TWI398412B - Process and apparatus for treating waste liquid containing inorganic salt - Google Patents
Process and apparatus for treating waste liquid containing inorganic salt Download PDFInfo
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- TWI398412B TWI398412B TW98117725A TW98117725A TWI398412B TW I398412 B TWI398412 B TW I398412B TW 98117725 A TW98117725 A TW 98117725A TW 98117725 A TW98117725 A TW 98117725A TW I398412 B TWI398412 B TW I398412B
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- 239000007788 liquid Substances 0.000 title claims description 48
- 239000002699 waste material Substances 0.000 title claims description 45
- 229910017053 inorganic salt Inorganic materials 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 15
- 239000000243 solution Substances 0.000 claims description 42
- 150000003839 salts Chemical class 0.000 claims description 31
- 239000012535 impurity Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 24
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 23
- 238000000909 electrodialysis Methods 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 21
- 238000000926 separation method Methods 0.000 claims description 21
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims 1
- 239000013078 crystal Substances 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000011033 desalting Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
- -1 nitrate ions Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 4
- 229940009827 aluminum acetate Drugs 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 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
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [H+].[H+].[Na+].[O-]S([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
本發明係有關於一種含有無機鹽之廢液之處理方法及裝置，其係用以處理工廠排水或滲出水等含有無機鹽之廢液者。The present invention relates to a method and a device for treating a waste liquid containing an inorganic salt, which are used for treating waste liquid containing inorganic salts such as factory drainage or effluent water.
處理包含有硫酸鈉(芒硝)或氯化鈉等各種無機鹽之廢液之方法迄今已知的是使用電透析裝置而自廢液回收酸及鹼之方法，舉例言知，於專利文獻1中揭示有一種方法，其係在將硫酸鹽之鹼性廢液進行脫鹼處理後供給至離子交換膜電透析裝置，藉此，抑制電透析裝置之陰離子交換膜之劣化。A method of treating a waste liquid containing various inorganic salts such as sodium sulfate (salva) or sodium chloride has hitherto been known as a method of recovering an acid and a base from a waste liquid using an electrodialysis apparatus, and is exemplified in Patent Document 1. There is disclosed a method of supplying an alkaline waste liquid of sulphate to an ion exchange membrane electrodialysis apparatus after de-alkali treatment, thereby suppressing deterioration of an anion exchange membrane of the electrodialysis apparatus.
[專利文獻1]日本專利第3015486號公報[Patent Document 1] Japanese Patent No. 3015486
然而，於專利文獻1中所揭示之處理方法係由於用以將廢液供給至電透析裝置之前處理仍是藉由使用離子交換膜電透析裝置之脫鹼處理來進行，因此會有無法避免於前處理中所使用的離子交換膜劣化之問題。However, the treatment method disclosed in Patent Document 1 is carried out by the de-alkali treatment using the ion exchange membrane electrodialysis apparatus before the waste liquid is supplied to the electrodialysis apparatus, and thus it is unavoidable The problem of deterioration of the ion exchange membrane used in the pretreatment.
又，由於氯離子、硝酸離子、氫氟酸離子等難以藉由習知前處理來去除之雜質，在所回收的硫酸中會混入鹽酸、硝酸、氫氟酸等，且容易變成腐蝕性高的酸，因此，若由維持耐蝕性之觀點來看，則亦具有設備之材料成本或經常成本提高之問題。In addition, it is difficult to remove impurities such as chloride ions, nitrate ions, hydrofluoric acid ions, etc. by conventional pretreatment, and hydrochloric acid, nitric acid, hydrofluoric acid, etc. are mixed in the recovered sulfuric acid, and it is easy to become highly corrosive. Acid, therefore, also has the problem of increasing the material cost or the recurring cost of the equipment from the viewpoint of maintaining corrosion resistance.
故，本發明之目的係提供一種含有無機鹽之廢液之處理方法及裝置，其係可充分地去除包含於含有無機鹽之廢液中的雜質，且以低成本回收高品質的酸及鹼。Therefore, an object of the present invention is to provide a method and an apparatus for treating a waste liquid containing an inorganic salt, which can sufficiently remove impurities contained in a waste liquid containing an inorganic salt, and recover high-quality acid and alkali at low cost. .
本發明之前述目的可藉由下述含有無機鹽之廢液之處理方法來達成，即，包含有：去除雜質步驟，係自含有無機鹽之廢液去除雜質者；及回收步驟，係藉由電透析，將前處理後之廢液分離成酸溶液及鹼溶液而進行回收者，又，前述去除雜質步驟包含有：鹽分離步驟，係將包含於廢液中的無機鹽進行晶析分離者；及溶解步驟，係生成業已分離之無機鹽之溶液者，又，前述回收步驟係對藉由前述溶解步驟所生成之溶液進行電透析。The foregoing object of the present invention can be attained by the following method for treating a waste liquid containing an inorganic salt, that is, comprising: removing an impurity, removing impurities from a waste liquid containing an inorganic salt; and recovering the step by The electrodialysis is carried out by separating the pre-treated waste liquid into an acid solution and an alkali solution for recycling. Further, the step of removing impurities includes: a salt separation step of separating the inorganic salt contained in the waste liquid by crystallization. And a dissolution step of generating a solution of the separated inorganic salt, and the recovery step is performing electrodialysis on the solution formed by the aforementioned dissolution step.
該含有無機鹽之廢液之處理方法宜進一步地包含有濃縮步驟，且該濃縮步驟係將藉由前述鹽分離步驟所生成之濾液蒸發濃縮者，又，前述鹽分離步驟宜包含有將殘留於濃縮後之濾液中的無機鹽進行晶析分離之步驟。再者，前述濃縮步驟宜包含有將業已藉由前述回收步驟分離酸溶液及鹼溶液之稀鹽溶液蒸發濃縮之步驟。The treatment method of the waste liquid containing the inorganic salt preferably further comprises a concentration step, wherein the concentration step is to evaporate the concentrate obtained by the salt separation step, and the salt separation step preferably comprises remaining The inorganic salt in the concentrated filtrate is subjected to a step of crystallization separation. Furthermore, the concentration step preferably includes a step of evaporating and concentrating the dilute salt solution from which the acid solution and the alkali solution have been separated by the aforementioned recovery step.
又，本發明之前述目的可藉由下述含有無機鹽之廢液之處理裝置來達成，即，包含有：去除雜質裝置，係自含有無機鹽之廢液去除雜質者；及電透析裝置，係藉由電透析，將前處理後之廢液分離成酸溶液及鹼溶液而進行回收者，又，前述去除雜質裝置包含有：晶析裝置，係將包含於廢液中的無機鹽析出者；鹽分離裝置，係將業已析出之無機鹽與濾液分離者；溶解槽，係生成業已分離之無機鹽之溶液者；及濃縮裝置，係將藉由前述鹽分離裝置所生成之濾液蒸發濃縮者，又，構成為將藉由前述濃縮裝置所生成之濃縮後之濾液供給至前述晶析裝置。Moreover, the above object of the present invention can be attained by the following treatment apparatus for a waste liquid containing an inorganic salt, that is, an apparatus for removing impurities, which is a substance for removing impurities from a waste liquid containing an inorganic salt; and an electrodialysis apparatus, The apparatus for removing impurities by separating the pre-treated waste liquid into an acid solution and an alkali solution by electrodialysis, and the apparatus for removing impurities includes: a crystallization apparatus for depositing inorganic salt contained in the waste liquid a salt separation device for separating the inorganic salt which has been separated from the filtrate; a dissolution tank for generating a solution of the separated inorganic salt; and a concentration device for evaporating the filtrate obtained by the salt separation device Further, the concentrated filtrate generated by the concentrating device is supplied to the crystallization device.
若藉由本發明，則可提供一種含有無機鹽之廢液之處理方法及裝置，其係可充分地去除包含於含有無機鹽之廢液中的雜質，且以低成本回收高品質的酸及鹼。According to the present invention, it is possible to provide a method and an apparatus for treating a waste liquid containing an inorganic salt, which can sufficiently remove impurities contained in a waste liquid containing an inorganic salt, and recover high-quality acid and alkali at low cost. .
以下參照附圖說明本發明之實施形態。第1圖係顯示有關本發明一實施形態的含有無機鹽之廢液之處理裝置的概略構造圖。該處理裝置1包含有：去除雜質裝置10，係自含有無機鹽之廢液去除雜質者；及電透析裝置20，係藉由電透析，將前處理後之廢液分離成酸溶液及鹼溶液而進行回收者。Embodiments of the present invention will be described below with reference to the drawings. Fig. 1 is a schematic structural view showing a treatment apparatus for a waste liquid containing an inorganic salt according to an embodiment of the present invention. The processing device 1 includes: an impurity removing device 10 for removing impurities from a waste liquid containing an inorganic salt; and an electrodialysis device 20 for separating the pre-treated waste liquid into an acid solution and an alkali solution by electrodialysis. And the recycler.
去除雜質裝置10包含有：前處理裝置11，係具有捕捉包含於廢液中的懸浮物質(SS成分)之過濾器而進行中和或過濾等操作者；晶析裝置12，係將業已通過前處理裝置之廢液進行晶析而析出無機鹽之結晶者；鹽分離裝置13，係將業已析出之無機鹽與濾液分離者；溶解槽14，係生成業已分離之無機鹽之溶液者；及濃縮裝置15，係將藉由鹽分離裝置13所生成之濾液蒸發濃縮者，又，業已藉由濃縮裝置15濃縮之濾液係再度地供給至晶析裝置12。The impurity removal device 10 includes a pretreatment device 11 that has a filter for capturing a suspended substance (SS component) contained in the waste liquid, and is neutralized or filtered; the crystallization device 12 is passed before The waste liquid of the treatment device is crystallized to precipitate crystals of the inorganic salt; the salt separation device 13 separates the precipitated inorganic salt from the filtrate; the dissolution tank 14 is a solution of the separated inorganic salt; and the concentration The apparatus 15 evaporates the concentrate by the filtrate generated by the salt separating apparatus 13, and the filtrate which has been concentrated by the concentrating apparatus 15 is again supplied to the crystallization apparatus 12.
於本實施形態中，晶析裝置12係使用冷卻晶析裝置，且該冷卻晶析裝置係藉由冷卻晶析罐，將所供給的廢液進行冷卻而析出為目標之無機鹽之結晶，然而，只要是析出純度高之結晶的晶析方法即可，舉例言之，可使用蒸發晶析裝置、再結晶裝置等。In the present embodiment, the crystallization apparatus 12 uses a cooling crystallization apparatus which cools the crystallization tank and cools the supplied waste liquid to precipitate a crystal of the target inorganic salt. The crystallization method may be used as long as it is a crystal having a high purity. For example, an evaporation crystallization apparatus, a recrystallization apparatus, or the like can be used.
鹽分離裝置13係構成為自業已析出無機鹽之廢液的漿液將結晶進行離心分離，且無機鹽之結晶係供給至溶解槽14。溶解槽14係將所供給的無機鹽之結晶溶解於水中，以構成所期望之濃度而生成無機鹽之溶液，並供給至電透析裝置20。The salt separation device 13 is configured to centrifugally separate crystals from a slurry in which a waste liquid of an inorganic salt has been precipitated, and the crystals of the inorganic salt are supplied to the dissolution tank 14. The dissolution tank 14 dissolves the crystal of the supplied inorganic salt in water to form a desired concentration to form a solution of the inorganic salt, and supplies it to the electrodialysis device 20.
另一方面，業已藉由鹽分離裝置13分離無機鹽之濾液係供給至濃縮裝置15。濃縮裝置15可使用於減壓下將濾液散佈至加熱流體通過內部之複數傳熱管之表面而使其加熱蒸發的公知蒸發濃縮裝置，並將少量地包含於濾液中的無機鹽濃縮。濃縮後之濾液係再度地供給至晶析裝置12，然而，由於包含有雜質，因此將一部分作成醋酸鋁溶液而排出，且該排出比例可藉由閥開度之調整而設定為所期望之值。On the other hand, the filtrate from which the inorganic salt has been separated by the salt separation device 13 is supplied to the concentration device 15. The concentrating device 15 can be used to diffuse the filtrate under reduced pressure to a known evaporative concentration device that heats and evaporates the surface of the heat transfer tube through the inside of the heat transfer tube, and concentrates a small amount of the inorganic salt contained in the filtrate. The concentrated filtrate is supplied to the crystallization apparatus 12 again. However, since impurities are contained, a part of the filtrate is discharged as an aluminum acetate solution, and the discharge ratio can be set to a desired value by adjusting the valve opening degree. .
電透析裝置20可使用：具有陽離子交換膜、雙極膜及陰離子交換膜之單元於陽極與陰極間複數積層的三室單元方式之雙極膜電透析裝置等公知者，且於藉由陽離子交換膜及陰離子交換膜所形成的脫鹽室導入無機鹽之溶液。又，於藉由陽離子交換膜及雙極膜所形成的鹼室與藉由雙極膜及陰離子交換膜所形成的酸室分別導入水，且自鹼室及酸室分別回收鹼溶液及酸溶液。於脫鹽室中的脫鹽後之稀鹽溶液係供給至濃縮裝置15。As the electrodialysis apparatus 20, a bipolar membrane electrodialysis apparatus having a cation exchange membrane, a bipolar membrane, and an anion exchange membrane in which a unit is stacked in a plurality of layers between an anode and a cathode can be used, and a cation exchange membrane is used. And a desalting chamber formed by the anion exchange membrane is introduced into a solution of an inorganic salt. Further, water is introduced into the alkali chamber formed by the cation exchange membrane and the bipolar membrane, and the acid chamber formed by the bipolar membrane and the anion exchange membrane, and the alkali solution and the acid solution are separately recovered from the alkali chamber and the acid chamber. . The salt solution after desalting in the desalting compartment is supplied to the concentration device 15.
其次，說明具有前述構造的含有無機鹽之廢液之處理裝置1的作用。本實施形態之處理裝置1適合用來處理含有鹽酸、硫酸、氫氟酸、磷酸等強酸與鉀、鈉等鹼金屬或鹼土金屬之無機鹽的工廠排水或滲出水等廢液，以下以含有硫酸鈉(芒硝)作為無機鹽之廢液之處理為例來進行說明。Next, the action of the treatment apparatus 1 having the inorganic salt-containing waste liquid having the above-described configuration will be described. The treatment apparatus 1 of the present embodiment is suitable for treating waste liquids such as factory drainage or effluent water containing a strong acid such as hydrochloric acid, sulfuric acid, hydrofluoric acid or phosphoric acid, and an alkali metal such as potassium or sodium, or an alkaline earth metal. The treatment of sodium (glauber salt) as a waste liquid of an inorganic salt will be described as an example.
業已供給至去除雜質裝置10之廢液係於通過前處理裝置11時去除懸浮物質(SS成分)後，導入晶析裝置12。於晶析裝置12中，利用飽和溶解度或溶解度之溫度依存性依據鹽的不同而不同之情形，而僅將目標之鹽結晶析出，於本實施形態中，乃利用氯化鈉之溶解度之溫度依存性小於含水芒硝者之情形。即，藉由冷卻至供給濃度中的氯化鈉之析出溫度以上、含水芒硝之析出溫度以下，而僅析出含水芒硝。又，其他微量雜質係於溶液側溶解，藉此，可提升結晶純度。依此，析出硫酸鈉之結晶且廢液構成漿液狀，同時該廢液係於鹽分離裝置13中固液分離。The waste liquid supplied to the impurity removing device 10 is introduced into the crystallization device 12 after the suspended matter (SS component) is removed by the pretreatment device 11. In the crystallization apparatus 12, the temperature dependency of the saturated solubility or the solubility differs depending on the salt, and only the target salt crystal is precipitated. In the present embodiment, the temperature dependence of the solubility of sodium chloride is used. The situation is less than that of water-bearing thenards. That is, only the water-containing Glauber's salt is precipitated by cooling to a temperature higher than the precipitation temperature of sodium chloride in the supply concentration and below the precipitation temperature of the aqueous salt water. Further, other trace impurities are dissolved on the solution side, whereby the crystal purity can be improved. According to this, the crystal of sodium sulfate is precipitated and the waste liquid is in the form of a slurry, and the waste liquid is solid-liquid separated in the salt separation device 13.
業已藉由鹽分離裝置13分離之硫酸鈉之結晶係於溶解槽14中溶解於純水中而構成溶液，並供給至電透析裝置20。由於該溶液係經由晶析裝置12及鹽分離裝置13而提高溶解鹽之純度，因此可將所生成之酸溶液及鹼溶液(即，硫酸溶液及苛性鈉溶液)作成高品質者，且可回收業已充分提高濃度之有價值的酸及鹼。又，藉由充分地降低包含於溶液中的氯離子、硝酸離子、氟離子等雜質，可抑制材料腐蝕之問題，並大幅地改善回收設備之期初成本、經常成本，因此酸及鹼的回收效益大。The crystals of sodium sulfate separated by the salt separation device 13 are dissolved in pure water in the dissolution tank 14 to form a solution, and supplied to the electrodialysis device 20. Since the solution improves the purity of the dissolved salt through the crystallization apparatus 12 and the salt separation apparatus 13, the generated acid solution and the alkali solution (that is, the sulfuric acid solution and the caustic soda solution) can be made high quality and can be recovered. The valuable acids and bases have been fully increased in concentration. Further, by sufficiently reducing impurities such as chloride ions, nitrate ions, and fluoride ions contained in the solution, the problem of corrosion of the material can be suppressed, and the initial cost and the frequent cost of the recovery equipment can be greatly improved, so that the recovery efficiency of the acid and the alkali is improved. Big.
另一方面，藉由鹽分離裝置13所生成之濾液係供給至濃縮裝置15而蒸發濃縮後，再度地供給至晶析裝置12，藉此，少量地殘留於濾液中的硫酸鈉會濃縮而於容易析出之狀態下再度地進行晶析，因此可提高電透析裝置20中的酸溶液及鹼溶液之回收率。藉由濃縮裝置15所生成之蒸氣可作成冷凝水而回收。On the other hand, the filtrate produced by the salt separation device 13 is supplied to the concentration device 15 to be evaporated and concentrated, and then supplied again to the crystallization device 12, whereby a small amount of sodium sulfate remaining in the filtrate is concentrated. Since crystallization is performed again in a state where precipitation is easy, the recovery rates of the acid solution and the alkali solution in the electrodialysis apparatus 20 can be improved. The vapor generated by the concentrating device 15 can be recovered as condensed water.
藉由利用濃縮裝置15反覆濃縮濾液，由於雜質亦與硫酸鈉(含水芒硝)同時地濃縮，因此，於藉由鹽分離裝置13所生成之結晶鹽中容易混入雜質，且有所回收的酸、鹼品質降低之虞。此時，連續地進行對晶析裝置12之廢液之供給，並將藉由濃縮裝置15所生成之濃縮液之一部分作成醋酸鋁溶液而朝外部連續地排出，藉此，可抑制供給至晶析裝置12之濃縮液的雜質濃度之增加。醋酸鋁溶液之排出量越多，所回收的酸、鹼品質會越高，但另一方面回收率會降低，因此，宜監測濾液中的雜質濃度等而適當地調整醋酸鋁溶液之排出量。By gradually concentrating the filtrate by the concentrating device 15, since the impurities are simultaneously concentrated with sodium sulfate (aqueous thenardite), impurities are easily mixed in the crystal salt formed by the salt separating device 13, and the recovered acid, The alkali quality is reduced. At this time, the supply of the waste liquid to the crystallization apparatus 12 is continuously performed, and a part of the concentrated liquid produced by the concentrating apparatus 15 is partially formed into an aluminum acetate solution, and is continuously discharged to the outside, whereby supply to the crystal can be suppressed. The increase in the impurity concentration of the concentrate of the analyzer 12. The more the amount of the aluminum acetate solution is discharged, the higher the quality of the recovered acid and alkali, but on the other hand, the recovery rate is lowered. Therefore, it is preferable to appropriately adjust the discharge amount of the aluminum acetate solution by monitoring the impurity concentration in the filtrate.
業已供給至電透析裝置20之硫酸鈉之溶液係於通過脫鹽室時，大部分會作成酸溶液及鹼溶液而回收，然而，於自脫鹽室排出之液中亦會少量地含有硫酸鈉。該稀鹽溶液係與藉由鹽分離裝置13所生成之濾液同時地供給至濃縮裝置15而蒸發濃縮，藉此，可藉由鹽分離裝置13再度地析出硫酸鈉，且可進一步地提高酸及鹼之回收率。The sodium sulfate solution which has been supplied to the electrodialysis device 20 is mostly recovered as an acid solution and an alkali solution when it passes through the desalting compartment, however, sodium sulfate is also contained in a small amount in the liquid discharged from the desalting compartment. The diluted salt solution is supplied to the concentrating device 15 simultaneously with the filtrate generated by the salt separating device 13 to be concentrated by evaporation, whereby the sodium sulfate can be precipitated again by the salt separating device 13, and the acid and the acid can be further improved. Recovery of alkali.
1．．．處理裝置1. . . Processing device
10．．．去除雜質裝置10. . . Removal of impurity devices
11．．．前處理裝置11. . . Pretreatment device
12．．．晶析裝置12. . . Crystallization device
13．．．鹽分離裝置13. . . Salt separation device
14．．．溶解槽14. . . Dissolution tank
15．．．濃縮裝置15. . . Concentrator
20．．．電透析裝置20. . . Electrodialysis unit
第1圖係顯示有關本發明一實施形態的含有無機鹽之廢液之處理裝置的概略構造圖。Fig. 1 is a schematic structural view showing a treatment apparatus for a waste liquid containing an inorganic salt according to an embodiment of the present invention.
1．．．處理裝置1. . . Processing device
10．．．去除雜質裝置10. . . Removal of impurity devices
11．．．前處理裝置11. . . Pretreatment device
12．．．晶析裝置12. . . Crystallization device
13．．．鹽分離裝置13. . . Salt separation device
14．．．溶解槽14. . . Dissolution tank
15．．．濃縮裝置15. . . Concentrator
20．．．電透析裝置20. . . Electrodialysis unit
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04277016A (en) * | 1991-03-01 | 1992-10-02 | Tokuyama Soda Co Ltd | Waste liquid treatment method |
| US5681782A (en) * | 1996-02-28 | 1997-10-28 | Corning Incorporated | Light pink glassware |
| JP2001026418A (en) * | 1999-07-16 | 2001-01-30 | Taiheiyo Cement Corp | Method for recovering industrially useful inorganic material and industrially useful inorganic material recovered by the recovery method |
| JP2004174439A (en) * | 2002-11-28 | 2004-06-24 | Matsushita Environment Airconditioning Eng Co Ltd | Method for treating fluorine-containing waste water and treating apparatus therefor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04277016A (en) * | 1991-03-01 | 1992-10-02 | Tokuyama Soda Co Ltd | Waste liquid treatment method |
| US5681782A (en) * | 1996-02-28 | 1997-10-28 | Corning Incorporated | Light pink glassware |
| JP2001026418A (en) * | 1999-07-16 | 2001-01-30 | Taiheiyo Cement Corp | Method for recovering industrially useful inorganic material and industrially useful inorganic material recovered by the recovery method |
| JP2004174439A (en) * | 2002-11-28 | 2004-06-24 | Matsushita Environment Airconditioning Eng Co Ltd | Method for treating fluorine-containing waste water and treating apparatus therefor |
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