Patent Application
20230285903
The present invention relates to a method for operating a desalting device, and specifically, to a method for operating a desalting device including a first desalting device and a second desalting device.
In desalting devices such as reverse osmosis membranes, long-term operation causes precipitation of scale such as calcium carbonate, silica, and calcium fluoride and membrane clogging due to organic matter, which results in deterioration of the desalting device performance such as a decrease in a salt removal rate and a decrease in the amount of permeate water. In the case of scale clogging, in order to prevent the desalting device performance from deteriorating, a method of measuring an ion concentration in raw water and performing an operation so that the saturation index is not exceeded in concentrated water of the desalting device is used. Here, “saturation index” generally refers to a logarithmic value of the value obtained by dividing the product of the concentration and ionic strength of each ion species involved in scale generation by the solubility product. The desalting device is operated in a range in which the saturation index does not exceed zero. In addition, when the saturation index is exceeded, for example, the desalting device is operated after generation of scale is reduced by adding a scale inhibitor.
In cases where water quality greatly exceeds the saturation index, and it cannot be reduced even by adding a scale inhibitor, chemical washing such as acid washing or alkaline washing has been performed in order to remove scale in the related art. However, general washing is a process in which a device is stopped, a washing solution is adjusted and washing is then performed, a washing solution is recovered and then water passing starts, which results in a problem of high washing cost. Therefore, it has been desired to operate a desalting device in which performance of the desalting device does not deteriorate even after long-term operation and that does not require chemical washing.
One method for operating a desalting device is, for example, a flushing method. Here, flushing refers to an operation of discharging water supplied from a concentrated water discharge pipe to the outside of the system by opening an on-off valve of the concentrated water discharge pipe while a water supply pump continues to operate. When water is passed at a higher flow rate than during a normal operation, it is possible to effectively wash away contaminants that clog the membrane surface. Flushing is generally performed at a frequency of 1 to 10 times/day for 30 to 120 seconds/time. However, there is a problem that flushing for several minutes/time is not sufficient to recover the performance of a desalting device whose performance has deteriorated, and washing eventually has to be performed. In addition, when flushing is performed, since the on-off valve on the concentrated water pipe is opened, it is not possible to produce permeate water during flushing, and the recovery rate of the desalting device decreases.
As another method, there is a method of reversing a flow direction of to-be-treated water in the module. According to this method, it is possible to easily detach suspended matter accumulated in the raw water spacer, and the stability of the desalting device is improved. However, there is a problem that the number of valves required for reversing the flow significantly increases, and the initial cost is significantly high. In addition, if the valve fails, the valve cannot be switched, and the stability of the device is greatly impaired. In addition, there is no description of a detachment effect on scale matter due to flow reversal.
Japanese Patent Laid-Open No. 2004-141846
Japanese Patent Laid-Open No. 2004-261724
The present invention has been made in view of the above problems, and an objective of the present invention is to provide a method for operating a desalting device in which it is possible to recover desalting performance of a desalting device that has deteriorated without stopping the operation of the desalting device.
A method for operating a desalting device of the present invention including a first desalting device and a second desalting device includes a normal operation step in which to-be-treated water is supplied to a first desalting device and separated into first concentrated water and first desalted water, and the first concentrated water is supplied to a second desalting device and separated into second concentrated water and second desalted water; and a recovery operation step in which to-be-treated water is supplied to the first desalting device and separated into first concentrated water and first permeate water, and dilute water having a lower concentration than that of the first concentrated water is passed through the second desalting device, and desalting performance of the second desalting device is recovered.
In one aspect of the present invention, a plurality of second desalting devices are installed in parallel, and while the normal operation step is performed in some second desalting devices, the recovery operation step is performed in other second desalting devices.
In one aspect of the present invention, in the recovery operation step, dilute water is passed for 5 to 60 minutes through the second desalting device.
In one aspect of the present invention, the to-be-treated water is used as dilute water.
In one aspect of the present invention, desalted water in the first desalting device is used as dilute water.
In one aspect of the present invention, a scale inhibitor is added to dilute water.
In one aspect of the present invention, the desalting device is a reverse osmosis membrane device.
In one aspect of the present invention, the passing rate of dilute water is 0.001 to 0.1 m/s.
In one aspect of the present invention, the water quality of the first concentrated water is any one of the following a to e:
In one aspect of the present invention, the first concentrated water is concentrated water obtained by concentrating water supplied from the first desalting device by a factor of 3 or more.
In the normal operation step in the method for operating a desalting device of the present invention, to-be-treated water is passed through the first desalting device and separated into first desalted water and first concentrated water, and the first concentrated water is passed through the second desalting device and separated into second desalted water and second concentrated water. When desalting performance of the second desalting device decreases by performing the normal operation step, if dilute water is passed through the second desalting device while continuing the operation of the first desalting device, it is possible to recover the desalting performance of the second desalting device.
Here, in an aspect in which desalted water in the first desalting device is used as dilute water when the flux recovery operation is performed in the second desalting device, auxiliary facilities such as tanks are unnecessary, and the device configuration is simplified. In addition, when water with a low salt concentration called permeate water in the first desalting device is used as dilute water, it is possible to greatly improve the recovery effect of the second desalting device whose performance has deteriorated compared to when to-be-treated water is used as dilute water.
Hereinafter, a first embodiment will be described with reference to
During a normal operation, as shown in
Concentrated water (first concentrated water) in the first RO device 4 is introduced into a relay tank 10 through pipes 7 and 8 and a valve 9. The first concentrated water in the relay tank 10 is supplied to a second RO device 15 from a pipe 13 having a pump 11 and a valve 12 through a pipe 14.
Permeate water in the second RO device 15 is taken out as second permeate water through a pipe 17 having a valve 16. Concentrated water in the second RO device 15 is taken out as second concentrated water through a pipe 18, a valve 19, and pipes 20 and 21.
During this normal water passing, the pumps 2 and 11 are operated. In addition, the valves 5, 9, 12, 16, and 19 are opened, and valves 24 and 28, which will be described below, are closed.
In the desalting device in
In the drawings, PI indicates a pressure sensor, and FI indicates a flow rate sensor.
During a flux recovery operation in which the flux of the second RO device 15 is recovered, as shown in
Raw water in the raw water tank 1 is supplied to the first RO device 4 through the pump 2 and the pipe 3, and the first permeate water is taken out from the pipe 6 through the valve 5. The first concentrated water is taken out through the pipes 7 and 23, the valve 24, and the pipes 25 and 21.
In addition, during the flux recovery operation of the second RO device 15, some raw water supplied as dilute water by the pump 2 is supplied to the second RO device 15 through the pipe 27, the valve 28, and the pipes 29 and 14 branching from the pipe 3. Permeate water in the second RO device 15 is taken out through the valve 16 and the pipe 17. Concentrated water in the second RO device 15 is discharged to the pipe 21 through the pipe 18, the valve 19, and the pipe 20 and joins with the first concentrated water from the pipe 25 and is taken out as concentrated water.
In this method for operating a desalting device, when the flux of the second RO device 15 decreases due to the normal operation, by performing an operation of passing dilute water in the second RO device 15 while an operation of producing permeate water in the first RO device 4 continues, the flux of the second RO device 15 is recovered and a significant decrease in the recovery rate can be prevented without stopping the desalting device. In particular, by passing dilute water (in
Here, normally, dilute water is passed from the water supply side of the desalting device, but it may be passed from the concentrated water side of the desalting device.
Hereinafter, a second embodiment will be described with reference to
In the embodiment of
As shown in
Concentrated water (first concentrated water) in the first RO device 4 is supplied to one second RO device 51 through pipes 34 and 35, a valve 36, and a pipe 37.
Desalted water (permeate water) in the second RO device 51 joins the flow of the pipe 33 through pipes 61 and 62 and is taken out as desalted water. Concentrated water in the second RO device 51 is taken out as concentrated water through a pipe 63, a valve 64, a pipe 65, a valve 66, and a pipe 67.
A pipe 38 branching from the pipe 34 is connected to a water supply port of the other second desalting device 52 via a valve 39 and a pipe 40. In
In the desalting device in
During the flux recovery operation of the other second RO device 52, desalted water in the other second RO device 52 joins the flow of the pipe 33 through pipes 73 and 62 and is taken out as desalted water. Concentrated water in the second RO device 52 is returned to the raw water tank 1 through pipes 74 and 77, a valve 78, and pipes 79 and 71.
In contrast to
In
Desalted water (permeate water) in the second RO device 52 joins the flow of the pipe 33 through the pipes 73 and 62 and is taken out as desalted water. Concentrated water in the second RO device 52 flows to the pipe 65 through the pipe 74 and a valve 76 and is taken out as concentrated water.
In addition, in
Accordingly, in the method for operating a desalting device in
In
To-be-treated water is distributed and supplied to the first RO devices 4A to 4D through the pipe 3 and a pipe 81 branching therefrom, and desalted water in each of the first RO devices 4A to 4D is taken out as desalted water through pipes 82, 31, and 33.
Concentrated water in the first RO devices 4A to 4D can be switched from a confluent pipe 83 and supplied to the second RO devices 51 and 52 and second RO devices 53 and 54 through branch pipes 88 to 91 having valves 84 to 87, respectively. In addition, the branch pipes 88 to 91 are connected to the desalted water pipe 31 through the pipes 91, 93, 95, and 97 having valves 92, 94, 96, and 98.
In
Desalted water in each of the second RO devices 51 to 54 joins the flow of the pipe 33 from pipes 101, 103, 105, and 107 and is taken out as desalted water.
Concentrated water in the second RO devices 51 to 54 is taken out as concentrated water through pipes 102, 104, 106, and 108 and a confluent pipe 109.
By reversing the opening and closing of the valves 84 to 87, and the valves 92, 94, 96, and 98, a flux recovery operation is performed in the second RO devices 51 and 52, and a normal operation is performed in the second RO devices 53 and 54.
Although four first RO devices and four second RO devices are shown in
In
The passing rate of dilute water can be appropriately determined according to the clogging state of the desalting device, and is, for example, 0.001 to 1 m/s, and particularly preferably 0.02 to 0.2 m/s in the case of the reverse osmosis membrane. Specifically, it is preferably 300 to 2,000 L/Hr per one 4-inch module and preferably 1.8 to 10 m3/Hr per one 8-inch module. In addition, the pressure on the concentrated water discharge side of the desalting device is preferably 0.1 to 2 MPa.
[Switching Timing from Normal Operation to Recovery Operation]
In the present invention, when a normal operation is performed for a predetermined time, the operation can be switched to a recovery operation, but it is preferable to perform switching when scale is generated in the second desalting device.
When a case in which a reverse osmosis membrane is used as the desalting device is exemplified, switching is performed when the transmission flux of the second RO device decreases by a set proportion from the initial stage of the operation, for example, decreases by 5%. Here, this 5% is an example, and the set proportion may be a value selected from 1 to 20%, and particularly from 1 to 10%. In particular, it is preferable to measure a change in the transmission flux of the most concentrated terminal RO in the second RO device.
Since the actual transmission flux is affected by the operation pressure, the water temperature, and the salt concentration during water supply, it is desirable to determine the corrected transmission flux as data indicating performance of the RO device.
Here, the corrected transmission flux is generally calculated by the method described in standardization methods of reverse osmosis membrane elements and module permeate water amount performance data as shown in JIS K 3805: 1990.
That is, the permeate water amount performance data is corrected by the following Formula (1) to calculate the corrected transmission flux Fps.
ΔPtba: module differential pressure under actual operation conditions (kPa)
The normal operation may be switched to the recovery operation based on an excessive differential pressure of the second desalting device, a decrease in the amount of treated water in the second desalting device, a decrease in the permeate water amount of the small RO that is additionally set on the concentrated water side of the second desalting device, and whether supersaturated precipitates are detected in the pipe using a sensor utilizing ultrasound that is set in the pipe, in addition to the amount of decrease from the initial corrected transmission flux.
While raw water is used as dilute water in the above embodiment, permeate water in the first RO device or second RO device may be used as dilute water. In addition, a mixture of permeate water in the first RO device or second RO device and raw water may be used as dilute water. In addition, a mixture of permeate water in the first RO device or second RO device and first concentrated water may be used as dilute water.
The present invention can be suitably used when calcium fluoride scale or calcium carbonate scale is generated in the second RO device. Specifically, it can be suitably used when first concentrated water supplied to the second RO device satisfies the following a to e. Here, a and b are cases in which calcium fluoride scale is generated, and c is a case in which calcium carbonate scale is generated.
It is preferable to add a scale inhibitor to dilute water. When a scale inhibitor is added, effects of improving dissolving power of scale and preventing re-attachment of dissolved scale can be obtained.
The scale inhibitor can be appropriately selected according to the type of the desalting device used and raw water, a reverse osmosis membrane device is used as the desalting device, and in the case of to-be-treated water in which calcium carbonate scale is produced, phosphonic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, copolymerization polymers of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid, polyacrylic acids or the like can be used, and in the case of to-be-treated water in which calcium fluoride scale is generated, phosphonic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, polyacrylic acids or the like can be used. In addition, the amount of these scale inhibitors added is about 10 to 1,000 mg/L.
Here, when a pH adjusting agent is added to dilute water, effects of improving dissolving power of scale and preventing re-attachment of dissolved scale can be obtained.
When raw water is passed as dilute water as shown in
While the RO devices are installed in two stages in the above embodiment, they may be installed in three or more stages. Here, when the RO devices are installed in three or more stages, it is preferable that the desalting device through which dilute water is passed be provided at the last stage.
A fine calcium carbonate particle dispersion liquid and a fine calcium fluoride particle dispersion liquid were prepared, dilute water was added to each liquid, and the dissolution property of the fine particles was measured.
500 mL of ultra-pure water was put into a 500 mL conical beaker, an aqueous solution containing 340 mg/L of calcium chloride, 10 mg/L of a scale inhibitor, and 1,300 mg/L of sodium hydrogen carbonate was prepared, and additionally, the pH was adjusted to 8.5 with a sodium hydroxide aqueous solution or hydrochloric acid aqueous solution to prepare a starting solution. Under a room temperature condition of 25° C., until scale was generated, the starting solution was stirred with a stirrer and left for a predetermined time. A scale solution with different particle sizes was prepared by changing the time for which it was left.
500 mL of ultra-pure water was put into a 500 mL conical beaker, an aqueous solution containing 100 mg/L of sodium fluoride, 5 mg/L of a scale inhibitor, and 400 mg/L of calcium chloride was prepared, and additionally, the pH was adjusted to 5.5 with a sodium hydroxide aqueous solution or hydrochloric acid aqueous solution to prepare a starting solution. Under a room temperature condition of 25° C., until scale was generated, the starting solution was stirred with a stirrer and left for a predetermined time. A scale solution with different particle sizes was prepared by changing the time for which it was left.
For each liquid, the particle size of the generated scale was measured using a particle size distribution meter (SALD-7500nano, commercially available from Shimadzu Corporation).
<Mixing with Dilute Water>
In a 500 mL conical beaker, the fine particle dispersion liquid prepared as described above and dilute water (RO permeate water of RO membrane permeate water for wastewater recovery at Kurita Global Technology Center (Nogi-machi, Shimotsuga-gun, Tochigi)) were mixed at ratios shown in Table 1, and the mixed liquid after 5 minutes was visually observed, the particle size distribution was measured, and whether fine particles were dissolved was checked. The results are shown in Table 1.
In Nos. 1 and 2 (CaCO3 scale particle size of 5 μm), fine scale particles were dissolved by adding dilute water, but in Nos. 4 and 5 (a mixing ratio of 50/50 or 60/40) and Nos. 6 to 9 (CaCO3 scale particle size of 20 μm), fine scale particles remained undissolved.
In No. 3 (CaF2 scale particle size of 0.1 μm, a mixing ratio of 10/90), fine particles were dissolved by adding dilute water, but in Nos. 10 to 12 (a mixing ratio of 20/80 to 60/40), fine scale particles remained undissolved.
In a flat film type RO device 200 in
First simulated raw water passing step: simulated raw water was passed at an initial transmission flux of 0.45 m/D and a water passing flow rate of 0.1 m/s, and the operation was performed with a constant permeate water amount (therefore, the corrected transmission flux gradually decreased over time).
Dilute water passing step: after the corrected transmission flux after water was passed for a certain time decreased by 20 to 25% compared to the initial corrected transmission flux, dilute water was passed at a water passing flow rate of 0.1 m/s for a time shown in Table 2.
Second simulated raw water passing step: simulated raw water was passed at the same pressure and permeate water amount as in the first simulated raw water passing step.
Calcium chloride dehydrate and sodium hydrogen carbonate were dissolved in pure water at a Ca concentration of 600 mg/L and a Na concentration of 600 mg/L to prepare simulated raw water.
M alkalinity: 850 mg/L as CaCO3
pH: 8.4 to 8.5
water temperature: 30° C.
Simulated dilute water with the Ca and Na concentrations which were 1/10 of those of the simulated raw water was used. The pH was 7.2 to 7.3, and the water temperature was 30° C.
<Simulated Dilute Water with Scale Inhibitor Added>
A sample obtained by adding 10 mg/L of 2-phosphonobutane-1,2,4-tricarboxylic acid as a scale inhibitor to the above simulated dilute water was used.
Simulated raw water was passed in the same manner as in Example 1 except that dilute water was not passed.
The ratio F/F0 of the flux F immediately before the first simulated raw water passing step was completed and the initial flux F0 is shown as “flux ratio before dilute water passing” in Table 2.
The ratio F′/F0 of the flux F′ immediately after the second simulated raw water passing step started and the initial flux F0 is shown as “flux ratio after dilute water passing” in Table 2.
The value of [flux ratio after dilute water passing]/[flux ratio before dilute water passing] is shown as a “recovery ratio” in Table 2.
As shown in Table 2, the dilute water passing step was performed and thus the flux was recovered (increased). In particular, as in Examples 1 to 4, the dilute water passing step was performed for 10 minutes or more, and particularly, 30 minutes or more, and thus the flux was sufficiently recovered. In addition, as in Example 4, a scale inhibitor was added to dilute water, and thus the flux was more sufficiently recovered.
As simulated raw water, a sample obtained by dissolving calcium chloride dihydrate, magnesium chloride, aluminum chloride and sodium fluoride in pure water so that the Ca, Mg, Al, and F concentrations were as follows was used.
As dilute water, permeate water obtained by passing simulated raw water through the RO device in
The water passing order was as follows. The water passing time in each step was set as shown in
First simulated raw water passing step: simulated raw water was passed at a certain permeate water amount (0.45 m/D).
Dilute water passing step: dilute water was passed for 45 minutes.
Second simulated raw water passing step: simulated raw water was passed at the same water supply pressure as in the first simulated raw water passing step.
The results are shown in Table 3 and
88%
85%
Simulated raw water and dilute water were prepared in the same manner as in the simulated raw water preparation method in Example 7 so that the Ca, Mg, Al and F concentrations were as follows.
The water passing order was the same as in Example 7. The water passing time was set as shown in
The results are shown in Table 3 and
In the flat film type RO device in
First simulated raw water passing step: simulated raw water was passed at an initial transmission flux of 0.45 m/D and a water passing flow rate of 0.1 m/s, and the operation was performed with a constant permeate water amount (therefore, the corrected transmission flux gradually decreased over time).
Dilute water passing step: after the corrected transmission flux after water was passed for a certain time decreased by 20 to 25% compared to the initial corrected transmission flux, dilute water was passed at a water passing flow rate of 0.1 m/s for a time shown in Table 2.
Second simulated raw water passing step: simulated raw water was passed at the same pressure and permeate water amount as in the first simulated raw water passing step.
Calcium chloride dehydrate and sodium fluoride were dissolved in pure water at a Ca concentration of 650 mg/L and a F concentration of 70 mg/L to prepare simulated raw water.
In Example 8, as simulated dilute water, RO-treated water in an RO instrument in a wastewater treatment instrument in the development center (commercially available from Kurita Water Industries Ltd.) was used (pH: 5.5)
<Simulated Dilute Water with Scale Inhibitor Added>
In Example 9, a sample obtained by adding 10 mg/L of 2-phosphonobutane-1,2,4-tricarboxylic acid as a scale inhibitor to the simulated dilute water of Example 8 was used.
In Example 10, a sample obtained by additionally adding calcium chloride dehydrate and sodium fluoride to the simulated dilute water of Example 9 so that the concentrations were as shown in Table 3 was used.
In Comparative Example 3, a sample obtained by additionally adding calcium chloride dehydrate and sodium fluoride to the simulated dilute water of Example 9 so that the concentrations were as shown in Table 3 was used.
In Comparative Example 4, a sample obtained by adjusting the pH of the simulated dilute water of Comparative Example 3 to 3.5 with hydrochloric acid was used.
In Comparative Examples 5 and 6, a sample obtained by additionally adding calcium chloride dehydrate and sodium fluoride to the simulated dilute water of Example 9 so that the concentrations were as shown in Table 3 and adjusting the pH to 3 with hydrochloric acid was used.
The ratio F/F0 of the flux F immediately before the first simulated raw water passing step was completed and the initial flux F0 is shown as “flux ratio before dilute water passing” in Table 4.
The ratio F′/F0 of the flux F′ immediately after the second simulated raw water passing step started and the initial flux F0 is shown as “flux ratio after dilute water passing” in Table 4.
The value of [flux ratio after dilute water passing]/[flux ratio before dilute water passing] is shown as a “recovery ratio” in Table 4.
As shown in Table 4, the dilute water passing step was performed and thus the flux was recovered (increased). In particular, as in Examples 8 and 9, the salt concentration of dilute water decreased and thus the flux was sufficiently recovered.
While the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention.
Priority is claimed on Japanese Patent Application No. 2020-151433, filed Sep. 9, 2020, and Japanese Patent Application No. 2021-005064, filed Jan. 15, 2021, the content of which is incorporated herein by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-151433 | Sep 2020 | JP | national |
| 2021-005064 | Jan 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/032302 | 9/2/2021 | WO |
