CN106927973A - A kind of repairing fertiliser of heavy-metal contaminated soil - Google Patents
A kind of repairing fertiliser of heavy-metal contaminated soil Download PDFInfo
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- CN106927973A CN106927973A CN201710117866.4A CN201710117866A CN106927973A CN 106927973 A CN106927973 A CN 106927973A CN 201710117866 A CN201710117866 A CN 201710117866A CN 106927973 A CN106927973 A CN 106927973A
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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
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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Abstract
The present invention relates to technical field of fertilizers, and in particular to a kind of repairing fertiliser of heavy-metal contaminated soil；It is made up of following raw material by weight：Urea 35~40, urea phosphate 10~15, potassium dihydrogen phosphate 15~20, potassium sulfate 15~20, potassium chloride 25~30, potassium nitrate 13~18, sodium carbonate 25~30, potassium carbonate 10~15, weathered coal 10~15, thiourea dioxide 8~12, EDTA chelates 6~9, pomelo peel processed material 10~15, modified ferrous sulfate 15~20, modified corn core 25~30, modified activated carbon 20~25；This Fertilizer nutrient is enriched, contain various a great number of elements and micronutrient element necessary to crop, nitrogen, phosphorus, potassium total nutrient >=75.2%, rich in various nutrient elements, the present invention reaches more than 92.1%, more than 87.9% is reached to the chromium removal efficiency in soil to Arsenic in Soil removal efficiency, more than 94.4% is reached to the mercury removal rate in soil, by taking paddy rice as an example, 11.4~12.8% can be increased production, realize the double benefit of high yield and removing heavy metal.
Description
Technical field
The present invention relates to technical field of fertilizers, and in particular to a kind of repairing fertiliser of heavy-metal contaminated soil.
Background technology
At present, developing rapidly with industrialization and urbanization, heavy metal pollution of soil has turned into the protrusion that can not be ignored
Environmental problem, heavy metal is highly enriched in soil, deteriorates soil environment quality, influences the yield and quality of crops, seriously
The ecological circulation of soil is endangered, it passes through food chain and enters human body, and harm people's is healthy, threatens the existence ring of the mankind
Border, heavy metal pollution can not only cause the change of composition of the soil, 26S Proteasome Structure and Function, additionally it is possible to suppress crop root growth and
Photosynthesis, cause crop failure even have no harvest, it is even more important that heavy metal be also possible to by food chain move to animal,
In human body, serious harm animal, health, the report of the harm of the heavy metal pollution such as cadmium rice, arsenic poison, blood lead in recent years are shown in not repeatly
It is fresh.
Since chemical fertilizer is applied since the crop, wherein containing nutrients such as abundant N, P, K, it is aobvious to crop yield effect
Write, but due to the discharge of pollution sources, the deterioration of environment so that heavy metal content in soil is exceeded, the pollution to soil is increasingly tight
Weight, greatly reduces crop and fertilizer is absorbed, and reduces the utilization rate of fertilizer, meanwhile, sowed in heavy metal pollution
, there is great edible safety in the crop of plant, therefore, in efficient, quick development instantly, research and development are a kind of nutritious, both
It is current agricultural outside comprising the necessary nutriment of plant growth, moreover it is possible to the fertilizer of effective reparation is carried out to heavy metal-polluted soil
The trend of development, can plant out healthy, safe crop, while, moreover it is possible to excellent modified, reduction dirt is carried out to soil
Dye, realizes the double benefit of high yield and removing heavy metals, has become the emphasis of the research of current planting industry and fertilizer trade.
The content of the invention
The present invention is in order to solve the above technical problems, there is provided a kind of repairing fertiliser of heavy-metal contaminated soil.This fertilizer is sought
Support abundant, contain various a great number of elements and micronutrient element necessary to crop.Fertilizer of the invention not only heavy metal removing rate
Height, also with abundant nutrition, is capable of achieving the double benefit of high yield and removing heavy metal.
Realized particular by following technical scheme：
A kind of repairing fertiliser of heavy-metal contaminated soil, is made up of following raw material by weight：Urea 35~40, phosphorus
Sour urea 10~15, potassium dihydrogen phosphate 15~20, potassium sulfate 15~20, potassium chloride 25~30, potassium nitrate 13~18, sodium carbonate 25~
30th, potassium carbonate 10~15, weathered coal 10~15, thiourea dioxide 8~12, EDTA chelates 6~9, pomelo peel processed material 10~
15th, be modified ferrous sulfate 15~20, modified corn core 25~30, modified activated carbon 20~25.
Preferably, it is made up of following raw material by weight：Urea 38, urea phosphate 13, potassium dihydrogen phosphate 18, potassium sulfate
18th, potassium chloride 28, potassium nitrate 15, sodium carbonate 28, potassium carbonate 13, weathered coal 13, thiourea dioxide 10, EDTA chelates 8, shaddock
Skin processed material 13, modified ferrous sulfate 18, modified corn core 28, modified activated carbon 23.
Further, described EDTA chelates, are the three kinds or more of chelated iron, chelated zinc, chelated magnesium, chelated copper
Composition.
Further, described pomelo peel processed material, by the white flesh part of pomelo peel, add water 45~50min of infusion, pulls out,
The sodium hydroxide solution of 0.05~0.08mol/L is added, 1~1.2h is soaked, tartaric acid is added, regulation solution pH value is 2~3,
2.5~3h of immersion, pulls out, adds ethyl acetate to extract 1~1.5h, reclaims ethyl acetate, and drying crushed 20~40 mesh sieves i.e.
Can.
Further, described modified ferrous sulfate, be by ferrous sulfate aqueous solution by electrolytic cell be electrolysed 3~5min after,
Power-off, add ferrous sulfate quality 15~20% diatomite in powder, 100~120KHz frequency ultrasound treatment 20~
25min, is centrifuged 25~30min under the rotating speed of 1000~1200r/min, takes supernatant, adds the 25 of ferrous sulfate quality
~30% hydrogen peroxide, after water bath with thermostatic control is heated to 50~60 DEG C, stirs 35~40min, you can.
Further, described modified corn core, preparation method is that, by corncob, drying to water content is 6~8wt%, powder
The mesh sieve of broken mistake 60~80, adds oxalic acid, and oxalic acid addition is 1.5~2 times of corncob quality, and magnetic stirring apparatus is at 50~55 DEG C
After 25~30min of lower stirring, 0.3~0.35 times of corncob weight of bentonite is added, after continuing to stir 40~45min, mistake
Filter, drying.
Further, the modified activated carbon, its preparation method is by the immersion of activated carbon oxalic acid, 75~80 DEG C of waters bath with thermostatic control
Under, 35~40min of magnetic stirrer, it is 7 to adjust pH value with the NaOH of 0.9~1.2mol/L, stirs 10min, is dragged for
Go out, with hydrogen peroxide dipping, under 60~65 DEG C of waters bath with thermostatic control, 65~70min of magnetic stirrer adds quality of activated carbon
0.3~0.35 times of bentonite, stand 1~1.5h after, filtering, under nitrogen protection, at 280~285 DEG C calcine 1.8~
2.2h, crushed 60~80 mesh sieves.
Further, the urea, urea phosphate, potassium nitrate, nitrogen pool >=52.5%, described urea phosphate, potassium dihydrogen phosphate,
In terms of phosphorus pentoxide, total phosphorus content >=42.1%, described potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate, with
Potassium oxide meter, general potassium amount >=50%.
Further, the repairing fertiliser of described heavy-metal contaminated soil, its preparation method is comprised the following steps：
(1) weathered coal is calcined into 2~2.5h at 135~140 DEG C, crushed 30~40 mesh sieves, with thiourea dioxide and
EDTA chelates are mixed by formula ratio, and 8~12min is vibrated on the vibratory sieve of 100~120 times/min, obtain material 1；
(2) urea, urea phosphate, potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate and potassium carbonate are existed respectively
Melted under its respective fusing point, spray-dried separately, then dried each raw material is mixed in proportion, 180~
Ultrasonically treated 10~12min under the frequency of 200KHz, obtains material 2；
(3) pomelo peel processed material, modified ferrous sulfate, modified corn core and modified activated carbon are mixed by formula material,
It is fitted into the flask of 1000ml, adds water, material 3~3.5cm of plane is higher by, under the pressure of 0.06~0.08Mpa, with 3
Temperature is risen to 65~70 DEG C by the speed of~3.5 DEG C/min, 20~25min of magnetic stirrer, then with 10~11 DEG C/min
Speed cool the temperature to 8~12 DEG C, under the rotating speed of 600~800r/min, 5~7min is centrifuged, take precipitation, drying obtains material 3；
(4) will expect that 1, material 2 and material 3 mix, under the vibration frequency of 60~80 times/min, vibrate 25~30min, then with frequently
Rate is the ultrasonically treated 6~9min of 100~110KHz, loads granulator granulation, packaging.
In sum, the beneficial effects of the present invention are：
1) this Fertilizer nutrient is enriched, and containing various a great number of elements and micronutrient element necessary to crop, nitrogen, phosphorus, potassium are total
Nutrient >=75.2%, rich in various nutrient elements, the present invention reaches more than 92.1% to Arsenic in Soil removal efficiency, in soil
Chromium removal efficiency reaches more than 87.9%, reaches more than 94.4% to the mercury removal rate in soil, the paddy rice of present invention plantation, wherein
Content of beary metal reached country to the required standard of paddy rice content of beary metal, total arsenic content≤0.5mg/kg, sexavalence
Chromium content≤1.0mg/kg, the standard of total mercury content≤0.02mg/kg, it is ensured that the edible safety of paddy rice, fertilizer of the invention
Not only heavy metal removing rate is high for material, also with abundant nutrition, by taking paddy rice as an example, has been effectively promoted the growth of paddy rice, per mu yield
Amount can increase production 11.4~12.8% relative to control group, realize the double benefit of high yield and removing heavy metal.
2) the pomelo peel processed material in the present invention, by alkalization, in acidifying, improves the micropore grid knot inside the white flesh of shaddock
Structure, increase specific surface area are big, increase the quantity of porous active functional group, effectively enhance the adsorption capacity of heavy metal.
3) the modified ferrous sulfate in the present invention, by ionization and oxidation so that ferrous ion reaction generation hydration
Ferriferous oxide, the heavy metal being effectively combined in soil forms co-precipitate, so as to reach the purpose of removal heavy metal contaminants
4) the modified corn core in the present invention, after being modified by oxalic acid and bentonite, effectively activates corn wicking surface
With heavy metal be complexed active function groups, improve pore structure, increase corn wicking surface specific surface area, increase active function groups
Quantity, effectively lifting corncob adsorption capacity, reduce soil content of beary metal.
5) modified activated carbon in the present invention, changing for high-temperature calcination is protected by acidifying, alkalization, oxidation, bentonite, nitrogen
Property side tries, and increased the active function groups being complexed with heavy metal of activated carbon surface, increases the specific surface area of activated carbon, effectively carries
The adsorption capacity of activated carbon high, reduces the content of beary metal of soil.
6) chelate comprising substantial amounts of EDTA trace elements in the raw material in the present invention, after, can quickly supplement
The trace element of plant growth, promotes crop quickly to absorb, and effectively improves crop anti-adversity, and improving quality improves yield.
Specific embodiment
Specific embodiment of the invention is described in further detail below, but the invention is not limited in these realities
Mode is applied, any improvement or replacement on the present embodiment essence spirit still falls within the claims in the present invention required for protection
Scope.
Embodiment 1
A kind of repairing fertiliser of heavy-metal contaminated soil, is made up of following raw material by weight：Urea 35kg, phosphoric acid
Urea 10kg, potassium dihydrogen phosphate 15kg, potassium sulfate 15kg, potassium chloride 25kg, potassium nitrate 13kg, sodium carbonate 25kg, potassium carbonate 10kg,
It is weathered coal 10kg, thiourea dioxide 8kg, EDTA chelate 6kg, pomelo peel processed material 10kg, modified ferrous sulfate 15kg, modified
Corncob 25kg, modified activated carbon 20kg.
Described EDTA chelates, are chelated iron, chelated zinc, chelated magnesium.
Described pomelo peel processed material, by the white flesh part of pomelo peel, add water infusion 45min, pulls out, adds 0.05mol/
The sodium hydroxide solution of L, soaks 1h, adds tartaric acid, and regulation solution pH value is 2~3, soaks 2.5h, is pulled out, adds acetic acid second
Ester extracts 1h, reclaims ethyl acetate, and 20 mesh sieves were crushed in drying.
Described modified ferrous sulfate, is that by ferrous sulfate aqueous solution after electrolytic cell is electrolysed 3min, power-off adds sulphur
The diatomite in powder of the 15% of sour ferrous quality, the frequency ultrasound treatment 20min of 100KHz, under the rotating speed of 1000r/min from
Heart 25min, takes supernatant, adds the 25% of ferrous sulfate quality hydrogen peroxide, after water bath with thermostatic control is heated to 50 DEG C, stirring
35min, you can.
Described modified corn core, preparation method is that, by corncob, drying to water content is 6wt%, crushes 60 mesh sieves,
Oxalic acid is added, oxalic acid addition is 1.5 times of corncob quality, after magnetic stirring apparatus stirs 25min at 50 DEG C, adds corn
The bentonite of 0.3 times of core weight, after continuing to stir 40min, filtering, drying.
The modified activated carbon, its preparation method is by the immersion of activated carbon oxalic acid, under 75 DEG C of waters bath with thermostatic control, magnetic agitation
Device stirs 35min, and it is 7 to adjust pH value with the NaOH of 0.9mol/L, stirs 10min, is pulled out, with hydrogen peroxide dipping, 60 DEG C
Under water bath with thermostatic control, magnetic stirrer 65min adds 0.3 times of quality of activated carbon of bentonite, after standing 1h, filtering,
Under nitrogen protection, 1.8h is calcined at 280 DEG C, crushed 60 mesh sieves.
The urea, urea phosphate, potassium nitrate, nitrogen pool >=52.5%；Described urea phosphate, potassium dihydrogen phosphate, with five oxygen
Change two phosphorus meters, total phosphorus content >=42.1%；Described potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate, with potassium oxide
Meter, general potassium amount >=50%.The nitrogen pool, refers to the weight/mass percentage composition of the nitrogen in urea, urea phosphate, potassium nitrate；Institute
Total phosphorus content is stated, refers to by the quality that the P elements mass transitions in urea phosphate and potassium dihydrogen phosphate are phosphorus pentoxide, so as to count
Calculate the weight/mass percentage composition of the phosphorus pentoxide in urea phosphate and potassium dihydrogen phosphate；The general potassium amount, refer to by potassium dihydrogen phosphate,
Potassium element mass transitions in potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate, potassium carbonate are the quality of potassium oxide, so as to calculate phosphorus
The weight/mass percentage composition of the potassium oxide in acid dihydride potassium, potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate, potassium carbonate.
The repairing fertiliser of described heavy-metal contaminated soil, its preparation method is comprised the following steps：
(1) weathered coal is calcined into 2h at 135 DEG C, crushed 30~40 mesh sieves, with thiourea dioxide and EDTA chelates
Mix by formula ratio, 8min is vibrated on the vibratory sieve of 100 times/min, obtain material 1；
(2) urea, urea phosphate, potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate and potassium carbonate are existed respectively
Melted under its respective fusing point, spray-dried separately, then dried each raw material is mixed in proportion, in the frequency of 180KHz
Ultrasonically treated 10min under rate, obtains material 2；
(3) pomelo peel processed material, modified ferrous sulfate, modified corn core and modified activated carbon are mixed by formula material,
It is fitted into the flask of 1000ml, adds water, be higher by material plane 3cm, under the pressure of 0.06Mpa, with the speed of 3 DEG C/min
Temperature is risen to 65 DEG C, magnetic stirrer 20min, then 8 DEG C are cooled the temperature to the speed of 10 DEG C/min, 600r/min's
Under rotating speed, 5min is centrifuged, takes precipitation, dry, obtain material 3；
(4) material 1, material 2 and material 3 are mixed, under the vibration frequency of 60 times/min, vibrates 25min, reuse frequency is
The ultrasonically treated 6min of 100KHz, loads granulator granulation, packaging.
Embodiment 2
A kind of repairing fertiliser of heavy-metal contaminated soil, is made up of following raw material by weight：Urea 40kg, phosphoric acid
Urea 15kg, potassium dihydrogen phosphate 20kg, potassium sulfate 20kg, potassium chloride 30kg, potassium nitrate 18kg, sodium carbonate 30kg, potassium carbonate 15kg,
Weathered coal 15kg, thiourea dioxide 12kg, EDTA chelate 9kg, pomelo peel processed material 15kg, modified ferrous sulfate 20kg, change
Property corncob 30kg, modified activated carbon 25kg.
Described EDTA chelates, are chelated zinc, chelated magnesium, chelated copper.
Described pomelo peel processed material, by the white flesh part of pomelo peel, add water infusion 50min, pulls out, adds 0.08mol/
The sodium hydroxide solution of L, soaks 1.2h, adds tartaric acid, and regulation solution pH value is 2~3, soaks 3h, is pulled out, adds acetic acid second
Ester extracts 1.5h, reclaims ethyl acetate, and 40 mesh sieves were crushed in drying.
Described modified ferrous sulfate, is that by ferrous sulfate aqueous solution after electrolytic cell is electrolysed 5min, power-off adds sulphur
The diatomite in powder of the 20% of sour ferrous quality, the frequency ultrasound treatment 25min of 120KHz, under the rotating speed of 1200r/min from
Heart 30min, takes supernatant, adds the 30% of ferrous sulfate quality hydrogen peroxide, after water bath with thermostatic control is heated to 60 DEG C, stirring
40min, you can.
Described modified corn core, preparation method is that, by corncob, drying to water content is 8wt%, crushes 80 mesh sieves,
Oxalic acid is added, oxalic acid addition is 2 times of corncob quality, after magnetic stirring apparatus stirs 30min at 55 DEG C, adds corncob
The bentonite of 0.35 times of weight, after continuing to stir 45min, filtering, drying.
The modified activated carbon, its preparation method is by the immersion of activated carbon oxalic acid, under 80 DEG C of waters bath with thermostatic control, magnetic agitation
Device stirs 40min, and it is 7 to adjust pH value with the NaOH of 1.2mol/L, stirs 10min, is pulled out, with hydrogen peroxide dipping, 65 DEG C
Under water bath with thermostatic control, magnetic stirrer 70min adds 0.35 times of quality of activated carbon of bentonite, after standing 1.5h, mistake
Filter, under nitrogen protection .2h is calcined at 285 DEG C, crushes 80 mesh sieves.
The urea, urea phosphate, potassium nitrate, nitrogen pool >=52.5%；Described urea phosphate, potassium dihydrogen phosphate, with five oxygen
Change two phosphorus meters, total phosphorus content >=42.1%；Described potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate, with potassium oxide
Meter, general potassium amount >=50%.
The repairing fertiliser of described heavy-metal contaminated soil, its preparation method is comprised the following steps：
(1) weathered coal is calcined into 2.5h at 140 DEG C, crushed 40 mesh sieves, pressed with thiourea dioxide and EDTA chelates
Formula ratio mixes, and 12min is vibrated on the vibratory sieve of 120 times/min, obtains material 1；
(2) urea, urea phosphate, potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate and potassium carbonate are existed respectively
Melted under its respective fusing point, spray-dried separately, then dried each raw material is mixed in proportion, in the frequency of 200KHz
Ultrasonically treated 12min under rate, obtains material 2；
(3) pomelo peel processed material, modified ferrous sulfate, modified corn core and modified activated carbon are mixed by formula material,
It is fitted into the flask of 1000ml, adds water, be higher by material plane 3.5cm, under the pressure of 0.08Mpa, with 3.5 DEG C/min's
Temperature is risen to 70 DEG C by speed, magnetic stirrer 25min, then cools the temperature to 12 DEG C, 800r/ with the speed of 11 DEG C/min
Under the rotating speed of min, 7min is centrifuged, takes precipitation, dry, obtain material 3；
(4) material 1, material 2 and material 3 are mixed, under the vibration frequency of 80 times/min, vibrates 30min, reuse frequency is
The ultrasonically treated 9min of 110KHz, loads granulator granulation, packaging.
Embodiment 3
A kind of repairing fertiliser of heavy-metal contaminated soil, is made up of following raw material by weight：Urea 38kg, phosphoric acid
Urea 13kg, potassium dihydrogen phosphate 18kg, potassium sulfate 18kg, potassium chloride 28kg, potassium nitrate 15kg, sodium carbonate 28kg, potassium carbonate 13kg,
Weathered coal 13kg, thiourea dioxide 10kg, EDTA chelate 8kg, pomelo peel processed material 13kg, modified ferrous sulfate 18kg, change
Property corncob 28kg, modified activated carbon 23kg.
Described EDTA chelates, are chelated iron, chelated magnesium, chelated copper.
Described pomelo peel processed material, by the white flesh part of pomelo peel, add water infusion 48min, pulls out, adds 0.07mol/
The sodium hydroxide solution of L, soaks 1.1h, adds tartaric acid, and regulation solution pH value is 2~3, soaks 2.8h, is pulled out, adds acetic acid
Ethyl ester extracts 1.3h, reclaims ethyl acetate, and 30 mesh sieves were crushed in drying.
Described modified ferrous sulfate, is that by ferrous sulfate aqueous solution after electrolytic cell is electrolysed 4min, power-off adds sulphur
The diatomite in powder of the 18% of sour ferrous quality, the frequency ultrasound treatment 23min of 110KHz, under the rotating speed of 1100r/min from
Heart 28min, takes supernatant, adds the 28% of ferrous sulfate quality hydrogen peroxide, after water bath with thermostatic control is heated to 55 DEG C, stirring
38min, you can.
Described modified corn core, preparation method is that, by corncob, drying to water content is 7wt%, crushes 70 mesh sieves,
Oxalic acid is added, oxalic acid addition is 1.8 times of corncob quality, and magnetic stirring apparatus is stirred at 53 DEG C, after 28min, added beautiful
The bentonite of 0.33 times of rice core weight, after continuing to stir 43min, filtering, drying.
The modified activated carbon, its preparation method is by the immersion of activated carbon oxalic acid, under 78 DEG C of waters bath with thermostatic control, magnetic agitation
Device stirs 38min, and it is 7 to adjust pH value with the NaOH of 1mol/L, stirs 10min, is pulled out, with hydrogen peroxide dipping, 63 DEG C of perseverances
Under tepidarium, magnetic stirrer 68min adds 0.33 times of quality of activated carbon of bentonite, after standing 1.3h, filtering,
Under nitrogen protection, 2h is calcined at 283.5 DEG C, crushed 70 mesh sieves.
The urea, urea phosphate, potassium nitrate, nitrogen pool >=52.5%；Described urea phosphate, potassium dihydrogen phosphate, with five oxygen
Change two phosphorus meters, total phosphorus content >=42.1%；Described potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate, with potassium oxide
Meter, general potassium amount >=50%.
The repairing fertiliser of described heavy-metal contaminated soil, its preparation method is comprised the following steps：
(1) weathered coal is calcined into 2.3h at 138 DEG C, crushed 35 mesh sieves, pressed with thiourea dioxide and EDTA chelates
Formula ratio mixes, and 10min is vibrated on the vibratory sieve of 110 times/min, obtains material 1；
(2) urea, urea phosphate, potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate and potassium carbonate are existed respectively
Melted under its respective fusing point, spray-dried separately, then dried each raw material is mixed in proportion, in the frequency of 190KHz
Ultrasonically treated 11min under rate, obtains material 2；
(3) pomelo peel processed material, modified ferrous sulfate, modified corn core and modified activated carbon are mixed by formula material,
It is fitted into the flask of 1000ml, adds water, be higher by material plane 3.3cm, under the pressure of 0.07Mpa, with 3.3 DEG C/min's
Temperature is risen to 68 DEG C by speed, magnetic stirrer 23min, then cools the temperature to 10 DEG C with the speed of 10.5 DEG C/min,
Under the rotating speed of 700r/min, 6min is centrifuged, takes precipitation, dry, obtain material 3；
(4) material 1, material 2 and material 3 are mixed, under the vibration frequency of 70 times/min, vibrates 28min, reuse frequency is
The ultrasonically treated 8min of 105KHz, loads granulator granulation, packaging.
Embodiment 4
A kind of repairing fertiliser of heavy-metal contaminated soil, is made up of following raw material by weight：Urea 35kg, phosphoric acid
Urea 15kg, potassium dihydrogen phosphate 15kg, potassium sulfate 20kg, potassium chloride 25kg, potassium nitrate 18kg, sodium carbonate 30kg, potassium carbonate 10kg,
It is weathered coal 15kg, thiourea dioxide 8kg, EDTA chelate 9kg, pomelo peel processed material 10kg, modified ferrous sulfate 20kg, modified
Corncob 30kg, modified activated carbon 20kg.
Described EDTA chelates, are chelated iron, chelated zinc, chelated copper.
Described pomelo peel processed material, by the white flesh part of pomelo peel, add water infusion 45min, pulls out, adds 0.05mol/
The sodium hydroxide solution of L, soaks 1.2h, adds tartaric acid, and regulation solution pH value is 2~3, soaks 3h, is pulled out, adds acetic acid second
Ester extracts 1.5h, reclaims ethyl acetate, and 20 mesh sieves were crushed in drying.
Described modified ferrous sulfate, is that by ferrous sulfate aqueous solution after electrolytic cell is electrolysed 3min, power-off adds sulphur
The diatomite in powder of the 20% of sour ferrous quality, the frequency ultrasound treatment 25min of 100KHz, under the rotating speed of 1000r/min from
Heart 25min, takes supernatant, adds the 25% of ferrous sulfate quality hydrogen peroxide, after water bath with thermostatic control is heated to 60 DEG C, stirring
35min, you can.
Described modified corn core, preparation method is that, by corncob, drying to water content is 6wt%, crushes 80 mesh sieves,
Oxalic acid is added, oxalic acid addition is 2 times of corncob quality, after magnetic stirring apparatus stirs 25~30min at 50 DEG C, added beautiful
The bentonite of 0.3 times of rice core weight, after continuing to stir 40min, filtering, drying.
The modified activated carbon, its preparation method is by the immersion of activated carbon oxalic acid, under 75 DEG C of waters bath with thermostatic control, magnetic agitation
Device stirs 40min, and it is 7 to adjust pH value with the NaOH of 0.9mol/L, stirs 10min, is pulled out, with hydrogen peroxide dipping, 65 DEG C
Under water bath with thermostatic control, magnetic stirrer 65min adds 0.3 times of quality of activated carbon of bentonite, after standing 1.5h, filtering,
Under nitrogen protection, 2.2h is calcined at 280 DEG C, crushed 80 mesh sieves.
The urea, urea phosphate, potassium nitrate, nitrogen pool >=52.5%；Described urea phosphate, potassium dihydrogen phosphate, with five oxygen
Change two phosphorus meters, total phosphorus content >=42.1%；Described potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate, with potassium oxide
Meter, general potassium amount >=50%.
The repairing fertiliser of described heavy-metal contaminated soil, its preparation method is comprised the following steps：
(1) weathered coal is calcined into 2.5h at 135 DEG C, crushed 30 mesh sieves, pressed with thiourea dioxide and EDTA chelates
Formula ratio mixes, and 8min is vibrated on the vibratory sieve of 120 times/min, obtains material 1；
(2) urea, urea phosphate, potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate and potassium carbonate are existed respectively
Melted under its respective fusing point, spray-dried separately, then dried each raw material is mixed in proportion, in the frequency of 180KHz
Ultrasonically treated 10min under rate, obtains material 2；
(3) pomelo peel processed material, modified ferrous sulfate, modified corn core and modified activated carbon are mixed by formula material,
It is fitted into the flask of 1000ml, adds water, be higher by material plane 3cm, under the pressure of 0.08Mpa, with the speed of 3 DEG C/min
Temperature is risen to 65 DEG C, magnetic stirrer 25min, then 8 DEG C are cooled the temperature to the speed of 10 DEG C/min, 800r/min's
Under rotating speed, 5min is centrifuged, takes precipitation, dry, obtain material 3；
(4) material 1, material 2 and material 3 are mixed, under the vibration frequency of 70 times/min, vibrates 25min, reuse frequency is
The ultrasonically treated 7min of 100KHz, loads granulator granulation, packaging.
Embodiment 5
A kind of repairing fertiliser of heavy-metal contaminated soil, is made up of following raw material by weight：Urea 35kg, phosphoric acid
Urea 10kg, potassium dihydrogen phosphate 15kg, potassium sulfate 20kg, potassium chloride 30kg, potassium nitrate 18kg, sodium carbonate 30kg, potassium carbonate 10kg,
It is weathered coal 10kg, thiourea dioxide 8kg, EDTA chelate 9kg, pomelo peel processed material 15kg, modified ferrous sulfate 20kg, modified
Corncob 25kg, modified activated carbon 20kg.
Described EDTA chelates, are chelated iron, chelated zinc, chelated magnesium, chelated copper.
Described pomelo peel processed material, by the white flesh part of pomelo peel, add water infusion 50min, pulls out, adds 0.05mol/
The sodium hydroxide solution of L, soaks 1.2h, adds tartaric acid, and regulation solution pH value is 2~3, soaks 2.5h, is pulled out, adds acetic acid
Ethyl ester extracts 1h, reclaims ethyl acetate, and 20 mesh sieves were crushed in drying.
Described modified ferrous sulfate, is that by ferrous sulfate aqueous solution after electrolytic cell is electrolysed 3min, power-off adds sulphur
The diatomite in powder of the 15% of sour ferrous quality, the frequency ultrasound treatment 25min of 120KHz, under the rotating speed of 1000r/min from
Heart 30min, takes supernatant, adds the 30% of ferrous sulfate quality hydrogen peroxide, after water bath with thermostatic control is heated to 50 DEG C, stirring
40min, you can.
Described modified corn core, preparation method is that, by corncob, drying to water content is 6wt%, crushes 80 mesh sieves,
Oxalic acid is added, oxalic acid addition is 2 times of corncob quality, after magnetic stirring apparatus stirs 25min at 50 DEG C, adds corncob
The bentonite of 0.35 times of weight, after continuing to stir 45min, filtering, drying.
The modified activated carbon, its preparation method is by the immersion of activated carbon oxalic acid, under 80 DEG C of waters bath with thermostatic control, magnetic agitation
Device stirs 40min, and it is 7 to adjust pH value with the NaOH of 0.9mol/L, stirs 10min, is pulled out, with hydrogen peroxide dipping, 60 DEG C
Under water bath with thermostatic control, magnetic stirrer 6min adds 0.35 times of quality of activated carbon of bentonite, after standing 1h, filtering,
Under nitrogen protection, 1.8h is calcined at 285 DEG C, crushed 60 mesh sieves.
The urea, urea phosphate, potassium nitrate, nitrogen pool >=52.5%, described urea phosphate, potassium dihydrogen phosphate, with five oxygen
Change two phosphorus meters, total phosphorus content >=42.1%, described potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium carbonate, with potassium oxide
Meter, general potassium amount >=50%.
The repairing fertiliser of described heavy-metal contaminated soil, its preparation method is comprised the following steps：
(1) weathered coal is calcined into 2.5h at 135 DEG C, crushed 40 mesh sieves, pressed with thiourea dioxide and EDTA chelates
Formula ratio mixes, and 12min is vibrated on the vibratory sieve of 100 times/min, obtains material 1；
(2) urea, urea phosphate, potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate and potassium carbonate are existed respectively
Melted under its respective fusing point, spray-dried separately, then dried each raw material is mixed in proportion, in the frequency of 200KHz
Ultrasonically treated 10min under rate, obtains material 2；
(3) pomelo peel processed material, modified ferrous sulfate, modified corn core and modified activated carbon are mixed by formula material,
It is fitted into the flask of 1000ml, adds water, be higher by material plane 3.5cm, under the pressure of 0.06Mpa, with 3.5 DEG C/min's
Temperature is risen to 70 DEG C by speed, magnetic stirrer 20min, then cools the temperature to 8 DEG C, 800r/ with the speed of 11 DEG C/min
Under the rotating speed of min, 5min is centrifuged, takes precipitation, dry, obtain material 3；
(4) material 1, material 2 and material 3 are mixed, under the vibration frequency of 60 times/min, vibrates 30min, reuse frequency is
The ultrasonically treated 9min of 100KHz, loads granulator granulation, packaging.
Experimental example
In order to further illustrate application value of the invention, inventor have chosen 6 pieces of rice test fields of heavy metal pollution,
One of to use common fertilizer as a control group during rice cultivation, another 5 pieces use the embodiment of the present invention 1~5 respectively
Used as experimental group, after testing, 6 pieces of total arsenic content average values on ground are 251.2mg/kg, total chrome content average bits to fertilizer
652.5mg/kg, total mercury content average value enters during 10.5mg/kg, plantation to 6 pieces of total arsenic of soil, total chromium, total mercury contents
Row sampling analysis, is counted with reference to rice yield, as a result as shown in table 1, and to 6 blocks of total arsenic to rice of product, total chromium, total
Mercury content is measured, as a result as shown in table 2：
Table 1
Explanation：The present invention reaches more than 92.1% to Arsenic in Soil removal efficiency, and the chromium removal efficiency in soil is reached
More than 87.9%, more than 94.4% is reached to the mercury removal rate in soil, common fertilizer does not possess rehabilitating soil, and due to mesh
Preceding commercially available fertilizer also contains the heavy metals such as part chromium so that arsenic, chromium in soil, mercury content are enriched with, and increased soil
Load.Not only heavy metal removing rate is high for fertilizer of the invention, also with abundant nutrition, by taking paddy rice as an example, is effectively promoted
The growth of paddy rice, per mu yield can increase production 11.4~12.8% relative to control group, realize the dual of high yield and removing heavy metal
Benefit.
Table 2
Explanation：The paddy rice of present invention plantation, content of beary metal therein has reached country to paddy rice content of beary metal
Required standard, total arsenic content≤0.5mg/kg, total chrome content≤1.0mg/kg, the standard of total mercury content≤0.02mg/kg is protected
The edible safety of paddy rice is demonstrate,proved.
Claims (9)
1. a kind of repairing fertiliser of heavy-metal contaminated soil, it is characterised in that be made up of following raw material by weight：Urea
35~40, urea phosphate 10~15, potassium dihydrogen phosphate 15~20, potassium sulfate 15~20, potassium chloride 25~30, potassium nitrate 13~18,
Sodium carbonate 25~30, potassium carbonate 10~15, weathered coal 10~15, thiourea dioxide 8~12, EDTA chelates 6~9, pomelo peel
Processed material 10~15, modified ferrous sulfate 15~20, modified corn core 25~30, modified activated carbon 20~25.
2. the repairing fertiliser of heavy-metal contaminated soil as claimed in claim 1, it is characterised in that by it is following by weight
Raw material is constituted：Urea 38, urea phosphate 13, potassium dihydrogen phosphate 18, potassium sulfate 18, potassium chloride 28, potassium nitrate 15, sodium carbonate 28, carbon
Sour potassium 13, weathered coal 13, thiourea dioxide 10, EDTA chelates 8, pomelo peel processed material 13, modified ferrous sulfate 18, modified jade
Rice core 28, modified activated carbon 23.
3. the repairing fertiliser of heavy-metal contaminated soil as claimed in claim 1, it is characterised in that described EDTA chelates,
It is chelated iron, chelated zinc, chelated magnesium, the composition of the three kinds or more of chelated copper.
4. the repairing fertiliser of heavy-metal contaminated soil as claimed in claim 1, it is characterised in that described pomelo peel treatment
Thing, by the white flesh part of pomelo peel, add water 45~50min of infusion, pulls out, adds the NaOH of 0.05~0.08mol/L molten
Liquid, soaks 1~1.2h, adds tartaric acid, and regulation solution pH value is 2~3, soaks 2.5~3h, is pulled out, adds ethyl acetate leaching
1~1.5h is carried, ethyl acetate is reclaimed, 20~40 mesh sieves were crushed in drying.
5. the repairing fertiliser of heavy-metal contaminated soil as claimed in claim 1, it is characterised in that described modified sulfuric acid is sub-
Iron, be by ferrous sulfate aqueous solution by electrolytic cell be electrolysed 3~5min after, power-off, add ferrous sulfate quality 15~
20% diatomite in powder, the frequency ultrasound of 100~120KHz processes 20~25min, under the rotating speed of 1000~1200r/min from
25~30min of the heart, takes supernatant, adds the 25~30% of ferrous sulfate quality hydrogen peroxide, and water bath with thermostatic control is heated to 50~
After 60 DEG C, 35~40min is stirred, you can.
6. the repairing fertiliser of heavy-metal contaminated soil as claimed in claim 1, it is characterised in that described modified corn core,
Preparation method is that, by corncob, drying to water content is 6~8wt%, crushes 60~80 mesh sieves, adds oxalic acid, oxalic acid to add
Amount is 1.5~2 times of corncob quality, after magnetic stirring apparatus stirs 25~30min at 50~55 DEG C, adds corncob weight
0.3~0.35 times of bentonite, after continuing to stir 40~45min, filtering, drying.
7. the repairing fertiliser of heavy-metal contaminated soil as claimed in claim 1, it is characterised in that the modified activated carbon, its
Preparation method is by the immersion of activated carbon oxalic acid, under 75~80 DEG C of waters bath with thermostatic control, 35~40min of magnetic stirrer, with 0.9
The NaOH regulation pH value of~1.2mol/L is 7, stirs 10min, is pulled out, with hydrogen peroxide dipping, 60~65 DEG C of waters bath with thermostatic control
Under, 65~70min of magnetic stirrer adds 0.3~0.35 times of quality of activated carbon of bentonite, after standing 1~1.5h,
Filtering, under nitrogen protection, calcines 1.8~2.2h at 280~285 DEG C, crushed 60~80 mesh sieves.
8. the repairing fertiliser of heavy-metal contaminated soil as claimed in claim 1, it is characterised in that the urea, urea phosphate, nitre
Sour potassium, nitrogen pool >=52.5%；Described urea phosphate, potassium dihydrogen phosphate, in terms of phosphorus pentoxide, total phosphorus content >=42.1%；Institute
Potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, the potassium carbonate stated, in terms of potassium oxide, general potassium amount >=50%.
9. the repairing fertiliser of heavy-metal contaminated soil as claimed in claim 1, it is characterised in that its preparation method includes following
Step：
(1) weathered coal is calcined into 2~2.5h at 135~140 DEG C, crushed 30~40 mesh sieves, with thiourea dioxide and EDTA
Chelate is mixed by formula ratio, and 8~12min is vibrated on the vibratory sieve of 100~120 times/min, obtains material 1；
(2) it is urea, urea phosphate, potassium dihydrogen phosphate, potassium sulfate, potassium chloride, potassium nitrate, sodium carbonate and potassium carbonate is each at its respectively
From fusing point under melted, spray-dried separately, then dried each raw material is mixed in proportion, 180~200KHz's
Ultrasonically treated 10~12min under frequency, obtains material 2；
(3) pomelo peel processed material, modified ferrous sulfate, modified corn core and modified activated carbon are mixed by formula material, is loaded
In the flask of 1000ml, add water, material 3~3.5cm of plane is higher by, under the pressure of 0.06~0.08Mpa, with 3~3.5
DEG C/temperature rises to 65~70 DEG C by the speed of min, 20~25min of magnetic stirrer, then with the speed of 10~11 DEG C/min
8~12 DEG C, under the rotating speed of 600~800r/min are cooled the temperature to, 5~7min is centrifuged, take precipitation, dried, obtain material 3；
(4) material 1, material 2 and material 3 are mixed, under the vibration frequency of 60~80 times/min, vibrates 25~30min, reuse frequency is
Ultrasonically treated 6~the 9min of 100~110KHz, loads granulator granulation, packaging.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129231A (en) * | 2017-12-20 | 2018-06-08 | 铜陵羽康农业有限责任公司 | A kind of repairing fertiliser of soil pollution by heavy metal |
| CN113582767A (en) * | 2021-09-01 | 2021-11-02 | 上海久绿生物有机肥有限公司 | Fertilizer for greening planting soil and preparation method thereof |
| CN117322286A (en) * | 2023-12-01 | 2024-01-02 | 山东寿光蔬菜种业集团有限公司 | Tomato cultivation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103430730A (en) * | 2013-07-25 | 2013-12-11 | 王运海 | Radix glehniae growing method |
| CN106220329A (en) * | 2016-07-25 | 2016-12-14 | 左邦庆 | Fertilizer special for cotton |
| CN106431779A (en) * | 2016-12-28 | 2017-02-22 | 贵州大学 | Phenanthrene-contaminated soil restoring fertilizer |
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2017
- 2017-03-01 CN CN201710117866.4A patent/CN106927973A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103430730A (en) * | 2013-07-25 | 2013-12-11 | 王运海 | Radix glehniae growing method |
| CN106220329A (en) * | 2016-07-25 | 2016-12-14 | 左邦庆 | Fertilizer special for cotton |
| CN106431779A (en) * | 2016-12-28 | 2017-02-22 | 贵州大学 | Phenanthrene-contaminated soil restoring fertilizer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129231A (en) * | 2017-12-20 | 2018-06-08 | 铜陵羽康农业有限责任公司 | A kind of repairing fertiliser of soil pollution by heavy metal |
| CN113582767A (en) * | 2021-09-01 | 2021-11-02 | 上海久绿生物有机肥有限公司 | Fertilizer for greening planting soil and preparation method thereof |
| CN117322286A (en) * | 2023-12-01 | 2024-01-02 | 山东寿光蔬菜种业集团有限公司 | Tomato cultivation method |
| CN117322286B (en) * | 2023-12-01 | 2024-04-09 | 山东寿光蔬菜种业集团有限公司 | Tomato cultivation method |
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