WO2002081779A2 - Regeneration par extraction liquide-liquide des acides a partir de solution aqueuse contenant des metaux - Google Patents
Regeneration par extraction liquide-liquide des acides a partir de solution aqueuse contenant des metaux Download PDFInfo
- Publication number
- WO2002081779A2 WO2002081779A2 PCT/FR2002/001231 FR0201231W WO02081779A2 WO 2002081779 A2 WO2002081779 A2 WO 2002081779A2 FR 0201231 W FR0201231 W FR 0201231W WO 02081779 A2 WO02081779 A2 WO 02081779A2
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- WO
- WIPO (PCT)
- Prior art keywords
- acid
- mol
- organic solvent
- organic
- solution containing
- Prior art date
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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
Definitions
- the present invention relates to a regeneration process by liquid-liquid extraction of acids from an aqueous solution containing metals.
- the invention is particularly suitable for the regeneration of sulfuric and / or hydrochloric acids contained in aqueous solutions from industrial plants, in particular in acidic aqueous baths used in the surface treatment industry or in the steel industry.
- the concentration of metals in the etching bath can increase until saturation and that, depending on the case, pieces of metal oxides fall to the bottom of the pickling tank and partially fill it. These pieces of metal oxides are gradually dissolved by the pickling solution, which consumes acid and shortens the life of the bath, but the speed of this dissolution is low. It follows from these phenomena that the pickling bath loses its effectiveness since it becomes "less aggressive" vis-à-vis the parts to be stripped.
- the first type of treatment consists in destroying the used volumes of pickling bath by simple neutralization at the manufacturer or in an approved center.
- This first type of treatment has the drawbacks of generating a large volume of sludge due to the precipitation of the metals present in solution in the form of metal hydroxides during the neutralization of the acid, and of requiring the purchase of base by the operator for this neutralization of the acid. The operator must buy back acid to replace the pickling bath which has thus been destroyed.
- the second type of treatment consists of regenerating or having regenerated sulfuric acid in a sulfur and hydrochloric acid by a thermal process. This implies that the services of an external sulphate plant are used or that the farm is equipped with its own sulphate plant. These two alternatives impose significant additional costs.
- the distillation technique is implemented in the case of a hydrochloric acid pickling bath.
- the main processes have been developed by the companies KERAMCHEMIE and RUTHNER.
- the reaction takes place at 850 ° C. and makes it possible to obtain a directly reusable hydrochloric acid as well as an iron oxide which it is possible to recover.
- these processes require a lot of energy.
- the pickled steel contains addition elements, such as in particular silica, aluminum or copper, etc., it will be less easy to recover since these addition elements represent impurities.
- the crystallization technique is applied in the case of a sulfuric acid pickling bath.
- the baths are regenerated in a sulfation plant by cooling the solution to 0-10 ° C which causes precipitation of ferrous sulfate heptahydrate. Due to its low purity, this sulfate is difficult to recover. This technique nevertheless remains a rustic and simple method of purifying baths.
- ion exchange is generally implemented using ion exchange resins, which makes it possible to retain the free acids and to separate them from the metal salts contained in the pickling bath to be treated. Water is then circulated against the flow direction of the bath solution to be treated to regenerate the resins and recycle the acids.
- the used pickling baths must first be filtered so as not to clog the resins.
- the regenerated acids must be concentrated before being recycled. In addition, it is only the free acids that are regenerated and not all of the acids.
- trapped metals must be neutralized in a physicochemical station before their transport and storage in a Class 1 Technical Landfill Center.
- Membrane electrolysis was used in particular in a process by the company KERAMCHEMIE GMBH in 1983 for sulfuric acid baths.
- the electrolysis takes place in a reactor with two compartments separated by a diaphragm.
- the spent pickling bath passes after filtration, either in the anolyte where the sulfuric acid is regenerated, or in the catholyte where the iron is electro - deposited at the cathode.
- An addition of ammonium sulphate seems to favor this latter reaction.
- this type of installation cannot regenerate more than 500 l / h of spent bath.
- it is then necessary to get rid of the ammonium ions which are pollutants which the physico-chemical stations have difficulty in eliminating.
- the SEPRAC process applied to hydrochloric acid pickling baths, is based on what was formerly called "electro-electrodialysis" (EDD).
- EDD electro-electrodialysis
- the electrolyser used has three compartments separated by a cationic membrane and an anionic membrane.
- the spent bath circulates in the middle and cathode compartments and the anolyte is composed of dilute sulfuric acid.
- Several pilot cells have been installed (4kA / cell) but it seems that . the anionic membrane did not exhibit sufficient strength and selectivity. Cells of this type are no longer used.
- Patent applications FR 2 631 329 and FR 2 723 001 describe the implementation of liquid-liquid extraction for the recovery of phosphoric acid from the brightening baths.
- these methods are not adaptable to the other acids usually used in the surface treatment industry, such as sulfuric acids for example. and hydrochloric.
- steps are carried out: extraction of sulfuric acid from an aqueous solution containing metals by bringing said aqueous solution into contact with an organic solution containing a tertiary amine and a solvent; separation of the aqueous and organic phases; of sulfuric acid extraction by bringing said organic phase into contact with water.
- the organic solvent advocated by this patent is a mixture of hydrocarbons to which a long chain alcohol is added, the function of which is to prevent the separation of the amine salt from the solvent in the extraction step and to accelerate the separation of phases.
- US Pat. No. 3,211,526 advocates the use: either of an amine with relatively high extracting power and with relatively low de-extracting power, either of a relatively low extracting power and relatively high deextracting power.
- extraction is understood to mean the extraction of the acid to be regenerated from the organic phase to the aqueous phase, that is to say the second extraction step indicated above.
- the invention relates to a regeneration process by liquid-liquid extraction of hydrochloric and / or sulfuric acids from aqueous solutions containing metals using an amine carrying one or more long linear or branched chains on a carbon atom close to the atom. nitrogen.
- This amine is highly congested, which makes it an amine with low power extracting acid from the aqueous phase to the organic phase.
- the weak extracting power of this amine is however compensated by the use of a high molecular weight alcohol which it was surprisingly found to have an extracting power.
- the invention relates to a process for regenerating sulfuric acid, or its mixture with hydrochloric acid, from a aqueous solution containing metals, characterized in that it successively comprises: a step of extracting the acid to be regenerated by bringing the aqueous solution containing metals into contact with an organic solvent, said organic solvent comprising at least one alcohol having a high molar mass ranging from 100 to 250 g.mol -1 and at least one amine carrying one or more long linear or branched chains on a carbon atom close to the nitrogen atom and optionally at least one organic acid ; a step of separation of the organic and aqueous phases; and a step of extracting the acid to be regenerated by bringing the organic phase recovered in the previous step into contact with water.
- the invention is a process for regenerating hydrochloric acid from an aqueous solution containing metals, characterized in that it successively comprises:
- a step of extracting the acid by bringing the aqueous solution containing metals into contact with an organic solvent, said organic solvent containing at least one amine carrying one or more long linear or branched chains on a carbon atom close to the nitrogen atom and at least one alcohol and optionally at least one organic acid;
- the process according to the invention is particularly suitable for the regeneration of sulfuric acid, hydrochloric acid, or their mixtures, from aqueous solutions obtained from industrial installations, in particular from acid aqueous baths used in the surface treatment or steel industry.
- the process according to the invention is particularly effective for treating aqueous solutions containing hydrochloric and / or sulfuric acid, having concentrations ranging from 0.5 mol.L -1 to 8 mol.L "1 , or even
- the process which is the subject of the invention has above all demonstrated its qualities for concentrations greater than 5 mol.L -1 .
- the organic solvent which is used for the extraction can be advantageously chosen from the group including - linear or branched alcohols and alkanes or their mixtures in all proportions.
- the preferred alcohols are those having a high molar mass, that is to say ranging from 100 to 250 g.mol -1 , in particular 1 octanol.
- these alcohols in particular octanol, not only have the function of solvent, but that they play an extraction role, especially in the treatment of solutions with high concentrations of hydrochloric acid and / or sulfuric, in particular greater than 5 mol.L -1 .
- the use of these alcohols, in particular octanol in combination with an amine results surprisingly in a synergy allowing an improved regeneration of hydrochloric and / or sulfuric acid.
- the preferred linear or branched alkanes are those having a high molar mass, that is to say ranging from 150 to 200 g.mol -1 , in particular dodecane.
- the organic solvent contains at least one amine which carries one or more long straight or branched chains on a carbon atom close to the nitrogen atom of the amino function.
- This amine is especially chosen from the group consisting of tris-2-ethylhexyl a iné (TEHA), trioctyla ine (TOA), N-dodecyl-1, 3, 5-dimethylhexylamine (Amberlite LA-2), 1,3,5,7,9- dimethyldecylamine (Primene JMT), and preferably tris-2-ethylhexylamine (TEHA) or trioctylamine (TOA).
- TEHA tris-2-ethylhexyl a iné
- TOA trioctyla ine
- N-dodecyl-1 3, 5-dimethylhexylamine
- Amberlite LA-2 1,3,5,7,9- dimethyldecylamine
- Primarymene JMT 1,3,5,7,9- dimethylde
- the low extraction power of these amines in the first stage is compensated for by the action of alcohol, in particular octanol which has an extraction function.
- alcohol in particular octanol which has an extraction function.
- the acid to be regenerated is therefore effectively extracted from the aqueous solution to the organic phase.
- the good capacity for the extraction of these amines makes it possible to extract the acid to be regenerated from the organic phase to the aqueous phase.
- the process according to the invention achieves very high yields since more than 90% of the sulfuric acid can be regenerated. Such yields allow an improvement so far unmatched in the life of pickling baths.
- the organic solvent contains at least one organic acid, preferably an organophosphorus acid, chosen in particular from the group consisting of di-2-ethylhexylphosphoric acid (D 2 EHPA), di-2,4,4-trimethylpentylphosphinic acid (Cyanex 272) and di- 2,4,4-trimethylpentylmonothiophosphinic acid (Cyanex 302).
- pure water is preferably used.
- the aqueous solution containing metals can be treated continuously or in discrete volumes.
- the acid extracted from the organic phase enriched in acid with water can advantageously be recycled to the pickling bath after adjusting the acidity by adding concentrated pure acid.
- the pickling bath retains all its qualities.
- the recycling of acids is very advantageous from an environmental point of view. Indeed, not only the consumption of acid and base, for the neutralization, is reduced in a significant way but also the volume of waste is reduced.
- the organic solvent can be recovered after extraction of the acid with pure water and can advantageously be recycled to again extract the acid from the solution containing the acid to be regenerated.
- the recycling of the solvent is advantageous both with regard to operating costs and with regard to the environment.
- the organic solvent is advantageously a mixture of dodecane-octanol in proportions ranging from 100 to 0% of dodecane and from 0 to 100% of octanol by volume, preferably 70-30% by volume and it contains an amine.
- This amine is preferably tris-2-ethylhexyl amine (TEHA) at a concentration ranging from 0.1 to 1 mol.L -1 and more preferably 0.5 mol.L -1 .
- the organic solvent is preferably an alcohol having a high molar mass, that is to say ranging from 100 to 250 g.mol -1 and more preferably octanol.
- This organic solvent preferably contains on the one hand an amine, and more preferably trioctylamine (TOA) at a concentration preferably ranging from 0.05 to 0.5 mol.L -1 , and more preferably 0.2 mol.L -1 , and on the other hand optionally an organic acid, which is preferably di-2-ethylhexylphosphoric acid (D 2 EHPA) at a concentration preferably ranging from 0.05 to 0.5 mol.L -1 and more preferably 0.2 mol.L -1 .
- TOA trioctylamine
- D 2 EHPA di-2-ethylhexylphosphoric acid
- the extraction of acids is carried out selectively with respect to metals and the extraction with water of the organic phase enriched in acid has the advantage of recovering the pure acid, without significant presence of metals since the concentration of metals is generally less than 6.10 -5 gL -1 .
- Ferric iron is extracted at the same time as hydrochloric acid, but this is not a problem since its presence activates pickling.
- the method according to the invention can be implemented at room temperature since its effectiveness is little affected in the temperature range from 20 to 60 ° C.
- this process can be advantageously implemented in devices fitted with contactors. usually used in industrial acid regeneration processes.
- the process according to the invention is therefore easily transposable, without significant modification of the devices currently used in the surface treatment and steel industry.
- a solution containing 40 gL -1 of ferrous iron Fe (II), 2 gL -1 of ferric iron Fe (III) and 200 gL -1 of sulfuric acid (2 mol.L -1 ) is brought into contact with a solvent.
- the volume ratio is 1.
- a solution simulating a pickling bath containing 200 gL -1 of sulfuric acid (2 mol.L -1 ) is treated.
- the total flow is 35 mL.min -1 .
- the concentration of the raffinate is 0.3 mol. L -1 .
- a solution simulating a spent pickling bath containing 2 mol.L -1 sulfuric acid is treated.
- the total flow rate is 35 mL.min "1.
- 80% of the iron-free sulfuric acid is thus recovered at a concentration of 1.125 mol.L -1
- the concentration of the raffinate is 0.4 mol.L -1 .
- a solution simulating a spent pickling bath containing 2 mol.L -1 sulfuric acid is treated.
- the concentration of the raffinate is 0.16 mol.L -1 .
- a solution simulating a spent pickling bath containing 2 mol.L -1 sulfuric acid is treated.
- the concentration of the raffinate is 0.9 mol.L " 1 .
- EXAMPLE 2.1 Regeneration of hydrochloric acid in the absence of iron
- a solution simulating a pickling bath containing 8 mol.L -1 of hydrochloric acid is treated.
- the total flow is 35.5 mL.min -1 .
- the concentration in the raffinate is 1.8 mol.L -1 .
- a solution simulating a pickling bath containing 8 mol.L -1 of hydrochloric acid, 30 gL -1 of Fe (II) and 1.5 gL -1 of Fe (III) is treated.
- the total flow rate is 35 mL.min "1 .
- the concentration of ferric iron is 3g. L -1 and for the rest of the metals 6.10 -5 gL -1 .
- a solution simulating a pickling bath containing 8 mol.L “1 of hydrochloric acid, 30 gL “ 1 of Fe (II) and 1.5 gL -1 of Fe (III) is treated.
- TOA trioctylamine
- D 2 EHPA di-2-ethylhexylphosphoric acid
- the concentration of acid in the raffinate is 0.5 mol.L -1 .
- TOA trioctylamine
- D 2 EHPA di-2-ethylhexylphosphoric acid
- the concentration of acid in the raffinate is 2.5 mol.L -1 .
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL02363073A PL363073A1 (en) | 2001-04-09 | 2002-04-09 | Regeneration by liquid-liquid extraction of acids from aqueous solution containing metals |
EP02759825A EP1386022A2 (fr) | 2001-04-09 | 2002-04-09 | Regeneration par extraction liquide-liquide des acides a partir de solution aqueuse contenant des metaux |
NO20034520A NO20034520L (no) | 2001-04-09 | 2003-10-09 | Regenerering ved v¶ske-v¶ske-ekstrahering av syrer fra vannholdige lösninger som inneholder metaller |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0104794A FR2823195B1 (fr) | 2001-04-09 | 2001-04-09 | Regeneration par extraction liquide-liquide des acides a partir de solution aqueuse contenant des metaux |
FR01/04794 | 2001-04-09 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002081779A2 true WO2002081779A2 (fr) | 2002-10-17 |
WO2002081779A3 WO2002081779A3 (fr) | 2002-11-21 |
Family
ID=8862099
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/001231 WO2002081779A2 (fr) | 2001-04-09 | 2002-04-09 | Regeneration par extraction liquide-liquide des acides a partir de solution aqueuse contenant des metaux |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1386022A2 (fr) |
FR (1) | FR2823195B1 (fr) |
NO (1) | NO20034520L (fr) |
PL (1) | PL363073A1 (fr) |
WO (1) | WO2002081779A2 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009124393A1 (fr) | 2008-04-11 | 2009-10-15 | Cardarelli Francois | Procédé électrochimique de récupération de valeurs de fer métallique et d’acide sulfurique à partir de déchets sulfatés riches en fer, de résidus d’exploitation et de lessives de décapage. |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102045523B1 (ko) * | 2016-11-09 | 2019-11-18 | 주식회사 엘지화학 | 폐염산 정제 방법 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3211526A (en) * | 1963-08-06 | 1965-10-12 | Jr David J Crouse | Recovery of sulfuric acid from an aqueous solution containing metal values by extraction with tertiary amines |
US3870060A (en) * | 1974-02-26 | 1975-03-11 | Stora Kopparbergs Bergslags Ab | Method of removing monovalent inorganic acids from an aqueous solution containing metal salts of the acids |
DE2635025A1 (de) * | 1976-08-04 | 1978-02-09 | Gewerk Keramchemie | Verfahren zur entfernung von zink- und/oder phosphat-ionen aus eisenchloridhaltigen, sauren loesungen |
EP0517580A1 (fr) * | 1991-06-04 | 1992-12-09 | Commissariat A L'energie Atomique | Procédé de purification et de récupération d'acide orthophosphorique par extraction liquide-liquide |
-
2001
- 2001-04-09 FR FR0104794A patent/FR2823195B1/fr not_active Expired - Fee Related
-
2002
- 2002-04-09 EP EP02759825A patent/EP1386022A2/fr not_active Withdrawn
- 2002-04-09 PL PL02363073A patent/PL363073A1/xx not_active Application Discontinuation
- 2002-04-09 WO PCT/FR2002/001231 patent/WO2002081779A2/fr not_active Application Discontinuation
-
2003
- 2003-10-09 NO NO20034520A patent/NO20034520L/no not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3211526A (en) * | 1963-08-06 | 1965-10-12 | Jr David J Crouse | Recovery of sulfuric acid from an aqueous solution containing metal values by extraction with tertiary amines |
US3870060A (en) * | 1974-02-26 | 1975-03-11 | Stora Kopparbergs Bergslags Ab | Method of removing monovalent inorganic acids from an aqueous solution containing metal salts of the acids |
DE2635025A1 (de) * | 1976-08-04 | 1978-02-09 | Gewerk Keramchemie | Verfahren zur entfernung von zink- und/oder phosphat-ionen aus eisenchloridhaltigen, sauren loesungen |
EP0517580A1 (fr) * | 1991-06-04 | 1992-12-09 | Commissariat A L'energie Atomique | Procédé de purification et de récupération d'acide orthophosphorique par extraction liquide-liquide |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009124393A1 (fr) | 2008-04-11 | 2009-10-15 | Cardarelli Francois | Procédé électrochimique de récupération de valeurs de fer métallique et d’acide sulfurique à partir de déchets sulfatés riches en fer, de résidus d’exploitation et de lessives de décapage. |
Also Published As
Publication number | Publication date |
---|---|
NO20034520D0 (no) | 2003-10-09 |
FR2823195A1 (fr) | 2002-10-11 |
FR2823195B1 (fr) | 2004-07-02 |
PL363073A1 (en) | 2004-11-15 |
WO2002081779A3 (fr) | 2002-11-21 |
NO20034520L (no) | 2003-11-19 |
EP1386022A2 (fr) | 2004-02-04 |
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