CN103894406A - Method for restoring polluted chromium-containing soil by combining wet detoxification and stabilization - Google Patents
Method for restoring polluted chromium-containing soil by combining wet detoxification and stabilization Download PDFInfo
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- CN103894406A CN103894406A CN201410099423.3A CN201410099423A CN103894406A CN 103894406 A CN103894406 A CN 103894406A CN 201410099423 A CN201410099423 A CN 201410099423A CN 103894406 A CN103894406 A CN 103894406A
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Abstract
The invention relates to a method for restoring polluted chromium-containing soil by combining wet detoxification and stabilization. The method comprises the following steps of performing wet ball grinding on the polluted chromium-containing soil in a ball grinding machine, adding a sodium sulfide reducing agent and uniformly mixing, then performing reducing reaction to reduce water-soluble hexavalent chromium from chromium-containing slurry, adding inorganic acid into the chromium-containing slurry and uniformly mixing, adjusting the pH of the chromium-containing slurry to be 4-6, and dissolving out acid-soluble hexavalent chromium in the chromium-containing slurry; adding the reducing agent into the chromium-containing slurry with the adjusted pH, uniformly mixing the reducing agent and the chromium-containing slurry, performing secondary reducing treatment, controlling the reaction time within 2-4 hours, curing a product for 6-12 hours, reducing the acid-soluble hexavalent chromium in the chromium-containing slurry into trivalent chromium, performing solid-liquid separation on the chromium-containing slurry subjected to secondary reducing, and returning separated filtrate into the ball grinding machine; adding a stabilizing agent into the separated detoxified chromium polluted soil for stabilization. The method has the characteristics of good treatment effect, low operating cost, no secondary pollution and high adaptability.
Description
Technical field
The present invention relates to the method for a kind of wet method detoxifcation associating stabilisation reparation containing chromium-polluted soil, belong to heavy metal soil remediation technical field.
Background technology
Pollution of chromium source is mainly industry containing the discharge of chromium waste gas and waste water, waste residue.As industry such as metal processing, ferrochrome smelting, plating, process hides, pigment, refractory material and chemical industry.Chromium is as one of five poisonous creatures: scorpion, viper, centipede, house lizard, toad element, has the extremely strong disease carcinogenesis that causes, and people's Environmental Health has been caused to serious threat.Wherein, chromic toxicity will be far longer than trivalent chromium.Cr VI has stronger carcinogenic and mutagenesis characteristic, is one of internationally recognized 47 kinds of refuses the most dangerous.
Therefore the improvement of soil pollution also generally paid attention to.The governance way of pollution of chromium is mainly contained to two kinds, the one, chromium is removed from contaminated soil, but complex process, processing cost is high.Another kind is to change chromium to have a form in soil, is trivalent chromium by hexavalent chrome reduction, reduces its transfer ability and bioavailability in environment.Change chromium and in soil, exist the processing method of form to mainly contain dry method and two kinds of removing toxic substances modes of wet method, wherein wet method detoxifcation technique, due to advantages such as operating cost are low, treatment effect is good, environmental pollution is little, is in multiple large projects, to have practical application in recent years.Utilize wet method detoxifcation technique to solve the problem of pollution of chromium soil, although easily reach the detoxifying effect of short-term, the soil after wet method detoxifcation does not carry out subsequent treatment, likely there will be rebound phenomena in long-standing environment in the future, cause Cr VI again to exceed standard, affect Environmental security.Especially be subject in the place of chromium slag muck film playback sound, soil Cr is polluted and is mainly existed with water-soluble and acid-soluble chromium, and therefore common method is difficult to reach the thoroughly requirement of removing toxic substances of chromium-polluted soil at present.
Summary of the invention
The wet method detoxifcation associating stabilisation reparation of the object of this invention is to provide that a kind for the treatment of effect is good, low, the non-secondary pollution of operation price, applicability are strong is containing the method for chromium-polluted soil.
Patent of the present invention is that the technical scheme achieving the above object is: the reparation of a kind of wet method detoxifcation associating stabilisation, containing the method for chromium-polluted soil, is characterized in that: comprise the following steps:
(1), will in ball mill, carry out containing pollution of chromium soil wet ball grinding, make a material that contains chromium slip more than 150 orders, be controlled at 40-60 ° of B é containing under the Baume degrees room temperature of chromium slip, and add vulcanized sodium reducing agent evenly to mix, reduction reaction is controlled at 1-2 hour, to carry out water-soluble hexavalent chrome reduction containing chromium slip, in mass ratio, the dosage of vulcanized sodium reducing agent is with native than being 0.001-0.01:1 containing pollution of chromium;
(2), inorganic acid is added containing evenly mixing in chromium slip, will be adjusted to 4-6 containing the pH value of chromium slip, by the acid-soluble Cr VI stripping containing in chromium slip;
(3), reducing agent is added to pH value regulates containing in chromium slip and evenly mix and reduce for the second time processing, in mass ratio, the dosage of described reducing agent is with native than being 0.02-0.1:1 containing pollution of chromium, the reduction reaction time is controlled at 2-4 hour for the second time, reaction post curing 6-12 hour, to reduce and form trivalent chromium containing acid-soluble Cr VI in chromium slip, described reducing agent be wherein one or more the arbitrary composition of ferrous sulfate, sodium pyrosulfite, sodium sulfite, frerrous chloride;
, to carrying out Separation of Solid and Liquid containing chromium slip after reduction for the second time, the filtrate after separation drains into flow container or is back in ball mill, the stabilization processes that the removing toxic substances pollution of chromium soil after separation enters next step;
(5), add stabilizing agent to carry out stabilization processes to removing toxic substances pollution of chromium soil, wherein, by mass percentage, the dosage of stabilizing agent is the 0.02-0.15:1 containing pollution of chromium soil, after stirring reaction, obtain the soil after repairing, wherein: the component of described stabilizing agent by mass percentage, comprise the lime of 30-50%, the modification organoclay that is rich in silicon components and 20-40% of 20-30%, the wherein said silicon components that is rich in comprises blast-furnace cinder, basalt, one of them of kaolin or flyash or two or more arbitrary compositions, described modification organoclay is montmorillonite, bentonite, wherein one or more arbitrary compositions in hectorite or attapulgite.
The present invention has the following advantages after adopting technique scheme:
1, the present invention adopts two step reduction and detoxication and stabilization processes, first to adding different reducing agents containing chromium-polluted soil at suitable separately reaction environment, to carry out wet ball grinding fragmentation and add vulcanized sodium containing chromium-polluted soil for the first time, water-soluble Cr VI in contaminated soil is reduced, to contain chromium-polluted soil under sour environment for the second time, add ferrous sulfate, sodium pyrosulfite, sodium sulfite, the reducing agents such as frerrous chloride, acid-soluble hexavalent chrome reduction in contaminated soil is become to trivalent chromium, can make the Cr VI in contaminated soil fully be detoxified by two step reduction method.
Concrete chemical equation is as follows:
Water-soluble hexavalent chrome reduction: 8CrO
4 2-+ 6S
2-+ 23H
2o → 8Cr (OH)
3↓+3S
2o
3 2-+ 22OH
-,
Acid-soluble Cr VI stripping: 2C
acrO
4+ 4H
+→ 2C
a 2++ H
2cr
2o
7+ H
2o,
Acid-soluble hexavalent chrome reduction: CrO
4 2-+ 3F
e 2++ 8H
+→ 3F
e 3++ Cr
3++ 4H
2o,
4CrO
4 2-+3S
2O
5 2-+14H
+→4Cr
3++6SO
4 2-+7H
2O，
The present invention is after two step reduction phases, then continues to add stabilizing agent to what obtain after Separation of Solid and Liquid containing chromic removing toxic substances pollution of chromium soil, and trivalent chromium is carried out to stabilization processes: Cr
3++ 3OH
-→ Cr (OH)
3by the lime in stabilizing agent of the present invention, after impelling reparation, soil can keep certain alkaline environment, reduce the solubility of chromium, promote chromium to form chromium hydroxide precipitation, because the pH value of soil raises, soil surface negative electrical charge is strengthened, thereby make the affinity of chromium strengthen, improve its adsorption capacity, the cohesiveness that adding of while alkaline matter also improves soil texture, increases colloid.The silicon that is rich in stabilizing agent of the present invention has good specific area and higher ion exchange capacity and stronger ion-exchange capacity, therefore can form mixture or be combined into stable form with other forms with chromium, after can making to detoxify, in soil, chromic transfer ability and biological effectiveness are farthest reduced, guarantee that the chromium soil after removing toxic substances there will not be rebound phenomena, can be suitable for the removing toxic substances repair process of the chromium-polluted soil of different soils characteristic, different content.
2, the present invention combines wet method detoxifcation and stabilisation, by carrying out after wet ball grinding fragmentation and acid-soluble processing containing chromium-polluted soil, wherein Cr VI stripping is in liquid phase, the present invention becomes trivalent chromium by the collaborative processes such as redox reaction, coprecipitation reaction by hexavalent chrome reduction and is stabilized in soil, and in the soil after reparation, the Steep cencentration of Cr VI and total chromium is effectively controlled.The present invention can guarantee that the chromium soil after removing toxic substances there will not be rebound phenomena after adopting stable processing, combines by wet method detoxifcation and stabilisation, can reach more effectively more fully reparation target.
3, each composition of stabilizing agent of the present invention is simple and easy to get, and cost is low, and in stabilizing agent be rich in silicon components and the contained element of modification organoclay is all the component of soil itself, can not bring secondary pollution to soil.The present invention, by the synergy of the each component of stabilizing agent, can realize out best stabilization processes efficiency in repair process, can be good at, by minimum pollution of chromium Risk Reduction, there will not be the phenomenon of pollution rebound by stabilizing agent.
Detailed description of the invention
Wet method detoxifcation associating stabilisation of the present invention reparation, containing the method for chromium-polluted soil, comprises the following steps:
(1), to in ball mill, carry out containing pollution of chromium soil wet ball grinding, can be at normal temperatures to containing pollution of chromium soil wet ball grinding form slurry, make a material that contains chromium slip more than 150 orders, be controlled at 40-60 ° of B é containing under the Baume degrees room temperature of chromium slip, preferably containing under the Baume degrees room temperature of chromium slip is 45-55 ° of B é, add vulcanized sodium reducing agent evenly to mix, vulcanized sodium reducing agent can directly add in ball mill, or vulcanized sodium reducing agent is added in containing in chromium slip, reduction reaction is controlled at 1-2 hour, to carry out water-soluble hexavalent chrome reduction containing chromium slip, its chemical equation is: 8CrO
4 2-+ 6S
2-+ 23H
2o → 8Cr (OH)
3↓+3S
2o
3 2-+22OH
-, water-soluble Cr VI in contaminated soil is reduced.In mass ratio, the dosage of vulcanized sodium reducing agent is with native than being 0.001-0.01:1 containing pollution of chromium, preferably the dosage of vulcanized sodium reducing agent with containing pollution of chromium soil than at 0.003-0.008:1, the present invention is shown in Table 1 containing Baume degrees and the concrete dosage of vulcanized sodium reducing agent of chromium slip
Table 1
(2), inorganic acid is added containing evenly mixing in chromium slip, pH value containing chromium slip is adjusted to 4-6, by the acid-soluble Cr VI stripping containing in chromium slip, inorganic acid of the present invention is one of them of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrobromic acid, hydroiodic acid or hydrofluoric acid, and its chemical equation is: 2CaCrO
4+ 4H
+→ 2C
a 2++ H
2cr
2o
7+ H
2o, strengthens soil surface negative electrical charge, thereby makes the affinity of chromium strengthen, and improves its adsorption capacity, be shown in Table 2 containing the pH value of chromium slip,
Table 2
(3), reducing agent is added containing evenly mixing in chromium slip and reduces for the second time processing, reducing agent of the present invention is wherein one or more the arbitrary composition of ferrous sulfate, sodium pyrosulfite, sodium sulfite, frerrous chloride; The reduction reaction time is controlled at 2-4 hour for the second time, and reaction disposed slurry slaking 6-12 hour, will reduce and form trivalent chromium containing acid-soluble Cr VI in chromium slip, and its chemical equation is: CrO
4 2-+ 3Fe
2++ 8H
+→ 3Fe
3++ Cr
3++ 4H
2o, 4CrO
4 2-+ 3S
2o
5 2-+ 14H
+→ 4Cr
3++ 6SO
4 2-+ 7H
2o, is fully detoxified the Cr VI in contaminated soil.The concrete dosage of reducing agent of the present invention is shown in Table 3,
Table 3
| Inorganic acid | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Ferrous sulfate | ? | ? | ? | 0.05：1 | ? | ? | ? | 0.1：1 |
| Sodium pyrosulfite | 0.02：1 | 0.01：1 | ? | ? | ? | 0.08：1 | ? | ? |
| Sodium sulfite | ? | 0.02：1 | ? | ? | 0.06：1 | ? | ? | ? |
| Frerrous chloride | ? | ? | 0.04：1 | ? | ? | ? | 0.09：1 | ? |
(4), the chromium slip that contains after reduction is for the second time carried out to Separation of Solid and Liquid, can adopt vacuum filter or filter press to carry out Separation of Solid and Liquid, filtrate after separation drains into flow container or is back to ball mill, to recycle, and the stabilization processes that the removing toxic substances pollution of chromium soil after separation enters next step.
(5), add stabilizing agent to carry out stabilization processes to removing toxic substances pollution of chromium soil, the component of stabilizing agent of the present invention by mass percentage, comprise the lime of 30-50%, the modification organoclay that is rich in silicon components and 20-40% of 20-30%, preferably stabilizing agent comprises the lime of 35-45%, the modification organoclay that is rich in silicon components and 25-35% of 22-28%, the component that is rich in silicon of the present invention comprises blast-furnace cinder, basalt, one of them of kaolin or flyash or two or more arbitrary compositions, modification organoclay is montmorillonite, bentonite, wherein one or more arbitrary compositions in hectorite or attapulgite, contained element is all the component of soil itself, can not bring secondary pollution to soil, mass percent, the concrete component of stabilizing agent of the present invention is by being shown in Table 4,
Table 4
By mass percentage, the dosage of stabilizing agent of the present invention is the 0.02-0.15:1 containing pollution of chromium soil, and the dosage of stabilizing agent preferably, containing the 0.05-0.12:1 of pollution of chromium soil, is cured containing pollution of chromium soil.The concrete dosage of stabilizing agent of the present invention is shown in Table 5,
Table 5
The pollution of chromium soil that contains that is added with stabilizing agent is stirred to the soil obtaining after reparation, and the present invention, by soil after detoxifying is added to stabilizer treatment, guarantees that the chromium soil after removing toxic substances there will not be rebound phenomena.
Test plot is the place that former chromium slag muck is put, and owing to being subject to the impact of chromium slag, pending polluted soil is subject to serious pollution of chromium, and total chromium content in soil content is 102-7162mg/kg, and content of 6-valence Cr ions is 9.8-1940mg/kg.
On the pollution of chromium place of need reparation, excavate Polluted Soil, send into ball mill and carry out wet-milling, more than pollution of chromium soil is crushed to 150 orders, and add a certain amount of process recycled water or clear water to adjust solid-to-liquid ratio before entering retort, containing being controlled at 50 ° of B é left and right under the Baume degrees room temperature of chromium slip, by table 1, each embodiment adds vulcanized sodium reducing agent successively, react 1.5 hours, for the first time after reduction reaction, with slag stock pump will be containing chromium slurry pipeline transport to reduction and detoxication retort, add while stirring organic acid to be acidified to pH value stabilization in table 2, add reducing agent by table 3 again, react 2 hours, continue slaking 10 hours containing chromium slurry, the hexavalent chrome reduction that makes stripping is trivalent chromium, send into filter press and carry out filter-press dehydration, filtrate discharge exists in tank, or deliver to ball mill to recycle, removing toxic substances pollution of chromium soil after dehydration adds the stabilizing agent making by table 5, fully stir and carry out stabilization processes.Detect and process after contaminated soil the 7th day and the 28th day soil Cr VI, total chromium leaching concentration with each embodiment, concrete testing result is as shown in table 6.The preparation of leachate is carried out with reference to HJ/T299-2007 " solid waste Leaching leaching method sulfuric acid nitrate method ", Cr VI leaching concentration is measured by standard GBT15555.4-1995 " the chromic mensuration diphenyl carbazide spectrophotometry of solid waste ", and total chromium leaching concentration is measured by standard GB15555.5-1995 " the total chromium of solid waste is measured diphenyl carbazide spectrophotometry ".
Table 6
As seen from Table 6, adopt wet method detoxifcation associating stabilisation restorative procedure of the present invention to have good treatment effect, in leachate, hexavalent chromium concentration is all lower than 0.27mg/L, and the concentration of total chromium, all lower than 0.37mg/L, can be repaired the pollution containing chromium-polluted soil effectively.And soil after repairing can be used as general industry discarded object and directly enters landfill yard security landfill, or carry out other safe disposals or recycling.
Claims (6)
1. the reparation of wet method detoxifcation associating stabilisation, containing a method for chromium-polluted soil, is characterized in that: comprise the following steps:
(1), will in ball mill, carry out containing pollution of chromium soil wet ball grinding, make a material that contains chromium slip more than 150 orders, be controlled at 40-60 ° of B é containing under the Baume degrees room temperature of chromium slip, and add vulcanized sodium reducing agent evenly to mix, reduction reaction is controlled at 1-2 hour, to carry out water-soluble hexavalent chrome reduction containing chromium slip, in mass ratio, the dosage of vulcanized sodium reducing agent is with native than being 0.001-0.01:1 containing pollution of chromium;
(2), inorganic acid is added containing evenly mixing in chromium slip, will be adjusted to 4-6 containing the pH value of chromium slip, by the acid-soluble Cr VI stripping containing in chromium slip;
(3), reducing agent is added to pH value regulates containing in chromium slip and evenly mix and reduce for the second time processing, in mass ratio, the dosage of described reducing agent is with native than being 0.02-0.1:1 containing pollution of chromium, the reduction reaction time is controlled at 2-4 hour for the second time, reaction post curing 6-12 hour, to reduce and form trivalent chromium containing acid-soluble Cr VI in chromium slip, described reducing agent be wherein one or more the arbitrary composition of ferrous sulfate, sodium pyrosulfite, sodium sulfite, frerrous chloride;
, to carrying out Separation of Solid and Liquid containing chromium slip after reduction for the second time, the filtrate after separation drains into flow container or is back in ball mill, the stabilization processes that the removing toxic substances pollution of chromium soil after separation enters next step;
(5), add stabilizing agent to carry out stabilization processes to removing toxic substances pollution of chromium soil, wherein, by mass percentage, the dosage of stabilizing agent is the 0.02-0.15:1 containing pollution of chromium soil, after stirring reaction, obtain the soil after repairing, wherein: the component of described stabilizing agent by mass percentage, comprise the lime of 30-50%, the modification organoclay that is rich in silicon components and 20-40% of 20-30%, the wherein said silicon components that is rich in comprises blast-furnace cinder, basalt, one of them of kaolin or flyash or two or more arbitrary composition, described modification organoclay is montmorillonite, bentonite, wherein one or more arbitrary compositions in hectorite or attapulgite.
2. wet method detoxifcation associating stabilisation according to claim 1 reparation, containing the method for chromium-polluted soil, is characterized in that: be 45-55 ° of B é described containing under the Baume degrees room temperature of chromium slip.
3. wet method detoxifcation associating stabilisation according to claim 1 reparation, containing the method for chromium-polluted soil, is characterized in that: the dosage of described vulcanized sodium reducing agent is 0.003-0.008:1 with the mass ratio containing pollution of chromium soil.
4. wet method detoxifcation associating stabilisation according to claim 1 reparation, containing the method for chromium-polluted soil, is characterized in that: the dosage of described inorganic acid is 0.04-0.8:1 with the mass ratio containing pollution of chromium soil.
5. wet method detoxifcation associating stabilisation according to claim 1 reparation, containing the method for chromium-polluted soil, is characterized in that: described inorganic acid is one of them of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrobromic acid, hydroiodic acid or hydrofluoric acid.
6. wet method detoxifcation associating stabilisation according to claim 1 reparation, containing the method for chromium-polluted soil, is characterized in that: described stabilizing agent comprises the modification organoclay that is rich in silicon components and 25-35% of the lime of 35-45%, 22-28%.
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