Patent Application
20240228340
The present invention relates to a system and a method to measure the amount of a gas dissolved in a fluid. More precisely, the invention relates to a system and method for measuring the amount of a gas dissolved in a fluid, where the pH of the fluid is adjusted before the amount of gas is measured. The invention is particularly suited to measure gases in fluids where the pH-adjustment of the fluid changes the equilibrium of the gas dissolved in the fluid so that the amount of said gas in the fluid increases.
In farming installations for marine organisms, such as fish, ammonium (NH3) will be generated from faeces and the fishes' exhalation of air. Concentrations of ammonium in such farming fluids are typically in the range of 1-30 ppb (parts per billion). The ammonium formed in the farming fluid is poisonous to the fish and must be removed from the water. It is especially important to remove dissolved ammonium from the water in farming installations where the water is recycled back into the plant, i.e., in so called RAS installations. The removal of ammonium dissolved in the water is carried out in the biofilters of the installation, where ammonium (NH3(aq) is converted to nitrite (NO2(aq)) and nitrate (NO3(aq)).
The concentration of NH3 in the fluid is so low that it is practically impossible to measure the concentration.
Systems exist to continuously measure the concentration of a gas dissolved in a fluid, where the fluid is transported to a closed container, and where the amount of gas is measured during the gas phase above the fluid in the closed container. Such a system is described in U.S. Pat. No. 3,942,792 where the container is arranged in the tank itself where the fluid is collected. However, such a system cannot measure the low amounts of NH3 dissolved in a fluid.
U.S. Pat. No. 5,882,937 describes a system to regulate the amount of NH3 in water, where an alkaline or an acid is added to the fluid container itself, by the fluid being brought into contact with an alkaline or acid containing solid phase. Such a solution is impossible to use when measuring the concentration of gases in a farm installation, as the pH adjustment will lead to injury and death of the fish.
The present invention has as an objective to provide an improved system and method for measuring the concentration of a gas dissolved in a fluid.
It is an objective to enable continuous measurement of the concentration of a gas in the fluid, i.e., without having to obtain samples from the fluid for analysis.
In particular, it is an objective of the invention to enable measurement of the amount of NH3 gas dissolved in fluid, such as a fluid for the farming of marine organisms, like fish. Thus, it will be appropriate to use the system and method of the invention to measure the amount of NH3 dissolved at any time in the farming installation, but the system and method may also be used to measure other gases dissolved in fluid, and may be used for other fluids, such as tap water, purification plants, etc. Furthermore, it is an objective of the invention that the adjustment of the pH is not performed in the farming fluid in the tank itself, i.e., that the pH adjustment takes place downstream of the farming tank and is transferred to a separate container to measure the amount of gas.
The present invention relates in a first aspect to a system to determine the amount of a gas dissolved in a fluid in a container, wherein the system comprising an equilibrator arranged to set an equilibrium between gases in a gas phase and fluid phase, a sensor device to measure the amount of gas in the gas phase, and a container upstream of the equilibrator to regulate the pH of the fluid before it is transferred to the equilibrator.
In a preferred embodiment, the container is arranged to regulate the pH in the fluid and comprises means to add a pH regulating agent to the container.
In preferred embodiments, the pH regulating agent is in the form of a gas, a fluid, or a solid.
In one embodiment, the system comprises a gas transporter arranged to cause circulation of gases from the gas phase to the fluid phase.
In one embodiment, the equilibrator has an outlet with a water lock to regulate the fluid level in the equilibrator.
In one embodiment, the sensor device measures the amount of one or many gasses directly in the gas phase in the equilibrator.
In one embodiment, one or many gases are added to the fluid phase in the equilibrator.
In one embodiment, the said one or many gases is air or oxygen.
In one embodiment, the gas transporter transports gases in a closed circuit from the gas phase to the fluid phase in the equilibrator.
In one embodiment, the gas transporter comprises a pump and a pipeline for transport of gases from the gas phase to the fluid phase in the equilibrator.
In one embodiment, the system comprises a closed loop and that gases from the gas phase are transported by a gas transporter to the fluid phase in the equilibrator via this loop, and that a sensor device is arranged in the loop, and which measures the amount of one or many gases in the gas phase.
In one embodiment, the gas from the gas phase is directed in a closed loop via a sensor device to measure the amount of a specific gas.
In one embodiment, the gas supply unit is a hose equipped with an air pump to pick up gas from the gas phase and add it to the fluid phase in the equilibrator.
In one embodiment, the gas transporter is an ejector.
In one embodiment, the fluid is fed via pump and pipelines to the top of the equilibrator and the ejector arranged in the fluid phase in the equilibrator, and that gases from the gas phase in the equilibrator is sucked into the ejector via a pipeline.
In one embodiment, an anti-foaming agent is arranged in the equilibrator.
In one embodiment, the anti-foaming agent is arranged in the equilibrator so that there is a gas phase above the anti-foaming agent.
In one embodiment, gases are sucked into the sensor device from the gas phase below or above the anti-foaming agent.
In one embodiment, gases returning from the sensor device are returned to the equilibrator via the gas phase (80a) above or below the anti-foaming agent.
In one embodiment, fluids are added to the equilibrator via a nozzle, arranged to distribute the water over the cross section of the equilibrator.
In one embodiment, the gas transporter is a diffusor.
In one embodiment, gases from the gas phase are directed via a pump from the anti-foaming agent to the diffusor.
In one embodiment, the equilibrator is arranged substantially horizontally and that gases are circulated in a closed loop through the gas phase in the equilibrator using a pump or propel.
In one embodiment, the sensor device is connected to the closed circuit.
In one embodiment, the fluid is transferred to the equilibrator via nozzles, and directed to the end edge of the equilibrator where it flows out through pipeline arranged with a water lock.
In one embodiment, the measurements of amount of gas are calibrated with measurements of a gas mixture, such as air, with a known gas composition.
In one embodiment, the calibration takes place in a closed circuit equipped with valves, and that the calibration is performed automatically at given times.
In one embodiment, fluid supplied to the equilibrator is obtained from a first container.
In one embodiment, the system comprises means to measure the pH in the container before and after addition of pH adjusting agent.
In one embodiment, the system comprises means to measure pH in the fluid in a container before addition of pH adjusting agent, and in container after addition of pH adjusting agent.
Alternatively, the container for pH adjustment may comprise means to measure pH both before and after addition of pH adjusting agent.
In one embodiment, the system comprises means to measure the amount of pH adjusting agent added.
In one embodiment, the system comprises means to measure pH in fluid after addition of pH adjusting agent, and that information about pH in the fluid after addition of pH adjusting agent is used to adjust the amount of pH adjusting agent being added to the container.
In another aspect, the present invention relates to a method to determine the amount of gas dissolved in a fluid, where the fluid is continuously added to an equilibrator arranged to set an equilibrium between the gases in a gas phase and the gasses dissolved in a fluid phase in the equilibrator, and where a pH adjusting agent to adjust the pH is added to the fluid before it is transferred to the equilibrator so that the equilibrium between said gases dissolved in the fluid and its ions dissolved in the fluid shift so that more gas is dissolved in the fluid.
In one embodiment, one or more gasses are added to the fluid phase to set the equilibrium between the gas phase and the fluid phase in the equilibrator more rapidly.
In one embodiment, gases from the gas phase in a closed volume is brought in contact with the fluid phase, and that a sensor device measures the amount of one or several gases in the gas phase.
In one embodiment, a gas transporter causes circulation of gasses from the gas phase to the fluid phase.
In one embodiment, the gas transporter is a pump and a pipeline for transport of gases from the gas phase to the fluid phase in the equilibrator.
In one embodiment, gasses are transported from the gas phase by a gas transporter to the fluid phase in a closed loop, and that a sensor device is arranged in the loop and measures the amount of one or more gasses in the gas phase.
In one embodiment, the gas from the gas phase is directed in a closed loop via a sensor device to measure the amount of a specific gas.
In one embodiment, the gas transporter is a hose equipped with an air pump to collect gas from the gas phase and add it to the fluid phase.
In one embodiment, the gas transporter is an ejector.
In one embodiment, the gas transporter is a diffusor.
In one embodiment, the sensor device measures the amount of one or more gasses selected from among hydrogen sulphide, carbon dioxide, oxygen, and ammonium.
In one embodiment, the said gas being measured is ammonium (NH3)
In one embodiment, the flow-through velocity, and the amount of fluid through the equilibrator are measured or estimated, so that absolute amount of gas dissolved in the fluid may be calculated.
In one embodiment, the gas transporter generates micro-bubbles in the fluid phase.
In one embodiment, the fluid is transferred continuously from a first container to the equilibrator.
In one embodiment, a system is arranged according to the present invention, as indicated above, in several places in a fish farm.
In one embodiment, the system is arranged to measure amounts of gases in a fluid which is released into the farming tank.
In one embodiment, the system is arranged to measure amounts of gas released from the installation via the CO2 stripper.
In one embodiment, the system is arranged between one or more, or all of the modules in a fish farm, such as a RAS installation.
In one embodiment, the measurements are taken in real-time, and that a transmitter device on the sensor device transmits data to a controller unit.
In one embodiment, the system is set up with valves so that via programmable intervals it is possible to connect one calibrator gas with known concentrations to control drifting of the sensors.
In one embodiment, change of pH as a result of addition of pH adjusting agent is used to calculate the amount of fluid in a container based on measurements of amounts of said gas in the gas phase corrected for the change in amount of gas as a result of the change of pH.
In one embodiment, the amount of pH adjusting agent added is measured, and that amount of pH adjusting agent added is used to calculate the change of pH before and after addition of pH adjusting agent, and that change of pH is used to calculate amount of gas dissolved in fluid in container based on measurements of amounts of said gas in the has phase (80a) corrected for the change of amount of gas as a result of the change of pH.
Below, preferred embodiments of the invention will be discussed in more detail with reference to the attached Figures, where:
As mentioned above, there are no solutions available to measure the low concentrations of dissolved NH3 in fluid that are formed in fish farms. Even low levels of NH3 is harmful to the fish, and with the present invention a solution is provided which makes it possible to detect extremely low levels of NH3, i.e., levels of NH3 in the range harmful for the fish.
In fluids, the amount of NH3 gas dissolved in the fluid is an equilibrium with ammonium ions NH4+. In a normal fish farm, this equilibrium of NH3 in fluid is influenced by the pH of the fluid. The pH of the fluid in a normal fish farm, including a RAS installation, is in the ranges of 6.8 to 7.5. As is shown in the figure below, a change in pH to a more alkaline value will displace the equilibrium between NH3(aq) and NH4+(aq) and settle at a level where the relationship between NH3 and NH4+ increases, i.e., more NH3 gas will be dissolved in the fluid. Thereby, it is possible to increase the amount of NH3 gas dissolved in fluid to a level which it is practically possible to measure. Other conditions influencing the equilibrium between NH3 and NH4+, is temperature and saline content of the fluid. Therefore, it is necessary to use a table, and perform the corrections which apply to the actual temperature and the actual saline content.
It is not possible to perform this displacement of the equilibrium, i.e., increase pH, in the farming installation itself as the amounts of NH3 that will form will be highly toxic to the fish in the installation.
As shown in
Thus, the core of the invention is to transfer the fluid to the equilibrator 80 so that the amount of gas may be measured in the gas phase 80a that sets above the fluid phase 80b in the equilibrator 80, and that in addition, the pH of the fluid is adjusted before it is fed into the equilibrator 80 to influence the equilibrium between gas dissolved in fluid and the corresponding ions in the fluid. This is explained with reference to the figure above for the NH3—NH4+ equilibrium which is influenced by the pH of the solution. A higher, more alkaline pH displaces the equilibrium so that the fluid contains proportionally more NH3. This brings the amount of NH3 up to levels measurable in the gas phase 80a in an equilibrator 80. By calculating added amount of pH adjusting agent (such as NaOH) or by measuring the pH before and after addition of pH adjusting agent, it is possible to calculate how many times the NH3 concentration has increased in the fluid, and it is possible from the measurements of NH3 after pH adjustment to calculate how much NH3 the original fluid of the farming installation contained. Thereby, a system and method is provided to measure amounts of NH3 even when they are so low that they cannot be measured with conventional measuring methods. In many cases it will not be necessary to measure absolute amounts of NH3, as it will be sufficient to consider the development of NH3 over time. The method according to the invention is performed continuously and monitors the relative measurement of NH3. It is also possible to carry out chemical measurements of amount of NH3 in the farming container 11 and relate these to the measured values of NH3 in the pH adjusted fluid in the equilibrator 80.
In PCT application PCT/NO2020/050280 the proprietor of the present patent application has described transfer of fluid to an equilibrator to allow for the measurement of low amounts of gasses dissolved in a fluid. The proprietor is active in the aqua culture industry, and the invention of PCT/NO2020/050280 is exemplified by measurements of hydrogen sulphide gas, i.e., H2S (aq) in a fluid. The present invention relates to an improved measuring method for gases in fluid, for gases where an adjustment of pH increases the amount of gas in the fluid by displacing the equilibrium between gas and ions in the fluid more towards gas, either by increasing the pH of the fluid (as with the NH3 system) or by reducing the pH.
Downstream of the container 11 (for example the farming tank in the fish farm), the fluid is transferred to a container 20 for adjustment of the pH. In case of measurement of NH3, an alkaline will be added to the container 20, i.e., an agent adjusting the pH to higher, more alkaline values. An example of such an agent, is NaOH. The pH adjusted fluid is then fed from container 20 to equilibrator 80.
In association with the equilibrator 80, a water lock 70 is arranged at the outlet to enable the regulation of the level of fluid in the equilibrator 80. After a given time, an equilibrium will set for the gas it is desirable to measure, between amount of gas dissolved in the fluid 80b in the equilibrator 80 and amount of gas dissolved in the gas phase 80a above the fluid level in the equilibrator 80. It is preferable that this equilibrium between gas dissolved in the fluid phase 80b and the gas phase 80a, respectively, sets rapidly so that it is possible to continuously carry out the measurements of actual amounts of the gas, which is measured using sensors 200 in the gas phase 80a. To effectuate a rapid setting of this equilibrium between gas in the fluid phase 80b and the gas phase 80a, the system is preferably equipped with means to cause a circulation of the gas phase 80a to the fluid phase 80b. If the gases from the gas phase 80a are transported to the fluid phase 80b, and preferably also transported through the fluid phase 80b, then the equilibrium between gases in the fluid phase 80b and the gas phase 80a will set more rapidly. These means to transport gases through the fluid phase 80b are in some of the figures schematically depicted as a gas transporter with reference number 100. In a simple, preferred embodiment the gas measured in sensor 200 is transported to a lower level in the fluid phase 80b so that bubbles of gas phase 80a raise up through the fluid phase 80b.
It is not necessary to use gases from the gas phase 80a for transport of gases through the fluid phase 80b. Any gas directed through the fluid phase 80b will cause a more rapid setting of the equilibrium between gas in the gas phase 80a and the fluid phase 80b. Therefore, it is often preferable to bubble another gas, such as air or oxygen, through the fluid phase 80b to cause this more rapid setting of the fluid phase. For example, it is possible to add air or oxygen using an injector or ejector directly into the fluid phase 80b. It is preferred that the gas (for example air) which is to be added to the fluid phase 80b, form small bubbles, preferably micro-bubbles, in the fluid phase 80b. Such bubbles, and preferably micro-bubbles, establishes a rather large interfacing surface between gases in the gas phase 80a (which also comprise the volume inside the bubbles) and gases in the fluid phase 80b. A larger interfacing surface accelerates the establishment of the equilibrium.
Addition of gas or gasses to the fluid phase 80b may be carried out in many ways, and the gas transporters may therefore be different. In
The anti-foaming agent 120 may be placed at different levels of the equilibrator 80 Above the anti-foaming agent 120 there is a gas space, where for example it is possible to suction gases to the sensor box 200. Foam should not enter into this space. Gases returning from the sensor box 200 travel through the anti-foaming agent 120 so that these gases interchange with gases arriving from the ejector 100′. Should foam enter the anti-foaming agent 120, it will be sucked down again to the ejector 100′ together with the gases. When foam is sucked down to the ejector 100′, then the function of this will be impaired and therefore also generate less foam. In this manner, we prevent foam for crossing over to the anti-foaming agent 120. The anti-foaming agent 120 has openings 120a causing the gases to circulate through it, but foam with higher density is sucked into the return and down to the ejector 100′.
Alternatively, measuring pH both before and after addition of pH adjusting agent, it is possible to dosage in pH adjusting agent to obtain complete control over how much agent is added. When it is known how much pH adjusting agent has been added, and what also effect this addition has on the equilibrium of the fluid 10, then it is possible to calculate what the pH value will be after addition and use this calculated value to determine how many times amount of the relevant gas, such as NH3, have increased with the pH adjustment. In
The system and method according to the invention is described for measurement of NH3 in a farming installation, but we would like to emphasise that also other gasses may be measured, and then in particular other gasses shifting the equilibrium between gas and ions dissolved in fluid if a change of pH is enforced. We also want to emphasise that other gases may be measured using the system and the method, i.e., without adjustment of pH, or without this influencing the amount of said gas in the fluid 10, that it is possible to actually use the effect of transferring the fluid to an equilibrator to enable the measurement of amount of gas in the gas phase 80a and not in the fluid 10 itself. In addition, we want to emphasise that it is possible to measure several gases at the same time using several sensors 200, where each one of them is specific for at least one of the mentioned gases to be measured. With the invention is provided an option for continuous measurement of gases in fluids in an installation, such as a farming installation. Separately, and by combining the two principles; (i) measurement of gas level in the gas phase when the fluid is in an equilibrator 80 and is set to an equilibrium between said gas in the gas phase 80a and the fluid phase 80b, and ii) change of pH in the fluid 10 to displace the equilibrium towards more dissolved gas in the fluid to be able to indirectly measure smaller amounts of gas in fluid, are provided new means to maintain continuous control over the concentration of gases in fluid, and especially gases that may have harmful effects on the species, such as fish, being farmed in the fluid 10 in container 11. With the method and the system is provided a possibility for obtaining continuous control over the development of gases in the fluid. Measuring of relative values is simple, i.e., measuring changes in amount of a given gas, but it is also simple to calculate the absolute values and clarify whether these are approaching a level that will be harmful for the fish so that remedies must be implemented.
Below follows a more detailed description of how the method according to the invention is performed for measurement of NH3. The embodiment may be as depicted in
The challenges associated with measuring NH3 at low ppb levels, is that existing sensors do not have a sufficiently accurate (sufficiently sensitive) measuring range. Therefore, we will adjust up pH as mentioned previously, to increase the percentage of NH3, so that we obtain an amount of dissolved NH3 within a measurable level.
The signal emitted from a typical NH3 sensor is in the form of an analogue tension in the dimension of about 15 μV per ppb. To measure these low levels, it is necessary to build a conditioning circuit which adapts the signal emitted from the sensor to a sensible measuring range for an A/D converter. In this embodiment, we use a 16 bits A/D converter with a measuring range of 0 to 3.3 Volt. To optimally utilize the measuring range of the converter, the conditioning circuit must remove DC offset from the sensor and amplify the signal at the same time so that it fits the entry stage of the A/D converter. In this embodiment, precision tension reference and differential amplifiers are used to convert the signal emitted from the sensor to suitable values for the A/D converter. To reduce the noise, both analogue and digital noise filters are implemented. Digital filtering is necessary to smooth out the signal. This filter may have a time constant of typically around 5 mins.
The signal emitted from the conditioning circuit is sent to the A/D converter, which converts mV voltage to a 16 bits number. We now have a scale where 1 ppb concentration is equivalent to approximately 2 stages on the A/D converter. We have managed to obtain a mV voltage which depends on the NH3 level of the gas we are measuring, and that the mV signal is in a detectable range for A/D conversion.
However, this mV voltage strongly depends on varying temperature, and to enable conversion from mV to NH3 concentration, it is first necessary to determine the relationship between temperature and mV at a given concentration of NH3.
This is carried out experimentally by obtaining a long series of measurements where the sensor first has clean air (NH3-0) and then reading mV voltage from the sensor at varying temperatures. Thereafter, we build up a table over mV voltage vs. temperature, where temperature ranges from for example 0 to 20° C. in 1° ° C. intervals.
When this is done, the same experiment is made over again, but now with sensor exposed to air with an upper limit of NH3 concentration. The air is in a closed circuit, where we establish equilibrium between gas and fluid phase as described. Using established set of formula, we calculate the NH3 concentration in the water being measured.
The tables we build in this manner, are converted to liners or polynomic trend lines which are then used in the set of formulas to implement temperature correction.
The sensor is linear in the range of interest to us. Using the performed tests, we have arrived at mV distension at the lower and higher measuring ranges. These values may be used to define the formula to convert from mV to temperature corrected ppb NH3. The sensor will measure the NH3 gas concentration at intervals of 1 second.
A practical test was performed where a mixture of with a concentration of Total ammonium of approximately 2 mg/L.
As indicated above, the proportion of NH3 in water with a certain Total Ammonium Level depends mainly on pH, and less on temperature and salinity.
Ammonium chloride in a concentration of 9% with NH4OH was used. Approximately 0.5 ml ammonium chloride was added to a bucket 10L bucket. pH was measured to 7.5. Approximately 1 litre of the water was added to a container with a lid. A small air pocket was left at the top of the container. The container was shaken so that the gas in the air pocket was brought into equilibrium with the water. The gas phase above the water and the amount of gas in the water set as an equilibrium, similar to the equilibrator explained above. Thereafter, the NH3 sensor was placed under the lid and the concentration of NH3 in the gas phase under the lid was measured. It was measure to 0.015 mg/L (10 ppb in air) using a gas sensor of the type Aquasense. This is estimated to approximately 0.9% of Total Ammonium in the container. An alkaline was then added to the container to raise the pH. pH was measured to approximately 9.0. Thereafter, the lid was put back on and the container shaken for air to be brought into equilibrium with the water. The concentration of NH3 was measured once again and now showed 0.40 mg/L (approximately 270 ppb in air) using the same sensor of the type Aquasense. By calculations, the proportion of NH3 should be approximately 21.5% of Total Ammonium.
This demonstrates that by raising the pH in the water to be measured for amount of NH3 gas dissolved, the equilibrium will be displaced towards NH3 gas (as explained above) and the fraction of NH3 will increase considerably (more than 20 times). This means that it is possible to indirectly measure amounts of NH3 that are more than 20 times lower than when the pH is not adjusted, and it is therefore possible to utilise sensors with a range that is higher and more easily accessible thereby.
By use of known formulas/tables it is thereafter possible to calculate back to the level that was in the water before an alkaline was added to increase the pH.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20210604 | May 2021 | NO | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/NO2022/000002 | 5/11/2022 | WO |
