CN107857674A - Oyster shell soil-repairing agent and preparation method thereof - Google Patents
Oyster shell soil-repairing agent and preparation method thereof Download PDFInfo
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- CN107857674A CN107857674A CN201711085753.7A CN201711085753A CN107857674A CN 107857674 A CN107857674 A CN 107857674A CN 201711085753 A CN201711085753 A CN 201711085753A CN 107857674 A CN107857674 A CN 107857674A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F3/00—Fertilisers from human or animal excrements, e.g. manure
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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
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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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- C09K2101/00—Agricultural use
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Abstract
The invention discloses a kind of oyster shell soil-repairing agent, the oyster shell soil-repairing agent includes component A and component B；Wherein component A is oyster shell powder, and component B is agricultural fibre discarded object, the mixture of pig manure.The ratio of the component A and component B are 15 30%wt:70 85%wt, it is preferably in a proportion of 20 40%wt:60 80%wt.The content of organic matter >=90% of oyster shell soil-repairing agent of the present invention, N P and K total content >=8%, calcium content >=6%, heavy metal Cd, Pb, Cr clearance >=85%.The invention also discloses a kind of method for preparing above-mentioned soil-repairing agent.Raw material sources of the present invention are extensive and technique is simple, are not required to the consersion unit of complexity, and its agronomical value, social value are notable.
Description
Technical field
The invention belongs to technical field of biological environmental protection, and in particular to a kind of oyster shell soil-repairing agent and preparation method thereof.
Background technology
The many Soils In The Regions in China are by serious heavy metal pollution, and content of beary metal has exceeded III in soil and river
Class standard, and contaminated area is constantly expanding, pollution level is also being aggravated；Such as radio and television system mine tailing area, Delta of the Pearl River portion
Divide section etc., its heavy metal biological availability is high, larger potential hazard to the ecosystem around be present.According to ring in 2014
Border protection portion and the national Investigation of Soil Pollution publication of Ministry of Land and Resources's issue show that the national total exceeding standard rate of heavy metal-polluted soil is
16.1%, wherein slightly, slightly, moderate and serious pollution point position ratio be respectively 11.2%, 2.3%, 1.5% and 1.1%.It is dirty
Type is contaminated based on inorganic type, and organic type takes second place, and compound pollution proportion is smaller；Exceeded digit of inorganic pollution accounts for all super
The 82.8% of punctuation bit.Illustrate that heavy metal pollution of soil has turned into the matter of utmost importance of China's soil pollution.
Heavy metal cadmium and its compound are respectively provided with certain toxicity, once cause Japanese " itai-itai " pollution nuisance event
Pollution sources.And according to national Investigation of Soil Pollution publication, in cadmium, mercury, arsenic, copper, lead, chromium, zinc, the heavy metal species pollutant of nickel 8,
Cadmium pollution ranks first, and it is put position exceeding standard rate and reaches 7%.Meanwhile cadmium is also an important pollutant of Farmland contamination.A soil huge sum of money
The reparation problem of category has caused the great attention of society.
Oyster shell is made up of inanimate matter and organic matter two parts.The main component of wherein inanimate matter is calcium carbonate, is accounted for complete
The 88.59%~99.20% of chitin composition, the content of calcium is about 40% or so.Additionally containing copper, iron, zinc, manganese, saw, chromium,
Nickel, lead, mercury, sodium, magnesium, potassium, aluminium, silicon etc. is micro or trace element.Organic matter accounts for the 3%~5% of oyster shell quality, mainly into
It is amino acid to divide, including 17 kinds of amino acid such as L-aminobutanedioic acid, glycine, isoleucine.According to its generation type and institutional framework
Difference, oyster shell can be divided into 3 layers：One layer of outermost be cuticula or cortex (periostracum, contain conchiolin, it is right
The corrosion of extraneous chemically article has stronger resistance；Centre is prismatic layer (prismaticlayer, by polygonal prismatic
The calcareous deposit of crystallization is formed, the hole containing a large amount of 2-10um；Internal layer is nacre (pearl layer, mainly by calcite
Form, can progressive additive, with the increase at oyster age, the level of nacre also can be more.Oyster shell is due to this
Special physique, various organic matter and the inanimate matter compositions contained along with it, can be as in general adsorbent
Heavy metal ion is adsorbed, and its main component is calcium carbonate, the interaction mechanism between calcium carbonate and heavy metal ion is main
Be included in concentration of heavy metal ion it is higher when the precipitation reaction that occurs, and handed in the ion of the relatively low generation of concentration of heavy metal ion
Change and surface complexation.At present, scholar is provided again according to the organic composition and property of oyster shell using crushing, modification technology to it
Sourceization is using a series of exploration is carried out, such as calcium additive, soil conditioner, heavy metal adsorption removal, sewage disposal material
Material etc., production and application is had been put into some, but its added value is relatively low, and modification technology is mainly forged using 950 DEG C of high temperature above
Burn, addition chemical reagent method, industrial device requires high, and easily produces secondary gaseous contamination and water pollution, and improvement takes
With big, the cost of industrialization is big.
Subcritical technology is a kind of new and high technology developed in recent years, refer to heat the water to boiling point (100 DEG C,
More than 0.1MPa), below, and control system pressure makes water be maintained as liquid for critical point (374.2 DEG C, 22.1MPa).Due to Asia
Critical has acid-base catalysis performance in itself, and because it has high heat endurance, low dielectric constant, low viscosity and height
The advantages that diffusivity, it is a kind of suitable reaction medium, organic matter can be rapidly decomposed into small-molecule substance using it, such as
CO2、H2O etc., and decompose it is complete, reaction terminate rear product can carry out Selective Separation, it is pollution-free, without wastewater treatment etc., no
Any secondary pollution can be caused to environment, had a good application prospect.
The content of the invention
It is an object of the invention to provide a kind of oyster shell soil-repairing agent and preparation method thereof.To achieve the above object, originally
Invention adopts the following technical scheme that：
A kind of oyster shell soil-repairing agent, including component A and component B, wherein,
Component A is oyster shell powder；
Component B is agricultural fibre discarded object, the mixture of pig manure.
The ratio of the component A and component B are 15-30%wt:70-85%wt.
The ratio of agriculture fiber wastes and pig manure is 20-40%wt in the component B:60-80%wt.
The particle diameter of the component A is less than 2mm；
Agricultural fibre discarded object in the component B includes wood chip, stalk, mushroom slag etc..
The content of organic matter >=90% of the soil-repairing agent, N P and K total content >=8%, calcium content >=6%, to a huge sum of money
Belong to Cd, Pb, Cr clearance >=85%.
Another object of the present invention is to provide a kind of preparation method of above-mentioned oyster shell soil-repairing agent, including following step
Suddenly：
(1) component A preparation：Oyster shell is cleaned, removes silt；It will be carried out in oyster shell input pyroreaction kettle subcritical
Hydrolysis；Pressure release discharges；Crushing material after subcritical hydrolysis is obtained into the component A for the powder less than 2mm.
(2) component B preparation：Agricultural fibre element discarded object is mixed in proportion with pig manure, obtains mixture；Gained is mixed
Subcritical hydrolysis is carried out in compound input pyroreaction kettle；Pressure release discharges；100 DEG C of drying 2h；By gained subcritical hydrolysis product
Crush and obtain component B for the powder less than 2mm；
(3) gained component A and component B are mixed in proportion and produces the oyster shell soil-repairing agent.
Subcritical hydrolysis condition in the step (1) is 200 DEG C -250 DEG C, pressure 1.5-3.2Mpa of temperature, during processing
Between be 30min-60 min.
Subcritical hydrolysis condition in the step (2) is 160 DEG C -200 DEG C, pressure 0.5-2.0Mpa of temperature, during processing
Between be 10min-30 min.
The advantage of the invention is that：
Treatment technology currently with oyster shell is mostly chemical modification or 500 DEG C of high-temperature process；The present invention utilizes subcritical
Technology for hydrolyzing is handled oyster shell, and organic matter is degraded to small-molecule substance in oyster shell, and the mechanics for destroying shell is tough
Property framework, make subsequent treatment eased, while promote porous formation, increase micropore area, improve oyster shell heavy metal
Adsorptivity.
Component B mixed in proportion with pig manure by agricultural fibre discarded objects such as wood chip, stalk, mushroom slags after through subcritical hydrolysis work
Skill processing forms, its content of organic matter >=90%, N P and K total content >=6%, middle trace element >=1%, seed germination index
>=110%.
The organic fertilizer that oyster shell powder and agricultural fibre discarded object, pig manure etc. are prepared is prepared by mixing into by the present invention
Oyster shell soil-repairing agent；Wherein oyster shell powder due to its small volume, micropore quantity it is big, therefore compared to traditional oyster shell
Heavy metal absorbent product, it has bigger micropore area, and heavy metal adsorption greatly promotes.The present invention is by oyster shell powder
End is combined with organic components B, and prepared soil-repairing agent can also substantially improve while heavy metal contaminants are adsorbed
Soil nutrient composition.
Raw material sources of the present invention are extensive and technique is simple, are not required to the consersion unit of complexity, and its agronomical value, social value show
Write.
Brief description of the drawings
The clearance of Fig. 1 oyster shell powder foot couple difference heavy metals；
Influence of Fig. 2 heavy metals addition to oyster shell powder heavy metal removing rate；
Influence of Fig. 3 heavy metals addition to oyster shell powder heavy metal adsorption rate；
Influence of Fig. 4 heavy metals initial concentration to oyster shell powder heavy metal removing rate；
Influence of Fig. 5 heavy metals initial concentration to oyster shell powder heavy metal adsorption rate；
Embodiment
It is following further explaination to be done to the present invention in conjunction with specific embodiments.
The preparation of the component A oyster shell powder of embodiment 1
1.1 preparation method
Component A preparation：Oyster shell is cleaned, removes silt；Oyster shell is put into pyroreaction kettle and carries out subcritical water
Solution, subcritical hydrolysis condition is 200 DEG C -250 DEG C, pressure 1.5-3.2Mpa, processing time 30min-60min of temperature；Pressure release
Discharging；Crushing material after subcritical hydrolysis is obtained into the component A for the powder less than 2mm.
1.1.1 the influence of heavy metal is adsorbed in subcritical hydrolysis processing to oyster shell powder under different temperatures
By treatment of different temperature (respectively at normal temperature and pressure, 200 DEG C of 1.5Mpa；250℃3.2Mpa；300 DEG C of 4.4Mpa conditions
Lower processing 1h) oyster shell grind after excessively a diameter of 2mm sieve, it is respectively 1mg/L's to weigh oyster shell powder to be added to concentration
In Cd, Pb, Cr, Zn heavy metal solution, the final volume for controlling solution is 50mL, and the addition of oyster shell powder is 5g/L, molten
The initial pH of liquid is 6, is vibrated at normal temperatures, stands 12h.After standing adsorption, filter, cross 0.22 μm of film, the sample profit prepared
Elementary analysis detection is carried out with inductive coupling plasma emission spectrograph.
1.1.2 identical subcritical hydrolysis condition Different treatments adsorb the influence of heavy metal to oyster shell powder
Sample 1 is ground after being 250 DEG C of processing 1h, and sample 2 is first to grind oyster shell, then 250 DEG C of processing 1h.Two samples
Excessively a diameter of 2mm sieve, weighs quantitative oyster shell powder after drying, be added to Cd, Pb, Cr that concentration is respectively 1mg/L,
In Zn, Cu heavy metal solution, the final volume for controlling solution is 50mL, and the initial pH of solution is 6, is vibrated at normal temperatures, is stood
2h.After standing adsorption, filter, cross 0.22 μm of film, the sample prepared is entered using inductive coupling plasma emission spectrograph
Row element analysis detection.
1.1.3 Different adding amount adsorbs the influence of heavy metal to oyster shell powder
After 250 DEG C of processing 1h, after grinding and excessively a diameter of 2mm sieve is prepared into oyster shell powder, according to 1g/L, 5g/L,
10g/L, 50g/L addition add Cd, Pb, Cr, Zn, Cu heavy metal solution (concentration of each heavy metal is respectively 10mg/L),
The final volume for controlling solution is 50mL, pH 5, is vibrated at normal temperatures, stands 12h.Sample filtering is taken out, crosses 0.22 μm
Film, the sample prepared carries out elementary analysis detection using inductive coupling plasma emission spectrograph, to be not added with adsorbent
Solution is as blank control.
1.1.4 the initial concentration of different heavy metals adsorbs the influence of heavy metal to oyster shell powder
After 250 DEG C of processing 1h, after grinding and excessively a diameter of 2mm sieve is prepared into oyster shell powder, according to 10g/L addition
Amount adds Cd, Pb, Cr, Zn, Cu heavy metal solution, and the concentration of each heavy metal is respectively 1mg/L, 10mg/L, 100mg/L, is controlled
The final volume of solution is 50mL, pH 5, is vibrated at normal temperatures, stands 12h.Sample filtering is taken out, crosses 0.22 μm of film, system
The sample got ready carries out elementary analysis detection using inductive coupling plasma emission spectrograph, to be not added with the solution of adsorbent work
For blank control.
1.2 results are with discussing
1.2.1 treatment of different temperature adsorbs the influence of heavy metal to oyster shell powder
Test result indicates that under 200 DEG C and 250 DEG C for the treatment of conditions, Cd, Pb, Cr, Zn clearance are all higher than control
The clearance of group, wherein Cd is 76.25%, and 16.67% is improved than control；Pb clearance is 87.61%, is improved than control
1.9%；Cr clearance is 86.96%, and 32.58% is improved than control group.It can be seen that after subcritical hydrolysis is handled,
The adsorption capacity of oyster shell heavy metal can be improved, its reason be probably high-temperature and high-pressure conditions within the specific limits promote it is male
Oyster shell forms porous tubular structure, and there is a certain degree of increase in absorption aperture.
The influence of removing heavy metals is gone in subcritical hydrolysis processing to oyster shell powder under the different temperatures of table 1
1.2.2 Different adding amount adsorbs the influence of heavy metal to oyster shell powder
Test result indicates that (sample 1) is ground under the conditions of identical subcritical hydrolysis, after first high-temperature process with first grinding
The adsorption capacity difference of two kinds of pretreatment mode heavy metals of high-temperature process (sample 2) is larger afterwards, grinding pair after high-temperature process
The clearance of heavy metal high-temperature process apparently higher than after first grinding, Cd, Pb, Cr, Zn, Cu of sample 1 clearance are than sample 2
Heavy metal removing rate has been respectively increased 53.35%, 24.62%, 8.81%, 44.89%, 22.64%, it is seen that is utilizing oyster shell
Prepare the technological process of soil-repairing agent so can not only improve the removal of heavy metal using being crushed after first high-temperature process
Rate, but also broken efficiency can be improved, it is organic big just because of these because oyster shell contains 3%~5% organic matter
The presence of molecule, the mechanical property of oyster shell is set to improve several orders of magnitude than common calcium carbonate, at subcritical hydrolysis
After reason, organic metallic substance of oyster shell is dissolved, and greatly reduces the mechanical stiffness of oyster shell, so as to be more prone to broken.
2 mutually synthermal different disposal of table goes the influence of removing heavy metals to oyster shell powder
| Clearance | Cd | Pb | Cr | Zn | Cu |
| Sample 1：Ground after first high-temperature process | 76.25% | 87.61% | 86.96% | 72.83% | 63.14% |
| Sample 2：High-temperature process after first grinding | 22.90% | 63.00% | 78.15% | 27.94% | 40.50% |
| Sample 1 is than 2 increased percentage of sample | 53.35% | 24.62% | 8.81% | 44.89% | 22.64% |
| Adsorbance mg/g | Cd | Pb | Cr | Zn | Cu |
| Ground after first high-temperature process | 141.21 | 162.25 | 161.04 | 134.87 | 116.92 |
| High-temperature process after first grinding | 42.41 | 116.66 | 144.73 | 51.74 | 74.99 |
1.2.3 different heavy metal additions adsorb the influence of heavy metal to oyster shell powder
From Fig. 2, Fig. 3 and table 3, with the increase of oyster shell powder addition, its heavy metal Cd, Pb, Cr, Zn, Cu
Adsorption rate, which is presented, first rises the changing rule that tends to be steady afterwards, the clearance of heavy metal can reach 87.36%, 98.68%,
98.67%th, 81.16%, 80.51%.Adsorbance then shows the trend being gradually reduced with the increase of oyster shell powder addition,
Illustrate that oyster shell powder absorption heavy metal belongs to physical absorption, after unit mass adsorption site reaches saturation, the raising of addition
Adsorbance can not be improved.In order to preferably adsorb heavy metal and improve adsorption efficiency (selection high adsorption rate and high absorption simultaneously
The addition of amount reaches effect), it is 1g/L~5g/L to remove heavy metal Pb, Cr, Zn, Cu suggestion addition in solution.
The Different adding amount of table 3 goes the influence of removing heavy metals to oyster shell powder
1.2.4 different initial concentrations adsorb the influence of heavy metal to oyster shell powder
The trend reduced with the increase of concentration is presented by Fig. 5 and the clearance of the visible oyster shell heavy metal of table 4.
In low concentration (1 mg/L) heavy metal solution, addition 5g/L, pH be under 6 treatment conditions, its heavy metal Cd, Pb, Cr,
Zn, Cu clearance can reach 95.99%, 90.72%, 88.13%, 93.22%, 59.60%.In high concentration (100mg/L) weight
In metallic solution, Cd, Pb, Cr, Zn, Cu saturated extent of adsorption are respectively 6.84,7.09,8.73,6.95,8.06mg/g, by result
Understand, absorption of the oyster shell powder to this 5 heavy metal species ion meets pseudo-second order kinetic equation and Langmuir Isothermal Models.
4 different initial concentrations of table go the influence of removing heavy metals to oyster shell powder
1.3 conclusion
(1) after subcritical hydrolysis is handled, the adsorption capacity of oyster shell heavy metal can be improved.At 200 DEG C and 250
DEG C treatment conditions under, Cd, Pb, Cr, Zn clearance is all higher than control group, and wherein Cd clearance is 76.25%, than control
Improve 16.67%；Pb clearance is 87.61%, and 1.9% is improved than control；Cr clearance is 86.96%, is compared
32.58% is improved according to group.
(2) crushed after the technological process that soil-repairing agent is prepared using oyster shell can use first high-temperature process, so not
The clearance of heavy metal can be only improved, but also broken efficiency can be improved, because oyster shell contains 3%~5%
Organic matter, just because of the presence of these organic macromolecules, make oyster shell mechanical property improved than common calcium carbonate it is several
The individual order of magnitude, after subcritical hydrolysis is handled, organic metallic substance of oyster shell is dissolved, and greatly reduces the mechanics of oyster shell
Hardness, so as to be more prone to broken.Oyster shell grinds the clearance of (sample 1) heavy metal apparently higher than elder generation after high-temperature process
High-temperature process (sample 2) after grinding, Cd, Pb, Cr, Zn, Cu of sample 1 clearance are distinguished than the heavy metal removing rate of sample 2
Improve 53.35%, 24.62%, 8.81%, 44.89%, 22.64%.
(3) as the increase of oyster shell powder addition, its heavy metal Cd, Pb, Cr, Zn, Cu clearance reach as high as
To 87.36%, 98.68%, 98.67%, 81.16%, 80.51%.In order to preferably adsorb heavy metal and improve absorption simultaneously
Efficiency, if removing Cd, it is proposed that addition is 5g/L~10g/L, and the suggestion addition for removing Pb, Cr, Zn, Cu is 1g/L~5g/
L。
The trend reduced with the increase of concentration is presented in the clearance of oyster shell heavy metal.At low concentration (1mg/L)
In heavy metal solution, its heavy metal Cd, Pb, Cr, Zn, Cu clearance can reach 95.99%, 90.72%, 88.13%,
93.22%th, 59.60%.In high concentration (100mg/L) heavy metal solution, Cd, Pb, Cr, Zn, Cu saturated extent of adsorption are respectively
6.84th, 7.09,8.73,6.95,8.06mg/g, from result, absorption of the oyster shell powder to this 5 heavy metal species ion meets
Pseudo-second order kinetic equation and Langmuir Isothermal Models.
The component B of embodiment 2 preparation
2.1 preparation method
Component B preparation：Agricultural fibre element discarded object is mixed in proportion respectively with pig manure, obtains mixture；By gained
Subcritical hydrolysis is carried out in mixture input pyroreaction kettle, and subcritical hydrolysis condition is 160 DEG C -200 DEG C of temperature, pressure 0.5-
2.0Mpa, processing time 10min-30min；Pressure release discharges；100 DEG C of drying 2h；Gained subcritical hydrolysis product is crushed and is
Powder less than 2mm obtains component B.
Wherein, sample 1：Agricultural fibre element discarded object:Pig manure=20%wt:80%wt；Subcritical hydrolysis condition is：200
DEG C, 2.0MPa；
Sample 2：Agricultural fibre element discarded object:Pig manure=50%wt:50%wt；Subcritical hydrolysis condition is：200 DEG C,
2.0MPa
Component B nutrition content is determined, its result is as shown in table 5, table 6：
The nutrient of table 5 determines (%)
| Numbering | The content of organic matter | Nitrogen content | Potassium content | Phosphorus content | N P and K total nutrient | pH |
| Sample 1 | 92.41 | 3.70 | 1.74 | 1.29 | 6.73 | 5.95 |
| Sample 2 | 95.12 | 1.93 | 0.58 | 0.52 | 3.03 | 4.93 |
Determination of trace element (%) in table 6
| Numbering | Ca | Fe | Mn | B | Cu | Zn | Six kinds of element summations |
| 4 | 0.931 | 0.091 | 0.016 | 0.002 | 0.022 | 0.023 | 1.085 |
In low concentration (1mg/L) heavy metal solution, when component B addition is 5g/L, pH is under 6 treatment conditions,
Heavy metal adsorption before being hydrolyzed to sample 1 and after hydrolysis is probed into.As a result show, as shown in table 7, by hydrolysis process
Afterwards, the adsorption capacity of mixture heavy metal substantially increases, and the adsorbance that Cd adsorbance improves 68.4%, Pb improves
1 times, Cr adsorbance improves 36.9%.
Heavy metal adsorption determines before and after the subcritical hydrolysis of 7 sample of table 1
After the hydrolysis of sample 1 Cd, Pb, Cr, heavy metal solution are added according to 1g/L, 5g/L, 10g/L, 50g/L addition
(concentration of each heavy metal is respectively 10mg/L), the final volume for controlling solution is 50mL, pH 5, is vibrated at normal temperatures, is stood
12h.Sample filtering is taken out, crosses 0.22 μm of film, the sample prepared is carried out using inductive coupling plasma emission spectrograph
Elementary analysis detects, and the solution to be not added with adsorbent is used as blank control.
It is visible with the increase of mixture addition after hydrolysis, its heavy metal Cd, Pb, Cr, Zn, Cu adsorption rate by table 8
Present and first rise the changing rule that tends to be steady afterwards, the clearance of heavy metal can reach 78.35%, 90.88%,
64.72%.
Heavy metal removing rate determines after the sub-critical treatment of 8 sample of table 1
The oyster shell soil-repairing agent 1 of embodiment 3
(1) component A preparation：Oyster shell is cleaned, removes silt；It will be carried out in oyster shell input pyroreaction kettle subcritical
Hydrolysis, subcritical hydrolysis condition is 220 DEG C, pressure 2.6Mpa, processing time 30min of temperature；Pressure release discharges；By subcritical water
Crushing material after solution obtains the component A for the powder less than 2mm.
(2) component B preparation：Agricultural fibre element discarded object is mixed in proportion with pig manure, obtains mixture；Gained is mixed
Subcritical hydrolysis is carried out in compound input pyroreaction kettle, subcritical hydrolysis condition is 200 DEG C, pressure 2.0Mpa of temperature, processing
Time is 20min；Pressure release discharges；100 DEG C of drying 2h；Gained subcritical hydrolysis product is crushed and obtained for the powder less than 2mm
Component B；
(3) by gained component A and component B by weight component A:Component B=15%:85% mixes and produces the oyster shell
Soil-repairing agent.The nutrition content of the soil-repairing agent is determined, as shown in table 9.
After measured, the soil-repairing agent content of organic matter >=90%, N P and K total content >=8%, calcium content >=6% are right
Clearance >=85% of heavy metal Cd, Pb, Cr.
The nutrition content measure (%) of the soil-repairing agent 1 of table 9
| Sequence number | pH | Organic matter | Nitrogen (N) | Phosphorus (P2O5) | Potassium (K2O) | Total nutrient |
| Soil-repairing agent | 7.75 | 93.10% | 4.43% | 3.16% | 2.15% | 9.74% |
The Determination of trace elements (%) of the soil-repairing agent 1 of table 10
| Element term | Ca | Fe | Mn | B | Cu | Zn |
| Content | 6.83 | 0.15 | 0.03 | 0.01 | 0.06 | 0.05 |
The heavy metal pollution of soil renovation agent 1 of preparation is added in low concentration (1mg/L) heavy metal solution (pH 6),
Addition is 50g/L.The final volume for controlling solution is 50mL, and the initial pH of solution is 6, is vibrated at normal temperatures, stands 2h.Stand
After absorption, filter, cross 0.22 μm of film, the sample prepared enters row element point using inductive coupling plasma emission spectrograph
Analysis detection.Testing result show soil-repairing agent 1 be respectively 88.93% to Cd, Pb, Cr clearance, 99.76%,
98.45%.
The heavy metal removing rate of the soil-repairing agent 1 of table 11
Planting effect：The soil-repairing agent 1 of preparation is with field soil with 1：Plantation passion fruit after 15 ratio mixing, as a result shows
Show, the growth of passion fruit can be promoted, the leaf than the passion fruit of control group (field soil) plantation has more 5 leaves, and bud green, and plant height is high
Go out 6.8cm.
The oyster shell soil-repairing agent 2 of embodiment 4
(1) component A preparation：Oyster shell is cleaned, removes silt；It will be carried out in oyster shell input pyroreaction kettle subcritical
Hydrolysis, subcritical hydrolysis condition is 240 DEG C, pressure 3.0Mpa, processing time 30min of temperature；Pressure release discharges；By subcritical water
Crushing material after solution obtains the component A for the powder less than 2mm.
(2) component B preparation：Agricultural fibre element discarded object is mixed in proportion with pig manure, obtains mixture；Gained is mixed
Subcritical hydrolysis is carried out in compound input pyroreaction kettle, subcritical hydrolysis condition is 180 DEG C, pressure 1.2Mpa of temperature, processing
Time is 30min；Pressure release discharges；100 DEG C of drying 2h；Gained subcritical hydrolysis product is crushed and obtained for the powder less than 2mm
Component B；
(3) by gained component A and component B by weight component A:Component B=25%:75% mixes and produces the oyster shell
Soil-repairing agent.
The oyster shell soil-repairing agent 3 of embodiment 5
(1) component A preparation：Oyster shell is cleaned, removes silt；It will be carried out in oyster shell input pyroreaction kettle subcritical
Hydrolysis, subcritical hydrolysis condition is 200 DEG C, pressure 3.2Mpa, processing time 60min of temperature；Pressure release discharges；By subcritical water
Crushing material after solution obtains the component A for the powder less than 2mm.
(2) component B preparation：Agricultural fibre element discarded object is mixed in proportion with pig manure, obtains mixture；Gained is mixed
Subcritical hydrolysis is carried out in compound input pyroreaction kettle, subcritical hydrolysis condition is 160 DEG C, pressure 2.0Mpa of temperature, processing
Time is 10min；Pressure release discharges；100 DEG C of drying 2h；Gained subcritical hydrolysis product is crushed and obtained for the powder less than 2mm
Component B；
(3) by gained component A and component B by weight component A:Component B=20%:80% mixes and produces the oyster shell
Soil-repairing agent.
The oyster shell soil-repairing agent 4 of embodiment 6
(1) component A preparation：Oyster shell is cleaned, removes silt；It will be carried out in oyster shell input pyroreaction kettle subcritical
Hydrolysis, subcritical hydrolysis condition is 250 DEG C, pressure 3.2Mpa, processing time 40min of temperature；Pressure release discharges；By subcritical water
Crushing material after solution obtains the component A for the powder less than 2mm.
(2) component B preparation：Agricultural fibre element discarded object is mixed in proportion with pig manure, obtains mixture；Gained is mixed
Subcritical hydrolysis is carried out in compound input pyroreaction kettle, subcritical hydrolysis condition is 190 DEG C, pressure 1.6Mpa of temperature, processing
Time is 30min；Pressure release discharges；100 DEG C of drying 2h；Gained subcritical hydrolysis product is crushed and obtained for the powder less than 2mm
Component B；
(3) by gained component A and component B by weight component A:Component B=40%:60% mixes and produces the oyster shell
Soil-repairing agent.
Claims (8)
- A kind of 1. oyster shell soil-repairing agent, it is characterised in that including component A and component B, wherein,Component A is oyster shell powder；Component B is agricultural fibre discarded object, the mixture of pig manure.
- 2. a kind of oyster shell soil-repairing agent according to claim 1, it is characterised in that the ratio of the component A and component B Example is 15-30%wt:70-85%wt.
- 3. a kind of oyster shell soil-repairing agent according to claim 1 or 2, it is characterised in that agricultural is fine in the component B The ratio for tieing up discarded object and pig manure is 20-40%wt:60-80%wt.
- A kind of 4. oyster shell soil-repairing agent according to claim 1 or 2, it is characterised in thatThe particle diameter of the component A is less than 2mm；Agricultural fibre discarded object in the component B includes wood chip, stalk, mushroom slag.
- A kind of 5. oyster shell soil-repairing agent according to claim 1, it is characterised in that the soil-repairing agent it is organic Matter content >=90%, N P and K total content >=8%, calcium content >=6%, heavy metal Cd, Pb, Cr clearance >=85%.
- 6. the preparation method of oyster shell soil-repairing agent described in a kind of claim 1-5, it is characterised in that comprise the following steps：(1) component A preparation：Oyster shell is cleaned, removes silt；Oyster shell is put into pyroreaction kettle and carries out subcritical water Solution；Pressure release discharges；Crushing material after subcritical hydrolysis is obtained into the component A for the powder less than 2mm.(2) component B preparation：Agricultural fibre element discarded object is mixed in proportion with pig manure, obtains mixture；By gained mixture Subcritical hydrolysis is carried out in input pyroreaction kettle；Pressure release discharges；100 DEG C of drying 2h；Gained subcritical hydrolysis product is crushed Component B is obtained for the powder less than 2mm；(3) gained component A and component B are mixed in proportion and produces the oyster shell soil-repairing agent.
- A kind of 7. preparation method of oyster shell soil-repairing agent according to claim 6, it is characterised in that the step (1) the subcritical hydrolysis condition in is 200 DEG C -250 DEG C, pressure 1.5-3.2Mpa, processing time 30min-60min of temperature.
- A kind of 8. preparation method of oyster shell soil-repairing agent according to claim 6, it is characterised in that the step (2) the subcritical hydrolysis condition in is 160 DEG C -200 DEG C, pressure 0.5-2.0Mpa, processing time 10min-30min of temperature.
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| CN110149832A (en) * | 2019-05-16 | 2019-08-23 | 沈阳农业大学 | Cadmium method drops in a kind of rice drop cadmium conditioner and rice |
| CN111334308A (en) * | 2020-04-20 | 2020-06-26 | 深圳市芭田生态工程股份有限公司 | Soil heavy metal passivator, preparation method thereof and soil remediation method |
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