CN109111926A - A kind of preparation method of the green repair materials of heavy-metal contaminated soil - Google Patents
A kind of preparation method of the green repair materials of heavy-metal contaminated soil Download PDFInfo
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- CN109111926A CN109111926A CN201811003545.2A CN201811003545A CN109111926A CN 109111926 A CN109111926 A CN 109111926A CN 201811003545 A CN201811003545 A CN 201811003545A CN 109111926 A CN109111926 A CN 109111926A
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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
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of preparation methods of the green repair materials of heavy-metal contaminated soil, it includes following operating procedure: 1) air-drying plant fibrous waste after decomposed, it is washed respectively with water and deionized water after air-drying, then after natural air drying, it dries, is cut short to 1-2cm in 105 DEG C;2) the plant fibrous waste after cutting short is pyrolyzed in the absence of air conditions;3) product after pyrolysis is put into acid solution and impregnates 12h, filtered after immersion, take filter residue;4) filter residue is first washed with deionized, is then placed in the deionized water boiled to boil and is washed till neutrality, then at 70-105 DEG C constant temperature drying 12-for 24 hours to get to green repair materials.The raw material sources that the method for the present invention uses are wide, and at low cost, preparation process is simple;Green repair materials obtained have good characterization of adsorption to heavy metal, while having good repairing effect to heavy metal in soil, and the long-term storage that can be converged with carbon can't cause secondary pollution to environment in the soil, realize the resource utilization of agricultural wastes.
Description
Technical field
The invention belongs to remediation of heavy metal-contaminated soil field, the green of specifically a kind of heavy-metal contaminated soil is repaired
The preparation method of multiple material.
Background technique
Recently as industrial expansion, human factor causes a large amount of heavy metal to enter environment.Soil is as ecosystem
System is most basic and most important constituent, heavy metal pollution also become a kind of very universal environmental phenomenon.Heavy metal-polluted soil
Pollution refers to makes the content of heavy metal in soil be more than soil background since mankind's activity causes heavy metal to enter soil,
And the phenomenon that causing existing or potential assessing index, ecology and bad environments.
The artificial source of heavy metal-polluted soil can be divided into industrial source and agricultural origin, but with the development of urbanization, city
Source is increasingly becoming a kind of main source.Since heavy metal cannot degrade, the improvement of heavy metal in soil can be divided
For four class methods, the first kind is completely isolated by the soil of heavy metal pollution;Second class takes physical chemistry or biological means will
Summarize metal to be transferred out from soil;Dilution method can be used by heavy metal in the case of pollution level is lighter in third class
Concentration drops to safe concentration once;4th class changes heavy metal form existing for soil by physical chemistry or biological means,
Reduce its mobility and biological effectiveness.And it is easy to operate to use passivation recovery technique to have more compared to other restorative procedures,
It is low-cost, the advantages such as comprehensive benefit is good.Biological carbon adsorption in passivating technique has carried out chemisorption to heavy metal-polluted soil
And physical absorption, rehabilitating soil while, not will cause " secondary pollution ", and low in cost.
Chinese agriculture waste, which recycles, has long history, compost and biogas technology to guide in traditional Ecological Concept
Under be widely used, from more than 370 a ecological agriculture utility modes that national Eco-agricultural Demonstration County is collected into, 1/3 be with
The recycle utilization of agricultural wastes is that tie is coupled the efficient production model to be formed.In recent years, China's agricultural wastes
The mode of resource reutilization mainly has energy, Fertilizer Transformed, fodder and materialized etc..Although China's agricultural waste utilization has
Long history, but the utilization rate of agricultural wastes is still very low at present, such as the utilization of stalk, most of or use
The mode of direct combustion heat supplying or returning to the field, lacks advanced utilization technology.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of preparations of the green repair materials of heavy-metal contaminated soil
Method, it not only solves the handling problems of agricultural wastes, improves the use value of agricultural wastes, and also solves
The reparation problem of heavy-metal contaminated soil, and it is without secondary pollution, reach environment protecting.
The present invention solves above-mentioned technical problem with following technical solution:
A kind of preparation method of the green repair materials of heavy-metal contaminated soil of the present invention, which is characterized in that it includes such as
Lower operating procedure:
Plant fibrous waste is air-dried after decomposed, is washed respectively with water and deionized water after air-drying by the first step
It washs, then after natural air drying, dries, cut short to 1-2cm in 105 DEG C, it is spare;
Second step, the plant fibrous waste after cutting short are pyrolyzed in the absence of air conditions;
Product after pyrolysis is put into acid solution and impregnates 12h, filter after immersion, takes filter residue by third step;
Filter residue is first washed with deionized 4th step, is then placed in the deionized water boiled to boil and is washed till neutrality, then
Constant temperature drying 12-is for 24 hours to get to green repair materials at 70-105 DEG C.
In the first step, the plant fibrous waste is balsam pear tendril, pumpkin tendril, sponge gourd tendril, tomato tendril
One of.
In the first step, the decomposed time of plant fibrous waste is 72h or 72h or more.
In the first step, first it is washed with water 5-6 times after air-drying, then be washed with deionized 2-3 times.
In second step, the process of the pyrolysis includes warming-up section, soaking zone and temperature descending section, and warming-up section is with 10 DEG C/min-
15 DEG C/min heating rate is warming up to 450-550 DEG C, and soaking zone is heat preservation 60min-90min under the conditions of 450-550 DEG C,
Temperature descending section is natural cooling process, keeps being passed through inert gas as carrier gas in entire pyrolytic process.
The flow of the carrier gas is 120-150ml/min, and inert gas is selected from one of nitrogen, argon gas.
In third step, the acid solution uses concentration for the hydrochloric acid solution of 0.4-0.6mol/L, the product after pyrolysis with
The mass ratio of acid solution is 1:500.
The method of the present invention has the advantages that
1) climbing plant is prepared into green and repaired by the green repair materials raw material sources used in plant fibrous waste
Multiple material can not only improve its use value, reduce the pollution of environment, turn waste into wealth.
2) climbing plant is carried out biological charing process by the present invention, can be enhanced its absorption property, be improved it to soil remediation
Effect can't cause secondary pollution to environment, environmentally protective.
3) repair materials products application of the invention is extensive, can be used for heavy metal water pollution control, moreover it can be used to a huge sum of money
Belong to remediation contaminated soil.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below, and however, it is not limited to this.
Embodiment 1
A kind of preparation method of the green repair materials of heavy-metal contaminated soil, operating process are as follows:
Plant fibrous waste balsampear stem by decomposed 72h and after air-drying originally is washed 5 times, then is washed with deionized water 2
It is secondary, after natural air drying, for 24 hours in 105 DEG C of drying, cut short as 2cm, it is spare;The balsam pear tendril cut short is placed into heat in Muffle furnace
Solution, pyrolytic process includes warming-up section, soaking zone and temperature descending section, and warming-up section is warming up to 450 DEG C with 10 DEG C/min;Soaking zone is 450
90min is kept the temperature under the conditions of DEG C;Temperature descending section keeps being passed through nitrogen as carrier gas, carrier gas stream in entire pyrolytic process with natural cooling
Amount is 150ml/min;Then it takes and has been pyrolyzed the simultaneously product of natural cooling and the salt acid soak 12h of 0.4mol/L, wherein product
Mass ratio with hydrochloric acid solution is 1:500;The product deionized water for impregnating persalt is rinsed 4 times, puts it into and has boiled
It is boiled in the deionized water of boiling and is washed till neutral pH=7, drying 12h obtains green repair materials at being 105 DEG C in temperature.
Embodiment 2
A kind of green preparation method of restoration materials of heavy-metal contaminated soil, operating procedure are as follows:
Plant fibrous waste cushaw stem by decomposed 72h and after air-drying originally is washed 6 times, then is washed with deionized water 3
Secondary, after natural air drying, 105 DEG C of drying for 24 hours, are cut short as 1cm, spare.The pumpkin tendril cut short is placed in Muffle furnace and is pyrolyzed,
Pyrolytic process includes warming-up section, soaking zone and temperature descending section, and warming-up section is warming up to 500 DEG C with 15 DEG C/min;Soaking zone is in 500 DEG C of items
60min is kept the temperature under part;Temperature descending section keeps being passed through argon gas as carrier gas in entire pyrolytic process, carrier gas flux is with natural cooling
130ml/min.It takes and has been pyrolyzed the simultaneously product of natural cooling and the salt acid soak 12h of 0.5mol/L, wherein product and hydrochloric acid are molten
The mass ratio of liquid is 1:500.The product of persalt will be impregnated to be rinsed 4 times with deionized water, put it into going of having boiled from
It is boiled in sub- water and is washed till neutral pH=7, dried at being 75 DEG C in temperature and obtain green repair materials for 24 hours.
Embodiment 3
Plant fibrous waste luffa vine by decomposed 72h and after air-drying originally is washed 6 times, then is washed with deionized water 3
It is secondary, after natural air drying, for 24 hours in 105 DEG C of drying, cut short as 1cm, it is spare.The pumpkin tendril cut short is placed into heat in Muffle furnace
Solution, pyrolytic process includes warming-up section, soaking zone and temperature descending section, and warming-up section is warming up to 550 DEG C with 15 DEG C/min;Soaking zone is 550
60min is kept the temperature under the conditions of DEG C;Temperature descending section keeps being passed through nitrogen as carrier gas, carrier gas stream in entire pyrolytic process with natural cooling
Amount is 150ml/min.It takes and has been pyrolyzed the simultaneously product of natural cooling and the salt acid soak 12h of 0.6mol/L, wherein product and salt
The mass ratio of acid solution is 1:500.The product of persalt will be impregnated rinsed 4 times with deionized water, puts it into and boiled
It is boiled in deionized water and is washed till neutral pH=7, dried 12h at being 95 DEG C in temperature and obtain green repair materials.
Embodiment 4
Plant fibrous waste tomato vine by decomposed 72h and after air-drying originally is washed 6 times, then is washed with deionized water 3
It is secondary, after natural air drying, for 24 hours in 105 DEG C of drying, cut short as 1cm, it is spare.The pumpkin tendril cut short is placed into heat in Muffle furnace
Solution, pyrolytic process includes warming-up section, soaking zone and temperature descending section, and warming-up section is warming up to 550 DEG C with 15 DEG C/min;Soaking zone is 550
60min is kept the temperature under the conditions of DEG C;Temperature descending section keeps being passed through nitrogen as carrier gas, carrier gas stream in entire pyrolytic process with natural cooling
Amount is 150ml/min.It takes and has been pyrolyzed the simultaneously product of natural cooling and the salt acid soak 12h of 0.6mol/L, wherein product and salt
The mass ratio of acid solution is 1:500.The product of persalt will be impregnated rinsed 4 times with deionized water, puts it into and boiled
It is boiled in deionized water and is washed till neutral pH=7, dried 12h at being 95 DEG C in temperature and obtain green repair materials.
Application test case 1
Preparation simulation heavy metal polluted waste water, contained heavy metal cadmium ion concentration are 111mg/L.Take 100ml simulation weight
Metallic pollution waste water is placed in the clean conical flask of 100ml, adds green repair materials of the invention, and dosage is simulated wastewater matter
The 0.1% of amount filters after adsorbing 2h, measures the content of heavy metal in filtrate, calculates the adsorbance of green repair materials.By above-mentioned
Operating method is 39.22mg/g with adsorbance of the product of example 1 to heavy metal in simulated wastewater, with the product of example 2 to mould
The adsorbance of quasi- heavy metal in waste water is 32.62mg/g, is with adsorbance of the product of example 3 to heavy metal in simulated wastewater
35.36mg/g is 33.36mg/g with adsorbance of the product of example 4 to heavy metal in simulated wastewater.
Application test case 2
Addition external source Cd makes soil concentration 10mg/kg, stable equilibrium 15 days, obtains cadmium pollution simulation soil, Cd in soil
Total content concentration is 10.65mg/kg.It takes the cadmium pollution pre-processed simulation soil 100g in 500ml beaker, example 1 is made
The green repair materials got ready are put into contaminated soil in the ratio that soil quality percentage is 5%, are stirred evenly, and are during which controlled
Soil moisture is 30% or so and repeatedly mixes, and is cultivated 15 days.After 15 days, the soil after taking reparation is air-dried, the levigate 2mm that crosses is sieved,
The repairing effect of repair materials is determined using the toxicity leaching method of HJ/299-2007.Add the green repair materials of example 1
The leaching concentration of cadmium reduces by 23.61% in soil afterwards.
Claims (7)
1. a kind of preparation method of the green repair materials of heavy-metal contaminated soil, which is characterized in that it includes following operation step
It is rapid:
Plant fibrous waste is air-dried after decomposed, is washed respectively with water and deionized water after air-drying, so by the first step
Afterwards after natural air drying, dries, cut short to 1-2cm in 105 DEG C, it is spare;
Second step, the plant fibrous waste after cutting short are pyrolyzed in the absence of air conditions;
Product after pyrolysis is put into acid solution and impregnates 12h, filter after immersion, takes filter residue by third step;
Filter residue is first washed with deionized 4th step, is then placed in the deionized water boiled to boil and is washed till neutrality, then 70-
Constant temperature drying 12-is for 24 hours to get to green repair materials at 105 DEG C.
2. the preparation method of the green repair materials of heavy-metal contaminated soil according to claim 1, which is characterized in that first
In step, the plant fibrous waste is one of balsam pear tendril, pumpkin tendril, sponge gourd tendril, tomato tendril.
3. the preparation method of the green repair materials of heavy-metal contaminated soil according to claim 1, which is characterized in that first
In step, the decomposed time of plant fibrous waste is 72h or 72h or more.
4. the preparation method of the green repair materials of heavy-metal contaminated soil according to claim 1, which is characterized in that first
In step, first it is washed with water 5-6 times after air-drying, then be washed with deionized 2-3 times.
5. the preparation method of the green repair materials of heavy-metal contaminated soil according to claim 1, which is characterized in that second
In step, the process of the pyrolysis includes warming-up section, soaking zone and temperature descending section, and warming-up section is with 10 DEG C/min-, 15 DEG C/min heating
Rate is warming up to 450-550 DEG C, and soaking zone is heat preservation 60min-90min under the conditions of 450-550 DEG C, and temperature descending section is nature
Cooling procedure keeps in entire pyrolytic process being passed through inert gas as carrier gas.
6. the preparation method of the green repair materials of heavy-metal contaminated soil according to claim 5, which is characterized in that described
The flow of carrier gas is 120-150ml/min, and inert gas is selected from one of nitrogen, argon gas.
7. the preparation method of the green repair materials of heavy-metal contaminated soil according to claim 1, which is characterized in that third
In step, the acid solution uses concentration for the hydrochloric acid solution of 0.4-0.6mol/L, the matter of product and acid solution after pyrolysis
Amount is than being 1:500.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109777439A (en) * | 2019-03-07 | 2019-05-21 | 安徽省农业科学院土壤肥料研究所 | Soil heavy metal passivant and its application in reduction tomato Accumulation of heavy metals amount |
CN114042435A (en) * | 2021-11-03 | 2022-02-15 | 山东农业工程学院 | Method for preparing biochar by pretreating biomass through steam explosion |
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CN101993701A (en) * | 2010-11-24 | 2011-03-30 | 东华大学 | Method for preparing biomass carbon based on waste crop straw |
Non-Patent Citations (1)
Title |
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LOUKIA HADJITTOFI ET AL.: "Activated biochar derived from cactus fibers - Preparation, characterization and application on Cu (II) removal from aqueous solutions", 《BIORESOURCE TECHNOLOGY》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109777439A (en) * | 2019-03-07 | 2019-05-21 | 安徽省农业科学院土壤肥料研究所 | Soil heavy metal passivant and its application in reduction tomato Accumulation of heavy metals amount |
CN114042435A (en) * | 2021-11-03 | 2022-02-15 | 山东农业工程学院 | Method for preparing biochar by pretreating biomass through steam explosion |
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Application publication date: 20190101 |