05).
3 × 10 ³ m ³ ), total amount of recycled water removed (370 gp
m), and the retention time index (50 hours) is 2-NSA.
Was accurately quantified by and was consistent with the lithium results.

The use of a treatment formulation that also contained a 2-NSA fluorescent tracer (Test B) further demonstrated that the formulation was provided at only about 70% of the desired amount. Analysis of Zn ⁺² and phosphorus content incorrectly suggested that the treating agent concentration was below 70% of the desired value. Incorporation of 2-NSA into the treating agent formulation demonstrated: a) The total amount of recirculated water removed from the system was more than that indicated by the flow meter on the recirculated water blowdown pump. Was also much higher; b) Zn ⁺² and phosphorus analyzes were not performed properly,
It produced erroneously low results: c) Small amounts of treatment components were due to low treatment agent feed rates (no breakage of formulation to function effectively).

Therefore, the feed rate of the treating agent program was increased to offset the additional loss of recirculated water from the system.

From the above examples it can be seen that the use of one or more fluorescent tracers provides essential information regarding the efficient operation of the cooling water system and the proper application of the treating agent program. That information is especially important when the unknown manipulator causes a discrepancy between the "calculated" and observed results.

Example 3: Treatment in vessels, ponds or other chambers In addition to recirculating cooling water systems, chemical treating agents are added to the moving liquid in one or more containment structures and associated transfer lines to maintain proper operation of the system. There are numerous examples of industrial systems. In many cases, the chemical treating agent concentration, feed rate and potency are inaccurately known, and system characteristics (total volume, make-up and blowdown rate, retention time index, etc.) are calculated and variable. , Or unknown. Systems can generally be divided into three main types: closed, open, and flow-through. In each case, they can be effectively used to measure and continuously monitor fluorescent trainers, chemical treating agent concentrations and potencies and system operating conditions and unknown properties.

In "closed" systems, liquids and chemical treating agents generally remain in the system and add or drain a minimal amount of liquid. Common examples of closed systems are continuous casting processes in the metallurgical industry, refrigeration and air conditioning units, radiator units, and recirculating cooling water systems where water use or chemical emissions are severely restricted. In those systems, treating agents may be lost through chemical / microbial degradation, precipitation / corrosion processes, system leaks and low level emissions.

A common feature of "open" systems is the addition and draining of a variable and significant amount of liquid (make-up) and chemical treating agent from the working fluid (blowdown). The system is very good at pressurizing and not pressurizing and is susceptible to evaporation loss of the fluid. Common examples of open systems (in addition to Examples 1 and 2)
Are boilers, gas scrubbers and air scrubbers, municipal wastewater treatment, metalworking and manufacturing processes, paint spray booths, wood pulsing and papermaking. Chemical treating agents can be lost through system drains and leaks, deposition / corrosion processes, adsorption on particulate matter, chemical / microbial degradation, and the like.

A "flow-through" system generally includes fluids and chemical treatments that are added to the system, passed through the system once and then discharged as an effluent or transferred to another system. Much more water is required in these systems than comparable "closed" or "open" recirculation systems. Common examples of once-through systems are fining and filtration units, mineral washing and beneficiation, boilers, and utility and industrial process diversion cooling.

In each of the above situations, a chemical treating agent containing a known amount of a fluorescent tracer is distributed in and within the liquid system. The liquid can be continuously monitored for sampling at any point of addition from within the system or effluent. By comparing the fluorescence emission of the system liquid to a standard solution containing a known concentration of chemical treatment agent plus tracer, the concentration of chemical treatment agent in the liquid system was
taking measurement. Further, by measuring tracer concentrations at different points in the system, the uniformity of chemical treating agent distribution and the presence of low fluid flow and stagnation regions within the system can be quantified. Based on the results and techniques described in the previous section, the amount of fluorophore in the liquid was determined by many operating parameters (total volume,
Retention time index, blowdown rate, unknown system loss, chemical treating agent efficacy, etc.) can be accurately measured.

Example 4: Treatment in vessels, ponds or other chambers (including stagnation and low fluid flow regions) Stagnation or low fluid flow regions are inherent in some systems despite the continuous addition and drainage of one or more liquids. Is.
For example, oil field applications (drilling, secondary and tertiary acquisition, etc.)
Involves the addition of one or more chemical treating agents to a liquid that will slowly penetrate some parts of the larger system. Although the true total volume of the system cannot be accurately measured, the effective working volume and average concentration of chemical treating agent is
It can be quantified by comparing one or more tracer concentrations in the liquid entering and leaving the system (Figure 7). By comparing the individual concentrations of the treatment component and the fluorescent tracer, the potency and degradation of the treatment agent and its components can be measured.

There are numerous fluorescent tracers that can have equivalent performance as alternatives to 2-naphthalene sulfonic acid or Acid Yellow 7, and their concentrations may be quantitatively measured in trace amounts from ppt to ppm. These fluorescent tracers may be soluble in water, organic solvents, inorganic solvents or mixtures of solvents selected from one or more of the abovementioned types of liquids. Further, these tracers are substances that are excited by absorption of light and generate fluorescence emission [excitation and emission light is in the far-ultraviolet to near-infrared region (wavelengths of 200 to 80).
It occurs at any point within the range of 0 nm)]. A combination of one or more fluorescent tracers may also be used in combination with other fluorescent substances as long as the absorption of excitation light and the emission of fluorescence from other components do not interfere with the detection of emission from the fluorescent tracer (see FIG. 5). ). Further, the fluorescent tracer may be used in combination with other chemicals or an inert carrier, or may be used in combination with the non-fluorescent tracer as described above.

Some phosphors may have desirable and desirable properties in some applications. For example, rapid dissolution in water is desirable for fluorescent tracers to be used in aqueous systems. However, the concept of using fluorescent tracers to quantitatively measure the processing agent feed rate and the operating characteristics of the pre-prepared liquid in the contained system is quite general. Therefore, any substance capable of fluorescing while dissolved or present in the pre-prepared liquid of the system or the liquid used during the analytical measurement of fluorescence emission can serve as a fluorescent tracer.

The dependence of the fluorescent indicator 2-NSA could be demonstrated in two ways. It was found to be reliable when compared to the Li ⁺ indicator for an accurate response. Also, when comparing it with the second indicator, the two indicators gave identical results within experimental error. The method of using multiple indicators, which also helps to give an internal standard, gave a clear confirmation of the accuracy of the results. In fact, the use of a combination of tracers is readily available in the present invention as practical.

Quantitatively measuring fluorescent tracers in liquid systems using fluorometry has the following special advantages over other tracer analytical techniques. A) very good selectivity, since only a very small percentage of organic compounds fluoresces to a significant degree; b) the number of fluorescent compounds is very high, so it is optimal for any particular system. A tracer capable of exhibiting various properties (eg, spectral characteristics, solubility, chemical inertness, low toxicity, etc.); c) tracers ranging from polar solvents (eg, water and alcohol) to non-polar hydrocarbon solvents Can be used in a wide range of organic and inorganic liquid systems in the range of; d) Two spectral parameters can be modified and optimized as shown in Figure 5 (wavelength of light used to excite the tracer and observed Fluorescence emission wavelength), very good selectivity is obtained; e) proper selection of excitation light wavelength and fluorescence emission wavelength is
Gives the ability to individually quantify one or more tracers, even in the presence of other fluorophores (Fig. 5); f) exceptional detection with detection limits up to ppt without the need for highly complex equipment. Sensitivity; g) Appropriate selection of tolerase can minimize changes in fluorescence emission due to operating conditions of the system (eg, pH, temperature, dissolved salts, particulates, etc.).

Overall, the use of fluorescent tracers offers an exceptional combination of favorable properties and capabilities and ease of use.

In FIG. 1, the solid line represents the observed values; the dashed line represents the ideal situation. The vertical axis represents the relative light emission rate under excitation.
The tracer is the symbol T.

In Figure 2, most of the alphabetic symbols have been previously defined. CA represents one or more treatment components (eg, phosphorus compounds, zinc compounds, etc.) and G represents a device for measuring pH and conductivity. Other instrumentation may obviously be present.

In FIG. 3, the treatment component (CA) is P, meaning a phosphorus-containing compound (eg, an organic phosphorus compound as a scale / corrosion inhibitor); Zn indicating a zinc cation and a polymeric scale inhibitor. P'is also one of the processing components.
The symbol "capped" represents the deposit; x and y are the fractional amounts. B'is the unknown collection loss (B _P + B _L + B _D of the liquid from the system
Etc.)

In FIG. 4, P has the same meaning as in FIG. 3, and T has the same meaning as in FIG.

In FIG. 5, the broken line curve is the emission spectrum, and the solid line curve is the absorbance spectrum. The vertical axis on the left represents the relative luminescence rate (em%), and the vertical axis on the right represents the absorbance, which contrasts the two fluorescent tracers A and B. BK is background interference. FIG. 5 shows predetermined excitation (radiant energy;
In the case of (horizontal axis), the emission rates of the two tracers in the presence of each other are discernible and each may be present (as is different) from the interfering fluorescent compound (background). Show different things.

FIG. 7 represents Example 4. Here, the flow input to the system (S) is represented by the characteristic I and the flow discharge is D. T is a tracer. The outer solid line is the fluid boundary and the portion Z means the stagnation zone.

[Brief description of drawings]

Fig. 1 is a graph showing the calibration curve of fluorescein tracer concentration vs. fluorescence emission amount, Fig. 2 is a schematic diagram of a typical cooling tower system, and Fig. 3 is a fluorescent tracer used to accurately measure the concentration of a treating agent. Fig. 4 is a graph showing the performance comparison of two fluorescent tracers vs. phosphorus analysis for measuring product feed rate in a pilot cooling tower, and Fig. 5 is fluorescence with an appropriate selection of analysis conditions greater than 1. Graph showing a series of curves showing that the concentration of tracer can be measured and avoiding interfering agents, FIG. 6 is a graph showing the performance comparison of phosphor vs Li ⁺ tracer in a “Diaway” study of an industrial cooling water system. FIG. 7 shows the use of one or more fluorescent tracers in a system with stagnation and low fluid flow regimes to measure effective working volume and treating agent concentration.

Claims (17)

[Claims] 1. Consuming in-system as a whole while containing impurities and removing or neutralizing impurities in water bodies to determine whether the concentration of treatment components is acceptable under operating conditions. Or a method of monitoring an industrial or municipal water system of the type comprising a device for passing a moving body of water containing a quantified dose of a water treatment component which has the role of being absorbed, the system comprising: Add an amount of water-soluble fluorescent tracer in proportion to the amount of treated components (However, the fluorescence of the tracer is inert to water and is not affected by water,
Shall be inert to the device and shall not be affected by the device, and shall be inert to the treated components and shall not be affected by the treated components); (B) a sample of a body of water containing both the components and the tracer from the system. And subjecting the discharged sample to an analysis consisting essentially of comparing the tracer concentration to a standard on an emissivity basis to determine the concentration of tracer in the sample;
And, if the operating concentration is outside the acceptable operating range, (C) until the acceptable range of concentrations for the treatment components is achieved, the volume of water, the rate of addition or discharge of water or the treatment components A method of monitoring industrial or municipal water systems characterized by varying doses. 2. The method of claim 1, wherein the water system undergoes clarification to produce a clarified body of water and the treatment component removes impurities to produce a clarified body of water. 3. The method according to claim 1 or 2, wherein step (B) is repeated at different locations in the body of water to analyze the performance of the treatment components at different locations. 4. The method according to claim 1, 2 or 3, wherein the system is a water cooling system. 5. Step (B) identifies an unknown loss or increase in water volume in the water system and correspondingly increases the volume of water in the system or the rate of water addition or the rate of discharge from the system. 5. A method according to any one of claims 1 to 4, comprising the step of reducing. 6. The method according to claim 1, wherein the treating component is a scale inhibitor or a corrosion inhibitor. 7. The method according to any one of claims 1 to 6, wherein step (B) comprises the step of indicating the necessity of changing the dose of the component and changing the dose. 8. The method of claim 7, wherein step (B) is repeated and the system measures the rate corresponding to the altered amount of the component. 9. Step (B) performs a separate quantitative analysis of the amount of processing components to verify the accuracy of step (B) and to quantify the level of processing component consumption and product performance. The method according to any one of claims 1 to 8, which is used in combination with. 10. At least two different processing components are used in combination with at least two different fluorescent tracers, wherein the fluorescent tracers have distinctly different emissivity values, and the fluorescent tracers are emissive of the fluorescent background present. The method of any one of claims 1 to 9 having a value of emissivity that is distinguishably different from the value of. 11. A process according to claim 1, wherein step (B) includes the step of indicating the need to change both the volume of water and the dose of the treatment component, and making both changes. The method described in. 12. The method according to claim 1, wherein the system is an open system having an inlet and an outlet. 13. An outflow in which the body of water comprises water in the chamber containing the particulate solids to be removed and a stream of water in and out of the chamber, the treatment components facilitating the removal of the particulate solids and being removed from the chamber. 13. The method according to claim 12, which increases the clarity of water. 14. The method according to claim 1, wherein the fluorescent tracer is 2-naphthalenesulfonic acid or Acid Yellow 7. 15. A method according to any one of claims 1 to 13 wherein the system is a cooling water system and comprises the step of adding both scale inhibitor and corrosion inhibitor to form the treatment component. . 16. The method of claim 15 wherein step (B) comprises the step of identifying the incorrect dose of the treatment component and thus varying the dose of the treatment component until an acceptable operating range is achieved. The method described in. 17. The method of claim 15, wherein step (B) comprises identifying the need to correct for water loss in the system or water increase in the system, and making such a correction.