CN106756043A - The separation method of chromium and iron in a kind of hydrochloric acid system - Google Patents

The separation method of chromium and iron in a kind of hydrochloric acid system Download PDF

Info

Publication number
CN106756043A
CN106756043A CN201611180944.7A CN201611180944A CN106756043A CN 106756043 A CN106756043 A CN 106756043A CN 201611180944 A CN201611180944 A CN 201611180944A CN 106756043 A CN106756043 A CN 106756043A
Authority
CN
China
Prior art keywords
chromium
iron
hydrochloric acid
extractant
extraction
Prior art date
Application number
CN201611180944.7A
Other languages
Chinese (zh)
Inventor
王泽斌
张伟
张忠
Original Assignee
中成致远有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中成致远有限公司 filed Critical 中成致远有限公司
Priority to CN201611180944.7A priority Critical patent/CN106756043A/en
Publication of CN106756043A publication Critical patent/CN106756043A/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • C22B7/007Wet processes by acid leaching
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00Compounds of chromium
    • C01G37/02Oxides or hydrates thereof
    • C01G37/033Chromium trioxide; Chromic acid
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00Compounds of chromium
    • C01G37/04Chromium halides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/02Oxides; Hydroxides
    • C01G49/06Ferric oxide (Fe2O3)
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00Compounds of iron
    • C01G49/10Halides
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses the separation method of chromium and iron in a kind of hydrochloric acid system.It is comprised the following steps that:1st, salt Ore Leaching carbon ferrochrome gained chromium chloride and frerrous chloride mixed solution, first with hydrogen peroxide Fe2+It is fully oxidized to Fe3+, then according to iron-holder in solution, according to suitably comparing, add extractant to be extracted, it is mutually chromium chloride solution that water is obtained after extraction, and the back extraction of organic phase water obtains ferric chloride solution and extractant, and extractant is recycled;2nd, chromium chloride solution obtains chromium chloride crystal using direct crystallization method, it would however also be possible to employ plus alkali neutralization precipitation method is obtained chromium hydroxide, chromium hydroxide obtains chrome green through high-temperature calcination again;3rd, ferric chloride solution can directly be used as water purification agent, it would however also be possible to employ plus alkali neutralization precipitation method is obtained iron hydroxide, iron hydroxide obtains ferric oxide red colorant through high-temperature calcination again.Present invention process is simple, it is easy to operate, except iron rate is up to more than 99.95%.

Description

The separation method of chromium and iron in a kind of hydrochloric acid system
Technical field
The present invention relates to molten production chromic salts and the electroplating sludge hydrochloric acid leachate processing technology field of ferrochrome acid, specifically relate to And in a kind of hydrochloric acid system chromium and iron separation method.
Background technology
In molten production chromic salts and electroplating sludge hydrochloric acid leachate processing technology field, particularly the carbon ferrochrome hydrochloric acid of ferrochrome acid During leaching production chromic salts, because chromium and ferro element chemical property are close, with absorption-co-precipitation effect so that separation is removed Iron turns into problem, and the method that chromium, iron are separate in current existing hydrochloric acid medium mainly has:(1)The ferrous oxalate precipitation method, are to utilize The low principle of ferrous oxalate solubility product, is precipitated by ferrous oxalate and reaches the purpose that chromium, iron are separate, but the method is except iron rate 98% or so can be reached, it is impossible to yield products of quality, and except iron rate is to factors such as oxalic acid addition, reaction temperature, solution pH values Extremely sensitive, operating difficulties, hydrochloric acid medium is more difficult to implement than sulfuric acid medium.(2)Oxidation neutralization precipitation method, using oxygen such as hydrogen peroxide Agent is the Fe in leachate2+It is oxidized to Fe3+, then add alkali to neutralize, by controlling PH=2~3, generation Fe (OH)3Precipitation, then Through filtering, the purpose that chromium, iron are separate is reached.The method is extremely sensitive to factors such as reaction temperature, solution pH values except iron rate, pH value Height is high except iron rate, but the loss of chromium is big, and pH value is low except iron rate is low, it is impossible to reach de-ferrous effect, and the Fe (OH) for producing3Colloid It is allowed to filter extremely difficult, while adsorb chromium ion causing damage.(3)Phosphate removes iron processes, China Patent No. 201310008212X, discloses the chromium and iron selective separation method in a kind of hydrochloric acid system solution, with electroplating sludge containing ferrochrome Hydrochloric acid leachate is raw material, first adds alkali adjustment solution pH value to be 2.0 or so, soluble phosphate is subsequently adding, in optimum response Stirring reaction 2 hours under the conditions of 90 DEG C of temperature, generation chromium phosphate and chromium hydroxide complex precipitate, be separated by filtration chromium and Iron.Although the method can realize the separation of chromium and iron, except iron rate can only achieve 98% or so, and chromium loss is big, and higher Reaction temperature and the reaction time more long can cause the rising of cost surely, most obvious defect is that heavy chromium reaction is compared pH value Sensitivity, slightly mistake will produce the complex precipitate of colloidal chromium phosphate and chromium hydroxide so that filtering is extremely difficult.(4) Solvent extraction, have been reported that in hydrochloric acid medium using TBP extract chromium or P204 extraction iron method separate chromium and iron, but this two kinds There is chromium and iron common extraction in extractant, separating effect is bad, and except iron rate is low, chromium loss is big.Also have been reported that and use lauryl amine Or the method that octadecylamine carries out extract and separate chromium and iron as extractant, although the method can reach 99% except iron rate, require There is chromium and iron common extraction in solution pH value, emulsion is serious in extraction process 2 or so, in order to solve emulsification problem, need Temperature that will be higher(80 DEG C optimal), while also need to add the demulsifiers such as sodium chloride, and the back extraction of iron ion is also more difficult, mesh Preceding this method still rests on the laboratory research stage, cannot also realize industrialized production.
In sum, the present invention devises the separation method of chromium and iron in a kind of new hydrochloric acid system.
The content of the invention
For not enough present on prior art, the present invention seeks to be provide chromium and iron in a kind of hydrochloric acid system point From method, process is simple, it is easy to operate, except iron rate is up to more than 99.95%.
To achieve these goals, the present invention is to realize by the following technical solutions:In a kind of hydrochloric acid system chromium and The separation method of iron, it is comprised the following steps that:1st, salt Ore Leaching carbon ferrochrome gained chromium chloride and frerrous chloride mixing are molten Liquid, first with hydrogen peroxide Fe2+It is fully oxidized to Fe3+, then according to iron-holder in solution, according to suitably comparing, add extraction Agent is extracted, and it is mutually chromium chloride solution that water is obtained after extraction, and the back extraction of organic phase water obtains ferric chloride solution and extractant, Extractant is recycled;2nd, chromium chloride solution obtains chromium chloride crystal using direct crystallization method, it would however also be possible to employ plus alkali is neutralized Intermediate processing is obtained chromium hydroxide, and chromium hydroxide obtains chrome green through high-temperature calcination again;3rd, ferric chloride solution can be direct It is used as water purification agent, it would however also be possible to employ plus alkali neutralization precipitation method is obtained iron hydroxide, iron hydroxide obtains oxygen through high-temperature calcination again Change iron oxide red pigment.
Salt Ore Leaching carbon ferrochrome gained chromium chloride and frerrous chloride mixed solution in described step 1 can be replaced it The hydrochloric acid leachate of its ferrochrome, can also be the electroplating sludge hydrochloric acid leachate containing chromium and iron.
Extractant in described step 1 uses sec-octyl alcohol or sec-octyl alcohol and N235Mixture, using sulfonated kerosene as Diluent, preferably sec-octyl alcohol.
Extraction in described step 1 and back extraction can be carried out at normal temperatures, and it is short that two-phase reaches the extraction equilibrium time, no Emulsion is produced, split-phase is fast.
Extractant in described step 1 is recycled, and gained major-minor product is free of Cr6+
Beneficial effects of the present invention:Compared with the existing technical method from the acid mixed solution of chromium and iron except iron, Advantage the most prominent is process is simple, it is easy to operated, except iron rate is up to more than 99.95%, chromium not common extraction, chromium free of losses, gained Product high-quality, low cost, extractant are recycled, and without " three wastes " discharge, major-minor product is free of Cr6+, meet national chromium row Industry cleaner production policy, is typical new cleanproduction process, for the sound development of Chrome Salt Industry provides a new approach.
Brief description of the drawings
Describe the present invention in detail with reference to the accompanying drawings and detailed description;
Fig. 1 is process chart of the invention.
Specific embodiment
For technological means, creation characteristic, reached purpose and effect for making present invention realization are easy to understand, with reference to Specific embodiment, is expanded on further the present invention.
Reference picture 1, this specific embodiment uses following technical scheme:The separation side of chromium and iron in a kind of hydrochloric acid system Method, it is comprised the following steps that:1st, salt Ore Leaching carbon ferrochrome gained chromium chloride and frerrous chloride mixed solution, first use dioxygen Water is Fe2+It is fully oxidized to Fe3+, then according to iron-holder in solution, according to suitably comparing, add extractant to be extracted, It is mutually chromium chloride solution that water is obtained after extraction, and the back extraction of organic phase water obtains ferric chloride solution and extractant, extractant circulation Use;2nd, chromium chloride solution obtains chromium chloride crystal using direct crystallization method, it would however also be possible to employ plus alkali neutralization precipitation method system Chromium hydroxide is obtained, chromium hydroxide obtains chrome green through high-temperature calcination again;3rd, ferric chloride solution can directly be used as water purification agent, Can also be using adding alkali neutralization precipitation method that iron hydroxide is obtained, iron hydroxide obtains ferric oxide red colorant through high-temperature calcination again.
Embodiment 1:Chromium chloride and frerrous chloride mixed liquor obtained by salt Ore Leaching carbon ferrochrome as raw material, in solution Cr3+Concentration is 120.6g/l, Fe2+Concentration is 56.5g/l, according to Fe2+Content adds appropriate hydrogen peroxide, and stirring makes Fe under normal temperature2+ It is fully oxidized to Fe3+, it is subsequently adding sec-octyl alcohol extractant and is extracted, extraction phase compares O/A=2:1, through three-level counter-current extraction, obtain To water phase chromium chloride solution in Cr3+Concentration is 120.6g/l, Fe2+Concentration is 0.005g/l, except iron rate 99.99%, does not extract chromium, Chromium chloride solution obtains chromium chloride crystal using direct crystallization method, it would however also be possible to employ plus alkali neutralization precipitation method is obtained hydroxide Chromium, chromium hydroxide obtains chrome green through high-temperature calcination again;The back extraction of organic phase water obtains extractant sec-octyl alcohol and chlorination O/A=0.5 is compared in ferrous solution, back extraction:1, the back extraction ratio 100% of iron, extractant is recycled, and ferric chloride solution can directly be used as Water purification agent, it would however also be possible to employ plus alkali neutralization precipitation method is obtained iron hydroxide, iron hydroxide obtains iron oxide through high-temperature calcination again Red.
Embodiment 2:It is raw material with the electroplating sludge hydrochloric acid leachate containing chromium and iron, Cr in solution3+Concentration is 18g/l, Fe2 +Concentration is 12g/l, according to Fe2+Content adds appropriate hydrogen peroxide, and stirring makes Fe under normal temperature2+It is completely converted into Fe3+, it is subsequently adding Sec-octyl alcohol extractant is extracted, and extraction phase compares O/A=1:1, extracted through two stage countercurrents, Cr in the water phase chromium chloride solution for obtaining3+ Concentration is 18g/l, and Fe2+ concentration is 0.002g/l, except iron rate 99.98%, does not extract chromium, and chromium chloride solution uses direct crystallization method Obtain chromium chloride crystal, it would however also be possible to employ plus alkali neutralization precipitation method is obtained chromium hydroxide, chromium hydroxide is obtained through high-temperature calcination again To chrome green;The back extraction of organic phase water obtains extractant sec-octyl alcohol and ferric chloride solution, and O/A=1 is compared in back extraction:1, iron Back extraction ratio 100%, extractant recycles, and ferric chloride solution can directly be used as water purification agent, it would however also be possible to employ plus in alkali and heavy Shallow lake method is obtained iron hydroxide, and iron hydroxide obtains ferric oxide red colorant through high-temperature calcination again.
Embodiment 3:Chromium chloride and frerrous chloride mixed solution obtained by salt Ore Leaching carbon ferrochrome as raw material, in solution Cr3+Concentration is 118g/l, Fe2+Concentration is 55.8g/l, according to Fe2+Content adds appropriate hydrogen peroxide, and stirring makes Fe under normal temperature2+Entirely Portion changes into Fe3+, it is subsequently adding extractant and is extracted, extractant composition is N235 and the mixture of sec-octyl alcohol, sulfonated kerosene It is diluent, extraction phase compares O/A=1:1, through three-level counter-current extraction, Cr in the water phase chromium chloride solution for obtaining3+Concentration is 118g/ L, Fe2+Concentration is 0.02g/l, except iron rate 99.96%, does not extract chromium, and it is brilliant that chromium chloride solution obtains chromium chloride using direct crystallization method Body, it would however also be possible to employ plus alkali neutralization precipitation method is obtained chromium hydroxide, chromium hydroxide obtains chrome green through high-temperature calcination again; The back extraction of organic phase water obtains extractant sec-octyl alcohol and ferric chloride solution, and O/A=1 is compared in back extraction:1, the back extraction ratio 100% of iron, Extractant is recycled, and ferric chloride solution can directly be used as water purification agent, it would however also be possible to employ plus alkali neutralization precipitation method is obtained hydrogen Iron oxide, iron hydroxide obtains ferric oxide red colorant through high-temperature calcination again.
General principle of the invention and principal character and advantages of the present invention has been shown and described above.The technology of the industry Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its Equivalent thereof.

Claims (6)

1. in a kind of hydrochloric acid system chromium and iron separation method, it is characterised in that it is comprised the following steps that:(1), salt acidleach Go out carbon ferrochrome gained chromium chloride and frerrous chloride mixed solution, first with hydrogen peroxide Fe2+It is fully oxidized to Fe3+, then basis Iron-holder in solution, adds extractant to be extracted, and it is mutually chromium chloride solution that water is obtained after extraction, and organic phase water is stripped To ferric chloride solution and extractant, extractant recycling;(2), chromium chloride solution obtains chromium chloride using direct crystallization method Crystal, or using adding alkali neutralization precipitation method that chromium hydroxide is obtained, chromium hydroxide obtains chrome green through high-temperature calcination again; (3), ferric chloride solution is directly used as water purification agent, or using adding alkali neutralization precipitation method that iron hydroxide is obtained, iron hydroxide is passed through again High-temperature calcination obtains ferric oxide red colorant.
2. in a kind of hydrochloric acid system according to claim 1 chromium and iron separation method, it is characterised in that described step (1) salt Ore Leaching carbon ferrochrome gained chromium chloride and frerrous chloride mixed solution in replace with the hydrochloric acid leachate of ferrochrome Or the electroplating sludge hydrochloric acid leachate containing chromium and iron.
3. in a kind of hydrochloric acid system according to claim 1 chromium and iron separation method, it is characterised in that described step (1) extractant in uses sec-octyl alcohol and N235Mixture, using sulfonated kerosene as diluent.
4. in a kind of hydrochloric acid system according to claim 1 chromium and iron separation method, it is characterised in that described step (1) extractant in uses sec-octyl alcohol.
5. in a kind of hydrochloric acid system according to claim 1 chromium and iron separation method, it is characterised in that described step (1) extraction in and back extraction can be carried out at normal temperatures, and it is short that two-phase reaches the extraction equilibrium time, does not produce emulsion, point It is mutually fast.
6. in a kind of hydrochloric acid system according to claim 1 chromium and iron separation method, it is characterised in that described step (1) extractant in is recycled, and gained major-minor product is free of Cr6+
CN201611180944.7A 2016-12-20 2016-12-20 The separation method of chromium and iron in a kind of hydrochloric acid system CN106756043A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611180944.7A CN106756043A (en) 2016-12-20 2016-12-20 The separation method of chromium and iron in a kind of hydrochloric acid system

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611180944.7A CN106756043A (en) 2016-12-20 2016-12-20 The separation method of chromium and iron in a kind of hydrochloric acid system

Publications (1)

Publication Number Publication Date
CN106756043A true CN106756043A (en) 2017-05-31

Family

ID=58890889

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611180944.7A CN106756043A (en) 2016-12-20 2016-12-20 The separation method of chromium and iron in a kind of hydrochloric acid system

Country Status (1)

Country Link
CN (1) CN106756043A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109536708A (en) * 2018-12-17 2019-03-29 江苏永葆环保科技有限公司 The separation method of chromium and iron in a kind of pickle liquor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109536708A (en) * 2018-12-17 2019-03-29 江苏永葆环保科技有限公司 The separation method of chromium and iron in a kind of pickle liquor

Similar Documents

Publication Publication Date Title
CN105567978B (en) The method that copper zinc cobalt nickel is recycled from the various waste materials containing non-ferrous metal
Zeng et al. A literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurisation catalysts: Part II: Separation and purification
DE60010702T2 (en) TREATMENT OF TITANIUM FOR THE MANUFACTURE OF TITANIUM DIOXIDE PIGMENTS
CN103922416B (en) A kind of method of Separation and Recovery iron from red mud
JP2005350766A (en) Hydrometallurgical process of nickel oxide ore
US20200157696A1 (en) Metallurgical And Chemical Processes For Recovering Vanadium And Iron Values From Vanadiferous Titanomagnetite And Vanadiferous Feedstocks
CN104911364A (en) Environment-friendly and high-efficiency production method of antimony white by using Sb and As-containing ash
CN103757425B (en) A kind of clean process method being produced vanadic acid sodium and chromium acid sodium alkaline liquid by high chrome alum slag
CN102828025B (en) Method for extracting V2O5 from stone coal navajoite
CN104437536B (en) A kind of preparation method of manganese-zinc ferrite/bismuth oxide magnetic photocatalyst
Ning et al. High-efficient extraction of vanadium and its application in the utilization of the chromium-bearing vanadium slag
CN103146930B (en) Method for preparing vanadium oxide
US4273745A (en) Production of molybdenum oxide from ammonium molybdate solutions
CN105271632B (en) A kind of method of electroplating sludge synthetical recovery
CN100537435C (en) Method for manufacturing iron oxide with waste slag containing iron
EP3208352A1 (en) Method for recovering high-purity scandium
EP3138816B1 (en) Method for preparing nanometer titanium dioxide
CN101139338B (en) Preparation of 2,2'-disulfo-dibenzopyrene by oxygen process based on 2-mercaptan benzothiazole ammonia salt
CN106180138B (en) A kind of processing method of arsenic-containing waste
CN101871046A (en) Method for recycling heavy metal pollution wastes
CN105420519A (en) Method for extracting vanadium and chromium from materials containing vanadium or/and chromium
CN103342387A (en) Method for producing titanium dioxide by using titanium concentrate and acid-soluble titanium slag as materials employing sulfuric acid method
CN102094119A (en) Method for preparing electrolytic manganese metal with low-grade pyrolusite wet leaching
KR101441421B1 (en) Collection method of precursor material using disposed lithum-ion battery
JP2003300732A (en) Method for producing high purity iron oxide and its use

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination