Leak detection and responsive treatment in industrial water processes

Abstract: Leakage is detected between a process fluid and a temperature-conditioning fluid, or from a process fluid to a temperature-conditioning fluid, in an industrial process. The industrial process includes an A and a B fluid, and one of the A and B fluids receives heat from or transfer heat to the other of the A and the B fluids by an indirect contact method, and one but not both of the A and the B fluids is an industrial process fluid. At least one specie of tracer chemical is maintained in the A fluid, and that specie of tracer chemical is not a normal component of the B fluid. At least one of the A and the B fluids is subjected to at least one analysis at least one site. Such analysis at least detects the presence of the specie of tracer chemical when the fluid subjected to the analysis is the B fluid, and such analysis at least determines the concentration of the specie of tracer chemical when the fluid subjected to the analysis is the A fluid.

Description: The present invention is in the technical field of detection of leaks between temperature-conditioning fluids and process fluids in industrial water processes, optionally together with an appropriate responsive treatment of fluid contaminated by a leak. Many industrial processes are comprised of at least one body of process fluid, which is commonly an organic-based process fluid, serviced by at least one body of temperature-conditioning fluid, which is commonly an aqueous-based temperature-conditioning water, such as cooling water. These bodies are held within separate lines or other confines to prevent contamination of one body with the fluid of the other. The servicing of the process fluid by the temperature-conditioning fluid however generally requires such fluids to be brought into close proximity, such as being routed on opposite sides of a heat exchanger wall or surface. The close proximity of such distinct bodies of fluids creates a serious, but unavoidable, risk of leakage between bodies, whereby at least one body is contaminated by the fluid of the other. The ramifications of such process fluid/temperature-conditioning fluid leakage can be extremely serious because the makeups of such fluids are very dissimilar in most industries. Temperature-conditioning fluids routinely are waters that contain far less solutes or other non-H 2 O substances than process fluids. The non-H 2 O substances of temperature-conditioning waters are typically inorganic materials, and organic substances, whether naturally occurring or added as treatment chemicals, are present only in relatively minute amounts. In contrast, not only does the concentration of non-H 2 O substances in process fluids typically dwarf that of temperature-conditioning fluids, such non-H 2 O substances often include a significant proportion of organic materials. Leakage from process fluid to temperature-conditioning fluid not only represents a process fluid loss, which can significantly increase the overall manufacturing costs and can lead to serious fouling of the temperature-conditioning fluid system. Leakage from temperature-conditioning fluid to process fluid not only represents a temperature-conditioning fluid loss, which can throw off a temperature-conditioning fluid treatment program, but also can seriously taint the process fluids. These dissimilar fluids are not intended to contact each other or intermix in any manner, and when the mingling of some portion of one with the other occurs through leakage, a method whereby such leakage is not only detected, but also located and/or quantified, would be highly advantageous to the manufacturing process. It is an object of the present invention to provide a method for detecting the fact of and preferably the site of leakage between at least one body of temperature-conditioning fluid and at least one body of process fluid in an industrial process, preferably quantitatively and in such a way as to provide a method for responsive treatment of a body of temperature-conditioning fluid and/or a body of process fluid upon the detection, location and/or quantification of the leakage. In DE-A-4035092 a process for the off-line determination of leaks across a heat exchanger involves controlled variations in the concentration of a medium and timed detection of such changes. In JP-A-63214633 leakage past a piston is detected by having a fluorescent medium on one side of it and washing any leakage off from the other side into a receptacle. The present invention provides a method for detecting leakage between an industrial process fluid and a temperature-conditioning fluid comprising subjecting at least a sample of at least one of such fluids to analysis to detect the presence and/or the concentration of a fluorescent tracer chemical therein, and preferably, over time, the concentration change and/or concentration gradient of the tracer in at least one of such fluids. In a preferred embodiment at least one of such fluids is an aqueous-based fluid. The analysis is a fluorescence analysis or a combination of high pressure liquid chromatography and fluorescence analysis. These and other preferred embodiments are described in detail below. Preferred Embodiments of the Invention Temperature-conditioning fluids are used for process fluid temperature-conditioning in many industries. Process fluids of major industrial water processes that may be cooled or heated by indirect contact with temperature-conditioning fluid include without limitation the process fluids of the chemical industry, the steel industry, the food processing industry and the like. By process fluid is meant generally and herein a body of fluid, which commonly but not necessarily, is a stream, that contains a raw material, an intermediate or a product of a manufacturing process. The process of the present invention is not dependent on the specific type of process fluid. Temperature-conditioning fluids include cooling waters, such as once-through cooling waters, recirculating cooling waters, other indirect contact cooling waters, and heating waters, such as pasteurization waters. The primary function of temperature-conditioning fluids is that of heat source or heat receiver, and therefore there seldom would be any practical reason for employing a fluid other than water, but the use of some other fluid as the temperature-conditioning fluid does not exclude the applicability of the process of the present invention for that reason alone. In other words, the process of the present invention is not dependent on the specific type of temperature-conditioning fluid. Temperature-conditioning fluids and process fluids are generally brought into indirect contact for the purpose of heat transfer from the source fluid (which is the process fluid in a cooling water system) to the receiver (which is the cooling water in a cooling water system), during which heat transfer process the fluids are separated by a barrier that is a good conductor of heat, which barrier is called the heat transfer surface. An assembly comprised of at least one heat transfer barrier, which barrier has a process fluid side and a cooling fluid side, in a containment vessel, is called a heat-exchanger. A simple heat-exchanger may be comprised of a tube or pipe located concentrically inside of another (the shell). In such a shell-and-tube heat-exchanger the process fluid typically flows through the inner pipe, and the cooling fluid flows through the annulus between the inner pipe and the shell. In a parallel or cocurrent flow heat-exchanger, both fluid streams flow in the same direction. In a countercurrent flow heat-exchanger, the fluid streams flow in opposite directions. Regardless of the type or complexity of a heat-exchanger, a characteristic common to all is transfer of heat across a heat transfer surface that has a process fluid side and an opposite cooling fluid side. In a food processing process, the process fluid may be contained in one or a plurality of enclosed containers, such as jars or bottles, which are immersed in an elevated temperature-conditioning fluid, such as cooking or pasteurization waters, and the heat is transferred from the temperature-conditioning fluid across the wall(s) of the containers. Such an assembly can, and herein is, also considered a heat-exchanger. Leakage between a temperature-conditioning fluid and a process fluid most commonly occurs within a heat-exchanger because within a heat-exchanger there is generally only a single heat exchange surface or wall separating the fluid bodies. Moreover, there generally is a temperature gradient across such surface or wall and a significant stream flow along at least one side of such surface or wall, which conditions create material stresses that can lead to ruptures. Leakage between a temperature-conditioning fluid and a process fluid can of course also occur elsewhere, such as when such fluids are held or flow through vessels or lines or the like that have contiguous walls, or when a normally-closed flow path between such vessels or lines or the like is in some way breached. The process of the present invention is not dependent on the specific type of leakage site, and instead is applicable to any water industry process having a process fluid and a temperature-conditioning fluid that are normally, or desirably, kept isolated from each other to avoid any cross-contamination., although such fluids would commonly be brought into close proximity for indirect heat exchange purposes. Regardless of how leakage occurs, the dissimilarity between such fluids generally is a controlling factor as to the gravity of the problem(s) created by cross-contamination. For instance, pasteurization water is normally free of organic nutrients, and thus is not normally treated with biocide to control microbial growth. If a product container ruptures during the pasteurization process however, the product fluid released into such waters could well contain sufficient nutrient to trigger microbial growth and seriously foul such water. In many industries employing cooling water systems, the process streams contain significant amounts of hydrocarbons which would lead to cooling water fouling if leaked to the cooling water stream or basin. In many industries employing cooling water systems, cooling waters are treated with corrosion inhibitors, scale inhibitors, possibly biocides, and other agents, and while such agents are generally present in cooling waters in only minute amounts, even extremely minute amounts thereof may be sufficient to seriously taint the material in the process waters. Cross-contamination between temperature-conditioning fluids and process fluid can lead to such grave problems that the choice of temperature-conditioning fluid treatment agents may be limited to those agents having less potential for harm but less than optimum treatment effectiveness. The process of the present invention may in some instances open such limitations to more effective agents. As noted above, a very simple heat-exchanger may be comprised of concentric tubing, and in most industrial plants a heat-exchange system is comprised of more complex heat-exchangers and/or a plurality of heat-exchangers. The walls of the multitude of lines and/or vessels cannot conveniently be examined on a routine basis for ruptures or other breaches. Such an examination would require disruption of the process and often an extensive disassembly of the system. Leakage detection between temperature-conditioning fluids and process fluids, determining the site(s) of leakage, and/or quantifying the degree of leakage will minimize the cross-contamination potential and minimize the process disruption and/or system disassembly required to alleviate the cross-contamination potential. In addition, in an embodiment of the present invention the process includes a responsive activation of an appropriate treatment of the contaminated fluid upon the detection and/or quantification of leakage thereinto. For instance, if the leakage is due to container disruption releasing nutrient into pasteurization water, a process within the present invention activates a feed of biocide into the contaminated water. As another example, the leakage of concern in a system may be the contamination of cooling water with hydrocarbons, and the present invention may provide activation of a feed of oil dispersant to the cooling water system. The leakage may be, or also be, quantified and the level of dispersant feed determined by such quantification. Thus in a preferred embodiment of the invention, the detection and/or quantification of a leakage that releases a contaminant to one of the fluids also activates a feed of at least one treatment agent, preferably in an amount effective to decrease the deleterious effect of such contamination, to the contaminated fluid. The treatment agent may be any which is effective to decrease or lessen the harmful effect(s) of the contamination caused by leakage from one fluid to the other. Temperature-conditioning fluids, while containing generally a far lower concentration of components than process fluids, nonetheless can vary widely as to their makeup. The source of the fluid, the treatment programs employed and the concentration ratio of the fluid in the system are major factors determining the type of components and the concentration thereof. Among the solutes that are present in cooling water as taken from its source are calcium ions, magnesium ions, sulfate ions, silicate ions and suspended substantially inorganic solids. Among the solutes that may be introduced into cooling water in water-treatment programs are zinc, molybdates, silicates, polyphosphates, polyol esters, phosphonates, natural organics, synthetic organic polymers, nonoxidizing biocides, halogen-based biocides and ozone. Cooling waters prior to process fluid contamination generally can be characterized as having a pH of from about 6.5 to about 9.5, having a concentration of solutes of up to about 10,000 ppm, and having a concentration of suspended, or colloidal, solids of not more than up to about 200 ppm. Process fluids are even less susceptible to makeup characterizations than cooling waters. Process fluids are often, but not always, organic based, and generally have a wide concentration range of non-H 2 O material, including solutes, colloidal and suspended solids, and non-miscible fluids. While many process fluids contain organics, and a major concern may be contamination of the temperature-conditioning fluid with such organics, in other industrial water process the process fluids may instead contain inorganic material which is a major concern as to temperature-conditioning fluid contamination. The process of the present invention is not limited as to the nature of the potential contaminant, nor as to whether the primary concern is contamination of the temperature-conditioning fluid by process fluid or vice versa, or even both. The signature compound(s) may be a normal component of one of the fluids, for instance one or more aromatic hydrocarbons of a hydrocarbon-containing process fluid, or it may be a tagged version of a normal component of one of the fluids, for instance a polymeric cooling water treatment agent tagged with fluorescent group(s), or it may be a fluorescent compound(s) added to one of the fluids for,the primary purpose of being the tracer. The functional "tracer" terminology is also applicable to normal fluid components that act as tracers for the purposes of the present invention. The tracer is preferably selected from among those that are easily detectable by the analysis methods employed in the process, which include fluorescence analysis, and HPLC and fluorescence analysis combinations. Fluorescence Emission Spectroscopy The detection and quantification of specific substances by fluorescence emission spectroscopy is founded upon the proportionality between the amount of emitted light and the amount of fluoresced substance present. When energy in the form of light, including ultra violet and visible light, is directed into a sample cell, fluorescent substances therein will absorb the energy and then emit that energy as light having a longer wavelength than the absorbed light. The amount of emitted light is determined by a photodetector. In practice, the light is directed into the sample cell through an optical light filter so that the light transmitted is of a known wavelength, which is referred to as the excitation wavelength and generally reported in nanometers ("nm"). The emitted light is similarly screened through a filter so that the amount of emitted light is measured at a known wavelength or a spectrum of wavelengths, which is referred to as the emission wavelength and generally also reported in nanometers. When the measurement of specific substances or categories of substances at low concentrations is desired or required, such as often is the case for the process of the present invention, the filters are set for a specific combination of excitation and emission wavelengths, selected for substantially optimum low-level measurements. Fluorescence emission spectroscopy is one of the preferred analysis techniques for the process of the present invention. Certain compounds that normally occur in either the temperature-conditioning fluid or the process fluid are inherently tracers for a fluorescence analysis. For example, aromatic hydrocarbons are components of some process fluids, including hydrocarbon-containing process streams and process fluids held in discrete containers. Foodstuffs may contain one or more components that readily fluoresce, such as beer which has been found to test positive for fluorescence analysis and thus leakage by bottle breakage during pasteurization can be readily detected and quantified by fluorescence monitoring of the pasteurization waters, and activate a responsive feed of biological control agents or the like to such waters to lessen the harmful effects of contamination by a nutrient-containing substance. Some naturally fluorescent compounds are also water treatment agents, and thus may be among the normal components of cooling waters, such as aromatic organic corrosion inhibitors, such as aromatic(thio)(tri)azoles. Some water treatment agents may be susceptible to tagging with fluorescent groups, for instance as disclosed in US-A-5,128,419 wherein the tagging of polymers with pendant fluorescent groups by (trans)amidation derivatization of pre-existing polymers having carbonyl-type pendant groups is disclosed. Water-treatment polymers tagged with pendant fluorescent groups may of course be prepared by methods other than (trans)amidation derivatization. Other fluorescent chemical tracers and monitoring techniques are now known, for instance as disclosed in US-A-4,783,314, wherein inert fluorescent tracers are employed in combination with a fluorescence monitoring, such as the sodium salt of 2-naphthalenesulfonic acid and Acid Yellow dye. In general for most fluorescence emission spectroscopy methods having a reasonable degree of practicality, it is preferable to perform the analysis without isolating in any manner the fluorescent tracer. Thus there may be some degree of background fluorescence. In instances where the background fluorescence is low, the relative intensities (measured against a standard fluorescent compound at a standard concentration and assigned a relative intensity for instance 100) of the fluorescence of the tracer versus the background can be very high, for instance a ratio of 100/10 or 500/10 when certain combinations of excitation and emission wavelengths are employed even at low fluorescent compound concentrations, and such ratios would be representative of relative perfonnance (under like conditions) of respectively 10 and 50. For most cooling water backgrounds, a compound that has a relative performance of at least about 5 at a reasonable concentration is very suitable as a fluorescent tracer itself or as a tagging agent for water treatment polymers and the like when such compounds contain an appropriate reactive group for the tagging reaction. When there is or may be a specific chemical specie of reasonably high fluorescence in the background, the tracer and the excitation and/or emission wavelengths often can be selected to nullify or at least minimize any interference of the tracer measurement(s) caused by the presence of such specie. One method for the continuous on-stream monitoring of chemical tracers by fluorescence emission spectroscopy and other analysis methods is described in US-A-4,992,380. Combined HPLC-Fluorescence Analysis The combination of high-pressure liquid chromatography ("HPLC") and fluorescence analyses of fluorescent tracers is a powerful tool for the present leak detection process, particularly when very low levels of the fluorescent tracer are used or the background fluorescence encountered would otherwise interfere with the efficacy of the fluorescence analysis. The HPLC-fluoresccnce analysis method allows the tracer compound to be separated from the fluid matrix and then the tracer concentration can be measure. The combination of HPLC-fluorcscence analysis is particularly effective for measuring minute levels of tracer in highly contaminated fluids. The HPLC method can also be effectively employed to separate a tracer compound from a fluid matrix for the purposes of then employing a tracer-detection method other the fluorescence analysis, and such other tracer-detection methods include without limitation light absorbance, post-column derivatization, conductivity and the like. A fluorescent tracer may be selected for a given process based on a preference for one or more analytical techniques, or an analytical technique may be selected for a given process based on a preference for one or more chemical tracers. In preferred embodiment, the chemical compound(s) selected as the tracer should be soluble in at least one, and more preferably in both, of the temperature-conditioning fluid and process fluid of the industrial process, at least at the concentration levcl(s) expected in the respective fluid. For instance, a tracer may be fed to a temperature-conditioning fluid and its presence monitored in the process fluid, where its appearance would result only from leakage. The expected concentration in the process fluid upon such leakage occurring would of course be much less than the concentration of such tracer fed to, or maintained, in the temperature-conditioning fluid. If however only the decrease of tracer concentration in the fluid to which it is fed is to be monitored, its solubility in the other fluid is generally irrelevant. In preferred embodiment, the chemical compound(s) selected as a tracer should be either stable in the environment of at least one of the fluids, and preferably both of the fluids, for the useful life expected of the tracer, or its loss from the fluid due to degradation, deposition, complexation, or other phenomena should be predictable and compensative, particularly when it is desired not merely to detect the presence of some amount of the tracer, but also to determine the concentration thereof, or change in concentration. In preferred embodiment, the combination of the chemical compound(s) selected as the tracer and the analytical technique selected for determining the presence and/or concentration of such tracer, should permit such determination(s) without isolation of the tracer, and more preferably should permit such determination(s) on a continuous and/or on-line basis. In preferred embodiment, the analytical technique(s) selected for determining the presence and/or concentration of a tracer, should permit such determination(s) to provide a signal that can activate or regulate the feed of an appropriate treatment chemical(s) to the fluid being contaminated by virtue of the leak detected by the technique. One embodiment the process of the present invention is comprised of adding a fluorescent chemical tracer to one, but preferably not both, of the temperature-conditioning fluid and the process fluid, and monitoring the concentration of such tracer in the fluid to which it was added by an analytical technique effective for such tracer, and in preferred embodiment when the same fluid both receives the tracer feed and is subjected to the monitoring, the monitoring is conducted to determine any decrease in the concentration of the tracer in the receiving fluid across at least one potential leakage site, such as a heat-exchanger. In another and preferred embodiment the process of the present invention is comprised of adding a chemical tracer to one, but preferably not both, of the temperature-conditioning fluid and the process fluid, and monitoring the concentration of such tracer in the other fluid by an analytical technique effective for such tracer, and in preferred embodiment when the one fluid receives the tracer feed while the other is subjected to the monitoring, the monitoring is conducted to determine at least any appearance, and more preferably the concentration, of the tracer in the monitored fluid across at least one potential leakage site, such as a heat-exchanger. In further preferred embodiments, when the industrial process system has more than one potential leakage site, such as a heat-exchanger, the aforesaid monitorings are conducted across more than one of such potential leakage sites, and more preferably substantially across each of such potential leakage sites or heat-exchangers. By monitoring across separate heat-exchangers in bank of heat-exchangers, the location(s) of the leakage among such heat-exchangers can be determined, and the extent of leakage (rate of leakage), at separate leakage sites, may also be determined. In the drawings, Figure 1 is a diagram of a bank of four heat-exchange and sampling points used in an embodiment of the present invention. Example 1 Cooling water had been leaking into a monoethanolamine/water process stream ("MEA stream") of an industrial plant for several years. Such leakage necessitated frequent cleanups of the process stream, which significantly increased the operating costs of the plant. The site of the leakage was believed to be through one or more of the heat-exchangers in a bank of four heat exchangers and/or a separate heat-exchanger. The total cooling water leakage rate was known to be on the order of fiftieths of litres (tenths of gallons) per minute, which represents an extremely small volume of water per unit time in comparison to the flow rates of the process and cooling water streams (which were respectively 5,500 and 55,000 l/min (about 1,000 and about 10,000 gallons) per minute). The difficulty of site location of such a relatively small leakage was heightened by the possibility that the leakage was divided among a plurality of heat-exchangers. Complicating the use of a fluorescent compound to trace the location(s) of such leakage was the composition of the process stream, which contained treatment chemicals and other dissolved substances that fluoresced and exhibited high absorbance of ultraviolet light. The layout of the bank of four heat-exchangers is shown diagrammatically in FIGURE 1, in which the bank of heat-exchangers is designated generally by the reference numeral 10. The collateral industrial stream is the cooling water stream that flows through the cooling water lines from a cooling water inlet 12 through a first main line 14 to a first junction 16 whereat the first main line 14 divides into a west leg line 18 and an cast leg line 20. The cooling water stream flowing through the west leg line 18 serves the southwest heat-exchanger 22 and then the northwest heat-exchanger 24. The cooling water stream flowing through the east leg line 20 serves the southeast heat-exchanger 26 and then the northeast heat-exchanger 28. The west leg line 18 and the east leg line 20 then recombine at the second junction,30 to form a combined cooling water outlet line 32. The process stream is the MEA stream that is shown already divided into a west MEA line 34 and an east MEA line 36. The MEA stream of the west MEA line 34 flows first through the northwest heat-exchanger 24 and then the southwest heat-exchanger 22, entering through the northwest inlet 38 and leaving through the southwest outlet 40. The MEA stream of the east MEA line 36 flows through the northeast heat-exchanger 28 and then the southeast heat-exchanger 26, entering through the northeast inlet 42 and leaving through the southwest outlet 44. The west and east MEA lines 34, 36 eventually recombine at ajunction (not shown) to form a combined MEA stream. An aqueous solution of a fluorescent compound was injected into the cooling water system (at junction 16). Samples of the cooling water were taken at points A and E. Samples were taken of the process water at points B to D and F to H. The samples from each sample point were analyzed by a combination of high-pressure liquid chromatography ("HPLC") and fluorescence techniques. Based on an estimated MEA stream flow rate of 2750 l/m (500 gpm) into the west MEA line 34 and into the east MEA line 36, the leakage rate across the northwest, northeast and southeast heat-exchangers 24, 26 and 28, if any, must be less than 0.14 l/min (0.025 gpm) because tracer was not detected at sample points C to D and F to H. The leakage rate across the southwest heat-exchanger 22 was observed to be about 0.55 l/min (0.1 gpm) because the tracer was detected at sample point B. The use of a higher concentration of the fluorescent tracer would provide even a more precise determination of whether leakage was occurring at <0.14 l/min (<0.025 gpm) in the southeast, northeast and northwest heat-exchangers 24, 26 and 28. Then the leak(s) within the southwest heat-exchanger 22 were located (with that heat-exchanger off-line) by adding a fluorescent-containing liquid to the shell-side of the heat-exchanger (the side on which the process stream would flow in normal operation) and observing the appearance of fluorescence at specific tube ends and connections with the assistance of a UV-light to enhance visibility of the fluorescent leak detection compound. In certain embodiments of the invention, the process includes the preliminary steps of sampling the temperature-conditioning and/or the process fluid, preferably at all intended post-tracer-addition sampling sites , to determine baseline conditions. Such preliminary baseline condition(s) determination(s) may also be employed to narrow the selection choice of tracer chemicals or determine and/or modify the selection of post-tracer-addition sampling points. In certain preferred embodiments, the sampling points are at the inlet and outlet of at least one heat-exchanger line, and may be along either or both of the temperature-conditioning and process stream sides of such heat-exchanger. If the suspected leakage or the leakage of greatest concern is from the "A" fluid to the "B" fluid (the A fluid being one of the temperature-conditioning fluid or process fluid, and the B fluid being the other), it is feasible to monitor only the A fluid by the "tracer concentration decrease" version of the present invention that is noted above. It would be preferable to instead monitor the B fluid to detect the appearance of the tracer chemical because such monitoring on the side receiving the contamination often would be more sensitive to both the detection and quantification of the leak. Monitoring the B fluid in a given industrial installation may not, however, be the most practical. For instance, the B fluid lines may be less accessible to monitoring than the A fluid lines. The B fluid may provide a less desirable environment for monitoring, or be susceptible to monitoring only by a less desirable method. Thus while the monitoring of the fluid being or in greater jeopardy of being contaminated is a preferred embodiment, circumstances can render that approach less desirable for practical reasons. By sampling the fluid being monitored at least the outlet, and preferably at both the inlet and outlet, of at least one potential leakage site, and preferably all potential leakage sites, such as at least one heat-exchanger and preferably all heat-exchangers in a water system, one can narrow the potential leakage locations. For instance, if the B fluid (the contaminated or potentially contaminated fluid) is being monitored at the inlets and outlets of each of a plurality of heat-exchangers arranged in series with a countercurrent flow system, the first outlet appearance of the tracer chemical pinpoints the first heat-exchanger that contains a leak along the direction of the B fluid flowpath, and if the monitoring also includes a determination of the concentration of such tracer and/or the rate of change of such concentration, the magnitude of the leakage at that heat-exchanger site can be calculated using other operating parameters such a flow rates of the respective fluids. An increase in the concentration of the tracer in the B fluid downstream of the first leakage site will pinpoint an addition leakage site, and a determination that the tracer concentration in the B fluid has not increased across a downstream heat-exchanger will remove such heat-exchanger from the suspect category. Further for a countercurrent stream flow system, if the A stream is also monitored the first indication of leakage from the A fluid will occur across its most upstream leaking heat-exchanger, which is the most downstream leaking heat-exchanger for the B stream. Thus if the sensitivity of either monitoring in any way lessens downstream when there are plural leakage sites, in countercurrent flow systems the lessening of monitoring sensitivity in one flow stream is offset by the increasing sensitivity in the other flow stream when both fluids are monitored. Generally it is desirable to employ the least amount of tracer chemical that is practical for the circumstance, and the amount of the tracer added to the fluid should be at least an amount effective for the determinations desired. Seldom would a tracer be deliberately fed to a fluid in an amount grossly in excess of the minimum effective amount because there generally would be no practical purpose in doing so that would justify the costs involved and any deleterious effects on the quality of either of the fluids caused by the presence of the tracer chemical therein. The amount of tracer chemical to be added to the tracer-receiving fluid that is effective without being grossly excessive will vary with a wide variety of factors, including without limitation the tracer and monitoring method selected, the potential for background interference with the selected monitoring method, the magnitude of the suspected or potential leakage, the monitoring mode (on-line continuous, semi-continuous, slug-and-sample, and the like). Generally the dosage of tracer to one or the other of the fluids will be at least sufficient to provide a concentration of tracer therein of about 0.1 ppm, and more commonly at least about 10 or 100 ppm or higher. The specie of chemical tracer may be a normal component of the A fluid or process fluid. In certain preferred embodiments, the specie of chemical tracer is a synthetically tagged normal component of the A fluid or process fluid, for instance such as when a polymeric water treatment agent is tagged with pendant fluorescent groups by post-polymerization derivatization, as discussed above. On the other hand, the specie of chemical tracer may be foreign to the normal components of the A fluid or process fluid, for instance when an inert tracer is added for the purposes of the present invention, or both for the purposes of the present invention and for the purposes of a distinct tracer process. In certain preferred embodiments, the analysis is an on-line continuous or semi-continuous analysis, which may be of the B fluid, wherein at least a detection of the specie of chemical tracer activates or modifies a signal, and the signal upon activation or modification activates or modifies a feed of at least one treatment chemical to the B fluid, wherein the treatment chemical is effective to at least lessen at least a deleterious effect of a leakage of a portion of the A fluid or process fluid into the B fluid. The A fluid or process fluid and the B fluid may be fluid streams that each flow through a side of each of a plurality of heat-exchangers, and wherein at least one of the A and the B fluids are subjected to a plurality of analysis and at least two of the plurality of the analysis are conducted across at least one of the plurality of heat-exchangers. The determinative analysis may be for a spectral or chemical characteristic of the specie of chemical tracer that is proportional to the concentration of the specie of chemical tracer in the fluid analysed. Both of the A fluid or process fluid and the B fluid may be aqueous-based fluids. The chemical tracer should be substantially resistant to depletion mechanisms in the environment of at least one of the A and the B fluids, such as degradation, deposition, consumption and other like depletion mechanisms. When the process fluid contains a non-waste raw material or non-waste intermediate or non-waste product of the industrial process, such process fluids for many industrial processes may be extremely sensitive to contamination, and thus in serious need of an effective and practical method for determination of contamination from a temperature-conditioning fluid. The treatment chemical whose feed is activated or modified by a signal responsive to the detection of a leak may be a biocide. The activation or increase of a biocide feed, for instance into the temperature-conditioning fluid, is particularly important for those industrial processes in which a leakage from a process fluid may release an organic nutrient.

Claims: A process for detecting leakage between a process fluid and a temperature-conditioning fluid in an industrial process wherein said industrial process includes an A and a B fluid, and one of said A and B fluids receives heat from or transfers heat to the other of said A and said B fluids by an indirect contact method, and one but not both of said A and said B fluids is an industrial process fluid, and subjecting at least one of said A and said B fluids to at least one analysis at at least one site; characterized in maintaining in said A fluid at least one specie of fluorescent tracer chemical, which specie of tracer chemical is not a normal component of said B fluid; and (a) wherein said analysis is a fluorescence analysis and at least detects the presence of said specie of tracer chemical when said fluid subjected to said analysis is said B fluid, or (b) wherein said analysis is a fluorescence analysis and at least determines the concentration of said specie of tracer chemical when said fluid subjected to said analysis is said A fluid. A process according to claim 1 wherein the detection or determination of said specie of chemical tracer activates or modifies a signal, and said signal upon activation or modification activates or modifies a feed of at least one treatment chemical to said B fluid, said treatment chemical being effective to at least lessen a deleterious effect of a leakage of a portion of said A fluid into said B fluid. A process according to claim 2 wherein said treatment chemical is a biocide. A process according to claim 1, claim 2 or claim 3 wherein said specie of chemical tracer is a normal component of said A fluid or a synthetically tagged normal component of said A fluid or is foreign to the normal components of said A fluid. A process according to any one of the preceding claims wherein said analysis (b) is an on-line continuous or semi-continuous analysis of the B fluid. A process according to any one of the preceding claims wherein said A fluid and said B fluid are fluid streams that respectively flow through a side of each of a plurality of heat-exchangers, and wherein at least one of said A and said B fluids is subjected to a plurality of said analyses and at least two of said plurality of said analyses are conducted across at least one of said plurality of heat-exchangers. A process according to claim 6 which includes determining the site at which said specie of tracer chemical appears within the B containment means. A process according to claim 7 wherein said heat-exchanger is off-line at the time said specie of chemical tracer is maintained in said A containment means.

Inventors: BRUNDAGE ERIC R, EASTIN PHILIP M, HOOTS JOHN E, JENKINS BRIAN V, BRUNDAGE, ERIC R., EASTIN, PHILIP M., HOOTS, JOHN E., JENKINS, BRIAN V.
Applicants: NALCO CHEMICAL CO, NALCO CHEMICAL COMPANY
Application year: 1993
Main classification: G01M3
IPC codes: G01M3