CN104338728B - Biomass wet detoxification method of hexavalent chromium-contained waste residues - Google Patents
Biomass wet detoxification method of hexavalent chromium-contained waste residues Download PDFInfo
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Abstract
The invention relates to a biomass wet detoxification method of hexavalent chromium-contained waste residues. The method comprises the following steps: (1) chromium residues are pulpified to slurry; (2) the pH of the slurry is adjusted to 7.0-10.0; (3) after the slurry is heated, the slurry is added in biomasses for stirring and pulpifying; and (4) the slurry is filtered to obtain the qualified chromium residues with standard content of hexavalent chromium. The chromium residues obtained by the treatment method accord with the leaching toxicity [Cr(VI)] not more than 3 mg/L stated by the chromium residue pollution environmental protection technical specifications (HJ/T301-2007), also accord with the leaching toxicity [Cr(VI)] not more than 2.5 mg/L stated by the hazardous waste landfill pollution control standards (GB18598-2001), and can be embedded as general industrial solid wastes. Raw materials used by the method are easily obtained biomasses with low cost, and are low in detoxification temperature and treatment cost; and the method is simple in flow, is suitable for industrial production, and has better industrial application foreground.
Description
Technical field
The present invention relates to chromium compound clearer production technology field, particularly in a kind of direct detoxification chromium slag of living beings six
The chromic wastes disposal method of valency chromium.
Background technology
Cr VI has very strong toxicity, is a kind of strong carcinogen, encroaches on skin and respiratory tract, induces acute and chronic poison
Property, such as neurotoxicity, genetoxic, immunotoxicity etc..Chromium slag is the danger being difficult to administer of discharge in chromium compound production process
Dangerous solid waste, containing a certain amount of Cr VI, has extremely strong oxidation toxicity, easily causes severe contamination to water and soil.
The heap of chromium slag environment of being rivals in a contest has stronger harm, and chromium slag contaminated is unsolved world the difficult problem of environmental protection so far, so that chromaking is closed
Thing industry becomes inorganic chemical industry heavy polluted industry.
The hexavalent chromium polluted development that once annoying chromium compound industry, seeks economy, the efficient, improvement of non-secondary pollution
Method is to control chromium workers' focus of attention.For the improvement of chromium slag, primarily focus on removing toxic substances and comprehensively utilize, main method
Have：Dry detoxified method, wet method detoxifcation method, solidification isolation method, high temperature melting method, middle low temperature disintoxication and burying storage.Dry detoxified
Mainly use coal reduction method, using the Cr VI in the reducibility gas reduced chromium slag that coal fines high-temperature produces.Wet method detoxifcation
Research be concentrated mainly on method of chemical treatment, such as ferrous sulfate-lime method, sulfite reduction method, barium salt process etc., subsequently develop
The method that the materialization such as ferrite process, ion-exchange, activated carbon method, electrolysis, chelating method combines, and these methods or because of place
Reason effect bad it is difficult to up to standard；Or because of high cost, economically infeasible, largely limit its practical application.Its other party
Method there is also process cost of disposal height, eats the reasons such as the quantity of slag is little, popularization and application are not smooth, still can not thoroughly solve chromium slag contaminated asking
Topic, industrial applications cannot break through always.
CN1733373A discloses a kind of chromium slag soaking and reducing detoxification technique, using the weathering zoning stored up, first uses water logging
Bubble, except most Cr VI in the slag that dechromises, then soaks chromium slag with sodium sulfide solution again so that S2-Exist with the Cr VI in slag
Slow reaction under normal temperature, reaching hexavalent chrome reduction is chromic purpose.This invention is simple and practical, and equipment investment is few, method
Flexibly, can mass disposal, but the chromium hydroxide that generates of reduction in the basic conditions easily oxidation by air and regenerate six
Valency chromium is not so that removing toxic substances is thorough.
CN102614620A discloses a kind of wet method detoxifcation method containing Cr VI waste residue for alkalescence, using in chromium slurry material
Add lignosulfonates as stabilizer, ferrous sulfate etc., as reducing agent, the hexavalent chrome reduction in chromium slag is trivalent chromium.
This invention flow process is simple, and detoxification processes are easier to realize, and equipment investment is few, but still suffers from using a large amount of chemical reducing agents, ferrochrome from
There is oxidized risk in the complex compound that son is formed with lignosulfonates, a series of problems, such as processing cost accordingly increases.
CN1733375A discloses a kind of chromic chromic wastes disposal method in biological directly detoxification chromium slag, using wet-milling
Method makes chromium dreg slurry, then adjusts pH value and the salinity of chromium dreg slurry, and separation of solid and liquid obtains chromyl solution and consolidates
Body, inoculates anaerobic bacteria respectively, carries out micro-reduction reaction, hexavalent chrome reduction is become trivalent chromium.This invention is under low-temp low-pressure
Carry out, removing toxic substances thoroughly, but needs to cultivate resistance to chromium bacterium, and process time is long, and less efficient, treating capacity is little, be not suitable at high-volume
Reason chromium slag.
Content of the invention
For the deficiencies in the prior art, the present invention is intended to provide a kind of contain Cr VI using biomass processes cheap and easy to get
The wet method detoxifcation method of waste residue, solves the removing toxic substances high cost of existing method presence, and it is little that detoxifying effect has risk, treating capacity
Problem.
After by chromium slurry, acid adding makes the pH value of slurry drop to 7.0～10.0 to the present invention, in relatively low alkaline bar
Under part, add living beings, detoxify certain time, obtain innoxious chromium slag.
For reaching this purpose, the present invention employs the following technical solutions：
A kind of living beings wet method detoxifcation method containing Cr VI waste residue, the method comprising the steps of：
（1）Chromium slurry is obtained slurry；
（2）Adjust the pH to 7.0～10.0 of above-mentioned slurry；
（3）After slurry is heated, add living beings, stirring, carry out pulp process；
（4）Content of 6-valence Cr ions qualified chromium slag up to standard is obtained after filtration.
Biomass resource refers to the organic resource that plant is generated by photosynthesis, and the earth is produced through photosynthesis every year
Dry just have 173,000,000,000 tons.Living beings are mainly by cellulose（40～50%）, hemicellulose（25～35%）And lignin（15
～20%）Deng polymer substance composition, wherein contain substantial amounts of organic acid, polyphenol, alcohols, amino acid isoreactivity organic substance.Raw
Physical resources species various source ratio is wide, including timber waste, crop residues and stalk, various water plant, system
Sugar industry and food industry residue, organic garbage of city etc., these materials can serve as available resource.
Living beings comprise the groups such as hydroxyl, amino, carboxyl, sulfonic group, phenolic hydroxyl group, can be sexavalence as electron-donating group
Chromium provides reducing environment, has certain absorption the ability of reduction of hexavalent chromium ion, so that living beings is turned waste into wealth.Such as pericarp
In contain large amount of organic, hydroxyl, carboxyl, sulfonic group etc., these groups can detoxify the Cr VI in solution, and pericarp
Can be from the waste of municipal refuse and fruit juice, fruit trade, wide material sources.
The present invention adopts living beings cheap and easy to get as removing toxic substances raw material, processes chromium slag in the basic conditions, can save
A large amount of chemical reagent, reduce the cost of chromic wastes disposal, go for industrialized production.
Chromium slag of the present invention is alkaline waste residue containing Cr VI.Traditional have a calcium roasting method chromium slag, and the mass fraction of chromium is 3
～7%, and the chromium slag chromium content producing in liquid phase oxidation technique is 0.2% about.
On the basis of the technical scheme that the present invention provides, in step（1）Before pre-processed as follows：By chromium slurry,
Filter slurry is simultaneously washed, and obtains low concentration Cr VI chromium slag.In the chromium slag obtaining after pretreatment, content of 6-valence Cr ions is heavy less than it
The 0.2% of amount.The purpose of washing is to remove diffluent Cr VI.The washings that washing produces can be used as chromium compound
The washings of production process use.Make the Cr VI in chromium slag as much as possible using higher temperature in slurrying process as far as possible
Soluble in water.After pretreatment, the low concentration obtaining Cr VI chromium slag is carried out pulp process, carry out subsequent operation, make chromium slag
Detoxifying effect more preferable.
Filtered fluid in such scheme can also be as chromium compound production process water, with cost-effective.
Chromium slurry of the present invention turns to the basic operation that those skilled in the art can be known, can be according to its experience
And the operating condition such as time of this area knowledge-chosen pulp, temperature.Described pulp makes Cr VI be substantially soluble in water to can reach
Its purpose, is stirred when pulp is processed making pulp effect more preferable.
On the basis of the technical scheme that the present invention provides, step of the present invention（1）Described slurry time is 0.5～5h,
0.52～4.86h, 0.8～4.5h, 1.2～4.15h, 1.8～4h, 2.3～3.7h, 2.8～3.4h, 3.1h for example may be selected
Deng preferably 1～3h, more preferably 1.5h.
Described slurrying temperature is 30～120 DEG C, for example, may be selected 30.02～118.9 DEG C, 34～110 DEG C, 45～
100.5 DEG C, 52.6～92.3 DEG C, 58.9～85.6 DEG C, 63～80 DEG C, 69.2～75.1 DEG C, 71.4 DEG C etc., further preferred 50
～110 DEG C, most preferably 85 DEG C.
On the basis of the technical scheme that the present invention provides, step of the present invention（1）Liquid-solid ratio during described chromium slurry is
3:1～10:1, for example may be selected 3.1:1～9.8:1,3.7:1～9:1,5:1～8.2:1,5.5:1～7.6:1,6:1 etc., excellent
Select 4:1～8:1, more preferably 5:1.
On the basis of the technical scheme that the present invention provides, step（2）Adjust the pH value of slurry by acid adding.Described acid
For inorganic acid, more preferably nitric acid, hydrochloric acid, sulfuric acid or carbonic acid a kind of or at least two mixture.Typical case but non-
Restricted example includes：The combination of the combination of nitric acid, hydrochloric acid, carbonic acid, nitric acid and sulfuric acid, hydrochloric acid and carbonic acid, nitric acid, sulfuric acid and
The combination of carbonic acid, combination of nitric acid, hydrochloric acid, sulfuric acid and carbonic acid etc., all can be used for implementing the present invention.Described carbonic acid can by
It is passed through carbon dioxide in slurry to realize.Those skilled in the art can also select other inorganic according to professional standing and experience
Acid, such as nitric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, silicic acid, phosphoric acid, molybdic acid, carbonic acid, sulfurous acid etc..Described pH value range is preferred
For 8.45～9.40, for example, may be selected 8.46～9.37,8.59～9.24,8.63～9.12,8.95 etc., further preferably
8.95.
On the basis of the technical scheme that the present invention provides, described living beings are non-living body living beings.Described non-living body life
Material is selected from one of stalk, pericarp class or organic waste or at least two mixture, further preferred pericarp class life
Material, most preferably pomelo peel, banana skin or orange peel.
On the basis of the technical scheme that the present invention provides, step（3）The addition of described living beings is original chromium slag weight
The 5～500% of amount, for example optional 5.2～496.8%, 10～475%, 62～422%, 96～400%, 124～368%, 160～
325%, 186.7～300%, 204.2～286%, 254% etc., further preferred 10～90%, further preferred 10～30%.
On the basis of the technical scheme that the present invention provides, step（3）The described temperature adding living beings to carry out pulp process
Spend for 20～180 DEG C, for example, may be selected 20.1～179.6 DEG C, 26～165 DEG C, 38.7～145 DEG C, 55～123 DEG C, 63.4～
114 DEG C, 71～107 DEG C, 78.6～100.4 DEG C, 85～96.4 DEG C, 92 DEG C etc., preferably 50～150 DEG C, further preferred 70～
120℃.
The time that described pulp is processed is 0.5～5h, for example optional 0.51～4.96h, 0.7～4.63h, 1.04～
4.2h, 1.36～4h, 1.8～3.25h, 2.13～3h, 2.64h etc., preferably 1～3h, further preferred 1～2h.
A kind of living beings wet method detoxifcation method containing Cr VI waste residue of the present invention, includes after process conditions are optimized
Following steps：
（1）By chromium slurry, filter slurry is simultaneously washed, and obtains low concentration Cr VI chromium slag；
（2）By step（1）The chromium slag obtaining pulp 0.5～5h at 30～120 DEG C obtains slurry, during described chromium slurry
Liquid-solid ratio be 3:1～10:1；
（3）Acid adding adjusts the pH to 7.0～10.0 of above-mentioned slurry；
（4）After slurry is heated, add account for original chromium slag weight 5～500% living beings, stirring, at 20～180 DEG C
Under carry out pulp process 0.5～5h；
（5）Content of 6-valence Cr ions qualified chromium slag up to standard is obtained after filtration.
Compared with prior art scheme, the invention has the advantages that：
（1）Present invention removing toxic substances used biomass starting material is a kind of agricultural wastes cheap and easy to get, and its aboundresources comes
Source is extensive.Substantial amounts of agricultural wastes are dropped and not only pollute environment but also can not produce economic benefit, can be with waste as antidote
Using, the processing cost of reduction chromium slag, substantial amounts of chemical reducing agent can be saved again, take into account ecological and harmonious economic benefit.
（2）The present invention processes chromium slag in the basic conditions, is greatly reduced with acid amount.
（3）Filtrate can return to recycle in chromium compound production system, using water wisely.
（4）Obtained chromium residue meets《Chromium slag contaminated Environment control resist technology specification（HJ/T301-2007）》The leaching of regulation
Toxicity [Cr (VI)]≤3mg/L, meets simultaneously《Hazard waste landfill Environmental capacity standard（GB18598-2001）》The leaching of regulation
Go out toxicity [Cr (VI)]≤2.5mg/L, can be filled as general industry solid waste.
（5）Flow process of the present invention is simple, low cost of detoxifying, treatment temperature low it is adaptable to industrialized production, there is preferable work
Industry application prospect.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or restriction the scope of the present invention, protection scope of the present invention is defined by claims.
Specific embodiment
For the present invention is better described, readily appreciate technical scheme, the present invention's is typical but non-limiting
Embodiment is as follows：
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
After pulp 3h at 30 DEG C in slurrying tank of the chromium residue containing Cr VI 0.117%（Liquid-solid ratio is 10:1）, plus
Enter a certain amount of salt acid for adjusting pH to 9.40；Add orange peel in slurry, the addition of orange peel is original chromium slag weight
90%, pulp at 50 DEG C processes 5h.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate Cr VI
Concentration is 2.57mg/L, substantially conforms to the standard of landfill of general solid waste.
Embodiment 2
After pulp 2h at 50 DEG C in slurrying tank of the chromium residue containing Cr VI 0.135%（Liquid-solid ratio is 5:1）, plus
Enter a certain amount of nitre acid for adjusting pH to 9.23；Add orange peel in slurry, the addition of orange peel is original chromium slag weight
60%, process 3h at 70 DEG C.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate hexavalent chromium concentration
For 1.74mg/L, meet the standard of landfill of general solid waste.
Embodiment 3
After pulp 2h at 85 DEG C in slurrying tank of the chromium residue containing Cr VI 0.179%（Liquid-solid ratio is 5:1）, plus
Enter a certain amount of nitre acid for adjusting pH to 9.23；Add banana skin in slurry, the addition of banana skin is original chromium slag weight
30%, process 1h at 85 DEG C.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate hexavalent chromium concentration
For 2.34mg/L, meet the standard of landfill of general solid waste.
Embodiment 4
After pulp 0.5h at 120 DEG C in slurrying tank of the chromium residue containing Cr VI 0.169%（Liquid-solid ratio is 3:1）,
It is passed through a certain amount of CO2Adjust pH to 8.63；Add pomelo peel in slurry, the addition of pomelo peel is original chromium slag weight
20%, process 1h at 120 DEG C.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate Cr VI is dense
Spend for 0.69mg/L, meet the standard of landfill of general solid waste.
Embodiment 5
After pulp 1h at 70 DEG C in slurrying tank of the chromium residue containing Cr VI 0.147%（Liquid-solid ratio is 4:1）, plus
Enter a certain amount of sulphur acid for adjusting pH to 8.59；Add orange peel in slurry, the addition of orange peel is original chromium slag weight
20%, process 1.5h at 100 DEG C.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate Cr VI
Concentration is 0.86mg/L, meets the standard of landfill of general solid waste.
Embodiment 6
After pulp 1h at 110 DEG C in slurrying tank of the chromium residue containing Cr VI 0.175%（Liquid-solid ratio is 5:1）, plus
Enter a certain amount of nitre acid for adjusting pH to 8.95；Add banana skin in slurry, the addition of banana skin is original chromium slag weight
10%, process 1.5h at 110 DEG C.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate Cr VI
Concentration is 0.36mg/L, meets the standard of landfill of general solid waste.
Embodiment 7
After pulp 1h at 110 DEG C in slurrying tank of the chromium residue containing Cr VI 0.189%（Liquid-solid ratio is 4:1）, plus
Enter a certain amount of nitre acid for adjusting pH to 8.45；Add orange peel in slurry, the addition of orange peel is original chromium slag weight
15%, process 1h at 110 DEG C.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate Cr VI is dense
Spend for 0.44mg/L, meet the standard of landfill of general solid waste.
Embodiment 8
By the chromium residue pulp containing Cr VI 0.157%, filter slurry is simultaneously washed, and obtains low concentration Cr VI chromium slag；
After pulp 1.5h at 120 DEG C in slurrying tank of low concentration Cr VI chromium slag（Liquid-solid ratio is 8:1）, add a certain amount of phosphoric acid to adjust
Section pH to 7.0；Add maize straw in slurry, the addition of maize straw is the 5% of original chromium slag weight, locate at 150 DEG C
Reason 2h.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate hexavalent chromium concentration is 0.37mg/L, symbol
The standard of landfill of solid waste as unification.
Embodiment 9
After pulp 5h at 42 DEG C in slurrying tank of the chromium residue containing Cr VI 0.162%（Liquid-solid ratio is 3:1）, plus
Enter a certain amount of sulphur acid for adjusting pH to 10.0；Add banana skin in slurry, the addition of banana skin is original chromium slag weight
500%, process 0.5h at 180 DEG C.After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate Cr VI
Concentration is 1.48mg/L, meets the standard of landfill of general solid waste.
Embodiment 10
By the chromium residue pulp containing Cr VI 0.143%, filter slurry is simultaneously washed, and obtains low concentration Cr VI chromium slag；
After pulp 2h at 90 DEG C in slurrying tank of low concentration Cr VI chromium slag（Liquid-solid ratio is 10:1）, add a certain amount of nitric acid to adjust
PH to 8.3；Add orange peel in slurry, the addition of orange peel is the 55% of original chromium slag weight, process 4h at 20 DEG C.
After reaction terminates, the chromium being filtrated to get slag is done Leaching test, leachate hexavalent chromium concentration is 1.34mg/L, meet general
The standard of landfill of solid waste.
Applicant states, the present invention illustrates the process step of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned process step, that is, do not mean that the present invention has to rely on above-mentioned process step and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, the equivalence replacement to raw material selected by the present invention and auxiliary element
Interpolation, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (26)
1. a kind of living beings wet method detoxifcation method containing Cr VI waste residue is it is characterised in that the method comprising the steps of：
(1) chromium slurry is obtained slurry；
(2) adjust the pH to 7.0～10.0 of above-mentioned slurry；
(3), after slurry being heated, add living beings, under stirring, carry out pulp process；
(4) obtain content of 6-valence Cr ions qualified chromium slag up to standard after filtering；
Described chromium slag is alkaline waste residue containing Cr VI；
Pre-processed as follows before step (1)：By chromium slurry, filter slurry is simultaneously washed, and obtains low concentration Cr VI chromium slag；
Slurrying temperature described in step (1) is 30～120 DEG C；
Liquid-solid ratio during the described chromium slurry of step (1) is 3:1～10:1；
In the chromium slag obtaining after pretreatment, content of 6-valence Cr ions is less than the 0.2% of its weight；
The addition of the described living beings of step (3) is the 5～500% of original chromium slag weight.
2. the method for claim 1 is it is characterised in that the slurry time described in step (1) is 0.5～5h.
3. the method described in claim 2 is it is characterised in that the slurry time described in step (1) is 1～3h.
4. the method described in claim 3 is it is characterised in that the slurry time described in step (1) is 1.5h.
5. the method for claim 1 is it is characterised in that the slurrying temperature described in step (1) is 50～110 DEG C.
6. method as claimed in claim 5 is it is characterised in that the slurrying temperature described in step (1) is 85 DEG C.
7. the method for claim 1 is it is characterised in that liquid-solid ratio during the described chromium slurry of step (1) is 4:1～8:
1.
8. method as claimed in claim 7 is it is characterised in that liquid-solid ratio during the described chromium slurry of step (1) is 5:1.
9. the method for claim 1 is it is characterised in that step (2) adjusts the pH value of slurry by acid adding.
10. method as claimed in claim 9 is it is characterised in that described acid is inorganic acid.
11. methods as claimed in claim 10 it is characterised in that described acid for nitric acid, one kind of hydrochloric acid, sulfuric acid or carbonic acid or
The mixture of person at least two.
12. the method for claim 1 are it is characterised in that the described pH value range of step (2) is 8.45～9.40.
13. methods as claimed in claim 12 are it is characterised in that the described pH value range of step (2) is 8.95.
14. the method for claim 1 are it is characterised in that described living beings are non-living body living beings.
15. methods as claimed in claim 14 it is characterised in that described non-living body living beings be selected from stalk, pericarp class or
One of organic waste or at least two mixture.
16. methods as claimed in claim 15 are it is characterised in that described non-living body living beings are selected from pericarp biolobic material.
17. methods as claimed in claim 16 are it is characterised in that described non-living body living beings are selected from banana skin or orange peel.
18. the method for claim 1 are it is characterised in that the addition of the described living beings of step (3) is original chromium slag weight
The 10～90% of amount.
19. methods as claimed in claim 18 are it is characterised in that the addition of the described living beings of step (3) is original chromium slag
The 10～30% of weight.
20. the method for claim 1 are it is characterised in that step (3) described addition living beings carry out the temperature of pulp process
Spend for 20～180 DEG C.
21. methods as claimed in claim 20 add living beings to carry out pulp process it is characterised in that step (3) is described
Temperature is 50～150 DEG C.
22. methods as claimed in claim 21 add living beings to carry out pulp process it is characterised in that step (3) is described
Temperature is 70～120 DEG C.
23. the method for claim 1 are it is characterised in that the time that the described pulp of step (3) is processed is 0.5～5h.
24. methods as claimed in claim 23 are it is characterised in that the time that the described pulp of step (3) is processed is 1～3h.
25. methods as claimed in claim 24 are it is characterised in that the time that the described pulp of step (3) is processed is 1～2h.
26. methods as described in one of claim 1-25 are it is characterised in that the method comprising the steps of：
(1) by chromium slurry, filter slurry is simultaneously washed, and obtains low concentration Cr VI chromium slag；
(2) the chromium slag obtaining step (1) pulp 0.5～5h at 30～120 DEG C obtains slurry, liquid during described chromium slurry
Gu than for 3:1～10:1；
(3) acid adding adjusts the pH to 7.0～10.0 of above-mentioned slurry；
(4) after slurry being heated, add account for original chromium slag weight 5～500% living beings, stirring, enter at 20～180 DEG C
Row pulp processes 0.5～5h；
(5) obtain content of 6-valence Cr ions qualified chromium slag up to standard after filtering.
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| CN105396872A (en) * | 2015-12-15 | 2016-03-16 | 北京高能时代环境技术股份有限公司 | Wet process detoxifying processing device and method for chromium slag and contaminated soil of chromium slag |
| CN105753528A (en) * | 2016-03-01 | 2016-07-13 | 侯绪华 | Chromium slag detoxification system and method |
| CN106001059A (en) * | 2016-03-08 | 2016-10-12 | 侯绪华 | Chromium slag pulping, curing and detoxifying method |
| JP6224793B1 (en) * | 2016-09-01 | 2017-11-01 | 株式会社トーワ建設 | Method and agent for reducing hexavalent chromium |
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