CN110373198A - A kind of bone black composite material, preparation method and application - Google Patents
A kind of bone black composite material, preparation method and application Download PDFInfo
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- CN110373198A CN110373198A CN201910677761.3A CN201910677761A CN110373198A CN 110373198 A CN110373198 A CN 110373198A CN 201910677761 A CN201910677761 A CN 201910677761A CN 110373198 A CN110373198 A CN 110373198A
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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
- C09K17/06—Calcium compounds, e.g. lime
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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
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Abstract
The invention discloses a kind of bone black composite materials comprising the mass ratio of the bone black and lime sulfur crystal powder being mutually mixed, the bone black and the lime sulfur crystal powder is 1~10:1~5.Preparation method includes: S10, provides animal bone powder, and the animal bone powder after drying is pyrolyzed under protective atmosphere and forms bone black;S20, the bone black and lime sulfur crystal powder are mixed according to the ratio that mass ratio is 1~10:1~5, prepares the bone black composite material.Bone black composite material provided by the invention is applied to the improvement of heavy metal pollution of soil, can carry out in-situ immobilization to the soil of heavy metal pollution, has good repairing effect especially for the soil of neutral and alkali heavy metal pollution.
Description
Technical field
The invention belongs to remediation contaminated soil technical fields, and in particular to a kind of bone black composite material and preparation method and
Using.
Background technique
Economic fast development and size of population surge keep global environmental pollution situation increasingly serious, wherein heavy metal-polluted soil
Have become one of main problem of environmental pollution.Heavy metal-polluted soil has high toxicity, is not easily decomposed, easily spreads and pass through food chain
The features such as passing can dramatically increase the disease incidence of the malignant diseases such as cancer, cause to seriously threaten to people's health and ecological environment.This
Outside, the quality and yield for the crop cultivated on heavy-metal contaminated soil also occur significantly decline, cause potential grain and
Food-safety problem.
Fixation in situ recovery technique is a kind of heavy metal pollution of soil Treatment process of high-efficiency and economic, by adding into soil
Enter and be passivated agent material, apply heavy metal deactivator material into soil, can by absorption, precipitating, complexing, ion exchange and
Redox etc. one is the physics, chemistry and biological effect of class, reduces the biological effectiveness and migration of heavy metal ion.
Common soil heavy metal passivant mainly includes inorganic and organic, is respectively had to the heavy metal improvement in soil
Superiority and inferiority.The passivation effect of inorganic passivator is lasting, there is directly application and long term soil and soil texture is easily caused to destroy
Larger disadvantage;Organic passivator has both heavy metal-passivated and the characteristics of improve soil physico-chemical property, but it is in soil ring
It is easily decomposed in border, passivation cannot be lasting.In addition, soil ph be influence soil nutrient availability an important factor for it
One, currently on the market for the conditioner of acid soil research and development mostly to improve based on pH value, centering basic soil repairing effect is not
Obviously;And existing neutral and alkali soil conditioner product is mostly to administer saline-alkali soil, cannot be passivated heavy metal-polluted soil well.
Summary of the invention
In view of the shortcomings of the prior art, described the present invention provides a kind of bone black composite material and preparation method
Bone black composite material is applied to the improvement of heavy metal pollution of soil, and in-situ immobilization can be carried out to the soil of heavy metal pollution, special
It is not that there is good repairing effect for the soil of neutral and alkali heavy metal pollution.
For achieving the above object, present invention employs following technical solutions:
A kind of bone black composite material comprising the bone black and lime sulfur crystal powder being mutually mixed, the bone black and institute
The mass ratio for stating lime sulfur crystal powder is 1~10:1~5.
Specifically, the bone black is by animal bone powder through pyrogenous origin, and the animal bone powder is by animal skeleton through powder
Broken formation, the animal skeleton are selected from least one of pig bone, ox bone, sheep bone, chicken bone, duck bone and fish-bone.
The present invention also provides a kind of preparation methods of bone black composite material as described above comprising:
S10, animal bone powder is provided, the animal bone powder after drying is pyrolyzed under protective atmosphere and forms bone black;
S20, the bone black and lime sulfur crystal powder are mixed according to the ratio that mass ratio is 1~10:1~5, preparation
Obtain the bone black composite material.
Wherein, the step S10 is specifically included:
The animal bone powder after drying is put into crucible, is placed in the Muffle furnace of protective atmosphere;
The Muffle furnace is warming up to scheduled pyrolysis temperature with scheduled heating rate;
It is pyrolyzed 1~3h under the scheduled pyrolysis temperature, is then cooled to room temperature to the Muffle furnace, prepares institute
State bone black.
Specifically, the scheduled pyrolysis temperature is 300~700 DEG C.
Specifically, the protective atmosphere is at least one of nitrogen, helium, neon and argon gas.
Specifically, the scheduled heating rate is 15~25 DEG C/min.
Specifically, the step S10 further include: be ground the bone black prepared.
Specifically, in the step S20, the bone black and lime sulfur crystal powder are stirred in mixing machine.
Another aspect of the present invention is to provide a kind of bone black composite material as described above and administers in heavy metal pollution of soil
In application.
Bone black composite material and preparation method provided in an embodiment of the present invention is prepared using animal bone powder as raw material through pyrolysis
Bone black material, not only oxygen-containing functional group rich in, also rich in the hydroxyapatite (Ca with porous structure5(PO4)3
(OH)2, HAP) and the nutrients composition such as calcium, phosphorus and nitrogen, carbon therein be distributed in good biocompatibility and
In the porous structure of active nature mineral hydroxyapatite, containing organic matter and the soil nutrient elements such as hydroxyl and calcium, phosphorus at
Point, become the stabilization of heavy metal-polluted soil and improve the ideal material of soil physico-chemical property, bone black has heavy metal ion relatively strong
Stablizing effect, can be precipitated by surface, forms and the heavy metal such as complexing and fragrance complexing be acted on, improve to soil with
The crystallized ability of heavy metal ion in aqueous solution.Lime sulfur crystal powder is supported on bone black material, in guaranteeing soil
Under the premise of the biological effectiveness of heavy metal ion reduces, moreover it is possible to which the direction for reducing the pH environment of soil from alkalinity to pH carries out
It is slowly mobile, there is good repairing effect for the soil of neutral and alkali heavy metal pollution.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of bone black composite material provided in an embodiment of the present invention;
Fig. 2 is the SEM figure of the ox bone charcoal of the embodiment of the present invention 1.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, with reference to the accompanying drawing to specific reality of the invention
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in attached drawing and according to
The embodiments of the present invention of attached drawing description are only exemplary, and the present invention is not limited to these embodiments.
Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
Show with closely related structure and/or processing step according to the solution of the present invention, and be omitted little with relationship of the present invention
Other details.
Present embodiments provide a kind of bone black composite material comprising the bone black and lime sulfur crystal powder being mutually mixed
The mass ratio of end, the bone black and the lime sulfur crystal powder is 1~10:1~5.
Wherein, the bone black is by animal bone powder through pyrogenous origin.Specifically, the animal bone powder refers to animal waste
Object bone or the leftover bits and pieces of meat products processing are formed through crushing, and mainly also refer to animal skeleton, the animal skeleton is for example
It is at least one of pig bone, ox bone, sheep bone, chicken bone, duck bone and fish-bone.
Refering to fig. 1, bone black composite material as described above preparation method comprising steps of
S10, animal bone powder is provided, the animal bone powder after drying is pyrolyzed to (Pintsch process) formation under protective atmosphere
Bone black.The step specifically includes:
S11, the animal bone powder after drying is put into crucible, is placed in the Muffle furnace of protective atmosphere.Wherein,
Animal skeleton after drying is ground into bone meal in being put into crucible, the protective atmosphere is nitrogen, helium, neon and argon gas
At least one of.
S12, the Muffle furnace is warming up to scheduled pyrolysis temperature with scheduled heating rate.Wherein, described scheduled
Heating rate is preferably 10~25 DEG C/min;The scheduled pyrolysis temperature is preferably 300~700 DEG C.
S13, it is pyrolyzed 1~3h under the scheduled pyrolysis temperature, is then cooled to room temperature to the Muffle furnace, preparation obtains
Obtain the bone black.
In the preferred scheme, after above step prepares bone black, also the bone black is ground, is ground
Mill allow the bone black by 60 meshes more than.
S20, the bone black and lime sulfur crystal powder are mixed according to the ratio that mass ratio is 1~10:1~5, preparation
Obtain the bone black composite material.Specifically, the bone black and lime sulfur crystal powder are stirred in mixing machine.
The passivator that bone black composite material as provided above is administered as heavy metal pollution of soil, has the following advantages:
(1), the bone black material using animal bone powder as raw material through pyrolysis preparation, carbon are distributed in good biology
In the porous structure of compatibility and active natural mineral hydroxyapatite, sought containing organic matter and the soil such as hydroxyl and calcium, phosphorus
Elemental composition is supported, the stabilization of heavy metal-polluted soil is become and improves the ideal material of soil physico-chemical property, bone black is to heavy metal ion
With stronger stablizing effect, it can be acted on, be improved by the forms such as surface precipitating, complexing and fragrance complexing and heavy metal
To the crystallized ability of heavy metal ion in soil and aqueous solution.
(2), by lime sulfur crystal (calcium polysulfide, CPS) powder load on bone black material, a huge sum of money in guaranteeing soil
Under the premise of the biological effectiveness reduction for belonging to ion, moreover it is possible to which the direction for reducing the pH environment of soil from alkalinity to pH carries out slow
It is mobile, there is good repairing effect for middle severe alkaline heavy metal contaminated soil.Further, lime sulfur crystal exists
The S discharged in soil environment2-Or HS-Indissoluble can be combined into the heavy metal (heavy metal elements such as Cd, Cu, Pb and Zn) in soil
Substance, to alleviate the pollution of basic soil heavy metal.
CPS reagent enters in soil, and growth can be first presented in soil pH and the later period reduces the pH of soil slowly, it can
The pH of basic soil is set to play the role of that improvement is presented.The following are the action modes for applying CPS and heavy metal-polluted soil into soil:
CaSx+3/2O2→CaS2O3+(x-2)S;
CaSx+CO2+H2O→CaCO3+H2S+(x-1)S;
M2++CaS2O3+H2O→MS↓+CaSO4+2H+;
M2++H2S→MS↓+2H+;
Wherein M is typical heavy metal ion, such as Cd2+、Cu2+、Pb2+And Zn2+Deng.
If using single lime sulfur crystal as soil passivator, usage amount is big, and a large amount of lime sulfur is brilliant
Body directly contacts in soil environment, can cause short time edaphon environmental disruption and cause the degeneration of soil quality.Cause
Lime sulfur crystal powder, is supported on the soil heavy metal passivant material being combined on bone black material, on the one hand may be used by this
So that soil quality is not in the damage of short time, and also help the slow conversion of soil pH;On the other hand, it is rich in nutrition
The bone black material of element can also improve the structure and environment of soil, promote the quality and fertility of soil.
(3), the preparation process of the bone black composite material is simple, low in cost, is conducive on a large scale at production and for making
For the popularization of soil passivator.Wherein, the calcium polysulfide cost in raw material is cheap, and bone black be using animal waste preparation and
At, be conducive to the recycling of resource, turn waste into wealth.
Currently, people are huge to the consumption of various cattle foods in life, the poultry of generation give up bone quantity also with
Increase.Bone is given up by Commercial cultivation in spite of part poultry, however still fails to be fully used in the presence of the useless bone resource in part,
And the bad of processing just pollutes the environment.The present invention can effectively utilize the useless bone resource of animal, can generate biggish economy
Benefit and reduce this pollution of part waste to environment.
(4), lime sulfur is also equipped with good sterilizing ability, appropriate to use the content that soil germ is effectively reduced.
Application of the bone black composite material as described above in heavy metal pollution of soil improvement, specifically may is that will be described
Bone black composite material is dispersed in water as passivator, forms uniform suspension, and suspension is imposed on soil by spray pattern
Earth may further be such that passivator comes into full contact with soil by the measures such as mixing or turn over, and thus reaching reduces in soil
The purpose of the content of heavy metal (such as Pb, Cd, Cu and Zn etc.) available state.
Embodiment 1
The bovine bone powder obtained after Os Bovis seu Bubali after drying is crushed is put into crucible, is placed in the Muffle furnace of nitrogen protection
In, 450 DEG C are warming up to the heating rate of 10 DEG C/min, then continues to be pyrolyzed 2.0h at such a temperature;Continue after the completion of pyrolysis
Logical nitrogen, makes Muffle in-furnace temperature be down to room temperature, takes out black bone black.
Fig. 2 is the SEM figure for the ox bone charcoal that the present embodiment prepares, figure it is seen that bone black material is random several
What particulate material, and tiny gap structure is presented in material surface.
The present embodiment is additionally provided prepares ox bone charcoal sample under other different pyrolytical conditions, and measures preparation and obtain
The constituent content of the ox bone charcoal sample obtained is as shown in table 1 below.
In table 1, the pyrolytical condition of ox bone charcoal sample 1 are as follows: be warming up to 300 DEG C with the heating rate of 10 DEG C/min, then exist
Continue to be pyrolyzed 3.0h at this temperature;The pyrolytical condition of ox bone charcoal sample 2 are as follows: 450 DEG C are warming up to the heating rate of 10 DEG C/min,
Then continue to be pyrolyzed 2.0h at such a temperature;The pyrolytical condition of ox bone charcoal sample 3 are as follows: be warming up to the heating rate of 25 DEG C/min
600 DEG C, then continue to be pyrolyzed 1.0h at such a temperature.
The constituent content (%) of ox bone Carbon Materials under the different pyrolytical conditions of table 1
Sample | C (wt%) | N (wt%) | O (wt%) | P (wt%) | Ca (wt%) |
Ox bone charcoal sample 1 | 41.53 | 8.30 | 22.31 | 11.29 | 16.57 |
Ox bone charcoal sample 2 | 34.26 | 8.50 | 28.64 | 11.34 | 17.26 |
Ox bone charcoal sample 3 | 23.15 | 7.56 | 31.76 | 15.13 | 22.39 |
It can be found from table 1, not only containing the carbon and oxygen element in standard biologic charcoal in bone black material, also containing a large amount of
Ca, N and P etc. are conducive to the nutrient of soil property improvement.
Embodiment 2
By crush it is dry after ox bone bone meal be put into crucible, be placed in the Muffle furnace of nitrogen protection atmosphere, with 10 DEG C/
Min is warming up to 600 DEG C, continues to be pyrolyzed 2h at such a temperature, is cooled to Muffle furnace under conditions of continuing to be passed through protective gas
Room temperature is taken out black bio charcoal solid material (ox bone charcoal), is ground up, sieved.It is later that 1:1 weighs ox bone respectively according to mass ratio
Charcoal and lime sulfur crystal powder, stirring makes the two solid powder material be uniformly mixed acquisition bone black compound in V-type batch mixer
Material.
Fuyang, Zhejiang zinc smelting factory pollution arable land topsoil (0cm~20cm) is taken, which is successively rejected
Gravel and broken, after natural air drying, mixing, pulverize, crossing the processing of 18 mesh nylon mesh, as trying soil.For trying the pH of soil
Value be 7.63, in alkalescent, moisture content 13.71%, soil available Zn and Cd content be respectively 230mg/kg and
36.9mg/kg。
30g/ parts are weighed for trying soil, is 0.5% and 2.0% point for trying soil weight according to soil passivator amount of application
The bone black composite material for also known as the present embodiment being taken to prepare, every part is added in the water of 30.0mL and disperses, and is sprayed onto for examination soil
In earth, it is uniformly mixed it.After soil stabilization culture 21 days, the test of heavy metal available state is carried out after soil is air-dried:
Soil after 10.0g is air-dried is weighed, the available state of Zn and Cd in soil is extracted with 20.0mL DTPA.Through detecting, contaminated soil is through bone
The biologically effective state content of carbon composite heavy metal in soil Zn and Cd before and after the processing is as shown in table 2 below.
Table 2 is for the soil conditions before and after examination soil application soil passivator (bone black composite material)
Embodiment 3
By crush it is dry after ox bone bone meal be put into crucible, be placed in the Muffle furnace of nitrogen protection atmosphere, with 25 DEG C/
Min is warming up to 600 DEG C, continues to be pyrolyzed 1h at such a temperature, is cooled to Muffle furnace under conditions of continuing to be passed through protective gas
Room temperature is taken out black bio charcoal solid material (ox bone charcoal), is ground up, sieved.It is later that 3:1 weighs ox bone respectively according to mass ratio
Charcoal and lime sulfur crystal powder, stirring makes the two solid powder material be uniformly mixed acquisition bone black compound in V-type batch mixer
Material.
Fuyang, Zhejiang zinc smelting factory pollution arable land topsoil (0cm~20cm) is taken, which is successively rejected
Gravel and broken, after natural air drying, mixing, pulverize, crossing the processing of 18 mesh nylon mesh, as trying soil.For trying the pH of soil
Value be 7.63, in alkalescent, moisture content 13.71%, soil available Zn and Cd content be respectively 230mg/kg and
36.9mg/kg。
30g/ parts are weighed for trying soil, is 0.5% and 2.0% point for trying soil weight according to soil passivator amount of application
The bone black composite material for also known as the present embodiment being taken to prepare, every part is added in the water of 30.0mL and disperses, and is sprayed onto for examination soil
In earth, it is uniformly mixed it.After soil stabilization culture 21 days, the test of heavy metal available state is carried out after soil is air-dried:
Soil after 10.0g is air-dried is weighed, the available state of Zn and Cd in soil is extracted with 20.0mL DTPA.Through detecting, contaminated soil is through bone
The biologically effective state content of carbon composite heavy metal in soil Zn and Cd before and after the processing is as shown in table 3 below.
Table 3 is for the soil conditions before and after examination soil application soil passivator (bone black composite material)
Embodiment 4
By crush it is dry after ox bone bone meal be put into crucible, be placed in the Muffle furnace of nitrogen protection atmosphere, with 15 DEG C/
Min is warming up to 600 DEG C, continues to be pyrolyzed 2h at such a temperature, is cooled to Muffle furnace under conditions of continuing to be passed through protective gas
Room temperature is taken out black bio charcoal solid material (ox bone charcoal), is ground up, sieved.It is later that 1:1 weighs ox bone respectively according to mass ratio
Charcoal and lime sulfur crystal powder, stirring makes the two solid powder material be uniformly mixed acquisition bone black compound in V-type batch mixer
Material.
Tongling, Anhui Province somewhere copper tailing topsoil (0cm~20cm) is taken, which is successively carried out to reject gravel and broken
Root natural air drying, is mixed, is pulverized, after the processing of 18 mesh nylon mesh excessively, as trying soil.PH value for trying soil is 7.12,
It is in neutrality, moisture content 5.71%, Available Cu content are 598.0mg/kg.
30g/ parts are weighed for trying soil, is 0.5% and 2.0% point for trying soil weight according to soil passivator amount of application
The bone black composite material for also known as the present embodiment being taken to prepare, every part is added in the water of 30.0mL and disperses, and is sprayed onto for examination soil
In earth, it is uniformly mixed it.After soil stabilization culture 21 days, the test of heavy metal available state is carried out after soil is air-dried:
Soil after 10.0g is air-dried is weighed, the available state of copper in soil is extracted with 20.0mL DTPA.Through detecting, contaminated soil is multiple through bone black
The biologically effective state content of heavy metal copper in soil is as shown in table 4 below before and after condensation material.
Table 4 is for the soil conditions before and after examination soil application soil passivator (bone black composite material)
Embodiment 5
By crush it is dry after ox bone bone meal be put into crucible, be placed in the Muffle furnace of nitrogen protection atmosphere, with 10 DEG C/
Min is warming up to 500 DEG C, continues to be pyrolyzed 3h at such a temperature, is cooled to Muffle furnace under conditions of continuing to be passed through protective gas
Room temperature is taken out black bio charcoal solid material (ox bone charcoal), is ground up, sieved.It is later that 2:1 weighs ox bone respectively according to mass ratio
Charcoal and lime sulfur crystal powder, stirring makes the two solid powder material be uniformly mixed acquisition bone black compound in V-type batch mixer
Material.
Tongling, Anhui Province somewhere copper tailing topsoil (0cm~20cm) is taken, which is successively carried out to reject gravel and broken
Root natural air drying, is mixed, is pulverized, after the processing of 18 mesh nylon mesh excessively, as trying soil.PH value for trying soil is 7.12,
It is in neutrality, moisture content 5.71%, Available Cu content are 598.0mg/kg.
30g/ parts are weighed for trying soil, is 0.5% and 2.0% point for trying soil weight according to soil passivator amount of application
The bone black composite material for also known as the present embodiment being taken to prepare, every part is added in the water of 30.0mL and disperses, and is sprayed onto for examination soil
In earth, it is uniformly mixed it.After soil stabilization culture 21 days, the test of heavy metal available state is carried out after soil is air-dried:
Soil after 10.0g is air-dried is weighed, the available state of copper in soil is extracted with 20.0mL DTPA.Through detecting, contaminated soil is multiple through bone black
The biologically effective state content of heavy metal copper in soil is as shown in table 5 below before and after condensation material.
Table 5 is for the soil conditions before and after examination soil application soil passivator (bone black composite material)
It should be noted that be all that ox bone charcoal is selected to be illustrated as specific embodiment in above embodiments, this field
The content recorded according to specification of technical staff, the ox bone charcoal in each embodiment can be replaced with into other animal bone chars,
Such as pig bone, sheep bone, chicken bone, duck bone and fish-bone etc., the effect of preparation process and acquirement are all with using ox bone phase
As.
The above is only the specific embodiment of the application, it is noted that for the ordinary skill people of the art
For member, under the premise of not departing from the application principle, several improvements and modifications can also be made, these improvements and modifications are also answered
It is considered as the protection scope of the application.
Claims (10)
1. a kind of bone black composite material, which is characterized in that including the bone black and lime sulfur crystal powder being mutually mixed, the bone
The mass ratio of charcoal and the lime sulfur crystal powder is 1~10:1~5.
2. bone black composite material according to claim 1, which is characterized in that the bone black is to be given birth to by animal bone powder through pyrolysis
At, the animal bone powder be by animal skeleton through crush is formed, the animal skeleton selected from pig bone, ox bone, sheep bone, chicken bone,
At least one of duck bone and fish-bone.
3. a kind of preparation method of bone black composite material as claimed in claim 1 or 2 characterized by comprising
S10, animal bone powder is provided, the animal bone powder after drying is pyrolyzed under protective atmosphere and forms bone black;
S20, the bone black and lime sulfur crystal powder are mixed according to the ratio that mass ratio is 1~10:1~5, is prepared
The bone black composite material.
4. the preparation method of bone black composite material according to claim 3, which is characterized in that the step S10 is specifically wrapped
It includes:
The animal bone powder after drying is put into crucible, is placed in the Muffle furnace of protective atmosphere;
The Muffle furnace is warming up to scheduled pyrolysis temperature with scheduled heating rate;
It is pyrolyzed 1~3h under the scheduled pyrolysis temperature, is then cooled to room temperature to the Muffle furnace, prepares the bone
Charcoal.
5. the preparation method of bone black composite material according to claim 4, which is characterized in that the scheduled pyrolysis temperature
It is 300~700 DEG C.
6. the preparation method of bone black composite material according to claim 4, which is characterized in that the protective atmosphere is nitrogen
At least one of gas, helium, neon and argon gas.
7. the preparation method of bone black composite material according to claim 4, which is characterized in that the scheduled heating rate
For 15~25 DEG C/min.
8. the preparation method of bone black composite material according to claim 4, which is characterized in that the step S10 further include:
The bone black prepared is ground.
9. the preparation method of bone black composite material according to claim 3, which is characterized in that in the step S20, by institute
It states bone black and lime sulfur crystal powder is stirred in mixing machine.
10. a kind of application of bone black composite material as claimed in claim 1 or 2 in heavy metal pollution of soil improvement.
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