CN101816829A - Chromium residue detoxifying process - Google Patents

Chromium residue detoxifying process Download PDF

Info

Publication number
CN101816829A
CN101816829A CN 201010174908 CN201010174908A CN101816829A CN 101816829 A CN101816829 A CN 101816829A CN 201010174908 CN201010174908 CN 201010174908 CN 201010174908 A CN201010174908 A CN 201010174908A CN 101816829 A CN101816829 A CN 101816829A
Authority
CN
China
Prior art keywords
chromium
chromium residue
reducing agent
residue detoxifying
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 201010174908
Other languages
Chinese (zh)
Other versions
CN101816829B (en
Inventor
李顺灵
陈俊杰
杨秋岭
黄立志
袁明涛
李万灵
燕战军
赵豆豆
李常慧
张鋆浩
潘志恒
杨海龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HENAN JINGU ENVIRONMENTAL PROTECTION ENGINEERING EQUIPMENT Co Ltd
Original Assignee
HENAN JINGU ENVIRONMENTAL PROTECTION ENGINEERING EQUIPMENT Co Ltd
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 HENAN JINGU ENVIRONMENTAL PROTECTION ENGINEERING EQUIPMENT Co Ltd filed Critical HENAN JINGU ENVIRONMENTAL PROTECTION ENGINEERING EQUIPMENT Co Ltd
Priority to CN2010101749086A priority Critical patent/CN101816829B/en
Publication of CN101816829A publication Critical patent/CN101816829A/en
Application granted granted Critical
Publication of CN101816829B publication Critical patent/CN101816829B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention belongs to the technical field of chromium residue detoxifying, and discloses a chromium residue detoxifying process. The process comprises the following steps of: performing wet grinding on chromium residue, adding water into the chromium residue to prepare chromium residue slurry; and after being subjected to acid-leaching reduction reaction, performing solid-liquid separation on the chromium residue slurry to obtain a filter cake, namely the detoxified chromium residue. The process is characterized in that: under the condition of not changing the original alkaline environment of the chromium residue, a reducing agent 1 is added into the chromium residue directly, and then the reducing agent and the chromium residue are subjected to wet grinding to form particles with 100 to 300 meshes; and the water is added to prepare the chromium residue slurry with 30 to 45 baume degrees, wherein the reducing agent 1 is sodium sulphide, sodium bisulfide, sodium thiosulfate or sodium pyrosulfite. The process has simpleness, thorough detoxification, no chromium return phenomenon and easy implementation of mass production; and the process prolongs effective reduction reaction time, improves reaction efficiency, saves the using amount of acid during the acid-leaching reduction, and has low processing cost because Cr6+ in the chromium residue is subjected to two times of dissolution and reduction.

Description

A kind of chromium residue detoxifying process
Technical field
The invention belongs to the chromium residue detoxifying technical field, particularly a kind of chromium residue detoxifying process.
Background technology
The chromic salts industry is an important industry indispensable in the national economy, is mainly used in aspects such as plating, tanning, printing and dyeing, medicine, catalyst, corrosion inhibition for metal.The main waste residue that discharges in the chromium salt production process (being the chromium slag) is a kind of hazardous waste with severe toxicity, wherein Cr VI (Cr 6+) be the root of toxicity.According to analysis result, with Cr to China's part chromium dreg chemistry composition characteristics 2O 3Metering, total chromium average quality percentage composition is about 3～5% in the chromium slag, and Cr VI average quality percentage composition is about 1～5%.There are six kinds of components to contain Cr in the chromium slag 6+, be respectively Sodium Chromate Tetrahydrate 99, calcium chromate, chromium calcium aluminate and alkali formula ferric chromate, calcium silicates-calcium chromate solid solution and iron calcium aluminate-calcium chromate solid solution.Wherein Sodium Chromate Tetrahydrate 99 and free calcium chromate are water-soluble phase, by surface water, rainwater dissolving, are the origin that the chromium slag pollutes in the recent period easily; Though all the other four kinds of components are insoluble in water, but storing up in the open in the process for a long time, through weathering and aquation easily cause the chromium slag to environment in, long-term pollution.
Chromium residue detoxifying always is a headache difficult problem of chromic salts industry, the tradition detoxification is long too harsh or too high because of processing cost because of reaction condition because of the detoxifcation recovery time, causes not finding out yet so far real effective, an economic and workable chromium residue detoxifying process.
Summary of the invention
For overcoming the deficiencies in the prior art part, the object of the present invention is to provide a kind of reaction efficiency height, chromium residue detoxifying process that cost is low.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of chromium residue detoxifying process, with the wet lapping of chromium slag, add water and make the chromium dreg slurry, Separation of Solid and Liquid after the acidleach reduction reaction, separate the filter cake that obtains and be detoxification chromium slag, its special feature is: do not changing under the original alkaline environment condition of chromium slag, promptly directly to wherein adding reducing agent 1 therewith wet lapping to 100～300 orders, add water and make the chromium dreg slurry that concentration is 30～45 Baume degrees, described reducing agent 1 is vulcanized sodium (Na 2S), NaHS (NaHS), sodium thiosulfate (Na 2S 2O 3) or sodium pyrosulfite (Na 2S 2O 5), the addition of reducing agent 1 is reduced to trivalent chromium and is as the criterion will survey 60～90% of Cr VI total amount in the chromium slag.
Take all factors into consideration from treatment effect and financial cost, reducing agent 1 is preferably vulcanized sodium (Na 2S) or sodium pyrosulfite (Na 2S 2O 5).
During the acidleach reduction, used acid can be selected in those skilled in the art's normal ranges (mainly being dilute sulfuric acid and other spent acid), but the present invention advocates the preferred concentrated sulfuric acid.The concentrated sulfuric acid is meant mass concentration greater than 75% sulfuric acid, advocates among the present invention that the mass concentration of the concentrated sulfuric acid is 93% or 98%.
In the chromium dreg slurry of 30～45 Baume degrees; add acid and reducing agent 2 and carry out acidleach reduction reaction (reaction time, general 2～10h got final product); the addition of acid is 5～6 to be as the criterion with the pH value that can control the chromium dreg slurry, and the addition of reducing agent 2 is lower than national standard emission request " chromium slag contaminated improvement environmental protection technology standard " and (HJ/T301-2007) is as the criterion can control Cr VI final in the detoxification chromium slag and total chrome content.Reducing agent 2 wherein is that those skilled in the art's routine is selected, and specifically can be ferrous sulfate (FeSO 4).
For making waste water reach zero-emission, after the Separation of Solid and Liquid, the filtrate 1 that obtains returns wet lapping and system chromium dreg slurry operation is recycling.
Behind the operation certain hour, the salts substances of actual measurement (mainly is Mg in the waste water after the Separation of Solid and Liquid (being filtrate 1) 2+, Al 3+, Fe 3+, Cr 3+) and SO 4 2-When excessive concentration consequently influences detoxifying effect, in filtrate 1, add alkaline matter and regulate pH value to 6～9 of filtrate 1 with precipitation Mg wherein 2+, Al 3+, Fe 3+, Cr 3+And SO 4 2-, Separation of Solid and Liquid once more, the filtrate 2 that obtains returns wet lapping and system chromium dreg slurry operation is recycling.When the adding alkaline matter carried out wastewater treatment, the main chemical reactions of generation had:
Cr 3++3OH -→Cr(OH) 3↓；
M x++xOH -→M(OH) x↓；
M in the formula X+Represent salts substances Mg 2+, Al 3+, Fe 3+Or Cr 3+, and form Mg (OH) behind the alkali reaction 2, Al (OH) 3, Fe (OH) 3, Cr (OH) 3Deng sediment, SO 4 2-With Ca 2+Reaction forms CaSO 4Sediment, these sediments are deviate from from waste water through Separation of Solid and Liquid, thereby reduce salts substances and SO in the recirculated water 4 2-Concentration.
Described alkaline matter is NaOH, CaO or Ca (OH) 2
The sulfuric acid mist that the concentrated sulfuric acid adds fashionable generation absorbs with alkali lye or water, and the waste liquid after the absorption returns the wet method pulverizing and system chromium dreg slurry operation is recycling.Wherein alkali lye is those skilled in the art's routine selection, is generally NaOH solution.
For refuse is got utilization, detoxification chromium slag is cured landfill or is used as roadbed material or is used as cement building material so that general industry is useless admittedly.
Technological principle of the present invention: adopt the wet lapping technology that the chromium slag is fully ground in wet type ball (rod) mill, grind in the process, calcium chromate in the chromium slag and chromium calcium aluminate lattice structure are destroyed, under the effect of acidic circulation water/waste liquid, water-soluble Cr VI and the continuous stripping of solubility in acid Cr VI enter liquid phase in the chromium slag, and the poisonous Cr VI of stripping constantly with reducing agent 1 first time reduction reaction takes place and is converted into avirulent trivalent chromium; Continue to add water slurrying afterwards, add reducing agent 2, add acid simultaneously and adjust the pH value of slurries, the water-soluble Cr VI of surplus and the thorough stripping of solubility in acid Cr VI and the reducing agent 2 generation reduction reactions second time are carried out the acidleach reduction and detoxication in the chromium slag, Cr VI is converted into avirulent trivalent chromium fully the most at last, after the Separation of Solid and Liquid, adds alkaline matter and adjust the pH value in filtrate, making trivalent chromium conversion is in the chromium slag after chromium hydroxide precipitation is fixed on detoxifcation, thereby reaches the purpose of chromium residue detoxifying.The main reduction reaction that detoxification processes takes place has:
4Cr 2O 7 2-+3S 2-+16H 2O→8Cr(OH) 3↓+3SO 4 2-+8OH --------①
4Cr 2O 7 2-+6S 2-+19H 2O→8Cr(OH) 3↓+3S 2O 3 2-+14OH ------②
2Cr 2O 7 2-+3S 2O 5 2-+14H +→4Cr 3++6SO 4 2-+7H 2O----------③
Cr 2O 7 2-+6Fe 2++16H +→6Fe 3++2Cr 3++8H 2O--------------④
Formula 1., 2. select vulcanized sodium (Na for use for reducing agent 1 2S) reduction reaction that takes place the time, 3. formula selects sodium pyrosulfite (Na for use for reducing agent 1 2S 2O 5) time reduction reaction that takes place, 4. formula selects ferrous sulfate (FeSO for use for reducing agent 2 under sour environment 4) time reduction reaction that takes place.
Reducing agent uses financial cost relatively:
Compare ferrous sulfate (FeSO for example 4) and sodium pyrosulfite (Na 2S 2O 5) be used separately as the processing cost of reducing agent.Suppose Cr VI (Cr in the raw material chromium slag 6+) the quality percentage composition be 4% (with Na 2Cr 2O 72H 2The O meter), required reducing agent consumption of chromium residue detoxifying per ton and Economic and Efficiency Analysis are as follows:
(1) with ferrous sulfate (FeSO 4) make reducing agent
Na 2Cr 2O 7·2H 2O～6FeSO 4·7H 2O
298～6×278＝1668
1 ton of chromium slag needs reducing agent FeSO in theory 47H 2The consumption computing formula of O is:
χ theory=1688 * 4%/298=224 (kg)
(2) make reducing agent with sodium pyrosulfite
2Na 2Cr 2O 7·2H 2O～3Na 2S 2O 5
2×298＝596～3×190＝570
1 ton of chromium slag needs reducing agent Na in theory 2S 2O 5The consumption computing formula be:
χ theory=570 * 4%/596=38 (kg)
According to the existing market market, the ferrous (FeSO of commercial sulphuric acid 4) price by 400 yuan/ton, industrial sodium pyrosulfite (Na 2S 2O 5) price be 1700 yuan/ton, so 1 ton of chromium slag needs the cost of reducing agent to be respectively: ferrous sulfate (FeSO 4) be 89.6 yuan, sodium pyrosulfite (Na 2S 2O 5) be 64.6 yuan.Therefore, the present invention adds reducing agent at twice, compares traditional disposable interpolation reducing agent 2 (FeSO 4) carry out the acidleach reduction reaction, can reduce processing cost, improve a day treatment scale.Take all factors into consideration economic benefit and detoxifying effect, to be reduced to trivalent chromium be criterion to the use amount that the present invention recommends reducing agent 1 will survey 60～90% of Cr VI total amount in the chromium slag.
Good effect of the present invention is:
(1) directly carries out the reduction reaction first time not changing under the original alkaline environment condition of chromium slag to wherein adding reducing agent 1, and adding reducing agent 2 is proceeded reduction reaction for the second time under follow-up sour environment, prolonged effective reduction reaction time, improved reaction efficiency, the consumption of used acid when having saved the acidleach reduction reaction.On still being the mixing of materials uniformity, effective reaction time all is improved than conventional art.
(2) can directly add the concentrated sulfuric acid during acidleach reduction and detoxication, change the mode of tradition with diluting concentrated sulfuric acid, effectively utilized the reaction heat of the concentrated sulfuric acid on the one hand, maximum temperature can reach more than 70 ℃ during redox (being acidleach reduction reaction of the present invention), not only overcome the low obstacle of extremely frigid zones temperature, but also shortened the redox reaction time; Reduce material on the other hand with addition of amount, improved a day treatment scale.
(3) the chromium slag Separation of Solid and Liquid that obtains behind the acidleach reduction and detoxication, waste liquid (filtrate 1/ filtrate 2) is recycling, realizes wastewater zero discharge, and cost is saved in using water wisely.
(4) behind the acidleach reduction and detoxication, add alkaline matter and carry out wastewater treatment, form CaSO 4, Mg (OH) 2, Al 2(OH) 3, Fe 2(OH) 3And Cr (OH) 3Deng sediment, trivalent chromium (Cr 3+) all be converted into Cr (OH) 3Sediment is deviate from sediment from waste liquid, total chrome is reduced.
(5) the chromium slag after the technology detoxifcation of the present invention reaches " chromium slag contaminated improvement environmental protection technology standard " (HJ/T301-2007) standard-required fully; nontoxic chromium slag is with the useless admittedly landfill that is cured of general industry; perhaps as roadbed material; perhaps be used as cement building material and carry out the changing waste into resources utilization, effectively reduce and reduced Cr in the chromium slag 6+Pollution on the environment and destruction.
(6) technical process of the present invention is simple, the Cr VI (Cr in the chromium slag 6+) through twice stripping and twice reduction, detoxifcation is thorough, nothing is returned the chromium phenomenon, accomplishes scale production easily, processing cost is low.
Description of drawings
Accompanying drawing is a process chart of the present invention.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is done into a ground and introduce in detail, but protection scope of the present invention is not limited thereto:
Embodiment 1
Process chart as shown in drawings:
The first step places chromium slag and reducing agent 1 in wet type ball (rod) grinding machine, grinds to 200 orders the water-soluble and solubility in acid Cr VI (Cr in the chromium slag 6+) constantly stripping, the water-soluble (Cr of stripping 6+) constantly with reducing agent 1 first time reduction reaction takes place and be converted into trivalent chromium (Cr 3+), the chromium slag is tentatively detoxified.Wherein, reducing agent 1 is vulcanized sodium (Na 2S), to be reduced to trivalent chromium be criterion to its consumption in order will survey 90% of Cr VI total amount in the chromium slag.
Second step, chromium slag after the preliminary detoxifcation in the first step is inserted hollander tub, and feeding recirculated water prepares the chromium dreg slurry in hollander tub, controlling its concentration is 40 Baume degrees, then the chromium dreg slurry is pumped in the redox jar, and in the redox jar, adding the reducing agent 2 and the concentrated sulfuric acid (mass concentration 93%), control chromium dreg slurry pH is 5.5, makes the water-soluble and solubility in acid Cr VI (Cr in the chromium slag 6+) thorough stripping and reducing agent 2 generation reduction reaction----acidleach second time reduction and detoxications, the reaction of acidleach reduction and detoxication continues 2h, with Cr VI (Cr 6+) be reduced into trivalent chromium Cr fully 3+Wherein, reducing agent 2 is ferrous sulfate (FeSO 4), its addition is can control the Cr of final actual measurement in the detoxification chromium slag 6+Being lower than the national standard emission request with total chrome content is as the criterion.
The 3rd step; after the acidleach reduction and detoxication in second step carries out fully; the chromium dreg slurry is carried out Separation of Solid and Liquid; the filter cake that obtains is detoxification chromium slag; it meets " chromium slag contaminated improvement environmental protection technology standard " (HJ/T301-2007) standard-required fully; be cured landfill or be used as roadbed material or be used as cement building material and carry out the changing waste into resources utilization so that general industry is useless admittedly, filtrate 1 can be used as directly delivery cycle utilization in wet type ball (rod) grinding machine and hollander tub of recirculated water simultaneously.
Embodiment 2
Be with the difference of embodiment 1: in second step, the mass concentration of the concentrated sulfuric acid is 98%; In the 3rd step, after the Separation of Solid and Liquid, in the filtrate 1 that obtains, add the pH value to 6 that alkaline matter NaOH regulates filtrate 1, wait to survey Mg wherein 2+, Al 3+, Fe 3+, Cr 3+Post precipitation, Separation of Solid and Liquid once more, the filtrate 2 that obtains is returned in wet type ball (rod) grinding machine and the hollander tub recycling; Other is all with embodiment 1.
Embodiment 3
Be with the difference of embodiment 1: in the 3rd step, after the Separation of Solid and Liquid, in the filtrate 1 that obtains, add the pH value to 8 that alkaline matter CaO regulates filtrate 1, wait to survey Mg wherein 2+, Al 3+, Fe 3+, Cr 3+And SO 4 2-Post precipitation, Separation of Solid and Liquid once more, the filtrate 2 that obtains is returned in wet type ball (rod) grinding machine and the hollander tub recycling; Other is all with embodiment 1.
Embodiment 4
Be with the difference of embodiment 1: in second step, when in the redox jar, adding the concentrated sulfuric acid, the supporting acid mist absorption system (forming) that is provided with by absorption tower, air-introduced machine and circulating pump etc., absorb the sulfuric acid mist that produces with alkali lye NaOH solution, the waste liquid after the absorption returns in wet type ball (rod) grinding machine and the hollander tub recycling; Other is all with embodiment 1.
Embodiment 5
Be with the difference of embodiment 1: in second step, when in the redox jar, adding the concentrated sulfuric acid, the supporting acid mist absorption system (forming) that is provided with by absorption tower, air-introduced machine and circulating pump etc., water absorbs the sulfuric acid mist that produces, and the waste liquid after the absorption returns in wet type ball (rod) grinding machine and the hollander tub recycling; In the 3rd step, after the Separation of Solid and Liquid, in the filtrate 1 that obtains, add alkaline matter Ca (OH) 2Regulate the pH value to 9 of filtrate 1, wait to survey Mg wherein 2+, Al 3+, Fe 3+, Cr 3+And SO 4 2-Post precipitation, Separation of Solid and Liquid once more, the filtrate 2 that obtains is returned in wet type ball (rod) grinding machine and the hollander tub recycling; Other is all with embodiment 1.
Embodiment 6
Be with the difference of embodiment 5: in the first step, use wet type ball (rod) grinding machine that the chromium slag is ground to 100 orders, reducing agent 1 is sodium pyrosulfite (Na 2S 2O 5), to be reduced to trivalent chromium be criterion to its consumption in order will survey 60% of Cr VI total amount in the chromium slag; In second step, handling the chromium dreg slurry concentration that obtains through hollander tub is 30 Baume degrees, and control chromium dreg slurry pH is 6, carries out acidleach reduction and detoxication 10h in the redox jar; Other is all with embodiment 5.
Embodiment 7
Be with the difference of embodiment 5: in the first step, use wet type ball (rod) grinding machine that the chromium slag is ground to 300 orders, reducing agent 1 be NaHS (NaHS), and its consumption is will survey 70% of Cr VI total amount in the chromium slag to be reduced to trivalent chromium be criterion; In second step, handling the chromium dreg slurry concentration that obtains through hollander tub is 45 Baume degrees, and control chromium dreg slurry pH is 5, carries out acidleach reduction and detoxication 5h in the redox jar; Other is all with embodiment 5.
Embodiment 8
Be with the difference of embodiment 5: in the first step, reducing agent 1 is sodium thiosulfate (Na 2S 2O 3); Other is all with embodiment 5.

Claims (9)

1. chromium residue detoxifying process, with the wet lapping of chromium slag, add water and make the chromium dreg slurry, Separation of Solid and Liquid after the acidleach reduction reaction, separate the filter cake that obtains and be detoxification chromium slag, it is characterized in that: do not changing under the original alkaline environment condition of chromium slag directly to wherein adding reducing agent 1 therewith wet lapping to 100～300 orders, add water and make the chromium dreg slurry that concentration is 30～45 Baume degrees, described reducing agent 1 is a vulcanized sodium, NaHS, sodium thiosulfate or sodium pyrosulfite, the addition of reducing agent 1 is reduced to trivalent chromium and is as the criterion will survey 60～90% of Cr VI total amount in the chromium slag.
2. chromium residue detoxifying process as claimed in claim 1 is characterized in that: reducing agent 1 is preferably vulcanized sodium or sodium pyrosulfite.
3. chromium residue detoxifying process as claimed in claim 1 is characterized in that: during the acidleach reduction, used acid is preferably the concentrated sulfuric acid.
4. as any described chromium residue detoxifying process of claim 1～3, it is characterized in that: in the chromium dreg slurry of 30～45 Baume degrees, add acid and reducing agent 2 and carry out the acidleach reduction reaction, the addition of acid is 5～6 to be as the criterion with the pH value that can control the chromium dreg slurry, and the addition of reducing agent 2 is lower than the national standard emission request and is as the criterion can control Cr VI final in the detoxification chromium slag and total chrome content.
5. chromium residue detoxifying process as claimed in claim 4 is characterized in that: after the Separation of Solid and Liquid, the filtrate 1 that obtains returns wet lapping and system chromium dreg slurry operation is recycling.
6. chromium residue detoxifying process as claimed in claim 5 is characterized in that: add pH value to 6～9 that alkaline matter is regulated filtrate 1 in filtrate 1, remove wherein salts substances and SO 4 2-After, Separation of Solid and Liquid once more, the filtrate 2 that obtains is returned recycling.
7. chromium residue detoxifying process as claimed in claim 6 is characterized in that: described alkaline matter is NaOH, CaO or Ca (OH) 2
8. chromium residue detoxifying process as claimed in claim 7 is characterized in that: the sulfuric acid mist that the concentrated sulfuric acid adds fashionable generation absorbs with alkali lye or water, and the waste liquid after the absorption returns the wet method pulverizing and system chromium dreg slurry operation is recycling.
9. chromium residue detoxifying process as claimed in claim 8 is characterized in that: detoxification chromium slag is cured landfill or is used as roadbed material or is used as cement building material so that general industry is useless admittedly.
CN2010101749086A 2010-04-09 2010-04-28 Chromium residue detoxifying process Expired - Fee Related CN101816829B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010101749086A CN101816829B (en) 2010-04-09 2010-04-28 Chromium residue detoxifying process

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201010142943.X 2010-04-09
CN201010142943 2010-04-09
CN2010101749086A CN101816829B (en) 2010-04-09 2010-04-28 Chromium residue detoxifying process

Publications (2)

Publication Number Publication Date
CN101816829A true CN101816829A (en) 2010-09-01
CN101816829B CN101816829B (en) 2011-08-31

Family

ID=42652197

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010101749086A Expired - Fee Related CN101816829B (en) 2010-04-09 2010-04-28 Chromium residue detoxifying process

Country Status (1)

Country Link
CN (1) CN101816829B (en)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102274684A (en) * 2011-05-31 2011-12-14 重庆民丰化工有限责任公司 Chromium-containing tail gas treatment process
CN102274606A (en) * 2011-05-31 2011-12-14 重庆民丰化工有限责任公司 Alkaline detoxification process for chromium residue
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
CN102816933A (en) * 2011-06-08 2012-12-12 工信华鑫科技有限公司 Treatment process method of chrome slag
CN102826674A (en) * 2011-06-15 2012-12-19 上海丰信环保科技有限公司 Method for processing lead and chromium in wastewater
CN103233130A (en) * 2013-05-09 2013-08-07 贵阳中科融实新材料技术有限公司 Chromium slag treatment method
CN103232068A (en) * 2012-05-19 2013-08-07 唐翔 Recycling and reutilization process for treating chromium slag and wastewater
CN103757419A (en) * 2013-12-30 2014-04-30 武汉纺织大学 Method for preparing aluminium benzoate from calcium-free chromium slag
CN103771382A (en) * 2013-12-30 2014-05-07 武汉纺织大学 Method for preparing iron phosphate from calcium-free chromic slag
CN103934256A (en) * 2014-04-21 2014-07-23 江苏维尔利环保科技股份有限公司 Wet detoxification method for chromium slag and chromium-containing pollutants
CN107243499A (en) * 2017-06-28 2017-10-13 长沙世恒环保科技有限公司 A kind of NBSH wet methods chromic slag harmlessness disposal plant and its method
CN108379766A (en) * 2018-04-09 2018-08-10 重庆理工大学 A kind of chromite calcium-free roasting slag acidleach detoxification technique
CN108586766A (en) * 2018-05-09 2018-09-28 中钢集团洛阳耐火材料研究院有限公司 A kind of method of multiple tooth coordination polymer of the liquid phase method synthesis containing chromium
CN109047288A (en) * 2018-08-20 2018-12-21 湖南瀚洋环保科技有限公司 Cr VI industrial hazard offal treatment technique and device
CN109290333A (en) * 2018-11-16 2019-02-01 梅州市华智星技术服务有限公司 A kind of integrated application method of chromium slag landfill disposal
CN109449426A (en) * 2018-11-29 2019-03-08 华南理工大学 A method of lithium ion battery negative material is prepared using chromium slag
CN110369471A (en) * 2019-09-05 2019-10-25 中国科学院过程工程研究所 A kind of method of chromium-polluted soil reparation
CN110404226A (en) * 2019-07-02 2019-11-05 长春黄金研究院有限公司 A kind of chromic slag wet method detoxifcation process improving detoxifying effect
CN111348881A (en) * 2020-03-13 2020-06-30 常熟理工学院 Method for improving cement solidification chromium slag and product thereof
CN111437561A (en) * 2020-04-08 2020-07-24 北京高能时代环境技术股份有限公司 Chromium slag wet detoxification method based on mechanochemical strengthening
CN111621641A (en) * 2020-06-03 2020-09-04 中国恩菲工程技术有限公司 Method for removing hexavalent chromium in process of preparing nickel cobalt hydroxide from laterite-nickel ore
CN112707443A (en) * 2021-02-22 2021-04-27 山东同其信息科技有限公司 Chromium slag treatment process
CN113816847A (en) * 2021-10-08 2021-12-21 上海良仁化工有限公司 Method for preparing basic chromium acetate from chromium-containing sludge
CN114669591A (en) * 2022-03-22 2022-06-28 浙江卓锦环保科技股份有限公司 Wet detoxification process for hexavalent chromium contaminated soil

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110812773A (en) * 2019-11-17 2020-02-21 长春黄金研究院有限公司 Two-stage deep wet detoxification method for industrial chromium slag

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1085832A (en) * 1992-10-17 1994-04-27 曾庆琳 Process flow for treating leached-out chromium residue
JP2005007240A (en) * 2003-06-17 2005-01-13 Hazama Corp Method for cleaning soil and/or groundwater contaminated with hexavalent chromium in situ
CN1635170A (en) * 2003-12-29 2005-07-06 刘克柱 Method for treating chromic slag by acid pickling process
CN101168085A (en) * 2007-11-30 2008-04-30 河南工业大学 Chromium slag reduction detoxification technique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1085832A (en) * 1992-10-17 1994-04-27 曾庆琳 Process flow for treating leached-out chromium residue
JP2005007240A (en) * 2003-06-17 2005-01-13 Hazama Corp Method for cleaning soil and/or groundwater contaminated with hexavalent chromium in situ
CN1635170A (en) * 2003-12-29 2005-07-06 刘克柱 Method for treating chromic slag by acid pickling process
CN101168085A (en) * 2007-11-30 2008-04-30 河南工业大学 Chromium slag reduction detoxification technique

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102274606A (en) * 2011-05-31 2011-12-14 重庆民丰化工有限责任公司 Alkaline detoxification process for chromium residue
CN102274684A (en) * 2011-05-31 2011-12-14 重庆民丰化工有限责任公司 Chromium-containing tail gas treatment process
CN102816933B (en) * 2011-06-08 2014-07-30 工信华鑫科技有限公司 Treatment process method of chrome slag
CN102816933A (en) * 2011-06-08 2012-12-12 工信华鑫科技有限公司 Treatment process method of chrome slag
CN102826674A (en) * 2011-06-15 2012-12-19 上海丰信环保科技有限公司 Method for processing lead and chromium in wastewater
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
CN103232068A (en) * 2012-05-19 2013-08-07 唐翔 Recycling and reutilization process for treating chromium slag and wastewater
CN103233130A (en) * 2013-05-09 2013-08-07 贵阳中科融实新材料技术有限公司 Chromium slag treatment method
CN103757419A (en) * 2013-12-30 2014-04-30 武汉纺织大学 Method for preparing aluminium benzoate from calcium-free chromium slag
CN103771382A (en) * 2013-12-30 2014-05-07 武汉纺织大学 Method for preparing iron phosphate from calcium-free chromic slag
CN103771382B (en) * 2013-12-30 2015-06-24 武汉纺织大学 Method for preparing iron phosphate from calcium-free chromic slag
CN103757419B (en) * 2013-12-30 2015-12-09 陕西绿泉环保科技有限公司 A kind of from without the method preparing aluminum benzoate calcium chromium slag
CN103934256A (en) * 2014-04-21 2014-07-23 江苏维尔利环保科技股份有限公司 Wet detoxification method for chromium slag and chromium-containing pollutants
CN103934256B (en) * 2014-04-21 2019-06-04 江苏维尔利环保科技股份有限公司 Chromium slag and wet method detoxifcation method containing chromium pollutant
CN107243499A (en) * 2017-06-28 2017-10-13 长沙世恒环保科技有限公司 A kind of NBSH wet methods chromic slag harmlessness disposal plant and its method
CN108379766A (en) * 2018-04-09 2018-08-10 重庆理工大学 A kind of chromite calcium-free roasting slag acidleach detoxification technique
CN108586766A (en) * 2018-05-09 2018-09-28 中钢集团洛阳耐火材料研究院有限公司 A kind of method of multiple tooth coordination polymer of the liquid phase method synthesis containing chromium
CN109047288A (en) * 2018-08-20 2018-12-21 湖南瀚洋环保科技有限公司 Cr VI industrial hazard offal treatment technique and device
CN109290333A (en) * 2018-11-16 2019-02-01 梅州市华智星技术服务有限公司 A kind of integrated application method of chromium slag landfill disposal
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
CN109449426A (en) * 2018-11-29 2019-03-08 华南理工大学 A method of lithium ion battery negative material is prepared using chromium slag
CN110404226A (en) * 2019-07-02 2019-11-05 长春黄金研究院有限公司 A kind of chromic slag wet method detoxifcation process improving detoxifying effect
CN110369471A (en) * 2019-09-05 2019-10-25 中国科学院过程工程研究所 A kind of method of chromium-polluted soil reparation
CN111348881A (en) * 2020-03-13 2020-06-30 常熟理工学院 Method for improving cement solidification chromium slag and product thereof
CN111437561A (en) * 2020-04-08 2020-07-24 北京高能时代环境技术股份有限公司 Chromium slag wet detoxification method based on mechanochemical strengthening
CN111621641A (en) * 2020-06-03 2020-09-04 中国恩菲工程技术有限公司 Method for removing hexavalent chromium in process of preparing nickel cobalt hydroxide from laterite-nickel ore
CN112707443A (en) * 2021-02-22 2021-04-27 山东同其信息科技有限公司 Chromium slag treatment process
CN113816847A (en) * 2021-10-08 2021-12-21 上海良仁化工有限公司 Method for preparing basic chromium acetate from chromium-containing sludge
CN113816847B (en) * 2021-10-08 2023-09-19 上海良仁化工有限公司 Method for preparing basic chromium acetate from chromium-containing sludge
CN114669591A (en) * 2022-03-22 2022-06-28 浙江卓锦环保科技股份有限公司 Wet detoxification process for hexavalent chromium contaminated soil

Also Published As

Publication number Publication date
CN101816829B (en) 2011-08-31

Similar Documents

Publication Publication Date Title
CN101816829B (en) Chromium residue detoxifying process
CN101913785B (en) Incineration fly ash cement kiln synergic processing process
CN104310647A (en) Recycling method for treating stainless steel pickling acid pickle and wastewater
CN102674278B (en) Method for pre-treating phosphorus rock by titanium dioxide waste acid
CN103058253A (en) Method for preparing gypsum by free sulfuric acid in titanium dioxide wastewater
CN101380510A (en) Chromic slag wet method detoxifcation and resource comprehensive utilization new technique
CN101618929A (en) Method of treating alkaline sludge containing heavy metal as resources
CN108069449A (en) The method that Aluminum subtracts the devil liquor recovery aluminium hydroxide and sodium hydroxide of slag
CN102603098A (en) Circular processing method of stainless steel acid washing waste liquid
CN103601322A (en) Integrated process of recycle of aluminum profile production wastewater and comprehensive utilization of waste residue
CN104108814B (en) A kind of method processing Rutile type Titanium Dioxide waste water
CN109336236B (en) Method for preparing aluminum-iron flocculating agent from red mud
CN104030332A (en) Method for reclaiming cryolite from fluorine containing pesticide industrial waste residues
CN104609683A (en) Chrome tanning sludge heavy metal chromium regeneration method
CN111170349A (en) Acid leaching purification method suitable for fluorite ore
CN103484888B (en) The treatment process of chromium-containing acid waste liquor of sodium and sulfuric acid pickling waste liquid in a kind of stainless steel production
CN102431975A (en) Method for recovering and utilizing three wastes during titanium white production through sulfuric acid process
CN102701549A (en) Novel reclamation method of electroplating sludge
CN101671054A (en) Poly-ferric chloride purifying agent and preparation method and application thereof
CN208632118U (en) A kind of aluminium wastewater recycles the device of aluminium hydroxide using ammonia as precipitating reagent
CN106492752A (en) A kind of adsorbent new preparation process for processing waste water containing chrome
CN109251729B (en) Method for simultaneously preparing I-type and II-type snow melting agents by utilizing garbage fly ash
CN102825058A (en) Method for recycling calcium sulfate waste residues generated in titanium dioxide acidic waste water
CN103159419A (en) Chromium slag carbonation detoxification treatment method
CN102181647B (en) Method for extracting chromated nickel from low-grade stainless steel sludge by using stainless steel acid-washing waste mother liquor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110831

Termination date: 20210428

CF01 Termination of patent right due to non-payment of annual fee