CN106867541B - 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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- CN106867541B CN106867541B CN201710101309.3A CN201710101309A CN106867541B CN 106867541 B CN106867541 B CN 106867541B CN 201710101309 A CN201710101309 A CN 201710101309A CN 106867541 B CN106867541 B CN 106867541B
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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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- 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
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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 carry out grinding after protectiveness is calcined as oyster shell made from, sintering temperature is 600~800 DEG C, and roasting time be 8~12min, oyster shell into the flow of roasting apparatus be 0.2~0.4m3/ min, the rotating speed of roasting apparatus is 25~35r/min.The present invention can be repaired effectively mainly by the soil of 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, is 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 largely cause soil texture to be deteriorated using quick-acting fertilizer, nutrient mistake
Weighing apparatus, soil fertility decline, while also result in soil severe acidification, so as to influence the validity of fertilizer.Moreover, various industrial wastewaters, useless
Gas etc. make it that heavy metal in soil (cadmium, chromium, mercury, lead) pollution is also increasingly severe.The heavy metal one side shadow such as cadmium, chromium, mercury, lead
The normal growth of crop is rung, another side is entered in crop, influences health.
Coastal area abounds with oyster, and the disposal of oyster shell turns into serious environmental problem.Main component is in oyster shell
Calcium carbonate, it is slightly soluble in water in alkalescence, can be effectively improved the phenomenon of soil acidification, and improve lack calcareous soil and
It is passivated the effect of harmful heavy metal ions (cadmium, chromium, mercury, lead) in 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 after powder with other soil conditioning compositions (such as calcium oxide, chitosan powder, calcium superphosphate etc.), by oyster shell with
Other adsorbents are used cooperatively to improve the repairing effect of heavy metal contaminated soil；Second class is that powder is modified, example
Such as powder is modified using CNT, obtains modified powder；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
Benefit of helping 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 mainly based on cadmium pollution, and existing heavy metal renovation agent specific aim is not
By force, repairing effect need further to improve.
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 be effectively repaired mainly by the soil of cadmium pollution, products material is simple, low manufacture cost,
And with strong points, the advantages of good adsorption effect of product, the especially adsorption effect to 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 mainly by the soil of cadmium pollution.
The third object of the present invention is that providing above-mentioned environment-friendly type heavy metal renovation agent is preparing slow release heavy metal reparation
Application in fertilizer, its coating using oyster shell as raw material for preparing slow-release fertilizer, green, pollution-free, thus obtained slow-release fertilizer
The soil by heavy metal pollution can also be repaired, especially mainly by the soil of cadmium pollution.
What embodiments of the invention were realized in：
A kind of environment-friendly type heavy metal renovation agent, heavy metal renovation agent are prepared 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 were 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 account 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 carry out grinding after protectiveness is calcined as oyster shell made from, 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 the auxiliary of coating is made
Material, major ingredient include at least one of 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 is soil of the raw material as reparation by heavy metal pollution using oyster shell, passes through 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 the heavy metal renovation agent of the present invention into
Divide single so that product preparation section is simple, low manufacture cost.
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 suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
At present, the temperature when Study on adsorption properties on oyster shell absorption heavy metal includes the dosage of oyster shell powder, adsorbed
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, generally use is that the oyster shell powder of 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 referred 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 substantially, simultaneously to enter
One step finds that the difference that the lower oyster shell powder formed of different-grain diameter distribution is shown 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 for the heavy metal renovation agent by the serious soil of cadmium pollution, the huge sum of money
For the heavy metal renovation agent that category renovation agent is formed 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 using oyster shell as original
What material was prepared, it includes first level flour, second patent flour, three-level powder and level Four powder, and first level flour was under the sieve of 200-400 mesh sieves
Thing, second patent flour were 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 carry out grinding after protectiveness is calcined as oyster shell made from,
The sintering temperature of protectiveness roasting is 600-800 DEG C, roasting time 8-12min, and oyster shell enters the flow of roasting apparatus
For 0.2-0.4m3/ min, the rotating speed of roasting apparatus is 25-35r/min.
The inventors discovered that oyster shell 20-80 mesh particle size range compared to other particle sizes oyster shell powder, its
The adsorption effect of heavy metal cadmium (such as in 1h) in a short time is more prominent, therefore, the embodiment of the present invention using particle diameter as
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 with heavy metal cadmium, be used for
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
With cadmium passivation reaction occurs for ground, improves adsorption efficiency.Meanwhile the present embodiment is equipped with first level flour, second patent flour and level Four powder again, with
Heavy metal renovation agent continues that passivation occurs using the later stage, and heavy metal cadmium is persistently adsorbed, repaiied so as to improve whole heavy metal
The adsorption rate of multiple agent heavy metal cadmium, extend heavy metal renovation agent applies the 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 were the screenings of 30-60 mesh sieves, and level Four powder was the screenings of 10-16 mesh sieves, and according to weight hundred
Dividing and account for the 18-22% of heavy metal renovation agent total amount than meter, first level flour, 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 were 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 account 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 account 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 account 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 being made up of different-grain diameter is formed, and by adjusting the proportioning of every kind of oyster shell powder, obtain and be directed to cadmium
The heavy metal of heavy-metal contaminated soil based on pollution repairs agent prescription, with strong points, is compared with existing heavy metal renovation agent,
Compounded without other adsorbents are modified or added to oyster shell again, can just obtain the preferable absorption effect to cadmium
Fruit.
Further, the method for the preparation environment-friendly type heavy metal renovation agent of the embodiment of the present invention comprises 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 for remaining in oyster shell surface is removed by cleaning, oyster shell is carried out by simple crushing by coarse crushing, with convenient
Follow-up grinding, the rope for hanging culture oyster remained on oyster shell is removed by sorting, improves product quality.
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, retain the roasting of nutritional ingredient and micro- poly- pore structure in oyster shell as much as possible
Burning mode.Specifically, oyster shell is roasted under conditions of sintering temperature is 600~800 DEG C, roasting time is 8~12min
Burn.Because the sintering temperature of the embodiment of the present invention is relatively low, therefore, the nutriment in oyster shell can be retained to greatest extent,
And micro- poly- pore structure is avoided to destroy.
Can also increase micro- poly- pore structure of oyster shell powder by protectiveness roasting, specific surface area increase, so that
The ability enhancing of oyster shell powder absorption heavy metal.And oyster is calcined by 600~800 DEG C, 8~12min protectiveness
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 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, control oyster shell into the flow of roasting apparatus be 0.2~0.4m3/ min, roasting are set
Standby rotating speed is 25~35r/min.By the rotating speed for further controlling oyster shell flow and roasting apparatus so that in oyster shell
Active ingredient fully converts, while effectively avoids micro- poly- pore structure of oyster shell and trace element from being destroyed.
Further, be 600~800 DEG C by controlling sintering temperature, roasting time be 8~12min so that after roasting
Water content in oyster shell is maintained in the range of 8-10%, and water content, which is maintained in the range of this, to be advantageous 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
Cooling treatment is carried out to the roasting material after protectiveness is calcined.Specifically, the oyster shell after roasting and zeolite are entered
Row 10~15min of first time cooling, cooling is to be cooled down in its natural state for the first time, the temperature of roasting material is carried out tentatively
Cooling, second of 10~15min of cooling then is carried out with 15~25 DEG C/min rate of temperature fall to roasting material.
Oyster shell has micro- poly- pore structure, and in their crystal, molecule connects together as building a framework, and centre is formed
Many cavitys.Many hydrones in these cavitys being present, these moisture can eject when running into high temperature, but in temperature-fall period
In it can also reuptake water or other liquid again.Therefore, the embodiment of the present invention passes through cooling treatment modes different twice
The oyster shell after roasting is set to cool down completely, and can enough avoids the aqueous vapor that the oyster shell after roasting sucks 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, while avoid because of quick cooling pair
The infringement of roasting apparatus.Carried out for the second time when oyster shell temperature is reduced to one regularly, then with 15~25 DEG C/min rate of temperature fall
Cooling treatment, so as to rapidly reduce the temperature of oyster shell, oyster shell is cooled down completely, avoid the water in oyster shell absorption air
Point.Preferably, can be cooled down when carrying out second of cooling treatment by liquid nitrogen.
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
Heavy metal renovation agent with particle size is allocated according to aforementioned weight percentage, is used to prepare for cadmium pollution soil to obtain
The heavy metal renovation agent of earth.
The second aspect of the invention, there is provided a kind of slow release heavy metal remediation fertilizer, prepare the raw material bag of the slow-release fertilizer
Include major ingredient and auxiliary material, major ingredient includes at least one of organic fertilizer, potash fertilizer and boron fertilizer, for example, organic fertilizer or organic fertilizer and its
Any combination of his three.The one kind of organic fertilizer 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 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 can not 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 accounts for
The 30-35% of the gross weight of auxiliary material, binding agent account for the 15-20% of the gross weight of auxiliary material, and binding agent includes powder of straw and modification
Starch.Preferably, powder of straw and the weight of modified starch ratio are 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, has the oxygen-content active functional groups such as carboxyl, quinonyl, phenolic hydroxyl group and alcoholic extract hydroxyl group.
Humic acid has the characteristics that to improve utilization rate of fertilizer, enhancing crop anti-adversity, improved soil microbial profile, the embodiment of the present invention
Humic acid is added with to the structure for being beneficial to improve the soil by heavy metal pollution as one of auxiliary material, increased in soil beneficial to micro- life
The content of bacterium, maintain 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
Be raw material with waste paper pulp, by crop material and fowl and animal excrement it is clipped, crush after mix with waste paper pulp, through hydrolyzing, concentrating,
Fermentation is remixed to be made.Raw material need not consume the reagents such as substantial amounts of industrial soda acid in degradation process, whole preparation process without
High temperature, the reaction condition of high pressure are needed, and all raw materials can either reduce production cost and reduce producing both from discarded object
Technology difficulty, at the same it is again green, economize on resources.
The modified starch of the present embodiment is by forming oxidized starch after adding hydrogen peroxide into starch fluid, adding ring
Oxygen chloropropane modifying agent obtains oxidation-crosslinking composite modified starch and formed.Handled through hydrogen peroxide and epoxychloropropane modified dose
Starch fluid afterwards, its good film-forming property, meanwhile, modified starch is used as binding agent after being mixed with powder of straw, is advantageous to by major ingredient system
Into particle surface film forming, improve the slow release effect of fertilizer.It is additionally, since the embodiment of the present invention and coating is not carried out using resin,
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 comprises the following steps：
Step 2-1：Prepare major ingredient particle
It is that raw material is prepared into particle with least one of organic fertilizer, potash fertilizer and boron fertilizer., can when carrying out the step
To be carried out according to the conventional steps for preparing fertiliser granulates, or directly buying 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, glues
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 the weight of major ingredient and auxiliary material
Than for (1.5-3)：1 ratio, the major ingredient particle being prepared into by step 2-1 is placed in afore-mentioned slurry and infiltrated, and stirred, so
Additional size is separated with major ingredient particle by centrifuging afterwards, in centrifugal process, adds the 46-52% for the gross weight for accounting for auxiliary material
The embodiment of the present invention heavy metal renovation agent so that heavy metal renovation agent is adhered to particle surface, through dry go after produce it is slow
Release fertilizer.
Further, in other embodiments of the invention disk or rotary drum coating method can be used to carry out film forming, simultaneously
Disk or the further film forming of rotary drum coating method can also be added after infiltration centrifugal process prepares slow-release fertilizer, it is strong to improve slow-release fertilizer particle
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 be made coating, environment friendly and pollution-free, had good sustained release effect, while 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 fertilizer application, have 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 it can either improve the slow release of slow-release fertilizer, while can be adsorbed with heavy metal, repair the soil by heavy metal pollution
Earth.
Embodiment
Embodiment 1-1
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 600 DEG C, roasting time is 12min after pretreatment
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 subjected to first time cooling treatment and second of 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 15 DEG C/min cooling
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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 650 DEG C, roasting time is 10min after pretreatment
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 subjected to first time cooling treatment and second of 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 17 DEG C/min cooling
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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 680 DEG C, roasting time is 8min after pretreatment
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 subjected to first time cooling treatment and second of 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 20 DEG C/min cooling
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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 700 DEG C, roasting time is 10min after pretreatment
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 subjected to first time cooling treatment and second of 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 22 DEG C/min cooling
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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 720 DEG C, roasting time is 8min after pretreatment
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 subjected to first time cooling treatment and second of 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 the cooling speed with 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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 750 DEG C, roasting time is 8min after pretreatment
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 subjected to first time cooling treatment and second of 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 the cooling speed with 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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 780 DEG C, roasting time is 10min after pretreatment
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 subjected to first time cooling treatment and second of 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 the cooling speed with 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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 600 DEG C, roasting time is 10min after pretreatment
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 subjected to first time cooling treatment and second of 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 the cooling speed with 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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 650 DEG C, roasting time is 10min after pretreatment
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 subjected to first time cooling treatment and second of 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 16 DEG C/min cooling
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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 650 DEG C, roasting time is 10min after pretreatment
Roasting, during charging, the flow for controlling oyster shell is 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 subjected to first time cooling treatment and second of 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 16 DEG C/min cooling
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 accounts for
The 7.5% of heavy metal renovation agent total amount.
Embodiment 1-11
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 700 DEG C, roasting time is 12min after pretreatment
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 subjected to first time cooling treatment and second of 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 the cooling speed with 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
Oyster shell is subjected to protectiveness under conditions of sintering temperature is 700 DEG C, roasting time is 12min after pretreatment
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 subjected to first time cooling treatment and second of 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 the cooling speed with 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 the heavy metal renovation agent for accounting for auxiliary material gross weight 50%.By humic acid and binding agent according to foregoing
Percentage by weight is prepared into slurry after being mixed in mixer, stand-by.It is 1.5 according to the weight of major ingredient and auxiliary material ratio：1 ratio
Example, major ingredient particle is placed in afore-mentioned slurry and infiltrated, and is stirred, and is then separated additional size with major ingredient particle by centrifuging,
In centrifugal process, 50% embodiment 1-1 of the gross weight for accounting for auxiliary material heavy metal renovation agent is added so that heavy metal is repaiied
Multiple agent is adhered to particle surface, and slow release heavy metal remediation fertilizer is produced after drying and going.
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 the heavy metal renovation agent for accounting for auxiliary material gross weight 48%.By humic acid and binding agent according to foregoing
Percentage by weight is prepared into slurry after being mixed in mixer, stand-by.It is 2 according to the weight of major ingredient and auxiliary material ratio：1 ratio,
Major ingredient particle is placed in afore-mentioned slurry and infiltrated, and is stirred, is then separated additional size with major ingredient particle by centrifuging, from
During the heart, 48% embodiment 1-1 of the gross weight for accounting for auxiliary material heavy metal renovation agent is added so that heavy metal renovation agent
Particle surface is adhered to, slow release heavy metal remediation fertilizer is produced after drying and going.
Embodiment 2-14 to embodiment 2-24
Embodiment 2-14 to embodiment 2-24 prepare slow release heavy metal remediation fertilizer method and embodiment 2-13 it is basic
Identical, its difference is, the heavy metal renovation agent that embodiment 2-14 to embodiment 2-24 is used is embodiment 1-2 to implementation
1-12 heavy metal renovation agent.
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
Add ratio, those skilled in the art can be adjusted accordingly according to specific crop, and the present embodiment is not construed as limiting to this.Then,
Take the huge sum of money for accounting for the humic acid of auxiliary material gross weight 35%, accounting for the binding agent of auxiliary material gross weight 19% and accounting for auxiliary material gross weight 46%
Belong to 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 infiltrated, and stirred, then passed through
Centrifugation separates additional size with major ingredient particle, in centrifugal process, adds 46% embodiment 1- of the gross weight for accounting for auxiliary material
1 heavy metal renovation agent so that heavy metal renovation agent is adhered to particle surface, and slow release heavy metal reparation is produced after drying and going
Fertilizer.
Embodiment 2-26 to embodiment 2-36
Embodiment 2-26 to embodiment 2-36 prepare slow release heavy metal remediation fertilizer method and embodiment 2-25 it is basic
Identical, its difference is, the heavy metal renovation agent that embodiment 2-26 to embodiment 2-36 is used is embodiment 1-2 to implementation
1-12 heavy metal renovation agent.
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 be adjusted 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 the heavy metal renovation agent for accounting for 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 infiltrated, and stirred, then will be more by centrifugation
Remaining slurry material separates with major ingredient particle, in centrifugal process, adds 52% embodiment 1-1 of the gross weight for accounting for an auxiliary material huge sum of money
Belong to renovation agent so that heavy metal renovation agent is adhered to particle surface, and slow release heavy metal remediation fertilizer is produced after drying and going.
Embodiment 2-38 to embodiment 2-48
Embodiment 2-38 to embodiment 2-48 prepare slow release heavy metal remediation fertilizer method and embodiment 2-37 it is basic
Identical, its difference is, the heavy metal renovation agent that embodiment 2-38 to embodiment 2-48 is used is embodiment 1-2 to implementation
1-12 heavy metal renovation agent.
The raw material proportioning of embodiment 2-1 to embodiment 2-48 slow release heavy metal remediation fertilizers is listed in Table 4 below.
Table 4
Comparative example 1
The oyster shell powder of the commercially available mesh sieve of mistake 100.
Comparative example 2
The oyster shell powder of the commercially available mesh sieve of mistake 40.
Comparative example 3
This comparative example and embodiment 2-1 difference are that binding agent is different with oyster shell powder in auxiliary material, other conditions phase
Together, specifically：
Major ingredient using commercially available potash fertilizer as slow release heavy metal remediation fertilizer, with embodiment 2-1 identical heavy metal reparations
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, 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 cure, in fertility
Deng partially thin.Topsoil soils pH5.10 before experiment, it is 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
It is 0.48mg/kg to imitate potassium 215.49mg/kg, Cd content, and Pb contents are 40.11mg/kg.
1.2 test material：Heavy metal renovation agent provided in an embodiment of the present invention.
The particle diameter distribution of embodiment 1-1 to embodiment 1-12 heavy metal renovation agents is listed in Table 1 below.
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 program：By the embodiment 1-1 of equivalent to embodiment 1-12 heavy metal renovation agent respectively to for examination soil
Earth carries out heavy metal cadmium passivation experiment, and the area equation of examination soil, heavy metal renovation agent amount of application are supplied corresponding to each embodiment
It is 100Kg/ mus, calculates each embodiment in P in soil H values corresponding to 1h, 24h and 48h adsorption rate and detection, meanwhile,
By the mesh sieve of mistake 100 of market purchase and the oyster shell powder as a comparison case 1 and comparative example 2, and according to same as before of 40 mesh sieves
Method carries out heavy metal cadmium passivation experiment, the results are shown in Table 2.When being passivated experiment, oyster shell is applied to corresponding soil
Coupon, and mix, through after a while after (1h, 24h and 48h), the content of the available Cd in soil is detected, calculates suction
Attached rate.
The cadmium of table 2 adsorbs
As seen from Table 2, the heavy metal renovation agent of the embodiment of the present invention either improves acidified soil and still adsorbs heavy metal
The oyster shell powder for 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 wherein best embodiment 1-10 of adsorption effect adsorption rate carries
It is high by 23.6%.In addition, 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 adsorbs completely substantially, and reaches saturation state, no longer adsorbs, 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 adsorbs
| 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 is imitated by the dissolution rate and accumulative rate for detecting embodiment 2-1 and the potassium ion of comparative example 3 to evaluate sustained release
Fruit, testing result are 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, illustrate in the case of other conditions identical, using the humic acid and binding agent of the embodiment of the present invention as auxiliary material, it is slow
It is more preferable to release effect.
Need to illustrate 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 advantageous to improve fertilizer efficiency and increase the effective of soil fertility
It composition, will not enumerate, added according to this area conventional meanses herein.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
1. a kind of environment-friendly type heavy metal renovation agent, it is characterised in that the heavy metal renovation agent is prepared by raw material of oyster shell
Form, it includes first level flour, second patent flour, three-level powder and level Four powder, by the oyster shell successively using 200-400 mesh sieves,
100-150 mesh sieves, 20-80 mesh sieves and 10-18 mesh sieves are sieved, and reach the purpose of sizing screening, and the first level flour was
The screenings of 200-400 mesh sieves, the second patent flour were the screenings of 100-150 mesh sieves, and the three-level powder was 20-80
The screenings of mesh sieve, the level Four powder were the screenings of 10-18 mesh sieves, and in percentage by weight, the first level flour
The 15-25% of the heavy metal renovation agent total amount is accounted for, the second patent flour accounts for the 10-20% of the heavy metal renovation agent total amount,
The three-level powder accounts for the 55-68% of the heavy metal renovation agent total amount, and the level Four powder accounts for the heavy metal renovation agent total amount
5-10%；
The heavy metal renovation agent be carry out grinding after protectiveness is calcined as oyster shell made from, the roasting of protectiveness roasting
It is 600~800 DEG C to burn temperature, 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 use the oyster shell successively
300-400 mesh sieves, 120-140 mesh sieves, 30-60 mesh sieves and 10-16 mesh sieves are sieved, and reach the purpose of sizing screening,
The first level flour was the screenings of 300-400 mesh sieves, and the second patent flour was the screenings of 120-140 mesh sieves, described three
Level powder was the screenings of 30-60 mesh sieves, and the level Four powder was the screenings of 10-16 mesh sieves, and according to weight percent
Than meter, the first level flour accounts for the 18-22% of the heavy metal renovation agent total amount, and the second patent flour accounts for the heavy metal renovation agent
The 12-16% of total amount, the three-level powder account for the 58-62% of the heavy metal renovation agent total amount, and the level Four powder accounts for described heavy
The 7-8% of metal repair total amount.
3. environment-friendly type heavy metal renovation agent according to claim 2, it is characterised in that use the oyster shell successively
320-360 mesh sieves, 130-140 mesh sieves, 40-50 mesh sieves and 10-14 mesh sieves are sieved, and reach the purpose of sizing screening,
The first level flour was the screenings of 320-360 mesh sieves, and the second patent flour was the screenings of 130-140 mesh sieves, described three
Level powder was the screenings of 40-50 mesh sieves, and the level Four powder was the screenings of 10-14 mesh sieves, and according to weight percent
Than meter, the first level flour accounts for the 18.5-19.2% of the heavy metal renovation agent total amount, and the second patent flour accounts for the heavy metal and repaiied
The 14-14.6% of multiple agent total amount, the three-level powder account for the 59.3-60% of the heavy metal renovation agent total amount, the level Four powder
Account for the 7.5-7.8% of the heavy metal renovation agent total amount.
4. environment-friendly type heavy metal renovation agent according to claim 3, it is characterised in that use the oyster shell successively
350 mesh sieves, 136 mesh sieves, 48 mesh sieves and 12 mesh sieves are sieved, and reach the purpose of sizing screening, and the first level flour was 350 mesh
The screenings of sieve, the second patent flour were the screenings of 136 mesh sieves, and the three-level powder was the screenings of 48 mesh sieves, described four
Level 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 the three-level powder accounts for the heavy metal renovation agent
The 60% of total amount, the level Four powder account 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 of 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
It is (1.5-3) to measure ratio：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 account 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 include 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
Oxidized starch is formed after adding hydrogen peroxide in powder liquid, it is composite modified to add epoxychloropropane modified dose of acquisition oxidation-crosslinking
Starch forms.
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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| CN201710101309.3A CN106867541B (en) | 2017-02-23 | 2017-02-23 | A kind of environment-friendly type heavy metal renovation agent and its application and slow release heavy metal remediation fertilizer |
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| CN106867541B true CN106867541B (en) | 2018-01-19 |
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| 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 |
| CN110938435B (en) * | 2019-12-03 | 2022-04-22 | 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 |
| CN111996008B (en) * | 2020-08-24 | 2021-06-29 | 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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| 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 |
| KR101338239B1 (en) * | 2012-03-21 | 2014-01-02 | 서정율 | 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 |
| CN103788957B (en) * | 2014-01-22 | 2016-03-02 | 扬州红硕环境与生物工程研究有限公司 | Contaminated soil top layer repair materials and preparation method thereof |
| CN105642235B (en) * | 2016-01-15 | 2018-07-20 | 中国海洋大学 | A method of removing heavy metal using activation 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 |
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Address after: 363500 Xiwu Village, Sidu Town, Zhaoan County, Zhangzhou City, Fujian Province (beside Provincial Highway 309) Patentee after: Fujian Mata Ecology Technology Co., Ltd. Address before: 363500 Xiwu Village, Sidu Town, Zhaoan County, Zhangzhou City, Fujian Province (beside Provincial Highway 309) Patentee before: Fujian Mata Agricultural Development Co., Ltd. |
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