CN108148598A - A kind of heavy-metal contaminated soil passivator and preparation method thereof - Google Patents
A kind of heavy-metal contaminated soil passivator and preparation method thereof Download PDFInfo
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- CN108148598A CN108148598A CN201711315378.0A CN201711315378A CN108148598A CN 108148598 A CN108148598 A CN 108148598A CN 201711315378 A CN201711315378 A CN 201711315378A CN 108148598 A CN108148598 A CN 108148598A
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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
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
Abstract
The present invention relates to a kind of heavy-metal contaminated soil passivator and preparation method thereof, belong to technical field of land improvement.The present invention has large specific surface area,Stable structure,The features such as cation exchange capacity (CEC) is strong,By improving soil pH after being manured into soil,Enhance the organic substance in soil,Iron/aluminum oxide,The sequestering power of clay mineral,Make the adsorption capacity of soil enhance,The desorption ability of heavy metal reduces,The content of soluble metal into final decline low soil,Promote the precipitation of heavy metal ion conversion hydrate or carbonate deposition as generated solubility very little in soil,And then reduce the bioavailability of heavy metal,And plant ash is infiltrated with wood vinegar,Dissolving activation nutritional ingredient,It is reacted simultaneously by wood vinegar with attapulgite modified neutral and alkali oxide,Nutritional ingredient is effectively wrapped up and absorbs into slow release in activated biomass charcoal,The fertility of soil can be effectively improved,Restore the function of crops original ecological,Improve survival rate of planting and agricultural output.
Description
Technical field
The present invention relates to a kind of heavy-metal contaminated soil passivator and preparation method thereof, belong to technical field of land improvement.
Background technology
Soil is the base that terrestrial life breeds and multiplies, and is that the mankind are engaged in agricultural production the material base of labour.Pollution-free, nothing
The soil of damage is vital to the survival and development of the mankind, is not only related to the quantity safety and quality of grain-production
Safety, and it is related to the health status of entire ecological environment.The self-cleaning of soil, detoxification ability are limited, can not be fully against
The interference of foeign element, if the external contaminant total amount in soil has been more than the buffering limit of soil, the self-purification capacity of soil
Will lose, caused by pollution effect will be very serious irreversible.It can be said that soil is extremely fragile, easily by mankind's activity
The environmental element for influencing and damaging and destroying.The national soil pollution situation carried out according to China national Environmental Protection Agency in 2014
Investigation bulletin shows that national Environmental Quality of Cultivated Land is worsening, and contamination phenomenon protrudes.In terms of the exceeded situation of pollutant kind,
In a state that the exceeded situation of middle various heavy pollutant is in severe, heavy metal cadmium, Cu-W ore deposit object point position exceeding standard rate difference
For 7.0% and 2.1%, exceeded situation is serious, strong to animals and plants toxic.
Heavy metal pollution of soil problem is quite severe, and it is one of facing mankind difficult to repair and administer heavy-metal contaminated soil
Huge task.At present there are many repair and administer heavy-metal contaminated soil method, as peripheral doses technology, chemical remediation technology,
Phytoremediation technology, microorganism remediation technology etc..In recent years, chemical inactivators restorative procedure becomes home and abroad environment worker
There is of low cost, easy to operate, modifying agent to derive from a wealth of sources, to soil for one of soil remediation method generally used, this method
Structural perturbation itself is small, repairing effect is fast and significantly, the advantages that being suitable for administering pollution in wide area soil.
Chemical inactivators repairing method is that drop is added in into heavy-metal contaminated soil to the mode of heavy metal pollution soil remediation
The substance of low heavy metal activity（Rock phosphate in powder, flyash, iron powder, zeolite, bentonite, palygorskite, sepiolite, organic compost, crop
Stalk, rotten mosses ash, charcoal and new material etc.）, improve soil pH value, cation exchange capacity (CEC)（CEC）Etc. physicochemical properties, pass through
A series of chemical reaction occurs（Precipitation, absorption, complexing, ion exchange, redox）, by heavy metal in soil by available
State reduces its activity and migration in the soil to not converted using state, so as to which the biology for reducing heavy metal-polluted soil is poisoned
Property and reduce its migration and accumulation in crop products.The advantages of chemical modifying technology, is low processing cost, and
And a special disposal field is not needed to handle contaminated soil, it does not need to build complicated engineer equipment, can directly have
Therefore the carry out in-situ immobilization work of effect, is one of cost-effective contaminated soil remediation approach, but chemical inactivators and soil
The position position of earth heavy metal and mechanism are indefinite, and effect is unstable, and soil fertility can be impacted, therefore, need to also be into
One step researchs and develops.
Invention content
The technical problems to be solved by the invention：For chemical inactivators and heavy metal-polluted soil position position and mechanism not
Clearly, effect is unstable, and the problem of can be impacted to soil fertility, provide a kind of heavy-metal contaminated soil passivator and
Preparation method.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of heavy-metal contaminated soil passivator, which is characterized in that it includes following component in parts by weight：
50~100 parts attapulgite modified, 40~80 parts of activated biomass charcoals, 30~50 parts of hydroxyapatites, 30~50 parts of grass
Wood ash, 10~20 parts of wood vinegar.
It is described it is attapulgite modified is fitted into Muffle furnace for attapulgite, be heated to 700~800 DEG C and calcine 1~2h being made.
The biomass carbon that the activated biomass charcoal is prepared for reed carbonization, mixes with dipotassium hydrogen phosphate, diammonium hydrogen phosphate
Activation is made.
The carbonisation is under argon atmosphere, is heated to 400~500 DEG C of 1~2h of pyrolysis.
The biomass carbon, dipotassium hydrogen phosphate, diammonium hydrogen phosphate parts by weight for 50~100 parts of biomass carbons, 2~3 parts
Dipotassium hydrogen phosphate, 1~2 part of diammonium hydrogen phosphate.
The activation process is is heated to 300~400 DEG C of 1~2h of activation under nitrogen atmosphere.
A kind of heavy-metal contaminated soil passivator, which is characterized in that the specific steps are：
（1）Reed washing is taken to pulverize and sieve, and be transferred in Muffle furnace after drying, carbonization is pyrolyzed under argon atmosphere, obtains biomass
Charcoal；
（2）Biomass carbon, dipotassium hydrogen phosphate, diammonium hydrogen phosphate is taken to be fitted into Muffle furnace after mixing, is added under nitrogen atmosphere
1~2h of thermal activation obtains activated biomass charcoal；
（3）1~2h of heating and calcining in Muffle furnace is fitted into after taking attapulgite drying and crushing, is obtained attapulgite modified；
（4）Attapulgite modified, activated biomass charcoal, hydroxyapatite, plant ash, 20~30min of mixing and ball milling are taken, then is sprayed
It is transferred in comminutor and is granulated after wood vinegar, grain size is made as 1~3mm particles and packs envelope, obtain heavy-metal contaminated soil passivation
Agent.
Compared with other methods, advantageous effects are the present invention：
（1）The present invention utilizes the zeopan clay mineral attapulgite of layer chain structure, has cheap and easy to get, and inner duct
Prosperity, specific surface area are larger, have the performance of good adsorption and ion exchange to the heavy metal in environment, pass through height
Temperature is modified to change attapulgite crystal structure and duct, and the alkali such as generation CaO and MgO are decomposed while scission of link occurs for crystal structure
Property oxide, can improve surface soil alkalinity, cadmium, zinc is made to be passivated due to occurrence patterns are changed, and the Al on attapulgite-
After the fracture of OH keys, Al forms complex compound with arsenous anion, effectively promotes the performance of stabilizing heavy metal；
（2）The present invention with wood vinegar infiltrate plant ash, dissolving activation nutritional ingredient, while by wood vinegar with it is attapulgite modified
Neutral and alkali oxide reacts, and nutritional ingredient is effectively wrapped up and absorbs into slow release in activated biomass charcoal, can be effectively improved
The fertility of soil improves crop yield, improves quality of agricultural product, restores the function of crops original ecological, increase substantially plant
Set survival rate and agricultural output；
（3）The present invention has the features such as large specific surface area, stable structure, cation exchange capacity (CEC) is strong, by carrying after being manured into soil
High soil pH enhances the sequestering power of organic substance in soil, iron/aluminum oxide, clay mineral, makes the adsorption capacity of soil
Enhancing, the desorption ability of heavy metal reduce, until in the low soil of final decline soluble metal content, promote heavy metal in soil from
The precipitation of son conversion hydrate or carbonate deposition as generated solubility very little, and then reduce the bioavailable of heavy metal
Property.
Specific embodiment
It takes reed that clean rear drying is washed with deionized to air-dry, and be fitted into pulverizer and crush, crosses 60 mesh sieve, will be sieved
Powder afterwards is transferred in Muffle furnace, under argon atmosphere, is heated to 400~500 DEG C of 1~2h of pyrolysis, is obtained after being cooled to room temperature raw
Substance charcoal takes 50~100g biomass carbons, 2~3g dipotassium hydrogen phosphates, and the mixing of 1~2g diammonium hydrogen phosphates is added in ball mill, ball
It is fitted into Muffle furnace after 20~30min of mill, under nitrogen atmosphere, 300~400 DEG C of 1~2h of activation is heated to, after being cooled to room temperature
Activated biomass charcoal is obtained, attapulgite is taken to be placed in drying box, is dried at 105~110 DEG C to constant weight, then be transferred in pulverizer
It crushes, crosses 200 mesh sieve, the attapulgite powder after sieving is fitted into Muffle furnace, be heated to 700~800 DEG C of 1~2h of calcining,
Must be attapulgite modified after being cooled to room temperature, take 50~100g attapulgite modified, 40~80g activated biomass charcoals, 30~50g
Hydroxyapatite, 30~50g plant ash add in 20~30min of ball milling in ball mill, then spray 10~20g wood vinegar after mixing
After be transferred in comminutor and be granulated, grain size is made as 1~3mm particles and packs envelope, obtains heavy-metal contaminated soil passivator.
Example 1
It takes reed that clean rear drying is washed with deionized to air-dry, and be fitted into pulverizer and crush, 60 mesh sieve is crossed, after sieving
Powder is transferred in Muffle furnace, under argon atmosphere, is heated to 400 DEG C of pyrolysis 1h, biomass carbon is obtained after being cooled to room temperature, takes 50g
Biomass carbon, 2g dipotassium hydrogen phosphates, the mixing of 1g diammonium hydrogen phosphates are added in ball mill, are fitted into Muffle furnace after ball milling 20min,
Under nitrogen atmosphere, 300 DEG C of activation 1h are heated to, activated biomass charcoal is obtained after being cooled to room temperature, attapulgite is taken to be placed in drying box
In, it is dried at 105 DEG C to constant weight, then be transferred in pulverizer and crush, crosses 200 mesh sieve, the attapulgite powder after sieving is filled
Enter in Muffle furnace, be heated to 700 DEG C of calcining 1h, must be attapulgite modified after being cooled to room temperature, take 50g attapulgite modified, 40g
Activated biomass charcoal, 30g hydroxyapatites, 30g plant ash add in ball milling 20min in ball mill after mixing, then spray 10g wood
It is transferred in comminutor and is granulated after vinegar liquid, grain size is made as 1mm particles and packs envelope, obtain heavy-metal contaminated soil passivator.
Example 2
It takes reed that clean rear drying is washed with deionized to air-dry, and be fitted into pulverizer and crush, 60 mesh sieve is crossed, after sieving
Powder is transferred in Muffle furnace, under argon atmosphere, is heated to 450 DEG C of pyrolysis 1h, biomass carbon is obtained after being cooled to room temperature, takes 70g
Biomass carbon, 2g dipotassium hydrogen phosphates, the mixing of 1g diammonium hydrogen phosphates are added in ball mill, are fitted into Muffle furnace after ball milling 25min,
Under nitrogen atmosphere, 350 DEG C of activation 1h are heated to, activated biomass charcoal is obtained after being cooled to room temperature, attapulgite is taken to be placed in drying box
In, it is dried at 108 DEG C to constant weight, then be transferred in pulverizer and crush, crosses 200 mesh sieve, the attapulgite powder after sieving is filled
Enter in Muffle furnace, be heated to 750 DEG C of calcining 1h, must be attapulgite modified after being cooled to room temperature, take 70g attapulgite modified, 60g
Activated biomass charcoal, 40g hydroxyapatites, 40g plant ash add in ball milling 25min in ball mill after mixing, then spray 15g wood
It is transferred in comminutor and is granulated after vinegar liquid, grain size is made as 2mm particles and packs envelope, obtain heavy-metal contaminated soil passivator.
Example 3
It takes reed that clean rear drying is washed with deionized to air-dry, and be fitted into pulverizer and crush, 60 mesh sieve is crossed, after sieving
Powder is transferred in Muffle furnace, under argon atmosphere, is heated to 500 DEG C of pyrolysis 2h, biomass carbon is obtained after being cooled to room temperature, takes 100g
Biomass carbon, 3g dipotassium hydrogen phosphates, the mixing of 2g diammonium hydrogen phosphates are added in ball mill, are fitted into Muffle furnace after ball milling 30min,
Under nitrogen atmosphere, 400 DEG C of activation 2h are heated to, activated biomass charcoal is obtained after being cooled to room temperature, attapulgite is taken to be placed in drying box
In, it is dried at 110 DEG C to constant weight, then be transferred in pulverizer and crush, crosses 200 mesh sieve, the attapulgite powder after sieving is filled
Enter in Muffle furnace, be heated to 800 DEG C of calcining 2h, must be attapulgite modified after being cooled to room temperature, take 100g attapulgite modified,
80g activated biomass charcoals, 50g hydroxyapatites, 50g plant ash add in ball milling 30min in ball mill, then spray 20g after mixing
It is transferred in comminutor and is granulated after wood vinegar, grain size is made as 3mm particles and packs envelope, obtain heavy-metal contaminated soil passivator.
Reference examples：The passivator of Shandong Co., Ltd production.
The product testing effect of example and reference examples is detected, specific detection is as follows：
With Shanghai thunder, hereby pH meter measures soil pH value, and water and soil mass ratio is 2.5：1, pH meter model pH5-3C.Specific method is joined
According to national standard.
Soil CEC（Cation exchange capacity (CEC)）It is measured with spectrophotometry.
Specific testing result such as table 1.
Table 1
| Detection project | Example 1 | Example 2 | Example 3 | Reference examples |
| pH | 6.37 | 6.08 | 5.91 | 4.92 |
| CEC% | 52 | 49 | 46 | 20 |
As shown in Table 1, the application of passivator that prepared by the present invention significantly improves soil pH, Cation Exchange Capacity in Soils（CEC）,
Wherein soil pH improves to 6.37, CEC and improves 52%.Soil pH, cation exchange capacity (CEC)（CEC）It is extracted with soil Cu, Cd weak acid
Notable negative correlativing relation is presented in state（P<0.05）, add passivator, promote in soil Cu, Cd from the high weak acid extractable of activity to
The low Forms Transformation of activity, the key effect that passivator repairs Cu, Cd contaminated soil are to improve soil pH value and CEC contents.
Claims (7)
1. a kind of heavy-metal contaminated soil passivator, which is characterized in that it includes following component in parts by weight：
50~100 parts attapulgite modified, 40~80 parts of activated biomass charcoals, 30~50 parts of hydroxyapatites, 30~50 parts of grass
Wood ash, 10~20 parts of wood vinegar.
2. a kind of heavy-metal contaminated soil passivator as described in claim 1, which is characterized in that described attapulgite modified to be
Attapulgite is fitted into Muffle furnace, is heated to 700~800 DEG C of 1~2h of calcining and is made.
3. a kind of heavy-metal contaminated soil passivator as described in claim 1, which is characterized in that the activated biomass charcoal is
Biomass carbon prepared by reed carbonization, is made with dipotassium hydrogen phosphate, diammonium hydrogen phosphate admixture activation.
4. a kind of heavy-metal contaminated soil passivator as claimed in claim 3, which is characterized in that the carbonisation is in argon
Under atmosphere is enclosed, it is heated to 400~500 DEG C of 1~2h of pyrolysis.
5. a kind of heavy-metal contaminated soil passivator as claimed in claim 3, which is characterized in that the biomass carbon, phosphoric acid
Hydrogen dipotassium, diammonium hydrogen phosphate parts by weight for 50~100 parts of biomass carbons, 2~3 parts of dipotassium hydrogen phosphates, 1~2 part of phosphoric acid hydrogen two
Amine.
6. a kind of heavy-metal contaminated soil passivator as claimed in claim 3, which is characterized in that the activation process is in nitrogen
Atmosphere is heated to 300~400 DEG C of 1~2h of activation under enclosing.
A kind of 7. heavy-metal contaminated soil passivator as described in claim 1~6 any one, which is characterized in that specific step
Suddenly it is：
（1）Reed washing is taken to pulverize and sieve, and be transferred in Muffle furnace after drying, carbonization is pyrolyzed under argon atmosphere, obtains biomass
Charcoal；
（2）Biomass carbon, dipotassium hydrogen phosphate, diammonium hydrogen phosphate is taken to be fitted into Muffle furnace after mixing, is added under nitrogen atmosphere
1~2h of thermal activation obtains activated biomass charcoal；
（3）1~2h of heating and calcining in Muffle furnace is fitted into after taking attapulgite drying and crushing, is obtained attapulgite modified；
（4）Attapulgite modified, activated biomass charcoal, hydroxyapatite, plant ash, 20~30min of mixing and ball milling are taken, then is sprayed
It is transferred in comminutor and is granulated after wood vinegar, grain size is made as 1~3mm particles and packs envelope, obtain heavy-metal contaminated soil passivation
Agent.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108949188A (en) * | 2018-08-02 | 2018-12-07 | 佛山皖阳生物科技有限公司 | A kind of preparation method of antibacterial passivator |
| CN109504398A (en) * | 2018-12-30 | 2019-03-22 | 山东农大腐植酸高效利用工程技术研发有限公司 | A kind of humic acid nano zero valence iron soil Cr pollution amelioration agent and preparation method |
| CN110327882A (en) * | 2019-07-11 | 2019-10-15 | 江西省科学院 | The preparation method and application of multidigit activation and modified reed-south reed charcoal |
| CN110434164A (en) * | 2019-07-08 | 2019-11-12 | 迪天环境技术南京股份有限公司 | One heavy metal species reparation great Ye dandelion high yield method for planting |
| CN110934047A (en) * | 2019-11-08 | 2020-03-31 | 安徽农业大学 | Method for restoring heavy metal pollution of paddy field by using waste straws |
| CN111171830A (en) * | 2019-12-18 | 2020-05-19 | 浙江慧丰环保科技有限公司 | Passivator for soil heavy metal pollution treatment and preparation method thereof |
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| CN107350281A (en) * | 2017-05-11 | 2017-11-17 | 中国环境科学研究院 | One kind is applied to northern farmland soil of sewage irrigation area passivator and its application process |
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| CN105583223A (en) * | 2016-02-04 | 2016-05-18 | 周益辉 | Remediation agent and application for combined contaminated soil |
| CN106147778A (en) * | 2016-07-04 | 2016-11-23 | 河北省农林科学院农业资源环境研究所 | Passivator, preparation method and applications for repairing heavy metal in soil combined pollution |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108949188A (en) * | 2018-08-02 | 2018-12-07 | 佛山皖阳生物科技有限公司 | A kind of preparation method of antibacterial passivator |
| CN109504398A (en) * | 2018-12-30 | 2019-03-22 | 山东农大腐植酸高效利用工程技术研发有限公司 | A kind of humic acid nano zero valence iron soil Cr pollution amelioration agent and preparation method |
| CN110434164A (en) * | 2019-07-08 | 2019-11-12 | 迪天环境技术南京股份有限公司 | One heavy metal species reparation great Ye dandelion high yield method for planting |
| CN110327882A (en) * | 2019-07-11 | 2019-10-15 | 江西省科学院 | The preparation method and application of multidigit activation and modified reed-south reed charcoal |
| CN110327882B (en) * | 2019-07-11 | 2020-03-27 | 江西省科学院 | Preparation method and application of multiposition activated and modified reed-triarrhena sacchariflora biochar |
| CN110934047A (en) * | 2019-11-08 | 2020-03-31 | 安徽农业大学 | Method for restoring heavy metal pollution of paddy field by using waste straws |
| CN110934047B (en) * | 2019-11-08 | 2021-09-14 | 安徽农业大学 | Method for restoring heavy metal pollution of paddy field by using waste straws |
| CN111171830A (en) * | 2019-12-18 | 2020-05-19 | 浙江慧丰环保科技有限公司 | Passivator for soil heavy metal pollution treatment and preparation method thereof |
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