CN103232068A - Recycling and reutilization process for treating chromium slag and wastewater - Google Patents
Recycling and reutilization process for treating chromium slag and wastewater Download PDFInfo
- Publication number
- CN103232068A CN103232068A CN2013101352342A CN201310135234A CN103232068A CN 103232068 A CN103232068 A CN 103232068A CN 2013101352342 A CN2013101352342 A CN 2013101352342A CN 201310135234 A CN201310135234 A CN 201310135234A CN 103232068 A CN103232068 A CN 103232068A
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- chromium slag
- chromium
- product
- throw out
- make
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- 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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Abstract
The invention discloses a recycling and reutilization process for treating chromium slag and wastewater. According to the invention, chromium slag is dissolved by using acid; and a hexavalent chromium special treatment agent is added, such that chromium slag pollution can be completely removed, and substances in chromium slag can be extracted and directly prepared into series of other substance products. During the chromium slag treatment process, no three-waste discharge is caused, and no secondary pollution is caused. The process has the advantages of large chromium slag treatment capacity, low cost, and high comprehensive utilization rate. Products obtained by chromium slag treatment recycling have the advantages of good quality, high value, and large market demand. Therefore, the method has good economic and social benefits. With the method, circular economy development is greatly promoted.
Description
Technical field
The present invention relates to a kind of cycling and reutilization and handle chromium slag and waster water process, belong to and from industrial chromium slag and waste water, extract the technical field that the chemical substance direct production goes out Industrial products, be particularly suitable for chromium slag and wastewater treatment that chemical industry chromic salts enterprise produces.
Background technology
It is a global problem that the chromium slag that chromium salt production enterprise produces is handled, and all is devoted to seek the new technologies that the chromium slag is handled both at home and abroad.
Original chromium slag treatment process mainly adopts dry method high-temperature detoxification and wet method detoxifcation to handle, these methods all can not be directly from the chromium slag extracting substance produce series product.
Chromic slag dry method high-temperature detoxification treatment process: a kind of is that kiln dry method high-temperature detoxification is handled, with the chromium slag through pyroprocessing more than 1200 ℃, be trivalent chromium with the hexavalent chrome reduction in the chromium slag, the chromium slag after the processing joins in the ratio of 1%-3% as mineralizer and produces cement in the cement; Another kind is that the chromium slag is transported to Steel Plant as the additive in the ferrochrome production.This kind chromic slag dry method high-temperature detoxification treatment process has high input, and power consumption is high, and treatment capacity is few, and comprehensive utilization ratio is low, and the wasting of resources is big.
The chromic slag wet method detoxifcation treatment process adopts to add acid or alkali dissolution chromium slag, and adding reductive agent again is trivalent chromium with the hexavalent chrome reduction in the chromium slag, plays the purpose of part detoxifcation.Disclosed Chinese invention patent " treatment technology of leached residue for alkaline hydrolysis of chromium ", the patent No.: CN94110910.0, publication number: CN1110196, open day: 1995.10.18, there is following problem in this invention:
1. this technology is not extracted the material production product in the chromium slag;
2. adopt Na
2CO
3Can not be with violent in toxicity CaCrO in the chromium slag
4Stripping still contains sexavalent chrome in the chromium slag after the processing;
3. add Na
2S can not reduce and handle CaCrO
4In sexavalent chrome;
4. this art breading flow process is numerous and diverse, and the cost height does not reach the purpose of harmless treatment chromium slag.
Therefore, the chromium slag treatment process that adopts all is the loss operation at present, the processing cost height, and treatment capacity is few, and the practical application of chromic slag treatment process technology is not high.Country handles the chromium slag and pays much attention to, though drop into a large amount of financial resources, material resources and manpower, it is in need of immediate treatment that up to a million tons of chromium slags have still been left in the present whole nation, and chromic salts enterprise increases few hundred thousand tonnes of chromium slag every year newly to be needed to handle.Enterprise, environmental protection, government press for the chromium slag treatment process of science of a kind of advanced person's practicality, the pollution and the harm that solve the chromium slag as early as possible.
Summary of the invention
The objective of the invention is to cycling and reutilization and handle chromium slag and waste water, protection environment and resource turn waste into wealth, and comprehensive utilization creates good economic benefit and social benefit.
The objective of the invention is to reach by following measure:
A kind of cycling and reutilization is handled chromium slag and waster water process flow process, it is characterized in that: in chromium slag and wastewater treatment process, can thoroughly remove chromium slag contaminatedly, the material in the chromium slag be extracted directly make series chemical product, step is as follows:
1. carefully be 200 orders with chromium sizing, (its composition is Cr in the chromium slag
2O
3, CaO, MgO, AI
2O
3, Fe
2O
3, SiO
2, CaCrO
4, Na
2CrO
4) adding acid, the reaction dissolving adds hexavalent chromium-treatments agent: Na
2S
2O
5, Na
2SO
3, NaHSO
3, FeSO
4, Na
2S, stirring reaction is added to the water and makes soluble substance become ion, and the metal ion in the mixing solutions is: Cr
3+, Ca
2+, Fe
3+, Mg
2+, AI
3+, Na
+, throw out is: Cr
2O
3, Fe
2O
3(γ-Mg (Fe.AI)
2O
4), AI
2O
3And SiO
2
2. discharge solution filters throw out, and washing separates, and drying makes product F e
2O
3(γ-Mg (Fe.AI)
2O
4) and Cr
2O
3, AI
2O
3, SiO
2Mix product;
3. (Cr in the mixing solutions
3+, Ca
2+, Fe
3+, Mg
2+, AI
3+, Na
+) add NaOH, make Fe
3+Be precipitated as Fe (OH) fully
3, discharge solution, throw out to be filtered, washs, drying makes product F e (OH)
3
4. (Cr in the mixing solutions
3+, Ca
2+, Mg
2+, AI
3+, Na
+) add NaOH, make Cr
3+, AI
3+Be precipitated as Cr (OH) fully
3And AI (OH)
3, discharge solution, throw out to be filtered, washs, drying makes Cr (OH)
3And AI (OH)
3Mix product;
5. (Ca in the mixing solutions
2+, Mg
2+, Na+) add NaOH, make Ca
2+Be precipitated as CaSO fully
4, discharge solution, throw out to be filtered, washs, drying makes products C aSO
4
6. (Mg in the mixing solutions
2+, Na
+) add NaOH, make Mg
2+Be precipitated as Mg (OH) fully
2, discharge solution, throw out to be filtered, washs, drying makes product Mg (OH)
2
7. add sulfuric acid in the solution, evaporative crystallization, drying makes product Na
2SO
4
8. with Na
2SO
4Mix through the High Temperature Furnaces Heating Apparatus calcining with reductive agent, re-leaching, separation, evaporation make product Na
2S;
9. solution (Na
+, SO
4 2-) directly discharge and enter Na in the chromium salt production flow process
2SO
4In the treatment process.
Embodiment
For improving this invention technology, become scientific and technological productive forces.In on 03 18th, the 2012 chromium slags to Jinshi Chemical Industry Co., Ltd., Gansu of chromic salts enterprise (this enterprise adopts calcium-free roasting method to produce chromic salts), handle concrete performance according to this technical process:
1. getting 1 ton of no calcium chromium slag levigate is 200 orders, adds sulfuric acid 200kg, and the reaction dissolving adds hexavalent chromium-treatments agent: Na
2SO
350kg, stirring reaction is added to the water and makes soluble substance become ion, and the metal ion in the mixing solutions is: Cr
3+, Fe
3+, Mg
2+, AI
3+, Na
+, throw out is: Cr
2O
3, Fe
2O
3(γ-Mg (Fe.AI)
2O
4), AI
2O
3And SiO
2
2. discharge solution filters throw out, and washing separates, and drying makes product F e
2O
3(γ-Mg (Fe.AI)
2O
4) 310kg, and Cr
2O
3, AI
2O
3, SiO
2Mix product 130kg;
3. (Cr in the mixing solutions
3+, Fe
3+, Mg
2+, AI
3+, Na
+) add NaOH195kg, make Fe
3+Be precipitated as Fe (OH) fully
3, discharge solution, throw out to be filtered, washs, drying makes product F e (OH)
3220kg;
4. (Cr in the mixing solutions
3+, Mg
2+, AI
3+, Na
+) add NaOH170kg, make Cr
3+, AI
3+Be precipitated as Cr (OH) fully
3And AI (OH)
3, discharge solution, throw out to be filtered, washs, drying makes Cr (OH)
3And AI (OH)
3Mix product 180kg;
5. (Mg in the mixing solutions
2+, Na
+) add NaOH20kg, make Mg
2+Be precipitated as Mg (OH) fully
2, discharge solution, throw out to be filtered, washs, drying makes product Mg (OH)
212kg;
6. add sulfuric acid 50kg in the solution, evaporative crystallization, drying makes product Na
2SO
4310kg.
The result shows:
1. all substances are extracted and produce series chemical product in the chromium slag, and the product that comprehensive utilization ratio 99.0% (wherein 1% is ashes) is produced by 1 ton of chromium slag of every processing extracting substance calculates finished product: Fe (OH)
3220kg, Fe
2O
3(γ-Mg (Fe.AI)
2O
4) 310kg, Cr
2O
3, AI
2O
3And SiO
2Mix product 130kg, Mg (OH)
212kg, Cr (OH)
3And AI (OH)
3Mix product 180kg, Na
2SO
4310kg.
2. whole art breading flow process non-secondary pollution, the waste water cycling and reutilization after the processing does not have " three wastes " discharging, environmental protection, energy-conservation, cleaning.
Practice shows that this invention technical application is strong, and the market requirement is wide, can promote recycling economy development greatly, and good benefits in environment, economic benefit and social benefit are arranged.
Claims (1)
1. a cycling and reutilization is handled chromium slag and waster water process flow process, it is characterized in that: in chromium slag and wastewater treatment process, can thoroughly remove chromium slag contaminatedly, the material in the chromium slag be extracted directly make series chemical product, step is as follows:
1). carefully be 200 orders with chromium sizing, (its composition is Cr in the chromium slag
2O
3, CaO, MgO, AI
2O
3, Fe
2O
3, SiO
2, CaCrO
4, Na
2CrO
4) adding acid, the reaction dissolving adds hexavalent chromium-treatments agent: Na
2S
2O
5, Na
2SO
3, NaHSO
3, FeSO
4, Na
2S, stirring reaction is added to the water and makes soluble substance become ion, and the metal ion in the mixing solutions is: Cr
3+, Ca
2+, Fe
3+, Mg
2+, AI
3+, Na
+, throw out is: Cr
2O
3, Fe
2O
3(γ-Mg (Fe.AI)
2O
4), AI
2O
3And SiO
2
2). discharge solution, throw out is filtered, washing separates, and drying makes product F e
2O
3(γ-Mg (Fe.AI)
2O
4) and Cr
2O
3, AI
2O
3, SiO
2Mix product;
3). (Cr in the mixing solutions
3+, Ca
2+, Fe
3+, Mg
2+, AI
3+, Na
+) add NaOH, make Fe
3+Be precipitated as Fe (OH) fully
3, discharge solution, throw out to be filtered, washs, drying makes product F e (OH)
3
4). (Cr in the mixing solutions
3+, Ca
2+, Mg
2+, AI
3+, Na
+) add NaOH, make Cr
3+, AI
3+Be precipitated as Cr (OH) fully
3And AI (OH)
3, discharge solution, throw out to be filtered, washs, drying makes Cr (OH)
3And AI (OH)
3Mix product;
5). (Ca in the mixing solutions
2+, Mg
2+, Na+) add NaOH, make Ca
2+Be precipitated as CaSO fully
4, discharge solution, throw out to be filtered, washs, drying makes products C aSO
4
6). (Mg in the mixing solutions
2+, Na
+) add NaOH, make Mg
2+Be precipitated as Mg (OH) fully
2, discharge solution, throw out to be filtered, washs, drying makes product Mg (OH)
2
7). add sulfuric acid in the solution, evaporative crystallization, drying makes product Na
2SO
4
8). with Na
2SO
4Mix through the High Temperature Furnaces Heating Apparatus calcining with reductive agent, re-leaching, separation, evaporation make product Na
2S;
9). solution (Na
+, SO
4 2-) directly discharge and enter Na in the chromium salt production flow process
2SO
4In the treatment process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101352342A CN103232068A (en) | 2012-05-19 | 2013-04-09 | Recycling and reutilization process for treating chromium slag and wastewater |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210165408.5 | 2012-05-19 | ||
| CN2012101654085A CN102699006A (en) | 2012-05-19 | 2012-05-19 | Process for processing, recycling and reusing chromic slag and waste water |
| CN2013101352342A CN103232068A (en) | 2012-05-19 | 2013-04-09 | Recycling and reutilization process for treating chromium slag and wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103232068A true CN103232068A (en) | 2013-08-07 |
Family
ID=46892225
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101654085A Pending CN102699006A (en) | 2012-05-19 | 2012-05-19 | Process for processing, recycling and reusing chromic slag and waste water |
| CN2013101352342A Pending CN103232068A (en) | 2012-05-19 | 2013-04-09 | Recycling and reutilization process for treating chromium slag and wastewater |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101654085A Pending CN102699006A (en) | 2012-05-19 | 2012-05-19 | Process for processing, recycling and reusing chromic slag and waste water |
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| Country | Link |
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| CN (2) | CN102699006A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602975A (en) * | 2013-11-22 | 2014-02-26 | 大连碧城环保科技有限公司 | Metal high-temperature bluing (blacking) clean production process |
| CN103757419A (en) * | 2013-12-30 | 2014-04-30 | 武汉纺织大学 | Method for preparing aluminium benzoate from calcium-free chromium slag |
| CN105016387A (en) * | 2015-07-20 | 2015-11-04 | 中国科学院过程工程研究所 | Chromium salt mud treatment method |
| CN105524637A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Method for preparing energy product by using PVC (polyvinyl chloride) plastics and simultaneously harmlessly treating chromium slag |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004919B (en) * | 2014-06-11 | 2016-03-23 | 张安良 | The environment-protective circulating recycling technique of waste residue in a kind of electrolytic manganese production |
| CN106145033A (en) * | 2015-04-08 | 2016-11-23 | 唐翔 | Cr VI technique is removed in chemical chromium slag and metallurgical slag comprehensive utilization |
| CN112551584A (en) * | 2020-12-25 | 2021-03-26 | 池州得奇环保科技有限公司 | Chromium-containing hazardous waste treatment method |
| CN114318004B (en) * | 2021-12-31 | 2023-12-01 | 中南林业科技大学 | Method for removing chromium from cobalt solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101816829A (en) * | 2010-04-09 | 2010-09-01 | 河南金谷环保工程设备有限公司 | Chromium residue detoxifying process |
| WO2011029269A1 (en) * | 2009-09-14 | 2011-03-17 | 重庆瑞帆再生资源开发有限公司 | Method for innocuously treating chromium residue using metallurgical roasting and blast furnace |
| CN102191390A (en) * | 2010-03-09 | 2011-09-21 | 刘杰 | Method for recovering hexavalent chromium resources from chromium slag |
-
2012
- 2012-05-19 CN CN2012101654085A patent/CN102699006A/en active Pending
-
2013
- 2013-04-09 CN CN2013101352342A patent/CN103232068A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011029269A1 (en) * | 2009-09-14 | 2011-03-17 | 重庆瑞帆再生资源开发有限公司 | Method for innocuously treating chromium residue using metallurgical roasting and blast furnace |
| CN102191390A (en) * | 2010-03-09 | 2011-09-21 | 刘杰 | Method for recovering hexavalent chromium resources from chromium slag |
| CN101816829A (en) * | 2010-04-09 | 2010-09-01 | 河南金谷环保工程设备有限公司 | Chromium residue detoxifying process |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602975A (en) * | 2013-11-22 | 2014-02-26 | 大连碧城环保科技有限公司 | Metal high-temperature bluing (blacking) clean production process |
| CN103602975B (en) * | 2013-11-22 | 2015-12-30 | 大连碧城环保科技股份有限公司 | Metallic high temperature turns blue (blackout) process for cleanly preparing |
| CN103757419A (en) * | 2013-12-30 | 2014-04-30 | 武汉纺织大学 | Method for preparing aluminium benzoate from calcium-free chromium 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 |
| CN105016387A (en) * | 2015-07-20 | 2015-11-04 | 中国科学院过程工程研究所 | Chromium salt mud treatment method |
| CN105524637A (en) * | 2016-01-19 | 2016-04-27 | 青岛理工大学 | Method for preparing energy product by using PVC (polyvinyl chloride) plastics and simultaneously harmlessly treating chromium slag |
| CN105524637B (en) * | 2016-01-19 | 2019-10-22 | 青岛理工大学 | Method for preparing energy product by using PVC (polyvinyl chloride) plastics and simultaneously harmlessly treating chromium slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102699006A (en) | 2012-10-03 |
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Application publication date: 20130807 |