CN108484298A - A kind of biological organic complex fertilizer of repairing heavy metal in soil and preparation method thereof - Google Patents
A kind of biological organic complex fertilizer of repairing heavy metal in soil and preparation method thereof Download PDFInfo
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- CN108484298A CN108484298A CN201810650429.3A CN201810650429A CN108484298A CN 108484298 A CN108484298 A CN 108484298A CN 201810650429 A CN201810650429 A CN 201810650429A CN 108484298 A CN108484298 A CN 108484298A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
-
- 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
-
- 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
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Abstract
The invention discloses a kind of biological organic complex fertilizers of repairing heavy metal in soil and preparation method thereof.The fertilizer is made of urea, tobacco waste, riverway sludge, rice hulls, calgon, zinc ion porphyrin nano complex compound, modified manometer silicon dioxide, potassium dihydrogen phosphate, complex micro organism fungicide, vermiculite power, potassium sulfate, trace element according to certain weight proportion.The fertilizer of the present invention can significantly reduce the content of heavy metal in soil apply for years after, repairing heavy metal in soil pollution improves soil texture, enhance soil water-reataining fertilizer-keeping ability and improve utilization rate of fertilizer.
Description
Technical field
The present invention relates to a kind of bio-organic fertilizer, specifically a kind of biological organic of repairing heavy metal in soil is compound
Fertilizer and preparation method thereof.
Background technology
With the development of social progress and modern chemical industry agricultural, influence of the mankind to natural environment is more and more far-reaching.From
The chemical fertilizer of agricultural, pesticide, genetically modified organism to " three wastes " and sewage, the rubbish in daily life of industry, then arrive state
Anti-, aerospace industry space trash, they affect the Nature invariably, result in various environmental problems, more outstanding among these
It is heavy metal pollution problem.Heavy metal pollution of soil not only influences agricultural output and quality, and is related to air and water environment
Quality, and the life and health of animals and humans can be endangered by food chain.Currently, China's heavy metals pollution in agricultural is total
Body characteristics are that the degree of pollution is gradually aggravated, and the area of pollution expands year by year, and pluralistic trend is presented in pollution sources.Cut-off
The end of the year 2011, China are accounted for about total cultivated area 1/5 by nearly 20,000,000 mu of the cultivated area of the heavy metal pollutions such as Cd, As, Cr, Pb.
Annual contaminated by heavy metals grain exceedes 12,000,000 t.Heavy metal contaminants poor mobility in agricultural soil, the residence time is long,
It is not easy by the microbial degradation of soil, agricultural soil is the most strong a kind of soil of the effect of human activity, and environmental aspect is direct
Closely bound up with health of people, heavy metals pollution in agricultural prevention and control and improvement are very urgent.
Heavy metal pollution of soil derives from various aspects, wherein unreasonable fertilising also results in soil fertility decline, weight
Metallic pollution is aggravated.In recent years, China's grain yield does not dramatically increase and applying quantity of chemical fertilizer increases nearly 30%, chemical fertilizer profit
It is lower and lower with rate.It is long-term excessive using chemical fertilizer such as ammonium nitrate, ammonium phosphate, composite fertilizers in agricultural soil, it can make in soil
The content of arsenic reaches 50-60 mg/kg.With the increase for entering heavy metal-polluted soil, effectively content of beary metal can also increase in soil,
The amount that crop absorbs, which can also increase, continuously emerges the exceeded phenomenon of crop heavy metal.Heavy metal in these crops is logical
It crosses food chain and enters human body, seriously endanger human health.Thus, the heavy metal pollution how repaired and administer in agricultural soil is asked
Topic has become the research hotspot of people.
Invention content
For problems of the prior art, the present invention provides it is a kind of can repairing heavy metal in soil biological organic it is multiple
Hefei and preparation method thereof.The fertilizer formula is reasonable, and nutrients release is balanced permanent, and utilization rate of fertilizer is high, can effectively inhibit soil
The harmful microbes such as fungi, bacterium, virus in earth are grown, and effectively prevent the generation of various pest and disease damages.The fertilizer of the present invention
The content of heavy metal in soil can also be significantly reduced apply for years after, repairing heavy metal in soil pollution improves soil knot
Structure, enhancing soil water-reataining fertilizer-keeping ability and raising utilization rate of fertilizer.
The present invention uses following technical scheme：
A kind of biological organic complex fertilizer of repairing heavy metal in soil, it is made of the raw material of following parts by weight：Urea 80-120
Part, 800-1000 parts of tobacco waste, 800-1000 parts of riverway sludge, 600-800 parts of rice hulls, 10-20 parts of calgon,
Zinc ion -1-5 parts of porphyrin nano complex compound, 1-3 parts of modified manometer silicon dioxide, 50-80 parts of potassium dihydrogen phosphate, complex microorganism
5-8 parts of microbial inoculum, 60-80 parts of vermiculite power, 20-40 parts of potassium sulfate, 5-10 parts of trace element.
The complex micro organism fungicide is Bacillus cereus and trichoderma harzianum according to 3:1 weight ratio is made into.
The modified manometer silicon dioxide is prepared using following methods：Accurately weighs nano silicon dioxide and send
Enter in reactor, be then heated to 300 DEG C, pretreatment is passed through nitrogen after 15 minutes, when temperature rises to 300 DEG C again, is added
Accounting for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55%, the reaction was continued 15 minutes, continues logical nitrogen 8 after reaction
Minute, holding nitrogen flow is 0.5m3/ h, then cooling close nitrogen discharging up to modified manometer silicon dioxide.
The zinc ion-porphyrin nano complex compound is prepared using following methods：By 10ml 1mol/L zinc acetates
Solution is added in reaction bulb together with the acetum of four pyridylporphyrins of 1.5ml 0.05mmol/L and is mixed at room temperature
After reacting 24 hours to obtain the final product.
The trace element is sodium molybdate, manganese sulfate, borax, copper sulphate and zinc sulfate according to 1:5:5:10:15 weight
Than being formulated.
Preferably, the biological organic complex fertilizer of the repairing heavy metal in soil is made of the raw material of following parts by weight：
100 parts of urea, 900 parts of tobacco waste, 900 parts of riverway sludge, 700 parts of rice hulls, 15 parts of calgon, zinc ion-porphin
3 parts of quinoline complexing nano object, 2 parts of modified manometer silicon dioxide, 70 parts of potassium dihydrogen phosphate, 7 parts of complex micro organism fungicide, vermiculite power 70
Part, 30 parts of potassium sulfate, 8 parts of trace element.
A kind of preparation method of the biological organic complex fertilizer of above-mentioned repairing heavy metal in soil, it includes the following steps：
（1）Tobacco waste is weighed according to formula ratio, then thereto according to solid-liquid ratio 1kg：MgCl is added in 30ml2Solution is not
Disconnected to stir, the sodium hydroxide solution that the 3.0mol/L for accounting for solid material weight ratio 3 ~ 5% is added after stirring 30min continues to stir
10 ~ 15min obtains mixed material A after then being dried in baking oven, and material A is continued to be placed in Muffle furnace in closed isolation sky
It is roasted 3 ~ 6 hours at 450 ~ 650 DEG C under conditions of gas, after being cooled to room temperature, is ground into the powder material B not less than 100 mesh；
（2）Riverway sludge, rice hulls are uniformly mixed, amount of water is added, keep water content 40 ~ 50%, then to mixture
Middle addition complex micro organism fungicide, which stirs evenly, to be started to ferment, primary every stirring in 4 days after temperature is increased to 60 DEG C or more, hair
Ferment obtains tunning after 20 days；
（3）10ml 1mol/L acetic acid zinc solutions are added together with the acetum of four pyridylporphyrins of 1.5ml 0.05mmol/L
Zinc ion-porphyrin nano complex compound is obtained after entering into reaction bulb to be mixed reaction at room temperature 24 hours；
（4）By step（3）Gained zinc ion-porphyrin nano complex compound is uniformly sprayed at step（2）In product after fermentation, then
Dries pulverizing obtains fermentation powder C；
（5）It accurately weighs nano silicon dioxide and is sent into reactor, be then heated to 300 DEG C, pretreatment is passed through after 15 minutes
Nitrogen, when temperature rises to 300 DEG C again, be added account for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55% after
Continuous reaction 15 minutes, continues logical nitrogen 8 minutes after reaction, and holding nitrogen flow is 0.5m3/ h, then cooling are closed nitrogen and are unloaded
Expect up to modified manometer silicon dioxide, it is spare；
（6）By urea, calgon, modified manometer silicon dioxide, potassium dihydrogen phosphate, vermiculite power, potassium sulfate, trace element with
Powder material B and fermentation powder C are uniformly mixed, and are then fed into comminutor granulation, dry, are dispensed up to fertilizer of the present invention.
The step（1）Middle MgCl2Solution concentration is 0.5M.
The beneficial effects of the invention are as follows：First, rich in a large amount of after the added complex micro organism fungicide fermentation of fertilizer of the present invention
Beneficial activity bacterium breeds rapidly using each strain after fertilizer of the present invention, and fertilizer formula is reasonable, and nutrients release is balanced, can be effective
Inhibit the growth of the harmful microbes such as fungi, bacterium, the virus in soil, effectively prevents the generation of various pest and disease damages.Secondly, originally
The powder material B with biomass carbon ingredient, zinc ion-porphyrin nano complex compound and the modified Nano that invention is prepared by tobacco waste
Silica acts synergistically, and significantly reduces the content of heavy metal in soil ion.In addition, the present invention fertilizer by riverway sludge with
Rice hulls add the product after microbial bacterial agent fermentation further with the nothings such as urea, calgon, potassium dihydrogen phosphate, potassium sulfate
Machine fertilizer mixes, and soil physico-chemical property is also significantly improved while the nutrient supplemented with fertilizer, increases soil aggregate structure, delays
Soil hardening problem is solved, soil permeability and retain water and nutrients ability is improved, improves utilization rate of fertilizer.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1
A kind of biological organic complex fertilizer of repairing heavy metal in soil, it is made of the raw material of following parts by weight：80 parts of urea, cigarette
800 parts of careless waste, 800 parts of riverway sludge, 600 parts of rice hulls, 10 parts of calgon, zinc ion-porphyrin nano complex compound 1
Part, 1 part of modified manometer silicon dioxide, 50 parts of potassium dihydrogen phosphate, 5 parts of complex micro organism fungicide, 60 parts of vermiculite power, potassium sulfate 20
Part, 5 parts of trace element.
The complex micro organism fungicide is Bacillus cereus and trichoderma harzianum according to 3:1 weight ratio is made into.It is used
Bacillus cereus is purchased from quality inspection Bioisystech Co., Ltd of BeiJing ZhongKe, product identification：CMCC(B)63301.Kazakhstan thatch wood used
Mould is purchased from Tianjin Jin Nuo chemical science and technologies Co., Ltd.
The trace element is sodium molybdate, manganese sulfate, borax, copper sulphate and zinc sulfate according to 1:5:5:10:15 weight
Than being formulated.
The preparation method of the biological organic complex fertilizer of above-mentioned repairing heavy metal in soil is as follows：
（1）Tobacco waste is weighed according to formula ratio, then thereto according to solid-liquid ratio 1kg：0.5M MgCl are added in 30ml2
Solution is stirred continuously, stir add after 30min the sodium hydroxide solution of the 3.0mol/L for accounting for solid material weight ratio 3 ~ 5% after
10 ~ 15min of continuous stirring, obtains mixed material A after then being dried in baking oven, material A is continued to be placed in Muffle furnace closed
It is roasted 3 ~ 6 hours at 450 ~ 650 DEG C under conditions of isolation air, after being cooled to room temperature, is ground into the powder not less than 100 mesh
Expect B；
（2）Riverway sludge, rice hulls are uniformly mixed, amount of water is added, keep water content 40 ~ 50%, then to mixture
Middle addition complex micro organism fungicide, which stirs evenly, to be started to ferment, primary every stirring in 4 days after temperature is increased to 60 DEG C or more, hair
Ferment obtains tunning after 20 days；
（3）10ml 1mol/L acetic acid zinc solutions are added together with the acetum of four pyridylporphyrins of 1.5ml 0.05mmol/L
Zinc ion-porphyrin nano complex compound is obtained after entering into reaction bulb to be mixed reaction at room temperature 24 hours；
（4）By step（3）Gained zinc ion-porphyrin nano complex compound is uniformly sprayed at step（2）In product after fermentation, then
Dries pulverizing obtains fermentation powder C；
（5）It accurately weighs nano silicon dioxide and is sent into reactor, be then heated to 300 DEG C, pretreatment is passed through after 15 minutes
Nitrogen, when temperature rises to 300 DEG C again, be added account for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55% after
Continuous reaction 15 minutes, continues logical nitrogen 8 minutes after reaction, and holding nitrogen flow is 0.5m3/ h, then cooling are closed nitrogen and are unloaded
Expect up to modified manometer silicon dioxide, it is spare；
（6）By urea, calgon, modified manometer silicon dioxide, potassium dihydrogen phosphate, vermiculite power, potassium sulfate, trace element with
Powder material B and fermentation powder C are uniformly mixed, and are then fed into comminutor granulation, dry, are dispensed up to fertilizer of the present invention.
Embodiment 2
A kind of biological organic complex fertilizer of repairing heavy metal in soil, it is made of the raw material of following parts by weight：120 parts of urea,
1000 parts of tobacco waste, 1000 parts of riverway sludge, 800 parts of rice hulls, 20 parts of calgon, zinc ion-porphyrin nano network
Close 5 parts of object, 3 parts of modified manometer silicon dioxide, 80 parts of potassium dihydrogen phosphate, 8 parts of complex micro organism fungicide, 80 parts of vermiculite power, sulfuric acid
40 parts of potassium, 10 parts of trace element.
The complex micro organism fungicide is Bacillus cereus and trichoderma harzianum according to 3:1 weight ratio is made into.It is used
Bacillus cereus is purchased from quality inspection Bioisystech Co., Ltd of BeiJing ZhongKe, product identification：CMCC(B)63301.Kazakhstan thatch wood used
Mould is purchased from Tianjin Jin Nuo chemical science and technologies Co., Ltd.
The trace element is sodium molybdate, manganese sulfate, borax, copper sulphate and zinc sulfate according to 1:5:5:10:15 weight
Than being formulated.
The preparation method of the biological organic complex fertilizer of above-mentioned repairing heavy metal in soil is as follows：
（1）Tobacco waste is weighed according to formula ratio, then thereto according to solid-liquid ratio 1kg：0.5M MgCl are added in 30ml2
Solution is stirred continuously, stir add after 30min the sodium hydroxide solution of the 3.0mol/L for accounting for solid material weight ratio 3 ~ 5% after
10 ~ 15min of continuous stirring, obtains mixed material A after then being dried in baking oven, material A is continued to be placed in Muffle furnace closed
It is roasted 3 ~ 6 hours at 450 ~ 650 DEG C under conditions of isolation air, after being cooled to room temperature, is ground into the powder not less than 100 mesh
Expect B；
（2）Riverway sludge, rice hulls are uniformly mixed, amount of water is added, keep water content 40 ~ 50%, then to mixture
Middle addition complex micro organism fungicide, which stirs evenly, to be started to ferment, primary every stirring in 4 days after temperature is increased to 60 DEG C or more, hair
Ferment obtains tunning after 20 days；
（3）10ml 1mol/L acetic acid zinc solutions are added together with the acetum of four pyridylporphyrins of 1.5ml 0.05mmol/L
Zinc ion-porphyrin nano complex compound is obtained after entering into reaction bulb to be mixed reaction at room temperature 24 hours；
（4）By step（3）Gained zinc ion-porphyrin nano complex compound is uniformly sprayed at step（2）In product after fermentation, then
Dries pulverizing obtains fermentation powder C；
（5）It accurately weighs nano silicon dioxide and is sent into reactor, be then heated to 300 DEG C, pretreatment is passed through after 15 minutes
Nitrogen, when temperature rises to 300 DEG C again, be added account for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55% after
Continuous reaction 15 minutes, continues logical nitrogen 8 minutes after reaction, and holding nitrogen flow is 0.5m3/ h, then cooling are closed nitrogen and are unloaded
Expect up to modified manometer silicon dioxide, it is spare；
（6）By urea, calgon, modified manometer silicon dioxide, potassium dihydrogen phosphate, vermiculite power, potassium sulfate, trace element with
Powder material B and fermentation powder C are uniformly mixed, and are then fed into comminutor granulation, dry, are dispensed up to fertilizer of the present invention.
Embodiment 3
A kind of biological organic complex fertilizer of repairing heavy metal in soil, it is made of the raw material of following parts by weight：100 parts of urea,
900 parts of tobacco waste, 900 parts of riverway sludge, 700 parts of rice hulls, 15 parts of calgon, zinc ion-porphyrin nano complexing
3 parts of object, 2 parts of modified manometer silicon dioxide, 70 parts of potassium dihydrogen phosphate, 7 parts of complex micro organism fungicide, 70 parts of vermiculite power, potassium sulfate
30 parts, 8 parts of trace element.
The complex micro organism fungicide is Bacillus cereus and trichoderma harzianum according to 3:1 weight ratio is made into.It is used
Bacillus cereus is purchased from quality inspection Bioisystech Co., Ltd of BeiJing ZhongKe, product identification：CMCC(B)63301.Kazakhstan thatch wood used
Mould is purchased from Tianjin Jin Nuo chemical science and technologies Co., Ltd.
The trace element is sodium molybdate, manganese sulfate, borax, copper sulphate and zinc sulfate according to 1:5:5:10:15 weight
Than being formulated.
The preparation method of the biological organic complex fertilizer of above-mentioned repairing heavy metal in soil is as follows：
（1）Tobacco waste is weighed according to formula ratio, then thereto according to solid-liquid ratio 1kg：0.5M MgCl are added in 30ml2
Solution is stirred continuously, stir add after 30min the sodium hydroxide solution of the 3.0mol/L for accounting for solid material weight ratio 3 ~ 5% after
10 ~ 15min of continuous stirring, obtains mixed material A after then being dried in baking oven, material A is continued to be placed in Muffle furnace closed
It is roasted 3 ~ 6 hours at 450 ~ 650 DEG C under conditions of isolation air, after being cooled to room temperature, is ground into the powder not less than 100 mesh
Expect B；
（2）Riverway sludge, rice hulls are uniformly mixed, amount of water is added, keep water content 40 ~ 50%, then to mixture
Middle addition complex micro organism fungicide, which stirs evenly, to be started to ferment, primary every stirring in 4 days after temperature is increased to 60 DEG C or more, hair
Ferment obtains tunning after 20 days；
（3）10ml 1mol/L acetic acid zinc solutions are added together with the acetum of four pyridylporphyrins of 1.5ml 0.05mmol/L
Zinc ion-porphyrin nano complex compound is obtained after entering into reaction bulb to be mixed reaction at room temperature 24 hours；
（4）By step（3）Gained zinc ion-porphyrin nano complex compound is uniformly sprayed at step（2）In product after fermentation, then
Dries pulverizing obtains fermentation powder C；
（5）It accurately weighs nano silicon dioxide and is sent into reactor, be then heated to 300 DEG C, pretreatment is passed through after 15 minutes
Nitrogen, when temperature rises to 300 DEG C again, be added account for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55% after
Continuous reaction 15 minutes, continues logical nitrogen 8 minutes after reaction, and holding nitrogen flow is 0.5m3/ h, then cooling are closed nitrogen and are unloaded
Expect up to modified manometer silicon dioxide, it is spare；
（6）By urea, calgon, modified manometer silicon dioxide, potassium dihydrogen phosphate, vermiculite power, potassium sulfate, trace element with
Powder material B and fermentation powder C are uniformly mixed, and are then fed into comminutor granulation, dry, are dispensed up to fertilizer of the present invention.
Comparative example 1
A kind of biological organic complex fertilizer of repairing heavy metal in soil, it is made of the raw material of following parts by weight：100 parts of urea,
900 parts of tobacco waste, 900 parts of riverway sludge, 700 parts of rice hulls, 15 parts of calgon, 2 parts of modified manometer silicon dioxide,
70 parts of potassium dihydrogen phosphate, 7 parts of complex micro organism fungicide, 70 parts of vermiculite power, 30 parts of potassium sulfate, 8 parts of trace element.
The complex micro organism fungicide is Bacillus cereus and trichoderma harzianum according to 3:1 weight ratio is made into.It is used
Bacillus cereus is purchased from quality inspection Bioisystech Co., Ltd of BeiJing ZhongKe, product identification：CMCC(B)63301.Kazakhstan thatch wood used
Mould is purchased from Tianjin Jin Nuo chemical science and technologies Co., Ltd.
The trace element is sodium molybdate, manganese sulfate, borax, copper sulphate and zinc sulfate according to 1:5:5:10:15 weight
Than being formulated.
The preparation method of the biological organic complex fertilizer of above-mentioned repairing heavy metal in soil is as follows：
（1）Tobacco waste is weighed according to formula ratio, then thereto according to solid-liquid ratio 1kg：0.5M MgCl are added in 30ml2
Solution is stirred continuously, stir add after 30min the sodium hydroxide solution of the 3.0mol/L for accounting for solid material weight ratio 3 ~ 5% after
10 ~ 15min of continuous stirring, obtains mixed material A after then being dried in baking oven, material A is continued to be placed in Muffle furnace closed
It is roasted 3 ~ 6 hours at 450 ~ 650 DEG C under conditions of isolation air, after being cooled to room temperature, is ground into the powder not less than 100 mesh
Expect B；
（2）Riverway sludge, rice hulls are uniformly mixed, amount of water is added, keep water content 40 ~ 50%, then to mixture
Middle addition complex micro organism fungicide, which stirs evenly, to be started to ferment, primary every stirring in 4 days after temperature is increased to 60 DEG C or more, hair
Ferment obtains tunning after 20 days, then dries pulverizing obtains fermentation powder C；
（3）It accurately weighs nano silicon dioxide and is sent into reactor, be then heated to 300 DEG C, pretreatment is passed through after 15 minutes
Nitrogen, when temperature rises to 300 DEG C again, be added account for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55% after
Continuous reaction 15 minutes, continues logical nitrogen 8 minutes after reaction, and holding nitrogen flow is 0.5m3/ h, then cooling are closed nitrogen and are unloaded
Expect up to modified manometer silicon dioxide, it is spare；
（4）By urea, calgon, modified manometer silicon dioxide, potassium dihydrogen phosphate, vermiculite power, potassium sulfate, trace element with
Powder material B and fermentation powder C are uniformly mixed, and are then fed into comminutor granulation, dry, are dispensed up to fertilizer.
Comparative example 2
A kind of biological organic complex fertilizer of repairing heavy metal in soil, it is made of the raw material of following parts by weight：100 parts of urea,
900 parts of tobacco waste, 900 parts of riverway sludge, 700 parts of rice hulls, 15 parts of calgon, zinc ion-porphyrin nano complexing
3 parts of object, 70 parts of potassium dihydrogen phosphate, 7 parts of complex micro organism fungicide, 70 parts of vermiculite power, 30 parts of potassium sulfate, 8 parts of trace element.
The complex micro organism fungicide is Bacillus cereus and trichoderma harzianum according to 3:1 weight ratio is made into.It is used
Bacillus cereus is purchased from quality inspection Bioisystech Co., Ltd of BeiJing ZhongKe, product identification：CMCC(B)63301.Kazakhstan thatch wood used
Mould is purchased from Tianjin Jin Nuo chemical science and technologies Co., Ltd.
The trace element is sodium molybdate, manganese sulfate, borax, copper sulphate and zinc sulfate according to 1:5:5:10:15 weight
Than being formulated.
The preparation method of the biological organic complex fertilizer of above-mentioned repairing heavy metal in soil is as follows：
（1）Tobacco waste is weighed according to formula ratio, then thereto according to solid-liquid ratio 1kg：0.5M MgCl are added in 30ml2
Solution is stirred continuously, stir add after 30min the sodium hydroxide solution of the 3.0mol/L for accounting for solid material weight ratio 3 ~ 5% after
10 ~ 15min of continuous stirring, obtains mixed material A after then being dried in baking oven, material A is continued to be placed in Muffle furnace closed
It is roasted 3 ~ 6 hours at 450 ~ 650 DEG C under conditions of isolation air, after being cooled to room temperature, is ground into the powder not less than 100 mesh
Expect B；
（2）Riverway sludge, rice hulls are uniformly mixed, amount of water is added, keep water content 40 ~ 50%, then to mixture
Middle addition complex micro organism fungicide, which stirs evenly, to be started to ferment, primary every stirring in 4 days after temperature is increased to 60 DEG C or more, hair
Ferment obtains tunning after 20 days；
（3）10ml 1mol/L acetic acid zinc solutions are added together with the acetum of four pyridylporphyrins of 1.5ml 0.05mmol/L
Zinc ion-porphyrin nano complex compound is obtained after entering into reaction bulb to be mixed reaction at room temperature 24 hours；
（4）By step（3）Gained zinc ion-porphyrin nano complex compound is uniformly sprayed at step（2）In product after fermentation, then
Dries pulverizing obtains fermentation powder C；
（5）It accurately weighs nano silicon dioxide and is sent into reactor, be then heated to 300 DEG C, pretreatment is passed through after 15 minutes
Nitrogen, when temperature rises to 300 DEG C again, be added account for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55% after
Continuous reaction 15 minutes, continues logical nitrogen 8 minutes after reaction, and holding nitrogen flow is 0.5m3/ h, then cooling are closed nitrogen and are unloaded
Expect up to modified manometer silicon dioxide, it is spare；
（6）By urea, calgon, modified manometer silicon dioxide, potassium dihydrogen phosphate, vermiculite power, potassium sulfate, trace element with
Powder material B and fermentation powder C are uniformly mixed, and are then fed into comminutor granulation, dry, are dispensed up to fertilizer.
Comparative example 3
A kind of biological organic complex fertilizer of repairing heavy metal in soil, it is made of the raw material of following parts by weight：100 parts of urea,
900 parts of riverway sludge, 700 parts of rice hulls, 15 parts of calgon, zinc ion -3 parts of porphyrin nano complex compound, modified Nano two
2 parts of silica, 70 parts of potassium dihydrogen phosphate, 7 parts of complex micro organism fungicide, 70 parts of vermiculite power, 30 parts of potassium sulfate, 8 parts of trace element.
The complex micro organism fungicide is Bacillus cereus and trichoderma harzianum according to 3:1 weight ratio is made into.It is used
Bacillus cereus is purchased from quality inspection Bioisystech Co., Ltd of BeiJing ZhongKe, product identification：CMCC(B)63301.Kazakhstan thatch wood used
Mould is purchased from Tianjin Jin Nuo chemical science and technologies Co., Ltd.
The trace element is sodium molybdate, manganese sulfate, borax, copper sulphate and zinc sulfate according to 1:5:5:10:15 weight
Than being formulated.
The preparation method of the biological organic complex fertilizer of above-mentioned repairing heavy metal in soil is as follows：
（1）Riverway sludge, rice hulls are uniformly mixed, amount of water is added, keep water content 40 ~ 50%, then to mixture
Middle addition complex micro organism fungicide, which stirs evenly, to be started to ferment, primary every stirring in 4 days after temperature is increased to 60 DEG C or more, hair
Ferment obtains tunning after 20 days；
（2）10ml 1mol/L acetic acid zinc solutions are added together with the acetum of four pyridylporphyrins of 1.5ml 0.05mmol/L
Zinc ion-porphyrin nano complex compound is obtained after entering into reaction bulb to be mixed reaction at room temperature 24 hours；
（3）By step（2）Gained zinc ion-porphyrin nano complex compound is uniformly sprayed at step（1）In product after fermentation, then
Dries pulverizing obtains fermentation powder C；
（4）It accurately weighs nano silicon dioxide and is sent into reactor, be then heated to 300 DEG C, pretreatment is passed through after 15 minutes
Nitrogen, when temperature rises to 300 DEG C again, be added account for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55% after
Continuous reaction 15 minutes, continues logical nitrogen 8 minutes after reaction, and holding nitrogen flow is 0.5m3/ h, then cooling are closed nitrogen and are unloaded
Expect up to modified manometer silicon dioxide, it is spare；
（5）By urea, calgon, modified manometer silicon dioxide, potassium dihydrogen phosphate, vermiculite power, potassium sulfate, trace element with
The powder C that ferments is uniformly mixed, and is then fed into comminutor granulation, dry, is dispensed up to fertilizer.
Using test case
Soil compaction phenomenon and the exceeded more serious a piece of soil of heavy metal ion at Zibo City of Shandong Province Yiyuan County one is chosen to make
For wheat planting experimental plot, the fertilizer application effect of the present invention is studied within continuous 3 years 2014 to 2016 on the experimental plot；Examination
Lead content is 258.3 mg/kg in the soil before testing, and chromium content 53.2mg/kg, arsenic content is 172.3mg/kg.It draws in experimental plot
It is divided into 7 pieces of same size, wheat application rate is identical in every piece of experimental plot, applies fertilizer obtained in embodiment 1-3, right respectively
Ratio 1-3 fertilizer and application Common compound fertilizer material（N:P2O5:K2O=17-6-20, total nutrient >=45%）As a contrast.Embodiment
Identical with comparative example fertilizer fertilizing method, each processing group carries out dose in a manner of reducing 10kg every year, other management
Conventionally carry out.Wheat yield and wheat powdery mildew incidence were counted in continuous 3 years, while to soil after 3 years
In heavy metal ion be further detected, test result is specifically shown in Table 1-2.
Table 1 continuous 3 year wheat yield and pest and disease damage statistical result
2 heavy metal in soil ion detection result of table
| Pb（mg/kg） | Cd（mg/kg） | As（mg/kg） | |
| Embodiment 1 | 76.3 | 22.1 | 56.5 |
| Embodiment 2 | 88.2 | 23.5 | 58.3 |
| Embodiment 3 | 79.1 | 25.1 | 59.4 |
| Comparative example 1 | 212.5 | 45.3 | 159.5 |
| Comparative example 2 | 189.3 | 49.2 | 148.2 |
| Comparative example 3 | 242.6 | 50.1 | 163.1 |
| Commercially available control | 289.6 | 69.3 | 199.5 |
After can be seen that fertilizer continuous use of the invention 3 years by the result in above-mentioned table 2, with soil when initial plantation
In content of beary metal situation compare, the content of heavy metal is decreased obviously.After commercially available common fertilizer group continuously plants 3 years wheats,
Anti- increasing does not drop in heavy metal in soil Pb, Cd, As content；After continuously planting 3 years wheats in comparative example 1-3 groups, heavy metal in soil
Pb, Cd, As content slightly reduce but amplitude is little.This is due primarily to have biology by prepared by tobacco waste in the present invention
Powder material B, zinc ion-porphyrin nano complex compound and the modified manometer silicon dioxide three synergistic effect of matter charcoal ingredient, can significantly drop
The content of low heavy metal in soil ion, and three is indispensable.
In addition, after the fertilizer that the data in table 1 can be seen that using 1-3 of the embodiment of the present invention, wheat yield continuous 3
The trend increased year by year is presented in year, and powdery mildew incidence also reduces year by year；And comparative example 1-3 fertilizer be used continuously 3 years in wheat
Yield is without obviously increasing, and powdery mildew incidence is without significant decrease；Commercially available control group wheat yield then successively decreases year after year, and powdery mildew
Incidence improves year after year.This is mainly due to use in riverway sludge and rice hulls to add complex microorganism in the fertilizer of the present invention
Microbial inoculum simultaneously ferments, and stimulation complex micro organism fungicide produces the activity of more kinds of biologically active enzymes, such as cellulase, wood
Dextranase etc., these enzymes dissolve solable matter, can promote suction of the plant to minerals to decompose the organic matter in soil
It receives, promotes the growth of plant, improve the growth quality of crops.These enzymes can also act synergistically with other nutrients simultaneously, have
Effect improves the physical behavior of soil, enhances the ventilative of soil, water conservation, fertilizer-preserving ability, improves soil hardening situation, improves fertilizer profit
With rate.
Claims (8)
1. a kind of biological organic complex fertilizer of repairing heavy metal in soil, which is characterized in that it is by the raw material system of following parts by weight
At：80-120 parts of urea, 800-1000 parts of tobacco waste, 800-1000 parts of riverway sludge, 600-800 parts of rice hulls, six are partially
10-20 parts of sodium phosphate, zinc ion -1-5 parts of porphyrin nano complex compound, 1-3 parts of modified manometer silicon dioxide, potassium dihydrogen phosphate 50-
80 parts, 5-8 parts of complex micro organism fungicide, 60-80 parts of vermiculite power, 20-40 parts of potassium sulfate, 5-10 parts of trace element.
2. the biological organic complex fertilizer of repairing heavy metal in soil according to claim 1, which is characterized in that described compound micro-
Bacteria agent is Bacillus cereus and trichoderma harzianum according to 3:1 weight ratio is made into.
3. the biological organic complex fertilizer of repairing heavy metal in soil according to claim 1, which is characterized in that the modification is received
Rice silica is prepared using following methods：It accurately weighs nano silicon dioxide and is sent into reactor, then add
For heat to 300 DEG C, pretreatment is passed through nitrogen after 15 minutes, and when temperature rises to 300 DEG C again, addition accounts for nano silicon dioxide quality
The reaction was continued 15 minutes for 55% modifying agent hexamethyldisilazane, continues logical nitrogen after reaction 8 minutes, keeps nitrogen flow
For 0.5m3/ h, then cooling close nitrogen discharging up to modified manometer silicon dioxide.
4. the biological organic complex fertilizer of repairing heavy metal in soil according to claim 1, which is characterized in that the zinc from
Son-porphyrin nano complex compound is prepared using following methods：By 10ml 1mol/L acetic acid zinc solutions and 1.5ml
After the acetum of four pyridylporphyrins of 0.05mmol/L is added in reaction bulb mixing reaction at room temperature 24 hours together
To obtain the final product.
5. the biological organic complex fertilizer of repairing heavy metal in soil according to claim 1, which is characterized in that the micro member
Element is sodium molybdate, manganese sulfate, borax, copper sulphate and zinc sulfate according to 1:5:5:10:15 weight ratio is formulated.
6. the biological organic complex fertilizer of repairing heavy metal in soil according to claim 1, which is characterized in that it is by following
The raw material of parts by weight is made：100 parts of urea, 900 parts of tobacco waste, 900 parts of riverway sludge, 700 parts of rice hulls, hexa metaphosphoric acid
15 parts of sodium, zinc ion -3 parts of porphyrin nano complex compound, 2 parts of modified manometer silicon dioxide, 70 parts of potassium dihydrogen phosphate, complex microorganism
7 parts of microbial inoculum, 70 parts of vermiculite power, 30 parts of potassium sulfate, 8 parts of trace element.
7. the preparation method of the biological organic complex fertilizer of the repairing heavy metal in soil described in a kind of any one of claim 1-6,
It is characterized in that, it includes the following steps：
（1）Tobacco waste is weighed according to formula ratio, then thereto according to solid-liquid ratio 1kg：MgCl is added in 30ml2Solution is not
Disconnected to stir, the sodium hydroxide solution that the 3.0mol/L for accounting for solid material weight ratio 3 ~ 5% is added after stirring 30min continues to stir
10 ~ 15min obtains mixed material A after then being dried in baking oven, and material A is continued to be placed in Muffle furnace in closed isolation sky
It is roasted 3 ~ 6 hours at 450 ~ 650 DEG C under conditions of gas, after being cooled to room temperature, is ground into the powder material B not less than 100 mesh；
（2）Riverway sludge, rice hulls are uniformly mixed, amount of water is added, keep water content 40 ~ 50%, then to mixture
Middle addition complex micro organism fungicide, which stirs evenly, to be started to ferment, primary every stirring in 4 days after temperature is increased to 60 DEG C or more, hair
Ferment obtains tunning after 20 days；
（3）10ml 1mol/L acetic acid zinc solutions are added together with the acetum of four pyridylporphyrins of 1.5ml 0.05mmol/L
Zinc ion-porphyrin nano complex compound is obtained after entering into reaction bulb to be mixed reaction at room temperature 24 hours；
（4）By step（3）Gained zinc ion-porphyrin nano complex compound is uniformly sprayed at step（2）In product after fermentation, then
Dries pulverizing obtains fermentation powder C；
（5）It accurately weighs nano silicon dioxide and is sent into reactor, be then heated to 300 DEG C, pretreatment is passed through after 15 minutes
Nitrogen, when temperature rises to 300 DEG C again, be added account for the modifying agent hexamethyldisilazane of nano silicon dioxide quality 55% after
Continuous reaction 15 minutes, continues logical nitrogen 8 minutes after reaction, and holding nitrogen flow is 0.5m3/ h, then cooling are closed nitrogen and are unloaded
Expect up to modified manometer silicon dioxide, it is spare；
（6）By urea, calgon, modified manometer silicon dioxide, potassium dihydrogen phosphate, vermiculite power, potassium sulfate, trace element with
Powder material B and fermentation powder C are uniformly mixed, and are then fed into comminutor granulation, dry, are dispensed up to fertilizer of the present invention.
8. the preparation method of the biological organic complex fertilizer of repairing heavy metal in soil according to claim 7, which is characterized in that
The step（1）Middle MgCl2Solution concentration is 0.5M.
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