TW201924770A - Reverse osmosis membrane concentrated water treatment method - Google Patents
Reverse osmosis membrane concentrated water treatment method Download PDFInfo
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- TW201924770A TW201924770A TW107132907A TW107132907A TW201924770A TW 201924770 A TW201924770 A TW 201924770A TW 107132907 A TW107132907 A TW 107132907A TW 107132907 A TW107132907 A TW 107132907A TW 201924770 A TW201924770 A TW 201924770A
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- 239000012528 membrane Substances 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005341 cation exchange Methods 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000909 electrodialysis Methods 0.000 claims abstract description 8
- 239000002455 scale inhibitor Substances 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- 238000011033 desalting Methods 0.000 claims description 13
- 239000008400 supply water Substances 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003011 anion exchange membrane Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000005115 demineralization Methods 0.000 description 4
- 230000002328 demineralizing effect Effects 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 238000001728 nano-filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000003657 drainage water Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- -1 sodium Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000002349 well water Substances 0.000 description 2
- 235000020681 well water Nutrition 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000000262 chemical ionisation mass spectrometry Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/463—Apparatus therefor comprising the membrane sequence AC or CA, where C is a cation exchange membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/54—Controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
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- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Urology & Nephrology (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- Nanotechnology (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
本發明係關於逆滲透膜之濃縮水處理方法，特別是把藉由使用逆滲透膜之水處理所產生的濃縮水使用離子交換膜進行處理的方法。The present invention relates to a concentrated water treatment method for a reverse osmosis membrane, and more particularly to a method of treating concentrated water produced by water treatment using a reverse osmosis membrane using an ion exchange membrane.
有把藉由逆滲透膜處理河川水、井水、自來水、工業用水、排水回收水等水分離為脫鹽水與濃縮水的場合所產生的濃縮水進而加以濃縮，或者濃縮、脫水使固型化之技術。Condensed water produced by separating water such as river water, well water, tap water, industrial water, and drainage water by reverse osmosis membrane into desalted water and concentrated water, and then concentrated, or concentrated, dehydrated to solidify Technology.
作為濃縮逆滲透膜的濃縮水之技術，可以舉出蒸發法、逆滲透膜/奈米過濾膜法、電氣透析法(參見專利文獻1之0002～0006段)。蒸發法伴隨著相變化，所以能量消耗很大。另一方面，逆滲透膜/奈米過濾膜法或電氣透析法為節能技術。Examples of the technique of concentrating water for concentrating the reverse osmosis membrane include an evaporation method, a reverse osmosis membrane/nanofiltration membrane method, and an electrodialysis method (see paragraphs 0002 to 0006 of Patent Document 1). The evaporation method is accompanied by a phase change, so the energy consumption is large. On the other hand, the reverse osmosis membrane/nanofiltration membrane method or the electrodialysis method is an energy saving technique.
在逆滲透膜/奈米過濾膜法，鈣那樣的2價離子阻止率比鈉那樣的1價離子還要高，所以2價離子容易濃縮。在電氣透析法也是鈣那樣的2價離子移動度比鈉那樣的1價離子還要大，所以2價離子容易濃縮。濃縮鈣離子濃度高的原水會產生水垢，產生附著於逆滲透膜/奈米過濾膜或電氣透析膜而使性能降低之問題。In the reverse osmosis membrane/nanofiltration membrane method, the divalent ion blocking rate such as calcium is higher than that of monovalent ions such as sodium, so that divalent ions are easily concentrated. In the electrodialysis method, the divalent ion mobility such as calcium is larger than that of monovalent ions such as sodium, and thus the divalent ions are easily concentrated. Concentrated raw water having a high concentration of calcium ions generates scale and causes problems of adhesion to a reverse osmosis membrane/nanofiltration membrane or an electrical dialysis membrane to lower the performance.
為了抑制濃縮室之鈣離子濃度上升，現行方式是於製鹽工序等作為電氣透析膜使用1價選擇性陽離子交換膜來處理海水(非專利文獻1)。In order to suppress an increase in the calcium ion concentration in the concentrating compartment, the present invention is to treat seawater using a monovalent selective cation exchange membrane as an electrical dialysis membrane in a salt-making process or the like (Non-Patent Document 1).
[專利文獻1] 日本特開平11-262738號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-262738
[非專利文獻1] 花田，鍵山，大村，J.ION Exhanege、Vol.16,No.3,153-156(2005)[Non-Patent Document 1] Hanada, Kanayama, Omura, J. ION Exhanege, Vol. 16, No. 3, 153-156 (2005)
本發明之目的在於提供可以安定地電氣透析處理逆滲透膜的濃縮水之逆滲透膜之濃縮水處理方法。SUMMARY OF THE INVENTION An object of the present invention is to provide a concentrated water treatment method for a reverse osmosis membrane which can stably dialysis a concentrated water of a reverse osmosis membrane.
本發明之逆滲透膜之濃縮水處理方法，係藉由電氣透析處理逆滲透膜之濃縮水之方法，特徵為：陽離子交換膜之一部分或全部使用1價選擇性陽離子交換膜。The concentrated water treatment method of the reverse osmosis membrane of the present invention is a method of treating concentrated water of a reverse osmosis membrane by electrodialysis, characterized in that a part or all of the cation exchange membrane is a monovalent selective cation exchange membrane.
在本發明之一態樣，逆滲透膜之濃縮水中的鈣濃度為2mM以上。In one aspect of the invention, the concentration of calcium in the concentrated water of the reverse osmosis membrane is 2 mM or more.
在本發明之一態樣，使電氣透析之濃縮室的流速比脫鹽室之流速更高。In one aspect of the invention, the flow rate of the concentrating chamber for electrical dialysis is higher than the flow rate for the desalting chamber.
在本發明之一態樣，於往濃縮室之供給水添加鹽酸、硫酸及硝酸之中的至少一種。In one aspect of the invention, at least one of hydrochloric acid, sulfuric acid and nitric acid is added to the supply water to the concentration chamber.
在本發明之一態樣，於往濃縮室之供給水添加水垢抑制劑。In one aspect of the invention, a scale inhibitor is added to the feed water to the concentrating compartment.
在本發明之一態樣，水垢抑制劑具有磷酸基或磺酸基。 [發明之效果]In one aspect of the invention, the scale inhibitor has a phosphate or sulfonate group. [Effects of the Invention]
在本發明之逆滲透膜之濃縮水處理方法，使至少一部分之陽離子交換膜為1價選擇性陽離子交換膜，所以往濃縮室之鈣離子、鎂離子等多價陽離子之移動被抑制，在濃縮室之水垢生成受到抑制。藉此，可以安定地電氣透析處理鈣等濃度高之逆滲透膜濃縮水。In the concentrated water treatment method of the reverse osmosis membrane of the present invention, at least a part of the cation exchange membrane is a monovalent selective cation exchange membrane, and the movement of polyvalent cations such as calcium ions and magnesium ions in the conventional concentration chamber is suppressed, and concentration is performed. Scale formation in the chamber is inhibited. Thereby, the reverse osmosis membrane concentrated water having a high concentration such as calcium can be safely electrodialyzed.
此外，抑制濃縮室之鈣的濃度極化，使生成的水垢流出，所以對於提高濃縮室之流速也有效。進而，於濃縮室即使鈣濃度增加也抑制水垢的生成，所以酸之添加、水垢抑制劑的添加也有效。Further, since the concentration of calcium in the concentration chamber is suppressed from being polarized and the generated scale is discharged, it is also effective for increasing the flow rate of the concentration chamber. Further, even if the calcium concentration is increased in the concentration chamber, the generation of scale is suppressed, so the addition of an acid and the addition of a scale inhibitor are also effective.
藉由本發明，可以由逆滲透膜之濃縮水，安定地得到進而使離子濃縮之部分濃縮水、與可以轉用於排水或是其他工序之部分脫鹽水。According to the present invention, it is possible to stably obtain a part of the concentrated water which is further concentrated by the ions from the concentrated water of the reverse osmosis membrane, and a part of the desalted water which can be used for drainage or other processes.
以下，進而詳細說明本發明。Hereinafter, the present invention will be described in detail.
在本發明，使用1價選擇性陽離子交換膜處理把河川水、井水、自來水、工業用水、排水回收水等以逆滲透膜進行膜分離處理時所產生的濃縮水。此濃縮水，通常，無機鹽分濃度為0.5～2重量百分比程度，鈣濃度為2mM以上，例如2～20mM程度，有機物濃度以TOC計通常為5～100mg/L程度。In the present invention, concentrated water generated by membrane separation treatment of a reverse osmosis membrane such as river water, well water, tap water, industrial water, and drainage water is treated by using a monovalent selective cation exchange membrane. The concentrated water usually has an inorganic salt concentration of about 0.5 to 2% by weight, a calcium concentration of 2 mM or more, for example, 2 to 20 mM, and an organic concentration of usually 5 to 100 mg/L in terms of TOC.
在本發明，使用1價選擇性陽離子交換膜處理此濃縮水。通常以具備1價選擇性陽離子交換膜之電氣透析裝置進行處理。圖1顯示此電氣透析裝置之適宜的一例。此電氣透析裝置，係在陽極與陰極之間，分別中介著正電極室及雙極膜BPM而設置酸室、陰離子交換膜AM、脫鹽室、第1陽離子交換膜CM、濃縮室、脫鹽室、第2陽離子交換膜CM、鹼室，雙極膜BPM、負電極室。又，陰離子交換膜、脫鹽室、第1陽離子交換膜、濃縮室為反覆單位設置複數個(n個)，第n個反覆單位之濃縮室中介著陰離子交換膜、脫鹽室及第2陽離子交換膜而連接於鹼室的方式設置亦可。In the present invention, this concentrated water is treated with a monovalent selective cation exchange membrane. It is usually treated with an electrodialysis unit having a monovalent selective cation exchange membrane. Figure 1 shows a suitable example of this electrical dialysis device. The electric dialysis device is provided between the anode and the cathode, and is provided with a positive electrode chamber and a bipolar membrane BPM to provide an acid chamber, an anion exchange membrane AM, a desalting chamber, a first cation exchange membrane CM, a concentrating chamber, a desalting chamber, and The second cation exchange membrane CM, the alkali chamber, the bipolar membrane BPM, and the negative electrode chamber. Further, the anion exchange membrane, the desalting compartment, the first cation exchange membrane, and the concentrating compartment are provided in a plurality of (n) repeating units, and the concentrating compartment of the nth reverse unit intercalates the anion exchange membrane, the desalting compartment, and the second cation exchange membrane. The method of connecting to the alkali chamber can also be set.
在此電氣透析裝置，藉由使構成通過脫鹽室內的被處理水中的鹽類(XY)的陰離子X- 及陽離子Y+ 分別通過陰離子交換膜AM、陽離子交換膜CM而在濃縮室內被濃縮，由脫鹽室得到被除去鹽份的脫鹽水，另一方面，由濃縮室得到鹽份濃縮液。In the electric dialysis apparatus, the anion X - and the cation Y + constituting the salt (XY) in the water to be treated which passes through the demineralization chamber are respectively concentrated in the concentration chamber through the anion exchange membrane AM and the cation exchange membrane CM, and are concentrated in the concentration chamber. The demineralization chamber obtains the desalted water from which the salt is removed, and on the other hand, the salt concentrate is obtained from the concentration chamber.
在本發明，於此電氣透析裝置，作為第1陽離子交換膜(第1CM)，使用1價選擇性陽離子交換膜。藉此，脫鹽室內的陽離子之中，1價陽離子優先透過第1陽離子交換膜(第1CM)移動至濃縮室。因此，濃縮室內的2價陽離子特別是鈣離子、鎂離子的濃度上升受到抑制，在濃縮室的水垢生成受到抑制，電氣透析裝置可以跨長期間安定地運作。In the present invention, in the electric dialysis apparatus, a monovalent selective cation exchange membrane is used as the first cation exchange membrane (first CM). Thereby, among the cations in the demineralization chamber, the monovalent cation is preferentially moved to the concentration chamber through the first cation exchange membrane (first CM). Therefore, the increase in the concentration of divalent cations, particularly calcium ions and magnesium ions in the concentrating compartment, is suppressed, scale formation in the concentrating compartment is suppressed, and the electric dialysis apparatus can be stably operated over a long period of time.
提高濃縮室的流速，或者是對濃縮室添加酸或水垢抑制劑亦對於抑制在濃縮室的水垢生成為有效。Increasing the flow rate of the concentrating compartment, or adding an acid or scale inhibitor to the concentrating compartment, is also effective for suppressing scale formation in the concentrating compartment.
具體而言，使濃縮室的流速為脫鹽室的流速的2倍以上，例如2～10倍，特別是3～5倍為適宜。酸以鹽酸、硫酸或硝酸為適宜，以添加後的pH成為1～3程度的方式添加為適宜。水垢抑制劑以具有磷酸基或磺酸基者為適宜。 [實施例]Specifically, the flow rate of the concentration chamber is twice or more the flow rate of the desalting chamber, for example, 2 to 10 times, particularly preferably 3 to 5 times. The acid is preferably hydrochloric acid, sulfuric acid or nitric acid, and is preferably added so that the pH after the addition is about 1 to 3. The scale inhibitor is preferably one having a phosphate group or a sulfonic acid group. [Examples]
以下，說明比較例及實施例。又，在以下之比較例及實施例，作為逆滲透膜濃縮水，使用2.5mM氯化鈣、2.5mM碳酸氫鈉、25mM氯化鈉之水溶液，以鹽酸水溶液與氫氧化鈉水溶液調整至pH7之模擬逆滲透膜濃縮水。此模擬逆滲透膜濃縮水之電導度(電氣傳導度)為360mS/m。Hereinafter, comparative examples and examples will be described. Further, in the following comparative examples and examples, as a reverse osmosis membrane concentrated water, an aqueous solution of 2.5 mM calcium chloride, 2.5 mM sodium hydrogencarbonate, and 25 mM sodium chloride was used, and the aqueous hydrochloric acid solution and the aqueous sodium hydroxide solution were adjusted to pH 7. Simulate reverse osmosis membrane to concentrate water. The electric conductivity (electrical conductivity) of the simulated reverse osmosis membrane concentrated water was 360 mS/m.
[比較例1] 使用圖1所示的膜配列構造之電氣透析裝置進行模擬逆滲透膜濃縮水之處理。[Comparative Example 1] The treatment of the reverse osmosis membrane concentrated water was carried out using an electric dialysis apparatus having the membrane array structure shown in Fig. 1 .
具體而言，作為電氣透析裝置，使用了依雙極膜((股)Astom製造之BP1-E)、陰離子交換膜((股)Astom製造之AHA)、陽離子交換膜((股)Astom製造之CMX)、陰離子交換膜((股)Astom製造之AHA)、陽離子交換膜((股)Astom製造之CMX)、雙極膜((股)Astom製造之BP1-E)之順序層積膜而成的7室(正極室，酸室、脫鹽室、濃縮室、脫鹽室、鹼室、負極室)之電氣透析裝置。Specifically, as an electric dialysis apparatus, a bipolar membrane (BP1-E manufactured by Astom), an anion exchange membrane (AHA manufactured by Astom), and a cation exchange membrane (manufactured by Astom) are used. CMX), anion exchange membrane (AHA manufactured by Astom), cation exchange membrane (CMX manufactured by Astom), and bipolar membrane (BP1-E manufactured by Astom) are sequentially laminated. An electrical dialysis device for the 7-chamber (electrode compartment, acid compartment, desalting compartment, concentration compartment, desalting compartment, alkali compartment, and anode compartment).
於此電氣透析裝置之正、負各電極室以100mL/min之流速使0.5M之氫氧化鈉水溶液通液，於脫鹽室、濃縮室以5mL/min之流速使模擬逆滲透膜濃縮水通液，於酸室、鹼室以5mL/min之流速使25mM之氯化鈉水溶液通液。The positive and negative electrode chambers of the electric dialysis device were passed through a 0.5 M aqueous sodium hydroxide solution at a flow rate of 100 mL/min, and the simulated reverse osmosis membrane was condensed in a desalting chamber and a concentration chamber at a flow rate of 5 mL/min. A 25 mM aqueous solution of sodium chloride was passed through the acid chamber and the alkali chamber at a flow rate of 5 mL/min.
處理為50V之定電壓運作，進行1小時的處理時，直到最初的15分鐘為止來自脫鹽室的處理液之電導度為100mS/m以下，但是其後超過100mS/m，上升到接近250mS/m為止(參照圖2)。此外，於濃縮室看到很多碳酸鈣水垢。When the treatment is performed at a constant voltage of 50 V and the treatment is performed for 1 hour, the conductivity of the treatment liquid from the desalination chamber is 100 mS/m or less until the first 15 minutes, but thereafter exceeds 100 mS/m, and rises to nearly 250 mS/m. So far (see Figure 2). In addition, many calcium carbonate scales were seen in the concentrating compartment.
[實施例1] 除了脫鹽室與濃縮室之間的第1陽離子交換膜(第1CM)改用1價選擇性陽離子交換膜((股)Astom製造之CIMS)以外使用與比較例1為同一構造之電氣透析裝置，以與比較例1相同的條件處理了同一模擬逆滲透膜濃縮水。[Example 1] The same configuration as in Comparative Example 1 was used except that the first cation exchange membrane (first CM) between the desalting compartment and the concentrating compartment was changed to a monovalent selective cation exchange membrane (CIMS manufactured by Astom). In the electric dialysis apparatus, the same simulated reverse osmosis membrane concentrated water was treated under the same conditions as in Comparative Example 1.
結果，如圖2所示，來自脫鹽室的處理液之電導度為100mS/m以下。於濃縮室看到若干碳酸鈣水垢。As a result, as shown in Fig. 2, the electrical conductivity of the treatment liquid from the desalting compartment was 100 mS/m or less. Several calcium carbonate scales were seen in the concentrating compartment.
[實施例2] 除了在濃縮室入口把1M鹽酸以稀釋100倍的方式添加，使濃縮室之流速為15mL/min以外，以與實施例1同樣的條件處理了同一模擬逆滲透膜濃縮水。結果，來自脫鹽室的處理液之電導度在最初的30分鐘為100mS/m以下，其後在100mS/m上升到125mS/m之間(參照圖2)。此外，於濃縮室未見到碳酸鈣之水垢。[Example 2] The same simulated reverse osmosis membrane concentrated water was treated under the same conditions as in Example 1 except that 1 M hydrochloric acid was added at a concentration of 100 times in the concentration at the inlet of the concentration chamber, and the flow rate in the concentration chamber was 15 mL/min. As a result, the electrical conductivity of the treatment liquid from the desalting compartment was 100 mS/m or less in the first 30 minutes, and then increased to 150 mS/m in 100 mS/m (refer to FIG. 2). In addition, no scale of calcium carbonate was observed in the concentrating compartment.
由以上的比較例及實施例，可確認如本發明這樣藉著使用1價選擇性陽離子交換膜，可使來自脫鹽室的處理水質安定，濃縮室之碳酸鈣水垢的生成也可抑制。此外，也可認為藉由對濃縮室添加酸、使濃縮室之流速提高，進而抑制了碳酸鈣水垢的生成。From the above comparative examples and examples, it was confirmed that the treatment of the water quality from the demineralization chamber can be stabilized by using the monovalent selective cation exchange membrane as in the present invention, and the formation of calcium carbonate scale in the concentration chamber can be suppressed. Further, it is considered that the addition of acid to the concentration chamber increases the flow rate of the concentration chamber, thereby suppressing the formation of calcium carbonate scale.
以上使用特定的型態詳細地說明了本發明，但對於所屬技術領域具有通常知識者而言顯然可以在沒有脫離本發明的意圖與範圍的前提下進行種種的變更。 本申請案係根據2017年12月7日提出申請的日本專利申請案特願2017-235319而主張優先權，在此藉由引用而援用其所有內容。The present invention has been described in detail above with reference to the specific embodiments thereof. It is obvious to those skilled in the art that the invention can be variously modified without departing from the spirit and scope of the invention. Priority is claimed on Japanese Patent Application No. 2017-235319, filed on Dec.
圖1係顯示電氣透析裝置之一例之模式剖面圖。 圖2係顯示實施例與比較例的結果之圖。Fig. 1 is a schematic cross-sectional view showing an example of an electric dialysis apparatus. Fig. 2 is a view showing the results of the examples and comparative examples.
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