CN106699027B - A kind of processing method of chromium residue - Google Patents
A kind of processing method of chromium residue Download PDFInfo
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- CN106699027B CN106699027B CN201611112280.0A CN201611112280A CN106699027B CN 106699027 B CN106699027 B CN 106699027B CN 201611112280 A CN201611112280 A CN 201611112280A CN 106699027 B CN106699027 B CN 106699027B
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- chromium
- residue
- processing method
- chromium residue
- waste residue
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
- C04B2111/00784—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes for disposal only
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Sludge (AREA)
Abstract
The present invention relates to a kind of processing methods of chromium residue, belong to hazardous waste harmless treatment disposal technology field.The chromium residue processing method includes the following steps：（1）Uniform chromium slag, which will be ground, adds water to be stirred uniformly, and adding medicine reacts and adjusts pH to acidity；（2）Stirring after a certain period of time, is added reducing agent and carries out reduction reaction；（3）Complete reaction（2）Afterwards, flocculant is added to carry out flocculation sediment again under alkaline condition；（4）Firming body is in alkalescent after adjusting reaction；（5）Addition curing agent simultaneously conserves.The method of the invention normal temperature and pressure operates, simple for process, strong applicability, and industrialization operational effect is stablized；Medicament price used is low, will not cause secondary pollution, economic and social benefit notable to environment；The leaching rate of total chromium and hexavalent chromium is low, it can be ensured that reaches National Hazard waste reclamation standard.
Description
Technical field
This method belongs to resource and environment technical field, especially hazardous waste harmless treatment disposal technology, specifically relates to
And a kind of processing method of high concentration chromium residue.
Background technology
In the 21st century, human society faces various challenges, wherein including just problem of environmental pollution of people's attention.Chromium is dirty
Dye is the problem that people must take seriously.For many years, it is had been reported that when the example that pollution of chromium damages human health, especially
International cancer research institution can be carcinogenic about 6 valence chromium conclusion, make pollution of chromium be even more have a bad reputation.
Waste containing chromium is the main hazard waste of the industries such as plating and leather manufacture, and is divided into danger register
21 class wastes.The chemical valence of common chromium has positive divalent, positive trivalent and positive 6 valence.The toxicity of chromium is related with its valence state, and crome metal is without poison
Property, and 6 valence chromium in compound are strong carcinogenic mutagenic matters, can induce the cancers such as lung cancer and nasopharyngeal carcinoma, 6 valence chromium also Yi Beiren
Body is absorbed and is accumulated in vivo.
In Chemical Manufacture, the chromium salt production in China generally has calcium roasting technology using backward, is carried out using this technology
Production often produces 1 ton of chromic salts, will generate 2 ~ 3 tons of discarded chromium slag, there are about 75 ~ 900,000 newly-increased danger containing chromium is useless in the annual whole nation
Object generates.According to investigations, national because chromium slag has resulted in more than 100 contaminated sites, there are about 5 square kilometres for contaminated area, even in
The content of part place, total chromium and Cr VI is higher, and far beyond examination criteria value, and the health for having seriously affected resident is raw
Production and life.Such as nearby there is cancer village by chromium slag contaminated place in Luliang, more people are because cancer stricken is dead, death toll
Every year there are about 6 ~ 7 people, also cancer stricken is dead by the minimum child for 9 years old.Now, the innocuity treatment problem of chromium slag is recognized
For the bottleneck problem for being China's Chrome Salt Industry sound development and global problem.
Currently, the method for disposition chromium slag is mainly the following：Stocking and storing method, solidification method, harmless treatment, melting and solidification
Method, cement solidification method, complexometry, electrochemical process, biological clarification etc..These methods of single use, it is higher that there are costs, technique
More complex problem can not be really achieved the requirement of economy, practicability and validity.So the processing for chromium slag, comprehensive
A variety of methods are closed, disposing technique is simplified, reduce the development trend that cost is healthy effectively disposition chromium slag.
CN201310692868.8 discloses a kind of processing method containing inorganic salt organic waste water and chromium residue, including：
(a) it provides and contains inorganic salt organic waste water, chromium residue is added in the case where it is with pH0.1-4.0；(b) by gained mixture in 150-
400 DEG C of progress liquid phase reactors, after filter to get filtrate and filter residue；(c) reducing agent is added optionally into gained filtrate to restore residual
Chromium, after filter to get filtrate and filter residue；(d) the gained filtrate crystallisation by step (b) or (c), obtains inorganic salt crystal and mother liquor；(e) will
Step (d) is mother liquid obtained to be adjusted to pH6.5-7.0, and precipitation is precipitated, and detaches to obtain precipitation and filtrate；And (f) optionally by step (e) institute
It obtains after filtrate returns to production or desalination and discharges.This method not only effectively removes organic waste Organic substance in water, but also recyclable has
Inorganic salts in machine waste water, processed waste water can return to direct emission after commercial Application or simple desalination, in addition chromium residue
Middle chromium is recycled.
CN201610038396.8 discloses a kind of method for the treatment of of wastes produced containing chromium, and its step are as follows：A) Cr VI is collected
Content is the waste residue or waste liquid of 5wt%, and acid pickle is first added and stirs 10-30min, adds chemical waste liquid reaction 2-6h；B) to
It is 7-9 that lime is added in waste after step a) reactions and adjusts pH value, stirs 20-60min, then curing process.
CN201210333264.X discloses a kind of processing method of steel and iron industry chromium residue, solves existing useless containing chromium
Slag pollutes the low problem of environment, economic benefit.Technical solution includes that chromium residue is put into stirred tank, adds hydrochloric acid solution
It is stirred pickling, it includes the soluble matter dissolving including chromium to make chromium residue；Then the pH value of mixed liquor is adjusted to after 5~6
Filtering, filter residue are Chrome-free or low chromium waste residue, and filtrate is as combustion-supporting agent for fuel coal.
A kind of processing method of chromium residue is now invented, medicament price used is low, and secondary pollution will not be caused to environment, warp
Ji and social benefit are notable.
Invention content
The purpose of the present invention is to overcome the deficiency in the prior art, and provide that a kind for the treatment of process is simple, cost of disposal is low and
And the processing method of the high concentration chromium residue of operational effect stabilization.
A kind of processing method of chromium residue, specific implementation step include as follows：
（1）Acidic materials are added to being added in the chromium residue after water stirs evenly, reducing agent progress is added after adjusting pH
Reduction reaction；
Preferentially, step（1）For the acidic materials to be sulfuric acid, the adjustable range of pH is 2 ~ 4；
Preferentially, step（1）The reducing agent is sodium thiosulfate；
Preferentially, step（1）The reducing agent addition amount is the 10%~25% of the waste residue total weight；
Preferentially, step（1）25~35min of the reduction reaction time；
（2）Take a small amount of reaction（1）Suitable quantity of water is added in waste residue after reduction, and the color of water becomes after observation waste residue is mixed with water
Change；
Preferentially, step（2）The color change of the water refers to becoming green from yellow；
（3）In step（2）Alkaline matter is added in backward waste residue and adjusts pH;
Preferentially, step（3）The alkaline matter is lime；
Preferentially, step（3）The adjusting pH is that the pH of the waste residue after reaction is adjusted to 7 ~ 9；
（4）In step（3）Addition flocculant, which is sufficiently stirred and controls waste residue, in backward waste residue is in alkalescent;
Preferentially, step（4）The flocculant is polyaluminium sulfate；
Preferentially, step（4）The weakly alkaline pH value is 7 ~ 8.5；
Preferentially, step（4）The time being sufficiently stirred is 10 ~ 15min；
（5）In step（4）Curing agent is added in backward waste residue and is sufficiently stirred and controls waste residue and is in alkalescent；
Preferentially, step（5）The time being sufficiently stirred is 5 ~ 15min；
Preferentially, step（5）The weakly alkaline pH value is 7 ~ 8；
（6）In step（5）The firming body of waste residue is conserved afterwards；
Preferentially, step（6）The curing time is 3 ~ 5 days.
Inventor has carried out a large number of experiments research to the processing method of chromium residue, and operation principle is：（1）Pass through addition
Sulfuric acid adjusts the pH of waste residue between 3 ~ 5, and suitable sodium thiosulfate is added, on the one hand that chromium residue Poisoning is larger
Cr6+It is reduced into Cr3+, while the acid condition by controlling waste residue adjusts the reduction reaction time（pH<3 reactions terminate quickly, but
Reaction is more violent）；（2）Cr6+Waste residue to be dissolved in color after water be yellow, Cr3+Color be green, reduction reaction degree can lead to
The variation of color is crossed to judge；（3）Polyaluminium sulfate is composite polymer polymer, and molecular structure is huge, and adsorption capacity is strong,
Coagulation speed is fast, the heavy metal ion in waste residue can be effectively removed, to reduce leaching content.（4）The Cr of generation（OH)3Precipitation
For amphoteric hydroxide, acid-base property must keep being in alkalescent after reaction process（5）Cement is mixed with the waste residue after reacting
Processing forms firming body and, second is that heavy metal ion is wrapped up, further prevents the leaching of chromium first, can reinforce the intensity of waste residue
Go out and forms secondary pollution.
Consersion unit used in the present invention is existing known device.
The present invention has the following advantages and effect compared with existing treatment technology：
Normal temperature and pressure operates, easy control of reaction conditions, strong applicability, and industrialization operational effect is stablized；Medicament adds class
Not few, cost is relatively low, will not cause secondary pollution, economic and social benefit notable to environment；The leaching of total chromium and hexavalent chromium
Extracting rate is low, it can be ensured that reaches National Hazard waste reclamation standard.
Specific implementation mode
The invention will be further elaborated in conjunction with the embodiments, but embodiments of the present invention are not limited to the content.
Embodiment 1
It is process object, the original ingredient of waste residue with the chromium residue of certain electroplate factory：PH=4.67, total Cr=389mg/L,
Cr6+= 366mg/L；
This waste residue is handled using the method for the invention：
Waste residue is individually stirred evenly, suitable quantity of water is added thereto makes it at sposh shape, stirring 5min or so, adds sulfuric acid anti-
PH should and be adjusted to 4, and the sodium thiosulfate solid of waste residue total amount 10% is added, be sufficiently stirred 30min；Wait for that its color becomes green
Lime is added after color, the pH of waste residue is adjusted to 8.5；The polyaluminium sulfate of waste residue total weight 8% is taken to carry out flocculation reaction 10min, most
After detect pH, when the pH of waste residue is adjusted to 8, the cement of addition waste residue total amount 15% carries out curing conservation；
Maintenance carries out leaching experiment detection after 4 days：Total Cr=9.6mg/L, Cr6+= 0.088mg/L。
Embodiment 2
It is process object, the original ingredient of waste residue with the chromium residue of certain Leather Factory：PH=5.2, total Cr=1160mg/L,
Cr6+= 416mg/L；
This waste residue is handled using the method for the invention：
Waste residue is individually stirred evenly, suitable quantity of water is added thereto makes it at sposh shape, stirring 10min or so, is added suitable
PH is adjusted to 2 by the sulfuric acid of amount, and the sodium thiosulfate solid of waste residue total amount 20% is added, and is sufficiently stirred 30min；Knot to be mixed
Shu Hou takes on a small quantity, is dissolved in suitable quantity of water, and observing its color becomes green；Then lime is added, the pH of waste residue is adjusted to 8.5 or so；
Then it takes the polyaluminium sulfate of waste residue total weight 15% to carry out flocculation reaction 15min, finally detects pH, the pH of waste residue is adjusted to 7.5
When, the cement of addition waste residue total amount 20% is cured；
Maintenance carries out leaching experiment detection after 4 days：Total Cr=8.56mg/L, Cr6+= 0.093mg/L。
Embodiment 3
It is process object, the original ingredient of waste residue with the chromium residue of certain electroplate factory：PH=6.4, total Cr=678mg/L, Cr6+
=112mg/L；
This waste residue is handled using the method for the invention：
Waste residue is individually stirred evenly, suitable quantity of water is added thereto makes it at sposh shape, stirring 8min or so, is added appropriate
Sulfuric acid reaction, and its pH is adjusted to 3 or so, and the sodium thiosulfate solid of waste residue total amount 15% is added, is sufficiently stirred
30min；After to be mixed, take a small amount of, being dissolved in suitable quantity of water and observing its color becomes green；Then lime is added, by waste residue
PH is adjusted to 8.5；Then it takes the polyaluminium sulfate of waste residue total weight 8% to carry out flocculation reaction 10min, pH is finally detected, by waste residue
When pH is adjusted to 8, the cement of addition waste residue total amount 10% is cured；
Maintenance carries out leaching experiment detection after 5 days：Total Cr=10.52mg/L, Cr6+=0.130mg/L.
Embodiment 4
It is process object, the original ingredient of waste residue with the chromium residue of certain Leather Factory：PH=5.8, total Cr=865mg/L, Cr6+
=216mg/L；
This waste residue is handled using the method for the invention：
Waste residue is individually stirred evenly, suitable quantity of water is added thereto makes it at sposh shape, stirring 10min or so, is added suitable
The sulfuric acid reaction of amount, and its pH is adjusted to 3 or so, and the sodium thiosulfate solid of waste residue total amount 17% is added, it is sufficiently stirred
30min；After to be mixed, take and be dissolved in suitable quantity of water on a small quantity, observe its color to become green；Then lime is added by waste residue
PH is adjusted to 8.5 or so；Then it takes the polyaluminium sulfate of waste residue total weight 10% to carry out flocculation reaction 10min, finally detects pH, it will
When the pH of waste residue is adjusted to 8, the cement of addition waste residue total amount 15% is cured；
Maintenance carries out leaching experiment detection after 5 days：Total Cr=7.46mg/L, Cr6+=0.098mg/L.
The above is only the preferred embodiment of the present invention, is not intended to restrict the invention；Others are any not to depart from this
Modification, replacement, simplification, the improvement etc. that the principle and concept thereof of invention are made, are considered as equivalent substitute mode, in the present invention
Protection domain within.
Claims (14)
1. a kind of processing method of chromium residue, it is characterised in that：Specific implementation step is as follows：
（1）Chromium residue grinding is uniform, after adding water to be stirred to react, acid adding, and pH value is adjusted in acidity, obtain waste residue I；
（2）Reducing agent is added in waste residue I and carries out reduction reaction, is sufficiently stirred, obtains waste residue II；
（3）Take the waste residue II after a small amount of reduction that suitable quantity of water is added, until waste residue mixed with water after water color change；
（4）Step（3）The pH of waste residue II is adjusted afterwards in alkalinity, and addition flocculant is sufficiently stirred carry out precipitation reaction, obtains waste residue III；
（5）Step（4）After adjust pH, control waste residue be in alkalescent, and addition curing agent is sufficiently stirred, obtains residue stabilization body；
（6）Step（5）Residue stabilization body is conserved afterwards.
2. the processing method of chromium residue according to claim 1, it is characterised in that：Step（1）Described plus water stirs
The moisture content of waste residue after water is added to reach 20% -40%.
3. the processing method of chromium residue according to claim 1, it is characterised in that：Step（1）The acid refers to
Sulfuric acid.
4. the processing method of chromium residue according to claim 1, it is characterised in that：Step（1）The pH value is in acid
Property be pH value be 2-4.
5. the processing method of chromium residue according to claim 1, it is characterised in that：Step（2）The reducing agent is
Sodium thiosulfate, the addition of reducing agent are 10%-the 25% of total chromium residue.
6. the processing method of chromium residue according to claim 1, it is characterised in that：Step（2）Described is sufficiently stirred
For 25~35min of reaction time.
7. the processing method of chromium residue according to claim 1, it is characterised in that：Step（3）The color of the water
Variation is to become green from yellow.
8. the processing method of chromium residue according to claim 1, it is characterised in that：Step（4）The alkalinity is pH
Value is 7-9.
9. the processing method of chromium residue according to claim 1, it is characterised in that：Step（4）The flocculant is
Polyaluminium sulfate, the addition of flocculant are 5%-the 15% of total chromium residue.
10. the processing method of chromium residue according to claim 1, it is characterised in that：Step（4）Described is sufficiently stirred
It carries out precipitation reaction to be being 10-25min in the reaction time.
11. the processing method of chromium residue according to claim 1, it is characterised in that：Step（5）The adjusting pH is
PH value is 7-8.
12. the processing method of chromium residue according to claim 1, it is characterised in that：Step（5）The curing agent is
Cement, the addition of curing agent are 15%-the 25% of total chromium residue.
13. the processing method of chromium residue according to claim 1, it is characterised in that：Step（5）Described is sufficiently stirred
Time be 5 ~ 20min.
14. the processing method of chromium residue according to claim 1, it is characterised in that：Step（6）The maintenance is foster
It is 4-7 days to protect the period.
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| CN113666529A (en) * | 2021-06-25 | 2021-11-19 | 湖南瀚洋环保科技有限公司 | Chromium pollutant treating agent and using method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515174A (en) * | 2011-12-07 | 2012-06-27 | 唐翔 | Process for recycling treatment of chromium slag and waste water |
| CN105648224A (en) * | 2016-03-25 | 2016-06-08 | 大连理工大学 | Method for extracting chromium, treating and recycling harmful waste and preparing chromium compound |
| CN105710106A (en) * | 2016-01-20 | 2016-06-29 | 合肥市吴山固体废物处置有限责任公司 | Treatment method for chromium-containing waste |
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2016
- 2016-12-07 CN CN201611112280.0A patent/CN106699027B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515174A (en) * | 2011-12-07 | 2012-06-27 | 唐翔 | Process for recycling treatment of chromium slag and waste water |
| CN105710106A (en) * | 2016-01-20 | 2016-06-29 | 合肥市吴山固体废物处置有限责任公司 | Treatment method for chromium-containing waste |
| CN105648224A (en) * | 2016-03-25 | 2016-06-08 | 大连理工大学 | Method for extracting chromium, treating and recycling harmful waste and preparing chromium compound |
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Denomination of invention: A treatment method of chromium containing waste residue Effective date of registration: 20211021 Granted publication date: 20181023 Pledgee: Industrial Bank Co.,Ltd. Kunming Branch Pledgor: YUNNAN DADI FENGYUAN ENVIRONMENTAL PROTECTION Co.,Ltd. Registration number: Y2021530000020 |
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