Fluorescence measurement of film-forming amines

Abstract

One embodiment provides a method for measuring an amine in a solution, comprising: preparing an indicator-metal complex, wherein the indicator-metal complex comprises an indicator and a metal; introducing the indicator-metal complex into the solution, wherein the solution contains a certain amount of amine, and wherein the amine activates the indicator-metal complex, thereby causing a change in the fluorescence intensity of the indicator-metal complex; and measuring the amount of amine in the solution by measuring the change in the fluorescence intensity of the indicator-metal complex. Other aspects are described and claimed.

Description

Technical Field

[0001] This application generally relates to measuring filming amines in aqueous or liquid samples, and more particularly, to using fluorescence techniques to measure filming amines. Background Art

[0002] Many processes require the use of steam cycle chemistry. The steam cycle can be the cycle of feed water and condensate systems. The steam cycle may require maintenance. One maintenance item can be to ensure that the steam cycle system is not clogged, damaged, corroded, etc. One method for preventing corrosion inside the steam cycle system is to use amines in the solution. Amines can prevent corrosion inside pipes, tanks, heating chambers, etc. of the steam cycle by forming a protective film. A method for measuring the amount of amines in the steam cycle system is needed. Summary of the Invention

[0003] Generally speaking, one embodiment provides a method for measuring amines in a solution, the method comprising: preparing an indicator-metal complex, wherein the indicator-metal complex comprises an indicator and a metal; introducing the indicator-metal complex into the solution, wherein the solution contains a certain amount of amines, wherein the amines activate the indicator-metal complex, causing a change in the fluorescence intensity of the indicator-metal complex; and measuring the amount of amines in the solution by measuring the change in the fluorescence intensity of the indicator-metal complex.

[0004] Another embodiment provides a measuring device for measuring amines in a solution, the measuring device comprising: a processor; and a memory storing instructions executable by the processor to: prepare an indicator-metal complex, wherein the indicator-metal complex comprises an indicator and a metal; introduce the indicator-metal complex into the solution, wherein the solution contains a certain amount of amines, wherein the amines activate the indicator-metal complex, causing a change in the fluorescence intensity of the indicator-metal complex; and measure the amount of amines in the solution by measuring the fluorescence intensity of the indicator-metal complex.

[0005] Another embodiment provides a method for measuring an amine in a solution, the method comprising: preparing an indicator-metal complex, wherein the indicator-metal complex comprises calcein blue derivative and a metal; introducing the indicator-metal complex into a solution, wherein the solution contains a certain amount of amine, wherein the amine activates the indicator-metal complex, causing a change in the fluorescence intensity of the indicator-metal complex, wherein the solution comprises a fluid for a steam cycle system; and measuring the amount of amine in the solution by measuring the fluorescence intensity of the indicator-metal complex, wherein the indicator-metal complex is weakly fluorescent, and wherein the amine activates the indicator-metal complex by removing the metal from the indicator-metal complex, thereby causing the change in fluorescence intensity.

[0006] The foregoing is an overview and thus may contain simplifications, generalizations and omissions of details; accordingly, those skilled in the art will understand that this overview is merely exemplary and not intended to be limiting in any way.

[0007] The following description will be made with reference to the accompanying drawings in order to better understand the embodiments as well as other and further features and their advantages. The scope of the invention will be pointed out in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 A flowchart of an exemplary filming amine measurement system is shown.

[0009] Figure 2 A chemical equation of an exemplary fluorescent indicator for detecting filming amine is shown.

[0010] Figure 3 An exemplary fluorescence intensity measurement of an amine-sensitive indicator is shown.

[0011] Figure 4 An exemplary fluorescence intensity measurement of an amine-sensitive indicator in the presence of filming amine is shown.

[0012] Figure 5 An example of a computer circuit system is shown. DETAILED DESCRIPTION

[0013] It will be readily understood that the components of the embodiments generally described and illustrated in the drawings herein may be arranged and designed in a variety of different configurations in addition to the described exemplary embodiments. Thus, the following more detailed description of the exemplary embodiments, as shown in the drawings, is not intended to limit the scope of the claimed embodiments, but is merely representative of exemplary embodiments.

[0014] Throughout the specification, references to "one embodiment" or "an embodiment" (etc.) mean that the particular features, structures, or characteristics described in connection with the embodiment are included in at least one embodiment. Thus, the phrases "in one embodiment" or "in an embodiment" etc. that appear throughout this specification do not necessarily all refer to the same embodiment.

[0015] In addition, in one or more embodiments, the described features, structures, or characteristics may be combined in any suitable manner. In the following description, numerous specific details are provided to give a thorough understanding of the embodiments. However, those skilled in the relevant art will recognize that various embodiments may be practiced without one or more of the specific details or using other methods, components, materials, etc. In other instances, well-known structures, materials, or operations are not shown or described in detail. The following description is only intended to be exemplary and simply illustrates certain examples.

[0016] Traditional steam cycle systems have many disadvantages. For example, water can be heated in a heat transfer unit and then piped to a condenser for cooling. The water in a closed-loop system may contain contaminants such as impurities, rust, etc. These contaminants may reduce the ability of the steam cycle system to work effectively. For example, impurities (such as dissolved gases) in the steam cycle water may cause thinning of the metal within the system, which may lead to pipeline failures. During the normal operation and / or installation of a steam cycle chemical system, film-forming amines can be used to prevent this type of corrosion.

[0017] One method for preventing corrosion inside a steam cycle system is to use film-forming amines. Film-forming amines can be used in both closed-loop and open-loop steam cycle chemical systems. Film-forming amines can be biodegradable and may not contain harmful substances. These properties make film-forming amines a good choice for steam cycle systems. Additionally, film-forming amines can have an affinity for metal surfaces. Film-forming amines can have a hydrophobic tail that can adapt to the steam cycle fluid or steam. Thus, film-forming amines provide a barrier for the steam cycle system, thereby preventing corrosion and the like.

[0018] However, the use of filming amines does involve time, energy, and facility costs. For example, the amount of filming amine in a steam cycle system can be monitored. Monitoring may require a facility to send personnel out to areas of the steam cycle system to collect system samples. The samples can be from the condensate of the steam cycle system. The samples may need to be returned to a laboratory for analysis. This represents a cost in terms of time and facilities. Additionally, filming amines can be a significant cost to a facility. The amount of filming amine required for a steam cycle system can depend on the type of filming amine used and / or whether the filming amine is used for continuous operation, storage, or a combination thereof. Filling and / or replenishing the system can be a significant cost to a facility. What is needed is a method and system for measuring the amount of filming amine in a steam cycle system.

[0019] Accordingly, one embodiment provides a system and method for measuring filming amines using an indicator-metal complex. The indicator-metal complex includes an indicator and a metal. The indicator can be calcein blue derivative, methyl calcein blue, or calcein blue. The metal can be copper (II), cobalt (II), nickel (II), or iron (II). The indicator-metal complex can be introduced into a solution containing an amine. The amine can cause a change in the fluorescence intensity of the indicator-metal complex. The change in fluorescence intensity can be correlated with the amount of amine in the solution. Additionally or alternatively, the intensity of the fluorescence can be correlated with a particular type of amine. The indicator-metal complex can detect amines such as ethanolamine, diethylenetriamine, (Kurita America, Inc.), (Helamin, France), (SUEZ Trevose PA), (Solenis, Wilmington DE), etc. In one embodiment, the indicator-metal complex can be weakly fluorescent. The amine can activate the indicator-metal complex by removing the metal from the indicator-metal complex, thereby causing a change in fluorescence intensity. In one embodiment, the indicator-metal complex is weakly fluorescent and wherein the change in fluorescence intensity is caused by the amine removing the metal from the indicator-metal complex and releasing the indicator. The methods and systems described herein can be used to quantify the amount of filming amine in a steam cycle system using the change in fluorescence intensity of the indicator-metal complex.

[0020] The exemplary embodiments shown will be best understood by reference to the accompanying drawings. The following description is intended to be exemplary only and shows only certain exemplary embodiments.

[0021] Refer to Figure 1, an exemplary system and method for detecting amines in a solution are shown. In one embodiment, an indicator-metal complex can be prepared. The indicator-metal complex can be introduced into a solution containing an amine. In one embodiment, the presence of an amine can cause a change in the fluorescence intensity of the indicator-metal complex. The change in fluorescence intensity can be related to the concentration of the amine in the solution.

[0022] At 101, in one embodiment, an indicator-metal complex can be prepared. The indicator-metal complex can comprise an indicator and a metal. The indicator can be calcein blue derivative or calcein blue. The metal can be copper (II), cobalt (II), nickel (II), or iron (II). Refer to Figure 2 , an exemplary reaction of an indicator-metal complex is shown. In one embodiment, the indicator-metal complex can detect an amine in a solution. In the presence or absence of an amine, the indicator-metal complex can undergo a structural change. For example, in the absence of an amine, the copper of the indicator-metal complex can bond with oxygen and nitrogen. In the absence of an amine, the indicator-metal complex can be weakly fluorescent. In the presence of an amine, the bond can break, releasing the copper. In the presence of an amine, the indicator-metal complex can be fluorescent. Thus, based on the amount of amine in the solution, the indicator can undergo a change in fluorescence intensity.

[0023] At 102, in one embodiment, the indicator-metal complex can be introduced into a solution. The solution can contain an amine or amines. The solution can be an aqueous sample, which can include samples from a facility steam cycle system, natural water bodies, storage tanks, treatment tanks, pipelines, etc. The solution can be continuously flowing, a static volume of liquid, or any combination thereof. In one embodiment, the solution can be introduced into the indicator-metal complex, such as into a test chamber of a measuring device. In one embodiment, the measuring device can be a handheld device. Alternatively, the measuring device can be a larger benchtop device. Introducing the solution into the measuring device can include placing or introducing the solution into the test chamber manually by a user or using mechanical means such as gravity flow, pumps, pressure, fluid flow, etc. For example, a water sample for amine testing can be introduced into the measuring chamber or test chamber using a pump. In one embodiment, valves, etc. can control the inflow or outflow of the solution into or out of one or more chambers (if any). Alternatively, the measuring device can be directly connected to the steam cycle system. For example, a change in fluorescence intensity can be measured in a sample of the solution flowing through the measuring device from the steam cycle system.

[0024] Additionally or alternatively, a measuring device may be present or introduced into a volume of solution. The measuring device is then exposed to the volume of solution where the device may make measurements. The system may be a flow-through system where the solution and / or reagents are automatically mixed and measured. Once the sample contacts the measurement system, the system may measure the amine of the sample as discussed further herein in detail. In one embodiment, the measuring device may include one or more chambers where one or more method steps may be carried out.

[0025] At 103, in one embodiment, the system and method may utilize a change in fluorescence intensity to measure the amount of amine in a solution. In one embodiment, the indicator-metal complex may be weakly fluorescent in the absence of amine and fluorescent in the presence of amine as described above and Figure 2 as described in. Referring to Figure 3 , an exemplary indicator-metal complex is shown. For example, the indicator-metal complex of calcein blue and copper in the presence of amine shows an increase in fluorescence intensity based on amine concentration. In one embodiment, calcein blue, calcein blue derivatives, or methyl calcein blue at a concentration of about 0.5 to 10 μM may be used. In one embodiment, an emission wavelength of 445 nm may be used. A borate buffer may be used during the measurement. In one embodiment, the amine may be measured in the range of 0.05 - 2.5 ppm. However, the reaction parameters may be adjusted to obtain optimal results and the values are purely illustrative. In one embodiment, the indicator-metal complex may detect amines such as, but not limited to: ethanolamine, diethylenetriamine, cetamine, and Helamin.

[0026] At 104, in one embodiment, the system and method may determine whether the amount of amine in a solution can be measured. In one embodiment, the presence of amine in an aqueous solution may cause an increase in the fluorescence intensity of the indicator-metal complex. Examples of different commercially available film-forming amines and the excitation / emission spectra associated with the indicator-metal complex may be illustrated in Figure 4 . Thus, the fluorescence intensity of a solution containing a certain amount of amine may be related to the concentration of amine in the aqueous solution. Fluorescence curves may be generated for a series of amine concentrations, different indicator-metal complexes, any different conditions that may affect the absorption or fluorescence values (e.g., temperature, sample content, turbidity, viscosity, measuring device, aqueous sample chamber, etc.), etc.

[0027] Alternatively or additionally, amine concentration measurements can be made at periodic intervals set by the user or at a pre-programmed frequency in the device. Measuring the amine through the device allows for real-time data to be obtained with minimal human involvement in the measurement process. Cleaning of the fluorescence chamber may be required at unspecified time intervals. A programmed calibration curve can be input into the device.

[0028] A chamber, container, cell, cubicle, etc. can hold an aqueous sample, at least one indicator-metal complex, and associated reagents such as buffers and / or additives. The aqueous sample can be a solution from a steam cycle system containing amines. The device can house one or more reagent bottles containing the necessary reagents. The reagents contained in one or more bottles can be pump-fed or gravity-fed. The flow rate of the reagents can be metered to ensure proper volume delivery to the measurement cell. The aqueous sample can be fed through a pressurized inlet, container, etc. The aqueous sample can be introduced into the measurement chamber by a pump or gravity feed. The sampling device can be in series or parallel with the water stream. The device can have a system to ensure proper mixing of the aqueous sample, indicator-metal complex, and associated reagents.

[0029] The fluorescence intensity or amine concentration can be an output on the device in the form of a display, print, storage, audio, tactile feedback, etc. Alternatively or additionally, the output can be sent to another device via wired, wireless, fiber optic, near-field communication, etc. One embodiment can use an alarm to warn of measurement values or concentrations that exceed acceptable levels. One embodiment can use a system to shut off the water output or divert water from a source with unacceptable levels. For example, an analyte measurement device can use a relay, etc. coupled to an electro-actuated valve.

[0030] At 106, in one embodiment, if the concentration of the amine cannot be determined, the system can continue to measure the amine. Additionally or alternatively, the system can output an alarm, record the event, etc.

[0031] At 105, if the concentration of the amine can be determined, the system can provide a measurement of the amount of amine in the solution. The system can be connected to a communication network. The system can alert the user or the network. Such an alarm can occur whether or not the amine measurement is determined. The alarm can be in the form of audio, visual, data, storing data to a storage device, sending an output via a connected or wireless system, a printout, etc. The system can record information such as the measurement location, corrective actions, geographical location, time, date, number of measurement cycles, etc. The alarm or log can be automated, meaning the system can automatically output whether a correction is needed. The system can also have associated alarms, limits, or predefined thresholds. For example, whether the amine concentration has reached a threshold. The alarms or logs can be analyzed in real-time, stored for later use, or any combination thereof.

[0032] Accordingly, the various embodiments described herein represent technological improvements over conventional amine measurement techniques. Using the techniques described herein, one embodiment can use an indicator-metal complex to measure the amount of amine in a solution. This is in contrast to taking samples throughout a steam cycle system for laboratory analysis. The methods and systems described herein provide a faster and more cost-effective way to measure amines in an aqueous or liquid solution.

[0033] Regarding the instrumentation for amine measurement according to any of the various embodiments described herein, although various other circuits, circuit systems, or components may be used in an information processing device, an example is shown in Figure 5 The device circuit system 10' can include a measurement system on a chip design, such as a particular computing platform (e.g., mobile computing, desktop computing, etc.). Software and one or more processors are combined in a single chip 11'. The processor includes internal arithmetic units, registers, caches, buses, I / O ports, etc., as is well known in the art. Although the internal buses, etc., depend on different vendors, essentially all peripherals (12') can be attached to the single chip 11'. The circuit system 10' combines the processor, memory control, and I / O controller hubs all into a single chip 11'. Also, this type of system 10' typically does not use SATA or PCI or LPC. For example, common interfaces include SDIO and I2C.

[0034] There is one or more power management chips 13', such as a battery management unit BMU, which manages power supplied, for example, via a rechargeable battery 14', which can be charged by connection to a power source (not shown). In at least one design, a single chip (such as 11') is used to supply functions similar to BIOS and DRAM memory.

[0035] The system 10' typically includes one or more of a WWAN transceiver 15' and a WLAN transceiver 16' for connection to various networks, such as telecommunications networks and wireless Internet devices, such as access points. Additionally, devices 12' are typically included, such as transmit and receive antennas, oscillators, PLLs, etc. The system 10' includes input / output devices 17' for data input and display / rendering (e.g., positioned at a computing location away from the user for easy access in a single-beam system). The system 10' typically also includes various storage devices, such as flash memory 18' and SDRAM 19'.

[0036] As can be understood from the foregoing, the electronic components of one or more systems or devices may include, but are not limited to, at least one processing unit, a memory, and a communication bus or communication device coupled to various components including the memory of the processing unit. The system or device may include or may have access to various device-readable media. The system memory may include volatile and / or non-volatile memory such as device-readable storage media in the form of read-only memory (ROM) and / or random access memory (RAM). By way of example and not limitation, the system memory may also include an operating system, application programs, other program modules, and program data. The disclosed system may be used in embodiments to perform amine measurements of aqueous samples.

[0037] As will be appreciated by those skilled in the art, the various aspects may be embodied as a system, method, or device program product. Accordingly, the aspects may take the form of an entirely hardware embodiment or an embodiment including software, which in this document may generally be collectively referred to as “circuitry,” “module,” or “system.” In addition, the aspects may take the form of a device program product embodied in one or more device-readable media having device-readable program code embodied therewith.

[0038] It should be noted that the various functions described herein may be implemented using instructions stored on a device-readable storage medium such as a non-signal storage device, where the instructions are executed by a processor. In the context of this document, a storage device is not a signal, and “non-transitory” includes all media other than a signal medium.

[0039] The program code for performing the operations may be written in any combination of one or more programming languages. The program code may be executed entirely on a single device, partially on a single device as a stand-alone software package, partially on a single device and partially on another device, or entirely on another device. In some cases, the devices may be connected by any type of connection or network including a local area network (LAN) or wide area network (WAN), or the connection may be made through other devices (e.g., via the Internet using an Internet service provider), by a wireless connection such as near field communication, or by a hardwired connection (such as via a USB connection).

[0040] Exemplary embodiments are described herein with reference to the accompanying drawings, which illustrate example methods, devices, and products in accordance with various exemplary embodiments. It is to be understood that the acts and functions may be at least partially implemented by program instructions. These program instructions may be provided to a processor of a device (e.g., a handheld measurement device), or other programmable data processing device, to produce a machine such that the instructions executed via the processor of the device implement the specified function / act.

[0041] Note that the values provided herein are to be interpreted as including equivalent values indicated by use of the term “about.” Equivalent values will be apparent to those of ordinary skill in the art, but will include at least values obtained by rounding the last significant digit in a conventional manner.

[0042] While the present disclosure has been presented for purposes of illustration and description, it is not intended to be exhaustive or limiting. Many modifications and variations will be apparent to those of ordinary skill in the art. Exemplary embodiments were chosen and described in order to explain the principles and practical applications and to enable others of ordinary skill in the art to understand the disclosure of various embodiments with various modifications that are suited to particular uses contemplated.

[0043] Accordingly, while exemplary embodiments have been described herein with reference to the accompanying drawings, it is to be understood that the description is not limiting, and that various other changes and modifications may be made therein by those of ordinary skill in the art without departing from the scope or spirit of the invention.

Claims

1. A method for measuring a film-forming amine having a hydrophobic tail in an aqueous solution from a steam cycle system, the method comprising: Preparing an indicator-metal complex, wherein the indicator comprises calcein blue or a calcein blue derivative, and the metal is selected from the group consisting of: copper (II), cobalt (II), nickel (II), and iron (II); Introducing the indicator-metal complex into the aqueous solution, wherein the aqueous solution contains a certain amount of a film-forming amine having a hydrophobic tail, wherein the amine activates the indicator-metal complex, causing a change in the fluorescence intensity of the indicator-metal complex; and Measuring the amount of amine in the aqueous solution by measuring the change in the fluorescence intensity of the indicator-metal complex, wherein the amine is selected from the group consisting of: cetylamine, Helamin, Steamate, and DPL-674.

2. The method according to claim 1, wherein the aqueous solution further comprises at least one of the following: a borate buffer and a carbonate buffer.

3. The method according to claim 1, wherein the indicator-metal complex is weakly fluorescent, and wherein the amine activates the indicator-metal complex by removing the metal from the indicator-metal complex, thereby causing the change in fluorescence intensity.

4. The method according to claim 1, wherein the indicator-metal complex is weakly fluorescent, and wherein the change in fluorescence intensity is caused by the amine removing the metal from the indicator-metal complex and releasing the indicator.

5. The method according to claim 1, wherein the fluorescence intensity is related to the amount of amine in the above solution.

6. A measuring device for measuring a film-forming amine having a hydrophobic tail in an aqueous solution from a steam cycle system, the device comprising: A processor; And A memory storing instructions that can be executed by the processor to: Preparing an indicator-metal complex, wherein the indicator comprises calcein blue or a calcein blue derivative, and the metal is selected from the group consisting of: copper (II), cobalt (II), nickel (II), and iron (II); Introducing the indicator-metal complex into the aqueous solution, wherein the aqueous solution contains a certain amount of a film-forming amine having a hydrophobic tail, wherein the amine activates the indicator-metal complex, thereby causing a change in the fluorescence intensity of the indicator-metal complex; and Measuring the amount of amine in the aqueous solution by measuring the fluorescence intensity of the indicator-metal complex, wherein the amine is selected from the group consisting of: cetylamine, Helamin, Steamate, and DPL-674.

7. The device according to claim 6, wherein the solution further comprises at least one of the following: a borate buffer and a carbonate buffer.

8. The apparatus according to claim 6, wherein the indicator-metal complex is weakly fluorescent, and wherein the amine activates the indicator-metal complex by removing the metal from the indicator-metal complex, thereby causing the change in fluorescence intensity.

9. The apparatus according to claim 6, wherein the indicator-metal complex is weakly fluorescent, and wherein the change in fluorescence intensity is caused by the amine removing the metal from the indicator-metal complex and releasing the indicator.

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