WO2014076375A1 - Procédé de recueil de métaux - Google Patents

Procédé de recueil de métaux Download PDF

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Publication number
WO2014076375A1
WO2014076375A1 PCT/FI2013/051079 FI2013051079W WO2014076375A1 WO 2014076375 A1 WO2014076375 A1 WO 2014076375A1 FI 2013051079 W FI2013051079 W FI 2013051079W WO 2014076375 A1 WO2014076375 A1 WO 2014076375A1
Authority
WO
WIPO (PCT)
Prior art keywords
metals
metal
liquid
precipitation
hydroxide
Prior art date
Application number
PCT/FI2013/051079
Other languages
English (en)
Inventor
Vesa Rissanen
Original Assignee
Global Ecoprocess Services Oy
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
Application filed by Global Ecoprocess Services Oy filed Critical Global Ecoprocess Services Oy
Publication of WO2014076375A1 publication Critical patent/WO2014076375A1/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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C02F1/64—Heavy metal compounds of iron or manganese
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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

Definitions

  • the invention relates to a method for recovery of metals as presented in the preamble of the appended claim 1.
  • Liquids are produced in many processes, metals being present in dissolved form in the liquids.
  • Such processes include various types of processes, in which metals in solid form or metal-containing solids are treated.
  • a result is often substances in liquid state which are classified as waste and in which the metals are present in dissolved form, for example in the form of a salt.
  • waste may be formed not only in treatment processes carried out on purpose but also when metals or metal-containing substances come into contact with liquids in another way.
  • the purification 1 of such liquids from metals, many of which (for example heavy metals) are harmful for the health or for the environment, is complicated by their low content or other substances present in the solution.
  • ion exchange has been used, wherein a harmful metal cation is replaced with a harmless cation.
  • such ion exchange applications are expensive.
  • the invention is characterized in that hydroxide is used together with a boron compound for the precipitation of metals.
  • the boron compound can be a suitable hydroxo compound of boron or a compound that contains boron in the form of an oxoanion.
  • An example of the former is boron acids (oxyacids, particularly boric acid H3BO3.
  • An example of the latter is borate salts, particularly borax.
  • Boric acid H3BO3 is the most common acid of boron and it is an inexpensive precipitation chemical which is capable of forming poorly soluble precipitates with metal hydroxides.
  • Borax in turn, is a commonly found form of boron acting in the same way.
  • the precipitate is a borate, to which the metal to be sepa- rated is bound.
  • the method can be used for recovering metals in order to bind the metals which are present in soluble form (ions) into a permanently solid form, for disposal or further utilization of metals.
  • the solution, from which the dis- solved metal is recovered by utilizing precipitation by adding a boron compound can be an aqueous solution, in which the metal has been dissolved as an ion in some conditions. It can be effluent from the processing of metal or metal-containing material, water that contains entrained metals accumulated in other conditions, or process water produced on purpose in processes of dissolving metals, for the recovery of the metal from the process water.
  • Two or more metals are precipitated by first adding a sufficient quantity of a boron compound to the liquid that contains the metals, and then gradually increasing the pH of the liquid by adding an alkaline compound that brings hydroxide ions.
  • the metals are precipitated in the form of borates in the order of formation of their hydroxide precipitates as a function of the pH value. In this way, a given metal / given metals can be left in the liquid by first precipi- tating the metal/metals precipitating at a lower pH in the form of a borate / mixed borate, and by isolating the precipitate from the liquid.
  • the remaining liquid can be processed in another way or the metal/metals can be precipitated from it separately by continuing the pH increase by adding an alkaline compound to a range in which this metal is / these metals are precipitated in the form of borates.
  • all the metals can be precipitated as a mixed borate by increasing the pH by adding an alkaline compound all the way to the range of borate precipitation of the last metal, after which the mixed borate precipitate that contains all the metals to be precipitated with borate is separated from the liquid.
  • the substances that form a permanent precipitate are marked in square brackets.
  • the solution remaining after the precipitate contains sulphuric acid which has many uses. It can be, for example, recirculated for dissolving met- als in acidic conditions.
  • Sulphuric acid can be separated from a solution by means of heat, whereby it evaporates. The heat can be obtained from an exothermic reaction, or if reaction heat alone is not sufficient, the solution can be heated. Underpressure can be utilized in the recovery.
  • the equation is not to be understood as the only possibility, because borates are a very versatile group of salts and they can be present, for example, in various ratios of boron and oxygen and in various quantities of bound water; in addition, there are various ways of notation of these compounds. What is essential is that the metal to be removed is bound to the borate.
  • Manganese can be a divalent metal (a metal that forms a divalent metal ion), for example Cu, Fe, Ni, Co, Mn, Mg, or Zn.
  • the method can be used for recover- ing dissolved valuable metals from process waters and/or effluents of the mining industry in order to separate the metal from the precipitate later on.
  • borax can be used for precipitation.
  • the hydroxide can also be other than sodium hydroxide, because the only important thing is to introduce hydroxide ions to the solution.
  • the alkaline compound can be, for example, calcium hydroxide, if an addition of sodium to the liquid is to be avoided.
  • calcium is capable of precipitating sulphate in the form of calcium sulphate (gypsum precipitate), which is useful if the liquid contains metals in the form of sulphates and the sulphate is to be removed from the liquid.
  • Calcium hydroxide can be used, if the metal to be removed from the liquid by the precipitation method is, for example, sodium itself, in which case the method is particularly suitable for the treatment of sodium-containing effluents and process waters.
  • the sodium can be disposed with the precipitate, or it can be recovered from the precipitate by a separation method.
  • the precipitation can be performed in containers or larger reservoirs (for example various waste tanks and storage reservoirs), into which the hydroxide and the boron compound is introduced.
  • containers or larger reservoirs for example various waste tanks and storage reservoirs
  • the hydroxide and the boron compound is introduced.
  • the method can also be used for recovering other metals, for example other divalent or monovalent, or also trivalent metals in such a way that they will not remain in the solution. It can be used for binding, for example, sodium sulphate from water.
  • the monovalent metal to be recovered can be any alkali metal, that is, sodium, potassium, lithium, or cesium.
  • the invention can also be used for cleaning contaminated solid material, for example by suspending solid material in water, in which the soluble metal salts present in the solid material are thus dissolved, and they can be removed by adding said chemical precipitants. The metals can then be removed from the solution as presented above.
  • the chemical precipitants can be directly admixed to the solid material, and the borate precipitate formed of the metal that was in soluble form in the solid material can be left in the solid material, because no more metal is dissolved. Examples
  • the aim was to provide pure water to be discharged in the nature, and to isolate metal residues and thereby also sulphate in a precipitated bottom product (precipitate) that is easily storable,
  • a precipitated bottom product precipitate
  • Each example describes how the desired end result can be achieved with a correctly adjusted pH value and the metals can be separated alone and/or separately.
  • Chromium-containing effluent is present in a secondary flow as part of a neutralization process by an industrial enterprise whose business is surface plating.
  • the effluent is a concentrate that also contains traces of other dissolved metals, but their total content remains lower than 0.1 % by weight.
  • the concentrate only contains chromium in two different oxidation levels, namely hexavalent and trivalent chromium, dissolved as sulphates in sulphuric acid.
  • the pH of the solution was 1.4.
  • borax was added in a molar ratio of :2 (metal: borax), after which the pH was adjusted with sodium hydroxide to the value of 7.8.
  • the solution was allowed to settle. After the settling, a slightly greenish clear liquid supernatant and a ligand-like bottom precipitate had separated in the concentrate.
  • the separated bottom product consisted of 99.99 % pure chromium borate.
  • the supernatant contained the other metals (Ni, Mg, Mn) of the original solution, because they did not yet precipitate in this pH range.
  • Example 2 An industrial secondary flow consisted of effluent containing 85.0 wt-% of copper, 13.5 wt-% of nickel, and 1.5 wt-% of magnesium, the pH being 1.0. Boric acid was added to the solution at a metal:molar ratio of 1 :2, and the pH was increased with sodium hydroxide to the value of 9.2. The solution was mixed and allowed to settle. After the settling, 100 % copper-nickel mixed borate was separated as a bottom product. Magnesium was still dissolved in the supernatant, because its precipitation had not yet started.
  • a secondary flow relating to disposal in mining industry had been purified of all transition metals but it still included a considerable content of alkali metal sodium bound in sulphate and a minor content of lime from preceding process steps. Because of the salt content, the water could not be discharged in natural water system, in which it causes eutrophication.
  • the water contained 70.6 wt-% of Na and 29.4 wt-% of Ca, the pH being 7.0.
  • boric acid at a molar ratio of metal: boric acid of :2
  • the pH was first reduced to a value of about 4.

Abstract

Dans le cadre d'un procédé de recueil de métaux à partir d'un liquide dans lequel ces derniers sont présents à l'état dissous, au moins un métal est séparé par addition au liquide d'un hydroxyde en même temps que d'un composé de bore, ce qui a pour effet la formation d'un précipité permanent.
PCT/FI2013/051079 2012-11-16 2013-11-18 Procédé de recueil de métaux WO2014076375A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20120381A FI124262B (fi) 2012-11-16 2012-11-16 Menetelmä metallien talteenottamiseksi
FI20120381 2012-11-16

Publications (1)

Publication Number Publication Date
WO2014076375A1 true WO2014076375A1 (fr) 2014-05-22

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FI (1) FI124262B (fr)
WO (1) WO2014076375A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015036658A1 (fr) * 2013-09-12 2015-03-19 Global Ecoprocess Services Oy Procédé pour le traitement de métaux
CN105198125A (zh) * 2015-10-28 2015-12-30 武汉钢铁(集团)公司 处理工业废水中六价铬离子的方法
WO2017153634A1 (fr) * 2016-03-11 2017-09-14 Global Ecoprocess Services Oy Procédé de séparation de métaux
CN108658284A (zh) * 2017-03-31 2018-10-16 上海梅山钢铁股份有限公司 冷轧含铬废水深度处理的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49104100A (fr) * 1973-02-12 1974-10-02
JPH1147713A (ja) * 1997-08-01 1999-02-23 Tsukishima Kikai Co Ltd 焼却灰類の処理方法
JPH1199370A (ja) * 1997-09-29 1999-04-13 Nippon Kayaku Co Ltd 重金属含有廃棄物用処理剤及び重金属含有廃棄物の安定化処理法
US7419604B1 (en) * 2004-12-29 2008-09-02 University Of Kentucky Research Foundation Use of boron compounds to precipitate uranium from water

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49104100A (fr) * 1973-02-12 1974-10-02
JPH1147713A (ja) * 1997-08-01 1999-02-23 Tsukishima Kikai Co Ltd 焼却灰類の処理方法
JPH1199370A (ja) * 1997-09-29 1999-04-13 Nippon Kayaku Co Ltd 重金属含有廃棄物用処理剤及び重金属含有廃棄物の安定化処理法
US7419604B1 (en) * 2004-12-29 2008-09-02 University Of Kentucky Research Foundation Use of boron compounds to precipitate uranium from water

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [o] ACS; 5 June 2013 (2013-06-05), retrieved from STN Database accession no. 1955:27198 *
KHEIFETS V. L. ET AL.: "Composition of sparingly soluble compounds precipitated by alkali from solutions of nickel salts in the presence of boric acid.", ZHURNAL OBSHCHEI KHIMII, vol. 24, 1954, pages 1486 - 1490 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015036658A1 (fr) * 2013-09-12 2015-03-19 Global Ecoprocess Services Oy Procédé pour le traitement de métaux
CN105873644A (zh) * 2013-09-12 2016-08-17 环球生态工艺服务有限公司 金属处理方法
EP3043874A4 (fr) * 2013-09-12 2017-05-17 Global Ecoprocess Services OY Procédé pour le traitement de métaux
EA031327B1 (ru) * 2013-09-12 2018-12-28 Глобал Экопроусесс Сервисез Ой Способ осаждения металлосодержащих отходов
US10214434B2 (en) 2013-09-12 2019-02-26 Global Ecoprocess Services Oy Method for the treatment of metals
CN105198125A (zh) * 2015-10-28 2015-12-30 武汉钢铁(集团)公司 处理工业废水中六价铬离子的方法
WO2017153634A1 (fr) * 2016-03-11 2017-09-14 Global Ecoprocess Services Oy Procédé de séparation de métaux
CN108658284A (zh) * 2017-03-31 2018-10-16 上海梅山钢铁股份有限公司 冷轧含铬废水深度处理的方法

Also Published As

Publication number Publication date
FI20120381A (fi) 2014-05-17
FI124262B (fi) 2014-05-30

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