WO2010125205A1 - Procédé de fabrication de sulfate de fer à partir de cendres de pyrite - Google Patents

Procédé de fabrication de sulfate de fer à partir de cendres de pyrite Download PDF

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Publication number
WO2010125205A1
WO2010125205A1 PCT/ES2009/070120 ES2009070120W WO2010125205A1 WO 2010125205 A1 WO2010125205 A1 WO 2010125205A1 ES 2009070120 W ES2009070120 W ES 2009070120W WO 2010125205 A1 WO2010125205 A1 WO 2010125205A1
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WO
WIPO (PCT)
Prior art keywords
ferrous sulfate
pyrite
ashes
iron
stage
Prior art date
Application number
PCT/ES2009/070120
Other languages
English (en)
Spanish (es)
Inventor
Stephen Michael Jones
Antonio Daigo San Andres
Original Assignee
Tioxide Europe, 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
Application filed by Tioxide Europe, S.L. filed Critical Tioxide Europe, S.L.
Priority to PCT/ES2009/070120 priority Critical patent/WO2010125205A1/fr
Publication of WO2010125205A1 publication Critical patent/WO2010125205A1/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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/14—Sulfates
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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 object of the present invention relates to the production of ferrous sulfate having as raw material the ashes obtained in the production of sulfuric acid by roasting pyrites.
  • a solution of ferrous sulfate in acidic aqueous medium is first obtained.
  • the dissolution of iron sulfates is reduced to pass all the ions to the ferrous form, using iron scrap.
  • the solid products obtained, heptahydrate or monohydrate have applications in the field of agriculture, contribution of iron to crops; in cement, as a Cr6 + reducer; in water treatment, as primary flocculant; in iron oxide pigment manufacturing or in animal feed, among others.
  • the most widely used ferrous salt is SO 4 Fe • 7H 2 O sulfate, which is commercially known as green or coated vitriol. It is obtained in the form of monoclinic crystals, green in color, by evaporation of an iron solution in dilute sulfuric acid and in Depending on the evaporation conditions, pressure, temperature, ion concentrations, etc., the heptahydrate form or the monohydrate form SO 4 Fe • H 2 O can be precipitated, more difficult to achieve but with an iron content noticeably older
  • the source of the acid solution of ferrous sulfate is the metallurgical industry, in the pickling of ferrous metals by means of sulfuric acid and the titanium dioxide industry, where ilmenite is attacked with sulfuric acid producing a solution of iron sulfates and titanium, from which ferrous sulfate is separated by vacuum crystallization.
  • the Sierra de Huelva (Spain) is historically known as an area rich in metal sulphides and the development of the area has been based on the extraction and use of this mineral to recover the components of these sulphides.
  • the method object of the invention consists in attacking the ashes of pyrite (ferric oxide) with sulfuric acid, to produce an iron sulfate liquor, which once reduced serves as raw material for the manufacture of ferrous sulfate in two forms of hydrate. tion, heptahydrate and monohydrate.
  • the process begins by recovering the pyrite ashes from the old tanks and transporting the mineral to the treatment plant where, first, the ore is dried and ground by ball mills until a smaller particle size is achieved. to 45 microns.
  • the sulfuric acid used can be fresh, with a concentration of 98.5%, or recycled from other stages of the process or from other processes that generate sulfuric acid as a coproduct.
  • the concentration can range from 10% to 98.5%.
  • Different parameters such as times, reagent temperatures, liquid addition sequences, stirring and mixing periods are controlled in order to achieve the highest possible reaction efficiency, around 95%.
  • the reaction product, pasty liquid is dissolved in weak acids or in clean water, obtaining the digestion liquor.
  • the weight ratio of acid / mineral weight can be between 1 and 5 and the reaction temperature is maintained between 5O 0 C and 15O 0 C by means of steam supplying the reaction mass.
  • the digestion liquor is formed by the sulfuric acid that was put in excess to achieve the highest attack efficiency and the soluble sulfates of the metals present in the pyrite ash, mainly ferric sulfate, which must be reduced to obtain the ferrous sulfate.
  • the reduction is carried out using iron scrap, by passing the digestion liquor through the scrap we managed to transform the ferric ion into ferrous while increasing the concentration of iron in the solution called reduced liquor.
  • the reduction of the content of ferric ions is made up to values below 10 grams per liter.
  • the next stage aims to purify that reduced liquor by eliminating the solids present in the solution and which are a consequence of the fact that the efficiency of the attack phase is not 100%.
  • the solids are removed by passing the solution through decanters, where a flocculant is added that agglomerates insoluble particles that are separated from the liquid phase, allowing to obtain a liquor free of insoluble materials.
  • the decanters purges pass through rotary filters in which the solids are destined for other applications outside this process and the liquid obtained is joined with the clean liquor.
  • the clean liquor is pumped into vacuum crystallizers, where by means of steam ejectors a strong vacuum is produced that allows the boiling of the liquor and the consequent evaporation of part of the water of the solution, considerably reducing the temperature and reaching the solubility product of ferrous sulfate heptahydrate according to the phase diagram of the solutions of ferrous sulfate in acidic medium.
  • the temperature of the input solution of sulfates in aqueous acidic medium to crystallization may be between 30 and 70 0 C and the output from 40 to 10 0 C.
  • the crystalline suspension formed here can be sent to a second crystallizer, connected to a heat exchanger that allows its cooling by means of a refrigerating group, and which facilitates the formation of ferrous sulfate heptahydrate crystals.
  • the output current of this second crystallizer is sent to a thickener where, due to gravity, a purge rich in crystals is achieved at the bottom of the thickener, while a clean liquid of solids overflows from the top.
  • the purge of this thickener is fed to centrifuges that separate the crystals from the liquid phase by sieves. This liquid phase joins with the thickener overflow and is part of the diluted acids used in the attack or dissolution phase of pyrite ashes.
  • the process consists in bringing the purified liquor in the decanters to special tanks, with an anti-acid coating and a very slow stirring, where a quantity is added on the liquor determined from concentrated sulfuric acid, in proportions that vary between 1 part of acid and 4 parts of liquor and 3 parts of acid and 4 parts of liquor, and hot precipitation of ferrous sulfate monohydrate occurs.
  • a quantity is added on the liquor determined from concentrated sulfuric acid, in proportions that vary between 1 part of acid and 4 parts of liquor and 3 parts of acid and 4 parts of liquor, and hot precipitation of ferrous sulfate monohydrate occurs.
  • With slow agitation maturation and growth of the monohydrate crystals that separate into spark plug filters occur, in which the solid separated in the filters is dried by means of an air stream inside the filters themselves. spark plugs, obtaining acid filtrates that are used in the attack phase of the mineral and a solid formed mostly by ferrous sulfate monohydrate.
  • ferrous sulfate monohydrate which consists in eliminating the stage of purification of the reduced liquor, so that the process would be to feed the reduced tanks with reduced liquor, where the corresponding amount of Sulfuric acid to produce the precipitation of ferrous sulfate monohydrate and after the growth and maturation of the crystals, the spark plug filters would be fed, separating the liquid phase that would return to the attack of the mineral and the solid phase that would be the ferrous sulfate monohydrate.
  • This monohydrate can be marketed directly or the free acidity that accompanies it can be neutralized, with limestones, dolomites or any other material that reacts with sulfuric acid and that gives us reaction products that either bring some benefit to the product final or contribute inert. Once the product has been neutralized, it can be granulated, palletized or compacted in order to obtain an easier and more stable handling product.
  • the acid will be added in specially coated and thermally insulated tanks, with constant and slow stirring, to favor the formation and growth of ferrous sulfate monohydrate crystals.
  • the product obtained by the above methods and which in its composition contains an amount of iron, in ferrous form, between 15% and 32% of the total weight of the product finally obtained is also object of the present invention.
  • a flocculant is added to the reduced liquor to agglutinate the micro particles of the undigested digestion residues, which are separated by decantation or filtration, leaving us a clear and clean liquor that will enter the crystallization stage.
  • reaction mass After 16 minutes mixture is heated and the reaction is initiated and maintained at 9O 0 C for 180 minutes, after which it stops heating and added 1900 ml of water to dissolve the reaction mass.
  • This digestion liquor is reacted with 91 g of iron scrap, obtaining 3000 ml of reduced liquor, which contains 111 g / 1 of total iron, without the presence of ferric iron.
  • This digestion liquor is reacted with 123 g of iron scrap, obtaining 3100 ml of reduced liquor, which contains 129 g / 1 of total iron, with 3 g / 1 of ferric iron.
  • Water treatment Directly as primary flocculant for wastewater or after its transformation into ferric sulfate for treatment and purification of drinking and wastewater.
  • Manufacturing of pigments As raw material for the manufacture of pigment based on iron oxides, for printer toner.
  • Animal feed As raw material for obtaining products based on iron sulfate suitable for manufacturing compound feed for animal feed
  • Animal feed As a raw material for obtaining products based on iron sulfate from high purity, suitable for manufacturing compound feed for animal feed
  • Granulate is used for:

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

Abstract

L'invention concerne l'obtention d'une dissolution de sulfate de fer, en milieu aqueux acide, au moyen, en tant que matière première, de cendres obtenues dans la production d'acide sulfurique par grillage de pyrites. La dissolution de sulfates de fer est réduite pour faire passer tous les ions sous forme ferrique, au moyen de ferraille. À partir de la dissolution de sulfate de fer, on obtient de l'heptahydrate, solide, par cristallisation à vide ou du monohydrate, également solide, par ajout d'acide sulfurique concentré. Les produits solides obtenus, heptahydrate ou monohydrate, peuvent être utilisés dans le domaine de l'agriculture, pour l'apport de fer aux cultures; dans l'industrie du ciment, en tant que réducteur du Cr6+; dans le traitement des eaux, en tant que floculant primaire; dans la fabrication de pigment d'oxyde de fer; dans l'alimentation animale, etc.
PCT/ES2009/070120 2009-04-27 2009-04-27 Procédé de fabrication de sulfate de fer à partir de cendres de pyrite WO2010125205A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/ES2009/070120 WO2010125205A1 (fr) 2009-04-27 2009-04-27 Procédé de fabrication de sulfate de fer à partir de cendres de pyrite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2009/070120 WO2010125205A1 (fr) 2009-04-27 2009-04-27 Procédé de fabrication de sulfate de fer à partir de cendres de pyrite

Publications (1)

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WO2010125205A1 true WO2010125205A1 (fr) 2010-11-04

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011144927A1 (fr) * 2010-05-17 2011-11-24 Tioxide Europe Limited Monohydrate de sulfate ferreux
CN105906019A (zh) * 2016-06-23 2016-08-31 江门市江海区炜洁净水材料有限公司 一种聚合磷硫酸铁净水剂的制备方法
CN105906018A (zh) * 2016-06-23 2016-08-31 江门市江海区炜洁净水材料有限公司 一种聚合氯化硫酸铁净水剂的制备方法
CN105906020A (zh) * 2016-06-23 2016-08-31 江门市江海区炜洁净水材料有限公司 一种三氯化铁净水剂的制备方法
CN108083346A (zh) * 2017-12-18 2018-05-29 襄阳华虹高科新材料有限公司 一种电池级硫酸亚铁溶液的深度净化方法
CN109133190A (zh) * 2018-08-03 2019-01-04 武钢资源集团有限公司 磁黄铁矿的加工方法
CN112456831A (zh) * 2020-10-13 2021-03-09 唐山冀东水泥外加剂有限责任公司 一种耐高温的水泥六价铬还原剂

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB656142A (en) * 1946-12-09 1951-08-15 Marvin J Udy Improvements in metallurgy
US3053651A (en) * 1958-01-21 1962-09-11 Chemetals Corp Treatment of sulfide minerals
GB1119236A (en) * 1965-06-24 1968-07-10 Chemical Construction Corp A method for the recovery of iron salts and sulphonic acid from spent pickle liquors
CN1114638A (zh) * 1994-07-08 1996-01-10 江兴全 硫酸浸取硫铁矿烧渣生产硫酸亚铁的工艺
JPH11322342A (ja) * 1998-05-15 1999-11-24 Asahi Chem Ind Co Ltd 硫酸第１鉄１水塩の製造法
CN1597537A (zh) * 2004-08-06 2005-03-23 太原理工大学 从赤铁矿生产七水硫酸亚铁工艺
WO2008028244A1 (fr) * 2006-09-06 2008-03-13 Bhp Billiton Innovation Pty Ltd Procédé au sulfate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB656142A (en) * 1946-12-09 1951-08-15 Marvin J Udy Improvements in metallurgy
US3053651A (en) * 1958-01-21 1962-09-11 Chemetals Corp Treatment of sulfide minerals
GB1119236A (en) * 1965-06-24 1968-07-10 Chemical Construction Corp A method for the recovery of iron salts and sulphonic acid from spent pickle liquors
CN1114638A (zh) * 1994-07-08 1996-01-10 江兴全 硫酸浸取硫铁矿烧渣生产硫酸亚铁的工艺
JPH11322342A (ja) * 1998-05-15 1999-11-24 Asahi Chem Ind Co Ltd 硫酸第１鉄１水塩の製造法
CN1597537A (zh) * 2004-08-06 2005-03-23 太原理工大学 从赤铁矿生产七水硫酸亚铁工艺
WO2008028244A1 (fr) * 2006-09-06 2008-03-13 Bhp Billiton Innovation Pty Ltd Procédé au sulfate

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011144927A1 (fr) * 2010-05-17 2011-11-24 Tioxide Europe Limited Monohydrate de sulfate ferreux
CN105906019A (zh) * 2016-06-23 2016-08-31 江门市江海区炜洁净水材料有限公司 一种聚合磷硫酸铁净水剂的制备方法
CN105906018A (zh) * 2016-06-23 2016-08-31 江门市江海区炜洁净水材料有限公司 一种聚合氯化硫酸铁净水剂的制备方法
CN105906020A (zh) * 2016-06-23 2016-08-31 江门市江海区炜洁净水材料有限公司 一种三氯化铁净水剂的制备方法
CN108083346A (zh) * 2017-12-18 2018-05-29 襄阳华虹高科新材料有限公司 一种电池级硫酸亚铁溶液的深度净化方法
CN109133190A (zh) * 2018-08-03 2019-01-04 武钢资源集团有限公司 磁黄铁矿的加工方法
CN109133190B (zh) * 2018-08-03 2020-12-29 武钢资源集团大冶铁矿有限公司 磁黄铁矿的加工方法
CN112456831A (zh) * 2020-10-13 2021-03-09 唐山冀东水泥外加剂有限责任公司 一种耐高温的水泥六价铬还原剂
CN112456831B (zh) * 2020-10-13 2023-10-03 唐山冀东水泥外加剂有限责任公司 一种耐高温的水泥六价铬还原剂

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