WO2005040436A1 - Method for processing heavy metal chloride residues - Google Patents
Method for processing heavy metal chloride residues Download PDFInfo
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- WO2005040436A1 WO2005040436A1 PCT/EP2004/010981 EP2004010981W WO2005040436A1 WO 2005040436 A1 WO2005040436 A1 WO 2005040436A1 EP 2004010981 W EP2004010981 W EP 2004010981W WO 2005040436 A1 WO2005040436 A1 WO 2005040436A1
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- WO
- WIPO (PCT)
- Prior art keywords
- sulfuric acid
- iron
- spent sulfuric
- sulfate
- metal
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
- C22B34/1222—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes using a halogen containing agent
-
- 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
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- 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
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/40—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture or use of photosensitive materials
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- 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 invention pertains to a method for processing metal chloride residues that are contaminated with heavy metals and generated during the manufacture of titanium dioxide using the chloride process.
- Metal chloride residues that are contaminated with heavy metals are generated during the manufacture of titanium dioxide using the chloride process. After separating them from the stream of titanium tetrachloride - generally by means of a cyclone that is serially connected downstream of the fluidized-bed reactor - a mixture of solids is obtained which is also designated cyclone dust and which comprises non-decomposed titanium dioxide, silicon dioxide, coke, iron (II) chloride, as well as other chlorides. Processing of the residues is expensive as a result of their heavy metal content in particular and is described inter alia in US 3,867,515, EP390 293 Al , and DE 42 43 559 Al .
- the object underlying the present invention is to provide a method, which is improved from the environmental and cost standpoints, for the disposal or utilization of metal chloride residues from the manufacture of titanium dioxide.
- this problem is solved by a method in which the metal chloride residues from the manufacture of titanium dioxide using the chloride process are reacted with sulfuric acid, whereby iron (II) sulfate is obtained.
- HC1 is preferably obtained in addition in this way, and this can be separated and reused in gaseous form and/or as aqueous hydrochloric acid.
- concentration of the sulfuric acid is not particularly restricted, and generally amounts to 10-90%, and preferably to 20-50%.
- the sulfuric acid is preferably spent sulfuric acid.
- the spent sulfuric acid, or the material that is obtained therefrom derives, in particular, preferably from the manufacture of titanium dioxide using the sulfate process, or from gas purification procedures, or from the smelting of copper, lead, or zinc, or it is generated as a byproduct of an organic synthesis, or it is a solution from a metal-pickling plant (a solution resulting from the pickling of steel with sulfuric acid) .
- direct use can be made of dilute acid with an H 2 SO4 concentration of 20-30% in the form in which it is obtained during the manufacture of titanium dioxide using the sulfate process.
- use can be made of washing acids or process acids that contain dilute acid and that have a low concentration of H2SO4. Prior to the reaction, however, the acid can be concentrated, e.g., to a concentration of 50-70%, or even 70-90%.
- the sulfuric acid preferably contains iron ions, and it can also contain additional metal ions, such as manganese and titanium.
- the concentration of iron ions preferably amounts to 2-22 wt%.
- Use can also preferably be made of waste sulfuric acid from gas purification procedures, e.g., from the drying of chlorine.
- This can be particularly advantage ous, since the contaminants in the sulfuric acid that are chlorides or - chlorine do not act in an interfering manner in this case - whereby this is in contrast to other utilization processes.
- the use of sulfuric acid that is utilized for drying chlorine, which is generated during the manufacture of titanium dioxide using the chloride process, is particularly advantageous.
- the metal chloride residues which derive from the manufacture of titanium dioxide and which are reacted with the sulfuric acid, also contain other additional metal chlorides, such as those of chromium, vanadium, niobium, and zirconium, along with iron chloride.
- the residues can be present in the form of a solid, a suspension, or a solution in hydrochloric acid, and preferably as a solution in hydrochloric acid.
- the residues preferably contain iron chloride in a quantity of 10-30 wt%. However, the iron chloride can also be present in a quantity of 30- 60 wt% in the case where solids, slurries, or suspensions are present.
- the metal chloride residue is preferably a so-called cyclone dust, or a material that is obtained therefrom, and, in particular, preferably a solution that is obtained by dissolving the cyclone dust in dilute hydrochloric acid and separating the water-insoluble components or by leaching them out with hydrochloric acid, whereby this solution contains predominantly iron (II) chloride and, in addition, aluminum chloride, manganese chloride, magnesium chloride, zirconium chloride, and the trace elements chromium, niobium, and vanadium in the form of their chlorides .
- the metal chloride residues are reacted with the sulfuric acid, whereby the temperature control is selected in such a way that iron (II) sulfate is precipitated.
- the reaction conditions can also be configured in such a way that predominantly iron sulfate monohydrate crystallizes out.
- the selection of the parameters naturally depends on the requirements of the iron sulfate in regard to its further usage .
- High temperatures during the reaction and high concentrations of sulfuric acid favor the crystallization of iron sulfate monohydrate, while low temperatures during the reaction and low concentrations of sulfuric acid favor the crystallization of iron sulfate heptahydrate.
- the process of crystallizing the iron sulfate heptahydrate is generally preferred since, as a result of the high quantity of water of crystallization, concentrating the solution is required only to a minor extent, or such concentrating can even be omitted completely.
- the iron (II) sulfate is precipitated in the form of the heptahydrate, and this is particularly preferred.
- Parameters can be selected such that the other metal sulfates, which can originate both from the sulfuric acid and from the metal chloride residues, do not reach their solubility product under the conditions of the reaction, and they therefore remain in solution (thus the situation is achieved in which iron (II) sulfate is obtained in high purity) ; or the parameters can be selected in such a way that the other metal sulfates crystallize out essentially together with the iron sulfate. The selection of the parameters naturally depends on the purity requirements for the iron sulfate in light of its further usage.
- sulfuric acid of low concentration e.g., dilute acid from the production of titanium dioxide
- reaction with a solution of metal chlorides of low concentration can be particularly advantageous .
- degrees of freedom can also be utilized in order to crystallize iron sulfate monohydrate or iron sulfate heptahydrate in a controlled manner .
- a supernatant which contains the other metals
- the metals can be precipitated in the form of their hydroxides, and then dried.
- the pH value is preferably increased in steps in this connection in order to permit selective precipitation.
- Reaction with Ca compounds is particularly preferable such that only fractions remain behind which have a low solubility in water, and this is in contrast to the neutralization of the metal chlorides with Ca compounds .
- This manufacture of iron (II) sulfate from metal chloride residues from the manufacture of titanium dioxide, using the chloride process, with the help of waste sulfuric acid represents a particularly economical use of these waste products, especially in titanium dioxide plants in which titanium dioxide is manufactured using both the sulfate process and the chloride process, and the waste sulfuric acid generated during the sulfate process can be used.
- the sulfate sludge comprises crystalline metal sulfates that are suspended in sulfuric acid; its iron content typically is approximately 4-10 wt% (as Fe) .
- sulfate sludge containing approximately the stoichiometrically required quantity of sulfuric acid
- the sulfate sludge comprises crystalline metal sulfates that are suspended in sulfuric acid; its iron content typically is approximately 4-10 wt% (as Fe) .
- Example 4 88.4 g of a mixture of metal chlorides with insoluble residues from the manufacture of titanium dioxide using the chloride process, with the following composition
- the sulfate sludge comprises crystalline metal sulfates that are suspended in sulfuric acid; its iron content typically amounts to approximately 4-10 wt% (as Fe) .
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention pertains to a method for processing metal chloride residues that are contaminated with heavy metals and that are generated during the manufacture of titanium dioxide using the chloride process. The metal chloride residues are reacted with sulfuric acid, whereby iron (II) sulfate is obtained. The sulfuric acid that is utilized is preferably spent sulfuric acid.
Description
METHOD FOR PROCESSING HEAVY METAL CHLORIDE REDIDUES
The invention pertains to a method for processing metal chloride residues that are contaminated with heavy metals and generated during the manufacture of titanium dioxide using the chloride process.
Metal chloride residues that are contaminated with heavy metals are generated during the manufacture of titanium dioxide using the chloride process. After separating them from the stream of titanium tetrachloride - generally by means of a cyclone that is serially connected downstream of the fluidized-bed reactor - a mixture of solids is obtained which is also designated cyclone dust and which comprises non-decomposed titanium dioxide, silicon dioxide, coke, iron (II) chloride, as well as other chlorides. Processing of the residues is expensive as a result of their heavy metal content in particular and is described inter alia in US 3,867,515, EP390 293 Al , and DE 42 43 559 Al .
In light of this background, the object underlying the present invention is to provide a method, which is improved from the environmental and cost standpoints, for the disposal or utilization of metal chloride residues from the manufacture of titanium dioxide.
In accordance with the invention, this problem is solved by a method in which the metal chloride residues from the manufacture of titanium dioxide using the chloride process are reacted with sulfuric acid, whereby iron (II) sulfate is obtained. HC1 is preferably obtained in addition in this way, and this can be separated and reused in gaseous form and/or as aqueous hydrochloric acid.
The concentration of the sulfuric acid is not particularly restricted, and generally amounts to 10-90%, and preferably to 20-50%.
The sulfuric acid is preferably spent sulfuric acid. The spent sulfuric acid, or the material that is obtained therefrom, derives, in particular, preferably from the manufacture of titanium dioxide using the sulfate process, or from gas purification procedures, or from the smelting of copper, lead, or zinc, or it is generated as a byproduct of an organic synthesis, or it is a solution from a metal-pickling plant (a solution resulting from the pickling of steel with sulfuric acid) .
Thus, direct use can be made of dilute acid with an H2SO4 concentration of 20-30% in the form in which it is obtained during the manufacture of titanium dioxide using the sulfate process. Or use can be made of washing acids or process acids that contain dilute acid and that have a low concentration of H2SO4. Prior to the reaction, however, the acid can be concentrated, e.g., to a concentration of 50-70%, or even 70-90%.
The sulfuric acid preferably contains iron ions, and it can also contain additional metal ions, such as manganese and titanium. The concentration of iron ions preferably amounts to 2-22 wt%.
It is also possible to utilize products that are obtained from spent sulfuric acid, e.g.:
- spent sulfuric acid, that has been concentrated, containing suspended crystalline iron sulfate; solids that contain iron sulfate (e.g. a filter cake in the form in which it is generated during the separation of metal sulfates, which contain iron sulfate, from solutions that contain sulfuric acid)
together with sulfuric acid adhering thereto (filter salts) .
These products, which are obtained from spent sulfuric acid, can also be used in any desired combination with spent sulfuric acid that contains iron sulfate.
Use can also preferably be made of waste sulfuric acid from gas purification procedures, e.g., from the drying of chlorine. This can be particularly advantage ous, since the contaminants in the sulfuric acid that are chlorides or - chlorine do not act in an interfering manner in this case - whereby this is in contrast to other utilization processes. The use of sulfuric acid that is utilized for drying chlorine, which is generated during the manufacture of titanium dioxide using the chloride process, is particularly advantageous.
The metal chloride residues, which derive from the manufacture of titanium dioxide and which are reacted with the sulfuric acid, also contain other additional metal chlorides, such as those of chromium, vanadium, niobium, and zirconium, along with iron chloride. The residues can be present in the form of a solid, a suspension, or a solution in hydrochloric acid, and preferably as a solution in hydrochloric acid. The residues preferably contain iron chloride in a quantity of 10-30 wt%. However, the iron chloride can also be present in a quantity of 30- 60 wt% in the case where solids, slurries, or suspensions are present.
The metal chloride residue is preferably a so-called cyclone dust, or a material that is obtained therefrom, and, in particular, preferably a solution that is obtained by dissolving the cyclone dust in dilute hydrochloric acid and separating the water-insoluble components or by
leaching them out with hydrochloric acid, whereby this solution contains predominantly iron (II) chloride and, in addition, aluminum chloride, manganese chloride, magnesium chloride, zirconium chloride, and the trace elements chromium, niobium, and vanadium in the form of their chlorides .
The metal chloride residues are reacted with the sulfuric acid, whereby the temperature control is selected in such a way that iron (II) sulfate is precipitated.
As a result of a suitable selection of the parameters, a situation can be achieved in which the iron sulfate crystallizes out essentially in the form of iron sulfate heptahydrate. However, the reaction conditions can also be configured in such a way that predominantly iron sulfate monohydrate crystallizes out. The selection of the parameters naturally depends on the requirements of the iron sulfate in regard to its further usage . High temperatures during the reaction and high concentrations of sulfuric acid favor the crystallization of iron sulfate monohydrate, while low temperatures during the reaction and low concentrations of sulfuric acid favor the crystallization of iron sulfate heptahydrate. The process of crystallizing the iron sulfate heptahydrate is generally preferred since, as a result of the high quantity of water of crystallization, concentrating the solution is required only to a minor extent, or such concentrating can even be omitted completely.
With an appropriate control of the temperature in the reactor to maximally 50°C, and preferably 30-45°C, the iron (II) sulfate is precipitated in the form of the heptahydrate, and this is particularly preferred. Parameters can be selected such that the other metal sulfates, which can originate both from the sulfuric acid and from the metal chloride residues, do not reach their
solubility product under the conditions of the reaction, and they therefore remain in solution (thus the situation is achieved in which iron (II) sulfate is obtained in high purity) ; or the parameters can be selected in such a way that the other metal sulfates crystallize out essentially together with the iron sulfate. The selection of the parameters naturally depends on the purity requirements for the iron sulfate in light of its further usage.
A large number of degrees of freedom exist in the selection of a suitable concentration for the reaction of the metal chloride residues with the sulfuric acid which is to be as efficient as possible, and for the crystallization and .separation of the iron sulfate that are to be as efficient as possible; thus when using sulfuric acid of low concentration (e.g., dilute acid from the production of titanium dioxide) , reaction with the solid metal chlorides in a highly concentrated suspension of metal chlorides in aqueous solution can be particularly advantageous. Conversely, when using highly concentrated sulfuric acid (e.g., from gas purification procedures, or concentrated dilute acid from the production of titanium dioxide, or of metal sulfates in the form in which these are generated during the concentration of dilute acid from the production of titanium dioxide that can contain sulfuric acid that is still adhering thereto) , reaction with a solution of metal chlorides of low concentration can be particularly advantageous . These degrees of freedom can also be utilized in order to crystallize iron sulfate monohydrate or iron sulfate heptahydrate in a controlled manner .
By adding metallic iron or iron oxides or a mixture of both, moreover, it is possible - prior to the reaction with the other material in question - to reduce the acidity of the metal chloride residues and/or the sulfuric
acid and, simultaneously, to increase the concentration of iron.
If a supernatant is obtained, which contains the other metals, then this can be disposed of in a known manner. For example, the metals can be precipitated in the form of their hydroxides, and then dried. The pH value is preferably increased in steps in this connection in order to permit selective precipitation. Reaction with Ca compounds is particularly preferable such that only fractions remain behind which have a low solubility in water, and this is in contrast to the neutralization of the metal chlorides with Ca compounds .
This manufacture of iron (II) sulfate from metal chloride residues from the manufacture of titanium dioxide, using the chloride process, with the help of waste sulfuric acid represents a particularly economical use of these waste products, especially in titanium dioxide plants in which titanium dioxide is manufactured using both the sulfate process and the chloride process, and the waste sulfuric acid generated during the sulfate process can be used.
Example 1 : 100 mL (= 133.4 g) of an FeCl2 solution, in the form obtained from the process for the manufacture of titanium dioxide using the chloride process, with the following composition
FeCl2 = 250 g/1 Mn = 26 g/1 Nb = 8.1 g/1 Al = 7.7 g/1 Mg = 5.9 g/1 V = 4.3 g/1 Ti = 2.3 g/1
Cr = 2.1 g/1 HC1 = 24 g/1
were concentrated by evaporation in a rotary evaporator at 50°C and 11 millibar until a crystalline sludge was obtained, and then it was mixed with 45 g of 96% sulfuric acid (corresponding to approximately 120% of the stoichiometrically required quantity of sulfuric acid) .
After subsequent distillation at 103-107°C of the hydrochloric acid that is formed, approximately 79 g of a residue were obtained which were comprised of predominantly iron sulfate and approximately 0.2 wt% chloride.
Foam formation occurred during distillation.
Example 2 : 100 mL (= 133.4 g) of a FeCl2 solution, in the form in which it is obtained from the process for the manufacture of titanium dioxide using the chloride process, with the following composition
FeCl2 250 g/1 Mn 26 g/1 Nb 8. ■ l g/i Al 7. .7 g/1 Mg 5. .9 g/i V 4. .3 g/1 Ti 2. .3 g/1 Cr 2. .1 g/1 HC1 = 24 g/1
were mixed with 112.8 g of a sulfate sludge (containing approximately 120 % of the stoichiometrically required quantity of sulfuric acid) in the form generated during
the concentration of dilute acid from the manufacture of titanium dioxide using the sulfate process . The sulfate sludge comprises crystalline metal sulfates that are suspended in sulfuric acid; its iron content typically is approximately 4-10 wt% (as Fe) .
After subsequent separation by means of distillation at 103-107°C of the hydrochloric acid that is formed, approximately 118.6 g of a residue were obtained which were comprised of predominantly iron sulfate and approximately 0.1 wt% chloride.
Example 3 : 100 mL (= 133.4 g) of a FeCl2 solution, in the form in which it is obtained from the process for the manufacture of titanium dioxide using the chloride process, with the following composition
FeCl2 = 250 g/1 Mn = 26 g/1 Nb = 8.1 g/1 Al = 7.7 g/1 Mg = 5.9 g/1 V = 4.3 g/1 Ti = 2.3 g/1 Cr = 2.1 g/1 HC1 = 24 g/1
were mixed with 96 g of a sulfate sludge (containing approximately the stoichiometrically required quantity of sulfuric acid) in the form generated during the concentration of dilute acid from the manufacture of titanium dioxide using the sulfate process. The sulfate sludge comprises crystalline metal sulfates that are suspended in sulfuric acid; its iron content typically is approximately 4-10 wt% (as Fe) .
After subsequent separation by distillation at 103- 107°C of the hydrochloric acid that is formed, approximately 104.7 g of a residue were obtained which were comprised of predominantly iron sulfate and approximately 0.3 wt% chloride.
Example 4 : 88.4 g of a mixture of metal chlorides with insoluble residues from the manufacture of titanium dioxide using the chloride process, with the following composition
FeCl2 * 4 H20 = 43.6 g FeCl3 = 3.9 g nCl2 * 4 H20 = 8.3 g A1C13 * 6 H20 = 9.2 g MgCl2 * 6 H20 = 5.1 g TiCl4 = 4.7 g titanium slag = 7.2 g petroleum coke = 6.3 g
were mixed with 102.9 g of a sulfate sludge (containing approximately the stoichiometrically required quantity of sulfuric acid) in the form generated during the concentration of dilute acid from the manufacture of titanium dioxide using the sulfate process. The sulfate sludge comprises crystalline metal sulfates that are suspended in sulfuric acid; its iron content typically amounts to approximately 4-10 wt% (as Fe) .
After subsequent separation by distillation at 103- 107°C of the hydrochloric acid that is formed (80 min at an oil bath temperature of 180°C) , approximately 127.1 g of a residue were obtained which were comprised of predominantly iron sulfate and approximately 0.4 wt% chloride.
Claims
1. A method for processing metal chloride residues from the manufacture of titanium dioxide using the chloride process, in which the metal chloride residues are reacted with sulfuric acid, whereby iron (II) sulfate is obtained.
2. The method according to Claim 1, characterized in that the sulfuric acid is spent sulfuric acid, or a material that contains sulfuric acid and that is obtained therefrom.
3. The method according to Claim 2, characterized in that the spent sulfuric acid derives from the manufacture of titanium dioxide using the sulfate process.
4. The method according to Claim 2, characterized in that the spent sulfuric acid derives from a process for drying gases .
5. The method according to Claim 4, characterized in that the spent sulfuric acid derives from a process for drying chlorine .
6. The method according to Claim 2, characterized in that the spent sulfuric acid derives from the smelting of copper, the smelting of lead, or the smelting of zinc.
7. The method according to Claim 2 , characterized in that the spent sulfuric acid is a by- product of an organic synthesis .
8. The method according to Claim 2, characterized in that the spent sulfuric acid is a solution from a metal pickling plant.
9. The method according to any one of the preceding claims, whereby the spent sulfuric acid has an H2SO4 content of 10-90%.
10. The method according to Claim 9, characterized in that the spent sulfuric acid has an H2SO4 content of 20- 30%.
11. The method according to any one of the preceding claims, characterized in that the metal chloride residues contain 10-30 wt% of iron ions.
12. The method according to any one of Claims 2-11, characterized in that the concentration of the iron ions in the spent sulfuric acid, or in the material that is obtained from spent sulfuric acid, is in the range from 2-22 wt%, and preferably in the range from 8-22 wt% .
13. The method according to any one of the preceding claims, characterized in that the metal chloride residues contain the iron-containing metal chlorides that are deposited after chlorination.
14. The method according to any one of the preceding claims, characterized in that, as a result of adding metallic iron and/or iron oxides, either the metal chloride residues or the sulfuric acid is reduced in acidity and the concentration with respect to iron is simultaneously increased prior to the reaction with the other material in question, or the product after the reaction is reduced in acidity and the concentration with respect to iron is simultaneously increased.
15. The method according to any one of the preceding claims, characterized in that the metal sulfates, which are different from iron sulfate and which remain behind in solution after the crystallization of the iron sulfate, are carried off for separate utilization or disposal.
16. The method according to Claim 15, characterized in that the metal sulfates, which are different from iron sulfate, are neutralized with Ca compounds .
17. The method according to any one of the preceding claims, characterized in that the materials which contain iron chloride are reacted with spent sulfuric acid that is transported to the site of the reaction solely by means of a pipeline.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2003146339 DE10346339A1 (en) | 2003-10-06 | 2003-10-06 | Process for working up metal chloride residues |
| DE10346339.9 | 2003-10-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005040436A1 true WO2005040436A1 (en) | 2005-05-06 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2004/010981 WO2005040436A1 (en) | 2003-10-06 | 2004-10-01 | Method for processing heavy metal chloride residues |
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| DE (1) | DE10346339A1 (en) |
| WO (1) | WO2005040436A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102556981A (en) * | 2010-12-24 | 2012-07-11 | 漯河市兴茂钛业有限公司 | Comprehensive utilization method for solid wastes and waste acid in production process of titanium dioxide |
| CN102825060A (en) * | 2012-09-10 | 2012-12-19 | 武汉钢铁(集团)公司 | Treatment method for chromium-containing waste residue in steel industry |
| CN104961164A (en) * | 2015-06-30 | 2015-10-07 | 成都易胜科生物科技有限公司 | Method for producing ferrous sulfate monohydrate using acid waste residue in titanium dioxide production |
| CN109825711A (en) * | 2019-03-14 | 2019-05-31 | 何耀 | A kind of titanium dioxide waste acid by sulfuric acid process resource utilization method |
| CN110040696A (en) * | 2019-04-29 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101871045B (en) * | 2010-07-02 | 2012-01-25 | 攀枝花市东源锌业有限责任公司 | Method for producing zinc by utilizing sulphate process titanium dioxide waste acid |
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| JPS5884935A (en) * | 1981-11-14 | 1983-05-21 | Dowa Mining Co Ltd | Treatment of titanium refining residue |
| EP0390293A1 (en) * | 1989-03-30 | 1990-10-03 | Kemira Pigments B.V. | A process of treating metal chloride wastes |
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| US5407650A (en) * | 1992-12-22 | 1995-04-18 | Kronos, Inc. | Process for purifying a technical iron chloride solution by selective precipitation |
| JPH11322343A (en) * | 1998-05-21 | 1999-11-24 | Toshin Kagaku Kogyo Kk | Conversion of iron chloride into iron sulfate salt and production of basic ferric sulfate |
| CN1369574A (en) * | 2001-02-12 | 2002-09-18 | 朝宁工程顾问股份有限公司 | Process and equipment for extracting useful substances from use acid |
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| DE52803C (en) * | TH. PETERS in Chemnitz | Process for the recovery of iron residues which result from the reduction of organic nitro compounds | ||
| US5417955A (en) * | 1994-03-01 | 1995-05-23 | Connolly; David W. | Manufacture of ferric sulfate and hydrochloric acid from ferrous chloride |
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2003
- 2003-10-06 DE DE2003146339 patent/DE10346339A1/en not_active Withdrawn
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2004
- 2004-10-01 WO PCT/EP2004/010981 patent/WO2005040436A1/en active Application Filing
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102556981A (en) * | 2010-12-24 | 2012-07-11 | 漯河市兴茂钛业有限公司 | Comprehensive utilization method for solid wastes and waste acid in production process of titanium dioxide |
| CN102556981B (en) * | 2010-12-24 | 2013-10-09 | 漯河市兴茂钛业有限公司 | Comprehensive utilization method for solid wastes and waste acid in production process of titanium dioxide |
| CN102825060A (en) * | 2012-09-10 | 2012-12-19 | 武汉钢铁(集团)公司 | Treatment method for chromium-containing waste residue in steel industry |
| CN104961164A (en) * | 2015-06-30 | 2015-10-07 | 成都易胜科生物科技有限公司 | Method for producing ferrous sulfate monohydrate using acid waste residue in titanium dioxide production |
| CN109825711A (en) * | 2019-03-14 | 2019-05-31 | 何耀 | A kind of titanium dioxide waste acid by sulfuric acid process resource utilization method |
| CN110040696A (en) * | 2019-04-29 | 2019-07-23 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process |
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|---|---|
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