CN106867541A - A kind of environment-friendly type heavy metal renovation agent and its application and slow release heavy metal remediation fertilizer - Google Patents
A kind of environment-friendly type heavy metal renovation agent and its application and slow release heavy metal remediation fertilizer Download PDFInfo
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- CN106867541A CN106867541A CN201710101309.3A CN201710101309A CN106867541A CN 106867541 A CN106867541 A CN 106867541A CN 201710101309 A CN201710101309 A CN 201710101309A CN 106867541 A CN106867541 A CN 106867541A
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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
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
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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
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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
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
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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
- C09K2101/00—Agricultural use
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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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Abstract
The invention provides a kind of environment-friendly type heavy metal renovation agent and its application and slow release heavy metal remediation fertilizer, belong to remediation of heavy metal-contaminated soil field.The present invention includes first level flour, second patent flour, three-level powder and level Four powder, respectively cross the screenings of 200-400 mesh sieves, 100-150 mesh sieves, 20-80 mesh sieves and 10-18 mesh sieves, and in percentage by weight, its weight accounts for 15-25%, 10-20%, 55-68%, 5-10% of heavy metal renovation agent total amount respectively；Heavy metal renovation agent be as oyster shell through protectiveness be calcined after carry out grinding obtained in, sintering temperature be 600~800 DEG C, roasting time be 8~12min, oyster shell enter roasting apparatus flow be 0.2~0.4m3/ min, the rotating speed of roasting apparatus is 25~35r/min.The present invention can effectively repair the main soil by cadmium pollution, with strong points, advantages of good adsorption effect.
Description
Technical field
The present invention relates to remediation of heavy metal-contaminated soil field, repaiied in particular to a kind of environment-friendly type heavy metal
Multiple agent and its application and slow release heavy metal remediation fertilizer.
Background technology
Effect of natural conditions and long-term high intensity farming are largely to cause soil texture variation, nutrient to lose using quick-acting fertilizer
Weighing apparatus, soil fertility decline, while soil severe acidification is also resulted in, so as to influence the validity of fertilizer.And, it is various industrial wastewaters, useless
It is also increasingly severe that gas etc. causes that heavy metal in soil (cadmium, chromium, mercury, lead) pollutes.The heavy metal one side shadow such as cadmium, chromium, mercury, lead
The normal growth of crop is rung, another side is entered into crop, influence health.
Coastal area abounds with oyster, and the disposal of oyster shell has turned into serious environmental problem.Main component is in oyster shell
Calcium carbonate, it is slightly soluble in water and is in alkalescence, can be effectively improved the phenomenon of soil acidification, and improve the calcareous soil of shortage and
The effect of harmful heavy metal ions (cadmium, chromium, mercury, lead) in passivation soil.
In order to obtain the repairing effect of better heavy metal contaminated soil, researcher to by the use of oyster shell as
The method of conditioner raw material passivation heavy metal in soil is improved, and can be roughly divided into three classes：The first kind is to be processed into
Be used in mixed way with other soil conditioning compositions (such as calcium oxide, chitosan powder, calcium superphosphate etc.) after powder, by oyster shell with
Other adsorbents use cooperatively to improve the repairing effect of heavy metal contaminated soil；Equations of The Second Kind is that powder is modified, example
Powder is modified using CNT such as, modified powder is obtained；3rd class is to prepare nano composite material using powder, example
Reduction reaction is carried out in source of iron solution obtain Nanoscale Iron/oyster shell composite such as by powder.
Although the above method improves the repairing effect of conditioner heavy metal contaminated soil to a certain extent,
The preparation process of above-mentioned heavy metal renovation agent it is sufficiently complex, it is necessary to raw material it is more, production cost is higher, and low yield, warp
Ji benefit is not high.Meanwhile, the situation of the The Heavy Metal Contaminated Soil of different regions is different, for example, the regional soil having is main
Be based on lead contamination, the regional soil that has be mainly based on cadmium pollution, and existing heavy metal renovation agent specific aim is not
By force, repairing effect need further raising.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of environment-friendly type heavy metal renovation agent, in particular for based on cadmium pollution
The heavy metal renovation agent of soil, it can effectively repair the main soil by cadmium pollution, products material is simple, low manufacture cost,
And with strong points, the advantages of good adsorption effect of product, especially to the adsorption effect of cadmium.
The second object of the present invention is to provide a kind of slow release heavy metal remediation fertilizer, and it can be as chemical fertilizer application
The soil by heavy metal pollution can also be repaired simultaneously, especially the main soil by cadmium pollution.
The third object of the present invention is to provide above-mentioned environment-friendly type heavy metal renovation agent to prepare slow release heavy metal reparation
Application in fertilizer, it take oyster shell as the coating of raw material for preparing slow-release fertilizer, environmental protection, pollution-free, thus obtained slow-release fertilizer
The soil by heavy metal pollution can also be repaired, especially the main soil by cadmium pollution.
What embodiments of the invention were realized in：
A kind of environment-friendly type heavy metal renovation agent, heavy metal renovation agent is prepared from by raw material of oyster shell, and it includes
First level flour, second patent flour, three-level powder and level Four powder, first level flour were the screenings of 200-400 mesh sieves, and second patent flour was 100-
The screenings of 150 mesh sieves, three-level powder was the screenings of 20-80 mesh sieves, and level Four powder was the screenings of 10-18 mesh sieves, and
And in percentage by weight, first level flour accounts for the 15-25% of heavy metal renovation agent total amount, and it is total that second patent flour accounts for heavy metal renovation agent
The 10-20% of amount, three-level powder accounts for the 55-68% of heavy metal renovation agent total amount, and level Four powder accounts for the 5- of heavy metal renovation agent total amount
10%；Foregoing heavy metal renovation agent be as oyster shell through protectiveness be calcined after carry out grinding obtained in, protectiveness roasting roasting
Temperature is 600~800 DEG C, and roasting time is 8~12min, and the flow that oyster shell enters roasting apparatus is 0.2~0.4m3/ min,
The rotating speed of roasting apparatus is 25~35r/min.
A kind of slow release heavy metal remediation fertilizer, preparing the raw material of the slow-release fertilizer includes major ingredient and is used to be made the auxiliary of coating
Material, major ingredient includes at least one in organic fertilizer, potash fertilizer and boron fertilizer, and auxiliary material includes above-mentioned heavy metal renovation agent.
Application of the above-mentioned environment-friendly type heavy metal renovation agent in slow release heavy metal remediation fertilizer is prepared.
The beneficial effect of the embodiment of the present invention is：
The present invention using oyster shell be raw material as repair receive heavy metal pollution soil, by the particle diameter distribution of oyster shell powder
Pointedly repair the soil based on cadmium pollution, with strong points, advantages of good adsorption effect, and heavy metal renovation agent of the invention into
Divide single so that product preparation section is simple, low manufacture cost.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that can be obtained by commercially available purchase.
At present, the Study on adsorption properties on oyster shell Adsorption of Heavy Metals includes the temperature when dosage of oyster shell powder, absorption
The influence of the adsorption effect of the factor heavy metal such as degree, initial pH, adsorption time, by preferably going out optimum dosage, suction
Temperature, initial pH and adsorption time when attached etc., to obtain more excellent adsorption effect.At present for oyster shell in heavy metal
Application in terms of contaminated soil remediation, the oyster shell powder for generally using single particle size is repaired, but due to differently
The situation by heavy metal pollution in area is different, and the oyster shell powder of single particle size is irregular for the heavy metal adsorption effect of different regions
Uneven, specific aim is not strong, and effect is unsatisfactory.
In addition to temperature when dosage except the foregoing oyster shell powder for referring to, absorption etc. has an impact to adsorption effect, this hair
A person of good sense have been surprisingly found that the absorption of the particle size heavy metal of oyster shell also has an impact, and influence obvious, while entering
One step finds that the difference that the lower oyster shell powder for constituting of different-grain diameter distribution shows to the adsorption capacity of different heavy metals is obvious, leads to
The particle diameter distribution for changing oyster shell powder is crossed, is obtained specifically designed for the heavy metal renovation agent by the serious soil of cadmium pollution, this is with much money
For the heavy metal renovation agent that category renovation agent is constituted compared to the oyster shell powder that single particle size is distributed, its adsorption effect is more preferably bright
It is aobvious.
According to the first aspect of the invention, there is provided a kind of environment-friendly type heavy metal renovation agent, it is with oyster shell as former
Material is prepared from, and it includes first level flour, second patent flour, three-level powder and level Four powder, under first level flour was the sieve of 200-400 mesh sieves
Thing, second patent flour was the screenings of 100-150 mesh sieves, and three-level powder was the screenings of 20-80 mesh sieves, and level Four powder was 10-
The screenings of 18 mesh sieves, and in percentage by weight, first level flour accounts for the 15-25% of heavy metal renovation agent total amount, second patent flour
The 10-20% of heavy metal renovation agent total amount is accounted for, three-level powder accounts for the 55-68% of heavy metal renovation agent total amount, and level Four powder accounts for a huge sum of money
Belong to the 5-10% of renovation agent total amount；Foregoing heavy metal renovation agent be as oyster shell through protectiveness be calcined after carry out grinding obtained in,
The sintering temperature of protectiveness roasting is 600-800 DEG C, and roasting time is 8-12min, and oyster shell enters the flow of roasting apparatus
It is 0.2-0.4m3/ min, the rotating speed of roasting apparatus is 25-35r/min.
The inventors discovered that particle size range oyster shell powder compared to other particle sizes of the oyster shell in 20-80 mesh, its
Heavy metal cadmium adsorption effect in a short time (such as in 1h) is more protruded, therefore, the embodiment of the present invention is with particle diameter
The three-level powder of 20-80 mesh is attached most importance to the main component of metal repair, and it can first occur passivation reaction, be used for heavy metal cadmium
Adsorbed for the most heavy metal cadmium of content in soil so that the phase can quickly, effectively before administration for heavy metal renovation agent
There is passivation reaction in ground, improve adsorption efficiency with cadmium.Meanwhile, the present embodiment is equipped with first level flour, second patent flour and level Four powder again, with
Heavy metal renovation agent applies the later stage and continues passivation, and heavy metal cadmium is persistently adsorbed, so as to improve whole heavy metal repair
The adsorption rate of multiple agent heavy metal cadmium, extend heavy metal renovation agent applies cycle, reduces cost.
Preferably, above-mentioned first level flour was the screenings of 300-400 mesh sieves, and second patent flour was the sieve of 120-140 mesh sieves
Lower thing, three-level powder was the screenings of 30-60 mesh sieves, and level Four powder was the screenings of 10-16 mesh sieves, and according to weight hundred
Divide than meter, first level flour accounts for the 18-22% of heavy metal renovation agent total amount, and second patent flour accounts for the 12-16% of heavy metal renovation agent total amount,
Three-level powder accounts for the 58-62% of heavy metal renovation agent total amount, and level Four powder accounts for the 7-8% of heavy metal renovation agent total amount.
It is highly preferred that above-mentioned first level flour was the screenings of 320-360 mesh sieves, second patent flour was 130-140 mesh sieves
Screenings, three-level powder was the screenings of 40-50 mesh sieves, and level Four powder was the screenings of 10-14 mesh sieves, and according to weight
Percentages, first level flour accounts for the 18.5-19.2% of heavy metal renovation agent total amount, and second patent flour accounts for heavy metal renovation agent total amount
14-14.6%, three-level powder accounts for the 59.3-60% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal renovation agent total amount
7.5-7.8%.
Most preferably, above-mentioned first level flour was the screenings of 350 mesh sieves, and second patent flour was the screenings of 136 mesh sieves, three-level
Powder was the screenings of 48 mesh sieves, and level Four powder was the screenings of 12 mesh sieves, and in percentage by weight, first level flour accounts for weight
The 18.5% of metal repair total amount, second patent flour accounts for the 14% of heavy metal renovation agent total amount, and it is total that three-level powder accounts for heavy metal renovation agent
The 60% of amount, level Four powder accounts for the 7.5% of heavy metal renovation agent total amount.
The heavy metal renovation agent of the embodiment of the present invention includes first level flour, second patent flour, the three-level powder and four of different-grain diameter size
Level powder, the mixed powder that formation is made up of different-grain diameter, and by adjusting the proportioning of every kind of oyster shell powder, obtain and be directed to cadmium
The heavy metal of the heavy-metal contaminated soil based on pollution repairs agent prescription, with strong points, is compared with existing heavy metal renovation agent,
Compounded without being modified or adding other adsorbents to oyster shell again, can just obtain the preferable absorption effect to cadmium
Really.
Further, the method for the preparation environment-friendly type heavy metal renovation agent of the embodiment of the present invention is comprised the following steps：
Step 1-1：Pretreatment
Before being calcined to oyster shell, first oyster shell can be pre-processed.Pretreatment includes：Cleaning, coarse crushing and
Sorting.The impurity that oyster shell surface will be remained in by cleaning is removed, and oyster shell is carried out into simple crushing by coarse crushing, with convenient
Follow-up grinding, is removed, improve product quality by sorting the rope for hanging culture oyster that will be remained on oyster shell.
Step 1-2：Protectiveness is calcined
Oyster shell after will be broken carries out protectiveness roasting in roasting apparatus.The signified protectiveness roasting of the embodiment of the present invention
Burning refers to by controlling sintering temperature, roasting time, the roasting of nutritional ingredient and micro- poly- pore structure in oyster shell being retained as much as possible
Burning mode.Specifically, by oyster shell sintering temperature be 600~800 DEG C, roasting time be 8~12min under conditions of roasted
Burn.Because the sintering temperature of the embodiment of the present invention is relatively low, therefore, it can retain the nutriment in oyster shell to greatest extent,
And avoid micro- poly- pore structure from destroying.
Being calcined by protectiveness can also increase the micro- poly- pore structure of oyster shell powder, specific surface area increase, so that
The ability enhancing of oyster shell powder Adsorption of Heavy Metals.And it is calcined by the protectiveness of 600~800 DEG C, 8~12min and causes oyster
The micro- poly- hole size of shell powder changes, and is allowed to form the micro- poly- pore structure being adapted with heavy metal cadmium ion, by protectiveness
The size in the micro- poly- hole after calcination activation is just slightly less than the diameter of cadmium ion, so as under the attraction of molecular force by cadmium from
Son absorption finally realizes the reparation of heavy metal contaminated soil in micro- poly- hole.
Further, in roasting, the flow for controlling oyster shell to enter roasting apparatus is 0.2~0.4m3/ min, roasting sets
Standby rotating speed is 25~35r/min.By the rotating speed of further control oyster shell flow and roasting apparatus so that in oyster shell
Active ingredient is fully converted, while the micro- poly- pore structure and trace element that are prevented effectively from oyster shell are destroyed.
Further, it is 8~12min for 600~800 DEG C, roasting time by controlling sintering temperature so that after roasting
Water content in oyster shell is maintained in the range of 8-10%, and water content is maintained in the range of this and is conducive to subsequently crushing
During can both control oyster shell particle size, and ensure the completion of micro- poly- pore structure and avoid nutritional trace element
Loss.
Step 1-3：Cooling treatment
Roasting material after to being calcined through protectiveness carries out cooling treatment.Specifically, the oyster shell and zeolite after roasting are entered
Row cools down 10~15min for the first time, and cooling is to be cooled down in its natural state for the first time, and making the temperature of roasting material is carried out tentatively
Cooling, then carries out second 10~15min of cooling to roasting material with the rate of temperature fall of 15~25 DEG C/min.
Oyster shell has micro- poly- pore structure, and in their crystal, molecule connects together as building a framework, and centre is formed
Many cavitys.There are many hydrones in these cavitys, these moisture can be ejected when high temperature is run into, but in temperature-fall period
In it can also again reuptake water or other liquid.Therefore, the embodiment of the present invention is by cooling treatment modes different twice
The oyster shell after roasting is set to cool down completely, the aqueous vapor that the oyster shell after roasting can be avoided to suck again in air again.
When just beginning to cool down, because oyster shell temperature is higher, the moisture in air has little time just to be evaporated by oyster shell absorption, because
This by the way of natural cooling, can reduce cooling cost in first time cooling treatment, at the same avoid it is right because quickly cooling down
The infringement of roasting apparatus.When oyster shell temperature is reduced to a timing, then carried out second with the rate of temperature fall of 15~25 DEG C/min
Cooling treatment, so as to rapidly reduce the temperature of oyster shell, makes oyster shell cool down completely, it is to avoid the water in oyster shell absorption air
Point.Preferably, can be cooled down by liquid nitrogen when second cooling treatment is carried out.
Step 1-4：Crush
Oyster shell after cooling is crushed, and the oyster shell powder of different-grain diameter size is filtered out by selection by winnowing, will not
Allocated according to aforementioned weight percentage with the heavy metal renovation agent of particle size, to obtain for preparing for cadmium pollution soil
The heavy metal renovation agent of earth.
A kind of the second aspect of the invention, there is provided slow release heavy metal remediation fertilizer, prepares the raw material bag of the slow-release fertilizer
Include major ingredient and auxiliary material, major ingredient includes at least one in organic fertilizer, potash fertilizer and boron fertilizer, for example, organic fertilizer or organic fertilizer and its
Any combination of his three.Organic fertilizer is selected from the one kind in following fertilizer：Fecaluria fertilizer, compost made of stalks and green manure.The embodiment of the present invention
Organic fertilizer, potash fertilizer and boron fertilizer be it is commercially available.Auxiliary material includes above-mentioned heavy metal renovation agent.
Further, in the preferred embodiment, the weight ratio of above-mentioned major ingredient and auxiliary material is (1.5-3)：1.
In the proportion, the membrane wrapping thickness that auxiliary material is formed on the surface of the particle prepared by major ingredient is in 45-55g/m2In the range of,
Membrane wrapping thickness is moderate, can either ensure that slow-release fertilizer has good slow release effect, at the same avoid again because coating is too thin cannot be real
Existing slow release effect.
Further, in the preferred embodiment, above-mentioned heavy metal renovation agent accounts for the 46- of the gross weight of auxiliary material
52%.
Further, in the preferred embodiment, above-mentioned auxiliary material also includes humic acid and binding agent, and humic acid is accounted for
The 30-35% of the gross weight of auxiliary material, binding agent accounts for the 15-20% of the gross weight of auxiliary material, and binding agent includes powder of straw and is modified
Starch.Preferably, the weight ratio of powder of straw and modified starch is 1：1.
Humic acid (BHA), mainly by the remains of animals and plants, by a series of geochemical processes and microorganism
The natural organic substance for decomposing and being formed after converting, with the oxygen-content active such as carboxyl, quinonyl, phenolic hydroxyl group and alcoholic extract hydroxyl group functional group.
Humic acid has the features such as improving utilization rate of fertilizer, enhancing crop anti-adversity, improved soil microbial profile, the embodiment of the present invention
It is added with humic acid as one of auxiliary material beneficial to the structure for improving the soil by heavy metal pollution, increases beneficial micro- life in soil
The content of bacterium, maintains soil Carbon balance.
The humic acid of the embodiment of the present invention is different from humic acid prepared by traditional handicraft, and it is with crop material, fowl and animal excrement
With waste paper pulp be raw material, by crop material and fowl and animal excrement it is clipped, crush after mix with waste paper pulp, through hydrolysis, concentrate,
Fermentation is remixed to be obtained.Raw material need not consume the reagents such as substantial amounts of industrial soda acid in degradation process, whole preparation process without
The reaction condition of high temperature, high pressure, and all raw materials are needed both from discarded object, production cost can either be reduced and reduced producing
Technology difficulty, while environmental protection again, economizes on resources.
The modified starch of the present embodiment is to form oxidized starch after adding hydrogen peroxide in starch fluid, adds ring
Oxygen chloropropane modifying agent is aoxidized-is crosslinked composite modified starch and formed.Processed through hydrogen peroxide and epoxychloropropane modified dose
Starch fluid afterwards, its good film-forming property, meanwhile, modified starch mix with powder of straw after as binding agent, be conducive to by major ingredient system
Into particle surface film forming, improve fertilizer slow release effect.Being additionally, since the embodiment of the present invention and being provided without resin carries out coating,
It is environment friendly and pollution-free.
The preparation method of the slow release heavy metal remediation fertilizer of the embodiment of the present invention is comprised the following steps：
Step 2-1：Prepare major ingredient particle
Particle is prepared into by raw material of at least one in organic fertilizer, potash fertilizer and boron fertilizer.When the step is carried out, can
Carried out with according to the conventional steps for preparing fertiliser granulates, or directly bought on the market.
Step 2-2：Prepare auxiliary material
The humic acid and binding agent of the embodiment of the present invention are taken, wherein humic acid accounts for the 30-35% of the gross weight of auxiliary material, glued
Knot agent accounts for the 15-20% of the gross weight of auxiliary material.Humic acid and binding agent are mixed according to aforementioned weight percentage in mixer
After be prepared into slurry, it is stand-by.
Step 2-3：Film forming
Preferred infiltration centrifugal process prepares slow-release fertilizer in embodiments of the present invention.Specifically, according to major ingredient and the weight of auxiliary material
Than being (1.5-3)：1 ratio, the major ingredient particle that will be prepared into by step 2-1 is placed in afore-mentioned slurry and infiltrates, and stirs, so
Additional size is separated with major ingredient particle by centrifugation afterwards, in centrifugal process, addition accounts for the 46-52% of the gross weight of auxiliary material
The embodiment of the present invention heavy metal renovation agent so that heavy metal renovation agent sticks to particle surface, through drying go after obtain final product it is slow
Release fertilizer.
Further, film forming can be carried out using disk or rotary drum coating method in other embodiments of the invention, while
Disk or the further film forming of rotary drum coating method can also be added after infiltration centrifugal process prepares slow-release fertilizer, improve slow-release fertilizer particle strong
Degree and particle sphericity.
The slow-release fertilizer of the embodiment of the present invention use degradable crop material, waste paper pulp, fowl and animal excrement and starch for
Raw material is made coating, environment friendly and pollution-free, had good sustained release effect, at the same the embodiment of the present invention add prepared by different oyster shell powders and
Into heavy metal renovation agent, it can also repair contaminated by heavy metals soil while as Term Fertilization, with good
Economic benefit.
The third aspect of the invention, environment-friendly type heavy metal renovation agent answering in slow release heavy metal remediation fertilizer is prepared
With its slow release that can either improve slow-release fertilizer, while can be adsorbed with heavy metal, repairs the soil by heavy metal pollution
Earth.
Embodiment
Embodiment 1-1
By oyster shell after pretreatment sintering temperature be 600 DEG C, roasting time be 12min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.2m3/ min, the rotating speed of roasting apparatus is 25r/min.After roasting, oyster shell
In water content be 10% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively,
Wherein, the natural cooling time of first time cooling treatment is 10min, and the condition of the second cooling treatment is with the cooling of 15 DEG C/min
Speed carries out cooling 15min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 200 mesh sieves, and second patent flour was the screenings of 100 mesh sieves, and three-level powder was the screenings of 20 mesh sieves,
Level Four powder was the screenings of 18 mesh sieves, and in percentage by weight, first level flour accounts for the 15% of heavy metal renovation agent total amount,
Second patent flour accounts for the 10% of heavy metal renovation agent total amount, and three-level powder accounts for the 68% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal
The 7% of renovation agent total amount.
Embodiment 1-2
By oyster shell after pretreatment sintering temperature be 650 DEG C, roasting time be 10min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.3m3/ min, the rotating speed of roasting apparatus is 30r/min.After roasting, oyster shell
In water content be 9.5% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively,
Wherein, the natural cooling time of first time cooling treatment is 14min, and the condition of the second cooling treatment is with the cooling of 17 DEG C/min
Speed carries out cooling 11min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 220 mesh sieves, and second patent flour was the screenings of 120 mesh sieves, and three-level powder was the screenings of 30 mesh sieves,
Level Four powder was the screenings of 10 mesh sieves, and in percentage by weight, first level flour accounts for the 18% of heavy metal renovation agent total amount,
Second patent flour accounts for the 17% of heavy metal renovation agent total amount, and three-level powder accounts for the 55% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal
The 10% of renovation agent total amount.
Embodiment 1-3
By oyster shell after pretreatment sintering temperature be 680 DEG C, roasting time be 8min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.35m3/ min, the rotating speed of roasting apparatus is 35r/min.After roasting, oyster
Water content in shell is 9% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively,
Wherein, the natural cooling time of first time cooling treatment is 12min, and the condition of the second cooling treatment is with the cooling of 20 DEG C/min
Speed carries out cooling 10min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 240 mesh sieves, and second patent flour was the screenings of 140 mesh sieves, and three-level powder was the screenings of 40 mesh sieves,
Level Four powder was the screenings of 14 mesh sieves, and in percentage by weight, first level flour accounts for the 15% of heavy metal renovation agent total amount,
Second patent flour accounts for the 10% of heavy metal renovation agent total amount, and three-level powder accounts for the 65% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal
The 10% of renovation agent total amount.
Embodiment 1-4
By oyster shell after pretreatment sintering temperature be 700 DEG C, roasting time be 10min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.3m3/ min, the rotating speed of roasting apparatus is 25r/min.After roasting, oyster shell
In water content be 8.5% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively,
Wherein, the natural cooling time of first time cooling treatment is 10min, and the condition of the second cooling treatment is with the cooling of 22 DEG C/min
Speed carries out cooling 10min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 260 mesh sieves, and second patent flour was the screenings of 100 mesh sieves, and three-level powder was the screenings of 50 mesh sieves,
Level Four powder was the screenings of 15 mesh sieves, and in percentage by weight, first level flour accounts for the 25% of heavy metal renovation agent total amount,
Second patent flour accounts for the 12% of heavy metal renovation agent total amount, and three-level powder accounts for the 58% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal
The 5% of renovation agent total amount.
Embodiment 1-5
By oyster shell after pretreatment sintering temperature be 720 DEG C, roasting time be 8min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.4m3/ min, the rotating speed of roasting apparatus is 30r/min.After roasting, oyster shell
In water content be 8% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively, its
In, the natural cooling time of first time cooling treatment is 15min, and the condition of the second cooling treatment is with the cooling speed of 25 DEG C/min
Rate carries out cooling 10min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 300 mesh sieves, and second patent flour was the screenings of 120 mesh sieves, and three-level powder was the screenings of 60 mesh sieves,
Level Four powder was the screenings of 18 mesh sieves, and in percentage by weight, first level flour accounts for the 15% of heavy metal renovation agent total amount,
Second patent flour accounts for the 20% of heavy metal renovation agent total amount, and three-level powder accounts for the 57% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal
The 8% of renovation agent total amount.
Embodiment 1-6
By oyster shell after pretreatment sintering temperature be 750 DEG C, roasting time be 8min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.4m3/ min, the rotating speed of roasting apparatus is 20r/min.After roasting, oyster shell
In water content be 8% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively, its
In, the natural cooling time of first time cooling treatment is 12min, and the condition of the second cooling treatment is with the cooling speed of 20 DEG C/min
Rate carries out cooling 15min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 320 mesh sieves, and second patent flour was the screenings of 140 mesh sieves, and three-level powder was the screenings of 40 mesh sieves,
Level Four powder was the screenings of 12 mesh sieves, and in percentage by weight, first level flour accounts for the 15% of heavy metal renovation agent total amount,
Second patent flour accounts for the 12% of heavy metal renovation agent total amount, and three-level powder accounts for the 68% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal
The 5% of renovation agent total amount.
Embodiment 1-7
By oyster shell after pretreatment sintering temperature be 780 DEG C, roasting time be 10min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.4m3/ min, the rotating speed of roasting apparatus is 35r/min.After roasting, oyster shell
In water content be 8% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively, its
In, the natural cooling time of first time cooling treatment is 15min, and the condition of the second cooling treatment is with the cooling speed of 20 DEG C/min
Rate carries out cooling 10min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 340 mesh sieves, and second patent flour was the screenings of 150 mesh sieves, and three-level powder was the screenings of 50 mesh sieves,
Level Four powder was the screenings of 16 mesh sieves, and in percentage by weight, first level flour accounts for the 25% of heavy metal renovation agent total amount,
Second patent flour accounts for the 12% of heavy metal renovation agent total amount, and three-level powder accounts for the 58% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal
The 5% of renovation agent total amount.
Embodiment 1-8
By oyster shell after pretreatment sintering temperature be 600 DEG C, roasting time be 10min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.3m3/ min, the rotating speed of roasting apparatus is 30r/min.After roasting, oyster shell
In water content be 8% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively, its
In, the natural cooling time of first time cooling treatment is 10min, and the condition of the second cooling treatment is with the cooling speed of 18 DEG C/min
Rate carries out cooling 15min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 350 mesh sieves, and second patent flour was the screenings of 120 mesh sieves, and three-level powder was the screenings of 40 mesh sieves,
Level Four powder was the screenings of 14 mesh sieves, and in percentage by weight, first level flour accounts for the 18% of heavy metal renovation agent total amount,
Second patent flour accounts for the 12% of heavy metal renovation agent total amount, and three-level powder accounts for the 62% of heavy metal renovation agent total amount, and level Four powder accounts for heavy metal
The 8% of renovation agent total amount.
Embodiment 1-9
By oyster shell after pretreatment sintering temperature be 650 DEG C, roasting time be 10min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.35m3/ min, the rotating speed of roasting apparatus is 35r/min.After roasting, oyster
Water content in shell is 9% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively,
Wherein, the natural cooling time of first time cooling treatment is 15min, and the condition of the second cooling treatment is with the cooling of 16 DEG C/min
Speed carries out cooling 12min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 360 mesh sieves, and second patent flour was the screenings of 140 mesh sieves, and three-level powder was the screenings of 50 mesh sieves,
Level Four powder was the screenings of 12 mesh sieves, and in percentage by weight, first level flour accounts for heavy metal renovation agent total amount
18.5%, second patent flour accounts for the 14.6% of heavy metal renovation agent total amount, and three-level powder accounts for the 59.3% of heavy metal renovation agent total amount, level Four
Powder accounts for the 7.6% of heavy metal renovation agent total amount.
Embodiment 1-10
By oyster shell after pretreatment sintering temperature be 650 DEG C, roasting time be 10min under conditions of carry out protectiveness
Roasting, during charging, controls the flow of oyster shell for 0.35m3/min, and the rotating speed of roasting apparatus is 35r/min.After roasting, oyster
Water content in shell is 9% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively,
Wherein, the natural cooling time of first time cooling treatment is 15min, and the condition of the second cooling treatment is with the cooling of 16 DEG C/min
Speed carries out cooling 12min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 350 mesh sieves, and second patent flour was the screenings of 136 mesh sieves, and three-level powder was the screenings of 48 mesh sieves,
Level Four powder was the screenings of 12 mesh sieves, and in percentage by weight, first level flour accounts for heavy metal renovation agent total amount
18.5%, second patent flour accounts for the 14% of heavy metal renovation agent total amount, and three-level powder accounts for the 60% of heavy metal renovation agent total amount, and level Four powder is accounted for
The 7.5% of heavy metal renovation agent total amount.
Embodiment 1-11
By oyster shell after pretreatment sintering temperature be 700 DEG C, roasting time be 12min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.4m3/ min, the rotating speed of roasting apparatus is 35r/min.After roasting, oyster shell
In water content be 8% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively, its
In, the natural cooling time of first time cooling treatment is 15min, and the condition of the second cooling treatment is with the cooling speed of 16 DEG C/min
Rate carries out cooling 12min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 360 mesh sieves, and second patent flour was the screenings of 140 mesh sieves, and three-level powder was the screenings of 50 mesh sieves,
Level Four powder was the screenings of 14 mesh sieves, and in percentage by weight, first level flour accounts for heavy metal renovation agent total amount
19.2%, second patent flour accounts for the 14% of heavy metal renovation agent total amount, and three-level powder accounts for the 59.3% of heavy metal renovation agent total amount, level Four powder
Account for the 7.5% of heavy metal renovation agent total amount.
Embodiment 1-12
By oyster shell after pretreatment sintering temperature be 700 DEG C, roasting time be 12min under conditions of carry out protectiveness
Roasting, during charging, the flow for controlling oyster shell is 0.4m3/ min, the rotating speed of roasting apparatus is 35r/min.After roasting, oyster shell
In water content be 8% (percentage by weight).Oyster shell is carried out first time cooling treatment and second cooling treatment respectively, its
In, the natural cooling time of first time cooling treatment is 15min, and the condition of the second cooling treatment is with the cooling speed of 16 DEG C/min
Rate carries out cooling 12min.Then, oyster shell is crushed, the oyster shell powder of different-grain diameter size is filtered out through selection by winnowing.So
Afterwards, different size of oyster shell powder is prepared into heavy metal renovation agent, it includes first level flour, second patent flour, three-level powder and level Four powder.
First level flour was the screenings of 360 mesh sieves, and second patent flour was the screenings of 140 mesh sieves, and three-level powder was the screenings of 50 mesh sieves,
Level Four powder was the screenings of 14 mesh sieves, and in percentage by weight, first level flour accounts for heavy metal renovation agent total amount
18.8%, second patent flour accounts for the 14.1% of heavy metal renovation agent total amount, and three-level powder accounts for the 59.3% of heavy metal renovation agent total amount, level Four
Powder accounts for the 7.8% of heavy metal renovation agent total amount.
Embodiment 2-1
Major ingredient of the potash fertilizer as slow release heavy metal remediation fertilizer is taken, is taken and is accounted for the humic acid of auxiliary material gross weight 30%, accounts for auxiliary material
The binding agent of gross weight 20% and account for the heavy metal renovation agent of auxiliary material gross weight 50%.By humic acid and binding agent according to foregoing
Percentage by weight is prepared into slurry after mixing in mixer, stand-by.Weight ratio according to major ingredient and auxiliary material is 1.5：1 ratio
Example, major ingredient particle is placed in afore-mentioned slurry and is infiltrated, and is stirred, and then additional size is separated with major ingredient particle by being centrifuged,
In centrifugal process, addition accounts for the heavy metal renovation agent of the embodiment 1-1 of the 50% of the gross weight of auxiliary material so that heavy metal is repaiied
Multiple agent sticks to particle surface, and slow release heavy metal remediation fertilizer is obtained final product after being gone through drying.
Embodiment 2-2 to embodiment 2-12
Embodiment 2-2 to embodiment 2-12 prepares the method and the basic phases of embodiment 2-1 of slow release heavy metal remediation fertilizer
Together, its difference is, the heavy metal renovation agent that embodiment 2-2 to embodiment 2-12 is used is embodiment 1-2 to implementing 1-
12 heavy metal renovation agent.
Embodiment 2-13
Major ingredient of the boron fertilizer as slow release heavy metal remediation fertilizer is taken, is taken and is accounted for the humic acid of auxiliary material gross weight 32%, accounts for auxiliary material
The binding agent of gross weight 20% and account for the heavy metal renovation agent of auxiliary material gross weight 48%.By humic acid and binding agent according to foregoing
Percentage by weight is prepared into slurry after mixing in mixer, stand-by.Weight ratio according to major ingredient and auxiliary material is 2：1 ratio,
Major ingredient particle is placed in afore-mentioned slurry and is infiltrated, and stirred, then additional size separated with major ingredient particle by being centrifuged, from
During the heart, addition accounts for the heavy metal renovation agent of the embodiment 1-1 of the 48% of the gross weight of auxiliary material so that heavy metal renovation agent
Particle surface is sticked to, slow release heavy metal remediation fertilizer is obtained final product after being gone through drying.
Embodiment 2-14 to embodiment 2-24
The method that embodiment 2-14 to embodiment 2-24 prepares slow release heavy metal remediation fertilizer is basic with embodiment 2-13
Identical, its difference is that the heavy metal renovation agent that embodiment 2-14 to embodiment 2-24 is used is embodiment 1-2 to implementation
The heavy metal renovation agent of 1-12.
Embodiment 2-25
Take the major ingredient of boron fertilizer, organic fertilizer and potash fertilizer as slow release heavy metal remediation fertilizer, boron fertilizer, organic fertilizer and potash fertilizer add
Plus ratio, those skilled in the art can adjust accordingly according to specific crop, and the present embodiment is not construed as limiting to this.Then,
Take and account for the humic acid of auxiliary material gross weight 35%, account for the binding agent of auxiliary material gross weight 19% and account for a huge sum of money for auxiliary material gross weight 46%
Category renovation agent.Slurry is prepared into after humic acid and binding agent are mixed according to aforementioned weight percentage in mixer, it is stand-by.Press
License-master expects and the weight ratio of auxiliary material is 3：1 ratio, major ingredient particle is placed in afore-mentioned slurry and is infiltrated, and is stirred, and is then passed through
Centrifugation separates additional size with major ingredient particle, and in centrifugal process, addition accounts for the embodiment 1- of the 46% of the gross weight of auxiliary material
1 heavy metal renovation agent so that heavy metal renovation agent sticks to particle surface, slow release heavy metal reparation is obtained final product after being gone through drying
Fertilizer.
Embodiment 2-26 to embodiment 2-36
The method that embodiment 2-26 to embodiment 2-36 prepares slow release heavy metal remediation fertilizer is basic with embodiment 2-25
Identical, its difference is that the heavy metal renovation agent that embodiment 2-26 to embodiment 2-36 is used is embodiment 1-2 to implementation
The heavy metal renovation agent of 1-12.
Embodiment 2-37
The adding proportion of the major ingredient of boron fertilizer and organic fertilizer as slow release heavy metal remediation fertilizer, boron fertilizer and organic fertilizer is taken, this
Art personnel can adjust accordingly according to specific crop, and the present embodiment is not construed as limiting to this.Then, take that to account for auxiliary material total
The humic acid of weight 30%, the binding agent for accounting for auxiliary material gross weight 18% and account for the heavy metal renovation agent of auxiliary material gross weight 52%.
Slurry is prepared into after humic acid and binding agent are mixed according to aforementioned weight percentage in mixer, it is stand-by.According to major ingredient and
The weight ratio of auxiliary material is 2：1 ratio, major ingredient particle is placed in afore-mentioned slurry and is infiltrated, and is stirred, and then will be many by centrifugation
Remaining slurry material is separated with major ingredient particle, and in centrifugal process, addition accounts for a huge sum of money of the embodiment 1-1 of the 52% of the gross weight of auxiliary material
Category renovation agent so that heavy metal renovation agent sticks to particle surface, slow release heavy metal remediation fertilizer is obtained final product after being gone through drying.
Embodiment 2-38 to embodiment 2-48
The method that embodiment 2-38 to embodiment 2-48 prepares slow release heavy metal remediation fertilizer is basic with embodiment 2-37
Identical, its difference is that the heavy metal renovation agent that embodiment 2-38 to embodiment 2-48 is used is embodiment 1-2 to implementation
The heavy metal renovation agent of 1-12.
Embodiment 2-1 is listed in Table 4 below to the raw material proportioning of embodiment 2-48 slow release heavy metal remediation fertilizers.
Table 4
Comparative example 1
The oyster shell powder of the mesh sieve of commercially available mistake 100.
Comparative example 2
The oyster shell powder of the mesh sieve of commercially available mistake 40.
Comparative example 3
This comparative example is that binding agent is different with oyster shell powder in auxiliary material with the difference of embodiment 2-1, other conditions phase
Together, specifically：
Using commercially available potash fertilizer as the major ingredient of slow release heavy metal remediation fertilizer, repaired with embodiment 2-1 identicals heavy metal
Agent, commercially available humic acid and commercial polysterol are binding agent as auxiliary material, wherein polystyrene.Commercially available humic acid accounts for auxiliary material total amount
30%, polystyrene accounts for the 20% of auxiliary material total amount, commercially available oyster shell powder and accounts for the 50% of auxiliary material total amount.According to embodiment 2-1
Identical method prepares slow release heavy metal remediation fertilizer.It should be noted that in centrifugal process, being replaced with commercially available oyster shell powder
The heavy metal renovation agent of the embodiment of the present invention.
Detection experiment
Testing 1 heavy metal renovation agent improves the development test of acid soil and adsorbing heavy metal cadmium
1.1 for examination soil：The Red Paddy Soil of Quaternary Red Clays parent material development, soil property moderate curing, in fertility
Deng partially thin.Topsoil soils pH5.10 before experiment, acid, exchangeable hydrogen 4.82mmol/kg, exchangeable aluminum 28.66mmol/kg have
Machine matter 30.62g/kg, full nitrogen 1.39g/kg, full potassium 14.48g/kg, alkali-hydrolyzable nitrogen 56.43mg/kg, available nitrogen 32.41mg/kg, speed
Effect potassium 215.49mg/kg, Cd content are 0.48mg/kg, and Pb contents are 40.11mg/kg.
1.2 test materials：Heavy metal renovation agent provided in an embodiment of the present invention.
Embodiment 1-1 is listed in Table 1 below to the particle diameter distribution of embodiment 1-12 heavy metal renovation agents.
Table 1
| Embodiment | First level flour | Second patent flour | Three-level powder | Level Four powder |
| 1-1 | 200 mesh sieves 15% | 100 mesh sieves 10% | 20 mesh sieves 68% | 18 mesh sieves 7% |
| 1-2 | 220 mesh sieves 18% | 120 mesh sieves 17% | 30 mesh sieves 55% | 10 mesh sieves 10% |
| 1-3 | 240 mesh sieves 15% | 140 mesh sieves 10% | 40 mesh sieves 65% | 14 mesh sieves 10% |
| 1-4 | 260 mesh sieves 25% | 100 mesh sieves 12% | 50 mesh sieves 58% | 16 mesh sieves 5% |
| 1-5 | 300 mesh sieves 15% | 120 mesh sieves 20% | 60 mesh sieves 57% | 18 mesh sieves 8% |
| 1-6 | 320 mesh sieves 15% | 140 mesh sieves 12% | 40 mesh sieves 68% | 12 mesh sieves 5% |
| 1-7 | 340 mesh sieves 25% | 150 mesh sieves 12% | 50 mesh sieves 58% | 16 mesh sieves 5% |
| 1-8 | 350 mesh sieves 18% | 120 mesh sieves 12% | 40 mesh sieves 62% | 12 mesh sieves 8% |
| 1-9 | 360 mesh sieves 18.5% | 140 mesh sieves 14.6% | 50 mesh sieves 59.3% | 12 mesh sieves 7.6% |
| 1-10 | 350 mesh sieves 18.5% | 136 mesh sieves 14% | 48 mesh sieves 60% | 12 mesh sieves 7.5% |
| 1-11 | 360 mesh sieves 19.2% | 140 mesh sieves 14% | 50 mesh sieves 59.3% | 14 mesh sieves 7.5% |
| 1-12 | 360 mesh sieves 18.8% | 140 mesh sieves 14.1% | 50 mesh sieves 59.3% | 14 mesh sieves 7.8% |
1.3 testing programs：By the heavy metal renovation agent of the embodiment 1-1 of equivalent to embodiment 1-12 respectively to for examination soil
Earth carries out heavy metal cadmium passivation experiment, the corresponding area equation for examination soil of each embodiment, heavy metal renovation agent amount of application
100Kg/ mus is, each embodiment is calculated in the adsorption rate of 1h, 24h and 48h and is detected corresponding P in soil H values, meanwhile,
The mesh sieve of mistake 100 and the oyster shell powder of 40 mesh sieves that market is bought as a comparison case 1 and comparative example 2, and according to same as before
Method carries out heavy metal cadmium passivation experiment, the results are shown in Table 2.When experiment is passivated, oyster shell is applied to corresponding soil
Coupon, and mix, after (1h, 24h and 48h) after a while, the content of the available Cd in detection soil calculates suction
Attached rate.
The cadmium of table 2 is adsorbed
As seen from Table 2, the heavy metal renovation agent of the embodiment of the present invention either improves acidified soil or Adsorption of Heavy Metals
The oyster shell powder of the one-component that the effect of cadmium is all significantly larger than bought on the market, compared with comparative example 1 and comparative example 2, this hair
The adsorption rate to cadmium of bright embodiment at least improves 23%, and the adsorption rate of the wherein best embodiment 1-10 of adsorption effect is carried
It is high by 23.6%.Additionally, as can also be seen from Table 1, adsorption time is that 24h and 48h its adsorption rate changes are little, is illustrated when absorption
When time reaches 24h, the cadmium ion in soil is adsorbed completely substantially, and reaches saturation state, is no longer adsorbed, therefore, in order to
The repairing effect of heavy metal renovation agent heavy metal contaminated soil and the control to rehabilitation cost are further improved, is preferably applied
Cycle is 24h.
Meanwhile, the present inventor has also been unexpectedly found that the heavy metal renovation agent of the embodiment of the present invention to lead-contaminated soil
With significantly adsorption effect, testing result is shown in Table 3.
The lead of table 3 is adsorbed
| Embodiment | 1h adsorption rates | 24h adsorption rates | 48h adsorption rates |
| 1-1 | 80% | 85% | 85% |
| 1-2 | 81.2% | 84% | 84.3% |
| 1-3 | 82% | 85.3% | 85.5% |
| 1-4 | 81.5% | 86% | 99.2% |
| 1-5 | 80.6% | 81.5% | 81.7% |
| 1-6 | 80.2% | 81% | 81.2% |
| 1-7 | 80.8% | 82.6% | 82% |
| 1-8 | 81.3% | 83.3% | 83.4% |
| 1-9 | 83.4% | 84.6% | 84.6% |
| 1-10 | 84% | 85% | 85.3% |
| 1-11 | 82.8% | 84.2% | 84.5% |
| 1-12 | 83.6% | 85% | 85.1% |
| Comparative example 1 | 70% | 75% | 76% |
| Comparative example 2 | 68% | 70% | 72% |
From table 3 it can be seen that the heavy metal renovation agent of the embodiment of the present invention also shows excellent adsorption effect to lead, with
Comparative example 1 is compared with comparative example 2, and adsorption rate at least improves 10%.
Test the development test of the slow release effect of 2 slow release heavy metal remediation fertilizers
This experiment evaluates sustained release effect by detecting embodiment 2-1 with the dissolution rate and accumulative rate of the potassium ion of comparative example 3
Really, testing result is shown in Table 4.
The potassium ion dissolution rate of table 4 and cumulative percentage
From table 4, it can be seen that the dissolution rate of embodiment 2-1 potassium ions is respectively less than the dissolution of comparative example 3 at any time
Rate, illustrates in the case of other conditions identical, and using the humic acid and binding agent of the embodiment of the present invention as auxiliary material, it delays
Release effect more preferable.
Need explanation when, the slow release heavy metal remediation fertilizer of the embodiment of the present invention can also add micro- in preparation process
Mineral raw material (calcium, potassium, magnesium) and microorganism fungus kind are measured, or other are conducive to improving fertilizer efficiency and increase the effective of soil fertility
Composition, will not enumerate herein, be added according to this area conventional meanses.
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of environment-friendly type heavy metal renovation agent, it is characterised in that it with oyster shell is prepared by raw material that the heavy metal renovation agent is
, it includes first level flour, second patent flour, three-level powder and level Four powder, and the first level flour was the screenings of 200-400 mesh sieves,
The second patent flour was the screenings of 100-150 mesh sieves, and the three-level powder was the screenings of 20-80 mesh sieves, the level Four
Powder was the screenings of 10-18 mesh sieves, and in percentage by weight, it is total that the first level flour accounts for the heavy metal renovation agent
The 15-25% of amount, the second patent flour accounts for the 10-20% of the heavy metal renovation agent total amount, and the three-level powder accounts for the huge sum of money
Belong to the 55-68% of renovation agent total amount, the level Four powder accounts for the 5-10% of the heavy metal renovation agent total amount；
The heavy metal renovation agent be carry out grinding after being calcined through protectiveness as oyster shell obtained in, the roasting of protectiveness roasting
Burning temperature is 800 DEG C of 600 ￣, and roasting time is 8 ￣ 12min, and the flow that oyster shell enters roasting apparatus is 0.2 ￣ 0.4m3/
Min, the rotating speed of roasting apparatus is 25 ￣ 35r/min.
2. environment-friendly type heavy metal renovation agent according to claim 1, it is characterised in that the first level flour was 300-400
The screenings of mesh sieve, the second patent flour was the screenings of 120-140 mesh sieves, and the three-level powder was the sieve of 30-60 mesh sieves
Lower thing, the level Four powder was the screenings of 10-16 mesh sieves, and in percentage by weight, the first level flour accounts for described heavy
The 18-22% of metal repair total amount, the second patent flour accounts for the 12-16% of the heavy metal renovation agent total amount, the three-level
Powder accounts for the 58-62% of the heavy metal renovation agent total amount, and the level Four powder accounts for the 7-8% of the heavy metal renovation agent total amount.
3. environment-friendly type heavy metal renovation agent according to claim 2, it is characterised in that the first level flour was 320-360
The screenings of mesh sieve, the second patent flour was the screenings of 130-140 mesh sieves, and the three-level powder was the sieve of 40-50 mesh sieves
Lower thing, the level Four powder was the screenings of 10-14 mesh sieves, and in percentage by weight, the first level flour accounts for described heavy
The 18.5-19.2% of metal repair total amount, the second patent flour accounts for the 14-14.6% of the heavy metal renovation agent total amount, institute
The 59.3-60% that three-level powder accounts for the heavy metal renovation agent total amount is stated, the level Four powder accounts for the heavy metal renovation agent total amount
7.5-7.8%.
4. environment-friendly type heavy metal renovation agent according to claim 3, it is characterised in that the first level flour was 350 mesh sieves
Screenings, the second patent flour was the screenings of 136 mesh sieves, and the three-level powder was the screenings of 48 mesh sieves, the level Four
Powder was the screenings of 12 mesh sieves, and in percentage by weight, the first level flour accounts for the heavy metal renovation agent total amount
18.5%, the second patent flour accounts for the 14% of the heavy metal renovation agent total amount, and it is total that the three-level powder accounts for the heavy metal renovation agent
The 60% of amount, the level Four powder accounts for the 7.5% of the heavy metal renovation agent total amount.
5. a kind of slow release heavy metal remediation fertilizer, it is characterised in that preparing the raw material of the slow-release fertilizer includes major ingredient and be used for
The auxiliary material of coating is made, the major ingredient includes at least one in organic fertilizer, potash fertilizer and boron fertilizer, and the auxiliary material includes claim
Environment-friendly type heavy metal renovation agent any one of 1-4.
6. slow release heavy metal remediation fertilizer according to claim 5, it is characterised in that the weight of the major ingredient and the auxiliary material
Amount is than being (1.5-3)：1.
7. slow release heavy metal remediation fertilizer according to claim 5, it is characterised in that the heavy metal renovation agent accounts for described
The 46-52% of the gross weight of auxiliary material.
8. slow release heavy metal remediation fertilizer according to claim 5, it is characterised in that the auxiliary material also include humic acid and
Binding agent, the humic acid accounts for the 30-35% of the gross weight of the auxiliary material, and the binding agent accounts for the gross weight of the auxiliary material
15-20%, the binding agent includes powder of straw and modified starch.
9. slow release heavy metal remediation fertilizer according to claim 8, it is characterised in that the modified starch is by shallow lake
In powder liquid add hydrogen peroxide after form oxidized starch, add epoxychloropropane modified dose aoxidized-be crosslinked it is composite modified
Starch is formed.
10. the environment-friendly type heavy metal renovation agent any one of claim 1-4 is in slow release heavy metal remediation fertilizer is prepared
Application.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110408407A (en) * | 2019-08-21 | 2019-11-05 | 长沙凯泽工程设计有限公司 | A kind of tobacco-growing soil cadmium passivator and preparation method thereof |
| CN110511098A (en) * | 2019-06-28 | 2019-11-29 | 福建省农业科学院土壤肥料研究所 | It is a kind of improve heavy metallic activation characteristic of acid red soil composite soil conditioner and application |
| CN110938435A (en) * | 2019-12-03 | 2020-03-31 | 浙江省农业科学院 | Long-acting soil cadmium passivator, preparation method and application |
| CN111606769A (en) * | 2020-07-15 | 2020-09-01 | 江西普瑞丰生态科技有限公司 | Modifier for soil heavy metal pollution treatment and preparation method thereof |
| CN111996008A (en) * | 2020-08-24 | 2020-11-27 | 中国科学院青岛生物能源与过程研究所 | Method for immobilizing humic acid on surface of shell natural material |
| CN113105277A (en) * | 2021-03-25 | 2021-07-13 | 杭州师范大学 | Preparation method of functional earthworm cast with Pb and Cd adsorption performance |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161609A (en) * | 2006-10-13 | 2008-04-16 | 广东海洋大学 | Slow release fertilizer made of shuck |
| KR20120006269A (en) * | 2010-07-12 | 2012-01-18 | 김용하 | Omlitted |
| KR20130107134A (en) * | 2012-03-21 | 2013-10-01 | (주)지오엔바이로텍 | Stench and heavy metal removal composite and using the compost production method |
| CN103450906A (en) * | 2013-09-23 | 2013-12-18 | 福建省玛塔农业发展有限公司 | Soil conditioner and preparation method thereof |
| CN103551119A (en) * | 2013-11-07 | 2014-02-05 | 福建省水产研究所 | Oyster shell heavy metal ions absorbent and preparation method thereof |
| CN103788957A (en) * | 2014-01-22 | 2014-05-14 | 扬州红硕环境与生物工程研究有限公司 | Repair material on top layer of contaminated soil and preparation method thereof |
| CN105642235A (en) * | 2016-01-15 | 2016-06-08 | 中国海洋大学 | Method for removing heavy metal through activated oyster shell powder |
| CN106397045A (en) * | 2016-10-13 | 2017-02-15 | 高鹏 | High-efficiency slow-release fertilizer for high-efficiency cultivation of coix seeds in saline land |
-
2017
- 2017-02-23 CN CN201710101309.3A patent/CN106867541B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161609A (en) * | 2006-10-13 | 2008-04-16 | 广东海洋大学 | Slow release fertilizer made of shuck |
| KR20120006269A (en) * | 2010-07-12 | 2012-01-18 | 김용하 | Omlitted |
| KR20130107134A (en) * | 2012-03-21 | 2013-10-01 | (주)지오엔바이로텍 | Stench and heavy metal removal composite and using the compost production method |
| CN103450906A (en) * | 2013-09-23 | 2013-12-18 | 福建省玛塔农业发展有限公司 | Soil conditioner and preparation method thereof |
| CN103551119A (en) * | 2013-11-07 | 2014-02-05 | 福建省水产研究所 | Oyster shell heavy metal ions absorbent and preparation method thereof |
| CN103788957A (en) * | 2014-01-22 | 2014-05-14 | 扬州红硕环境与生物工程研究有限公司 | Repair material on top layer of contaminated soil and preparation method thereof |
| CN105642235A (en) * | 2016-01-15 | 2016-06-08 | 中国海洋大学 | Method for removing heavy metal through activated oyster shell powder |
| CN106397045A (en) * | 2016-10-13 | 2017-02-15 | 高鹏 | High-efficiency slow-release fertilizer for high-efficiency cultivation of coix seeds in saline land |
Non-Patent Citations (8)
| Title |
|---|
| 张刘东 等: "基于土壤粒径组成影响的重金属镉吸附容量试验及模拟研究", 《中国农村水利水电》 * |
| 张曦 等: "四种土壤调理剂对镉、铅的吸附效果研究", 《中国土壤与肥料》 * |
| 扈亲怀 等: "不同粒径磷矿粉钝化土壤重金属Cd、Pb的机制研究", 《农业资源与环境学报》 * |
| 曹英兰 等: "牡蛎壳粉对酸性土壤的修复及其对镉的钝化作用研究", 《环境科学与技术》 * |
| 王红旗 等: "《土壤环境学》", 31 July 2007, 高等教育出版社 * |
| 罗华汉 等: "牡蛎壳粉对水稻产量和土壤重金属钝化的影响", 《中国稻米》 * |
| 高艳娇 等: "牡蛎壳吸附重金属的试验研究", 《山东化工》 * |
| 黄岁梁 等: "泥沙粒径对重金属污染物吸附影响的研究", 《水利学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511098A (en) * | 2019-06-28 | 2019-11-29 | 福建省农业科学院土壤肥料研究所 | It is a kind of improve heavy metallic activation characteristic of acid red soil composite soil conditioner and application |
| CN110408407A (en) * | 2019-08-21 | 2019-11-05 | 长沙凯泽工程设计有限公司 | A kind of tobacco-growing soil cadmium passivator and preparation method thereof |
| CN110938435A (en) * | 2019-12-03 | 2020-03-31 | 浙江省农业科学院 | Long-acting soil cadmium passivator, preparation method and application |
| CN111606769A (en) * | 2020-07-15 | 2020-09-01 | 江西普瑞丰生态科技有限公司 | Modifier for soil heavy metal pollution treatment and preparation method thereof |
| CN111996008A (en) * | 2020-08-24 | 2020-11-27 | 中国科学院青岛生物能源与过程研究所 | Method for immobilizing humic acid on surface of shell natural material |
| CN113105277A (en) * | 2021-03-25 | 2021-07-13 | 杭州师范大学 | Preparation method of functional earthworm cast with Pb and Cd adsorption performance |
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