WO2007057504A1 - Method for decomposing metal sulphate - Google Patents

Method for decomposing metal sulphate Download PDF

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Publication number
WO2007057504A1
WO2007057504A1 PCT/FI2006/000361 FI2006000361W WO2007057504A1 WO 2007057504 A1 WO2007057504 A1 WO 2007057504A1 FI 2006000361 W FI2006000361 W FI 2006000361W WO 2007057504 A1 WO2007057504 A1 WO 2007057504A1
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WO
WIPO (PCT)
Prior art keywords
sulphate
decomposition
metal
sulphur
nickel
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/FI2006/000361
Other languages
French (fr)
Inventor
Maija-Leena Metsärinta
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.)
Metso Corp
Original Assignee
Outotec Oyj
Outokumpu Technology Oyj
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Filing date
Publication date
Application filed by Outotec Oyj, Outokumpu Technology Oyj filed Critical Outotec Oyj
Priority to AU2006314404A priority Critical patent/AU2006314404B2/en
Priority to EA200801102A priority patent/EA014826B1/en
Publication of WO2007057504A1 publication Critical patent/WO2007057504A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C01B13/185—Preparing mixtures of oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/52—Preparation of sulfur dioxide by roasting sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/745—Preparation from sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the method of the invention relates to the decomposition in a fluidised bed of metal sulphates generated in the metallurgical industry.
  • the decomposition of metal sulphates is carried out so that the metal oxides generated are recovered in such a pure form that they can be recycled to be used again in the manufacture of metal alloys such as steel.
  • sulphates containing nickel, iron and chrome are decomposed in oxidising conditions using pyrites or pyrrhotite as the former and fuel of the bed material.
  • Metal sulphates are generated in various metallurgical processes such as for example during steel pickling or in the electrolytic purification of metal into anodic sludge.
  • Mixed sulphate waste containing sulphuric acid cannot be used as such anywhere, and is largely hazardous waste.
  • US patent 4,824,655 describes a method for producing sulphur dioxide by the thermal decomposition of sulphur-containing metal sulphates in a fluidized bed.
  • the metal sulphate is mainly iron sulphate, which includes a small amount of other metals such as compounds of aluminium, magnesium, titanium, manganese, chrome and vanadium.
  • the sulphate originates largely from the manufacture of titanium.
  • the decomposition of metal sulphate occurs at a temperature of 800 - 1100 0 C. It is essential that sulphur- containing material, such as sulphur waste or fine pyrites, be used in sulphate reduction in order to produce the largest possible amount of sulphur dioxide.
  • the energy required for sulphate reduction is produced with a carbon-containing fuel such as coal, coke or heavy fuel oil.
  • a carbon-containing fuel such as coal, coke or heavy fuel oil.
  • the key point in the method is the production of sulphur dioxide, and there is no mention of the use of the metal-containing solids that are generated, so they go to waste. The amount of waste generated in this way is considerable.
  • the feed of extra fuel, particularly of extra liquid or gaseous fuel makes it difficult to keep the temperature regulated evenly, since localised feeding to the bed may result in hot spots, which cause the sintering of the bed.
  • Carbon-containing fuel creates carbon dioxide emissions, and the aim is to reduce the amount of these emissions.
  • the purpose of the method of this invention is to avoid the drawbacks of the method described above.
  • the aim of the method now developed is to decompose metal sulphates generated in the metallurgical industry, particularly mixed sulphates that contain nickel, so that the fuel used in their decomposition produces bed material on oxidising, whereupon the uniform distribution of fuel prevents the generation of hot spots.
  • the fuel does not contain carbon either, so that carbon dioxide emissions are not produced.
  • the invention relates to a method for the decomposition of a residue generated in the metallurgical industry, containing at least one metal sulphate, into oxides.
  • the decomposition of metal sulphide is performed in a fluidised bed furnace, whereby the energy required for decomposing the sulphate is obtained from roasting the iron sulphide used as the bed material.
  • Roasting is performed in oxidising conditions to form an oxide that is essentially free of sulphur for reuse in the steel industry, and the sulphur dioxide that is generated is used in the manufacture of sulphur and/or sulphuric acid.
  • the metal sulphate is a mixed sulphate, including nickel, chrome and iron sulphate.
  • Mixed sulphate is for instance the mixed sulphate generated during the pickling of steel.
  • the metal sulphate is nickel sulphate. Nickel sulphate is formed for instance during the electrolytic purification of copper.
  • the iron sulphide used as the fluidised bed material and energy producer is pyrite and/or pyrrhotite.
  • the decomposition of sulphate is carried out at a temperature of 800 - 900 0 C and the residence time in the bed is around 1 - 5 h.
  • the sulphur concentration of the alloy of the oxide or oxides formed is a maximum of 0.5%.
  • Impure sulphate sediments are generated in the metallurgical industry, such as in steel manufacture and the electrolytic purification of metals, which contain sulphates of nickel, chrome and iron etc. Sulphates are soluble enough that they cannot be removed from the circuit as they are but in addition their metal content should be recovered in an environment-friendly way.
  • sulphate residues in particular those generated during the manufacture of titanium, are treated in a fluidised bed furnace, but mainly in order to produce sulphur dioxide gas for the manufacture of sulphuric acid.
  • the end product of the pyrometallurgical fabrication of copper is copper anode, which is further purified electrolytically into pure cathode copper.
  • the anode sludge that is generated contains the impurities of the anode, of which nickel in the form of nickel sulphate is one of the most significant.
  • the decomposition of sulphates into oxides is an endothermic reaction.
  • the bed of the fluidised bed furnace was formed so that reducing sulphur-containing material and some of the carbon-containing fuel were mixed with the sulphates, pelletised and then fed into the furnace. In addition, part of the fuel was fed separately.
  • the fuel required for decomposition acts as the bed material i.e. no separate carbon-containing fuel is required at all.
  • Iron sulphide such as pyrite or pyrrhotite acts as the fuel and bed material, which is roasted and, simultaneously, the sulphates fed into the bed are decomposed into their oxides. The reactions that occur in iron sulphide roasting are so exothermic that the heat generated is enough for the endothermic reactions required in sulphate decomposition without the need for any extra heat.
  • Sulphate decomposition is carried out at a temperature of 800 - 900 0 C and the residence time in the bed is around 1 - 5 h.
  • the decomposition of nickel sulphate requires the temperature mentioned above, in order for the decomposition into oxides to take place in a reasonable time.
  • the invention relates thus to a method for the decomposition of one or more metal sulphates, where nickel sulphate is preferably one of the sulphates.
  • Sulphate decomposition is carried out in oxidising conditions, in order to avoid sulphur remaining in any form among the oxides. Sulphur-free oxides are fit for reuse e.g. in a steelworks.
  • the sulphur dioxide-containing gases that are formed are routed to sulphur and/or sulphuric acid manufacture, but the process is regulated on the basis of producing metal oxides that are as pure as possible rather than sulphur dioxide production. It is preferable to keep the sulphur content of the oxide alloy to be fed to the steelworks as small as possible, since it will reduce the demand for oxygen used for sulphur removal in conversion.
  • iron sulphides When iron sulphides are used as the energy producer in the fluidised bed decomposition of sulphates, it is easy to control the shutdown of the bed nor does a malfunction in the sulphate feed cause problems.
  • iron sulphides When using iron sulphides the operation is run in oxidising conditions, and there are no additional sulphides to be burnt in the bed. If the operation is run in reducing conditions and there is a malfunction, then the sulphides burn and hot spots, molten phase and sintering occur.
  • the decomposition of mixed sulphate was performed in a fluidised bed furnace, where the composition of the mixed sulphate was Fe 12.8%, Cr 1.8%, Ni 1.8%, Mo 0.08% and SO 4 44.4%. Pyrite was used as fuel and bed material. Air was used as the fluidising air and fluidising was carried out at a rate of 0.2 m/s in slightly oxidising conditions. After 1.5 h the sulphur concentration of the oxide mixture removed from the furnace was 0.32 % and after 3 h it was 0.17 %, so it was highly suitable for recycling to the steel industry.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The method of the invention relates to the decomposition in a fluidized bed of metal sulphates generated in the metallurgical industry. The decomposition of metal sulphates is carried out so that the metal oxides generated are recovered in such a pure form that they can be recycled to be reused in the manufacture of metal alloys such as steel. In particular, sulphates containing nickel, iron and chrome are decomposed in oxidising conditions using pyrites or pyrrhotite as the fuel and bed material.

Description

METHOD FOR DECOMPOSING METAL SULPHATE
FIELD OF THE INVENTION
The method of the invention relates to the decomposition in a fluidised bed of metal sulphates generated in the metallurgical industry. The decomposition of metal sulphates is carried out so that the metal oxides generated are recovered in such a pure form that they can be recycled to be used again in the manufacture of metal alloys such as steel. In particular, sulphates containing nickel, iron and chrome are decomposed in oxidising conditions using pyrites or pyrrhotite as the former and fuel of the bed material.
BACKGROUND OF THE INVENTION
Metal sulphates are generated in various metallurgical processes such as for example during steel pickling or in the electrolytic purification of metal into anodic sludge. Mixed sulphate waste containing sulphuric acid cannot be used as such anywhere, and is largely hazardous waste.
US patent 4,824,655 describes a method for producing sulphur dioxide by the thermal decomposition of sulphur-containing metal sulphates in a fluidized bed. The metal sulphate is mainly iron sulphate, which includes a small amount of other metals such as compounds of aluminium, magnesium, titanium, manganese, chrome and vanadium. The sulphate originates largely from the manufacture of titanium. The decomposition of metal sulphate occurs at a temperature of 800 - 11000C. It is essential that sulphur- containing material, such as sulphur waste or fine pyrites, be used in sulphate reduction in order to produce the largest possible amount of sulphur dioxide. The energy required for sulphate reduction is produced with a carbon-containing fuel such as coal, coke or heavy fuel oil. The majority of the fuel is introduced with the bed material, but some is fed separately with the carrier gas. The key point in the method is the production of sulphur dioxide, and there is no mention of the use of the metal-containing solids that are generated, so they go to waste. The amount of waste generated in this way is considerable. The feed of extra fuel, particularly of extra liquid or gaseous fuel, makes it difficult to keep the temperature regulated evenly, since localised feeding to the bed may result in hot spots, which cause the sintering of the bed. Carbon-containing fuel creates carbon dioxide emissions, and the aim is to reduce the amount of these emissions.
PURPOSE OF THE INVENTION
The purpose of the method of this invention is to avoid the drawbacks of the method described above. The aim of the method now developed is to decompose metal sulphates generated in the metallurgical industry, particularly mixed sulphates that contain nickel, so that the fuel used in their decomposition produces bed material on oxidising, whereupon the uniform distribution of fuel prevents the generation of hot spots. The fuel does not contain carbon either, so that carbon dioxide emissions are not produced.
SUMMARY OF THE INVENTION
The essential features of the invention will be made apparent in the attached claims.
The invention relates to a method for the decomposition of a residue generated in the metallurgical industry, containing at least one metal sulphate, into oxides. The decomposition of metal sulphide is performed in a fluidised bed furnace, whereby the energy required for decomposing the sulphate is obtained from roasting the iron sulphide used as the bed material. Roasting is performed in oxidising conditions to form an oxide that is essentially free of sulphur for reuse in the steel industry, and the sulphur dioxide that is generated is used in the manufacture of sulphur and/or sulphuric acid.
According to one embodiment of the invention the metal sulphate is a mixed sulphate, including nickel, chrome and iron sulphate. Mixed sulphate is for instance the mixed sulphate generated during the pickling of steel. According to another embodiment of the invention the metal sulphate is nickel sulphate. Nickel sulphate is formed for instance during the electrolytic purification of copper.
The iron sulphide used as the fluidised bed material and energy producer is pyrite and/or pyrrhotite. The decomposition of sulphate is carried out at a temperature of 800 - 9000C and the residence time in the bed is around 1 - 5 h. The sulphur concentration of the alloy of the oxide or oxides formed is a maximum of 0.5%.
DETAILED DESCRIPTION OF THE INVENTION
Impure sulphate sediments are generated in the metallurgical industry, such as in steel manufacture and the electrolytic purification of metals, which contain sulphates of nickel, chrome and iron etc. Sulphates are soluble enough that they cannot be removed from the circuit as they are but in addition their metal content should be recovered in an environment-friendly way. As described in the prior art, sulphate residues, in particular those generated during the manufacture of titanium, are treated in a fluidised bed furnace, but mainly in order to produce sulphur dioxide gas for the manufacture of sulphuric acid.
Mixed sulphate precipitate is generated in the pickling stage of steel manufacture, containing in addition to iron sulphates (FeSO4 HaO, Fβ2(Sθ4)3) also nickel and chrome sulphate (NiSO4, Cr2(SO4)3) and sulphuric acid. In oxidising conditions iron sulphates and chrome sulphate decompose at a far lower temperature than nickel sulphate. Nickel sulphate may also decompose at lower temperatures in reducing conditions, but then there is a danger that in addition to oxides, sulphides will also form. When the purpose is to produce a product fit for a steelworks for example, its sulphur content must be quite low i.e. below 0.5 %. The end product of the pyrometallurgical fabrication of copper is copper anode, which is further purified electrolytically into pure cathode copper. The anode sludge that is generated contains the impurities of the anode, of which nickel in the form of nickel sulphate is one of the most significant.
The decomposition of sulphates into oxides is an endothermic reaction. In the method according to the prior art, the bed of the fluidised bed furnace was formed so that reducing sulphur-containing material and some of the carbon-containing fuel were mixed with the sulphates, pelletised and then fed into the furnace. In addition, part of the fuel was fed separately. In the method now developed the fuel required for decomposition acts as the bed material i.e. no separate carbon-containing fuel is required at all. Iron sulphide such as pyrite or pyrrhotite acts as the fuel and bed material, which is roasted and, simultaneously, the sulphates fed into the bed are decomposed into their oxides. The reactions that occur in iron sulphide roasting are so exothermic that the heat generated is enough for the endothermic reactions required in sulphate decomposition without the need for any extra heat.
Sulphate decomposition is carried out at a temperature of 800 - 9000C and the residence time in the bed is around 1 - 5 h. In particular the decomposition of nickel sulphate requires the temperature mentioned above, in order for the decomposition into oxides to take place in a reasonable time. The invention relates thus to a method for the decomposition of one or more metal sulphates, where nickel sulphate is preferably one of the sulphates. Sulphate decomposition is carried out in oxidising conditions, in order to avoid sulphur remaining in any form among the oxides. Sulphur-free oxides are fit for reuse e.g. in a steelworks. The sulphur dioxide-containing gases that are formed are routed to sulphur and/or sulphuric acid manufacture, but the process is regulated on the basis of producing metal oxides that are as pure as possible rather than sulphur dioxide production. It is preferable to keep the sulphur content of the oxide alloy to be fed to the steelworks as small as possible, since it will reduce the demand for oxygen used for sulphur removal in conversion.
When all the energy required for sulphate decomposition is brought in the form of bed material, the drawbacks that can arise from feeding fuel to the bed separately can be avoided. The use of separate fuel is awkward because it is difficult to feed it into the bed so evenly that no localised hot spots are generated where the bed material and sulphates would be sintered. Hot localised points are also harmful to the equipment. Introducing a separate fuel to the fluidised bed means carbon-containing material, generally feeding gas into the bed. The drawback of carbon-containing fuel is that the fuel produces carbon dioxide emissions and in addition it requires a post-combustion chamber as additional equipment.
When iron sulphides are used as the energy producer in the fluidised bed decomposition of sulphates, it is easy to control the shutdown of the bed nor does a malfunction in the sulphate feed cause problems. When using iron sulphides the operation is run in oxidising conditions, and there are no additional sulphides to be burnt in the bed. If the operation is run in reducing conditions and there is a malfunction, then the sulphides burn and hot spots, molten phase and sintering occur.
EXAMPLES Example 1
The decomposition of impure nickel sulphate was carried out in a fluidised bed furnace using pyrite as bed material and fuel. Air was used as the fluidising air and fluidising was carried out at a rate of 0.2 m/s in slightly oxidising conditions. After 1.5 h the sulphur concentration of the nickel oxide removed from the furnace was 0.34 % and after 3 h it was 0.15 %, so that it was highly suitable for recycling to the steel industry. Example 2
The decomposition of mixed sulphate was performed in a fluidised bed furnace, where the composition of the mixed sulphate was Fe 12.8%, Cr 1.8%, Ni 1.8%, Mo 0.08% and SO4 44.4%. Pyrite was used as fuel and bed material. Air was used as the fluidising air and fluidising was carried out at a rate of 0.2 m/s in slightly oxidising conditions. After 1.5 h the sulphur concentration of the oxide mixture removed from the furnace was 0.32 % and after 3 h it was 0.17 %, so it was highly suitable for recycling to the steel industry.

Claims

PATENT CLAIMS
1. A method for decomposing a residue generated in the metallurgical industry that includes at least one metal sulphate into oxide, characterised in that the decomposition of the metal sulphate is carried out in a fluidised bed furnace, whereby the energy required for sulphate decomposition is obtained from roasting of an iron sulphide used as the furnace bed material, the decomposition is carried out in oxidising conditions to form an essentially sulphur-free oxide for recycling to the steel industry, and the sulphur dioxide that is generated is used for the manufacture of sulphur and/or sulphuric acid.
2. A method according to claim 1 , characterised in that the metal sulphate is a mixed sulphate, which includes nickel, chrome and iron sulphates.
3. A method according to claim 1 or 4, characterised in that the metal sulphate is the nickel-chrome-iron sulphate generated during pickling in steel industry.
4. A method according to claim 1 , characterised in that the metal sulphate is nickel sulphate.
5. A method according to claim 1 or 4, characterised in that the metal sulphate is the nickel sulphate generated in an electrolytic purification of copper.
6, A method according to any of claims 1 - 5, characterised in that the iron sulphide is pyrite and/or pyrrhotite.
7. A method according to any of claims 1 - 6, characterised in that the sulphate decomposition is carried out at a temperature of 800 - 9000C.
8. A method according to any of claims 1 - 7, characterised in that the decomposition time is 1 - 5 h.
9. A method according to any of claims 1 - 8, characterised in that the sulphur concentration of the oxide formed in the fluidised bed furnace is a maximum of 0.5%.
PCT/FI2006/000361 2005-11-18 2006-11-10 Method for decomposing metal sulphate Ceased WO2007057504A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2006314404A AU2006314404B2 (en) 2005-11-18 2006-11-10 Method for decomposing metal sulphate
EA200801102A EA014826B1 (en) 2005-11-18 2006-11-10 METHOD OF DECOMPOSITION OF METAL SULFATE

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20051180A FI120338B (en) 2005-11-18 2005-11-18 Process for decomposing a metal sulfate
FI20051180 2005-11-18

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WO2007057504A1 true WO2007057504A1 (en) 2007-05-24

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CN (2) CN101309858A (en)
AU (1) AU2006314404B2 (en)
EA (1) EA014826B1 (en)
FI (1) FI120338B (en)
WO (1) WO2007057504A1 (en)
ZA (1) ZA200804071B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103318849A (en) * 2013-07-10 2013-09-25 四川大学 Method for recycling sulfur-iron resources

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109365799B (en) * 2018-09-19 2024-04-23 上海新池能源科技有限公司 Preparation method of graphene-coated metal powder and metal-based-graphene electrical contact

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB721591A (en) * 1951-03-28 1955-01-12 British Titan Products Improvements relating to processes for the recovery of sulphur-values from waste products
GB727799A (en) * 1952-01-01 1955-04-06 Dorr Co Simultaneous decomposition of pyrite and feso
US3053626A (en) * 1959-05-08 1962-09-11 Chempro Inc Decomposition of heavy metal sulfate solutions with the recovery of sulfur dioxide and the heavy metal oxide
GB1484811A (en) * 1974-01-17 1977-09-08 Metallgesellschaft Ag Process for the thermal splitting of metal sulphates
EP0262564A2 (en) * 1986-10-03 1988-04-06 Bayer Ag Process for the preparation of sulphur dioxide

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB721591A (en) * 1951-03-28 1955-01-12 British Titan Products Improvements relating to processes for the recovery of sulphur-values from waste products
GB727799A (en) * 1952-01-01 1955-04-06 Dorr Co Simultaneous decomposition of pyrite and feso
US3053626A (en) * 1959-05-08 1962-09-11 Chempro Inc Decomposition of heavy metal sulfate solutions with the recovery of sulfur dioxide and the heavy metal oxide
GB1484811A (en) * 1974-01-17 1977-09-08 Metallgesellschaft Ag Process for the thermal splitting of metal sulphates
EP0262564A2 (en) * 1986-10-03 1988-04-06 Bayer Ag Process for the preparation of sulphur dioxide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103318849A (en) * 2013-07-10 2013-09-25 四川大学 Method for recycling sulfur-iron resources

Also Published As

Publication number Publication date
FI20051180A0 (en) 2005-11-18
AU2006314404B2 (en) 2012-04-19
CN104129819A (en) 2014-11-05
ZA200804071B (en) 2009-04-29
CN101309858A (en) 2008-11-19
EA200801102A1 (en) 2008-10-30
EA014826B1 (en) 2011-02-28
AU2006314404A1 (en) 2007-05-24
FI20051180L (en) 2007-05-19
FI120338B (en) 2009-09-30

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