WO1998013308A1 - Procede de traitement et de decontamination d'eaux acides contenant des metaux dissous et leur conversion en engrais (procede pidra) - Google Patents

Procede de traitement et de decontamination d'eaux acides contenant des metaux dissous et leur conversion en engrais (procede pidra) Download PDF

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Publication number
WO1998013308A1
WO1998013308A1 PCT/ES1997/000231 ES9700231W WO9813308A1 WO 1998013308 A1 WO1998013308 A1 WO 1998013308A1 ES 9700231 W ES9700231 W ES 9700231W WO 9813308 A1 WO9813308 A1 WO 9813308A1
Authority
WO
WIPO (PCT)
Prior art keywords
waters
metals
solution
acid
resin
Prior art date
Application number
PCT/ES1997/000231
Other languages
English (en)
Spanish (es)
Inventor
Manuel Valiente Malmagro
Original Assignee
Tecnologias Zero-Red, S.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from ES09602016A external-priority patent/ES2112804B1/es
Application filed by Tecnologias Zero-Red, S.L. filed Critical Tecnologias Zero-Red, S.L.
Priority to AU43023/97A priority Critical patent/AU4302397A/en
Publication of WO1998013308A1 publication Critical patent/WO1998013308A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/06—Aerobic processes using submerged filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1205—Particular type of activated sludge processes
    • C02F3/1226—Particular type of activated sludge processes comprising an absorbent material suspended in the mixed liquor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention object of the present report refers to an ecologically clean procedure for the integrated treatment and decontamination of acidic waters (Integral Process of Decontamination and Recovery of Acidic Waters (PLDRA Process)) that occur in the spiritual areas , either in exploitation or abandoned deposits, this procedure is also applicable to industrial facilities that produce acid effluents.
  • the process of the invention consists of three stages complementary to each other, such as: a) Selective removal of iron and acidity from the medium by biooxidation of Fe (II) and precipitation with alkalis (Ca (OH) 2 , NaOH, KOH or NH 4 OH) of the compounds of Fe (III). b) Taking advantage of the high sulphate content of mine acid waters for synthesis by ion exchange of K 2 SO 4 or (NH J ⁇ SO ⁇ , free of chlorides that can be used as fertilizers or marketed in other applications. c) Recovery of the metals contained in these waters: Cu 2+ , Al 3+ , Zn 2+ and Mg + .
  • Acid drains from metal sulfide mines constitute one of the most important ecological problems resulting from mining activity.
  • Acid mine waters originate from oxidation of metal sulphides in contact with water and the atmosphere.
  • Fe (II) is oxidized to Fe (III) by oxygen and by the action of bacteria such as Thiobacillus ferrooxidans and Thiobacillus thiooxidans, subsequently hydrolysis of the formed Fe (III) takes place and the subsequent generation of acid.
  • Acid mine waters are characterized by their low pH and high metal ion content and constitute a serious problem for nearby aquifers.
  • the treatment of this type of water is necessary both from an ecological and economic point of view.
  • the most frequently used methods for the treatment of industrial acid effluents with high metal ion content are a) Precipitation.
  • Precipitation is one of the most frequently used methods in industrial acid water treatment processes.
  • the most commonly used agents are alkalis (NaOH, CaCO ?, Ca (OH) 2 , Na 2 CO-, and mixtures thereof), sulphides and phosphates.
  • the main disadvantages of this type of process are '- Incomplete precipitation (especially in the case of soluble hydro-complexes)
  • Losses of solvent and organic reagent are possible both by evaporation and by solubility in the aqueous phase, which given the enormous volumes that are treated, suppose a high economic cost and a potential risk of contamination for e! environment.
  • interfaces are formed that prevent the rapid separation of the organic and aqueous phases c) Liquid membranes.
  • This new separation technique makes it possible to work at the high flows necessary for the treatment of this type of effluent and is suitable for the selective extraction of low metal concentrations.
  • it presents some problems especially related to the stability of the liquid membranes that make this technique inadvisable.
  • the process for the treatment of acidic waters object of the present invention comprises three stages:
  • the compounds of Fe (III) are removed by precipitation (2) separating as sludge (8). This is achieved by raising the pH of the solution to values between 3 and 4, by adding either KOH, K 2 CO 3 , Ca (OH) 2 , NaOH or NH 4 OH, (7) .
  • the second stage consists in taking advantage of the high sulphate content of these waters for the synthesis of K2SO4 or (H ⁇ SO- ,, chloride free by means of the ion exchange technique, products that can be used as fertilizers or marketed for other applications
  • the process is carried out using a cationic exchanger in potassium or ammonium form (3)
  • the passage of acidic water through the resin bed leads to the exchange of potassium or ammonium ions through the metal ions contained in the acidic water, obtaining a solution of K 2 S0 or NH4SO4, pure respectively (l ⁇ ).
  • the last stage consists in the elution of the metal ions retained in the sulfonic resin with a concentrated solution (hereinafter, primary elution solution), either of KC1, of KjSO 4 or of a mixture of both (in the if the sodium or ammonium form of the resin is used, the ammonium will substitute potassium in the chloride and sulfate salts used in the solution of p ⁇ maria elution) (9) and the selective recovery of the metal ions of the acidic water using cationic exchangers weak (carboxylic resin) and chelating resins (4).
  • primary elution solution either of KC1, of KjSO 4 or of a mixture of both (in the if the sodium or ammonium form of the resin is used, the ammonium will substitute potassium in the chloride and sulfate salts used in the solution of p ⁇ maria elution)
  • SUBSTITUTE SHEET (RULE 26) both) (14) in KC1, K 2 SO, medium, or the mixture of both (in the case of having used the ammonium form of the resin, the ammonium will replace potassium in the chloride and sulfate salts of the medium).
  • Magnesium is recovered as Mg (OH) 2 or passes to an additional ion exchange unit for separation along with the calcium remaining in the primary elution solution (5).
  • the elution of resins with H SO 4 (or HCl) allows to obtain liquors of CuSO 4 (1 1), Al 2 (S ⁇ 4) 3 (12) and ZnSO 4 (13), which, in In the case of Cu and Zn and prior adequate conditioning can be subjected to electrolysis to produce electrolytic Cu and Zn.
  • the Mg and Ca metals separated in the ion exchange unit are obtained as a mixture of the corresponding sulfates or chlorides after elution with the selected acid.
  • the spent primary elution solution as a result of the metal recovery stage, has a high potassium (or ammonium) content and a small amount of metal ions such as Mn + that have not been absorbed by the resins.
  • FIGURE 1 Flow chart of the procedure for the treatment of acidic waters.
  • FIGURE 2 Scheme of the arrangement of ion exchange columns for the synthesis of K 2 SO4 (or (NH 4 ) 2 S0 4 ) and the selective recovery of metals.
  • the Fe content of these samples is very high, between 4000 and 9000 ppm.
  • the concentration of Zn 2 " is also high. With cheers between 600 and 1500 ppm.
  • the concentration of Cu 2 * is about 10 times lower, between 60 and 250 ppm.
  • Other metals whose concentration is relatively high are: Al 5" (450 -650 ppm), M 2 (800-900 ppm), Ca 2 * (350-500 ppm) and Mn 2 " (70-100 ppm).
  • the sulfate content varies according to the samples between 18 and 32 g / L.
  • the pH varies between 1.8 and 2.2
  • the content of other metals as well as chlorides is practically negligible, b) Synthesis of K 2 SO 4 or (NEL ⁇ SO. ,, Through the Ionic Exchange Technique It has been used the high sulfate concentration of acidic waters to synthesize
  • the regeneration of the sulfonic resin is carried out with the primary elution solution which, as already described, is a concentrated solution of either KC1, either K 2 SO 4 or one of its mixtures (in the case of using the resin in ammonium form, the ammonium will replace potassium in the primary elution solution), which causes the elution of the metal ions retained in the resin.
  • the primary elution solution which, as already described, is a concentrated solution of either KC1, either K 2 SO 4 or one of its mixtures (in the case of using the resin in ammonium form, the ammonium will replace potassium in the primary elution solution), which causes the elution of the metal ions retained in the resin.
  • a concentrated solution of the different metal ions between 4 and 8 times
  • the wash water is recirculated and used for the preparation of the primary elution solution.
  • the recovery of the different metal ions of the acidic water is carried out using ion exchangers of appropriate selectivity for each case.
  • the carboxylic resin has been highly selective to Al ', + , being very suitable for the recovery of this metal. This selectivity increases dramatically with the increase in temperature of the loading solution, which is a way to achieve greater purity of the recovered aluminum.
  • the resin with iminodiacetic acid has been very selective for Cu 2 * . This resin also allows the recovery of Zn 2+ in the event that Cu 2+ and AT * are previously removed from the solution, since these two metals are preferentially absorbed. d) Integral Treatment of Acid Waters
  • the first stage consists of a pretreatment of acidic waters. This process consists of the biooxidation of Fe (II) by bacteria of the Thiobacillus Ferrooxidans type and subsequent precipitation of Fe (III) compounds by measuring the addition of alkali to a pH between 3 and 4 and adding a suitable flocculant for rapid total precipitation.
  • the next stage consists in the recovery of the different metals eluted from the sulfonic resin in the regeneration stage of said resin. Recovery takes place sequentially using a system of fixed bed columns connected in series (see Fig 2). Each column is tripled (two connected and one in regeneration), so that the process can be developed continuously and the treatment of the solution can be continued while elution and regeneration of the spent resin occurs.
  • Columns 1 and 2 are filter beds to remove suspended fines.
  • the synthesis of K 2 SO 4 (or (NH4) 2 SO 4 ) is carried out in columns 3 and 4 (Lewatit SP1 12) during the charging process with acidic waters.
  • the solution resulting from this process containing virtually pure K SO 4 or (NH4) SO 4 is treated in a reverse osmosis unit to achieve product concentration and a considerable volume of water suitable for irrigation.
  • the separation and recovery of C ⁇ r ⁇ is carried out in columns 5 and 6 (Lewatit TP-207), from the solution obtained during the regeneration process of the resin contained in
  • the removal of residual metal ions in the primary elution solution, after selective recovery of Cu 2+ , Al 3+ , Zn 2+ and Mg 2+ is carried out by precipitation by adjusting the pH between 10 and 12 with alkali appropriate.
  • the precipitate of metal hydroxides removed from the primary elution solution (practically Mn 2+ ) is separated for later recovery or sent to the process head (acid water inlet)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

Procédé de traitement et de décontamination d'eaux acides contenant de métaux dissous et leur conversion en engrais, ce procédé consistant en la combinaison de trois procédés spécifiques; a) élimination sélective du fer et de l'acidité du milieu par biooxydation de Fe (II) et précipitation avec des alcalis (Ca(OH)2, NaOH, KOH ou NH4OH) des composés de Fe (III); b) mise à profit de la teneur élevée en sulfates des eaux acides pour la synthèse, par échange ionique, de K2SO4 ou NH4SO4, exempt de chlorures qui peuvent être utilisés comme engrais ou être commercialisés pour d'autres applications; c) récupération des métaux contenus dans ces eaux: Cu?2+, Al3+, Zn2+ et Mg2+¿. Ce procédé peut s'appliquer aux eaux acides provenant des diverses sources: installation minière active, bassins fluviaux, torrents, lagons, etc., qui, en raison de leur contact avec des masses de minéraux, sont contaminés avec de l'acide sulfurique et des métaux lourds, ainsi que pour des installations industrielles qui produisent des effluents acides (par exemple, l'industrie galvanotechnique).
PCT/ES1997/000231 1996-09-24 1997-09-18 Procede de traitement et de decontamination d'eaux acides contenant des metaux dissous et leur conversion en engrais (procede pidra) WO1998013308A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43023/97A AU4302397A (en) 1996-09-24 1997-09-18 Process for the treatment and decontamination of acid waters which contain dissolved metals and their conversion into fertilizers (pidra process)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ES09602016A ES2112804B1 (es) 1996-09-24 1996-09-24 Procedimiento para el tratamiento y descontaminacion de aguas acidas que contienen metales disueltos y su conversion en fertilizantes.
ESP9602016 1996-09-24
ES9701958A ES2127157B1 (es) 1996-09-24 1997-09-18 Procedimiento para el tratamiento y descontaminacion de aguas acidas que contienen metales disueltos y su conversion en fertilizantes.
ESP9701958 1997-09-18

Publications (1)

Publication Number Publication Date
WO1998013308A1 true WO1998013308A1 (fr) 1998-04-02

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Application Number Title Priority Date Filing Date
PCT/ES1997/000231 WO1998013308A1 (fr) 1996-09-24 1997-09-18 Procede de traitement et de decontamination d'eaux acides contenant des metaux dissous et leur conversion en engrais (procede pidra)

Country Status (3)

Country Link
AU (1) AU4302397A (fr)
ES (1) ES2127157B1 (fr)
WO (1) WO1998013308A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007116247A2 (fr) * 2006-02-14 2007-10-18 Howard, Darryl Procédé de traitement d'effluent
CN104355498A (zh) * 2014-11-13 2015-02-18 国家电网公司 一种去除电镀废水中重金属以及cod的工艺
CN104355497A (zh) * 2014-11-13 2015-02-18 国家电网公司 一种处理电镀废水的方法
CN104445813A (zh) * 2014-11-14 2015-03-25 国家电网公司 一种去除污水中重金属离子和工业cod的制剂
WO2020225522A1 (fr) * 2019-05-03 2020-11-12 Agua Db Ltd Procédé de traitement de l'eau pour générer un produit de fertilisation ou de ferti-irrigation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882018A (en) * 1970-12-04 1975-05-06 Aerojet General Co Process for recovery of minerals from acidic streams
DE4128837A1 (de) * 1991-08-30 1993-03-04 Bitterfeld Wolfen Chemie Verfahren zur entfernung von kupfer und/oder nickel aus waessrigen medien
ES2033744T3 (es) * 1986-07-15 1993-04-01 The Dow Chemical Company Membrana combinada y procedimiento de sorcion para separar selectivamente iones.
ES2086263A1 (es) * 1994-09-13 1996-06-16 Rio Tinto Minera S A Procedimiento para el tratamiento y descontaminacion de aguas acidas de mina.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882018A (en) * 1970-12-04 1975-05-06 Aerojet General Co Process for recovery of minerals from acidic streams
ES2033744T3 (es) * 1986-07-15 1993-04-01 The Dow Chemical Company Membrana combinada y procedimiento de sorcion para separar selectivamente iones.
DE4128837A1 (de) * 1991-08-30 1993-03-04 Bitterfeld Wolfen Chemie Verfahren zur entfernung von kupfer und/oder nickel aus waessrigen medien
ES2086263A1 (es) * 1994-09-13 1996-06-16 Rio Tinto Minera S A Procedimiento para el tratamiento y descontaminacion de aguas acidas de mina.

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007116247A2 (fr) * 2006-02-14 2007-10-18 Howard, Darryl Procédé de traitement d'effluent
WO2007116247A3 (fr) * 2006-02-14 2008-02-28 Facilitating Innovative Res En Procédé de traitement d'effluent
CN104355498A (zh) * 2014-11-13 2015-02-18 国家电网公司 一种去除电镀废水中重金属以及cod的工艺
CN104355497A (zh) * 2014-11-13 2015-02-18 国家电网公司 一种处理电镀废水的方法
CN104445813A (zh) * 2014-11-14 2015-03-25 国家电网公司 一种去除污水中重金属离子和工业cod的制剂
WO2020225522A1 (fr) * 2019-05-03 2020-11-12 Agua Db Ltd Procédé de traitement de l'eau pour générer un produit de fertilisation ou de ferti-irrigation

Also Published As

Publication number Publication date
ES2127157B1 (es) 1999-12-01
AU4302397A (en) 1998-04-17
ES2127157A1 (es) 1999-04-01

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