CN104368306B - A kind of preparation method of the class charcoal repaired for heavy-metal contaminated soil - Google Patents
A kind of preparation method of the class charcoal repaired for heavy-metal contaminated soil Download PDFInfo
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- CN104368306B CN104368306B CN201410409206.XA CN201410409206A CN104368306B CN 104368306 B CN104368306 B CN 104368306B CN 201410409206 A CN201410409206 A CN 201410409206A CN 104368306 B CN104368306 B CN 104368306B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- 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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Abstract
The present invention relates to the preparation method of a kind of class charcoal repaired for heavy-metal contaminated soil, carbonize including pretreatment of raw material, material bacterium solution combined inoculation, low temperature pyrogenation, pulverize, the step such as screening, prepare the class charcoal repaired for heavy-metal contaminated soil as raw material using one or more in plant and animal residues, food market garbage or kitchen wet refuse.As compared to prior art, the such as technology such as displacement, electro reclamation, complexing drip washing, steam extraction, redox electric heating mechanics reparation, the present invention uses based technique for in-situ remediation, has the advantage such as manufacture, low, the effect stability of implementation cost.
Description
Technical field
The invention belongs to biological fermentation field, especially relate to a kind of class repaired for heavy-metal contaminated soil
The preparation method of charcoal.
Background technology
China has the living beings of substantial amounts of such as stalk, rice husk etc to suffer that burning is wasted every year, and this not only can
Cause environment pollution harm, also can cause waste and the loss of bioenergy.In recent years, along with pyrolysis skill
Art is progressively carried out in China so that abandoned biomass recycles and energy regeneration is achieved.But,
While obtaining regenerative resource and chemicals by biomass pyrolytic technology, also create large batch of by-product
Product--charcoal.The most fully and reasonably utilizing charcoal, how to make it turn waste into wealth, this is needs
People's problem demanding prompt solution, so far, charcoal is widely used in agriculturally, is such as used to soil
Earth improvement and soil remediation.Additionally, due to charcoal has certain distributional effects and adsorption effect,
Charcoal is the most gradually used as adsorbent, but, charcoal adsorption site own is very limited, so
Its absorption property and stability are very limited.Therefore, the life of high absorption property and stable in properties is prepared
Thing charcoal is significant.
The Chinese patent of Application No. 201310461243.0 discloses the preparation method of a kind of modification biological charcoal,
Comprise the steps: 1) take appropriate charcoal, add the concentrated sulfuric acid and the mixed liquor of red fuming nitric acid (RFNA), stir one section
Carry out after time filtering, wash, dry, obtain nitrification charcoal；2) to step 1) in the nitrification that obtains
Charcoal adds water and reducing agent, carries out temperature rising reflux process after stirring, carried out after the cooling of question response thing
Filter, wash, dry, i.e. obtain modification biological charcoal.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide one to make soil
In the heavy metal ion of plant absorption leachable, passive repairing for heavy-metal contaminated soil of being greatly decreased
The preparation method of class charcoal.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of the class charcoal repaired for heavy-metal contaminated soil, employing following steps:
(1) pretreatment of raw material:
Plastics, metal, bone impurity in a, removal raw material；
Raw material after b, preliminary sorting enters disintegrating machine, and after crushing, the particle diameter of raw material is 2～3cm；
C, broken after material enter squeezer, after squeezing, the moisture content of material is 45%～60%；
(2) material bacterium solution combined inoculation: use batch mixer to turn, bacterium solution is pressed with pretreated raw material
The ratio of weight ratio 1:1000 mixes；
(3) low temperature pyrogenation charing:
Bank coning heap body after turning uniformly, and heap body is passed to natural wind, in making heap body, portion is few
Measuring oxygen-containing, be in double oxygen condition, the compound bacteria of the inoculation in material is with protein degradable in material, oil
The carbohydrate such as fat, fat is nutrient source, is turned by organic chemical energy by metabolism, procreation etc.
Turn to heat energy, make the temperature of heap body maintain 70～90 DEG C.At the temperature of 70～90 DEG C and double oxygen, (heap body contains
Oxygen amount only maintains the metabolism of microorganism, procreation, and chemical energy is converted into heat energy, maintains heap temperature)
Under conditions of, cellulose, lignin and the most degradable organic matter gradually pyrolysis charring, the material in heap body
Specific surface area gradually step up.In supplementing once maintenance heap body week about, bacteria metabolism must with procreation
The carbon source of palpus and nitrogen source, supplement a moisture every other month, and the low temperature pyrogenation through 8～December carbonizes,
To the thick product of class charcoal, by using above-mentioned middle slow pyrolysis to carbonize, consume less energy than fast pyrogenation
Measure and produce more biological substance, and low temperature pyrogenation carbonization process produces without two English.
(4) pulverize: thick product is crushed to particle diameter 1～2mm；
(5) screening: using gravity screening, after removal pulverizing, in product, the non-class of big particle diameter and big density is raw
Thing charcoal material, obtains class charcoal finished product.
Described raw material is one or more in plant and animal residues, food market garbage or kitchen wet refuse.
Described bacterium solution is that bacillus cereus, Geobacillus stearothermophilus, aspergillus nidulans are according to 1:1:1
Bacterium solution volume proportion constitute composite bacteria liquid, bacteria containing amount is 1-9 × 1012Individual/ml.
Step was passed through natural wind 15 minutes every 1 hour to heap body in (3).
The carbon source and the nitrogen source that supplement in step (3) are industrial glucose and urea.
Step (3) is supplemented a moisture every other month, maintains moisture 45%～60%.
Compared with prior art, the class charcoal that the present invention prepares is pitchy powder, porous, appearance
Weight is little, specific surface area big, it is inspiratory good to absorb water.There is the cation of heat endurance, antidecomposition, superelevation
Exchange capacity and the feature of high charge density, hold abundant biochemical function group, and effective class biological carbon contains
Amount reaches 80～85%, and content of humic acid is 8～10%, a small amount of impurity and the effective microorganisms of enormous amount,
May be used for the soil remediation of heavy metal pollution, and possess following characteristics:
1, after class charcoal applies the soil of heavy metal pollution, can heavy metal ion in quick adsorption soil
(such as lead ion, cadmium ion etc.).
2, reduced the amount of heavy metal acid soluble state by adsorption and ion exchange, complexing, make gold
Belong to ion stabilized in the lattice of class charcoal chemical constitution, make leachable in soil, passive plant absorption
Heavy metal ion is greatly decreased 85～95%.
3, the animal migration to underground water and surface water body that can substantially eliminate contaminated soil is polluted, and reduces
Negative effect to Soil Biodiversity.
4, wherein humic acid can promote the fertility of soil simultaneously, in conjunction with the absorption feature of class biological carbon, and can be big
Width reduces the loss of the nutrients such as the humic acid in soil, makes soil fertility long-acting persistently.
5, wherein effective microorganisms, can promote the forward succession of soil ecology.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of preparation method of the class charcoal repaired for heavy-metal contaminated soil, employing following steps:
(1) pretreatment of raw material:
A, removal raw material, including plastics, metal, bone in plant and animal residues, food market garbage or kitchen wet refuse
Head impurity；
Raw material after b, preliminary sorting enters disintegrating machine, and after crushing, the particle diameter of raw material is 2～3cm；
C, broken after material enter squeezer, after squeezing, the moisture content of material is 45%～60%；
(2) material bacterium solution combined inoculation: use batch mixer to turn, bacterium solution is pressed with pretreated raw material
The ratio of weight ratio 1: 1000 mixes, and the bacterium solution of employing is bacillus cereus, stearothermophilus ground gemma
Bacillus, aspergillus nidulans are by the composite bacteria liquid constituted according to the bacterium solution volume proportion of 1: 1: 1, and bacteria containing amount is
1-9×1012Individual/ml；
(3) low temperature pyrogenation charing:
Bank coning heap body after turning uniformly, and heap body is passed to natural wind, right every 1 hour
It is the most oxygen-containing that heap body is passed through portion in natural wind makes heap body in 15 minutes, is in double oxygen condition, the inoculation in material
Compound bacteria with carbohydrates such as protein degradable in material, grease, fat as nutrient source, pass through
Organic chemical energy is converted into heat energy by metabolism, procreation etc., makes the temperature of heap body maintain 70～90
℃.The temperature of 70～90 DEG C and double oxygen (heap body oxygen content only maintains the metabolism of microorganism, procreation,
Chemical energy is converted into heat energy, maintains heap temperature) under conditions of, cellulose in heap body, lignin and
The most degradable organic matter gradually pyrolysis charring, the specific surface area of material gradually steps up.
Supplement week about and once maintain bacteria metabolism and the necessary carbon source of procreation and nitrogen source in heap body,
Industrial glucose and urea can be used.
Supplement a moisture every other month, maintain moisture 45%～60%.
Low temperature pyrogenation through 8～December carbonizes, and obtains the thick product of class charcoal.
(4) pulverize: thick product is crushed to particle diameter 1～2mm；
(5) screening: using gravity screening, after removal pulverizing, in product, the non-class of big particle diameter and big density is raw
Thing charcoal material, obtains class charcoal finished product.
Embodiment 2
A kind of preparation method of the class charcoal repaired for heavy-metal contaminated soil, employing following steps:
(1) pretreatment of raw material:
A, the plastics removed in plant and animal residues, food market garbage or kitchen wet refuse, metal, bone impurity；
Raw material after b, preliminary sorting enters disintegrating machine, and after crushing, the particle diameter of raw material is at 2cm；
C, broken after material enter squeezer, after squeezing, the moisture content of material is 45%；
(2) material bacterium solution combined inoculation: use batch mixer to turn, bacterium solution is pressed with pretreated raw material
The ratio of weight ratio 1: 1000 mixes, and the bacterium solution used in the present embodiment is bacillus cereus, thermophilic
The composite bacteria liquid that fat ground bacillus, aspergillus nidulans are constituted according to the bacterium solution volume proportion of 1: 1: 1, containing bacterium
Amount is 1 × 1012Individual/ml:
(3) low temperature pyrogenation charing:
Bank coning heap body after turning uniformly, and every 1 hour, heap body is passed through natural wind 15
Minute, in making heap body, portion is the most oxygen-containing, is in double oxygen condition, and the compound bacteria of the inoculation in material is with in material
The carbohydrates such as degradable protein, grease, fat are nutrient source, by metabolism, procreation etc.
Organic chemical energy is converted into heat energy, makes the temperature of heap body maintain 70 DEG C.At this temperature and double oxygen (heap
Body oxygen content only maintains the metabolism of microorganism, procreation, and chemical energy is converted into heat energy, maintains heap body temperature
Degree) under conditions of, cellulose, lignin and the most degradable organic matter gradually pyrolysis charring in heap body,
The specific surface area of material gradually steps up.Utilize industrial glucose and urea to supplement week about and once maintain heap
Internal bacteria metabolism and the necessary carbon source of procreation and nitrogen source, supplement a moisture, dimension every other month
Water holding divides 45%, and the low temperature pyrogenation through August carbonizes, and obtains the thick product of class charcoal, above-mentioned by using
Middle slow pyrolysis carbonizes, and consumes less energy than fast pyrogenation and produces more biological substance, and
Low temperature pyrogenation carbonization process produces without two English.
(4) pulverize: thick product is crushed to particle diameter 1mm；
(5) screening: using gravity screening, after removal pulverizing, in product, the non-class of big particle diameter and big density is raw
Thing charcoal material, obtains class charcoal finished product.
Embodiment 3
A kind of preparation method of the class charcoal repaired for heavy-metal contaminated soil, employing following steps:
(1) pretreatment of raw material:
A, the plastics removed in plant and animal residues, food market garbage or kitchen wet refuse, metal, bone impurity；
Raw material after b, preliminary sorting enters disintegrating machine, and after crushing, the particle diameter of raw material is at 3cm；
C, broken after material enter squeezer, after squeezing, the moisture content of material is 60%；
(2) material bacterium solution combined inoculation: use batch mixer to turn, bacterium solution is pressed with pretreated raw material
The ratio of weight ratio 1: 1000 mixes, and the bacterium solution used in the present embodiment is bacillus cereus, thermophilic
The composite bacteria liquid that fat ground bacillus, aspergillus nidulans are constituted according to the bacterium solution volume proportion of 1: 1: 1, containing bacterium
Amount is 9 × 1012Individual/ml；
(3) low temperature pyrogenation charing:
Bank coning heap body after turning uniformly, and every 1 hour, heap body is passed through natural wind 15
Minute, in making heap body, portion is the most oxygen-containing, is in double oxygen condition, and the compound bacteria of the inoculation in material is with in material
The carbohydrates such as degradable protein, grease, fat are nutrient source, by metabolism, procreation etc.
Organic chemical energy is converted into heat energy, makes the temperature of heap body maintain 90 DEG C.At this temperature and double oxygen (heap
Body oxygen content only maintains the metabolism of microorganism, procreation, and chemical energy is converted into heat energy, maintains heap body temperature
Degree) under conditions of, cellulose, lignin and the most degradable organic matter gradually pyrolysis charring in heap body,
The specific surface area of material gradually steps up.Utilize industrial glucose and urea to supplement week about and once maintain heap
Internal bacteria metabolism and the necessary carbon source of procreation and nitrogen source, supplement a moisture, dimension every other month
Water holding divides 60%, and the low temperature pyrogenation through December carbonizes, and obtains the thick product of class charcoal, on using
State the charing of middle slow pyrolysis, consume less energy than fast pyrogenation and produce more biological substance, and
And low temperature pyrogenation carbonization process produces without two English.
(4) pulverize: thick product is crushed to particle diameter 2mm；
(5) screening: using gravity screening, after removal pulverizing, in product, the non-class of big particle diameter and big density is raw
Thing charcoal material, obtains class charcoal finished product.
Application example:
1, target soil: carry out the application practice of class charcoal on the soil after cadmium pollution, in soil
Cadmium content background value is 89.3～92mg/kg.
2, test area: 4 pieces of each about 50m of area2Contaminated land, numbering 1#～4# plot respectively.
3, implementation:
1) on 1～3 plot, class charcoal cloth equably is sprinkled upon the surface of target soil.Cloth spills density
For 1m2Soil cloth spills 0.015m3The class charcoal prepared by embodiment 2,4# does not arranges in plot,
As ground control group.
2) use artificial scarifying mode, the soil of class charcoal with test top layer, plot 30cm turned uniformly,
The original place scarifying of 4# plot.
3) planting giantreed on 1#～4# plot, planting density is suitable.
4) in 4～the May and 8～9 months of giantreed growth course, carry out testing cadmium content in giantreed blade,
Data measured such as following table:
4, data analysis:
According to test the data obtained, wherein when 4～May, it is right that the average cadmium content of giantreed blade of test group only has
According to the 58.0% of group, when 8～September, the average cadmium content of giantreed blade of test group only has the 56.6% of control group；
5, interpretation of result:
Result of the test shows: in the target soil of heavy metal cadmium, uses class charcoal, can effectively reduce
Cadium In Polluted Soil can change the existing forms of Cadmium in Soil to the migration of organism, i.e. class charcoal, make with
The cadmium easily migrating form that soluble state etc. are unstable, is exchanged by class charcoal adsorption and ion, is complexed
Effect reduces the amount of heavy metal acid soluble state, makes the stable lattice in class charcoal chemical constitution of metal ion
In, heavy metal harm to organism is effectively greatly reduced.
Claims (5)
1. the preparation method of the class charcoal repaired for heavy-metal contaminated soil, it is characterised in that
The method employing following steps:
(1) pretreatment of raw material:
Plastics, metal, bone impurity in a, removal raw material；
Raw material after b, preliminary sorting enters disintegrating machine, and after crushing, the particle diameter of raw material is 2～3cm；
C, broken after material enter squeezer, after squeezing, the moisture content of material is 45%～60%；
(2) material bacterium solution combined inoculation: use batch mixer to turn, bacterium solution is pressed with pretreated raw material
The ratio of weight ratio 1:1000 mixes, and described bacterium solution is bacillus cereus, stearothermophilus ground gemma
The composite bacteria liquid that bacillus, aspergillus nidulans are constituted according to the bacterium solution volume proportion of 1:1:1, bacteria containing amount is (1-9) × 1012
Individual/ml；
(3) low temperature pyrogenation charing:
Bank coning heap body after turning uniformly, and heap body is passed to natural wind, in making heap body, portion is few
Measuring oxygen-containing, be in double oxygen condition, the temperature of heap body maintains 70～90 DEG C, supplements week about and once maintains
In heap body, bacteria metabolism and the necessary carbon source of procreation and nitrogen source, supplement a moisture every other month,
Low temperature pyrogenation through 8～December carbonizes, and obtains the thick product of class charcoal；
(4) pulverize: thick product is crushed to particle diameter 1～2mm；
(5) screening: big particle diameter and the non-class charcoal of big density in product after gravity screening is removed and pulverized
Material, obtains class charcoal finished product.
The system of a kind of class charcoal repaired for heavy-metal contaminated soil the most according to claim 1
Preparation Method, it is characterised in that described raw material is in plant and animal residues, food market garbage or kitchen wet refuse
One or more.
The system of a kind of class charcoal repaired for heavy-metal contaminated soil the most according to claim 1
Preparation Method, it is characterised in that step was passed through natural wind 15 minutes every 1 hour to heap body in (3).
The system of a kind of class charcoal repaired for heavy-metal contaminated soil the most according to claim 1
Preparation Method, it is characterised in that the carbon source and the nitrogen source that supplement in step (3) are industrial glucose and urea.
The system of a kind of class charcoal repaired for heavy-metal contaminated soil the most according to claim 1
Preparation Method, it is characterised in that supplement a moisture in step (3) every other month, maintains moisture to exist
45%～60%.
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| CN112774633A (en) * | 2021-01-15 | 2021-05-11 | 复旦大学 | Method for preparing biochar from wet garbage and application of biochar |
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