CN106119545B - A kind of cleaning detoxification treatment of chromium slag and the extracting method of chromium - Google Patents

A kind of cleaning detoxification treatment of chromium slag and the extracting method of chromium Download PDF

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CN106119545B
CN106119545B CN201610501716.9A CN201610501716A CN106119545B CN 106119545 B CN106119545 B CN 106119545B CN 201610501716 A CN201610501716 A CN 201610501716A CN 106119545 B CN106119545 B CN 106119545B
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chromium
slag
detoxification treatment
cleaning
chromium slag
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CN106119545A (en
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刘学明
林璋
刘炜珍
荣文聪
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a kind of cleaning detoxification treatment of chromium slag and the extracting method of chromium, belongs to the cleaning treatment of chromium slag and the cycling and reutilization field of resource.This method concretely comprises the following steps：1）Water is added into chromyl waste residue, is uniformly mixed；2）To step 1）Hydrogen peroxide is added in resulting solution, is sufficiently stirred, obtains mixed liquor；3）Using hydro-thermal method or directly heat processing mixed liquor；4）After heating, make solidliquid mixture cooled to room temperature, stand；5）Re-dry is washed with water by solid slag and separation of the supernatant containing chromium, and by filter residue；6）Chromium-containing solution is recycled and is returned in workshop section, or carries out recycling chromium processing.Mineralizer green non-pollution of the present invention, supernatant liquor after processing can the directly reuse in the technique that chromium salt production or chromic salts use, filter residue can be comprehensively utilized.The cleaning of this method technique is simple, small, quick, the recyclable Cr VI of investment, effectively administers pollution of chromium and does not cause secondary pollution again.

Description

A kind of cleaning detoxification treatment of chromium slag and the extracting method of chromium
Technical field
The invention belongs to the cleaning treatment of chromium slag and the cycling and reutilization field of resource, and in particular to a kind of chromium slag it is clear Clean detoxification treatment and the method for chromium extraction.
Background technology
Chromium slag refers to the chromyl waste residue produced in chromium salt production and application industry, and Cr VI toxicity is high, can be carcinogenic, It is listed in and the mankind is endangered with one of eight maximum big chemical substances.China's chromic salts yield and consumption figure height rank first in the world, and Chromium slag produces most countries, and the chromium slag for having stored up millions of tons is urgently handled, brought seriously to soil and groundwater Pollution.But China's chromium ore resource is poorer, verify at present the 0.825% of reserves Jin Zhan worlds gross reserves, by can meet need The degree asked is seen, belongs to deficient resources.Therefore, by chromium residue detoxifying and chromium resource can be recycled, has become processing chromium slag Preferable thinking.
For the processing of chromium slag, it is the method filled again after detoxifying to lead to common, its core is by highly dissoluble, high poison Hexavalent chrome reduction is fixed into the trivalent chromium of low toxicity.Not only chromium resource cannot be recycled and utilized, but also chromium still discharges in the environment, As trivalent chromium can be oxidized to Cr VI under natural environment long term again, secondary pollution is caused.Comparatively ideal method be by Chromium in chromium slag extracts separation from slag, is for recycling and reuse, and chromium resource is recycled while detoxification chromium slag.
Chinese patent " a kind of method that hexavalent chromium resources are recycled in slag from chromium "（CN102191390A）Using sulphur under room temperature Acid or the water-soluble and acid soluble Cr VI of salt Ore Leaching, then add reducing agent and precipitation in the solution of the Cr VI of leaching Chromium is recycled in agent, and 60% ~ 80% Cr VI is recycled from chromium slag.Chinese patent " cycling and reutilization handles chromium slag and waster water process " （CN102699006A）The recycling of chromium and the recycling of slag are take into account, it is first with acid that chromium slag is almost molten under normal temperature condition Solution, is then respectively adding different precipitating reagents, and the hybrid ionic in solution is precipitated and separated, but this method needs to consume The chemical reagent such as substantial amounts of acid and precipitating reagent, and technological process is numerous and diverse, and processing cost is higher.
Therefore, in view of the deficiencies of the prior art, there is an urgent need to a kind of practical, science chromic wastes disposal method, by Cr VI Fully extract and realize the removing toxic substances of chromium slag.
The content of the invention
The object of the present invention is to provide a kind of cleaning detoxification treatment of chromium slag and the extracting method of chromium, this method technique are clear It is clean, simple, investment is small, quick, can fully recycle Cr VI, removing toxic substances is thorough, effectively administer pollution of chromium do not cause again it is secondary Pollution.The chromium being recovered to using this method, among being again back to use in production or using other purposes, such as coating, face Material, papermaking etc., turn waste into wealth.The filter residue obtained using this method can be used for rubber, plastics, fertilizer, paint, weaving, papermaking etc. Industry.
The purpose of the present invention is achieved through the following technical solutions.
A kind of cleaning detoxification treatment of chromium slag and the extracting method of chromium, step are as follows：
1）Water is added into chromyl waste residue, is uniformly mixed；
2）To step 1）Mineralizer is added in resulting solution, is sufficiently stirred, obtains mixed liquor；The mineralizer is hydrogen peroxide；
3）Using hydro-thermal method or directly heat processing step 2）Gained mixed liquor；
4）By step 3）Gained solidliquid mixture cooled to room temperature, stands；
5）Re-dry is washed with water by solid slag and separation of the supernatant containing chromium, and by filter residue；
6）Chromium-containing solution is recycled and is returned in workshop section, or carries out recycling chromium processing.
Further, step 1）Solid-to-liquid ratio after addition water in the chromyl waste residue（w/w）For 1:0.5 ~ 1:10.
Further, step 2）Concentration of the hydrogen peroxide in mixed liquor is the mol/L of 0.1 mol/L ~ 5.
Further, step 3）The hydro-thermal method or direct-fired temperature are controlled at 50 DEG C ~ 250 DEG C.
Further, step 3）When middle soaking time is 2 ~ 10 small.
Further, step 4）When the time of the standing is 0.5 ~ 48 small.
Further, step 6）The recycling chromium processing concretely comprises the following steps：Reducing agent is added into chromium-containing solution, by solution Middle hexavalent chrome reduction is trivalent chromium, adds precipitating reagent NaOH production Cr (OH)3Precipitation, finally Cr (OH)3Precipitation is sintered into Cr2O3。
A kind of cleaning detoxification treatment of chromium slag and the extracting method of chromium, step are as follows：
（1）Chromyl waste residue and water are pressed into solid-to-liquid ratio 1:0.5 ~ 1:10（w/w）After mixing, hydrogen peroxide is added Make in solution hydrogen peroxide concentration for the mol/L of 0.1 mol/L ~ 5.
（2）It is sufficiently stirred, is sufficiently mixed waste residue and solution.
（3）Design temperature be 30 DEG C ~ 250 DEG C, be stirred for or do not stir lower soaking time for 2 ~ 10 it is small when.
（4）Stop heating, allow its natural cooling, time of repose for 0.5 ~ 48 it is small when.
（5）After hydro-thermal process or heating, waste residue solid is deposited in bottom, and supernatant liquor is higher containing concentration Cr VI.
（6）Solid slag is separated with supernatant liquid filtering containing chromium, and solid slag slag is washed, is dehydrated and dried.
（7）The supernatant liquor and the water of washing filter residue isolated can be back to use in production or carry out recycling chromium processing.
A kind of cleaning detoxification treatment of chromium slag provided by the invention and the extracting method principle of chromium are as follows：
The present invention adds mineralizer（Hydrogen peroxide）When carrying out hydro-thermal process or heating, under weak basic condition in chromium slag A small amount of trivalent chromium is easier to enter in solution by hydrogen peroxide oxidation for the dichromate ion with higher solubility；Fire-bar at the same time Excessive hydrogen peroxide can resolve into water and oxygen under part, cause solid particle crystal to give birth under hydrothermal under oxygen partial pressure Length, lattice are complete, so that specific surface area reduces, active adsorption sites are reduced, and realize that Cr VI is desorbed and separates from particle surface.
2Cr3+ + 4H2O2 →Cr2O7 2- + H2O
2H2O2 →2H2O + O2↑
Compared with prior art, the invention has the advantages that and technique effect：
The present invention solves the problems, such as that chromic wastes disposal is difficult, and used mineralizer green non-pollution, does not introduce miscellaneous in processing Ion, supernatant liquor after Solid state fermentation can the directly reuse in the technique that chromium salt production or chromic salts use, greatly reduce Entreprise cost.Filter residue after processing can be comprehensively utilized.The cleaning of this method technique is simple, investment it is small it is quick, recyclable six Valency chromium, effectively administers pollution of chromium and does not cause secondary pollution again.
Embodiment
The present invention is further described below in conjunction with specific embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1
1）The chromyl waste residues of 0.5 kg are taken to be put into water heating kettle, adding water makes solid-to-liquid ratio（w/w）For 1:1, fully Stirring, adds hydrogen peroxide, and it is 0.1mol/L to make the hydrogen peroxide concentration in system, and design temperature is 130 DEG C, keeps the temperature 6 h.
2）After 6 h, stop heating, be slowly cooled to room temperature naturally, stand 24 h.
3）After standing, the chromyl solution in upper strata is poured out.Centrifuge washing dehydration is carried out to the slag after hydro-thermal process, By filter residue and drying, white or white partially yellow solid is obtained.
4）Chromium-containing solution is back to use in production, or comes together in waste water processing station, is reduced, recycled, purified treatment, Add reducing agent（Such as vulcanized sodium, sodium hydrogensulfite）And precipitating reagent（NaOH）, it is trivalent chromium by solution hexavalent chrome reduction, and generate Cr(OH)3Precipitation, water can reach national standard of drainage after processing.In whole process, water can recycle in systems.
5）End product is mainly to contain CaSO respectively4Slag and main (OH) containing Cr3Chromium mud, calcium sulfate slag can conduct Raw material is used for industries such as rubber, plastics, fertilizer, pesticide, paint, weaving, papermaking.Chromium mud can be sintered into Cr2O3, realize chromium Recycling.
It is 272 mg/L that the original chromium slag of the present embodiment, which leaches hexavalent chromium concentration, and filter residue leaching hexavalent chromium concentration is after processing 2.53 mg/L。
Embodiment 2
1 kg waste residues containing Cr VI are taken to be put into water heating kettle, adding water makes solid-to-liquid ratio（w/w）For 1:0.5, it is sufficiently stirred, Hydrogen peroxide is added, it is 1 mol/L to make the hydrogen peroxide concentration in system, and design temperature is 50 DEG C, keeps the temperature 10 h, is stopped quiet after heating Put 48 h.Other technical process are same as Example 1.
It is 269 mg/L that the original chromium slag of the present embodiment, which leaches hexavalent chromium concentration, and filter residue leaching hexavalent chromium concentration is after processing 2.12 mg/L。
Embodiment 3
1.5kg waste residues containing Cr VI are taken to be put into water heating kettle, adding water makes solid-to-liquid ratio（w/w）For 1:10, it is sufficiently stirred, Hydrogen peroxide is added, it is 3 mol/L to make the hydrogen peroxide concentration in system, and design temperature is 200 DEG C, keeps the temperature 2 h, is stopped quiet after heating Set to 0 .5 h.Other technical process are same as Example 1.
It is 277 mg/L that the original chromium slag of the present embodiment, which leaches hexavalent chromium concentration, and filter residue leaching hexavalent chromium concentration is after processing 1.92 mg/L。
Embodiment 4
1 ton of waste residue containing Cr VI is taken to be put into water heating kettle, adding water makes solid-to-liquid ratio（w/w）For 1:5, it is sufficiently stirred, adds Enter hydrogen peroxide, it is 5 mol/L to make the hydrogen peroxide concentration in system, and design temperature is 180 DEG C, keeps the temperature 4 h, is stood after stopping heating 12 h.Other technical process are same as Example 1.
It is 265 mg/L that the original chromium slag of the present embodiment, which leaches hexavalent chromium concentration, and filter residue leaching hexavalent chromium concentration is after processing 1.43 mg/L。
The technical solution that the protection domain and this specification limited according to claim provides, moreover it is possible to provide multiple realities Case is applied, belongs to the scope of the present invention.

Claims (8)

1. a kind of cleaning detoxification treatment of chromium slag and the recovery method of chromium, contain trivalent chromium and Cr VI in the chromium slag；It is special The step of sign is, the method is as follows：
1）Water is added into chromium slag, is uniformly mixed；
2）To step 1）Mineralizer is added in gained solidliquid mixture, is sufficiently stirred, obtains mixed liquor；The mineralizer is dioxygen Water；
3）Using hydro-thermal method or directly heat processing step 2）Gained mixed liquor, the trivalent chromium in chromium slag are attached most importance to by hydrogen peroxide oxidation Chromate hence into solution among, while hydrogen peroxide is also thermally decomposed to generate water and oxygen, and oxygen promotes Cr VI from chromium slag Surface desorption；
4）By step 3）Gained solidliquid mixture cooled to room temperature, stands；
5）Re-dry is washed with water by solid slag and separation of the supernatant containing chromium, and by filter residue；
6）To step 5）In isolated chromium-containing solution carry out recycling chromium processing.
2. a kind of cleaning detoxification treatment of chromium slag according to claim 1 and the recovery method of chromium, it is characterised in that step 1）Solid-to-liquid ratio w/w is 1 after water is added in the chromium slag:0.5 ~ 1:10.
3. a kind of cleaning detoxification treatment of chromium slag according to claim 1 and the recovery method of chromium, it is characterised in that step 2）Concentration of the hydrogen peroxide in mixed liquor is the mol/L of 0.1 mol/L ~ 5.
4. a kind of cleaning detoxification treatment of chromium slag according to claim 1 and the recovery method of chromium, it is characterised in that step 3）The hydro-thermal method or direct-fired temperature are controlled at 50 DEG C ~ 250 DEG C.
5. a kind of cleaning detoxification treatment of chromium slag according to claim 1 and the recovery method of chromium, it is characterised in that step 3）When middle soaking time is 2 ~ 10 small.
6. a kind of cleaning detoxification treatment of chromium slag according to claim 1 and the recovery method of chromium, it is characterised in that step 4）When the time of the standing is 0.5 ~ 48 small.
7. a kind of cleaning detoxification treatment of chromium slag according to any one of claims 1 to 6 and the recovery method of chromium, its feature It is, step 6）The recycling chromium processing concretely comprises the following steps：Reducing agent is added into chromium-containing solution, by hexavalent chrome reduction in solution For trivalent chromium, precipitating reagent NaOH production Cr (OH) are added3Precipitation, finally Cr (OH)3Precipitation is sintered into Cr2O3。
8. a kind of cleaning detoxification treatment of chromium slag according to claim 7 and the recovery method of chromium, it is characterised in that described Reducing agent is vulcanized sodium or sodium hydrogensulfite.
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CN108220604B (en) * 2018-01-03 2019-04-09 华南理工大学 A kind of method of the detoxification and waste liqouor of chromium residue
CN108969957A (en) * 2018-07-03 2018-12-11 中国科学院生态环境研究中心 A kind of method of cellulose hydro-thermal high-efficiency detoxication chromium slag
CN109449426B (en) * 2018-11-29 2021-09-21 华南理工大学 Method for preparing lithium ion battery cathode material by using chromium slag
CN110343875A (en) * 2019-08-19 2019-10-18 辛集市理联化工有限公司 A kind of comprehensive utilization process of chromed leather wastes
CN110527838B (en) * 2019-09-29 2021-07-20 华南理工大学 Method for extracting chromium from electroplating sludge through cooperation of hydrothermal and oxidation
CN113322379A (en) * 2021-06-08 2021-08-31 辛集市理联化工有限公司 Comprehensive utilization process of chromium-containing waste
CN115069234B (en) * 2022-06-29 2023-09-29 华南理工大学 Chromium-containing waste salt detoxication and purification and simultaneous preparation of hollow CrO x /Al 2 O 3 Method for preparing catalyst and application thereof
CN115475824A (en) * 2022-09-23 2022-12-16 华南理工大学 Method for detoxifying chromium slag and preparing catalyst and application thereof

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CN102191390A (en) * 2010-03-09 2011-09-21 刘杰 Method for recovering hexavalent chromium resources from chromium slag

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CN102191390A (en) * 2010-03-09 2011-09-21 刘杰 Method for recovering hexavalent chromium resources from chromium slag

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