CN1597555A - Treatment method of chromium containing effluent waste slag - Google Patents
Treatment method of chromium containing effluent waste slag Download PDFInfo
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- CN1597555A CN1597555A CN 03147583 CN03147583A CN1597555A CN 1597555 A CN1597555 A CN 1597555A CN 03147583 CN03147583 CN 03147583 CN 03147583 A CN03147583 A CN 03147583A CN 1597555 A CN1597555 A CN 1597555A
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- waste water
- coal
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- contained substance
- chromium
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Abstract
A process for treating the Cr contained waste water ordregs includes such steps as removing impurities from the S-contained coal, pulverizing, mixing it with said Cr-contained waste water or dregs, stirring, reaction, depositing, solid-liquid separation, and recovering metallic sulfide.
Description
The invention belongs to the waste water and dregs treatment technology, more properly is a kind of treatment process of chromate waste water waste residue.
At present, the method for chromate waste water processing has: ion exchange method, active carbon adsorption, electroosmose process, reverse osmosis method, chemical reduction method, iron oxysome method etc., China generally adopts the chemical reduction method processing waste water containing chrome.The technology of chemical reduction method processing waste water containing chrome is: use reductive agents such as ferrous sulfate, Sodium Pyrosulfite under acidic conditions, hexavalent chrome reduction is become trivalent chromium, utilize generation chromium hydroxide precipitation such as sodium hydroxide, lime then and remove.But exist sedimentary chromium hydroxide to be difficult to handle, be easy to generate secondary pollution problem.In recent years, the present following several respects of research direction aspect processing waste water containing chrome and outcome table were that 1. usefulness natural mineral (pyrrhotite, medical stone, zeolite etc.) processing heavy metal wastewater thereby (for example: handle and contain Cr (VI) waste water Science Bulletin 2000.8 by natural pyrrhotite single stage method such as Lu Anhuai; Chinese patent: the improvement method of 99,109,634 1 kinds of chromate waste waters) 2. with solid waste (as flyash, cinder, iron slag, crop stalk) processing waste water containing chrome.3. with carbonaceous material (coal, peat etc.) processing waste water containing chrome.These achievements in research and report, the shortcoming of ubiquity poor removal effect, and can't implement.
At present, the treatment process of chromium residue has reduction roasting method, barium salt process etc., but can't implement because of cost is high.The Detoxication utilization of Chinese patent 96118100 barium and chromium slags, utilizing the barium slag to handle the chromium slag is the direction of Future Development, but exists the waste water pH value after the detoxifcation higher, needs to adjust with acid.
At present, do not see research and the report of using coal measures S-contained substance (high sulphur coal, coal measures sulfurous iron ore, high sulfur coal gangue, sulphur content is greater than 1.5%) processing waste water containing chrome waste residue as yet.
The objective of the invention is to propose a kind of simple to operate, cost is low, effective, the treatment of wastes with processes of wastes against one another, the improvement method of the chromate waste water waste residue of secondary pollution do not occur.
Realize main technical schemes of the present invention: the F in the coal measures S-contained substance (high sulphur coal, coal measures sulfurous iron ore, high sulfur coal gangue, sulphur content is greater than 1.5%)
eS
2Solubilizing reaction takes place in chromate waste water, makes a part of sexavalent chrome change into sulfide precipitation, a part of hexavalent chrome reduction becomes trivalent chromium; C in the coal measures S-contained substance has better reductive action to hexavalent chromium, and trivalent chromium is had adsorption preferably.At F
eS
2With the following hexavalent chromium that can remove in the chromate waste water waste residue of the acting in conjunction of C.
Improvement method of the present invention may further comprise the steps:
1. the step of coal measures S-contained substance processing waste water containing chrome:
1.1. coal measures S-contained substance (high sulphur coal, coal measures sulfurous iron ore, high sulfur coal gangue, sulphur content is greater than 1.5%) is pulverized, and granularity is the 50-300 order, impurity is removed in sorting.
Join (the F in the add-on of coal measures S-contained substance and the waste water in content of 6-valence Cr ions and the coal measures S-contained substance in the chromate waste water 1.2. obtain granulous coal measures S-contained substance with 1.1
eS
2Close with the C relation with contents), stirring, reaction, quiescent setting are three-decker: supernatant liquor, metallic sulfide and remaining coal measures S-contained substance after reaction finishes.
1.3. carry out solid-liquid separation.
1.4. adjusting the pH value that separates back liquid is about 7, liquid directly discharges.
1.5. sedimentary metallic sulfide is recycled according to a conventional method.
1.6. remaining coal measures S-contained substance can further utilize.
2. the coal measures S-contained substance is handled the step of chromium residue:
2.1. coal measures S-contained substance (high sulphur coal, coal measures sulfurous iron ore, high sulfur coal gangue, sulphur content is greater than 1.5%) is pulverized, and granularity is the 50-300 order, impurity is removed in sorting.
2.2. 2.1 resultant granulous coal measures S-contained substances are mixed by a certain percentage with chromium residue, add water, stirring, reaction, static, after finishing, reaction is three-decker: supernatant liquor, metallic sulfide, remaining coal measures S-contained substance and chromium slag.
2.3. carry out solid-liquid separation, liquid directly discharges.
2.4. sedimentary metallic sulfide is recycled according to a conventional method.
2.5. chromium slag after handling and remaining coal measures S-contained substance can further utilize.
Advantage of the present invention and positively effect:
1. method of the present invention is compared with existing chemical reduction method processing waste water containing chrome has the advantage that technology is simple, easy to operate, treatment effect is good.
2. method of the present invention is compared the generation that can reduce solid waste significantly with chemical reduction method, effectively solved the secondary pollution problem.
3. in the process of processing waste water containing chrome waste residue, the coal measures sulfurous iron ore can be regulated the pH value of liquid automatically, and the pH value after the chromate waste water of PH=3-10 is handled is compared with existing chemical reduction method processing waste water containing chrome at 5-7, saves a large amount of sodium hydroxide.Handle chromium residue and compare a large amount of acid of saving with Chinese patent 96118100.
4. present, coal measures sulfurous iron ore and high sulfur coal gangue are deposited in coal field as the solid waste of mining, and have not only wasted resource but also contaminate environment, and present method has realized the treatment of wastes with processes of wastes against one another, has opened up the new way of coal measures sulfurous iron ore and high sulfur coal gangue resource utilization.
5. use coal measures S-contained substance processing waste water containing chrome, raw material sources are extensive, price is low compares with existing chemical reduction method treatment process, handles same waste water and can reduce expense more than 50%.
6. after high sulphur coal was used for the processing waste water containing chrome waste residue, sulphur content reduced significantly, has improved Coal Quality, had opened up the new way of utilizing of high sulphur coal, also was a kind of new coal separation (desulfurization) method.
7. sedimentary metallic sulfide can further be recycled.
8. remaining coal measures S-contained substance can further utilize.
9. the coal measures S-contained substance not only can processing waste water containing chrome, and to containing (C
u 2+, N
i 2+, Pb
2+, S
n 2+, Hg
2+) wait heavy metal wastewater thereby to have decontamination effect improving preferably.
10. handle chromium residue with the coal measures S-contained substance and compare, can lower processing costs significantly with reduction roasting method and barium salt process processing chromium residue.
In sum, the inventive method is simple, cost is low, do not have secondary pollution, and the treatment of wastes with processes of wastes against one another, has bigger economic benefit, social benefit and environmental benefit.
Further specify characteristics of the present invention below in conjunction with specific examples:
Example 1
At content of 6-valence Cr ions is to add 180-200 purpose coal measures sulfurous iron ore 0.5g among the waste water 100ml of 100mg/L PH=4, stirs, reaction 30 minutes, precipitates 1 hour, chromic concentration is 0.05mg/L in the survey supernatant liquor, PH is 6.8, solid-liquid separation, and liquid directly discharges.Be three-decker after the reaction: supernatant liquor, metallic sulfide and remaining coal measures sulfurous iron ore.Metallic sulfide can reclaim chromium metal, and remaining coal measures sulfurous iron ore can also be further multiplexing.
Example 2
In chromium plating (content of 6-valence Cr ions is 130mg/L PH=5) waste water 2000ml, add 180-200 purpose coal measures sulfurous iron ore 25g, stir, reacted 40 minutes, precipitate 2 hours, chromic concentration is 0.05mg/L in the survey supernatant liquor, PH is 6.8, solid-liquid separation, and liquid directly discharges.
Example 3
At content of 6-valence Cr ions is to add 140-160 purpose coal measures sulfurous iron ore 3.0g among the 25mg/L PH=2 waste water 1000ml, stirs, reacts 40 minutes, precipitates 2 hours, chromic concentration is 0.05mg/L in the survey supernatant liquor, and PH is 4.5, solid-liquid separation, after the pH value of adjustment liquid was 7, liquid directly discharged.
Example 4
At content of 6-valence Cr ions is to add 100-120 purpose coal measures sulfurous iron ore 0.45g among the waste water 100ml of 25mg/L PH=9, stirs, reaction 30 minutes, precipitates 1 hour, chromic concentration is 0.05mg/L in the survey supernatant liquor, PH is 7.0, solid-liquid separation, and liquid directly discharges.
Example 5
At content of 6-valence Cr ions is to add 50-100 purpose coal measures sulfurous iron ore 0.6g among the waste water 100ml of 25mg/L PH=10, stirs, reaction 30 minutes, precipitates 1 hour, chromic concentration is 0.06mg/L in the survey supernatant liquor, PH is 7.0, solid-liquid separation, and liquid directly discharges.
Example 6
At content of 6-valence Cr ions is to add 180-200 purpose coal measures sulfurous iron ore 0.25g among the waste water 100ml of 75mg/L PH=1, stir, reacted 30 minutes, precipitate 1 hour, chromic concentration is 0.05mg/L in the survey supernatant liquor, PH is 1.7, solid-liquid separation, the pH value of adjusting liquid with sodium hydroxide is 7, liquid directly discharges.
Example 7
At content of 6-valence Cr ions is to add coal (sulphur content is 3.0%) 0.40g among the 25mg/L PH=3 waste water 100ml, stirs, reacts 40 minutes, precipitates 2 hours, chromic concentration is 0.05mg/L in the survey supernatant liquor, and PH is 5.4, solid-liquid separation, after the pH value of adjustment liquid was 7, liquid directly discharged.Be three-decker after the reaction: supernatant liquor, metallic sulfide, remaining coal.Metallic sulfide can reclaim chromium metal, and remaining coal can also further utilize.
Example 8
At content of 6-valence Cr ions is to add 180-200 purpose coal gangue (sulphur content is 2.5%) 0.70g among the 25mg/L PH=4 waste water 100ml, stirs, reacts 40 minutes, precipitates 2 hours, chromic concentration is 0.05mg/L in the survey supernatant liquor, PH is 6.8, solid-liquid separation, and liquid directly discharges.Be three-decker after the reaction: supernatant liquor, metallic sulfide, remaining coal gangue.Metallic sulfide can reclaim chromium metal, and remaining coal gangue can also further utilize.
Example 9
At Zn
2+Concentration is 1000mg/L, Cu
2+Concentration is 1500mg/L, Cd
2+Concentration is 200mg/L, Pb
2+Concentration is to add 200-300 purpose coal measures sulfurous iron ore, Zn in stirring, reaction, static back survey supernatant liquor in the waste liquid of 20mg/L
2+Concentration is 0.01mg/L, Cu
2+Concentration is 0.05mg/L, Cd
2+Concentration is 0.03mg/L, Pb
2+Concentration is 0.05mg/L.
Example 10
At Hg
2+Content is to add 180-200 purpose high sulphur coal 100g among the waste water 2000ml of 50mg/L, stirs, reaction 50 minutes, precipitate 1 hour, Hg in the survey supernatant liquor
2+Concentration be 0.06mg/L.
Example 11
At Pb
2+Content is to add 180-200 purpose coal measures sulfurous iron ore 0.3g among the waste water 100ml of 200mg/L, stirs, reaction 50 minutes, precipitate 1 hour, Pb in the survey supernatant liquor
2+Concentration be 0.06mg/L.
Example 12
Get the chromium slag 5g of 180-200, add 180-200 purpose coal measures sulfurous iron ore 5g, add 10ml water, stirring, reaction, static, precipitation, content of 6-valence Cr ions is 0.05mg/L in the survey supernatant liquor, and the pH value of reaction back liquid is 7, and liquid directly discharges.Be three-decker after the reaction: supernatant liquor, metallic sulfide, remaining coal measures sulfurous iron ore.Metallic sulfide can reclaim chromium metal, and remaining coal measures sulfurous iron ore can also be further multiplexing.
Example 13
Get the chromium slag 5g of 180-200, add 180-200 purpose high sulfur coal gangue 8g, add 13ml water, stirring, reaction, static, precipitation, content of 6-valence Cr ions is 0.4mg/L in the survey supernatant liquor, and the pH value of reaction back liquid is 7, and liquid directly discharges.Be three-decker after the reaction: supernatant liquor, metallic sulfide, remaining coal gangue.Metallic sulfide can reclaim chromium metal, and remaining coal gangue can also further utilize.
Claims (4)
1. the improvement method of a chromate waste water waste residue is characterized by: during processing waste water containing chrome, the coal measures S-contained substance is joined in the waste water that contains chromium, stir, react quiescent setting, solid-liquid separation, liquid discharge.Sedimentary metallic sulfide and remaining coal measures S-contained substance can further utilize.
2. the improvement method of a chromate waste water waste residue is characterized by: when handling chromium residue, coal measures S-contained substance and the waste residue that contains chromium is mixed in proportion, adds water, stirring, reaction, and static, carry out solid-liquid separation, liquid discharge.Chromium slag after sedimentary metallic sulfide, remaining coal measures S-contained substance and the processing can further utilize.
3. improvement method as claim 1,2 described chromate waste water waste residues, it is characterized in that: the coal measures S-contained substance is meant coal measures sulfurous iron ore, high sulfur coal gangue, high sulphur coal.
4. improvement method as claim 1,2 described chromate waste water waste residues, it is characterized in that: the granularity of used coal measures S-contained substance is the 50-300 order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03147583 CN1597555A (en) | 2003-09-17 | 2003-09-17 | Treatment method of chromium containing effluent waste slag |
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| CN 03147583 CN1597555A (en) | 2003-09-17 | 2003-09-17 | Treatment method of chromium containing effluent waste slag |
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| CN1597555A true CN1597555A (en) | 2005-03-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928083A (en) * | 2010-09-28 | 2010-12-29 | 同济大学 | Method for treatment of wastewater containing heavy metal molybdenum |
| CN111675278A (en) * | 2020-06-17 | 2020-09-18 | 武汉工程大学 | Method for directly treating hexavalent chromium-containing wastewater by using clay raw ore |
| CN114804412A (en) * | 2022-04-15 | 2022-07-29 | 桂林电子科技大学 | Treatment process of mixed waste liquid of water quality online monitoring equipment |
-
2003
- 2003-09-17 CN CN 03147583 patent/CN1597555A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928083A (en) * | 2010-09-28 | 2010-12-29 | 同济大学 | Method for treatment of wastewater containing heavy metal molybdenum |
| CN101928083B (en) * | 2010-09-28 | 2012-07-25 | 同济大学 | Method for treatment of wastewater containing heavy metal molybdenum |
| CN111675278A (en) * | 2020-06-17 | 2020-09-18 | 武汉工程大学 | Method for directly treating hexavalent chromium-containing wastewater by using clay raw ore |
| CN114804412A (en) * | 2022-04-15 | 2022-07-29 | 桂林电子科技大学 | Treatment process of mixed waste liquid of water quality online monitoring equipment |
| CN114804412B (en) * | 2022-04-15 | 2023-11-10 | 桂林电子科技大学 | Treatment process of mixed waste liquid of water quality on-line monitoring equipment |
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