WO2016191833A1 - Procédé de traitement de déchets industriels contenant du fer - Google Patents

Procédé de traitement de déchets industriels contenant du fer Download PDF

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Publication number
WO2016191833A1
WO2016191833A1 PCT/BG2015/000015 BG2015000015W WO2016191833A1 WO 2016191833 A1 WO2016191833 A1 WO 2016191833A1 BG 2015000015 W BG2015000015 W BG 2015000015W WO 2016191833 A1 WO2016191833 A1 WO 2016191833A1
Authority
WO
WIPO (PCT)
Prior art keywords
iron
oxalic acid
sodium hydroxide
solid phase
industrial waste
Prior art date
Application number
PCT/BG2015/000015
Other languages
English (en)
Inventor
Alexandar Assenov Dragomirov
Lubomir Dimitrov Teoharov
Original Assignee
Alcol Holding Group Ltd.
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 Alcol Holding Group Ltd. filed Critical Alcol Holding Group Ltd.
Priority to PCT/BG2015/000015 priority Critical patent/WO2016191833A1/fr
Publication of WO2016191833A1 publication Critical patent/WO2016191833A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/005—Preliminary treatment of scrap
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for extraction of iron from industrial waste, e.g. middling slime (waste) which is a refuse of the flotation processing of copper and other ore concentrates with a subsequent obtaining of iron oxide compounds - haematite, magnetite (iron(II, III) oxide), hydrated ferric oxide (ferrihydrite) and ferric hydrooxide using leaching with oxalic acid.
  • middling slime waste
  • iron oxide compounds - haematite, magnetite (iron(II, III) oxide), hydrated ferric oxide (ferrihydrite) and ferric hydrooxide using leaching with oxalic acid e.g. middling slime (waste) which is a refuse of the flotation processing of copper and other ore concentrates with a subsequent obtaining of iron oxide compounds - haematite, magnetite (iron(II, III) oxide), hydrated ferric oxide (ferrihydrite) and ferric hydrooxide using leaching
  • EPA 15000806 is disclosed a method of processing industrial waste including remnants of the flotation processing of ore concentrates - fayalite, the methods using leaching with oxalic acid, treatment with a aqueous alkali hydroxide and addition of an aqueous solution of hydrogen peroxide.
  • this method is used a preliminary magnetic separation of the reaction mixture and the used temperature regimes, sequence of added reagents and duration of their stay in the reactor have nothing in common with the stages of the proposed method according to the present invention.
  • the method of the European patent application is not quite suitable for processing of waste with content of heavy and rare earth metals.
  • the purpose of the invented method is to extract iron from middling slime which is a remnant of the flotation treatment of copper or other ore concentrates with a subsequent obtaining of iron oxide compounds (haematite, ferrihydrite or iron hydroxide).
  • the middling waste is characterized as iron containing silicate in which the prevailing phases are fayalite and magnetite but which contains also remnant quantities of other metal compounds in the form of their oxides or silicates as well as a free silicone dioxide.
  • the method of extraction according to the present invention represents a treatment of the middling slime with aqueous solution of sodium hydroxide during which are created defects in the silicate cover of the particles of the ore concentrate with the subsequent leaching of the iron in the form of a complex compound and its sedimentation to hydroxide forms.
  • a complex forming agent oxalic acid which has a low acid aggressiveness and during its use no harmful gases are eliminated into the environment.
  • the present method avoids the drawbacks of the technological methods reflecting the state of the art in the leaching with oxalic acid of iron containing industrial waste.
  • this method is applied a novel approach which activates the properties of the system oxalic acid-iron containing phases and in this manner the leaching is promoted and the purity of the obtained products is increased.
  • the method according to the present invention allows the separation of the impurities of heavy and rare earth metals which is a technological difficulty and is not proposed adequately by the prior art.
  • the oxalic acid has a reducing activity which impedes the depth of leaching of the iron.
  • a solution which reduces significantly the reducing activity of the oxalic acid by providing conditions for formation of a stable iron-oxalate complex with an alkali metal which is a novelty in the existing practice. In this manner are preserved simultaneously its properties as a strong complex-forming agent and its reducing properties are subdued.
  • the proposed method is directed mainly to processing of flotation refuses with high content of fayalite but it is suitable for other iron containing residual products of industrial activity.
  • the starting material is industrial waste containing as major components fayalite, magnetite, free silicone dioxide in amorphous and crystalline forms as well as other metals in lower concentrations with regard to the iron.
  • Accompanying elements usually are copper, calcium, magnesium, zinc, molybdenum and aluminum, and arsenic and lead are present at trace levels. In the industrial waste may be present impurities of other heavy and rare earth metals as well.
  • the method according to the invention comprises also a technological novelty allowing the processing of fayalite with content of heavy and rare earth metals, e.g. molybdenum, causing the separation of such metals from iron using the different solubility of their compounds in the conditions of their common treatment, in contrast to the existing methods of leaching wherein iron and molybdenum are present simultaneously and their separation represents a significant difficulty.
  • the method according to the invention is applicable for all types of fayalite irrespective of the presence of other elements. It affects the silicate matrix and the reaction of the oxalic acid with elements other than iron is a secondary reaction.
  • the method according to the invention is a method for extracting the iron from industrial waste by means of the transformation of its silicate and an additional interaction of accompanying iron oxide compounds to oxalates.
  • the formation of oxalates of other elements contained in the industrial waste is a consequence of their affinity to the oxalic acid as a strong complex- forming agent and the proposed method makes use of the fact that almost all oxalates of the heavy and rare earth metals are insoluble. This guarantees their separation from the iron because according to the method of the invention the iron is converted to a soluble complex salt such as the other elements do not form.
  • Step 1 The iron containing pulp is mixed with 25-40 % of aqueous sodium hydroxide solution and heated at stirring to 35-80°C
  • the concentration of the oxalic acid is from 118 g/1 at 20°C to 36 % by weight at 60°C measured as a dehydrate.
  • a 0.5 - 10% of hydrogen peroxide solution is added continuously so that an oxidative medium is maintained.
  • Step 3 The oxalic acid is added in excess of 5-10% with regard to the quantity which is necessary for the equimolar proportion and is heated at 25 to 80°C for 1 hour and no more hydrogen peroxide is added during the heating.
  • Step 4 The iron containing pulp which is a suspension of the solution of the complex salt and residual solid phase is filtered. The solid phase is separated and the filtrate is precipitated at alkali pH with a 5 to 15% sodium hydroxide solution in a precipitator, at temperature of 60-70°C.
  • Step 5 The obtained precipitate is washed with deionized water to neutral pH and is dried at temperature of 115-160°C.
  • Step 6 The solid phase obtained after the filtration of the sodium ferric oxalate contains residual iron in the form of magnetite but its reactivity is raised because of the destruction of the silicate matrix during the previous steps. This phase is treated with 15-30% sulphuric acid solution in order to extract at maximum the iron therefrom which is transformed into iron sulphate and is processed according to known methods to obtain pure iron.
  • the method comprises an additional Step 7. This step is applied in case of molybdenum content of the fayalite and carried out after the filtering of the sodium ferric oxalate.
  • Step 7 The obtained solid phase is treated with 11-15% sodium hydroxide solution which leads to the transformation of the molybdenum present in the phase as a highly insoluble molybdenum oxalate into the soluble sodium molybdate and the dissolving of the iron is impeded by the alkali medium.
  • the obtained sodium molybdate solution is processed according to known methods to extract the molybdenum in a pure form.
  • Sample 1 Content of total iron expressed as Fe - 29%. Content of free silicone dioxide 14%. Proportion of magnetite to fayalite 47:53.
  • Sample 2 Content of total iron expressed as Fe - 48%. Content of free silicone dioxide 28 %. Proportion of magnetite to fayalite 78:22.
  • Sample 3 Content of total iron expressed as Fe - 36 %. Content of free silicone dioxide 26 %. Proportion of magnetite to fayalite 67:33 and molybdenum content of 4%.
  • Example 2 10.0 g of fayalite (Sample 2) is put in a reactor and is treated with sodium hydroxide under the conditions of Example 1 but the concentration of the oxalic acid is 36% by weight.
  • the quantity of the sodium hydroxide is in an equivalent proportion of 3:1 with regard to the iron and the oxalic acid is in a molar proportion with regard to the sodium hydroxide of 1:1.15.
  • the reaction temperature is raised to 80°C and maintained for 1.5 hours adding 1,5-% of hydrogen peroxide during the treatment, in a weight proportion of 0.5 with regard to the iron.
  • the total iron content in the solid phase is 6.2%.
  • the solid phase is put in a reactor and is treated with a 20% aqueous sulphuric acid at temperature of 80°C for 1 hour with continuous stirring and equivalent proportion of l.T.lof the sulphuric acid to the iron. After cooling to the temperature of the environment the reaction mixture is filtered and the filtrate is evaporated until a crystallization is started at 95°C. Upon cooling crystals of ferric sulphate with iron content of 21% are formed. [0025] The iron content in the residual silicate phase is 0.85%.
  • fayalite (Sample 3) is treated with sodium hydroxide and oxalic acid identically to the methodology of the conditions and manner of Example 2 but without adding a hydrogen peroxide solution during the reaction. After the pulp is cooled to the environment temperature, the adding of 1.5% hydrogen peroxide solution is started, controlling the temperature not to be raised above 25-27°C. The weight proportion of peroxide to the iron is 1:0.3.
  • the filtrate is precipitated at pH 13 and temperature of 60°C to iron hydroxide and after the second filtration and washing the oxalate content expressed as oxalic acid is analyzed.
  • the degree of regeneration of the oxalic acid is 90 molar % and under the conditions of Example 2 this proportion is 86 molar %.
  • the present method does not create new chemical reactions but it uses known chemical interactions applying these purposefully in a non-traditional manner overcoming the drawbacks of the known practice and it has the following differences:

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Le procédé de l'invention consiste à: mélanger et transformer les déchets en pâte à papier avec 25 à 40% d'hydroxyde de sodium aqueux, et chauffer à 35 à 80°C avec agitation; ajouter en continu une solution d'acide oxalique et 0,5 à 10% de peroxyde d'hydrogène jusqu'à l'obtention d'un rapport molaire Na:Fe:C2O4 de 3:1:3; ajouter 5 à 10% d'acide oxalique excédentaire à la quantité déjà ajoutée dudit acide et chauffer à 25 à 80°C pendant 1 heure; filtrer le mélange réactionnel avec séparation de la phase solide et précipitation du filtrat avec 5 à 15% d'hydroxyde de sodium aqueux à 60 à 70°C; laver le précipité de l'étape précédente avec de l'eau déminéralisée et sécher à 115 à 160°C; traiter la phase solide séparée après la troisième étape avec 15 à 30% d'acide sulfurique. Dans un mode de réalisation, le procédé comprend une étape supplémentaire de traitement de la phase solide avec 11 à 15% d'hydroxyde de sodium.
PCT/BG2015/000015 2015-06-04 2015-06-04 Procédé de traitement de déchets industriels contenant du fer WO2016191833A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/BG2015/000015 WO2016191833A1 (fr) 2015-06-04 2015-06-04 Procédé de traitement de déchets industriels contenant du fer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/BG2015/000015 WO2016191833A1 (fr) 2015-06-04 2015-06-04 Procédé de traitement de déchets industriels contenant du fer

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WO2016191833A1 true WO2016191833A1 (fr) 2016-12-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115093320A (zh) * 2022-06-30 2022-09-23 西安建筑科技大学 一种焙烧氰化尾渣浸出液的资源化利用方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012136751A (ja) * 2010-12-27 2012-07-19 Nippon Parkerizing Co Ltd 鉄鋼材料用表面処理液および表面処理方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012136751A (ja) * 2010-12-27 2012-07-19 Nippon Parkerizing Co Ltd 鉄鋼材料用表面処理液および表面処理方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HERNANDEZ ET AL: "Recovery of metals from Cuban nickel tailings by leaching with organic acids followed by precipitation and magnetic separation", JOURNAL OF HAZARDOUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 139, no. 1, 24 November 2006 (2006-11-24), pages 25 - 30, XP005779813, ISSN: 0304-3894, DOI: 10.1016/J.JHAZMAT.2006.03.074 *
LEE ET AL: "Dissolution of iron oxide using oxalic acid", HYDROMETALLURGY, ELSEVIER SCIENTIFIC PUBLISHING CY. AMSTERDAM, NL, vol. 87, no. 3-4, 19 June 2007 (2007-06-19), pages 91 - 99, XP022120187, ISSN: 0304-386X, DOI: 10.1016/J.HYDROMET.2007.02.005 *
PAL A ET AL: "Treatment of iron ore slime for value addition", HYDROMETALLURGY, ELSEVIER SCIENTIFIC PUBLISHING CY. AMSTERDAM, NL, vol. 105, no. 1-2, 1 December 2010 (2010-12-01), pages 30 - 35, XP027486209, ISSN: 0304-386X, [retrieved on 20100715], DOI: 10.1016/J.HYDROMET.2010.07.005 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115093320A (zh) * 2022-06-30 2022-09-23 西安建筑科技大学 一种焙烧氰化尾渣浸出液的资源化利用方法

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