CN108841388A - It is a kind of for the medicament of cobalt pollution soil remediation, preparation method and restorative procedure - Google Patents
It is a kind of for the medicament of cobalt pollution soil remediation, preparation method and restorative procedure Download PDFInfo
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- CN108841388A CN108841388A CN201810733610.0A CN201810733610A CN108841388A CN 108841388 A CN108841388 A CN 108841388A CN 201810733610 A CN201810733610 A CN 201810733610A CN 108841388 A CN108841388 A CN 108841388A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
Abstract
The present invention relates to a kind of for the medicament of cobalt pollution soil remediation, preparation method and restorative procedure, and the composition and mass percent of the medicament are：Mn oxide 30-40%, ferriferous oxide 20-30%, clay mineral 15-25%, complexing agent 10-20%.Medicament of the present invention is by being ground to Mn oxide, ferriferous oxide, clay mineral and complexing agent and being prepared after being stirred, by being sufficiently mixed with contaminated soil, it is chemically reacted with the heavy metal contaminants in soil, so as to effectively be repaired to soil.
Description
Technical field
The invention belongs to soil remediations and recovery technique field, and in particular to a kind of medicine for cobalt pollution soil remediation
Agent, preparation method and restorative procedure.
Background technique
In recent years, along with a large amount of development and utilization of mineral resources, industrial fast development and various chemical products,
Pesticide and chemical fertilizer are widely used, and the soil environment problem that China faces is got worse, and especially heavy metal pollution is especially prominent.
The harm of heavy metal pollution is mainly reflected in two aspects：First is that heavy metal cannot degrade in the soil, can gather in vivo
Product leads to organism teratogenesis or mutation；Second is that heavy metal can be transmitted by food chain, greatly danger can be generated to human health
Evil.
Cobalt is the important source material for producing heat-resisting alloy, hard alloy, anti-corrosion alloy, magnetic alloy and various cobalt salts, wide
It is general to be applied to the industrial departments such as motor, machinery, chemical industry, aerospace, it is a kind of important strategy metal, consumption figure is year by year
Increase.And China is used as maximum refining cobalt production base in the world, soil pollution scale caused by cobalt can not look down upon.2017
October 27, the carcinogenic substance inventory edit reference that international cancer research institution of the World Health Organization announces, by cobalt and cobalt
Object is closed in 2B class carcinogenic substance inventory.
Currently, common heavy metals immobilization/stabilisation repairs medicament in the market, it is by precipitating, absorption, complexing, oxidation
The effects of reduction and cadmium, zinc, copper, lead, mercury in soil environment etc., common heavy metals chemically reacted, and formed heavy metal surely
Fixed chemical form prevents it from migrating, spread in the environment, to reduce the murder by poisoning degree of heavy metal in the environment.But this
Though a little heavy metals immobilizations/stabilisations are repaired, medicament is generally not satisfactory to the curing/stabilizing effect of cobalt or using effect
It is good, but required pharmaceutical quantities are larger, lead to higher operating costs.
Summary of the invention
It against the above deficiency, can be most the purpose of the present invention is to provide a kind of medicament for cobalt pollution soil remediation
The reparation speed of cobalt pollution soil is increased substantially, and secondary pollution will not be generated in use.
A kind of medicament for cobalt pollution soil remediation, the composition and mass percent of the medicament are：Mn oxide 30-
40%, ferriferous oxide 20-30%, clay mineral 15-25%, complexing agent 10-20%.
Preferably, the Mn oxide includes manganese dioxide.
Preferably, the ferriferous oxide include in ferroso-ferric oxide, di-iron trioxide and ferrous oxide any one or
It is a variety of.
Preferably, the clay mineral includes appointing in sepiolite, montmorillonite, sedimentary peat soil, kaolin and illite
It anticipates one or more.
Preferably, the complexing agent includes any one or more in phosphate, organic phosphonate and poly-aspartate.
A method of medicament is prepared, is included the following steps：
S100：It chooses Mn oxide, ferriferous oxide, clay mineral and complexing agent and is ground into the powder no more than 200 mesh respectively
End；
S200：By Mn oxide, ferriferous oxide, clay mineral and the complexing agent after grinding according to mass ratio be 30-40%,
20-30%, 15-25%, 10-20% are stirred mixing and obtain mixture；
S300：Mixture is continued for stirring, and according to fixed interval uniform sampling, and examine in aggregate sample to
The content of ingredient is examined, the coefficient of variation is calculated, the coefficient of variation is the mixture homogeneity of mixture, if detection gained mixture
Mixture homogeneity be not more than 5%, then the mixture is medicament.
A method of cobalt pollution soil being repaired using medicament, is included the following steps：
S1000：It excavates contaminated soil to be pre-processed, the pretreatment includes soil screening, broken and moisture content
It adjusts；
S2000：It weighs to pretreated soil, tests and analyzes the content of the cobalt and other heavy metals in soil,
Obtain the contamination index of heavy metal in soil；
S3000：According to contamination index, prepares and repair medicament；
S4000：Prepared reparation medicament is uniformly applied into the surface layer in preprocessed soil and is sufficiently mixed；
S5000：The moisture content of soil after mixing is adjusted, and carries out curing in airtight condition.
S6000：It tests to the content of beary metal in the soil for completing maintenance, if disqualified upon inspection, return step
S2000。
Preferably, the moisture content is 25%-35%.
Preferably, the pharmacy quality is the 1%-10% of contaminated soil quality.
Preferably, the time of the curing in airtight condition is 1-3 days.
Compared to the prior art, beneficial effects of the present invention are：
1, Mn oxide and ferriferous oxide used in reparation medicament of the invention not only can make cobalt by isomorphous substitution
Be present in iron and manganese oxides mineral lattice, can also by suction-operated by a large amount of cobalt sorption on iron and manganese oxides surface, Gu
Change/stabilization effect is significant；
2, clay mineral such as sepiolite, montmorillonite etc. used in reparation medicament of the invention are all pure natural, nontoxic, nothings
Taste, the clay mineral without asbestos, "dead" element have very big specific surface area and unique content cellular structure, absorption
Secondary pollution generation is not had in very capable and use process；
3, complexing agent complexing capacity used in reparation medicament of the invention is high, and complexing stability constant is big, metal ion etc.
It is not easy to dissociate after being complexed, and chemical-resistant stability is good, itself is substantially nontoxic, nuisanceless pollution；
4, reparation medicament of the invention can be not only used for the improvement of the single heavy metal contaminated soil of cobalt, to nickel, copper, arsenic
Equal Compound Heavy Metals soil is also effective.And lower usage amount is only needed, curing/stabilizing cobalt can be reached simultaneously
The purpose of ion and other heavy metal ion can be effectively reduced the expense put into needed for soil remediation；
5, contaminated soil remediation method of the invention can greatly improve the reparation speed of contaminated soil, and then preferably
The demand area in repair process to place is reduced, the expense put into needed for soil remediation can be further decreased.
Detailed description of the invention
Fig. 1 is a kind of preparation method flow chart of cobalt pollution soil remediation medicament of the embodiment of the present invention；
Fig. 2 is a kind of method flow diagram of reparation cobalt pollution soil of the embodiment of the present invention.
Specific embodiment
In order to better understand the present invention, with reference to the accompanying drawing 1 to 2 and embodiment technical solution of the present invention is carried out it is detailed
Describe in detail bright, but the present invention is not limited to following embodiment.
Embodiment 1：
A kind of medicament for cobalt pollution soil remediation, the group of the medicament are divided into Mn oxide, ferriferous oxide, clay mineral
And complexing agent, mass percent 30-40%, 20-30%, 15-25%, 10-20%.
The preferred manganese dioxide of Mn oxide.
Any one or more in ferroso-ferric oxide, di-iron trioxide and ferrous oxide can be selected in the ferriferous oxide.
Any one in sepiolite, montmorillonite, sedimentary peat soil, kaolin and illite can be selected in the clay mineral
Or it is a variety of.
Any one or more in phosphate, organic phosphonate and poly-aspartate can be selected in the complexing agent.
The present invention also provides a kind of preparation methods of medicament, are illustrated combined with specific embodiments below.
Embodiment 2：
A kind of preparation method of cobalt pollution soil remediation medicament, including：
Step S100：Manganese dioxide, ferroso-ferric oxide, sepiolite and phosphate is chosen to be ground into respectively no more than 200 mesh
Powder；
Step S200：By manganese dioxide, ferroso-ferric oxide, sepiolite and the phosphate after grinding according to mass percent
35%, 25%, 25%, 15% it is stirred mixing acquisition mixture；
Step S300：Mixture is continued for stirring, and according to fixed interval uniform sampling, and examines aggregate sample
In ingredient to be checked content, calculate the coefficient of variation, the coefficient of variation is the mixture homogeneity of mixture, if detection gained is mixed
The mixture homogeneity for closing object is not more than 5%, then the mixture is medicament.
In a particular embodiment, it is extracted from manganese dioxide, ferroso-ferric oxide, sepiolite and phosphatic stirring mixture
10 parts of sample, it is denoted as X1、X2、X3、X4、X5、X6、X7、X8、X9And X10, calculate average valueCalculate standard deviationBy average valueCoefficient of variation CV is calculated with standard deviation S,Gained coefficient of variation CV is mixture homogeneity.
Embodiment 3：
Different from embodiment 2, the present embodiment chooses manganese dioxide, di-iron trioxide, montmorillonite and organic phosphonate, and presses
Mixing, which is stirred, according to mass percent 40%, 30%, 20%, 10% obtains mixture.
Embodiment 4：
Different from embodiment 2,3, the present embodiment chooses manganese dioxide, ferrous oxide, sedimentary peat soil and poly-aspartate,
And mixing is stirred according to mass percent 30%, 30%, 25%, 15% and obtains mixture.
The present invention also provides a kind of methods for repairing cobalt pollution soil using above-mentioned medicament, are said below by embodiment
It is bright.
Embodiment 5：
The present embodiment also provides a kind of method for repairing cobalt pollution soil using above-mentioned medicament, specifically comprises the following steps：
S1000：It excavates contaminated soil to be pre-processed, the pretreatment includes soil screening, broken and moisture content
It adjusts；
S2000：It weighs to pretreated soil, tests and analyzes the content of the cobalt and other heavy metals in soil,
Obtain the contamination index of heavy metal in soil；
S3000：According to contamination index, prepares and repair medicament；
S4000：Prepared reparation medicament is uniformly applied into the surface layer in preprocessed soil and is sufficiently mixed；
S5000：The moisture content of mixed soil is adjusted, and carries out curing in airtight condition.
S6000：It tests to the content of beary metal in the soil for completing maintenance, if disqualified upon inspection, return step
S2000。
In the present embodiment, the Mn oxide in medicament and ferriferous oxide can make cobalt or other huge sum of moneys by isomorphous substitution
Category be present in iron and manganese oxides mineral lattice, can also by suction-operated by a large amount of cobalt sorption on iron and manganese oxides surface；
Clay mineral used in medicament such as sepiolite, montmorillonite etc. be all it is pure natural, nontoxic, tasteless, without asbestos, "dead" element
Clay mineral, have very big specific surface area and unique content cellular structure, adsorption capacity is stronger, being capable of effective adsorption of cobalt
And other heavy metals；Complexing agent complexing capacity used in medicament is high, and complexing stability constant is big, and heavy metal ion etc. is complexed
After be not easy to dissociate, and chemical-resistant stability is good.
In the following, the present invention will be further described above-mentioned restorative procedure in conjunction with specific experiment.
Experiment 1：
It tests soil and comes from Hainan Province's cobalt ore enterprise, cobalt, copper, mercury, nickel, the cadmium heavy metal concentration in the regional soil are equal
It is higher than《Standard of soil environment quality》(GB15618-1995) grade III Standard is also not up to through detection discovery cobalt, copper, mercury concentration
《Groundwater Environmental Quality standard》(GB/T14848-9) requirement of Group III.Therefore, according to the actual conditions of pollution carried out as
Under repair process：
(1) the reparation medicament that quality is soil 1% is mixed with contaminated soil, and by soil blender to mixed
Soil, which is stirred, makes its mixing sufficiently, and adds water to mixed soil to adjust the moisture content of soil to 25%-35%；
(2) medicament will be first repaired when mixing uniformly to sow on the surface of soil to be processed, and then this has been sowed again and has been repaired
The soil to be processed of multiple medicament is added soil blender and is further mixed, and the time stirred every time is 3-5 minutes,
It needs to carry out 5 stirrings in total, and needs to be spaced 7 minutes per mixing time twice；
(3) soil for being mixed with reparation medicament is conserved：The place of soil maintenance needs first to carry out cure process, and
Cover tarpaulin or waterproof cloth in soil surface with guarantee process that soil conserves it is calm, without each component in rain and soil not to
It is completed in the environment of exosmosis.The water content of soil is controlled in 25%-35%, maintenance after needing to mix in maintenance processes
Between be 1-3 days；
(4) soil after maintenance is detected：Through detecting, the leaching concentration of all kinds of heavy metals be can satisfy in soil
《Groundwater Environmental Quality standard》(GB/T14848-9) requirement of Group III, specific testing result are shown in Table 1：
1 experimental result of table
Seen from table 1, leaching concentration before leaching concentration is far smaller than handled after the processing of contained heavy metal in soil.
Experiment 2：
Soil collection is tested to use from the heavy metal concentration in Gansu Province's heavy metal pollution river bottom mud, the bed mud《In
State's background value of soil element》(China Environmental Science Press, 1990) and《Farming land standard of soil environment quality》It (consults on
Original text, instead of GB 15618-1995) evaluated after find it is obvious exceeded, it is therefore desirable to it is repaired, specific repair process
It is as follows：
(1) apply and repair medicament, heavy-metal contaminated soil is all excavated in feeding crusher with excavator and is crushed, percutaneously
Band is transmitted to mixer, and the reparation medicament that quality is soil 5% is mixed with contaminated soil；
(2) soil for being mixed with reparation medicament is conserved：The place of soil maintenance needs first to carry out cure process, and
Cover tarpaulin or waterproof cloth in soil surface with guarantee process that soil conserves it is calm, without each component in rain and soil not to
It is completed in the environment of exosmosis.The water content of soil is controlled in 25%-35%, maintenance after needing to mix in maintenance processes
Between be 1-3 days；
(3) soil after maintenance is detected：According to solid waste《Leaching leaching method sulfonitric method》
(HJ/T299-2007) leaching experiment is carried out using to the content of beary metal in bed mud.Through cobalt, the nickel, copper, lead in detection soil
Concentration reaches《Groundwater Environmental Quality standard》(GB/T14848-9) requirement of Group III, concrete outcome are shown in Table 2：
2 experimental result of table
| Detection project | Cobalt (Co) | Nickel (Ni) | Copper (Cu) | Lead (Pb) |
| Leaching concentration (mg/L) before handling | 1.54 | 0.78 | 3.57 | 0.89 |
| Leaching concentration (mg/L) after processing | < 0.01 | < 0.01 | 0.38 | < 0.01 |
As can be seen from Table 2, leaching concentration before leaching concentration is far smaller than handled after the processing of heavy metal in bed mud.
Experiment 3：
Soil is tested from mining company of Jiangxi Province, the said firm mainly produces ferro-cobalt, therefore the regional soil surface layer
In heavy metal cobalt concentration be apparently higher than《Standard of soil environment quality》(GB15618-1995) grade III Standard, regional area weight
For metal times of ultra standard up to 1800 times, repair process is as follows：
(1) apply and repair medicament, heavy-metal contaminated soil is all excavated in feeding crusher with excavator and is crushed, percutaneously
Band is transmitted to mixer, and the reparation medicament that quality is soil 10% is mixed with contaminated soil；
(2) soil for being mixed with reparation medicament is conserved：The place of soil maintenance needs first to carry out cure process, and
Cover tarpaulin or waterproof cloth in soil surface with guarantee process that soil conserves it is calm, without each component in rain and soil not to
It is completed in the environment of exosmosis.The water content of soil is controlled in 25%-35%, maintenance after needing to mix in maintenance processes
Between be 1-3 days；
(3) soil after maintenance is detected：According to solid waste《Leaching leaching method sulfonitric method》
(HJ/T299-2007) leaching experiment is carried out to soil using turnover oscillator, detects the content of beary metal in leachate.It takes and repairs
Three parallel samples after multiple in soil carry out detection discovery, and the leaching concentration of cobalt can achieve《Groundwater Environmental Quality mark
It is quasi-》(GB/T14848-9) requirement of Group III, specific testing result are shown in Table 3：
3 experimental result of table
Seen from table 3, leaching concentration before leaching concentration is far smaller than handled after the processing of contained heavy metal in soil.
Reparation medicament of the invention is applied not only to the improvement of the single heavy metal contaminated soil of cobalt, compound to nickel, copper, arsenic etc.
Heavy-metal contaminated soil is also effective, and only needs lower usage amount, can reach simultaneously curing/stabilizing cobalt ions and
The purpose of other heavy metal ion can be good at reducing expense input by soil remediation.
The present invention can greatly improve the reparation speed of cobalt pollution soil using the method that medicament repairs cobalt pollution soil is repaired
Degree, and then the demand area in repair process to place is preferably reduced, investment needed for soil remediation can be further decreased
Expense.
The above is only presently preferred embodiments of the present invention, is not that the invention has other forms of limitations, is appointed
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of medicament for cobalt pollution soil remediation, the composition and mass percent of the medicament are：Mn oxide 30-
40%, ferriferous oxide 20-30%, clay mineral 15-25%, complexing agent 10-20%.
2. medicament according to claim 1, which is characterized in that preferred, the Mn oxide includes manganese dioxide.
3. medicament according to claim 1, which is characterized in that the ferriferous oxide includes ferroso-ferric oxide, three oxidations two
Any one or more in iron and ferrous oxide.
4. medicament according to claim 1, which is characterized in that the clay mineral includes sepiolite, montmorillonite, sedimentary clay
Any one or more in charcoal soil, kaolin and illite.
5. medicament according to claim 1, which is characterized in that the complexing agent includes phosphate, organic phosphonate and gathers
Any one or more in aspartic acid.
6. a kind of method for preparing medicament described in claim 1, includes the following steps：
S100：Mn oxide, ferriferous oxide, clay mineral and complexing agent is chosen to be ground into respectively no more than 200 mesh powders；
S200：By Mn oxide, ferriferous oxide, clay mineral and the complexing agent after grinding according to mass ratio 30-40%, 20-
30%, 15-25%, 10-20% are stirred mixing to obtain mixture；
S300：Mixture is continued for stirring, and according to fixed interval uniform sampling, and examine in aggregate sample it is to be checked at
The content divided calculates the coefficient of variation, and the coefficient of variation is the mixture homogeneity of mixture, if detection gained mixture is mixed
It closes the uniformity and is not more than 5%, then the mixture is medicament.
7. a kind of method using medicament repairing polluted soil described in claim 1, includes the following steps：
S1000：It excavates contaminated soil to be pre-processed, the pretreatment includes that soil sieves, broken and moisture content is adjusted；
S2000：It weighs to pretreated soil, tests and analyzes the content of the cobalt and other heavy metals in soil, obtain
The contamination index of heavy metal in soil；
S3000：According to contamination index, prepares and repair medicament；
S4000：Prepared reparation medicament is uniformly applied into the surface layer in preprocessed soil and is sufficiently mixed；
S5000：The moisture content of soil after mixing is adjusted, and carries out curing in airtight condition；
S6000：It tests to the content of beary metal in the soil for completing maintenance, if disqualified upon inspection, return step
S2000。
8. the method according to the description of claim 7 is characterized in that the moisture content is 25%-35%.
9. the method according to the description of claim 7 is characterized in that the pharmacy quality is the 1%- of contaminated soil quality
10%.
10. the method according to the description of claim 7 is characterized in that the time of the curing in airtight condition is 1-3 days.
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Cited By (5)
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|---|---|---|---|---|
| CN109731901A (en) * | 2019-01-14 | 2019-05-10 | 北京泷涛环境修复有限公司 | A kind of the stabilisation reparation medicament and restorative procedure of fluoride pollution soil |
| CN109913223A (en) * | 2019-03-29 | 2019-06-21 | 武汉强丰新特科技有限公司 | A kind of soil-repairing agent and its application method |
| CN113975703A (en) * | 2021-11-05 | 2022-01-28 | 神美科技有限公司 | Waste incineration fly ash heavy metal chelating agent and preparation method thereof |
| CN114178304A (en) * | 2021-11-26 | 2022-03-15 | 山化中科(东营)石油科技有限公司 | Soil remediation and treatment method |
| CN114395402A (en) * | 2022-01-20 | 2022-04-26 | 中国科学院南京土壤研究所 | Composition for removing organic pollutants from farmland soil and application thereof |
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| CN114395402B (en) * | 2022-01-20 | 2023-01-03 | 中国科学院南京土壤研究所 | Composition for removing organic pollutants from farmland soil and application thereof |
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Application publication date: 20181120 |