CN102755985B - Integral leaching detoxication and landfill treatment method of chromium slag - Google Patents
Integral leaching detoxication and landfill treatment method of chromium slag Download PDFInfo
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- CN102755985B CN102755985B CN201210237672.5A CN201210237672A CN102755985B CN 102755985 B CN102755985 B CN 102755985B CN 201210237672 A CN201210237672 A CN 201210237672A CN 102755985 B CN102755985 B CN 102755985B
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Abstract
The invention discloses an integral leaching detoxication and landfill treatment method of chromium slag. The method comprises the steps of: 1) creating a detoxication pool on the ground: arranging an impermeable layer on the wall surface of a landfill pool, and arranging a flow guide system for guiding the flow outwards in the detoxication pool; 2) conveying the chromium slag to be treated in the detoxication pool, adding water in the detoxication pool, enabling the chromium slag to leach out hexavalent chromium and/or compound hexavalent chromium in the water, and the added water becomes lixivium; 3) recycling the lixivium through the flow guide system, adding water in the detoxication pool to perform circular percolation until the chromium slag is soaked for 5 months, adding alkali sulfide in the detoxication pool to reduce the hexavalent chromium if the content of the hexavalent chromium in the lixivium is not larger than 0.5-1g/L, and executing the detoxication reaction; and 4) burying and closing the detoxication pool after the detoxication treatment. The method disclosed by the invention treats the chromium slag through the integral leaching detoxication and landfill treatment technology, so that the method is an efficient chromium slag treatment having no secondary pollution and capable of really recycling the chromium resource.
Description
Technical field
The present invention relates to a kind of chromic wastes disposal method, particularly a kind of through detoxifying and solution can removing chromium slag toxicity and chromic processing method in chromium slag can be utilized after landfill.
Background technology
Chromium slag is the poisonous waste residue that the industry such as chromic salts and ferroalloy is discharged in process of production, Cr VI Cr (VI) in chromium slag is listed in one of eight kinds of maximum chemical substances of harm, being one of internationally recognized three kinds of carcinogenic metal objects, is also simultaneously one of U.S. EPA 129 kinds of priority pollutants of generally acknowledging.Developed countries mainly from reform chrominm salt production technology, reduces the residual volume of chromium in bed drain purge and slag, or adopts the method landfill of solidification safe disposal.And China started to produce chromic salts from 1958, just constantly explore the improvement of chromium slag, implemented or the chromium residue detoxifying technology of carrying out industrial test comprise sintered ironmaking, high temperature reduction (brickmaking, as glass colorant etc.), as cement mineralizing agent and dry method (rotary kiln) removing toxic substances etc.These methods all fail to realize the resource of chromium in chromium slag, and treatment cost is high, progress is slow and regulation effect is all not satisfactory.At present the storage of chromium slag has reached 4,000,000 tons more than according to incompletely statistics, and these chromium slags are annual as the malignant tumor still to be increased with the numeral of 100,000 tons, brings great threat to the environment of human survival.National environmental protection portion explicitly calls for: it is complete that left over by history has calcium chromium slag must administer before the end of the year 2012.Seek economy, treatment of chromate slag method that is efficient, non-secondary pollution has become environmental worker's problem demanding prompt solution.
Summary of the invention
The present inventor is on the basis of summing up treatment of chromate slag and comprehensive utilizating research in decades, look for another way, utilize leaching removing toxic substances to administer chromium slag with landfill integrated disposal technology, be intended to find inexpensive, practical, really can to realize chromium resource recycling chromic wastes disposal way.
An object of the present invention is safely, efficiently to process chromium slag to develop one, the integrated treatment way that Cr VI reclaims can be realized again.
For this reason, the invention provides a kind of chromium slag leaching removing toxic substances and landfill integrated processing method, wherein, comprise the following steps:
1) in ground structure removing toxic substances pond: according to the quantity of pending chromium slag in ground excavation or the landfill pond of piling up corresponding size, the wall in landfill pond arranges impervious barrier, and arrange the flow guide system of outside water conservancy diversion in landfill pond;
2) be delivered to by pending chromium slag in removing toxic substances pond, and add water in removing toxic substances pond, chromium slag leaches Cr VI in water and/or chemical combination goes out Cr VI, and the water now added becomes leachate;
3) leachate is reclaimed by flow guide system, water is added again afterwards, until soak the chromium slag time to reach more than 4 ~ 5 months, and when chromic content is no more than 0.5 ~ 1g/L in leachate in landfill pond, in removing toxic substances pond, add sodium sulfide reducing Cr VI, perform removing toxic substances reaction;
4) detoxified, buried and close removing toxic substances pond.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and in removing toxic substances pond, the loading thickness of chromium slag is 3 meters.
Preferably, described chromium slag leaching removing toxic substances with landfill integrated processing method, described step 1) in be also included in landfill pond aqueduct be set, to form water circulation with flow guide system.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and soaking chromium slag 4 ~ 5 months is water circulation type leaching.
Preferably, described chromium slag leaching is detoxified with landfill integrated processing method, in described step 3) in, the akali sulphide added is the akali sulphide aqueous solution, and its circulation adds described removing toxic substances pond, and forces diafiltration to be detoxified 1 ~ 3 month.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described impervious barrier comprises in successively from wall to wall the argillic horizon, the first nonwoven layer, high-density polyethylene layer and the second nonwoven layer that arrange.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described argillic horizon is the thickness of 1 meter and/or high-density polyethylene layer is 2 millimeters.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and immersed depth is 50 centimetres.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described flow guide system comprises:
Grit guide layer, it is arranged on the side in the middle of the close landfill pond of described second nonwoven layer, and the side in the middle of the close landfill pond of described grit guide layer is also provided with the 3rd nonwoven layer;
Mozzle, its one end is arranged in described grit guide layer, and the other end is arranged on the outside in described landfill pond.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described chromium slag is the chromium slag after weathering.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described removing toxic substances pond is before removing toxic substances completes, and the upper surface in described removing toxic substances pond is provided with brooder.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described removing toxic substances pond has multiple, and wherein, the water of circulation and the akali sulphide of circulation circulate between described multiple removing toxic substances pond.
Utilize chromium slag leaching of the present invention to detoxify and landfill integrated processing method, chromic in chromium slag being recycled can be realized, chromium slag can also be realized safely and thoroughly detoxify, remove the anxiety of environmental pollution.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of a kind of embodiment of chromium slag leaching of the present invention removing toxic substances and landfill integrated processing method.
Concrete embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
As shown in Figure 1, the invention provides a kind of chromium slag leaching removing toxic substances and landfill integrated processing method, wherein, comprise the following steps:
1) in ground structure removing toxic substances pond: the landfill pond going out corresponding size according to the quantity of pending chromium slag in ground excavation, the wall in landfill pond arranges impervious barrier, and arrange the flow guide system of outside water conservancy diversion in landfill pond;
2) be delivered to by pending chromium slag in removing toxic substances pond, and add water in removing toxic substances pond, chromium slag leaches Cr VI in water and/or chemical combination goes out Cr VI, and the water now added becomes leachate;
3) reclaim leachate by flow guide system, in landfill pond, add water more afterwards, until when chromic content is no more than 0.5 ~ 2g/L in the immersion chromium slag leachate of 4 ~ 5 months, in removing toxic substances pond, add sodium sulfide reducing Cr VI, perform removing toxic substances reaction;
4) detoxified, buried and close removing toxic substances pond.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and in removing toxic substances pond, the loading thickness of chromium slag is 3 meters.
Preferably, described chromium slag leaching removing toxic substances with landfill integrated processing method, described step 1) in be also included in landfill pond aqueduct be set, to form water circulation with flow guide system.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and soaking chromium slag 4 ~ 5 months is water circulation type leaching.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described impervious barrier comprises in successively from wall to wall the argillic horizon, the first nonwoven layer, high-density polyethylene layer and the second nonwoven layer that arrange.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described argillic horizon is the thickness of 1 meter and/or high-density polyethylene layer is 2 millimeters.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and immersed depth is 50 centimetres.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described flow guide system comprises:
Grit guide layer, it is arranged on the side in the middle of the close landfill pond of described second nonwoven layer, and the side in the middle of the close landfill pond of described grit guide layer is also provided with the 3rd nonwoven layer;
Mozzle, its one end is arranged in described grit guide layer, and the other end is arranged on the outside in described landfill pond.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described chromium slag is the chromium slag after weathering.
Preferably, described chromium slag leaching removing toxic substances is with landfill integrated processing method, and described removing toxic substances pond is before removing toxic substances completes, and the upper surface in described removing toxic substances pond is provided with brooder.
Described removing toxic substances pond has multiple, and wherein, the water of circulation and the akali sulphide of circulation circulate between described multiple removing toxic substances pond.Water or akali sulphide circulate successively in each removing toxic substances pond, form structure communicating together between each removing toxic substances pond.
Specifically, chromic slag wet method leaching detoxification technique is: build several removing toxic substances ponds according to chromium slag muck storage, once will store up chromium slag and all load (chromium thickness of slag layer 3 meters).Employing water is leaching agent, relies on seepage effect by water-solubility Cr (VI) stripping in chromium slag and recycles; Utilize the hydration of non-aqueous state Cr (VI) simultaneously, by circulation leaching in 4 ~ 5 months, non-aqueous state Cr (VI) also most of stripping is also collected and reclaims containing Cr (VI) lixivium; When Cr (VI) concentration is down to below 1g/L in lixivium, adopt the Cr (VI) in Gas with Sodium Sulfide Solution reduction and detoxication lixivium; After having detoxified, bury and close removing toxic substances pond.
Chromium slag leaching removing toxic substances pond (landfill yard) is provided with to be prevented blending flow guide system, is respectively 1m argillic horizon, non-woven fabrics, 2mm HDPE, non-woven fabrics, gravel guide layer, non-woven fabrics from bottom to up.It is stacked about 3m chromium slag blanket, leaching water depth is about 50cm.
Principle:
1. mineral pond leaching technology:
Mineral are put in the pond laying heelpiece (impervious barrier, filter layer) in advance, with the leachant chosen, the useful constituent in ore is dissolved, and transfer in liquid phase (leachate) with the form of ion or complex ion, then the leached ions in liquid phase is changed into the process of elemental metals or chemical products.The advantage such as this technique has that recovery rate is high, advantage of lower cost, technological process are simple
2. waste liqouor and chromium residue detoxifying mechanism:
(1) Cr VI is transferred to aqueous phase
Northwest chromium salt factory left over by history has calcium chromium slag Exemplary chemical composition as follows:
Table 1 has calcium chromium dreg chemistry analysis result
As shown in table 1, left over by history has acid-soluble chromium in calcium chromium slag, and (non-aqueous state Cr (VI) newer slag (representative value is 0.6-1.0) has remarkable reduction, analyze its reason to should be left over by history chromium slag muck to deposit the time longer, matrix weathering can be there is in the process of storing up, cause the change that mineral facies form, thus change the dissolution characteristic of Cr (VI), facilitate the transformation of non-aqueous state Cr (VI) to water-soluble state Cr (VI).
In addition, also Na is contained in chromium slag
2cO
3(9.74%), following reaction can be there is under water-soluble condition:
CaCrO
4+Na
2CO
3＝Na
2CrO
4+CaCO
3
CaO.Al
2O
3.CaCrO
4.12H
2O+Na
2CO
3＝2CaCO
3+2NaAlO
2+Na
2CrO
4+12H
2O
Above-mentioned reaction also makes part non-aqueous state Cr (VI) change water-soluble state Cr (VI) into.
There is in calcium chromium slag chromic existence form as following table:
Table 2 has chromic occurrence form in calcium chromium slag
| Thing phase composition | Water-soluble |
| Sodium Chromate Tetrahydrate 99 | Yi Rong |
| Calcium chromate | Slightly molten |
| The Cr VI of chromium calcium aluminate, alkali formula ferric chromate, chemisorbed | Slightly soluble |
| Dicalcium silicate calcium chromate solid solution | Indissoluble |
| Calcium aluminoferrite calcium chromate solid solution | Indissoluble |
As shown in table 2, in chromium slag, Cr VI has 7 kinds of existence forms, front 5 kinds of easy molten, slightly molten or slightly solubles in water, or under reducing agent or precipitating reagent exist, be comparatively easy to dissolving limit, limit reduction (precipitation), latter 2 kinds is the non-aqueous state Cr (VI) (representing with calcium chromate CaCrO4 below) be present in solid solution thereof in dicalcium silicate, calcium aluminoferrite, be insoluble in water, also being difficult to reducing agent or precipitating reagent complete reaction in the short time, is the key point thoroughly eliminated by Cr VI in chromium slag.
Non-aqueous state Cr (VI) whole in chromium slag is transferred to aqueous phase and has aquation method and acid extracting.Aquation method be utilize dicalcium silicate, calcium aluminoferrite have same water reaction performance, the calcium chromate in solid solution is dissociated in water, shown in (2-1) and formula (2-2).
Ca
2SiO
4-CaCrO
4+(x+1)H
2O＝CaSiO
3·xH
2O+CaCrO
4+Ca(OH)
2(2-1)
4CaO·Al
2O
3·Fe
2O
3-CaCrO
4+(y+6)H
2O＝CaO·Al
2O
3·yH
2O+2Fe(OH)
3+CaCrO
4+3Ca(OH)
2(2-2)
Hydration rate is with three kinds of factors are relevant below:
1. the less hydration rate of chromium slag particle degree is faster, and about 80 object chromium slag Cr VI leaching rates are higher than former slag 2 times;
2. leaching time longer Cr VI leaching rate is higher, and the Cr VI soaking 1.5h leaching is higher by 15% than soaking 0.5h;
3. the higher hydration rate of temperature is faster.Therefore, we by adding the material of similar plastics booth employing above removing toxic substances pond, can be formed as greenhouse effect to make removing toxic substances pond.The temperature in removing toxic substances pond can be increased like this, accelerate hydration rate.
In this chromium residue detoxifying method:
The first, the handled left over by history that is has calcium chromium slag, and the time of storing up reaches more than 6 years.Have passed through long-term slacking, most of graininess chromium slag efflorescence (through having calcium chromium slag to carry out wet concentration classification to northwest chromium salt factory left over by history, 200 reach 70% now), improves hydration rate to a certain extent;
The second, circulation diafiltration (immersion) time reaches 4-5 month, and leaching liquid dynamic circulation, make the thorough aquation of non-aqueous state Cr (VI) become possibility;
3rd, the Northwest's drought, summer, surface temperature can reach more than 30 degrees Celsius, greatly accelerated the hydration rate (winter process chromium slag can pass into steam heat) of non-aqueous state Cr (VI).
(2) Cr (VI) reclaims:
By adopting mineral pond leaching technology, with clear water, chromium slag being leached, obtaining the leachate (Cr (VI) content reaches more than 2g/L, existing recovery value) containing sodium chromate, recyclable recycling.In order to improve leachate, (Cr (VI) concentration can carry out leachate slag bath interior " self-loopa " or enter next slag bath participating in circulation leaching.This leachate is added sulphur, preparing hydrogen chromium oxide, main anti-as follows:
4Na2CrO4+6S+7H2O＝4Cr(OH)3+3Na2S2O3+2NaOH
(3) add sodium sulfide solution process chromium slag again after reclaiming sodium chromate leachate, Cr VI generation reduction reaction can be made.Chemical equation is:
8Na2CrO4+6Na2S+(11+4X)H2O＝4(Cr2O3.XH2O)+3Na2S2O3+22NaOH
Chromium slag, after long-time (more than 5 months for good) circulation diafiltration realizes Cr (VI) recovery, significantly can reduce reducing agent consumption, improve detoxification chromium slag stability.
3. detoxifying effect inspection
1) assay method of the various concentration of element of detoxification chromium slag, performs according to following table:
2) the chromium slag after removing toxic substances should meet the requirement of Equations of The Second Kind general industrial solid waste access landfill yard in HJ/T301-2007 " chromium slag contaminated Environment control protection specification ":
4. conclusion
3 meters of bed of materials have calcium chromium slag according to long-term (5 months) circulation diafiltration; after reclaiming the leachate containing sodium chromate; by the process conditions of 120% sodium sulfide solution removing toxic substances; carry out pond macerate poison (2 months), removing toxic substances slag meets the requirement of Equations of The Second Kind general industrial solid waste access landfill yard in HJ/T301-2007 " chromium slag contaminated Environment control protection specification ".
Show above and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (7)
1. chromium slag leaching removing toxic substances and a landfill integrated processing method, wherein, comprises the following steps:
1) in ground structure removing toxic substances pond: according to the quantity of pending chromium slag in ground excavation or the landfill pond of piling up corresponding size, the wall in landfill pond arranges impervious barrier, and flow guide system and the aqueduct of outside water conservancy diversion are set in landfill pond, aqueduct and flow guide system form water circulation; Wherein, described impervious barrier comprises in successively from wall to wall the argillic horizon, the first nonwoven layer, high-density polyethylene layer and the second nonwoven layer that arrange; Described flow guide system comprises grit guide layer, and it is arranged on the side in the middle of the close landfill pond of described second nonwoven layer, and the side in the middle of the close landfill pond of described grit guide layer is also provided with the 3rd nonwoven layer; Mozzle, its one end is arranged in described grit guide layer, and the other end is arranged on the outside in described landfill pond;
2) be delivered to by pending chromium slag in removing toxic substances pond, and add water in removing toxic substances pond, chromium slag leaches Cr VI in water and/or chemical combination goes out Cr VI, and the water now added becomes leachate;
3) leachate is reclaimed by flow guide system, water is added again afterwards, until soak the chromium slag time to reach 4 ~ 5 months, and when chromic content is 0.5 ~ 1g/L in leachate in landfill pond, in removing toxic substances pond, add sodium sulfide reducing Cr VI, perform removing toxic substances reaction;
4) described removing toxic substances pond is before removing toxic substances completes, and the upper surface in described removing toxic substances pond is provided with brooder, and removing toxic substances completes, and buries and closes removing toxic substances pond;
Wherein, described removing toxic substances pond has multiple, and the water of circulation and the akali sulphide of circulation circulate between described multiple removing toxic substances pond.
2. chromium slag leaching removing toxic substances as claimed in claim 1 and landfill integrated processing method, wherein, in removing toxic substances pond, the loading thickness of chromium slag is 3 meters.
3. chromium slag leaching removing toxic substances as claimed in claim 1 and landfill integrated processing method, wherein, soaking chromium slag 4 ~ 5 months is water circulation type leaching.
4. chromium slag leaching removing toxic substances as claimed in claim 1 and landfill integrated processing method, wherein, in described step 3) in, the akali sulphide added is the akali sulphide aqueous solution, and its circulation adds described removing toxic substances pond, and forces diafiltration to be detoxified 1 ~ 3 month.
5. chromium slag leaching removing toxic substances as claimed in claim 1 and landfill integrated processing method, wherein, described argillic horizon is the thickness of 1 meter and/or high-density polyethylene layer is 2 millimeters.
6. the chromium slag leaching removing toxic substances as described in claim 4 or 5 and landfill integrated processing method, wherein, immersed depth is 50 centimetres.
7. the chromium slag leaching removing toxic substances as described in claim 4 or 5 and landfill integrated processing method, wherein, described chromium slag is the chromium slag after weathering.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063232A (en) * | 1991-11-21 | 1992-08-05 | 邓绍齐 | Countercurrent circulation sectional leaching separation method for comprehensive utilization of chromium slag |
| CN1401800A (en) * | 2001-08-14 | 2003-03-12 | 重庆钢铁(集团)有限责任公司 | Six valence chromium ion-contg. waste slag comprehensive utilization and harmless treatment method |
| CN1733373A (en) * | 2004-08-13 | 2006-02-15 | 范玉瓒 | Chromic slag immersion, reduction and detoxification technique |
| CN1962096A (en) * | 2005-11-10 | 2007-05-16 | 中国科学院过程工程研究所 | Chromium slag processing method for chemical-biological coupling reduction of hexavalent chrome |
| CN202099865U (en) * | 2010-12-24 | 2012-01-04 | 天津合佳威立雅环境服务有限公司 | Leachate drainage system for hazardous waste safety landfill |
-
2012
- 2012-07-10 CN CN201210237672.5A patent/CN102755985B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063232A (en) * | 1991-11-21 | 1992-08-05 | 邓绍齐 | Countercurrent circulation sectional leaching separation method for comprehensive utilization of chromium slag |
| CN1401800A (en) * | 2001-08-14 | 2003-03-12 | 重庆钢铁(集团)有限责任公司 | Six valence chromium ion-contg. waste slag comprehensive utilization and harmless treatment method |
| CN1733373A (en) * | 2004-08-13 | 2006-02-15 | 范玉瓒 | Chromic slag immersion, reduction and detoxification technique |
| CN1962096A (en) * | 2005-11-10 | 2007-05-16 | 中国科学院过程工程研究所 | Chromium slag processing method for chemical-biological coupling reduction of hexavalent chrome |
| CN202099865U (en) * | 2010-12-24 | 2012-01-04 | 天津合佳威立雅环境服务有限公司 | Leachate drainage system for hazardous waste safety landfill |
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