CN103014340B - Selective separation method for chromium and iron in sulfuric acid system solution - Google Patents
Selective separation method for chromium and iron in sulfuric acid system solution Download PDFInfo
- Publication number
- CN103014340B CN103014340B CN201310008199.8A CN201310008199A CN103014340B CN 103014340 B CN103014340 B CN 103014340B CN 201310008199 A CN201310008199 A CN 201310008199A CN 103014340 B CN103014340 B CN 103014340B
- Authority
- CN
- China
- Prior art keywords
- chromium
- iron
- sulfuric acid
- acid system
- system solution
- 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.)
- Active
Links
Classifications
-
- 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
Abstract
A selective separation method of chromium and iron in a sulfuric acid system solution relates to the selective separation of chromium and iron in the sulfuric acid system solution in a hydrometallurgy process, in particular to a separation method of chromium and iron in a sulfuric acid leaching solution of chromium-containing electroplating sludge, which is characterized by sequentially comprising the following steps: (1) adding a reducing agent into a sulfuric acid system solution containing chromium and iron for pretreatment; (2) adjusting the pH value of the solution; (3) adding soluble phosphate, and performing selective phosphoric acid chromium precipitation reaction to form a composite coprecipitate of chromium phosphate and chromium hydroxide; (4) filtering and separating to obtain chromium phosphate and chromium hydroxide composite precipitate and ferrous sulfate containing filtrate to realize selective separation of ferrochrome. The method has the advantages of simple process, short flow and environment-friendly hydrometallurgy technology for extracting and separating chromium and iron, and is particularly suitable for the field of resource utilization of chromium-containing iron electroplating sludge.
Description
Technical field
A selective separation method for chromium and iron in sulfuric acid system solution, relates to the selective separation of chromium and iron in hydrometallurgy process sulfuric acid system solution, particularly containing chromium, iron separation method in ferrochrome electroplating sludge sulphuric leachate.
Background technology
In hydrometallurgy process, can produce the sulfuric acid system solution containing chromium and iron, form the mixing solutions that contains chromium sulphate and ferrous sulfate.Because chromium, ferro element chemical property are close, and absorption-co-precipitation effect, there is a difficult problem for separation and Extraction chromium, ferrous metal.
In the sulfuric acid system solution of having developed at present, chromium, iron separation method mainly contain:
(1) solvent extration, it has the features such as equipment is simple, process is easy to control and reagent can be recycled, extract through acid phosphine kind of extractants (as P204, P507), although the percentage extraction of iron can reach more than 99%, but the coextraction rate of chromium is also up to 25%, separating effect is not good, and chromium loss obviously;
(2) Mohr's salt crystallization process, is to react with ammonium sulfate based on ferrous sulfate, chromium sulphate, the chromic ammonium alum (NH of generation
4cr (SO
4)
212H
2and ferrous ammonium alum (Fe (NH O)
4)
2(SO
4)
26H
2o, i.e. Mohr's salt) there is obvious dissolubility difference, ferrous ammonium alum crystallization, chromium is retained in solution, to reach the object of effective separate chromium, iron.Although the chromium rate of loss of Mohr's salt crystallization process is lower, the method complex procedures is strict to operational requirement, is difficult for heavy industrialization;
(3) the Ferrox precipitator method are low by (2.1 × 10 based on Ferrox solubility product
-7) principle, precipitate to reach the object of separate chromium, iron by Ferrox.Although the Ferrox precipitator method can realize the deironing rate of 98% left and right at ambient temperature, deironing rate is to oxalic acid add-on and temperature factor sensitivity, strict to operational requirement, and preferably reacts pH approximately 4.0, large with load in initial soln.
(4) goethite process, deironing reclaim chromium from sulfuric acid chromium-containing solution, although separation of iron in goethite form rate up to 99%, the rate of loss of chromium is higher (approximately 15%) also.
Substantially in the laboratory study stage, also lack the economic and practical technology of supporting industryization application for the research of ferrochrome isolation technique, there is no at present the report of heavy industrialization application.This is also to perplex one of technical barrier containing secondary resource recycles such as chromium and iron electroplating sludges always, is unfavorable for the harmlessness disposing of chromium and high efficiente callback and the recycling of valuable constituent chromium metal.
In disclosed solution in the patent of separate chromium and iron ion method, the patent No. be the Chinese patent of 201010510631X disclosed be a kind of method by separate chromium ion and iron ion in Multi component, take the chromium sulphate after sulfuric acid leaching chromite and ferric sulfate mixing solutions as raw material, add extraction agent to extract, extraction agent is selected octadecyl dimethyl tertiary amine, octadecyl tertiary amine or two octadecyl tertiary amine, extraction agent add-on is 10%～50% of chromium sulphate and ferric sulfate mixed liquor volume, after extraction, obtaining non-organic phase is chromium sulfate solution, obtaining organic phase is extraction agent and ferric sulfate, then with sodium hydroxide solution, organic phase is stripped, regulating pH value is 9～10, obtain ironic hydroxide, metabisulfite solution and extraction agent, extraction agent recycles, the chromium sulfate solution that utilizes extraction to obtain, adopt the method for direct crystallization to prepare chromium sulphate, utilize ironic hydroxide to prepare ferric oxide red colorant with the method for high temperature crystallization for raw material.In industry, adopt the cost of extraction separating method higher, and in electroplating sludge extracting and separating chromium, iron process, may have third phase generation, can have a strong impact on extraction separation process.
Application number is that the Chinese patent of CN200710041574.3 is a kind of phosphate stabilizing treatment process of electroplating sludge, and its key step is as follows: through 102 ℃ of oven dry, then pulverize electroplating sludge (1), for subsequent use; (2) under 30-70 ℃ of temperature range, by analytically pure soluble phosphate with above-mentioned electroplating sludge by 1: 70-1: 90 part by weight mixes, and in stirrer strong stirring 4 hours, it is fully reacted; In reaction process, control its pH value within the scope of 8-11; (3) after reaction finishes, naturally cooling, obtains the sewage sludge solid sample that contains heavy metal composite phosphate, and test shows that this mud can reach the hazard waste landfill standard of national regulation.This method is electroplating sludge stabilization treatment, does not realize valuable metal recycling.
Summary of the invention
The object of the invention is the deficiency existing in above-mentioned prior art, provide that a kind of technique is simple, flow process is short, eco-friendly, can effectively extract the selective separation method of chromium and iron in the sulfuric acid system solution of separate chromium and iron.
The present invention is achieved by the following technical solutions.
A selective separation method for chromium and iron in sulfuric acid system solution, is characterized in that the step of its technological process comprises successively:
(1) in the sulfuric acid system solution containing chromium and iron, add reductive agent to carry out pre-treatment;
(2) adjust pH;
(3) add soluble phosphate, carry out the heavy chromium reaction of selectivity phosphoric acid, make Plessy's green and chromium hydroxide form compound coprecipitate;
(4) carry out filtering separation, obtain the ferrous filtrate of Plessy's green chromium hydroxide composite precipitation thing and sulfur acid, realize ferrochrome selective separation.
The selective separation method of chromium and iron in a kind of sulfuric acid system solution of the present invention, is characterized in that in the described sulfuric acid system solution containing chromium and iron, content of chromium ion is 0.1-30g/L, and iron ion content is 0.1-20g/L.
The selective separation method of chromium and iron in a kind of sulfuric acid system solution of the present invention, it is characterized in that the described reductive agent that adds carries out preprocessing process, be to add Sulfothiorine or S-WAT to carry out reduction pretreatment, make chromium, iron ion in solution remain on respectively Cr
3+, Fe
2+state.
The selective separation method of chromium and iron in a kind of sulfuric acid system solution of the present invention, is characterized in that described adjustment pH process is to add alkali lye to adjust pH, and making pH is 0.5～2.5.
The selective separation method of chromium and iron in a kind of sulfuric acid system solution of the present invention, it is characterized in that the described soluble phosphate that adds, carry out the heavy chromium reaction process of selectivity phosphoric acid, the amount of the soluble phosphate of interpolation is in phosphate radical, and phosphate radical and chromium ion mol ratio are 0.2～0.8.
The selective separation method of chromium and iron in a kind of sulfuric acid system solution of the present invention, is characterized in that the described soluble phosphate that adds, and the temperature of carrying out the heavy chromium reaction process of selectivity phosphoric acid is 60～90 ℃, and the time is 60～120min.
The selective separation method of chromium and iron in a kind of sulfuric acid system solution of the present invention, is characterized in that the described soluble phosphate that adds, and carries out the heavy chromium reaction process of selectivity phosphoric acid, stirs, and the linear velocity of stirring is 100～400 m/min.
The selective separation method of chromium and iron in a kind of sulfuric acid system solution of the present invention, is characterized in that after described filtering separation, chromium is kept in filter cake with throw out, and iron remains in solution.
Method of the present invention, utilizes Cr
3+, Fe
2+phosphoric acid salt dissolubility difference, the chromium of realization separates with the selective precipitation of iron.Due to CrPO
42H
2the solubility product K of O
spbe 2.4 × 10
-23, Cr (OH)
3solubility product K
spbe 6.3 × 10
-31, and Fe
3(PO
4)
2be slightly soluble in water, be soluble in acid, Plessy's green can be combined with chromium hydroxide and be generated colloidal composite precipitation thing, is controlled, adjusted the processing steps such as pH, chemical precipitation reaction, filtering separation by reduction, finally obtains Plessy's green chromium hydroxide composite precipitation thing and contains FeSO
4filtrate, realizes ferrochrome selective separation and extracts, and the rate of recovery of chromium and iron is more than 98.5%.The composite precipitation thing obtaining can become various chemical industry chromic salts or chromium hydroxide product at follow-up further deep processing, and phosphate radical can be recycled recycle simultaneously.
Method of the present invention, has the following advantages: (1) technological operation is simple, flow process is short, cost is low; (2) the heavy chromium method of phosphoric acid has strong selectivity within the scope of wider ionic concn, and chromium, iron separating effect ideal; (3) can high efficiente callback chromium metal, iron, the rate of recovery is all greater than 98.5%, remarkable in economical benefits; (4) the phosphate precipitating agent reusable edible using in process, production process is without secondary environmental pollution.
Embodiment
The selective separation method of chromium and iron in a kind of sulfuric acid system solution, the step of its technological process comprises successively: (1) is in the sulfuric acid system solution containing chromium and iron, content of chromium ion in solution is 0.1-30g/L, ferrous ion content is 0.1-20g/L, add reductive agent S-WAT or Sulfothiorine to carry out pre-treatment, make chromium, iron ion in solution remain on respectively Cr
3+, Fe
2+state; (2) adding alkali lye to adjust pH value is 0.5～2.5; (3) add soluble phosphate, as sodium phosphate, the phosphate radical adding and chromium ion mol ratio are 0.2～0.8, carry out the heavy chromium reaction of selectivity phosphoric acid, reaction process is at 60～90 ℃ of interval insulation 60～120min, in process, stirring linear velocity control is 100～400 m/min, makes Plessy's green and chromium hydroxide form compound coprecipitate; (4) carry out filtering separation, obtain the ferrous filtrate of Plessy's green chromium hydroxide composite precipitation thing and sulfur acid, realize ferrochrome selective separation.
Embodiment 1
Sulfuric acid system chromium, in iron mixing solutions, Cr content is 6.0 g/L, Fe content is 3.0 g/L, reductive agent is selected S-WAT, concentration 20% sodium sulfite solution and chromium, iron mixing solutions drips in 1:10 ratio average rate, add appropriate NaOH solution and adjust pH value of solution to 2.0, add sodium phosphate by the amount of phosphate radical and chromium ion mol ratio 0.4, under 90 ℃ of conditions, be incubated 60 min, in process, stir linear velocity and be controlled at 200 m/min, filtration obtains Plessy's green chromium hydroxide composite precipitation thing, chromium in filtrate, concentration of iron is respectively 0.086 g/L and 2.91 g/L, chromium recovery ratio is 98.53%, iron recovery is 98.58%, ferrochrome separation factor 67.7.
Embodiment 2
Sulfuric acid system chromium, the middle Cr content of iron mixing solutions is 20.0 g/L, Fe content is 15.0 g/L, reductive agent is selected S-WAT, concentration 20% sodium sulfite solution and chromium, iron mixing solutions drips in 1:5 ratio average rate, add appropriate NaOH solution and adjust pH value of solution to 2.0, add sodium phosphate by the amount of phosphate radical and chromium ion mol ratio 0.3, under 70 ℃ of conditions, be incubated 90 min, in process, stir linear velocity and be controlled at 300 m/min, filtration obtains Plessy's green chromium hydroxide composite precipitation thing, chromium in filtrate, concentration of iron is respectively 0.089 g/L and 14.89 g/L, chromium recovery ratio is 99.56%, iron recovery is 99.08%, ferrochrome separation factor 223.1.
Embodiment 3
Sulfuric acid system is containing chromium, the middle Cr content of iron mixing solutions is 6.0 g/L, Fe content is 3.0 g/L, reductive agent is selected Sulfothiorine, concentration 10% hypo solution and chromium, iron mixing solutions drips in 1:5 ratio average rate, add appropriate NaOH solution and adjust pH value of solution to 1.5, add sodium phosphate by the amount of phosphate radical and chromium ion mol ratio 0.5, under 80 ℃ of conditions, be incubated 60 min, in process, stir linear velocity and be controlled at 150 m/min, filtration obtains Plessy's green chromium hydroxide composite precipitation thing, chromium in filtrate, concentration of iron is respectively 0.053 g/L, 2.90 g/L, chromium recovery ratio is 99.10%, iron recovery is 99.03%, ferrochrome separation factor 109.4.
The above; it is only specific embodiment of the invention case; but can there be many improvement and change; therefore protection scope of the present invention is not limited to this; any be familiar with those skilled in the art the present invention disclose technical scope in; the variation that can expect easily or replacement, within all should being encompassed in protection scope of the present invention.
Claims (3)
1. a selective separation method for chromium and iron in sulfuric acid system solution, is characterized in that the step of its technological process comprises successively:
(1) in the sulfuric acid system solution containing chromium and iron, add reductive agent to carry out pre-treatment; In the described sulfuric acid system solution containing chromium and iron, content of chromium ion is 0.1-30g/L, and iron ion content is 0.1-20g/L; The described reductive agent that adds carries out preprocessing process, is to add Sulfothiorine or S-WAT to carry out reduction pretreatment, makes chromium, iron ion in solution remain on respectively Cr
3+, Fe
2+state;
(2) adjust pH; Described adjustment pH process is to add alkali lye to adjust pH, and making pH is 0.5～2.5;
(3) add soluble phosphate, carry out the heavy chromium reaction of selectivity phosphoric acid, make Plessy's green and chromium hydroxide form compound coprecipitate; The described soluble phosphate that adds, carries out the heavy chromium reaction process of selectivity phosphoric acid, and the amount of the soluble phosphate of interpolation is in phosphate radical, and phosphate radical and chromium ion mol ratio are 0.2～0.8; The described soluble phosphate that adds, the temperature of carrying out the heavy chromium reaction process of selectivity phosphoric acid is 60～90 ℃, the time is 60～120min; The described soluble phosphate that adds, carries out the heavy chromium reaction process of selectivity phosphoric acid, stirs, and the linear velocity of stirring is 100～400 m/min;
(4) carry out filtering separation, obtain the ferrous filtrate of Plessy's green chromium hydroxide composite precipitation thing and sulfur acid, realize ferrochrome selective separation.
2. the selective separation method of chromium and iron in a kind of sulfuric acid system solution according to claim 1, it is characterized in that adding soluble phosphate is sodium phosphate.
3. the selective separation method of chromium and iron in a kind of sulfuric acid system solution according to claim 1, is characterized in that the described sulfuric acid system solution containing chromium and iron is electroplating sludge sulphuric leachate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310008199.8A CN103014340B (en) | 2013-01-10 | 2013-01-10 | Selective separation method for chromium and iron in sulfuric acid system solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310008199.8A CN103014340B (en) | 2013-01-10 | 2013-01-10 | Selective separation method for chromium and iron in sulfuric acid system solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103014340A CN103014340A (en) | 2013-04-03 |
| CN103014340B true CN103014340B (en) | 2014-06-25 |
Family
ID=47963450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310008199.8A Active CN103014340B (en) | 2013-01-10 | 2013-01-10 | Selective separation method for chromium and iron in sulfuric acid system solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103014340B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483380A (en) * | 2014-09-16 | 2016-04-13 | 倪建国 | Method for treating chromium slag in electroplating sludge |
| CN104372380B (en) * | 2014-11-18 | 2016-08-24 | 辽宁石化职业技术学院 | A kind of low-temperature molten salt method prepares High Pure Chromium |
| CN104593598A (en) * | 2014-12-18 | 2015-05-06 | 北京矿冶研究总院 | Method for resource utilization of multiple metals in electroplating sludge |
| CN106244804B (en) * | 2016-07-29 | 2017-12-29 | 江西理工大学 | Villaumite acid system is preferentially complexed the ferrochrome separation method of the heavy iron of selectivity |
| CN106148706B (en) * | 2016-07-29 | 2017-12-08 | 江西理工大学 | The ferrochrome separation method of the heavy iron of sulfuric acid system selective complexation selective hydrolysis |
| CN106636651B (en) * | 2016-12-16 | 2018-05-08 | 江苏理工学院 | The separation method of chromium and iron aluminium in a kind of sulfuric acid system solution of aluminium containing ferrochrome |
| CN107201447B (en) * | 2017-06-19 | 2018-12-04 | 江西理工大学 | A method of complex-precipitation separates ferrochrome from electroplating sludge leachate |
| CN110436728B (en) * | 2019-09-06 | 2020-07-31 | 中南大学 | Method for in-situ stabilization repair of lead-polluted bottom mud by iron-based material and microorganisms |
| CN110963532B (en) * | 2019-12-26 | 2023-01-24 | 四川省银河化学股份有限公司 | Method for preparing trivalent chromium salt by ferrochrome acid dissolution |
| CN111592376B (en) * | 2020-06-08 | 2021-06-08 | 北京化工大学 | Preparation method of composite aerogel functional material based on ferroferric oxide nanowire/graphene oxide interpenetrating structure |
| CN113416847B (en) * | 2021-07-05 | 2022-05-31 | 昆明理工大学 | Method for recycling, reducing and harmlessly treating vanadium extraction tailings |
| CN114212763B (en) * | 2021-12-17 | 2023-06-16 | 南方锰业集团有限责任公司大新锰矿分公司 | Resource utilization method of cathode plate polishing waste liquid for electrolytic manganese metal |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001764A (en) * | 2010-10-18 | 2011-04-06 | 荆门市格林美新材料有限公司 | Method for removing chromium impurities from nickel leach liquor |
-
2013
- 2013-01-10 CN CN201310008199.8A patent/CN103014340B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001764A (en) * | 2010-10-18 | 2011-04-06 | 荆门市格林美新材料有限公司 | Method for removing chromium impurities from nickel leach liquor |
Non-Patent Citations (2)
| Title |
|---|
| 丁翼主编.磷酸沉淀法.《铬化合物生产与应用》.化学工业出版社,2003,第137页第5段、第138页第1段. * |
| 陈嘉甫,谭光薰主编.磷酸铬的制备方法.《磷酸盐的生产与应用》.成都科技大学出版社,1989,第323页最后一段至第324页第一段. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103014340A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103014340B (en) | Selective separation method for chromium and iron in sulfuric acid system solution | |
| CN106636651B (en) | The separation method of chromium and iron aluminium in a kind of sulfuric acid system solution of aluminium containing ferrochrome | |
| CN104593598A (en) | Method for resource utilization of multiple metals in electroplating sludge | |
| CN102796876B (en) | Method for extracting scandium oxide from titanium slag chloride waste | |
| CN102154550A (en) | Vanadium extracting method based on extraction-back extraction system | |
| CN103468978B (en) | A kind of method carrying scandium from laterite nickel ore by sulfuric acid leaching liquid | |
| CN104178632A (en) | Method for comprehensively utilizing titanium white waste acid | |
| CN103468979A (en) | Method for recycling scandium from lateritic nickel ore smelted iron aluminum slag | |
| CN103014341B (en) | Selective separation method for chromium and iron in hydrochloric acid system solution | |
| CN104531995A (en) | Method for extracting zinc from low-grade zinc-containing material leaching liquid | |
| CN104726724A (en) | Method for extracting scandium from nickel laterite ores | |
| CN107201447B (en) | A method of complex-precipitation separates ferrochrome from electroplating sludge leachate | |
| CN103436715A (en) | Method of extracting vanadium from stone coal | |
| CN105483400A (en) | Method for synchronously extracting and separating uranium and molybdenum | |
| CN109355502A (en) | A method of extracting lithium ion from acid system | |
| CN101974688B (en) | Method for separating chromium ions and iron ions in multicomponent solution | |
| CN103966448A (en) | Method for comprehensively recovering zinc from jarosite slag | |
| CN106244804A (en) | Villaumite acid system preferential complexation selectivity sinks the ferrochrome separation method of ferrum | |
| CN104032130A (en) | Method for precipitating and separating iron and nickel in serpentine leaching liquor | |
| CN103342635A (en) | Method for recovering sodium oxalate from waste water | |
| CN102876895A (en) | Method for recycling vanadium and chromium from low-concentration pentavalent vanadium and hexavalent chromium mixed liquor | |
| CN103572053B (en) | Abandoned car or plating wastes hydrometallurgic recovery method and poisoning extractant processing method thereof | |
| CN103241720B (en) | Method for preparing amorphous iron phosphate by using phosphate sludge | |
| CN109516443B (en) | Treatment method of aluminum-containing waste sulfuric acid | |
| CN107604163B (en) | A kind of technique of no scorification processing electroplating sludge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |