MD4103C1 - The method of wastewater treatment from ion fluoride - Google Patents
The method of wastewater treatment from ion fluoride Download PDFInfo
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- MD4103C1 MD4103C1 MDA20100120A MD20100120A MD4103C1 MD 4103 C1 MD4103 C1 MD 4103C1 MD A20100120 A MDA20100120 A MD A20100120A MD 20100120 A MD20100120 A MD 20100120A MD 4103 C1 MD4103 C1 MD 4103C1
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- treatment
- fluoride
- aluminum
- galvanic
- eluate
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- 238000000034 method Methods 0.000 title claims abstract description 35
- -1 ion fluoride Chemical class 0.000 title claims abstract description 28
- 238000004065 wastewater treatment Methods 0.000 title abstract description 5
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 239000010431 corundum Substances 0.000 claims abstract description 7
- 238000011069 regeneration method Methods 0.000 claims abstract description 5
- 239000011780 sodium chloride Substances 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003082 abrasive agent Substances 0.000 claims abstract description 4
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 4
- 230000008929 regeneration Effects 0.000 claims abstract description 4
- 238000004364 calculation method Methods 0.000 claims abstract description 3
- 239000013049 sediment Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000005345 coagulation Methods 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 238000005063 solubilization Methods 0.000 description 4
- 230000007928 solubilization Effects 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical class [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
Description
Invenţia se referă la procedeele de epurare a apelor reziduale şi de protecţie a mediului ambiant, şi anume la un procedeu de epurare a apelor reziduale de ioni de fluorură. The invention relates to waste water purification processes and environmental protection, namely to a fluoride ion waste water purification process.
Procedeul poate fi aplicat în producţiile galvano-chimice, tehnologiile de prelucrare a vaselor/buteliilor de sticlă pentru asigurarea purităţii ecologice a acestor producţii. The process can be applied in galvano-chemical productions, the processing technologies of glass vessels/bottles to ensure the ecological purity of these productions.
Este cunoscut procedeul de epurare a apelor uzate de ioni de fluorură, care include tratarea prin coagulare galvanică cu utilizarea cuplului electrochimic fier sau aluminiu/cocs şi sedimentarea ulterioară a nămolului format [1]. The process of purifying wastewater from fluoride ions is known, which includes treatment by galvanic coagulation using the iron or aluminum/coke electrochemical couple and the subsequent sedimentation of the formed sludge [1].
Însă acest procedeu este puţin eficient la epurarea apelor uzate cu conţinut de fluoruri şi necesită o durată lungă de tratare, până la 24 ore. However, this procedure is not very effective in purifying wastewater containing fluorides and requires a long treatment time, up to 24 hours.
De asemenea, este cunoscut procedeul de eliminare cu reactivi a fluorului prin intermediul hidroxidului de magneziu cu adaos de var [2]. The process of removing fluorine with reagents by means of magnesium hydroxide with the addition of lime is also known [2].
Însă şi acest procedeu este puţin eficient pentru epurarea apelor uzate cu conţinut înalt de poluanţi din cauza consumului înalt de reactivi şi necesităţii de dozare a acestora cu mare precizie, precum şi datorită complexităţii lui şi dificultăţii de operare. But even this process is not very effective for the purification of wastewater with a high content of pollutants due to the high consumption of reagents and the need to dose them with great precision, as well as due to its complexity and the difficulty of operation.
Cea mai apropiată soluţie este procedeul de epurare a apelor uzate de ionii de fluorură, care include tratarea lor prin coagulare galvanică cu utilizarea cuplului electrochimic aluminiu/cărbune activ cu adaos de material inert abraziv şi sedimentarea ulterioară a nămolului format [3]. The closest solution is the fluoride ions wastewater treatment process, which includes their treatment by galvanic coagulation with the use of the aluminum/activated carbon electrochemical couple with the addition of abrasive inert material and the subsequent sedimentation of the formed sludge [3].
Însă acest procedeu este acceptabil pentru eliminarea fluorului din apele naturale cu conţinut limitat al ionilor de fluorură, iar procesul de epurare a apelor uzate cu conţinut înalt de fluor este insuficient de stabil din cauza solubilităţii electrochimice a aluminiului rezultată din susceptibilitatea înaltă la pasivarea suprafeţei electrozilor. Afară de aceasta, conţinutul sporit de ioni de fluorură în apele uzate necesită un consum sporit de aluminiu, care constituie până la 3...5 g la 1 g de fluor eliminat. But this process is acceptable for the removal of fluoride from natural waters with a limited content of fluoride ions, and the process of purifying wastewater with a high content of fluoride is insufficiently stable due to the electrochemical solubility of aluminum resulting from the high susceptibility to the passivation of the electrode surface. Apart from this, the increased content of fluoride ions in wastewater requires an increased consumption of aluminum, which constitutes up to 3...5 g per 1 g of removed fluoride.
Problema pe care o soluţionează invenţia constă în creşterea eficienţei şi a randamentului procesului de eliminare a fluorului din apele uzate cu conţinut înalt de poluanţi, reducerea consumului specific de aluminiu cu ieftinirea concomitentă a procesului din contul utilizării deşeurilor industriale. The problem that the invention solves consists in increasing the efficiency and yield of the process of removing fluorine from wastewater with a high content of pollutants, reducing the specific consumption of aluminum with the simultaneous cheapening of the process due to the use of industrial waste.
Procedeul propus de epurare a apelor uzate de ionii de fluorură prevede tratarea acestora prin coagulare galvanică la acţiunea mecanică abrazivă cu utilizarea unui cuplu galvanic aluminiu/material carbonic cu adaos de corindon în calitate de material abraziv şi separarea ulterioară a sedimentului format, totodată, prealabil tratării, în apele uzate se introduce suplimentar un eluat, care se formează la regenerarea răşinilor schimbătoare de ioni cu clorură de sodiu, după dedurizarea apei. Totodată, eluatul se introduce reieşind din următorul calcul, 2…4 mg-echiv. de cationi de calciu şi magneziu la 1 mg de fluor eliminat, iar procesul de coagulare galvanică se efectuează la un pH de 4,6…5,0 în decurs de 8…10 min. The proposed procedure for the purification of wastewater from fluoride ions provides for their treatment by galvanic coagulation to abrasive mechanical action with the use of an aluminum galvanic couple/carbon material with the addition of corundum as an abrasive material and the subsequent separation of the sediment formed, at the same time, prior to treatment , an eluate is additionally introduced into the waste water, which is formed during the regeneration of ion exchange resins with sodium chloride, after softening the water. At the same time, the eluate is introduced based on the following calculation, 2...4 mg-equiv. of calcium and magnesium cations per 1 mg of eliminated fluorine, and the galvanic coagulation process is carried out at a pH of 4.6...5.0 within 8...10 min.
Rezultatul constă în majorarea eficienţei şi a randamentului procesului de eliminare a fluorului din apele reziduale, precum şi în ieftinirea lui. The result consists in increasing the efficiency and yield of the process of removing fluoride from waste water, as well as making it cheaper.
Rezultatul este condiţionat de faptul, că eluaţii introduşi în apele uzate supuse epurării conţin o cantitate mare de compuşi ai magneziului şi calciului, iar aceasta duce la formarea fluorurilor greu solubile ale acestor metale, iar conţinutul în componenţa eluaţilor a ionilor activi de clor înlesneşte preîntâmpinarea pasivizării suprafeţei particulelor de aluminiu metalic polarizate anodic şi solubilizarea lor eficientă la contactarea cu particulele de cărbune polarizate catodic. The result is conditioned by the fact that the eluates introduced into the wastewater undergoing purification contain a large amount of magnesium and calcium compounds, and this leads to the formation of hardly soluble fluorides of these metals, and the content of the active chlorine ions in the eluates facilitates the prevention of passivation of the surface of the anodically polarized metallic aluminum particles and their efficient solubilization upon contact with the cathodically polarized coal particles.
Compuşii de magneziu şi calciu sunt permanent prezenţi în apele subterane şi condiţionează duritatea lor. Pentru dedurizarea apei se utilizează foarte larg procedeul de cationizare cu sodiu, care se bazează pe absorbţia selectivă a bicarbonaţilor de calciu şi magneziu ale acestor elemente pe cationiţi conform reacţiei: Magnesium and calcium compounds are permanently present in underground waters and condition their hardness. To soften water, the cationization process with sodium is widely used, which is based on the selective absorption of calcium and magnesium bicarbonates of these elements on cations according to the reaction:
2[Cat]Na+Me(HCO3)2 = [Cat]2Me+2NaHCO3, 2[Cat]Na+Me(HCO3)2 = [Cat]2Me+2NaHCO3,
în care Me sunt ionii de Ca2+ şi Mg2+. where Me are Ca2+ and Mg2+ ions.
Regenerarea cationului, după epuizarea capacităţii lor de schimb ionic, se efectuează cu soluţie de 8...10% de sare de bucătărie NaCl: Regeneration of the cation, after the exhaustion of their ion exchange capacity, is carried out with a solution of 8...10% table salt NaCl:
[Cat]2Me + 2NaCl = 2[Cat]Na + MeCl2. [Cat]2Me + 2NaCl = 2[Cat]Na + MeCl2.
În urma acestei operaţii se formează eluaţi, care conţin, în funcţie de componenţa apei brute, 10...15 g/l de ioni de Mg2+ şi 25...30 g/l de ioni de Ca2+ şi, respectiv, 50...60 g/l de ioni liberi de clor. Astfel eluaţii sunt deşeuri neutilizabile de producţie, care se deversează în cantităţi importante în sistemele de canalizare ale CET, cazangeriilor mici şi mari, întreprinderilor industriale, care folosesc apă dedurizată. În acest scop se folosesc şi filtrele de absorbţie cu cărbune activ, care pe măsura epuizării capacităţii lui de absorbţie periodic este schimbat cu cărbune nou, iar cel uzat, din cauza lipsei metodelor de regenerare eficiente, de obicei, este ars. Însă el, de rând cu grafitul concasat, poate fi utilizat eficient în calitate de cuplu galvanic în procesul de coagulare electrochimică. Ajustarea pH-ului apelor uzate tratate în limitele 4,6...5,0 poate fi efectuată cu lapte de var - soluţie de Ca(OH)2 de 3...5%. Following this operation, eluates are formed, which contain, depending on the composition of the raw water, 10...15 g/l of Mg2+ ions and 25...30 g/l of Ca2+ ions and, respectively, 50.. .60 g/l of free chlorine ions. Thus eluates are unusable production waste, which are discharged in large quantities into the sewage systems of CET, small and large boiler houses, industrial enterprises, which use softened water. For this purpose, active carbon absorption filters are also used, which, as its absorption capacity is exhausted, is periodically replaced with new carbon, and the used one, due to the lack of efficient regeneration methods, is usually burned. But it, along with crushed graphite, can be used effectively as a galvanic couple in the electrochemical coagulation process. Adjusting the pH of the treated wastewater within the limits of 4.6...5.0 can be performed with milk of lime - Ca(OH)2 solution of 3...5%.
La introducerea eluaţilor care conţin o cantitate importantă de ioni de Ca şi Mg, aceştia din urmă intră în reacţie cu ioni de fluorură şi la valorile prescrise ale pH-ului, formează fluoruri greu solubile ale Ca şi Mg. În acelaşi timp, produsele de solubilitate ale acestor compuşi în apă sunt insuficiente pentru precipitarea completă a ionilor de fluorură, care devine posibilă la tratarea cu coagularea galvanică ulterioară a apei. When introducing eluates containing a significant amount of Ca and Mg ions, the latter react with fluoride ions and, at the prescribed pH values, form poorly soluble Ca and Mg fluorides. At the same time, the solubility products of these compounds in water are insufficient for the complete precipitation of fluoride ions, which becomes possible when treated with subsequent galvanic coagulation of water.
La trecerea apei prin umplutură şi la contactul aluminiului cu materialul carbonic apare un cuplu galvanic. În acest cuplu galvanic aluminiul, care posedă un potenţial electrochimic standard egal cu SA1 = -1,662 V, serveşte drept anod, pe când materialul carbonic, la care potenţialul electrochimic standard este egal cu Sc = +0,1316 V, este catod. Diferenţa mare de potenţial, care constituie în jur de 2V, asigură solubilizarea activă a aluminiului conform reacţiei: Al°-3e = Al3+. În procesul de hidratare a ionilor de aluminiu se formează hidroxid de aluminiu [Al(OH)3], precum şi un şir de alţi compuşi micşti, care la rândul lor reacţionează cu ionii de fluor, formând complecşi greu solubili de aluminofluoruri încărcaţi pozitiv de tipul {(H2O)5Al(H2O)HF}3+, [(H2O)5AlF]2+. Datorită sarcinii plasate pe suprafaţa exterioară, aceşti complecşi sunt absorbiţi pe suprafaţa hidroxidului de aluminiu, ceea ce asigură efectul de epurare a apei de fluor. When the water passes through the filling and when the aluminum comes into contact with the carbon material, a galvanic couple appears. In this galvanic couple, aluminum, which has a standard electrochemical potential equal to SA1 = -1.662 V, serves as the anode, while the carbon material, with a standard electrochemical potential equal to Sc = +0.1316 V, is the cathode. The large potential difference, which is around 2V, ensures the active solubilization of aluminum according to the reaction: Al°-3e = Al3+. In the process of hydration of aluminum ions, aluminum hydroxide [Al(OH)3] is formed, as well as a series of other small compounds, which in turn react with fluoride ions, forming poorly soluble complexes of positively charged aluminofluorides of the type {(H2O)5Al(H2O)HF}3+, [(H2O)5AlF]2+. Due to the charge placed on the outer surface, these complexes are absorbed on the surface of the aluminum hydroxide, which ensures the effect of purifying the water of fluoride.
Activarea suprafeţei aluminiului lichidează efectul specific de pasivizare a metalului şi majorează stabilitatea procesului de solubilizare galvano-chimică a aluminiului şi, respectiv, de defluorizare a apei prin impactul următorilor factori: The activation of the aluminum surface eliminates the specific passivation effect of the metal and increases the stability of the process of galvano-chemical solubilization of aluminum and, respectively, of water defluoridation through the impact of the following factors:
- activarea suprafeţei aluminiului, pentru solubilizarea şi dizolvarea electrochimică, datorită prezenţei ionilor de clor în componenţa eluaţilor introduşi proveniţi de la procesele de dedurizare a apei prin schimb de ioni; - activation of the aluminum surface, for solubilization and electrochemical dissolution, due to the presence of chlorine ions in the composition of the eluates introduced from the water softening processes through ion exchange;
- acţiunea mecanico-abrazivă a particulelor solide dispersate de corindon, care posedă proprietăţi abrazive, ceea ce contribuie la activarea mecanică a suprafeţei aluminiului datorită înlăturării de pe suprafaţa sa a compuşilor oxizi şi hidroxizi la agitarea umpluturii în timpul rotirii tamburului coagulatorului galvanic. - the mechanical-abrasive action of the solid particles dispersed by corundum, which possess abrasive properties, which contributes to the mechanical activation of the aluminum surface due to the removal of oxide and hydroxide compounds from its surface when the filling is stirred during the rotation of the galvanic coagulator drum.
Prezenţa în umplutură a cărbunele activ, care este un adsorbant natural, contribuie la adsorbţia compuşilor de fluorură de Mg şi Ca formaţi, precum şi a complecşilor aluminohidrofluoruraţi. The presence of active carbon in the filling, which is a natural adsorbent, contributes to the adsorption of the Mg and Ca fluoride compounds formed, as well as the aluminohydrofluorinated complexes.
O astfel de acţiune sumară a componentelor duce la epurarea eficientă a apelor uzate. În calitate de sursă a ionilor de aluminiu în acest procedeu se utilizează deşeuri ale aliajului de AOO, AO, D16, iar în calitate de material carbonic poate fi utilizat cărbune activ de marca BAU, ARB, ARA, ARB, precum şi grafit dispersat cu diametrul particulelor de 0,5...1,0 mm. Such a summary action of the components leads to the efficient purification of waste water. As a source of aluminum ions in this process, AOO, AO, D16 alloy waste is used, and as a carbonaceous material, BAU, ARB, ARA, ARB brand activated carbon can be used, as well as dispersed graphite with the diameter particles of 0.5...1.0 mm.
În calitate de material abraziv poate fi utilizat corindon sintetic, cu diametrul particulelor de 0,5...1,0 mm, obţinut industrial prin încălzirea amestecului de oxid de aluminiu sau a bauxitei cu cărbune în cuptorul electric cu arc, sau discuri de rectificat din corindon concasate cu dimensiunile particulelor de 1,0...3,0 mm. Synthetic corundum, with a particle diameter of 0.5...1.0 mm, obtained industrially by heating the mixture of aluminum oxide or bauxite with coal in the electric arc furnace, or grinding discs can be used as an abrasive material. from crushed corundum with particle sizes of 1.0...3.0 mm.
Procesul de coagulare galvanică poate fi realizat în coagulatoare galvanice cilindrice rotative de tip KB-1 sau alte tipuri, cu debitul apelor uzate de 1,0...1,3 m3/h şi timpul de retenţie în aparat de 5...8 min. Rotaţia cilindrului cu umplutură cu viteza de 10...15 rot/min asigură un schimb de masă a apei tratate şi contactul cuplurilor galvanice cu acţiunea mecanică abrazivă simultană asupra suprafeţei de dizolvare a aluminiului. Procesul de eliminare a fluorului din apele naturale se poate efectua în regim dinamic la un debit al fluxului de apă de 0,3...0,5 dm3/min sau în regim intermitent. După limpezirea apei tratate au loc fazele de sedimentare şi filtrare în mod obişnuit. The galvanic coagulation process can be carried out in rotating cylindrical galvanic coagulators of the KB-1 type or other types, with a wastewater flow rate of 1.0...1.3 m3/h and a retention time in the device of 5...8 min. The rotation of the cylinder with filling at the speed of 10...15 rpm ensures a mass exchange of the treated water and the contact of the galvanic couples with the simultaneous abrasive mechanical action on the aluminum dissolution surface. The process of removing fluoride from natural waters can be carried out in dynamic mode at a water flow rate of 0.3...0.5 dm3/min or in intermittent mode. After the clarification of the treated water, the sedimentation and filtration phases take place in the usual way.
În aşa mod se obţine sporirea eficienţei şi a productivităţii procesului de defluorizare a apelor uzate concomitent cu ieftinirea lui din contul utilizării deşeurilor industriale. In this way, the efficiency and productivity of the waste water defluoridation process is increased simultaneously with its cheapening due to the use of industrial waste.
Exemplu Example
În apele uzate de la mătuirea buteliilor de sticlă ce conţin 78 mg/l de ioni de fluorură s-au introdus eluaţi ai răşinilor schimbătoare de ioni, care conţineau compuşi ai Mg şi Ca în cantitate sumară de 3 mg-echiv/l la 1 mg de fluor eliminat, corectându-se pH-ul până la 5,0, iar mai apoi acestea au fost trecute printr-un coagulator galvanic, încărcat cu deşeuri de talaş de aluminiu marca D16 de la procesele de frezare mecanică amestecate cu grafit dispersat şi cărbune activ cu gradul de dispersare de 0,5...1,0 mm, corindon sub formă de deşeuri abrazive concasate cu fracţia particulelor fărâmiţate de 1,0...3,0 mm în raport de greutate (% mas.): 55 : 25 : 5, la viteza de rotaţie a coagulatorului galvanic de 15 rot/min. După aceasta apa a fost decantată şi filtrată. In the waste water from the washing of glass bottles containing 78 mg/l of fluoride ions, eluates of the ion-exchange resins were introduced, which contained Mg and Ca compounds in a total amount of 3 mg-equiv/l to 1 mg of fluorine removed, correcting the pH to 5.0, and then they were passed through a galvanic coagulator, loaded with D16 aluminum sawdust waste from mechanical milling processes mixed with dispersed graphite and coal active with the degree of dispersion of 0.5...1.0 mm, corundum in the form of crushed abrasive waste with the fraction of crushed particles of 1.0...3.0 mm in weight ratio (% wt.): 55 : 25 : 5, at the rotation speed of the galvanic coagulator of 15 rpm. After this, the water was decanted and filtered.
Determinarea ionilor de fluorură s-a efectuat cu ajutorul electrodului ionselectiv de marca EE-U1 cu electrod de comparaţie de argint clorurat la un pH-metru de marca pH-121. Au fost determinate gradul de epurare a apei de ioni de fluorură, consumul specific de aluminiu pentru 1 mg de fluor eliminat şi consumul de energie electrică. The determination of fluoride ions was carried out using the EE-U1 brand ion-selective electrode with a chlorinated silver comparison electrode to a pH-121 brand pH-meter. The degree of water purification of fluoride ions, the specific consumption of aluminum for 1 mg of fluoride removed and the consumption of electricity were determined.
Rezultatele sunt prezentate în tabel. The results are presented in the table.
Tabel Table
Nr. crt. Indicatorii procesului În condiţiile procedeului propus În condiţiile celei mai apropiate soluţii 1. Consumul specific de aluminiu, g Al/g fluor eliminat 2,5 12,5 2. Timpul de contact al apei tratate în coagulatorul galvanic, min 7 20 3. Gradul de epurare a apei de ionii de fluorură, % 98,5 75,3 No. crt. Process indicators Under the conditions of the proposed process Under the conditions of the closest solution 1. Specific aluminum consumption, g Al/g fluorine removed 2.5 12.5 2. Contact time of the treated water in the galvanic coagulator, min 7 20 3. Degree of water purification of fluoride ions, % 98.5 75.3
Cum se vede din datele prezentate în tabel, procesul de epurare a apelor uzate cu conţinut ridicat de ioni de fluorură în condiţiile propuse se caracterizează printr-un consum specific de aluminiu de 5 ori mai mic în raport cu condiţiile celei mai apropiate soluţii, iar gradul de epurare este cu 23,2% mai mare. Concentraţia reziduală a ionilor de fluorură în apa uzată epurată constituie 1,17 mg/l, ce corespunde cerinţelor pentru deversare în canalizarea publică şi la staţia de epurare biologică. Concomitent a fost redus timpul de retenţie în coagulatorul galvanic a apei tratate aproape de 3 ori, ceea ce permite majorarea productivităţii procesului. As can be seen from the data presented in the table, the wastewater treatment process with a high content of fluoride ions under the proposed conditions is characterized by a specific consumption of aluminum 5 times lower in relation to the conditions of the closest solution, and the degree of treatment is 23.2% higher. The residual concentration of fluoride ions in the treated wastewater is 1.17 mg/l, which corresponds to the requirements for discharge into the public sewer and at the biological treatment station. At the same time, the retention time in the galvanic coagulator of the treated water was reduced almost 3 times, which allows to increase the productivity of the process.
1. Чаитурия В.А., Солженкин П.М. Галванохимические методы очистки техногенных вод. Москва, Академкнига, 2005, с.75 1. Chaituriya V.A., Solzhenkin P.M. Galvanokhimicheskie methods of cleaning technogenic waters. Moscow, Akademkniga, 2005, p.75
2. Кульский А.Л. Теоретические основы и технология кондиционирования воды. Киев, Наукова Думка, 1980, с. 495-496 2. Kulsky A.L. Theoretical foundations and water conditioning technology. Киев, Наукова Думка, 1980, p. 495-496
3. MD 1760 G2 2001.10.31 3. MD 1760 G2 2001.10.31
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB569307A (en) * | 1942-06-24 | 1945-05-17 | Resinous Prod & Chemical Co | Removal of fluorine from water |
| MD1760G2 (en) * | 1999-04-08 | 2002-03-31 | Государственный Университет Молд0 | Process for defluorination of natural water |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB569307A (en) * | 1942-06-24 | 1945-05-17 | Resinous Prod & Chemical Co | Removal of fluorine from water |
| MD1760G2 (en) * | 1999-04-08 | 2002-03-31 | Государственный Университет Молд0 | Process for defluorination of natural water |
Non-Patent Citations (4)
| Title |
|---|
| А.Л. Теоретические основы и технология кондиционирования воды. Киев, Наукова Думка, 1980, с. 495-496 * |
| В.А., Солженкин П.М. Галванохимические методы очистки техногенных вод. Москва, Академкнига, 2005, с.75 * |
| Кульский А.Л. Теоретические основы и технология кондиционирования воды. Киев, Наукова Думка, 1980, с. 495-496 * |
| Чаитурия В.А., Солженкин П.М. Галванохимические методы очистки техногенных вод. Москва, Академкнига, 2005, с.75 * |
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