CN101138670A - Novel process of the high temperature reduction and detoxication of industrial chromic slag - Google Patents
Novel process of the high temperature reduction and detoxication of industrial chromic slag Download PDFInfo
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Abstract
The present invention relates to a method for reducing detoxification of chromium residue under a high temperature with industrial wastes. Reducing metallurgy wastes in a waste tank are heated and melted. When the temperature becomes constant, the chromium residue is added into the tank. The toxicant in the chromium residue is Cr6 mainly in the form of water-soluble Na (SUB)2(/SUB)CrO (SUB)4 (/SUB) and acid-soluble CaCrO (SUB)4(/SUB). Under the high temperature, Cr6 is reduced into intoxicant Cr3. After the chromium residue is cooled down to the room temperature naturally, the removal rate of Cr6 reaches over 99 percent in the final residue. The method is provided with an appropriate process flow, and the device is simple and easy for operation. Heat of the material itself is fully used, so the high efficiency is high, which is beneficial to the high-temperature reducing of chromium residue. The chromium residue is thoroughly detoxicated. Moreover, no environmental pollution is caused and the cost is low, so the method is applicable for scaled detoxification of chromium residue in the industry.
Description
1. technical field
The present invention relates to a kind of treatment process of detoxification chromium slag, particularly a kind of method of utilizing high temperature reduction and detoxication of industrial chromic slag.
2. background technology
The chromium slag is the discarded object that discharges in producing chromic salts or ferrochrome process, is one of 3 kinds of carcinogenic substances of generally acknowledging.At present, the detoxifcation of chromium slag is disposed and handled is the key issue of restriction China's chromic salts and the sustainable development of ferrochrome industry, also is to cause modern not reasonable, that effectively solve an as yet important technology difficult problem.
Treatment technology is disposed in the detoxifcation of chromium slag both at home and abroad can be summarized as follows four kinds of main method: solidification method, reducing process, complexometry and bioanalysis.
Solidification method promptly adopts method physics or chemistry, and the chromium slag is fixed or is enclosed among the end product that solid is a matrix, this end-product chemical stability height, permeability resistance is strong.Solidification method is divided into melting and solidification method and cement solidification method again.The melting and solidification method is that the chromium slag is joined in glass or the vitreous brick as glass colorant; Or join in iron-smelting raw material, cast stone, chromium slag wool, the ceramic material delivering as flux.This method technology is comparatively simple, but it is little to eat the quantity of slag.As the patent No. is a kind of method that 91106584.9 Chinese patent " production method and the goods thereof of special colour porcelain plate (brick) " discloses melting and solidification method detoxification chromium slag, be about to chromium slag, clay, other conventional ceramic raw material and be rich in raw material pulverizing such as acidic oxide to fineness less than 100 orders, be tabular biscuit with half-dried molded, plastic forming of the raw material of pulverizing or injection forming.Wherein the content of chromium slag is 5-70%, at 1050-1300 ℃ roller-way roasting in kilns, and the chromium slag porcelain plate of making.The patent No. is a kind of method that 63144159 Japan Patent " Black tiles of high strength and low porosity " also discloses the solidification method detoxification chromium slag, soon chromium slag, clay mix by 100: 43: 100 proportioning with water, moulded section, at 1260 ℃ of sintering 4h, be prepared into the black brick of high strength.Cement solidification method is the chromium slag to be joined realize in the cement solidifying, and external treatment of chromate slag mainly adopts cement solidification method, but the cement addition is big, and power consumption is big, cost is high, is not suitable for China's national situation.
Reducing process is to select one or more materials as reducing agent, virose Cr (VI) in the chromium slag is reduced into avirulent Cr (III) under certain condition, reaches the detoxifcation purpose.The thing of pressing reducing agent is different mutually, divides three types of gas phase, liquid phase and solid phase reductions, and two modes that combine are also arranged.Gas phase reduction process is with H
2, CH
4, imflammable gas such as CO is as reducing agent, this method flow process is simple, energy consumption is lower, detoxifcation is also more thorough, but that excessive fuel gas is dealt with improperly is kind, causes new pollution sources easily.Liquid phase reduction with ferrous sulfate, sulphite, alkali metal sulphide or sulfhydryl compound etc. as the reducing agent detoxification chromium slag.This method maturation, but reagent consumption is big, technology is loaded down with trivial details.As the patent No. is a kind of method that 200410023861.8 Chinese patent " a kind of treatment of chromate slag method " discloses the liquid phase reduction detoxification chromium slag, promptly earlier the iron-contained industrial spent acid is inserted in the blender, again ferrous sulfate and chromium slag are added in the blender, under agitation react Fe in control iron-contained industrial spent acid and the ferrous sulfate
2+Total amount, make it with the chromium slag in Cr (VI) react completely, the weight ratio of chromium slag and iron-contained industrial spent acid is 1: (2.0～3.0), at last slip is solidified discharging.The solid phase reduction method is a reducing agent with powdered carbon, wood chip, rice skin, gangue, ferrous salt, barium salt etc., Cr in the chromium slag (VI) is reduced into Cr (III), and form constitutionally stable spinelle phase, detoxification chromium slag is more thorough, but this method energy consumption is big, cost is high, need unfavorable factors such as inter-trade application, it is bigger that commercial scale is promoted difficulty.As the patent No. is a kind of method that 90107448.9 Chinese patent " chromium residue detoxifying, smelt the method that contains chromium pig iron " discloses solid phase reduction method detoxification chromium slag, being about to the chromium slag mixes according to a certain ratio with auxiliary materials such as flux fluorite, silicate, lime earlier, after sinter molding, enter blast furnace process with iron-bearing material, solid fuel etc. again, generation contains chromium pig iron.Under high temperature fused state, Cr in the chromium slag (VI) is reduced into Cr, the preparation ferrochrome.The patent No. is a kind of method that 200310105320.5 Chinese patent " the innoxious and recycling processing method and the application thereof of chromium slag " also discloses solid phase reduction method detoxification chromium slag, this method is with after gangue, carbon mix with the chromium slag, at 900-1200 ℃ of roasting 24-36h, the roasting afterproduct can directly use or be used for other aspects as construction material.The mass percent that the chromium slag accounts for gangue is 4%～6%.The patent No. is a kind of method that 19929551 Deutsche Bundespatent " Recovery of chromium from slag " also discloses solid phase reduction method detoxification chromium slag, this method is that chromium residue is joined in the electric furnace, add certain refuse, carbon and silicon again, in the high-temperature fusion process, Cr (VI) directly is reduced to crome metal or alloy by carbon and silicon.
Complexometry is after the Cr in the chromium slag (VI) is reduced into Cr (III), with certain solution generation complexing, generates stable comple.The characteristics of this method are that cost is low, but it is little to eat the quantity of slag, and technological process is long, uses restricted.As the patent No. is a kind of method that 85106006 Chinese patent " the steam transforming method is handled the chromium slag " discloses the complexometry detoxification chromium slag, be about to ferment gustatory production wastewater or smart sweet waste water and pending chromium slag mixes the slag slurry, place airtight vessel in heating, by discharging excess steam, controlled pressure is at 0.5-7kg/cm
2(gauge pressure) handles 30min in 320-360 ℃ superheated steam, make the Cr (VI) in the slag be reduced to Cr (III).Research and utilization FeSO is also arranged
4Earlier the Cr in the chromium slag (VI) is reduced to Cr (III), adds the lignosulfonates in the papermaking wastewater again, make itself and Cr (III) complexing, generate stable ferrochrome lignosulfonate, reach the chromium residue detoxifying effect.
Bioanalysis is to utilize the reduction of microbial strains to chromate in the chromium slag, makes Cr (VI) be reduced into Cr (III), and this is a kind of new method of chromium residue detoxifying in recent years, but this technology is immature, still is in conceptual phase.As the patent No. is a kind of method that 200410019642.2 Chinese patent " chromium slag landfill is done the comprehensive utilization technique of engineering soil or backfill soil " discloses the bioanalysis detoxification chromium slag, be about to the chromium slag place on the peat or mix in or be wrapped among the peat, top and laterally set up separation layer, utilize underground water dissolving and capillary diffusion, impel humic acid, organic matter, microorganism in Cr (VI) and the peat in the chromium slag to react, be reduced to Cr (III), and then generate more stable complex compound one humic acid chromium.
3. summary of the invention
The object of the invention provides a kind of industrial residue (reproducibility metallurgical slag) that utilizes, by the new method of high temperature reduction and detoxication chromium slag.This method technical flow design is reasonable, and equipment is simple, and is easy to operate, makes full use of the heat of material self, and thermal efficiency height helps chromium slag high temperature reduction, and detoxifcation is thorough, and non-environmental-pollution, and is with low cost, is suitable for the commercial scale detoxification chromium slag.
The object of the present invention is achieved like this: will be contained in the reproducibility metallurgical slag heat fused in the slag ladle, the temperature after the fusing is controlled at 1200-1450 ℃; After temperature constant, in slag ladle, add the chromium slag, chromium slag particle degree is below 20 orders, and addition is 2%～6% of a metallurgical slag total amount, and the reaction time is controlled at 5～15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches more than 99.9%.
In the chemical composition of described chromium slag, water-soluble chromic acid sodium (Na
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content range is respectively 0.5-1.5% and 0.2-1.0%.
The present invention makes full use of the physics heat of reproducibility metallurgical cinder self and the residual carbon in the slag, described reproducibility metallurgical slag can be one or more the mixing in blast furnace slag, electroslag, the blast furnace slag, residual carbon in the slag can be used as reducing agent, under hot conditions with in the chromium slag with Na
2CrO
4And CaCrO
4The toxic Cr (VI) that form exists is reduced into avirulent Cr (III).
The present invention has following good effect:
1, reproducibility metallurgical cinder temperature range is at 1200-1450 ℃, and the physics thermal capacity of liquid slag is big, promotes that chemical reaction carries out, and the heat energy of slag is effectively utilized;
2, the reproducibility metallurgical slag is an industrial residue, utilizes residual carbon in the slag to come reduction and detoxication as the reducing agent of chromium slag, the treatment of wastes with processes of wastes against one another, and operating cost is cheap;
3, the reduction reaction of chromium slag is carried out in the slag of slag ladle, and equipment is simple, easy operating;
4, need not add any additives, the chromium slag can be reduced detoxifcation, finally with magnesia chrome spinel MgOCr
2O
3, containing chronium grossularite Ca
3(Cr, Al)
2(SiO
4)
3Exist mutually etc. Stability Analysis of Structures, detoxifcation is thorough, and the finishing slag of generation can be done the building materials raw material, and resource is utilized effectively;
5, the chromium slag is the earthy powder, with a small amount of caking, only need simply pulverize and can use, and the preliminary treatment in early stage is simple.
4. description of drawings
Fig. 1: the process chart of high temperature reduction and detoxication of industrial chromic slag
Fig. 2 (a): the microstructure of chromium slag
Fig. 2 (b): the microstructure of industrial residue
Fig. 3 (a): the microstructure of finishing slag after 1200 ℃ of processing
Fig. 3 (b): the microstructure of finishing slag after 1450 ℃ of processing
5. the specific embodiment
Describe concrete technological process of the present invention in detail according to Fig. 1-3 and embodiment.
This method adopts following steps: take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200-1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content range be respectively 0.5-1.5% and 0.2-1.0%, chromium slag particle degree is controlled at below 20 orders, addition is 2%～6% of a metallurgical slag total amount, reaction time is controlled at 5～15min, naturally cool to room temperature, in the finishing slag that obtains, the clearance of Cr (VI) reaches more than 99.9%
Embodiment (1)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 0.5% and 0.2%, chromium slag particle degree is controlled at below 20 orders, and addition is 2% of a metallurgical slag total amount, and the reaction time is controlled at 5min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.93% finishing slag.
Embodiment (2)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 0.5% and 0.2%, chromium slag particle degree is controlled at below 20 orders, and addition is 2% of a metallurgical slag total amount, and the reaction time is controlled at 15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.95% finishing slag.
Embodiment (3)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 0.5% and 0.2%, chromium slag particle degree is controlled at below 20 orders, and addition is 6% of a metallurgical slag total amount, and the reaction time is controlled at 5min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.91% finishing slag.
Embodiment (4)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 0.5% and 0.2%, chromium slag particle degree is controlled at below 20 orders, and addition is 6% of a metallurgical slag total amount, and the reaction time is controlled at 15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.94% finishing slag.
Embodiment (5)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 0.5% and 0.2%, chromium slag particle degree is controlled at below 20 orders, and addition is 2% of a metallurgical slag total amount, and the reaction time is controlled at 5min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.97% finishing slag.
Embodiment (6)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 0.5% and 0.2%, chromium slag particle degree is controlled at below 20 orders, and addition is 2% of a metallurgical slag total amount, and the reaction time is controlled at 15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.99% finishing slag.
Embodiment (7)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 0.5% and 0.2%, chromium slag particle degree is controlled at below 20 orders, and addition is 6% of a metallurgical slag total amount, and the reaction time is controlled at 5min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.94% finishing slag.
Embodiment (8)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 0.5% and 0.2%, chromium slag particle degree is controlled at below 20 orders, and addition is 6% of a metallurgical slag total amount, and the reaction time is controlled at 15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.98% finishing slag.
Embodiment (9)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 1.5% and 1.0%, chromium slag particle degree is controlled at below 20 orders, and addition is 2% of a metallurgical slag total amount, and the reaction time is controlled at 5min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.92% finishing slag.
Embodiment (10)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 1.5% and 1.0%, chromium slag particle degree is controlled at below 20 orders, and addition is 2% of a metallurgical slag total amount, and the reaction time is controlled at 15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.94% finishing slag.
Embodiment (11)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 1.5% and 1.0%, chromium slag particle degree is controlled at below 20 orders, and addition is 6% of a metallurgical slag total amount, and the reaction time is controlled at 5min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.90% finishing slag.
Embodiment (12)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1200 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 1.5% and 1.0%, chromium slag particle degree is controlled at below 20 orders, and addition is 6% of a metallurgical slag total amount, and the reaction time is controlled at 15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.93% finishing slag.
Embodiment (13)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 1.5% and 1.0%, chromium slag particle degree is controlled at below 20 orders, and addition is 2% of a metallurgical slag total amount, and the reaction time is controlled at 5min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.96% finishing slag.
Embodiment (14)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 1.5% and 1.0%, chromium slag particle degree is controlled at below 20 orders, and addition is 2% of a metallurgical slag total amount, and the reaction time is controlled at 15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.97% finishing slag.
Embodiment (15)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 1.5% and 1.0%, chromium slag particle degree is controlled at below 20 orders, and addition is 6% of a metallurgical slag total amount, and the reaction time is controlled at 5min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.93% finishing slag.
Embodiment (16)
Take by weighing a certain amount of reproducibility metallurgical slag and be contained in the slag ladle, heat fused, the temperature after the fusing are controlled at 1450 ℃.After temperature constant, in slag ladle, add chromium slag, water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content is respectively 1.5% and 1.0%, chromium slag particle degree is controlled at below 20 orders, and addition is 6% of a metallurgical slag total amount, and the reaction time is controlled at 15min, naturally cools to room temperature, and in the finishing slag that obtains, the clearance of Cr (VI) reaches 99.96% finishing slag.
The main component of table 1 chromium slag (mass fraction, %)
| MgO | CaO | Fe 2O 3 | SiO 2 | Al 2O 3 | Cr 2O 3 | Na 2CrO 4 | CaCrO 4 |
| 28～30 | 26～28 | 8～10 | 8～10 | 6～8 | 4.5～5.2 | 0.5～1.5 | 0.2～1.0 |
The main component of table 2 industrial residue (mass fraction, %)
| CaO | SiO 2 | Al 2O 3 | MgO | S | C |
| 30～40 | 30～40 | 5～10 | 4～8 | 0.2-4 | ≥0.3 |
Claims (5)
1. method of utilizing high temperature reduction and detoxication of industrial chromic slag, it is characterized in that: this method is the reproducibility metallurgical slag heat fused that will be contained in the slag ladle, fusing back temperature is controlled at 1200-1450 ℃ of scope; After temperature constant, in slag ladle, add the chromium slag, chromium slag particle degree is below 20 orders, and addition is 2%～6% of a metallurgical slag total amount; Reaction time 5～15min; Naturally cool to room temperature, in the finishing slag that obtains, the clearance of virose Cr (VI) reaches more than 99.9%.
2. as the method for claims 1 described high temperature reduction and detoxication of industrial chromic slag, it is characterized in that: water-soluble chromic acid sodium (Na in the chromium slag
2CrO
4) and solubility in acid calcium chromate (CaCrO
4) content range be respectively 0.5-1.5% and 0.2-1.0%.
3. as the method for claims 1 described high temperature reduction and detoxication of industrial chromic slag, it is characterized in that: select industrial residue for use---the reproducibility metallurgical slag is as reducing agent, utilize in the slag residual carbon reduction and detoxication chromium slag at high temperature, used reproducibility metallurgical slag is one or more the mixing in blast furnace slag, electroslag, the blast furnace slag, contain residual carbon in the slag, charcoal can be reduced into avirulent Cr (III) with virose Cr (VI) in the chromium slag under hot conditions.
4. as the method for claims 1 described high temperature reduction and detoxication of industrial chromic slag, it is characterized in that: the temperature of reproducibility metallurgical cinder is controlled at 1200-1450 ℃ of scope, and the thermal capacity of slag is big, helps reduction reaction and carries out fully, and chromium residue detoxifying is thorough.
5. as the method for claims 1 described high temperature reduction and detoxication of industrial chromic slag, it is characterized in that: not outer doping directly joins the chromium slag below broken 20 orders in the slag ladle that fills metallurgical cinder.
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| CN102618726A (en) * | 2012-03-16 | 2012-08-01 | 江西省洁益源环保科技有限公司 | Treatment method for detoxifying and recycling chromium slag |
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| CN106187146A (en) * | 2016-07-26 | 2016-12-07 | 昆明理工大学 | A kind of technique of dry detoxified chromium slag |
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| CN101721784B (en) * | 2008-10-21 | 2011-12-21 | 宝山钢铁股份有限公司 | Harm-free and recycling treatment method for chromium slag |
| CN102618726A (en) * | 2012-03-16 | 2012-08-01 | 江西省洁益源环保科技有限公司 | Treatment method for detoxifying and recycling chromium slag |
| CN102657925A (en) * | 2012-04-12 | 2012-09-12 | 广东省生态环境与土壤研究所 | Clay-based heavy metal thermal curing agent and its method for curing heaving metal |
| CN102657925B (en) * | 2012-04-12 | 2018-01-05 | 广东省生态环境技术研究所 | The method of heavy metal thermal curing agents and its curing heavy metal based on clay |
| CN102864311A (en) * | 2012-09-21 | 2013-01-09 | 承德建龙特殊钢有限公司 | Recovery method of chromium in high chromium-content slag in steel making-LF (ladle furnace) working procedure |
| CN102864311B (en) * | 2012-09-21 | 2014-11-26 | 承德建龙特殊钢有限公司 | Recovery method of chromium in high chromium-content slag in steel making-LF (ladle furnace) working procedure |
| CN105039616A (en) * | 2015-09-08 | 2015-11-11 | 华北理工大学 | Coprocessing method for AOD stainless steel residues stored in piles and LF refining residues |
| CN105200172A (en) * | 2015-09-08 | 2015-12-30 | 华北理工大学 | Synergistic processing method of stacked EAF stainless steel slag and LF refining slag |
| CN105039615A (en) * | 2015-09-08 | 2015-11-11 | 华北理工大学 | Processing method for stockpiled AOD stainless steel slag |
| CN106180134A (en) * | 2016-07-08 | 2016-12-07 | 重庆百世星程环境科技有限公司 | The curing of the produced chromium residue of electroplating wastewater technique |
| CN106187146A (en) * | 2016-07-26 | 2016-12-07 | 昆明理工大学 | A kind of technique of dry detoxified chromium slag |
| CN109111108A (en) * | 2018-10-22 | 2019-01-01 | 深圳市优力凯环保生物技术有限公司 | A kind of foamed glass material and preparation method thereof improving soil |
| WO2023004925A1 (en) * | 2021-07-26 | 2023-02-02 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for enriching and recovering chromium resources by synergistic utilization of chromium-containing sludge and chromium-containing waste residue |
| CN114318420A (en) * | 2021-10-08 | 2022-04-12 | 重庆大学 | Chromium-containing mirabilite and aluminum cell overhaul slag co-processing method and system |
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