MD129Y - Process for the purification of galvanochemical production sewage waters from ammonium ions - Google Patents
Process for the purification of galvanochemical production sewage waters from ammonium ions Download PDFInfo
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- MD129Y MD129Y MDS20090028A MDS20090028A MD129Y MD 129 Y MD129 Y MD 129Y MD S20090028 A MDS20090028 A MD S20090028A MD S20090028 A MDS20090028 A MD S20090028A MD 129 Y MD129 Y MD 129Y
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- ammonium
- water
- ions
- magnesium
- ammonium ions
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- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 ammonium ions Chemical class 0.000 title claims abstract description 16
- 238000000746 purification Methods 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000003643 water by type Substances 0.000 title description 3
- 239000010865 sewage Substances 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 10
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 9
- 238000009297 electrocoagulation Methods 0.000 claims abstract description 8
- 239000003480 eluent Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000019801 trisodium phosphate Nutrition 0.000 claims abstract description 7
- 238000012824 chemical production Methods 0.000 claims abstract description 6
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- 238000005238 degreasing Methods 0.000 claims abstract description 5
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 4
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 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
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Inventia se refera la un procedeu de epurare a apelor uzate de la productiile galvano-chimice de ioni de amoniu. Procedeul de epurare a apelor uzate de la productiile galvano-chimice de ioni de amoniu include prelucrarea apei cu eluanti, continand ionii de Mg2+ obtinuti la regenerarea rasinilor schimbatoare de ioni utilizate la dedurizarea apei si cu solutiile uzate de la degresare alcalinizata continand trisodiufosfat la raportul masic [NH4+] : [Mg2+] : [PO43-] = 1 : (5,2…5,5) : (9,0…9,5) si pH-ul 8,5…10,0. Dupa care apa se prelucreaza prin electrocoagulare cu electrozi solubili de aluminiu la densitatea anodica a curentului de 0,2 … 0,5 Ŕ/dm2 si se separa prin electroflotare complexul compus din magneziu-amoniu-fosfat.The invention relates to a process for wastewater treatment from galvanic-chemical productions of ammonium ions. The process of wastewater treatment from galvanic-chemical productions of ammonium ions includes water processing with eluents, containing Mg2 + ions obtained at the regeneration of ion exchange resins used for water softening and with the solutions used from alkaline degreasing containing trisodiumphosphate. [NH4 +]: [Mg2 +]: [PO43-] = 1: (5.2 ... 5.5): (9.0 ... 9.5) and pH 8.5 ... 10.0. After that, the water is processed by electrocoagulation with soluble aluminum electrodes at an anodic current density of 0.2 ... 0.5 Ŕ / dm2 and the complex composed of magnesium-ammonium-phosphate is separated by electroflotation.
Description
Invenţia se referă la un procedeu de epurare a apelor uzate de la producţiile galvano-chimice de ioni de amoniu. The invention relates to a process for purifying wastewater from galvano-chemical production of ammonium ions.
Este cunoscut un procedeu de epurare a apelor reziduale de azot amoniacal, care include interacţiunea ionilor de amoniu ce se conţin în apă cu componentele ce conţin magneziu şi ioni fosfaţi cu separarea ulterioară a sedimentului de magneziu-amoniu-fosfat [1]. Acest procedeu este bazat pe extragerea hidroxidului de magneziu la electroliza apei de mare, care a fost adăugată în cantitate de 20% din volumul întreg de apă. Însă la o astfel de electroliză ionii de magneziu se află în stare legată din cauza dizolvării reduse a hidroxidului de magneziu, de aceea eficacitatea acestui procedeu e scăzută. Totodată, aplicarea practică a acestui procedeu este limitată din motivul că apa de mare este inaccesibilă, precum şi din cauza că ea conţine puţin compuşi ai magneziului. A process for the treatment of ammoniacal nitrogen wastewater is known, which includes the interaction of ammonium ions contained in water with magnesium-containing components and phosphate ions with the subsequent separation of the magnesium-ammonium-phosphate sediment [1]. This process is based on the extraction of magnesium hydroxide by electrolysis of seawater, which was added in an amount of 20% of the total volume of water. However, in such electrolysis, magnesium ions are in a bound state due to the low solubility of magnesium hydroxide, therefore the effectiveness of this process is low. At the same time, the practical application of this process is limited due to the inaccessibility of seawater, as well as the fact that it contains few magnesium compounds.
Problema pe care o rezolvă prezenta invenţie constă în majorarea eficacităţii epurării apelor uzate de la producerea galvanică de compuşii azotului, diminuarea cheltuielilor energetice, lărgirea bazei de materie primă şi diminuarea cheltuielilor. The problem solved by the present invention consists in increasing the efficiency of wastewater treatment from the galvanic production of nitrogen compounds, reducing energy costs, broadening the raw material base and reducing costs.
Procedeul de epurare a apelor uzate de la producţiile galvano-chimice de ioni de amoniu include prelucrarea apei cu eluanţi, conţinând ionii de Mg2+ obţinuţi la regenerarea răşinilor schimbătoare de ioni utilizate la dedurizarea apei şi cu soluţiile uzate de la degresare alcalinizată conţinând trisodiufosfat la raportul masic [NH4 +] : [Mg2+] : [PO4 3-] = 1 : (5,2…5,5) : (9,0…9,5) şi pH-ul 8,5…10,0. După care apa se prelucrează prin electrocoagulare cu electrozi solubili de aluminiu la densitatea anodică a curentului de 0,2 … 0,5 A/dm2 şi se separă prin electroflotare complexul compus din magneziu-amoniu-fosfat. The process of wastewater treatment from galvano-chemical production of ammonium ions includes the treatment of water with eluents containing Mg2+ ions obtained during the regeneration of ion exchange resins used for water softening and with spent solutions from alkaline degreasing containing trisodium phosphate at the mass ratio [NH4 +] : [Mg2+] : [PO4 3-] = 1 : (5.2…5.5) : (9.0…9.5) and pH 8.5…10.0. After which the water is processed by electrocoagulation with soluble aluminum electrodes at the anodic current density of 0.2…0.5 A/dm2 and the complex composed of magnesium-ammonium-phosphate is separated by electroflotation.
Rezultatul invenţii constă în majorarea eficacităţii epurării apelor uzate de la producerea galvanică de compuşii azotului, diminuarea cheltuielilor energetice, lărgirea bazei de materie primă şi diminuarea cheltuielilor. The result of the invention consists in increasing the efficiency of wastewater treatment from the galvanic production of nitrogen compounds, reducing energy costs, expanding the raw material base and reducing costs.
Acest rezultat este condiţionat de utilizarea deşeurilor de producţie a eluanţilor de la regenerarea răşinilor schimbătoare de ioni, precum şi posibilitatea de a utiliza în scopul epurării apelor reziduale a soluţiilor uzate de la degresare şi fosfatare cu conţinut majorat de ioni de fosfat, care se folosesc în galvanotehnică, din care cauză dispare necesitatea procurării sărurilor de acid ortofosforic. Aceasta ieftineşte procesul de epurare şi lărgeşte baza de materie primă pentru realizarea lui. Majorarea eficacităţii se datorează utilizării complete a sărurilor de magneziu introduse în formă solubilă, ceea ce diminuează consumul lor pentru formarea precipitatului greu dizolvabil de magneziu-amoniu-fosfat. This result is conditioned by the use of waste from the production of eluents from the regeneration of ion exchange resins, as well as the possibility of using for the purpose of wastewater treatment of waste solutions from degreasing and phosphating with an increased content of phosphate ions, which are used in electroplating, due to which the need to purchase salts of orthophosphoric acid disappears. This makes the purification process cheaper and broadens the raw material base for its implementation. The increase in efficiency is due to the complete use of magnesium salts introduced in soluble form, which reduces their consumption for the formation of a poorly soluble precipitate of magnesium-ammonium-phosphate.
În tehnologia galvanotehnică se utilizează pe larg electroliţii amoniacali pentru zincare, acoperire cu un strat de cadmiu, cu alte tipuri de acoperire electrochimică şi prelucrare a suprafeţelor. În tehnologia de producere a plăcilor sunt utilizate soluţiile amoniacale pentru tratarea selectivă a cuprului din dielectrici. În procesul de spălare a confecţiilor în apele de spălare se pot regăsi de rând cu ionii metalelor grele şi soluţii amoniacale şi ionii de fosfat. În legătură cu aceasta, la prima etapă de epurare a acestor ape reziduale este oportună mai întâi selectarea din apele reziduale a ionilor metalelor grele prin metode electrochimice şi chimice cunoscute. La cea de-a doua etapă are loc epurarea definitivă a apei de ionii de amoniu conform procedeului propus. Prelucrarea prin electrocoagulare a apelor reziduale cu precipitat suspendat de magneziu-amoniu-fosfat facilitează limpezirea mai rapidă a lor şi concomitent, asigură sedimentarea completă a cantităţii remanente de ioni ai metalelor grele şi a altor impurităţi. Prezenţa în apa prelucrară a cantităţilor majorate de ionilor de clor, introduse în eluanţi, facilitează activarea suprafeţelor electrozilor de aluminiu pentru dizolvarea anodică a acestora în procesele de electrocoagulare şi concomitent, majorează electroconductibilitatea apei tratate, ceea ce, respectiv, diminuează tensiunea la electrozi, adică micşorează cheltuielile energetice pentru acest proces. Analogic pot fi tratate şi soluţiile tehnologice ce conţin amoniu şi fosfaţi. In electroplating technology, ammonia electrolytes are widely used for zinc plating, cadmium plating, other types of electrochemical coating and surface treatment. In the technology of plate production, ammonia solutions are used for selective treatment of copper in dielectrics. In the process of washing clothes, ammonia solutions and phosphate ions can often be found in the washing water along with heavy metal ions. In this regard, at the first stage of purification of these wastewaters, it is advisable to first select heavy metal ions from the wastewater by known electrochemical and chemical methods. At the second stage, the final purification of the water from ammonium ions takes place according to the proposed process. Electrocoagulation treatment of wastewater with suspended magnesium-ammonium-phosphate precipitate facilitates their faster clarification and at the same time, ensures complete sedimentation of the remaining amount of heavy metal ions and other impurities. The presence in the processed water of increased amounts of chlorine ions, introduced into the eluents, facilitates the activation of the surfaces of aluminum electrodes for their anodic dissolution in electrocoagulation processes and at the same time, increases the electroconductivity of the treated water, which, respectively, reduces the voltage at the electrodes, i.e. reduces the energy costs for this process. Technological solutions containing ammonium and phosphates can be treated in a similar way.
Compuşii magneziului sunt mereu prezenţi în apele subterane şi arteziene, care împreună cu compuşii calciului determina duritatea apei. Pentru dedurizarea ei se aplică pe larg metoda sodiu-cationării bazată pe absorbţia selectivă a bicarbonaţilor de calciu şi magneziu pe cationit, în particular pentru magneziu conform reacţiei: Magnesium compounds are always present in groundwater and artesian waters, which together with calcium compounds determine the hardness of water. For its softening, the sodium-cationization method based on the selective absorption of calcium and magnesium bicarbonates on cationite, in particular for magnesium according to the reaction:
2[Cat]Na + Mg(HCO3)2 ↔ [Cat]2Mg + 2NaHCO3 2[Cat]Na + Mg(HCO3)2 ↔ [Cat]2Mg + 2NaHCO3
Regenerarea cationitului după uzarea capacităţii sale de schimb se face cu o soluţie de clorură de sodiu: The regeneration of the cation exchanger after its exchange capacity has been used up is done with a sodium chloride solution:
[Cat]2Mg + 2NaCl ↔ 2[Cat]Na + MgCl2. [Cat]2Mg + 2NaCl ↔ 2[Cat]Na + MgCl2.
Reacţii similare au loc şi cu ionii de calciu. Ca rezultat se formează eluanţi care, în funcţie de compoziţia iniţială a apei conţin de la 3 până la 10 g/L de ioni de magneziu sub formă de clorură. Aceşti eluanţi sunt nişte reziduuri neutilizate de către întreprinderi, aruncate în cantităţi mari în sistemele de canalizare de către centralele termoenergetice, cazangeriile mari şi mici şi de către întreprinderile industriale care folosesc apa dedurizată. Similar reactions occur with calcium ions. As a result, eluents are formed which, depending on the initial composition of the water, contain from 3 to 10 g/L of magnesium ions in the form of chloride. These eluents are unused residues from enterprises, dumped in large quantities into the sewage systems by thermal power plants, large and small boiler houses and by industrial enterprises that use softened water.
În urma interacţiunii ionilor de magneziu, de fosfaţi, precum şi a celor de amoniu, în apa tratată se formează un precipitat sub formă de suspensie hiperdispersivă, conform reacţiei generale: Mg2+ + PO4 3- + NH4 + →MgNH4PO4↓ + H2O. Following the interaction of magnesium, phosphate, and ammonium ions, a precipitate is formed in the treated water in the form of a hyperdispersive suspension, according to the general reaction: Mg2+ + PO4 3- + NH4 + →MgNH4PO4↓ + H2O.
Produsul solubilităţii compusului MgNH4PO4 este egal cu 2,5·10-13, şi anume MgNH4PO4 = [Mg2+]·[PO4 3-]·[NH4 +] = 2,5·10-13, ceea ce leagă ionii de amoniu şi ortofosfaţii, într-un compus greu solubil în apă. Un pH optim pentru acest proces este de 8,5…10, atins prin introducerea unei soluţii alcaline ce conţine trinitrofosfat. The solubility product of the compound MgNH4PO4 is equal to 2.5 10-13, namely MgNH4PO4 = [Mg2+] [PO4 3-] [NH4 +] = 2.5 10-13, which binds ammonium ions and orthophosphates, in a poorly water-soluble compound. An optimal pH for this process is 8.5…10, achieved by introducing an alkaline solution containing trinitrophosphate.
Prelucrarea prin electrocoagulare a apelor reziduale cu utilizarea electrozilor din aluminiu facilitează formarea de floculi de hidroxid de aluminiu, care facilitează concentrarea coagulativă a particulelor de magneziu-amoniu-fosfat şi sedimentarea lor mai rapidă. Concomitent, pe particulele astfel formate se absorb multe impurităţi, facilitând astfel curăţirea de ele a apei. Totodată, datorită prezenţei cantităţi majorate de ioni de clor introduşi în apă, este evitată pasivarea suprafeţei electrozilor de aluminiu şi ameliorarea gradului lor de solubilitate. Aceasta majorează electroconductibilitatea apei prelucrate, ceea ce permite realizarea procesului de electroliză la valori mici ale tensiunii la electrozi şi la o densitate a curentului anodic de 0,2…0,5 A/dm2. Electrocoagulation treatment of wastewater using aluminum electrodes facilitates the formation of aluminum hydroxide flocs, which facilitate the coagulative concentration of magnesium-ammonium-phosphate particles and their faster sedimentation. At the same time, many impurities are absorbed onto the particles thus formed, thus facilitating the purification of water from them. At the same time, due to the presence of an increased amount of chlorine ions introduced into the water, passivation of the surface of aluminum electrodes is avoided and their solubility is improved. This increases the electroconductivity of the processed water, which allows the electrolysis process to be carried out at low electrode voltage values and at an anode current density of 0.2…0.5 A/dm2.
Prelucrarea în două etape a apelor reziduale asigură nu doar epurarea de azot amoniacal, ci o tratare completă de metale grele şi alte impurităţi. Datorită conţinutului sedimentului de magneziu-amoniu-fosfat format, ele pot fi utilizate în calitate de îngrăşăminte din grupul II. Magneziu-amoniu-fosfatul este produs special în formă de mono- sau de hexahidrat MgNH4PO4 în calitate de îngrăşăminte minerale, ceea ce face posibilă utilizarea sedimentelor formate pentru aceste scopuri, apa epurată astfel poate fi utilizată repetat în scopuri tehnologice. Two-stage treatment of wastewater provides not only the removal of ammonia nitrogen, but also a complete treatment of heavy metals and other impurities. Due to the content of the formed magnesium-ammonium-phosphate sediment, they can be used as group II fertilizers. Magnesium-ammonium-phosphate is specially produced in the form of mono- or hexahydrate MgNH4PO4 as a mineral fertilizer, which makes it possible to use the formed sediment for these purposes, the water purified in this way can be reused for technological purposes.
Astfel se asigură atingerea scopurilor propuse orientate spre majorarea eficacităţii epurării apelor reziduale de la producerea galvano-chimică de compuşi ai azotului şi fosfatului, diminuarea consumului de energie, lărgirea bazei de materie primă şi ieftinirea procesului. This ensures the achievement of the proposed goals aimed at increasing the effectiveness of wastewater treatment from the galvano-chemical production of nitrogen and phosphate compounds, reducing energy consumption, expanding the raw material base and making the process cheaper.
Exemplu de realizare a procedeului Example of the process
Pentru experienţe au fost utilizate ape reziduale model cu volumul de 1 L în condiţie iniţială, respectiv, 50 şi 100 mg/L ioni de amoniu. Pentru epurarea acestora au fost utilizaţi eluanţii de la procesele de regenerare a răşinilor cu schimb de cationi de la procesele de dedurizare a apei prin cationare cu sodiu cu conţinutul iniţial de clorură de magneziu, Mg2+ şi soluţia uzată de la degresarea alcalină, ce conţine 30 g/L de trifosfat de sodiu sau 17,34 g în recalcul pe ionii de PO4 +3. Soluţiile acestor săruri au fost dozate în apele reziduale respectându-se raportul molar al cantităţii lor în raport cu ionii de NH4 + în apa iniţială, exprimată drept o unitate, care include: [NH4 +] : [MgCl2] : [Na3PO4] = 1 : 5,24 : 9,1, valoarea pH-ului era 9,0. For the experiments, model wastewaters with a volume of 1 L in the initial condition, respectively, 50 and 100 mg/L ammonium ions were used. For their purification, eluents from the regeneration processes of cation exchange resins from the water softening processes by sodium cationization with the initial content of magnesium chloride, Mg2+ and the spent solution from alkaline degreasing, containing 30 g/L of sodium triphosphate or 17.34 g in recalculation on PO4 +3 ions, were used. The solutions of these salts were dosed into the wastewater respecting the molar ratio of their quantity in relation to NH4 + ions in the initial water, expressed as a unit, which includes: [NH4 +] : [MgCl2] : [Na3PO4] = 1 : 5.24 : 9.1, the pH value was 9.0.
Cea de-a doua etapă a procesului de epurare a apelor reziduale a fost realizată prin electrocoagulare cu utilizarea electrozilor solubili de aluminiu la densitatea anodică a curentului de 0,5 A/dm2. The second stage of the wastewater treatment process was performed by electrocoagulation using soluble aluminum electrodes at an anodic current density of 0.5 A/dm2.
Concomitent au fost efectuate experienţe şi conform condiţiilor celei mai apropiate soluţii. At the same time, experiments were also carried out according to the conditions of the closest solution.
Determinarea prin metode chimice a cantităţilor remanente de ioni de amoniu a fost efectuată prin metode standard. Rezultatele experienţelor sunt prezentate în tabel. The determination of the residual amounts of ammonium ions by chemical methods was carried out by standard methods. The results of the experiments are presented in the table.
Procedeul propus asigură atingerea concentraţiei remanente de azot amoniacal în apele tratate în limitele normelor admisibile pentru sare a acestora în bazine deschise, adică de 0,2 mg/L. Totodată, diminuarea consumului de energie se face din contul diminuări consumului de energie pentru procesul de electrocoagulare mai mult decât de 2 ori comparativ cu electroliza apei de mare şi electroflotare, propuse conform celei mai apropiate soluţii. The proposed process ensures that the residual concentration of ammonia nitrogen in the treated waters is within the limits of the permissible norms for their salt in open pools, i.e. 0.2 mg/L. At the same time, the reduction in energy consumption is achieved by reducing the energy consumption for the electrocoagulation process by more than 2 times compared to seawater electrolysis and electroflotation, proposed according to the closest solution.
Tabelul 1 Table 1
Nr. Concen- Traţia iniţială a [NH4 +] în apă, mg/L Reactivi introduşi Raportul componentelor regenerante în apele reziduale, în următorul raport al maselor, [NH4 +]:[MgCl2]: [Na3PO4] Valo- rile pH Indicii de epurare a apei Indicatori electromagnetici ai procesului MgCl2 Na3PO4 Concen- traţia remanentă, [NH4 +] % epurării Densi- tatea curentului, A/dm2 Tensi- unea la electrozi, V Cheltuieli specifice de energie, kW·h/m3 de apă tratată Cantitatea de eluant, ml/L Cantitatea de MgCl2, mg Canti- tatea de soluţie, ml/L Canti- tatea Na3PO4, mg/L Conform condiţiilor propuse 1 50 12,4 262 15,15 455 1 : 5,24 : 9,1 9,0 0,15 99,7 0,3 5 1,5 2 100 24,8 524 30,3 910 1: 5,24 : 9,1 9,0 0,2 99,8 0,3 5 3 100 Conform condiţiilor celei mai apropiate soluţii 4,4 95,6 0,4 8 3,2No. Initial concentration of [NH4 +] in water, mg/L Reagents introduced Ratio of regenerating components in wastewater, in the following mass ratio, [NH4 +]:[MgCl2]: [Na3PO4] pH values Water purification indices Electromagnetic indicators of the process MgCl2 Na3PO4 Residual concentration, [NH4 +] % of purification Current density, A/dm2 Electrode voltage, V Specific energy expenditure, kW h/m3 of treated water Amount of eluant, ml/L Amount of MgCl2, mg Amount of solution, ml/L Amount of Na3PO4, mg/L According to the proposed conditions 1 50 12.4 262 15.15 455 1 : 5.24 : 9.1 9.0 0.15 99.7 0.3 5 1.5 2 100 24.8 524 30.3 910 1: 5.24 : 9.1 9.0 0.2 99.8 0.3 5 3 100 According to the conditions of the closest solution 4.4 95.6 0.4 8 3.2
1. Лукиных Н. А. и др. Методы доочисткии сточных вод. Москва, Стройиздат, 1978, с. 129-130 1. Лукиных Н. A. and others Methods of wastewater treatment. Moscow, Stroyizdat, 1978, p. 129-130
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