CN110125164A - Improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation - Google Patents
Improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation Download PDFInfo
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- CN110125164A CN110125164A CN201910456664.1A CN201910456664A CN110125164A CN 110125164 A CN110125164 A CN 110125164A CN 201910456664 A CN201910456664 A CN 201910456664A CN 110125164 A CN110125164 A CN 110125164A
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- Prior art keywords
- slurry
- acidification
- filtrate
- reduction reaction
- hexavalent chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
Abstract
The invention discloses a kind of improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation, Cr VI waste residue will be contained or hexavalent chromium polluted soil carries out wet ground, obtain slurry；Slurry is delivered in sulfuric acid-acetic acid mixed liquor and carries out acidification, obtains slurry；Slurry pipeline transport is subjected to reduction reaction into reducing agent solution, the Cr VI in slurry is made to be converted into trivalent chromium；Trivalent chromium slurry after reduction reaction is separated by solid-liquid separation, the filtrate portion circulation after separation is used for acidification, and the filter cake after separation carries out external maintenance processing.The present invention reduces the generation of wet method detoxifcation process calcium sulfate precipitation by addition acetic acid, so that calcium sulfate precipitation be avoided to wrap up hexavalent chromium polluted composition granule, improves the dissolution of acid leaching stage Cr VI；Slurry after acidification is added gradually in reducing agent solution by the present invention, so that hexavalent chromium polluted composition granule be promoted to come into full contact with reducing agent, and keeps being conducive to the microenvironment that reduction reaction occurs in reaction interface.
Description
Technical field
The present invention relates to pollutant abatement technology fields, and in particular to one kind is used for waste residue containing Cr VI or hexavalent chromium polluted soil
The improvement technique of earth wet method detoxifcation realizes the harmless treatment containing hexavalent chromium pollutant.
Background technique
Harmless treatment is had been obtained to waste residue containing Cr VI at present, but since the stockpiling of most of chromium slag storage yard is of long duration
Far and lack the measure for preventing Cr VI from spreading, the soil that chromium slag stacks ground also receives serious pollution, and part place contains sexavalence
Chromium waste residue is mixed with contaminated soil.Waste residue containing Cr VI, Cr VI serious pollution soil in place is carried out harmless
Change processing is the important link that comprehensive treatment is carried out to hexavalent chromium polluted place.
There is " brightness reversion ", the problems such as being not thorough of detoxifying after removing toxic substances, Wu Fada in the existing technique for chromic slag wet method detoxifcation
To the requirement of new standard.
The technique for being currently used for chromic slag wet method detoxifcation has the following problems:
1, it in slurry acidization, adds an acid in waste residue containing Cr VI or hexavalent chromium polluted soil slurry, it is unfavorable
It is thorough in acidification；
2, addition sulfuric acid carry out acidification, since most of chromium slag calcium content is higher, when add sulfuric acid, sulfate radical and
Calcium forms calcium sulfate, since slurry amount of water is few, the excessive concentration of calcium sulfate calcium sulfate precipitation (calcium sulfate easy to form in slurries
Solubility be about be 2g/L), cause slurry to become viscous and be not easy to stir；
3, during reduction reaction, reducing agent is added in waste residue containing Cr VI or hexavalent chromium polluted soil slurry,
It is unfavorable for the generation of reduction reaction；
4, medicament will be restored to cure in agitator tank with the Cr VI slurries after acidification, it is unfavorable if the curing time falls short of
With the reduction of Cr VI, if the curing time is too long, one side energy consumption is high, on the other hand can also reduce the effect of wet method detoxifcation system
Rate.
Summary of the invention
Aiming at the shortcomings existing in the above problems, the present invention provides a kind of dirty for waste residue containing Cr VI or Cr VI
The improvement technique for contaminating soil wet method detoxifcation, improves the completeness and long-term effect of wet method detoxifcation.
The invention discloses a kind of improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation, packets
It includes:
Cr VI waste residue will be contained or hexavalent chromium polluted soil carries out wet ground, obtain slurry；
The slurry is delivered in sulfuric acid-acetic acid mixed liquor and carries out acidification, obtains slurry；
The slurry pipeline transport is subjected to reduction reaction into reducing agent solution, the Cr VI in the slurry is made to be converted into three
Valence chromium；
Trivalent chromium slurry after reduction reaction is separated by solid-liquid separation, the filtrate portion circulation after separation is at acidification
Reason, the filter cake after separation carry out external maintenance processing.
As a further improvement of the present invention, described to contain at Cr VI waste residue or the progress wet-milling of hexavalent chromium polluted soil
Reason, obtains slurry；Include:
By the Cr VI waste residue ground by screening or hexavalent chromium polluted soil merging wet milling device, it is milled to 100
~150 mesh obtain the slurry.
As a further improvement of the present invention, the described slurry is delivered in sulfuric acid-acetic acid mixed liquor is acidified
Processing, obtains slurry；Include:
The slurry is gradually transported in acidification reaction tank, is stirred with the sulfuric acid in acidification reaction tank-acetic acid mixed liquor
Mixing makes the pH of the slurry maintain 5~6, and aging 5~6 hours.
As a further improvement of the present invention, the mass percent of the sulfuric acid is 10%~20%, the matter of the acetic acid
Measuring percentage is 5%~10%, and the volume ratio of the sulfuric acid and acetic acid is 1:1~3:1.
It is as a further improvement of the present invention, described that the slurry pipeline transport is subjected to reduction reaction into reducing agent solution,
The Cr VI in the slurry is set to be converted into trivalent chromium；Include:
The slurry is gradually transported in reduction reaction can, is stirred with the reducing agent solution in reduction reaction can,
The Cr VI in the slurry is converted trivalent chromium by reaction time 5-8 hour.
As a further improvement of the present invention, the reducing agent solution is the ferrous sulfate and pyrosulfurous acid being dissolved in water
The molar ratio of sodium solution, the ferrous sulfate and sodium pyrosulfite is 4:1~6:1, and ferrous sulfate is dense in configured solution
Degree is 15%~20%.
As a further improvement of the present invention, the trivalent chromium slurry by after reduction reaction is separated by solid-liquid separation, separation
Filtrate portion circulation afterwards is used for acidification, and the filter cake after separation carries out external maintenance processing；Include:
Slurry after reduction reaction is pumped into plate and frame filter press to be separated by solid-liquid separation, the filtrate after separation enters filtrate tank,
A part of filtrate cycle in the filtrate tank is used for acidification to acidification reaction tank；Filter cake after separation is stacked in maintenance
Curing in airtight condition is carried out in slot.
As a further improvement of the present invention, further includes:
The filter cake conserves 7~15 days, during maintenance in maintenance groove, sprays filter cake with filtrate, it is ensured that filter cake keeps wet
Profit state.
As a further improvement of the present invention, the maintenance groove is the circle by HDPE film and impervious, cement Anti-seeping technology
Slot is located at 2~3 meters of subsurface, and 4~6 meters of diameter, top covers HDPE film, and in top center equipped with for spraying
The spray head of filtrate, spray head are connected by pipeline with filtrate tank.
Compared with prior art, the invention has the benefit that
1, the slurry after wet ground is added gradually in sulfuric acid-acetum by the present invention, to promote slurry and acid
Solution comes into full contact with, and keeps being conducive to the microenvironment that acidification reaction carries out in reaction interface；
2, the present invention reduces the generation of wet method detoxifcation process calcium sulfate precipitation by addition acetic acid, to avoid calcium sulfate
Precipitating wraps up hexavalent chromium polluted composition granule, improves the dissolution of acid leaching stage Cr VI；
3, the slurry after acidification is added gradually in reducing agent solution by the present invention, to promote hexavalent chromium polluted composition granule
It is come into full contact with reducing agent, and keeps being conducive to the microenvironment that reduction reaction occurs in reaction interface；
4, the filter cake after separation be placed in external maintenance groove by the present invention conserves, and reduces in reduction reaction can
Ageing time, improve the production efficiency of wet method detoxifcation system and extend reaction time of Cr VI and reducing agent, be conducive to sexavalence
Chromium is thoroughly reduced to trivalent chromium.
Detailed description of the invention
Fig. 1, which is that an embodiment of the present invention is disclosed, is used for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation
Improve the flow chart of technique.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
Member's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
The present invention is described in further detail with reference to the accompanying drawing:
As shown in Figure 1, the present invention provides a kind of changing for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation
Into technique, comprising:
S1, Cr VI waste residue or hexavalent chromium polluted soil progress wet ground will be contained, and will obtain slurry；
Specifically:
By the Cr VI waste residue ground by screening or hexavalent chromium polluted soil merging wet milling device, it is milled to 100
~150 mesh, obtain slurry.
S2, it slurry is gradually added into carries out acidification into sulfuric acid-acetic acid mixed liquor, obtain slurry；
Specifically:
Sulfuric acid-acetic acid mixed liquor is first added in acidification reaction tank, then slurry is gradually transported in acidification reaction tank into
Row acidification, makes the pH of slurry maintain 5~6, and aging 5~6 hours；Wherein, the mass percent of sulfuric acid is 10%~20%, vinegar
The mass percent of acid is 5%~10%, and the volume ratio of sulfuric acid and acetic acid is 1:1~3:1.
The principle of the above-mentioned acidization order of addition of the present invention are as follows: different from traditional wet method detoxifcation technique, not being will be sour
Solution is added in slurry, but slurry is added gradually in acid solution, is had slurry with acid solution and is adequately contacted, it is ensured that
It is the microenvironment being acidified most beneficial for slurry in reaction interface.
The present invention selects sulfuric acid-acetic acid mixed liquor progress acidification principle are as follows:
Since most of chromium slag calcium content is higher, when adding sulfuric acid, sulfate radical and calcium form calcium sulfate, due to slurry plus
Water is few, and the excessive concentration of calcium sulfate calcium sulfate precipitation easy to form (solubility of calcium sulfate is about 2g/L), leads in slurries
It causes slurry to become viscous to be not easy to stir.The addition of acetic acid, it is possible to reduce the generation of calcium sulfate precipitation, the solubility that 20 DEG C of calcium acetate is about
For 340g/L, to be conducive to be stirred slurries, and can not be with acid after avoiding calcium sulfate precipitation from wrapping up chromium slag particle
The problem of reacting.
S3, slurry pipeline transport is subjected to reduction reaction into reducing agent solution, the Cr VI in slurry is made to be converted into trivalent chromium；
Specifically:
Slurry is gradually transported in reduction reaction can and is stirred with reducing agent solution, reaction time 5-8 hour will expect
Cr VI in slurry is converted into trivalent chromium；Wherein, reducing agent solution is that the ferrous sulfate being dissolved in water and sodium pyrosulfite are molten
The molar ratio of liquid, ferrous sulfate and sodium pyrosulfite is 4:1~6:1, and the concentration of ferrous sulfate is 15% in configured solution
~20%.
The principle of the above-mentioned reduction reaction order of addition of the present invention are as follows:
It is different from traditional wet method detoxifcation technique, it is not that reducing agent is added to waste residue containing Cr VI or hexavalent chromium polluted soil
In earth slurry, but Cr VI waste residue will be contained or hexavalent chromium polluted soil slurry is added in reducing agent solution, make slurry with also
Former agent has sufficient contact, it is ensured that is the microenvironment being reduced most beneficial for Cr VI in reaction interface.
S4, the trivalent chromium slurry after reduction reaction is separated by solid-liquid separation, the filtrate portion after separation is recycled for being acidified
Processing, the filter cake after separation carry out external maintenance processing；
Specifically:
Slurry after reduction reaction is pumped into plate and frame filter press to be separated by solid-liquid separation, the filtrate after separation enters filtrate tank,
A part of filtrate cycle in filtrate tank is used for acidification to acidification reaction tank；Filter cake after separation is stacked in maintenance groove
Carry out curing in airtight condition；Wherein, filter cake conserves 7~15 days, during maintenance in maintenance groove, sprays filter cake with filtrate, it is ensured that filter cake
Keep moisture state.Maintenance groove is to be located at 2~3 meters of subsurface, directly by the circular trough of HDPE film and impervious, cement Anti-seeping technology
4~6 meters of diameter, top covers HDPE film, and in top center equipped with the spray head for spraying filtrate, spray head passes through pipeline
It is connected with filtrate tank.
The principle of the above-mentioned maintenance processing of the present invention are as follows:
Filter cake needs after reduction reaction, dehydration conserve 7~15 days in maintenance groove, to reduce anti-in reduction
The ageing time in tank is answered, the production efficiency of wet method detoxifcation system is improved and extends the reaction time of Cr VI and reducing agent, benefit
Trivalent chromium is thoroughly reduced in Cr VI.
Embodiment 1:
The chromium slag of Baiyin chrome salt production enterprise former address and the mixture of soil, content of 6-valence Cr ions 2000-3000mg/
kg。
S1, wet-milling will be carried out in the muck mixture merging ball mill ground by screening, allowed to through 100 mesh
Sieve；
S2, first by volume ratio be 1:1 sulfuric acid (10% solution)-acetic acid (5% solution) mixed liquor be pumped into acidification reaction tank
In, then the logical slurry sieved with 100 mesh sieve is gradually pumped into acidification reaction tank and is mixed with acid solution, so that the pH of slurry is maintained 5
~6 ranges, aging 6 hours；
S3, by the slurry after acidification be gradually pumped into reduction reaction can with reduction medicament be stirred, pumping the used time 2 it is small
When, the reducing agent aqueous solution proportion in reduction reaction can is as follows: the molar ratio of ferrous sulfate and sodium pyrosulfite is 6:1, is restored
In agent aqueous solution the concentration of ferrous sulfate be 15%, the reaction time 5 hours；
S4, it slurry in reduction reaction can is pumped into plate and frame filter press is separated by solid-liquid separation, the filtrate after separation enters filtrate
Tank storage；
(2 meters deep, 4 meters of the diameter) maintenance in maintenance groove of S5, filter cake, during maintenance, is sprayed with the filtrate in filtrate holding vessel
Spill filter cake, it is ensured that filter cake keeps moisture state.After 7 days, 3 aggregate samples are taken in maintenance groove, detection obtains the content of Cr VI
It is respectively as follows: 0.14mg/kg, 0.20mg/L, 0.12mg/L；After 1 month, 3 aggregate samples are taken to the dregs after removing toxic substances, detection obtains
The content of Cr VI is respectively as follows: 0.13mg/kg, 0.17mg/L, 0.18mg/L.
S6, it the filtrate in filtrate holding vessel is pumped into acidification reaction tank recycles.
Embodiment 2:
The chromium slag of Gansu Zhangye chrome salt production enterprise former address and the mixture of soil, content of 6-valence Cr ions 4000-5000mg/
kg。
S1, wet-milling will be carried out in the muck mixture merging ball mill ground by screening, allowed to through 150 mesh
Sieve；
S2, sulfuric acid (20% solution)-acetic acid (10% solution) mixed liquor that volume ratio is 3:1 is pumped into acidification reaction tank,
Acidification reaction tank being gradually pumped by the slurry of 150 meshes again and acid solution being mixed, the pH of slurry is made to maintain 5~6
Range, aging 6 hours；
S3, by the slurry after acidification be gradually pumped into reduction reaction can with reduction medicament be stirred, pumping the used time 2 it is small
When, the reducing agent aqueous solution proportion in reduction reaction can is as follows: the molar ratio of ferrous sulfate and sodium pyrosulfite is 4:1, is restored
In agent aqueous solution the concentration of ferrous sulfate be 20%, the reaction time 8 hours；
S4, it slurry in reduction reaction can is pumped into plate and frame filter press is separated by solid-liquid separation, the filtrate after separation enters filtrate
Tank storage；
(3 meters deep, 5 meters of the diameter) maintenance in maintenance groove of S5, filter cake, during maintenance, is sprayed with the filtrate in filtrate holding vessel
Spill filter cake, it is ensured that filter cake keeps moisture state.After 15 days, 3 aggregate samples are taken in maintenance groove, detection obtains the content of Cr VI
It is respectively as follows: 0.25mg/kg, 0.18mg/L, 0.19mg/L, after 1 month, 3 aggregate samples is taken to the dregs after removing toxic substances, detection obtains
The content of Cr VI is respectively as follows: 0.15mg/kg, 0.20mg/L, 0.13mg/L.
S6, it the filtrate in filtrate holding vessel is pumped into acidification reaction tank recycles.
These are only the preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation characterized by comprising
Cr VI waste residue will be contained or hexavalent chromium polluted soil carries out wet ground, obtain slurry；
The slurry is delivered in sulfuric acid-acetic acid mixed liquor and carries out acidification, obtains slurry；
The slurry pipeline transport is subjected to reduction reaction into reducing agent solution, the Cr VI in the slurry is made to be converted into trivalent
Chromium；
Trivalent chromium slurry after reduction reaction is separated by solid-liquid separation, the filtrate portion circulation after separation is used for acidification, point
Filter cake from after carries out external maintenance processing.
2. improving technique as described in claim 1, which is characterized in that described to contain Cr VI waste residue or hexavalent chromium polluted soil
Wet ground is carried out, slurry is obtained；Include:
By the Cr VI waste residue ground by screening or hexavalent chromium polluted soil merging wet milling device, it is milled to 100~150
Mesh obtains the slurry.
3. improving technique as described in claim 1, which is characterized in that described that the slurry is delivered to sulfuric acid-acetic acid mixing
Acidification is carried out in liquid, obtains slurry；Include:
The slurry is gradually transported in acidification reaction tank, is stirred with the sulfuric acid in acidification reaction tank-acetic acid mixed liquor,
The pH of the slurry is set to maintain 5~6, aging 5~6 hours.
4. improving technique as claimed in claim 3, which is characterized in that the mass percent of the sulfuric acid is 10%~20%,
The mass percent of the acetic acid is 5%~10%, and the volume ratio of the sulfuric acid and acetic acid is 1:1~3:1.
5. as described in claim 1 improve technique, which is characterized in that it is described by the slurry pipeline transport into reducing agent solution into
Row reduction reaction makes the Cr VI in the slurry be converted into trivalent chromium；Include:
The slurry is gradually transported in reduction reaction can, is stirred with the reducing agent solution in reduction reaction can, is reacted
The Cr VI in the slurry is converted trivalent chromium by time 5-8 hour.
6. improving technique as claimed in claim 5, which is characterized in that the reducing agent solution is the sulfuric acid Asia being dissolved in water
The molar ratio of iron and sodium metabisulfite solution, the ferrous sulfate and sodium pyrosulfite is 4:1~6:1, in configured solution
The concentration of ferrous sulfate is 15%~20%.
7. improving technique as described in claim 1, which is characterized in that the trivalent chromium slurry by after reduction reaction is consolidated
Liquid separation, the filtrate portion circulation after separation are used for acidification, and the filter cake after separation carries out external maintenance processing；Include:
Slurry after reduction reaction is pumped into plate and frame filter press to be separated by solid-liquid separation, the filtrate after separation enters filtrate tank, described
A part of filtrate cycle in filtrate tank is used for acidification to acidification reaction tank；Filter cake after separation is stacked in maintenance groove
Carry out curing in airtight condition.
8. improving technique as claimed in claim 7, which is characterized in that further include:
The filter cake conserves 7~15 days, during maintenance in maintenance groove, sprays filter cake with filtrate, it is ensured that filter cake keeps wet shape
State.
9. improving technique as claimed in claim 8, which is characterized in that the maintenance groove is anti-by HDPE film and impervious, cement
The circular trough of processing is seeped, is located at 2~3 meters of subsurface, 4~6 meters of diameter, top covers HDPE film, and matches in top center
The spray head for spraying filtrate is had, spray head is connected by pipeline with filtrate tank.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910456664.1A CN110125164A (en) | 2019-05-29 | 2019-05-29 | Improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation |
| PCT/CN2020/085701 WO2020238479A1 (en) | 2019-05-29 | 2020-04-20 | Improved process for wet detoxification of hexavalent-chromium-containing waste residue or hexavalent chromium polluted soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910456664.1A CN110125164A (en) | 2019-05-29 | 2019-05-29 | Improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation |
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|---|---|
| CN110125164A true CN110125164A (en) | 2019-08-16 |
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| CN201910456664.1A Pending CN110125164A (en) | 2019-05-29 | 2019-05-29 | Improvement technique for waste residue containing Cr VI or hexavalent chromium polluted soil wet method detoxifcation |
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| WO (1) | WO2020238479A1 (en) |
Cited By (2)
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| CN111607401A (en) * | 2020-05-27 | 2020-09-01 | 重庆大学 | Repairing agent for in-situ repairing hexavalent chromium pollution and preparation method and application thereof |
| WO2020238479A1 (en) * | 2019-05-29 | 2020-12-03 | 北京高能时代环境技术股份有限公司 | Improved process for wet detoxification of hexavalent-chromium-containing waste residue or hexavalent chromium polluted soil |
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| WO2020238479A1 (en) | 2020-12-03 |
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