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WO2010068167A1 - Procédé de fabrication d'un alliage de manganèse - Google Patents

Procédé de fabrication d'un alliage de manganèse Download PDF

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Publication number
WO2010068167A1
WO2010068167A1 PCT/SE2009/051387 SE2009051387W WO2010068167A1 WO 2010068167 A1 WO2010068167 A1 WO 2010068167A1 SE 2009051387 W SE2009051387 W SE 2009051387W WO 2010068167 A1 WO2010068167 A1 WO 2010068167A1
Authority
WO
WIPO (PCT)
Prior art keywords
manganese
mixture
furnace
zinc
precipitating
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/SE2009/051387
Other languages
English (en)
Inventor
Jörgen LARSSON
Magnus Larsson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gosta Larssons Mekaniska Verkstad AB
Original Assignee
Gosta Larssons Mekaniska Verkstad AB
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 Gosta Larssons Mekaniska Verkstad AB filed Critical Gosta Larssons Mekaniska Verkstad AB
Publication of WO2010068167A1 publication Critical patent/WO2010068167A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid 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
    • C22B47/00—Obtaining manganese
    • C22B47/0018—Treating ocean floor nodules
    • C22B47/0036—Treating ocean floor nodules by dry processes, e.g. smelting
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase 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 present invention relates to a method for manufacturing a manganese alloy.
  • Manganese in the form of manganese alloys, is often used in iron and steel production e.g. due to its deoxidizing and alloying properties. Such manganese alloys are produced mainly from ore and coke under high temperatures. In the production of manganese alloys process gases containing metals are generated. Before being discharged these gases are normally purified by bringing them into contact with water in a wet scrubber. In the cleaning of the process gases a sludge containing metal particles is generated. Today, such sludge is placed on waste dumps at high costs. The handling and storage of the sludge may create working and environmental problems.
  • GB 1 371 113 discloses a method of utilizing manganese present in sludge generated by means of the cleaning of process gases discharged from a smelting furnace. However, this method is considered inefficient as regards economically and environmentally considerations.
  • a method for manufacturing a manganese alloy that enables reuse of valuable metals in the furnace gas is thus provided.
  • the recovered manganese is used as raw material in the production of a manganese alloy, i.e. the amount of required externally supplied raw material, e.g. manganese ore, may be reduced.
  • the presence of high levels of zinc prohibits the reuse of sludge as a source of manganese in the production of manganese alloys. The removal of zinc thus enables reuse of the valuable manganese in the furnace gas.
  • the method further comprises, after the step of adding acid to said manganese containing composition and before the step of adding a precipitating agent for precipitating zinc, a step of separating non- dissolved particles from said mixture having a pH of 2-6.
  • the separated material e.g.
  • the method further comprises, after said step of separating non-dissolved particles, including at least a portion of the precipitated zinc, from said mixture to form a liquid solution containing dissolved manganese, a step of adding a manganese precipitating agent for precipitating, at least partly, manganese from said liquid solution, and a step of separating said precipitated manganese from said liquid solution, said step of forwarding at least a portion of the manganese content of said liquid solution as a source of manganese to a furnace for being heated together with at least iron oxide and carbon comprising utilizing said precipitated manganese as said source of manganese.
  • said manganese precipitating agent comprises a carbonate and/or a hydroxide containing or hydroxide generating compound.
  • An advantage of this embodiment is that less water is forwarded to the furnace, which increases the energy efficiency thereof.
  • said step of adding acid to said manganese containing composition to form a mixture with a pH of 2-6 said added acid comprising sulphuric acid. It has been found that by choosing sulphuric acid the manganese containing mixture is dissolved in a cost efficient manner.
  • acid is preferably added in such a quantity that a mixture with a pH of 3.0-5.0, more preferably with a pH of 3.5-4.5, is formed in order to dissolve metal particles contained in the sludge acid in an even more efficient way.
  • acid is added in such a quantity that a mixture with a pH of 3.8-4.2 is formed.
  • ferroalloys refers to various per se known alloys of iron with a high proportion of one or more other elements, e.g. manganese or silicon.
  • ferromanganese is a ferroalloy with a high content of manganese
  • silicomanganese is a ferroalloy with a high content of manganese and silicon.
  • Ferromanganese and silicomanganese are also referred to as manganese alloys. Due to their deoxidizing and/or alloying properties manganese alloys are, e.g., used in the production of steel.
  • Ferromanganese is made by heating a mixture of manganese oxide,
  • iron oxide in the form of iron ore manganese oxide in the form of manganese ore, and carbon in the form of coke is used.
  • a method for manufacturing a manganese alloy in this case ferromanganese, according to an embodiment of the present invention will be described referring to Fig. 1 , illustrating the method in a schematical manner, and Fig. 2, illustrating the specific steps S1 to S8 of the method.
  • Fig. 1 illustrating the method in a schematical manner
  • Fig. 2 illustrating the specific steps S1 to S8 of the method.
  • the steps of heating raw materials, extracting a manganese alloy and cleaning process gas are known per se and they will therefore be described only briefly.
  • step S1 a mixture comprising iron oxide, Fe2 ⁇ 3, and manganese oxide, MnO2, is heated together with carbon, C, in a furnace 1 , such as a blast furnace or an electric arc furnace.
  • a furnace 1 such as a blast furnace or an electric arc furnace.
  • raw materials e.g. ores containing manganese and iron, and coke
  • the main source of manganese is often manganese containing ore, also referred to as manganese ore, such ore often containing also iron.
  • manganese in the form of a manganese containing liquid solution and/or in the form of a solid manganese salt, such as manganese carbonate, MnCO3, is supplied, as will be described later.
  • step S2 ferromanganese, FeMn, in the form of a molten metal, is extracted from the furnace 1 by means of conventional metallurgical processes. It is realized that the mixture inside the furnace 1 is melted together with coke at high temperature, e.g. 1400 0 C. The molten ferromanganese is tapped, as indicated by arrow B, through a tap hole 5 arranged in the lower portion of the furnace 1. As a by-product slag is generated. Molten slag is removed from the furnace 1 , as indicated by arrow C, through another tap hole 7 arranged in the lower portion of the furnace 1.
  • the melting of materials in the furnace 1 generates a hot process gas, also referred to as a furnace gas, containing various metals in the form of metal particles.
  • the furnace gas is forwarded to a wet scrubber 9 via a gas duct 10.
  • the wet scrubber 9 comprises a tower 11 , nozzles 13 for distributing a scrubbing solution 12 in the tower 11 , and a pipe 15 for recirculating scrubbing solution 12.
  • the scrubbing solution 12 is recirculated by means of a pump 17 arranged in the recirculation pipe 15.
  • the wet scrubber 9 also comprises a fresh water supply pipe, and, optionally, a pipe for supplying an absorbent, such as NaOH, both of which are not illustrated in Fig. 1 for reasons of clarity.
  • step S3 furnace gas is cleaned in the wet scrubber 9 to form clean furnace gas and a manganese containing composition, also referred to as sludge.
  • the clean furnace gas is forwarded to a stack 19, via a gas duct 21 , and is discharged to the atmosphere.
  • a portion of the scrubbing solution 12 flowing through the recirculating pipe 15 is forwarded to a conventional water treatment unit 23 via a pipe 25 connected on the high-presure side of the recirculating pipe 15.
  • the water treatment unit 23 includes, e.g., means 27, such as a series of tanks with agitators, for pH-adjustment and/or flocculation, and a sedimentation device 29, such as a sedimentation tank or a lamella separator.
  • scrubbing solution is thus treated in subsequent steps in order to form purified water, as indicated by arrow D, and a manganese containing sludge.
  • the purified water may be released to the recipient.
  • the water treatment unit 23 may comprise a sludge dewatering device 31 , in which water is removed from the sludge by means of, e.g., filtering using a filter press or a bucher press, to form solid filter cakes.
  • a sludge dewatering device 31 in which water is removed from the sludge by means of, e.g., filtering using a filter press or a bucher press, to form solid filter cakes.
  • water may be removed by means of sedimentation or centhfugation.
  • metal particles contained in the furnace gas is thus collected in the circulating scrubbing solution 12 of the wet scrubber 9, and is then, in the water treatment unit 23, precipitated and separated as a manganese containing composition.
  • the separated sludge contains, in general, elements such as Mn, Si, Fe, Al, Ca, Mg, Zn, C, Pb and water.
  • the composition of the sludge generated in the gas cleaning step S3 may vary due to, for instance, variations in raw material and process conditions. At least some of the mentioned elements contained in the sludge are in general present as oxides and/or carbonates.
  • the manganese containing sludge leaving the sedimentation device 29 may thus, optionally, be dewatered by means of the sludge dewatering device 31 , the resulting filter cakes leaving the sludge dewatering device 31 for being processed further as indicated by arrow E.
  • the manganese containing sludge is dewatered by means of the sludge dewatering device 31 and is forwarded to a waste dump 33, as indicated by arrow F, for being treated further at a later occasion, as indicated by arrow G.
  • sludge and/or the filter cakes is forwarded to a tank 35, as indicated by arrow H.
  • sludge is forwarded directly from the sedimentation device 29 to the tank 35.
  • step S4 acid, in this case sulphuric acid, arrow I, and water, arrow J, are supplied to the sludge 37 received in the tank 35. Consequently, the sludge 37 is diluted, and its content of metal salts, such as oxides and carbonates as indicated hereinbefore, is at least partly dissolved as a consequence of the pH of the sludge 37 being reduced.
  • metal salts such as oxides and carbonates as indicated hereinbefore
  • acid need to be added in such a quantity that the pH of the sludge 37 is reduced to a pH of 2-6. The lower the pH the more particles are dissolved. It is preferred to reduce the pH of the solution to a pH of typically about 4.
  • the mixture of sludge, water and acid is preferably stirred in order to accelerate the dissolving of particles.
  • step S6 a sulphide solution is added, as indicated by arrow L, to the liquid solution 39 in the tank 41 , in order to precipitate zinc.
  • a molar ratio of sulphide to zinc of 1.1-1.2 to 1 is preferred to effectively precipitate zinc present in the liquid solution 39.
  • the mixture of liquid solution and sulphide solution is preferably stirred to accelerate the precipitation of zinc.
  • disodium sulphide, Na 2 S dissolved zinc is precipitated from the liquid solution 39 in the form of solid zinc sulphide, ZnS.
  • step S7 zinc precipitated in step S6 is separated, e.g., by means of filtration, sedimentation or centrifugation, by means of a suitable separation device 42, such as a filter press or a belt filter, to form solid filter cakes leaving the device 42, as indicated by arrow M, to form a liquid solution containing dissolved manganese.
  • a suitable separation device 42 such as a filter press or a belt filter
  • step S8 the manganese content of the liquid solution obtained in step S7 is forwarded as a source of manganese to the production of a manganese alloy.
  • the liquid solution is in this case forwarded without further treatment to a furnace 1 , as indicated by the arrow N, for being heated together with manganese ore, iron ore and coke.
  • An advantage of this embodiment is that less water is forwarded to the furnace 1 , which increases the energy efficiency thereof.
  • a carbonate containing compound such as Na 2 COs
  • a hydroxide containing compound such as, NaOH
  • Example 1 In a first example manganese containing sludge was obtained in accordance with steps S1 , S2 and S3 described above.
  • 0.5 kg of the obtained sludge, with the chemical composition as displayed in Table 1 was mixed with 216.5g of water.
  • Sulfuric acid having a concentration of 96 percent by weight was added in step S4 for reducing the pH of the sample.
  • 235.4g of sulfuric acid was added.
  • the sample was then kept with intensive stirring for 2 hours at approximately 100 0 C. When the pH of the sample decreased below a pH of 6 the sample started to foam.
  • a defoamer, of the polyethyleneoxide-polypropyleneoxide modified fatty acid type was then added. The pH of the sample was reduced to a pH of 4.1. Table 1. Composition of initial sludge sample used in example 1.
  • Non-dissolved particles were then removed from the sample by filtration in step S5. Of the total amount of manganese and zinc in the initial sludge 8 % of the manganese and 10.5% of the zinc were removed in this filtration. The total weight of the removed particles was 77.7 g. The filter cake was washed with water to rinse out any remaining dissolved manganese. After the separation of non-dissolved particles the sample contained 974 g of liquid solution including 9.4 % Mn and 2.3 % Zn. To the liquid solution was then added, in step S6, 53.1 g of a Na2S solution having a concentration of 60 percent by weight, corresponding to 1.2 mol S to 1 mol Zn.
  • Zinc sulphide ZnS was formed and was removed, in step S7, by means of a second filtration of the sample. After this second filtration the remaining liquid sample had a weight of 884g and contained 10.4 % Mn and 0.004% Zn. The remaining liquid thus contained as much as 90 % of the amount of manganese of the initial sludge, but very little of the zinc. The total amount of Zn removed from the initial sludge as precipitated ZnS was 21.9g. Hence, as demonstrated, most of the manganese that leaves the furnace with the furnace gas can be brought back to the furnace, after treatment in accordance with one embodiment of the present invention, still avoiding to accumulate zinc in the system.
  • a method according to an embodiment of the present invention may be considered as a closed-loop method since manganese recovered from the furnace gas is reused in manufacturing a manganese alloy. It will be appreciated that the described embodiment of the invention can be modified and varied by a person skilled in the art without departing from the inventive concept defined in the claims.
  • step S8 the manganese content of the liquid solution obtained in S7 do not necessarily, in step S8, need to be forwarded to the furnace of step S1 , i.e., the furnace from which the furnace gas treated in step S3 originates.
  • Recovered manganese e.g., in the form of a liquid solution containing dissolved manganese or solid manganese in the form of MnCO3 precipitated therefrom, may thus be forwarded to any furnace for being heated together with at least iron oxide and carbon to manufacture a manganese alloy.
  • furnace gas from several furnaces may be forwarded to a wet scrubber for being processed further, or that furnace gas from one furnace may be divided between several wet scrubbers.
  • a first manganese alloy e.g. ferromanganese or silicomanganese
  • second manganese alloy e.g. ferromanganese or silicomanganese
  • manganese recovered from manufacturing of ferromanganese may be forwarded to a furnace, for being heated together with iron oxide, manganese oxide, silicon dioxide (SiO2) and carbon for manufacturing silicomanganese (SiMn).
  • step S6 a sulphide solution containing disodium sulphide is added in order to precipitate zinc.
  • other water soluble sulphide salts such as dipotassium sulphide
  • organo-sulphide containing compounds such as thmercapto-s-thazine trisodium salt, dithiocarbamate, or sodium trithiocarbonate to precipitate zinc.
  • sludge and/or filter cakes obtained from the gas cleaning step S3 may, for a shorter or longer period of time, be removed and placed on a waste dump 33 before being further treated in step S4.
  • the loop is closed when filter cakes are brought back and further treated in accordance with the steps S4, S6, S7 and S8 of an embodiment of the method.
  • sludge that has been recovered several years ago in a waste water treatment plant 23, and has then been transported to a waste dump 33 for being stored for many years, such as 2-20 years, may very well, in accordance with one embodiment of the present invention, be utilized for producing manganese, such that the manganese loop is closed.
  • the main source of manganese used in the manufacturing of a manganese alloy according to an embodiment of the present invention is manganese containing ore.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Ocean & Marine Engineering (AREA)
  • Oceanography (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un alliage de manganèse qui comprend les étapes consistant à faire chauffer au moins un oxyde de fer et un oxyde de manganèse avec du carbone dans un four; à extraire un alliage de manganèse dudit four; à épurer les gaz produits dans le four dans un dépoussiéreur par voie humide afin de former des gaz de four propre et une composition contenant du manganèse, à ajouter de l'acide à la composition contenant du manganèse pour former un mélange présentant un pH compris entre 2 et 6, à ajouter un agent de précipitation audit mélange afin de précipiter au moins partiellement le zinc du mélange, à séparer dudit mélange les particules non dissoutes, y compris au moins une partie du zinc précipité, afin de former une solution liquide contenant du manganèse dissous, à acheminer au moins une partie du manganèse de la solution liquide comme source de manganèse jusqu'à un four afin de la faire chauffer avec au moins un oxyde de fer et du carbone pour former un alliage de manganèse.
PCT/SE2009/051387 2008-12-12 2009-12-08 Procédé de fabrication d'un alliage de manganèse Ceased WO2010068167A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO20085206 2008-12-12
NO20085206A NO330140B1 (no) 2008-12-12 2008-12-12 Fremgangsmate for fremstilling av en manganlegering

Publications (1)

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WO2010068167A1 true WO2010068167A1 (fr) 2010-06-17

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PCT/SE2009/051387 Ceased WO2010068167A1 (fr) 2008-12-12 2009-12-08 Procédé de fabrication d'un alliage de manganèse

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1371113A (en) * 1971-11-05 1974-10-23 Elkem Spigerverket As Method of collecting sludge from waste water used in washing of gases from metallurgical processes
US5912402A (en) * 1995-10-30 1999-06-15 Drinkard Metalox, Inc. Metallurgical dust recycle process
US20070114136A1 (en) * 2004-05-25 2007-05-24 Sanchez Recio Juan C Method of obtaining electrolytic manganese from ferroalloy production waste

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1371113A (en) * 1971-11-05 1974-10-23 Elkem Spigerverket As Method of collecting sludge from waste water used in washing of gases from metallurgical processes
US5912402A (en) * 1995-10-30 1999-06-15 Drinkard Metalox, Inc. Metallurgical dust recycle process
US20070114136A1 (en) * 2004-05-25 2007-05-24 Sanchez Recio Juan C Method of obtaining electrolytic manganese from ferroalloy production waste

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HAMANO T. ET AL: "Manganese Furnace Dust: Drying and Reduction of Zinc Oxide by Tar", ISIJ INTERNATIONAL, vol. 48, no. 7, 2008, pages 906 - 911, XP003026421 *

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Publication number Publication date
NO20085206L (no) 2010-06-14
NO330140B1 (no) 2011-02-21

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