CN109536708A - The separation method of chromium and iron in a kind of pickle liquor - Google Patents

The separation method of chromium and iron in a kind of pickle liquor Download PDF

Info

Publication number
CN109536708A
CN109536708A CN201811543843.0A CN201811543843A CN109536708A CN 109536708 A CN109536708 A CN 109536708A CN 201811543843 A CN201811543843 A CN 201811543843A CN 109536708 A CN109536708 A CN 109536708A
Authority
CN
China
Prior art keywords
chromium
ion
iron
extraction
extractant
Prior art date
Application number
CN201811543843.0A
Other languages
Chinese (zh)
Inventor
朱松锋
蒋银峰
居银栋
蒋浩
李萍
Original Assignee
江苏永葆环保科技有限公司
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 江苏永葆环保科技有限公司 filed Critical 江苏永葆环保科技有限公司
Priority to CN201811543843.0A priority Critical patent/CN109536708A/en
Publication of CN109536708A publication Critical patent/CN109536708A/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
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/0004Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/0005Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds, e.g. acyclic or carbocyclic compounds, heterocyclic compounds, organo- metallic compounds, alcohols, ethers, or the like
    • C22B3/0006Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds, e.g. acyclic or carbocyclic compounds, heterocyclic compounds, organo- metallic compounds, alcohols, ethers, or the like using acyclic or carbocyclic compounds
    • C22B3/0032Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds, e.g. acyclic or carbocyclic compounds, heterocyclic compounds, organo- metallic compounds, alcohols, ethers, or the like using acyclic or carbocyclic compounds using mixtures of acyclic or carbocyclic compounds of different types
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G37/00Compounds of chromium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/0004Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/0005Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds, e.g. acyclic or carbocyclic compounds, heterocyclic compounds, organo- metallic compounds, alcohols, ethers, or the like
    • C22B3/004Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds, e.g. acyclic or carbocyclic compounds, heterocyclic compounds, organo- metallic compounds, alcohols, ethers, or the like using organo-metallic compounds or organo compounds of boron, silicon, phosphorus, selenium or tellurim
    • C22B3/0095Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds, e.g. acyclic or carbocyclic compounds, heterocyclic compounds, organo- metallic compounds, alcohols, ethers, or the like using organo-metallic compounds or organo compounds of boron, silicon, phosphorus, selenium or tellurim using a mixture of organic agents wherein one agent at least is an organo-metallic compound
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/30Obtaining chromium, molybdenum or tungsten
    • C22B34/32Obtaining chromium
    • 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
    • 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 methods of chromium and iron in a kind of pickle liquor.This method comprises the following steps: ferric iron extraction;It is stripped ferric iron;Chromium ion extraction;Chromium ion back extraction.Method of the invention first passes through organic extraction and sulfuric acid is stripped isolated ferric ion, avoid the halfway phenomenon of ferric iron back in reduction method, and avoid influence of the ferric iron to chromium ion extraction and separation, and then pass through the isolated chromium ion of specific extraction-back extraction system and ferrous iron solution, the chromic salts product of high price can be made in concentrated crystallization treatment, except the preparation that can be used for iron series water purifier containing ferrous acid solution after chromium, iron ion content is in 25ppm or less after extractant recycling of the invention, the content of chromium ion is in 28ppm or less, it can be recycled, extractant cost is saved, realize circular economy.

Description

The separation method of chromium and iron in a kind of pickle liquor

Technical field

The present invention relates to technical field of wastewater recovery, more particularly, to the separation side of chromium and iron in a kind of pickle liquor Method.

Background technique

Pickling is essential process in producing stainless steel process, not only ensure that the good quality of steel surface, but also be Further processing is ready.With the process of pickling, metal oxide constantly dissolves and enters in pickling solution.Originally pickling solution In hydrogen ion gradually replaced by metal salt, sour concentration gradually decreases, and metal salt concentrations increase, thus pickling solution is molten The speed of solution oxide slows down gradually, and needs that waste liquid constantly is discharged, feeds new pickling solution.This used pickling effect difference Waste liquid is pickle liquor.These waste liquid complicated components, contain contents of many kinds of heavy metal ion, such as Cu2+、Zn2+、Cr3+、Fe2+、Ni2+ Deng.Wherein especially Cr3+And Fe2+Content is obviously higher, will certainly be to environmental danger if be not pocessed.

The domestic separation method about ferrochrome in the pickling waste waters containing chromium of rich iron is mainly include the following types: (1) neutralizes at present The precipitation method utilize Cr by the way that alkaline matter is added into pickling waste waters3+And Fe2+Precipitating pH difference, control pH make chromium elder generation shape At chromium hydroxide precipitation, separate iron, chromium by filtering.This method is easy to operate, equipment requirement is not high, processing cost is low, but Ferrous ion is easy to coprecipitation therewith when being precipitating chromium, causes the separation of chromium and iron not high, separating effect is not It is good.(2) crystallisation generates siderotil crystal, separates iron, chromium through filtering by the way that alkali metal salt is added into pickling waste waters.The party Method has many advantages, such as that at low cost, resource recycling is good, easy to operate, the disadvantage is that the iron in solution is difficult precipitating completely, and iron Alum can adsorb a certain amount of chromium when precipitating, and chromium and iron is made to be difficult to be completely separated.(3) absorption method mainly utilizes active carbon, waste coal ash The adsorbent materials such as zeolite carry out materialization absorption, and the technological operation is simple, high treating effect.But a large amount of adsorbent waste residues can be generated Secondary pollution is attracted, and the chromium adsorbed cannot recycle, and cause the waste of resource.(4) extraction mainly utilizes metal ion Complex reaction occurs for the different solubility in organic phase and water phase, metal ion and extractant, has been extracted to from water phase In machine phase, water phase is then arrived by back extraction under alkaline condition again, organic extractant can recycle.But this method is to extractant Selectivity is more demanding, currently without good method for being mass produced.Prior art CN101974688A discloses one The method by separating chromium ion and iron ion in Multi component is planted, uses extractant that iron content organic phase is obtained by extraction in this method With the non-organic phase containing chromium, organic phase is stripped to obtain ferric hydroxide precipitate using Sodium Hydroxide Alkaline, and chromium ion then passes through crystallization It is precipitated, the ferrochrome separating effect that wherein alkaline condition extraction and crystallization precipitation can be realized is limited, the processing for rich iron waste water Good treatment effect can not be reached.

Therefore, the present invention provides the separation method of chromium and iron in a kind of pickle liquor with good ferrochrome separating effect For pickling waste waters processing, especially stainless steel acid cleaning waste water processing has very important significance.

Summary of the invention

It is difficult the technical problem to be solved by the present invention is to overcome existing pickle liquor iron ion and chromium ion separating effect are bad With the defect and deficiency being completely separated, the separation method of chromium and iron in a kind of pickle liquor is provided, using ferric iron and chromium ion Two step separating and extractings and back extraction, utilize the slective extraction of different extractants to realize being completely separated for chromium and iron.

Above-mentioned purpose of the present invention is achieved through the following technical solutions:

The separation method of chromium and iron, includes the following steps: in a kind of pickle liquor

S1. ferric iron extracts: iron organic extractant being added into pickle liquor, extracts ferric ion, it is organic to obtain ferric iron Phase and the water phase containing ferrous ion and chromium ion;

S2. it is stripped ferric iron: utilizing the ferric iron in sulfuric acid solution back extraction ferric iron organic phase;

S3. chromium ion extracts: adjusting the pH to 1.0 ~ 2.5 of the water phase containing ferrous ion and chromium ion, chromium organic extraction is added Agent obtains organic phase containing chromium and the aqueous solution containing ferrous ion;

S4. chromium ion is stripped: utilizing the chromium ion in sulfuric acid solution back extraction organic phase containing chromium.

The present invention in order to further increase the separation of chromium and iron in pickle liquor, first by can with the ferric iron of chromium co-extraction from Son extraction and separation from solution, separating effect ratio more thoroughly, avoid the halfway phenomenon of ferric iron back in reduction method, and extract The ferric iron of taking-up is purer, and impurity content is not higher than 0.5% in gained ferrous solution after being stripped, and can be back to industrial production, And after being stripped in remaining organic phase iron ion content in 25ppm hereinafter, can recycle, saved extraction cost.

The chromium ion extraction of the invention primary amine extractant big, cheap and easy to get using loading capacity, reacts in acid condition Under can carry out, save adjust pH during alkali consumption;The chromium of extraction enters in water phase after being stripped, and comparison of ingredients is pure Only, impurity content is not higher than 0.1%, and the chromic salts product of high price can be made in concentrated crystallization treatment, be stripped the organic phase of recycling It can also further be back in the extraction of chromium, save chromium extraction cost.

The reason of adjusting the pH to 1.0 ~ 2.5 of ferrous ion and chromium ion water phase are as follows: pH is too low, the extraction efficiency of extractant Low, pH is too high, and chromium ion is easy to produce precipitating, influences extracting operation progress.Such as the pH value of ferrous ion and chromium ion water phase can To be adjusted to 1.0,1.6,1.8,2.2 or 2.5.It is real except the preparation that can be used for iron series water purifier containing ferrous acid solution after chromium Existing circular economy.

The concentration that wherein present invention is stripped ferric sulfuric acid solution is preferably 0.3 ~ 3.0 mol/L, is stripped chromium Sulfuric acid concentration is preferably 1.0 ~ 5.0mol/L.The too low effect of extracting that will cause of sulfuric acid concentration is bad, although sulfuric acid concentration increases meeting Extraction quantity is improved, but on the one hand excessively high sulfuric acid concentration will increase extraction cost, on the other hand also will increase in practical operation Production cost, and the oxidisability of the sulfuric acid of high concentration is very strong, can aoxidize certain ingredients in organic extractant, in turn result in Machine extractant can not be recycled, and increase processing cost.

Preferably, iron organic extractant described in S1 is the mixture of extractant and diluent, and extractant accounts for the organic extraction of iron Take the 1 ~ 50% of agent total volume.It such as can be 1%, 40% or 50%.Diluent is added in extractant can be improved related extractant Mobility, facilitated extraction agent sufficiently merges with extracted substance, promotes effect of extracting.Extractant too high levels cannot reach Good dilution effect, mobility improvement is unobvious, and extraction agent content is too low, will affect whole extraction potential energy, causes to extract It is insufficient, so that can not extraction and separation.Wherein extractant of the invention is preferably three octyl tertiary amines, dodecyl tertiary amine, phosphorus Sour tributyl, Dodecyl Dimethyl Amine, N, one in N- dimethyl hexadecyl base tertiary amine or octadecyldimethyl tertiary amine Kind is several, and diluent is preferably the one or more of sulfonated kerosene, dimethylbenzene or toluene.

Preferably, extractant accounts for the 40 ~ 50% of iron organic extractant total volume.

Preferably, the additional amount of iron organic extractant is 0.5 ~ 3.0 times of pickle liquor quality in S1.It such as can be .5 Times, 1.4 times, 1.6 times or 3.0 times.

Preferably, extraction time described in S1 is 5 ~ 10min, and extraction revolving speed is 200~300r/min.

Preferably, the additional amount of sulfuric acid solution is 0.5 ~ 5.0 times of ferric iron organic phase quality in being stripped described in S2. The reason is that on the one hand guaranteeing sufficiently be extracted by extraction substance, on the other hand guarantees that extractant can utilize to greatest extent, keep away Exempt from the waste of extractant.

Preferably, the time of back extraction described in S2 is 3 ~ 5min, and extraction revolving speed is 200~300r/min.

Preferably, chromium organic extractant described in S3 is the mixture of extractant and diluent, and wherein extractant accounts for chromium and has The 20 ~ 80% of machine extractant total volume.The dilution processing of chromium extraction agent also needs to take into account the effect of extracting of chromium and the stream of extractant Dynamic property, and because chromium extraction liquid of the invention be extract to carry out in ferric extraction extraction raffinate in S1, wherein containing ferrous iron from Son and chromium ion, the bulk property that the process and effect of extracting of extractant need to comprehensively consider solution determines, and individual Chromium extraction is different.Chromium extraction agent of the invention is preferably methylpent butanone, dodecyl primary amine, decyl primary amine, cetyl One or more of primary amine, Cocoalkyl primary amine, diluent are preferably one of sulfonated kerosene, dimethylbenzene, toluene or several Kind.

Preferably, extractant accounts for the 60 ~ 80% of chromium organic extractant total volume.It such as can be 60%, 65% or 80%.

Preferably, the additional amount of chromium organic extractant is 0.5 ~ 2.5 times of ferrous ion and chromium ion water phase quality in S3. Such as it can be with 0.5 times, 1.0 times, 1.5 times, 2.0 times or 2.5 times.

Preferably, extraction time is 15 ~ 30min in S3, and extraction temperature is 50 ~ 70 DEG C, and extraction revolving speed is 200~300r/ min.The extraction of chromium is an endothermic process, is extracted under the conditions of certain temperature, and the flowing for promoting extractant is on the one hand facilitated Property, promote mass transport process and two phase stratification;On the other hand, additional heat energy facilitate promoted extraction reaction to positive reaction direction into Row promotes extraction efficiency.Extraction temperature is too low to slow down mass transport process, reduce effect of extracting, extraction temperature is excessively high, can lead The quick volatilization for causing organic extractant, causes the waste of extractant.The time for the chromium extraction that the present invention further preferably protects, when extraction Between it is too short will lead to extraction it is insufficient, influence extraction efficiency;Extraction time is too long, will lead to the appearance of emulsion, forms gas Alveolar layer influences the progress of extraction process.

Preferably, the additional amount that sulfuric acid solution is stripped described in S4 is 0.5 ~ 4.0 times of chromium ion organic phase quality.Example It such as can be 0.5 times, 1 times, 2 times or 4 times.

Preferably, the time of back extraction described in S4 be 15 ~ 25min, temperature be 40 ~ 60 DEG C, extraction revolving speed be 200~ 300r/min.Be stripped under the conditions of certain temperature, on the one hand facilitate promoted extractant mobility, promote mass transport process and Two phase stratification;On the other hand, additional heat energy helps to be promoted back extraction reaction to the progress of positive reaction direction, promotes extraction efficiency. Extraction temperature is too low to slow down mass transport process, reduce back extraction effect, extraction temperature is excessively high, and it will cause the waves of extractant Take.The time for the chromium extraction that the present invention further preferably protects, extraction time is too short, and to will lead to extraction insufficient, influences extraction efficiency; Extraction time is too long, will lead to the appearance of emulsion, forms bubble layer, influences the progress of extraction process.

The separation method of chromium and iron is chromium and the iron ion separation for a variety of spent acid in spent acid of the invention, especially suitable It is separated in the chromium and iron of stainless steel acid-washing waste liquid, being preferably applied to chromium ion concentration in pickle liquor is 0.5~5g/L, ferric iron Ion concentration is 0~8g/L, and ferrous ion concentration is the separation of the pickle liquor chromium and iron of 10~80g/L.

Compared with prior art, the beneficial effects of the present invention are:

The present invention provides the separation method of chromium and iron in a kind of pickle liquor, this method first passes through organic extraction and sulfuric acid back extraction Isolated ferric ion is taken, avoids the halfway phenomenon of ferric iron back in reduction method, and avoid ferric iron to chromium The influence of ion extractuin separation, and then by the isolated chromium ion of specific extraction-back extraction system and ferrous iron solution, through dense The chromic salts product of high price can be made in contracting crystallization treatment, except the system that can be used for iron series water purifier containing ferrous acid solution after chromium It is standby, after extractant recycling of the invention iron ion content in 25ppm hereinafter, the content of chromium ion in 28ppm hereinafter, recyclable make With having saved extractant cost, realized circular economy.

Specific embodiment

The present invention is further illustrated With reference to embodiment, but embodiment the present invention is not done it is any The restriction of form.Unless otherwise indicated, source chemicals used in the embodiment of the present invention are the source chemicals routinely bought.

The detection method of the content of chromium ion and iron ion in the present invention are as follows:

The measurement of chromium ion uses " electric heating atomic absorption spectrography (AAS) ", and iron ion measurement uses " dichromate titration "

Embodiment 1

The raw material of the present embodiment is 400 kilograms of stainless steel acid cleaning waste waters, and measuring its acidity (acidity of sulfuric acid) is 5.3%, and chromium ion contains Measure 4.5g/L, 2.8 g/L of ferric iron content, 75 g/L of divalent iron content.

The separation method of chromium and iron, includes the following steps: in a kind of pickle liquor

S1. ferric iron extracts: iron organic extractant being added into pickle liquor, carries out continuous centrifugal extraction and separation three under room temperature Valence iron ion obtains the water phase of ferric iron organic phase and ferrous ion and chromium ion, and wherein ferric iron extractant contains 20% 3 octane Base tertiary amine, 20% Dodecyl Dimethyl Amine, 10% tributyl phosphate, sulfonated kerosene 50%, additional amount are pickle liquor quality 0.5 times;

S2. it is stripped ferric iron: using the ferric iron in sulfuric acid solution back extraction ferric iron organic phase, wherein sulfuric acid solution Concentration is 0.5mol/L, and additional amount is 1 times of ferric iron organic phase quality, and organic extractant can return reactor tank and recycle;

S3. chromium ion extracts: the pH to 1.6 that soda ash adjusts ferrous ion and chromium ion water phase is added, chromium organic extraction is added Agent obtains the aqueous solution of chromium ion organic phase and ferrous ion, wherein the ingredient of chromium organic extractant are as follows: contains 30% dodecyl Primary amine, 20% decyl primary amine, 10% methylpent butanone, 40% sulfonated kerosene, additional amount are ferrous ion and chromium ion water phase quality 1 times, carry out level-one extraction, additional amount is 0.5 times of ferrous ion and chromium ion water phase quality, second level extraction is carried out, 50 Continuous centrifugal extraction and separation are carried out at DEG C, extraction revolving speed is 300r/min, and raffinate (ferric ion solutions) can be used for iron series flocculation The industrial production of agent;

S4. chromium ion is stripped: using the chromium ion in sulfuric acid solution back extraction chromium ion organic phase, wherein sulfuric acid solution Concentration is 2.0mol/L, and additional amount is 1 times of chromium ion organic phase quality, carries out level-one extraction, and additional amount is that chromium ion is organic 0.5 times of phase quality carries out second level extraction, 60 DEG C of extraction temperature, extracts revolving speed 300r/min, organic phase can directly return to extraction Workshop section utilizes.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 55 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 25ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion 6ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion 13ppm.

Embodiment 2

The raw material of the present embodiment is 500 kilograms of stainless steel acid cleaning waste waters, and measuring its acidity (acidity of sulfuric acid) is 4.1%, and chromium ion contains Measure 2.1g/L, 7.8 g/L of ferric iron content, 71 g/L of divalent iron content.

The separation method of chromium and iron, includes the following steps: in a kind of pickle liquor

S1. ferric iron extracts: iron organic extractant being added into pickle liquor, carries out continuous centrifugal extraction and separation three under room temperature Valence iron ion obtains the water phase of ferric iron organic phase and ferrous ion and chromium ion, and wherein ferric iron extractant contains 15% dodecane Base tertiary amine, 20% N, N- dimethyl hexadecyl base tertiary amine, 5% tributyl phosphate, sulfonated kerosene 60%, additional amount are pickle liquor matter 1.6 times of amount;

S2. it is stripped ferric iron: using the ferric iron in sulfuric acid solution back extraction ferric iron organic phase, wherein sulfuric acid solution Concentration is 0.7mol/L, and additional amount is 0.6 times of ferric iron organic phase quality, and organic extractant can return reactor tank circulation benefit With;

S3. chromium ion extracts: the pH to 1.8 that soda ash adjusts ferrous ion and chromium ion water phase is added, chromium organic extraction is added Agent obtains the aqueous solution of chromium ion organic phase and ferrous ion, wherein the ingredient of chromium organic extractant are as follows: contains 20% Cocoalkyl Primary amine, 40% cetyl primary amine, 5% methylpent butanone, 35% sulfonated kerosene, additional amount are ferrous ion and chromium ion water phase matter 1 times of amount carries out level-one extraction, and continuous centrifugal extraction and separation are carried out at 55 DEG C, and extraction revolving speed is 300r/min, raffinate (ferric ion solutions) can be used for the industrial production of iron-based flocculating agent;

S4. chromium ion is stripped: using the chromium ion in sulfuric acid solution back extraction chromium ion organic phase, wherein sulfuric acid solution Concentration is 1.5mol/L, and additional amount is 1 times of chromium ion organic phase quality, is extracted, 60 DEG C of extraction temperature, extracts revolving speed 300r/min, organic phase can directly return to extraction workshop section and utilize.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 42 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 16ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion 13ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion 22ppm.

Embodiment 3

The raw material of the present embodiment is 1000 kilograms of stainless steel acid cleaning waste waters, and measuring its acidity (acidity of sulfuric acid) is 3.8%, chromium ion Content 4.8g/L, 7.0 g/L of ferric iron content, 65 g/L of divalent iron content.

The separation method of chromium and iron, includes the following steps: in a kind of pickle liquor

S1. ferric iron extracts: iron organic extractant being added into pickle liquor, carries out continuous centrifugal extraction and separation three under room temperature Valence iron ion obtains the water phase of ferric iron organic phase and ferrous ion and chromium ion, and wherein ferric iron extractant contains 30% 3 octane Base tertiary amine, 10% dodecyl tertiary amine, 10% tributyl phosphate, sulfonated kerosene 50%, additional amount are 1.4 times of pickle liquor quality;

S2. it is stripped ferric iron: using the ferric iron in sulfuric acid solution back extraction ferric iron organic phase, wherein sulfuric acid solution Concentration is 2.0mol/L, and additional amount is 0.5 times of ferric iron organic phase quality, and organic extractant can return reactor tank circulation benefit With;

S3. chromium ion extracts: the pH to 2.2 that soda ash adjusts ferrous ion and chromium ion water phase is added, chromium organic extraction is added Agent obtains the aqueous solution of chromium ion organic phase and ferrous ion, wherein the ingredient of chromium organic extractant are as follows: contains 40% dodecyl Primary amine, 30% decyl primary amine, 10% methylpent butanone, 20% sulfonated kerosene, additional amount are ferrous ion and chromium ion water phase quality 1.5 times, extracted, at 55 DEG C carry out continuous centrifugal extraction and separation, extraction revolving speed be 300r/min, raffinate (iron from Sub- solution) it can be used for the industrial production of iron-based flocculating agent;

S4. chromium ion is stripped: using the chromium ion in sulfuric acid solution back extraction chromium ion organic phase, wherein sulfuric acid solution Concentration is 5mol/L, and additional amount is 0.5 times of chromium ion organic phase quality, is extracted, 40 DEG C of extraction temperature, extracts revolving speed 200r/min, organic phase can directly return to extraction workshop section and utilize.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 45 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 12ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion 18ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion 28ppm.

Embodiment 4

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: extractant three is pungent in S1 Alkyl tertiary amine accounts for the 1% of iron organic extractant total volume, and additional amount is 3.0 times of pickle liquor quality.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 12 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 20 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 10 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 16 ppm.

Embodiment 5

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: sulphur in back extraction in S2 The additional amount of acid solution is 5 times of ferric iron organic phase quality.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 48ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 6 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 15 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 12 ppm.

Embodiment 6

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: S3 adjusts ferrous ion With the pH to 1.0 of chromium ion water phase.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 53 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 22 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 24 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 10 ppm.

Embodiment 7

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: extractant 12 in S3 Kiber alkyl amine accounts for the 20% of chromium organic extractant total volume, and the additional amount of chromium organic extractant is ferrous ion and chromium ion water phase 2.5 times of volume.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 15 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 26ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 8 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 12 ppm.

Embodiment 8

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: extractant 12 in S3 Kiber alkyl amine accounts for the 80% of chromium organic extractant total volume, and the additional amount of chromium organic extractant is ferrous ion and chromium ion water phase 0.5 times of volume.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 41 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 19 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 29 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 15 ppm.

Embodiment 9

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: sulfuric acid is stripped in S4 The additional amount of solution is 4.0 times of chromium ion organic phase.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 39 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 22 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 11 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 6 ppm.

Embodiment 10

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: sulfuric acid solution in S4 Concentration is 1.0mol/L.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 42 ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 18 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 10 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 22 ppm.

Comparative example 1

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: sulfuric acid solution in S2 Concentration is 0.2mol/L.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 54ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 71 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 12 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 15 ppm.

Comparative example 2

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: sulfuric acid solution in S4 Concentration is 0.8mol/L.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 46ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 26 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 11 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 63 ppm.

Comparative example 3

The separation method of chromium and iron, essentially identical with embodiment 1 in a kind of pickle liquor, difference are as follows: adjusts in S3 containing Asia The pH to 4 of iron ion and chromium ion water phase.

Iron ion content in raffinate in S1 (chromium and ferrous ions soln) is detected, iron ion content are as follows: 54ppm。

Iron ion content in organic phase in S2 is detected, iron ion content is down to 24 ppm.

Content of chromium ion in raffinate in S3 is detected, content of chromium ion is 58 ppm;

The chromium ion concentration of organic phase after being stripped in S4 is detected, content of chromium ion is 10 ppm.

Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention Protection scope within.

Claims (10)

1. the separation method of chromium and iron in a kind of pickle liquor, which comprises the steps of:
S1. ferric iron extracts: iron organic extractant being added into pickle liquor, extracts ferric ion, it is organic to obtain ferric iron Phase and the water phase containing ferrous ion and chromium ion;
S2. it is stripped ferric iron: utilizing the ferric iron in sulfuric acid solution back extraction ferric iron organic phase;
S3. chromium ion extracts: adjusting the pH to 1.0 ~ 2.5 of the water phase containing ferrous ion and chromium ion, chromium organic extraction is added Agent obtains organic phase containing chromium and the aqueous solution containing ferrous ion;
S4. chromium ion is stripped: utilizing the chromium ion in sulfuric acid solution back extraction organic phase containing chromium.
2. separation method as described in claim 1, which is characterized in that iron organic extractant described in S1 is extractant and diluent Mixture, extractant accounts for the 1 ~ 50% of iron organic extractant total volume.
3. separation method as claimed in claim 2, which is characterized in that the additional amount of iron organic extractant is pickle liquor matter in S1 0.5 ~ 3 times of amount.
4. separation method as described in claim 1, which is characterized in that the additional amount of sulfuric acid solution is three in back extraction described in S2 0.5 ~ 5 times of valence iron organic phase quality.
5. separation method as described in claim 1, which is characterized in that chromium organic extractant described in S3 is extractant and diluent Mixture, wherein extractant accounts for the 20 ~ 80% of chromium organic extractant total volume.
6. separation method as claimed in claim 5, which is characterized in that in S3 the additional amount of chromium organic extractant be ferrous ion and 0.5 ~ 2.5 times of chromium ion water phase quality.
7. separation method as claimed in claim 6, which is characterized in that in S3 extraction time be 15 ~ 30min, extraction temperature be 50 ~ 70 DEG C, extraction revolving speed is 200~300r/min.
8. separation method as described in claim 1, which is characterized in that described in S4 be stripped sulfuric acid solution additional amount be chromium from 0.5 ~ 4.0 times of sub- organic phase quality.
9. separation method as claimed in claim 8, which is characterized in that the time of back extraction described in S4 is 15 ~ 25min, temperature It is 40 ~ 60 DEG C, extraction revolving speed is 200~300r/min.
10. the separation method as described in claim 1 ~ 9 any one, which is characterized in that chromium ion concentration in the pickle liquor For 0.5~5g/L, ferric ion concentration is 0~8g/L, and ferrous ion concentration is 10~80g/L.
CN201811543843.0A 2018-12-17 2018-12-17 The separation method of chromium and iron in a kind of pickle liquor CN109536708A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811543843.0A CN109536708A (en) 2018-12-17 2018-12-17 The separation method of chromium and iron in a kind of pickle liquor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811543843.0A CN109536708A (en) 2018-12-17 2018-12-17 The separation method of chromium and iron in a kind of pickle liquor

Publications (1)

Publication Number Publication Date
CN109536708A true CN109536708A (en) 2019-03-29

Family

ID=65855239

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811543843.0A CN109536708A (en) 2018-12-17 2018-12-17 The separation method of chromium and iron in a kind of pickle liquor

Country Status (1)

Country Link
CN (1) CN109536708A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226791A (en) * 1978-11-30 1980-10-07 Berol Kemi Ab Method and a reagent mixture for removing metal ions from an aqueous solution by means of liquid-liquid extraction
CN101974688A (en) * 2010-10-19 2011-02-16 东北大学 Method for separating chromium ions and iron ions in multicomponent solution
CN102634673A (en) * 2012-04-25 2012-08-15 中国科学院过程工程研究所 Method for deeply removing iron ions from chromium-containing waste residue pickle liquor
CN104805291A (en) * 2015-04-16 2015-07-29 南阳师范学院 Method for treating stainless steel pickling waste liquor and recovering iron, chromium and nickel
CN106756043A (en) * 2016-12-20 2017-05-31 中成致远有限公司 The separation method of chromium and iron in a kind of hydrochloric acid system
CN106929698A (en) * 2015-12-30 2017-07-07 核工业北京化工冶金研究院 A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226791A (en) * 1978-11-30 1980-10-07 Berol Kemi Ab Method and a reagent mixture for removing metal ions from an aqueous solution by means of liquid-liquid extraction
CN101974688A (en) * 2010-10-19 2011-02-16 东北大学 Method for separating chromium ions and iron ions in multicomponent solution
CN102634673A (en) * 2012-04-25 2012-08-15 中国科学院过程工程研究所 Method for deeply removing iron ions from chromium-containing waste residue pickle liquor
CN104805291A (en) * 2015-04-16 2015-07-29 南阳师范学院 Method for treating stainless steel pickling waste liquor and recovering iron, chromium and nickel
CN106929698A (en) * 2015-12-30 2017-07-07 核工业北京化工冶金研究院 A kind of processing method of chromium slag nitration mixture Strengthen education-extraction and recovery siderochrome
CN106756043A (en) * 2016-12-20 2017-05-31 中成致远有限公司 The separation method of chromium and iron in a kind of hydrochloric acid system

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
何汝迎等: "《不锈钢冷轧生产技术及产品应用》", 31 August 2014 *

Similar Documents

Publication Publication Date Title
TWI392745B (en) A method for recovering a valuable metal from a lithium battery residue containing Co, Ni, and Mn
CN101269871B (en) Method for processing chrome wastewater
CN102603097B (en) Advanced treatment and recycling process for wastewater containing heavy metal ions
CN101746874B (en) Processing method of wastewater desulfurized by fume wet method
Ning et al. Selective extraction and deep separation of V (V) and Cr (VI) in the leaching solution of chromium-bearing vanadium slag with primary amine LK-N21
CN101899574B (en) Method for comprehensively reclaiming arsenic caustic dross and sulfur dioxide flue gas in antimony pyrometallurgical smelting
Haifeng et al. Kinetics of reductive leaching of low-grade pyrolusite with molasses alcohol wastewater in H2SO4
CN106282585B (en) A kind of detoxification classification resource utilization method of domestic garbage incineration flyash
CN105316485A (en) Recovery method for neodymium iron boron waste free of wastewater discharge
CN102282106B (en) Utilisation of desalination waste
CN103643044B (en) The direct extracting copper of a kind of Bellamya aeruginosa wet method, zinc technology
CN102070198B (en) Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron
CN104310647A (en) Recycling method for treating stainless steel pickling acid pickle and wastewater
CN104805291B (en) The process of a kind of stainless steel acid-washing waste liquid and iron, chromium, the recovery method of nickel
CN103343235B (en) Method for recovering neodymium and iron from neodymium iron boron oil sludge through two-step co-precipitation
Yuan et al. The removal of COD from coking wastewater using extraction replacement–biodegradation coupling
Niu et al. Preparation and coagulation efficiency of polyaluminium ferric silicate chloride composite coagulant from wastewater of high-purity graphite production
CN105060599B (en) A kind of stainless steel acid cleaning waste water resource recycle method
CN104099474B (en) A kind of electroplating sludge recycles technique
CN106191463B (en) A kind of purification method of zinc hydrometallurgy leachate
CN105271436B (en) The method that poly ferric chloride flocculant agent is prepared using steel wire rope sludge and waste hydrochloric acid
CN103014340B (en) Method for selectively separating chromium and ferrum in sulfate solution
CN102329964B (en) Method for separating and recovering vanadium and chromium from vanadium-chromium reduced waste residue
Ning et al. High-efficient extraction of vanadium and its application in the utilization of the chromium-bearing vanadium slag
US10577676B2 (en) Process for recycling chromium from waste water containing hexavalent chromium

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