CN106748177A - A kind of functional form fertilizer for soil pollution - Google Patents
A kind of functional form fertilizer for soil pollution Download PDFInfo
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- CN106748177A CN106748177A CN201611230460.9A CN201611230460A CN106748177A CN 106748177 A CN106748177 A CN 106748177A CN 201611230460 A CN201611230460 A CN 201611230460A CN 106748177 A CN106748177 A CN 106748177A
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- oxalic acid
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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
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
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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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- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pest Control & Pesticides (AREA)
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Abstract
The present invention relates to technical field of fertilizers, and in particular to a kind of functional form fertilizer for soil pollution；It is made up of following raw material by weight：Urea 30~50, urea phosphate 20~25, calcium phosphate 15~20, potassium sulfate 25~30, peat soil 15~20, diatomite 8~12, bagasse 15~20, forsterite 10~15, oyster shell whiting 8~12, modified laterite 20~25, heavy metal accumulation agent 15~20, modified oxalic acid 10~20；This Fertilizer nutrient is enriched, contain various a great number of elements and micronutrient element necessary to crop, nitrogen, phosphorus, potassium total nutrient >=62.9%, rich in various nutrient elements, judging quota of the number turnover of invalid state as soil remediation is changed into available state, the present invention reaches more than 92.86% to the conversion ratio of zinc in soil metal, the present invention reaches more than 92.6% to the conversion ratio of soil nickel metal, the present invention reaches more than 95.2% to the conversion ratio of arsenic in soil metal, by taking beet as an example, 10.4~11% can be increased production, the double benefit of high yield and repairing heavy metal in soil is realized.
Description
Technical field
The present invention relates to technical field of fertilizers, and in particular to a kind of functional form fertilizer for soil pollution.
Background technology
With the progress of economic fast-developing and industrial technology, the harmful effect of work, agricultural production to environment constantly adds
Play, because solid waste is constantly stacked and toppled over to soil surface, harmful waste water constantly permeates in soil, harmful in air
During gas and floating dust also constantly drop to soil with rainwater, soil pollution is result in.Wherein, heavy metal pollution of soil has turned into not
Hold the prominent environmental problem ignored, farmland soil heavy metals pollution has huge harmfulness, and heavy metal in soil pollution not only can
Cause crop production reduction and quality decline, also people's human body can be entered through food chain by soil-plant system, be detrimental to health
And life security, the heavy metal pollution such as zinc rice, arsenic poison, blood arsenic in recent years harm report it is of common occurrence, with very big harm
Consciousness.Heavy metal pollution of soil has disguised, harm biological concentration of hysteresis quality, chronicity and biological chain heavy metal etc.
Feature, if these decide that heavy metal pollution of soil is recognized and administered delayed will bring the serious consequence for being difficult to expect.Such as 20
Century causes " itai-itai " environmental hazard to be exactly most typical example what Japan occurred because farmland Cd pollutes.China's agricultural land soil
Pollution is on the rise, and the report of the heavy metals exceeding standard such as soil, rice, vegetables sees space in a newspaper again and again, and relevant information shows, 1998
China is accounted for the 1/5 of total area under cultivation by nearly 20,000,000 hm2 of cultivated area of heavy metal pollution.Cause annual grain drop in production
More than 1000 ten thousand tons, contaminated grain adds up to economic loss up to 20,000,000,000 yuan ten thousand tons up to more than 1200.Triggered by heavy metal pollution
The problems such as ecological negative effect, agricultural product security, health and Green Trade Barrier, has caused extensive concern.And to soil pollution
Improvement mainly by engineering repairing method and phytoremediation, wherein engineering repairing method mainly includes soil amendment, electro reclamation, soil
Earth drip washing and heat treating process etc., engineering control measure are commonly available to small contaminated area, severe pollutant and the soil for easily spreading
Effect is more obvious, can fundamentally improved soil at all, but treatment cost is high, and easily forms secondary pollution, may be used also
Soil texture can be destroyed, soil fertility decline is easily caused.Phytoremediation technology typically cost is low, can improve soil organic matter content
And soil fertility, but the patience of plant heavy metal pollutant is limited, is only applicable to the soil remediation of medium pollution degree, while
A kind of plant is typically only capable to repair the soil of a certain heavy metal pollution, and is possible to other heavy metals in activating soil,
For various metals and the combined pollution effect on driving birds is not good of organic matter, super enriching plant is slow-growing, and usual repairing efficiency is more long, difficult
To meet the requirement that quick rehabilitating soil pollutes；Through research, the pollution condition of heavy metal-polluted soil is improved by the administration of fertilizer
It is with low cost at present, reparation situation is controllable, meets the new processing method of environment-friendly development, therefore, exploitation is a kind of low
Cost, simplicity, novel farmland fertilizer that is efficient, environment-friendly, can effectively alleviating soil contamination problem, can realize that crop increases
Produce, also can pollution that effectively remediating heavy metal brings to soil, its content in soil is reduced, to China's agricultural development and fertilizer
Material field has great significance and urgency.
The content of the invention
The present invention is in order to solve the above technical problems, there is provided a kind of functional form fertilizer for soil pollution.
Realized particular by following technical scheme：
A kind of functional form fertilizer for soil pollution, is made up of following raw material by weight：Urea 30~50, phosphorus
Sour urea 20~25, calcium phosphate 15~20, potassium sulfate 25~30, peat soil 15~20, diatomite 8~12, bagasse 15~20, magnesium olive
Olive stone 10~15, oyster shell whiting 8~12, modified laterite 20~25, heavy metal accumulation agent 15~20, modified oxalic acid 10~20.
Preferably, it is made up of following raw material by weight：Urea 40, urea phosphate 23, calcium phosphate 18, potassium sulfate 28,
Peat soil 18, diatomite 10, bagasse 18, forsterite 13, oyster shell whiting 10, modified laterite 23, heavy metal accumulation agent 18, modified grass
Acid 15.
Further, described modified laterite, remove laterite impurity, concentration be 25~30% saline sook 25~
30min, pulls out, adds oxalic acid, and at 85~90 DEG C, 2.5~3h of magnetic stirrer adds the 0.6~0.8 of laterite quality
Dodecyl sodium sulfate again, stirs 35~40min, pulls out, under conditions of 278~283 DEG C, after 45~55min of calcining, and leaching
Bubble in the amidin of concentration 25~30%, crush by ultrasonically treated 10~13min under the frequency of 200~230KHz, drying
Cross 20~40 mesh sieves, you can.
Further, described heavy metal accumulation agent, is made up of following raw material by weight：Earthworm powder 10~15, shellfish
Shell powder 15~20, Spartina alterniflora 6~9, blue algae powder 10~15, colliery powder 25~30, frogbit 12~18, alternanthera philoxeroides 6~
9th, citric acid 6~12,1,4-CHDM 8~14.
Further, described modified oxalic acid, just asparatate and 75~80% ethanol are mixed by 1: 5~6 mass ratio
Close, constant temperature stirs 15~20min at 60~65 DEG C, add the 40~45% of gross mass oxalic acid, the pressure of 0.05~0.07MPa
Under, 25~30min is stirred, 15~18h is placed at 5~7 DEG C, vacuum distillation is reclaimed ethanol, obtains residue, and add water stirring, with 5
Temperature is risen to 75~80 DEG C by the speed of~6 DEG C/min, adds dodecyl sodium sulfate, constant temperature to stir 25~30min, then with 15
~20 DEG C of speed cools the temperature to 8~10 DEG C, preserves 1~1.5h, and the oxalic acid that must be modified is dried in concentration, filtering.
Further, described urea, urea phosphate, nitrogen pool >=49%, described urea phosphate, calcium phosphate, with five oxidations two
Phosphorus meter, total phosphorus content >=40%, described potassium sulfate, in terms of potassium oxide, general potassium amount >=34%.
Further, the described functional form fertilizer for soil pollution, its preparation method is comprised the following steps
(1) by peat soil, diatomite after forsterite is weighed by formula ratio, at 245~265 DEG C, is forged under nitrogen protection
2~3h is burnt, 30~40 mesh sieves were crushed, after bagasse and oyster shell whiting mixing, with winestone 35~40min of acid soak, drying was crushed
20~40 mesh sieves, mix with the raw material after calcining, and 8~12min is vibrated on the vibratory sieve of 90~100 times/min, obtain material 1；
(2) by urea, urea phosphate, calcium phosphate and potassium sulfate are melted under its respective fusing point respectively, are sprayed respectively
Dry, then dried each raw material is mixed in proportion, ultrasonically treated 10~12min under the frequency of 25~30KHz obtains material 2；
(3) citric acid in heavy metal accumulation agent and 1,4-CHDM are mixed, in 55~60 DEG C of thermostatted water
Under bath environment, 6~8h of magnetic stirrer, vacuum drying is crushed, and obtains powder 1；The residue weighed in heavy metal accumulation agent is former
Material, mixing, crushed 20~40 mesh sieves, added water, 45~50min of infusion at 90~100 DEG C, and it is 70~75% to add concentration
Ethanol, flow back 60~70min at 60 DEG C, reclaims ethanol, adds ethyl acetate, extracts 18~22h, after reclaiming ethyl acetate,
Powder 1 is added, it is 15~20% to continue to stir to water content, 2~2.5h of standing at 5~8 DEG C, vacuum drying, crushing to expect
3；
(4) 1 will be expected, material 2, material 3, modified laterite, heavy metal accumulation agent and modified oxalic acid mix in proportion, 100~
Under the frequency of 120KHz, ultrasonically treated 10~15min, by granulator granulation, drying, you can.
In sum, the beneficial effects of the present invention are：This Fertilizer nutrient is enriched, and contains various a large amount of units necessary to crop
Element and micronutrient element, nitrogen, phosphorus, potassium total nutrient >=62.9%, rich in various nutrient elements, the present invention can effectively reduce soil
The activity of middle metal ion, changes form of the heavy metal in soil, by the heavy metal in soil from available state be changed into soil and/
Or crop is difficult to the invalid state that absorbs, the absorption of crop heavy metal is reduced, so as to reach the mesh of repairing heavy metal in soil pollution
, judging quota of the number turnover of invalid state as soil remediation, conversion of the present invention to zinc in soil metal are changed into available state
Rate reaches more than 92.86%, and the present invention reaches more than 92.6% to the conversion ratio of soil nickel metal, and the present invention is to arsenic in soil metal
Conversion ratio reach more than 95.2%, not only heavy metal repairing effect significantly, also with abundant nutrition, has fertilizer of the invention
Effect promotes the growth of crop, and by taking beet as an example, per mu yield can increase production 10.4~11% relative to control group, realize high yield and repair
The double benefit of multiple heavy metal-polluted soil.
Wherein, be modified laterite, is combined by modes such as salinization, acidifying, starch and high-temperature calcinations and laterite is modified,
Increase the specific surface area on laterite surface so that the increase of the cavity of laterite internal structure, meanwhile, also enhance original in laterite
The materials such as iron oxide, activated surface activity, increased the quantity of its functional group so that the adsorption effect to available heavy metal shows
Write.
The heavy metal accumulation agent that the plant for having suction-operated by heavy metal is made, by infusion, ethanol and acetic acid second
The extraction of ester, strengthens the bioactivity of plant, meanwhile, also by the esterification of citric acid, further have activated plant surface
Active function groups so that adsorption effect is notable.
Modified oxalic acid, by the addition of asparatate and dodecyl sodium sulfate, under given conditions, enhances oxalic acid
The active function groups on surface, so as to further enhance oxalic acid chelation in itself, effectively reduce available heavy metal
Content.
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 functional form fertilizer for soil pollution, is made up of following raw material by weight：Urea 30kg, phosphoric acid
Urea 20kg, calcium phosphate 15kg, potassium sulfate 25kg, peat soil 15kg, diatomite 8kg, bagasse 15kg, forsterite 10kg, shell
Powder 8kg, modified laterite 20kg, heavy metal accumulation agent 15kg, modified oxalic acid 10kg.
Described modified laterite, removes the impurity of laterite, and concentration is 25% saline sook 25min, is pulled out, adds grass
Acid, at 85 DEG C, magnetic stirrer 2.5h adds 0.6 times of laterite quality of dodecyl sodium sulfate, stirs 35min,
Pull out, under conditions of 278 DEG C, after calcining 45min, be immersed in the amidin of concentration 25%, under the frequency of 200KHz
Ultrasonically treated 10min, drying, crushed 20 mesh sieves, you can.
Described heavy metal accumulation agent, is made up of following raw material by weight：Earthworm powder 10kg, oyster shell whiting 15kg,
Spartina alterniflora 6kg, blue algae powder 10kg, colliery powder 25kg, frogbit 12kg, alternanthera philoxeroides 6kg, citric acid 6kg, Isosorbide-5-Nitrae-hexamethylene
Alkane dimethanol 8kg.
Described modified oxalic acid, just asparatate are mixed with 75% ethanol by 1: 5 mass ratio, and constant temperature is stirred at 60 DEG C
15min is mixed, the 40% of gross mass oxalic acid is added, under the pressure of 0.05MPa, 25min is stirred, 15h is placed at 5 DEG C, depressurized
Distillation recovery ethanol, obtains residue, and add water stirring, and temperature is risen into 75 DEG C with the speed of 5 DEG C/min, adds dodecyl sodium sulfonate
Sodium, constant temperature stirring 25min, then 8 DEG C are cooled the temperature to 15 DEG C of speed, and 1h is preserved, the oxalic acid that must be modified is dried in concentration, filtering.
Described urea, urea phosphate, nitrogen pool >=49%, described urea phosphate, calcium phosphate, in terms of phosphorus pentoxide, always
Phosphorus amount >=40%, described potassium sulfate, in terms of potassium oxide, general potassium amount >=34%.
The described functional form fertilizer for soil pollution, its preparation method is comprised the following steps
(1) by peat soil, diatomite, after forsterite is weighed by formula ratio, at 245 DEG C, the lower calcining 2h of nitrogen protection,
30 mesh sieves were crushed, after bagasse and oyster shell whiting mixing, with winestone acid soak 35min, drying crushed 20 mesh sieves, after calcining
Raw material mixing, vibrate 8min on the vibratory sieve of 90 times/min, obtain material 1；
(2) by urea, urea phosphate, calcium phosphate and potassium sulfate are melted under its respective fusing point respectively, are sprayed respectively
Dry, then dried each raw material is mixed in proportion, the ultrasonically treated 10min under the frequency of 25KHz obtains material 2；
(3) citric acid in heavy metal accumulation agent and 1,4-CHDM are mixed, in 55 DEG C of water bath with thermostatic control ring
Under border, magnetic stirrer 6h, vacuum drying is crushed, and obtains powder 1；The surplus stock in heavy metal accumulation agent is weighed, is mixed
Close, crushed 20 mesh sieves, add water, the infusion 45min at 90 DEG C adds the ethanol that concentration is 70%, and flow back 60min at 60 DEG C,
Ethanol is reclaimed, ethyl acetate is added, 18h is extracted, after reclaiming ethyl acetate, powder 1 is added, continuation is stirred to water content and is
15%, 2h is stood at 5 DEG C, it is vacuum dried, crushing must expect 3；
(4) 1 will be expected, material 2 expects 3, modified laterite, and heavy metal accumulation agent and modified oxalic acid mix in proportion, 100KHz's
Under frequency, ultrasonically treated 10min, by granulator granulation, drying, you can.
Embodiment 2
A kind of functional form fertilizer for soil pollution, is made up of following raw material by weight：Urea 50kg, phosphoric acid
Urea 25kg, calcium phosphate 20kg, potassium sulfate 30kg, peat soil 20kg, diatomite 12kg, bagasse 20kg, forsterite 15kg, shell
Powder 12kg, modified laterite 25kg, heavy metal accumulation agent 20kg, modified oxalic acid 20kg.
Described modified laterite, removes the impurity of laterite, and concentration is 30% saline sook 30min, is pulled out, adds grass
Acid, at 90 DEG C, magnetic stirrer 3h adds 0.8 times of laterite quality of dodecyl sodium sulfate, stirs 40min, drags for
Go out, under conditions of 283 DEG C, after calcining 55min, be immersed in the amidin of concentration 30%, surpass under the frequency of 230KHz
Sonication 13min, drying, crushed 40 mesh sieves, you can.
Described heavy metal accumulation agent, is made up of following raw material by weight：Earthworm powder 15kg, oyster shell whiting 20kg,
Spartina alterniflora 9kg, blue algae powder 15kg, colliery powder 30kg, frogbit 18kg, alternanthera philoxeroides 9kg, citric acid 12kg, Isosorbide-5-Nitrae-ring
Hexane dimethanol 14kg.
Described modified oxalic acid, just asparatate are mixed with 80% ethanol by 1: 6 mass ratio, and constant temperature is stirred at 65 DEG C
20min is mixed, the 45% of gross mass oxalic acid is added, under the pressure of 0.07MPa, 30min is stirred, 18h is placed at 7 DEG C, depressurized
Distillation recovery ethanol, obtains residue, and add water stirring, and temperature is risen into 80 DEG C with the speed of 6 DEG C/min, adds dodecyl sodium sulfonate
Sodium, constant temperature stirring 30min, then 10 DEG C are cooled the temperature to 20 DEG C of speed, and 1.5h is preserved, the grass that must be modified is dried in concentration, filtering
Acid.
Described urea, urea phosphate, nitrogen pool >=49%, described urea phosphate, calcium phosphate, in terms of phosphorus pentoxide, always
Phosphorus amount >=40%, described potassium sulfate, in terms of potassium oxide, general potassium amount >=34%.
The described functional form fertilizer for soil pollution, its preparation method is comprised the following steps
(1) by peat soil, diatomite, after forsterite is weighed by formula ratio, at 265 DEG C, the lower calcining 3h of nitrogen protection,
40 mesh sieves were crushed, after bagasse and oyster shell whiting mixing, with winestone acid soak 40min, drying crushed 40 mesh sieves, after calcining
Raw material mixing, vibrate 12min on the vibratory sieve of 100 times/min, obtain material 1；
(2) by urea, urea phosphate, calcium phosphate and potassium sulfate are melted under its respective fusing point respectively, are sprayed respectively
Dry, then dried each raw material is mixed in proportion, the ultrasonically treated 12min under the frequency of 30KHz obtains material 2；
(3) citric acid in heavy metal accumulation agent and 1,4-CHDM are mixed, in 60 DEG C of water bath with thermostatic control ring
Under border, magnetic stirrer 8h, vacuum drying is crushed, and obtains powder 1；The surplus stock in heavy metal accumulation agent is weighed, is mixed
Close, crushed 40 mesh sieves, add water, the infusion 50min at 100 DEG C adds the ethanol that concentration is 75%, and flow back 70min at 60 DEG C,
Ethanol is reclaimed, ethyl acetate is added, 22h is extracted, after reclaiming ethyl acetate, powder 1 is added, continuation is stirred to water content and is
20%, 2.5h is stood at 8 DEG C, it is vacuum dried, crushing must expect 3；
(4) 1 will be expected, material 2 expects 3, modified laterite, and heavy metal accumulation agent and modified oxalic acid mix in proportion, 120KHz's
Under frequency, ultrasonically treated 15min, by granulator granulation, drying, you can.
Embodiment 3
A kind of functional form fertilizer for soil pollution, is made up of following raw material by weight：Urea 40kg, phosphoric acid
Urea 23kg, calcium phosphate 18kg, potassium sulfate 28kg, peat soil 18kg, diatomite 10kg, bagasse 18kg, forsterite 13kg, shell
Powder 10kg, modified laterite 23kg, heavy metal accumulation agent 18kg, modified oxalic acid 15kg.
Described modified laterite, removes the impurity of laterite, and concentration is 28% saline sook 28min, is pulled out, adds grass
Acid, at 88 DEG C, magnetic stirrer 2.8h adds 0.7 times of laterite quality of dodecyl sodium sulfate, stirs 38min,
Pull out, under conditions of 280 DEG C, after calcining 50min, be immersed in the amidin of concentration 28%, under the frequency of 220KHz
Ultrasonically treated 11min, drying, crushed 30 mesh sieves, you can.
Described heavy metal accumulation agent, is made up of following raw material by weight：Earthworm powder 13kg, oyster shell whiting 18kg,
Spartina alterniflora 8kg, blue algae powder 13kg, colliery powder 28kg, frogbit 16kg, alternanthera philoxeroides 8kg, citric acid 10kg, Isosorbide-5-Nitrae-ring
Hexane dimethanol 10kg.
Described modified oxalic acid, just asparatate are mixed with 78% ethanol by 1: 5.5 mass ratio, constant temperature at 63 DEG C
Stirring 18min, adds the 43% of gross mass oxalic acid, under the pressure of 0.06MPa, stirs 28min, and 17h is placed at 6 DEG C, subtracts
Pressure Distillation recovery ethanol, obtains residue, and add water stirring, and temperature is risen into 78 DEG C with the speed of 5.5 DEG C/min, adds dodecyl
Sodium sulfonate, constant temperature stirs 25~30min, then cools the temperature to 9 DEG C with 18 DEG C of speed, preserves 1.3h, concentration, filtering, drying
Must be modified oxalic acid.
Described urea, urea phosphate, nitrogen pool >=49%, described urea phosphate, calcium phosphate, in terms of phosphorus pentoxide, always
Phosphorus amount >=40%, described potassium sulfate, in terms of potassium oxide, general potassium amount >=34%.
The described functional form fertilizer for soil pollution, its preparation method is comprised the following steps
(1) by peat soil, diatomite, after forsterite is weighed by formula ratio, at 250 DEG C, the lower calcining of nitrogen protection
2.5h, crushed 35 mesh sieves, and after bagasse and oyster shell whiting mixing, with winestone 35~40min of acid soak, 30 mesh sieves were crushed in drying,
Mix with the raw material after calcining, 10min is vibrated on the vibratory sieve of 95 times/min, obtain material 1；
(2) by urea, urea phosphate, calcium phosphate and potassium sulfate are melted under its respective fusing point respectively, are sprayed respectively
Dry, then dried each raw material is mixed in proportion, the ultrasonically treated 11min under the frequency of 28KHz obtains material 2；
(3) citric acid in heavy metal accumulation agent and 1,4-CHDM are mixed, in 58 DEG C of water bath with thermostatic control ring
Under border, magnetic stirrer 7, vacuum drying is crushed, and obtains powder 1；The surplus stock in heavy metal accumulation agent is weighed, is mixed,
30 mesh sieves were crushed, was added water, the infusion 48min at 95 DEG C added the ethanol that concentration is 73%, and flow back 65min at 60 DEG C, reclaimed
Ethanol, adds ethyl acetate, extracts 20h, after reclaiming ethyl acetate, adds powder 1, and it is 18% to continue to stir to water content,
2.3h is stood at 7 DEG C, is vacuum dried, crushing must expect 3；
(4) 1 will be expected, material 2 expects 3, modified laterite, and heavy metal accumulation agent and modified oxalic acid mix in proportion, 110KHz's
Under frequency, ultrasonically treated 13min, by granulator granulation, drying, you can.
Embodiment 4
A kind of functional form fertilizer for soil pollution, is made up of following raw material by weight：Urea 30kg, phosphoric acid
Urea 20kg, calcium phosphate 15kg, potassium sulfate 30kg, peat soil 20kg, diatomite 12kg, bagasse 20kg, forsterite 10kg, shell
Powder 8kg, modified laterite 20kg, heavy metal accumulation agent 15kg, modified oxalic acid 20kg.
Described modified laterite, removes the impurity of laterite, and concentration is 25% saline sook 25min, is pulled out, adds grass
Acid, at 85 DEG C, magnetic stirrer 3h adds 0.8 times of laterite quality of dodecyl sodium sulfate, stirs 40min, drags for
Go out, under conditions of 283 DEG C, after calcining 45min, be immersed in the amidin of concentration 25%, surpass under the frequency of 200KHz
Sonication 13min, drying, crushed 40 mesh sieves, you can.
Described heavy metal accumulation agent, is made up of following raw material by weight：Earthworm powder 10kg, oyster shell whiting 15kg,
Spartina alterniflora 6kg, blue algae powder 15kg, colliery powder 30kg, frogbit 18kg, alternanthera philoxeroides 6kg, citric acid 6kg, Isosorbide-5-Nitrae-hexamethylene
Alkane dimethanol 8kg.
Described modified oxalic acid, just asparatate are mixed with 75% ethanol by 1: 5 mass ratio, and constant temperature is stirred at 60 DEG C
15min is mixed, the 40% of gross mass oxalic acid is added, under the pressure of 0.05MPa, 30min is stirred, 15h is placed at 5 DEG C, depressurized
Distillation recovery ethanol, obtains residue, and add water stirring, and temperature is risen into 75 DEG C with the speed of 5 DEG C/min, adds dodecyl sodium sulfonate
Sodium, constant temperature stirring 25min, then 8 DEG C are cooled the temperature to 20 DEG C of speed, and 1h is preserved, the oxalic acid that must be modified is dried in concentration, filtering.
Described urea, urea phosphate, nitrogen pool >=49%, described urea phosphate, calcium phosphate, in terms of phosphorus pentoxide, always
Phosphorus amount >=40%, described potassium sulfate, in terms of potassium oxide, general potassium amount >=34%.
The described functional form fertilizer for soil pollution, its preparation method is comprised the following steps
(1) by peat soil, diatomite, after forsterite is weighed by formula ratio, at 245 DEG C, the lower calcining 2h of nitrogen protection,
30 mesh sieves were crushed, after bagasse and oyster shell whiting mixing, with winestone acid soak 35min, drying crushed 20 mesh sieves, after calcining
Raw material mixing, vibrate 8min on the vibratory sieve of 90 times/min, obtain material 1；
(2) by urea, urea phosphate, calcium phosphate and potassium sulfate are melted under its respective fusing point respectively, are sprayed respectively
Dry, then dried each raw material is mixed in proportion, the ultrasonically treated 10min under the frequency of 25KHz obtains material 2；
(3) citric acid in heavy metal accumulation agent and 1,4-CHDM are mixed, in 55 DEG C of water bath with thermostatic control ring
Under border, magnetic stirrer 6h, vacuum drying is crushed, and obtains powder 1；The surplus stock in heavy metal accumulation agent is weighed, is mixed
Close, crushed 20 mesh sieves, add water, the infusion 45min at 90 DEG C adds the ethanol that concentration is 70%, and flow back 60min at 60 DEG C,
Ethanol is reclaimed, ethyl acetate is added, 18h is extracted, after reclaiming ethyl acetate, powder 1 is added, continuation is stirred to water content and is
15%, 2h is stood at 5 DEG C, it is vacuum dried, crushing must expect 3；
(4) 1 will be expected, material 2 expects 3, modified laterite, and heavy metal accumulation agent and modified oxalic acid mix in proportion, 100KHz's
Under frequency, ultrasonically treated 10min, by granulator granulation, drying, you can.
Embodiment 5
A kind of functional form fertilizer for soil pollution, is made up of following raw material by weight：Urea 50kg, phosphoric acid
Urea 20kg, calcium phosphate 20kg, potassium sulfate 25kg, peat soil 20kg, diatomite 8kg, bagasse 20kg, forsterite 10kg, shell
Powder 12kg, modified laterite 20kg, heavy metal accumulation agent 20kg, modified oxalic acid 10kg.
Described modified laterite, removes the impurity of laterite, and concentration is 25% saline sook 25min, is pulled out, adds grass
Acid, at 90 DEG C, magnetic stirrer 3h adds 0.6 times of laterite quality of dodecyl sodium sulfate, stirs 35min, drags for
Go out, under conditions of 283 DEG C, after calcining 55min, be immersed in the amidin of concentration 25%, surpass under the frequency of 200KHz
Sonication 13min, drying, crushed 40 mesh sieves, you can.
Described heavy metal accumulation agent, is made up of following raw material by weight：Earthworm powder 15kg, oyster shell whiting 15kg,
Spartina alterniflora 9kg, blue algae powder 15kg, colliery powder 30kg, frogbit 12kg, alternanthera philoxeroides 9kg, citric acid 6kg, Isosorbide-5-Nitrae-hexamethylene
Alkane dimethanol 14kg.
Described modified oxalic acid, just asparatate are mixed with 75% ethanol by 1: 5 mass ratio, and constant temperature is stirred at 65 DEG C
20min is mixed, the 45% of gross mass oxalic acid is added, under the pressure of 0.05MPa, 30min is stirred, 15h is placed at 5 DEG C, depressurized
Distillation recovery ethanol, obtains residue, and add water stirring, and temperature is risen into 75 DEG C with the speed of 5 DEG C/min, adds dodecyl sodium sulfonate
Sodium, constant temperature stirring 25min, then 10 DEG C are cooled the temperature to 15 DEG C of speed, and 1h is preserved, the grass that must be modified is dried in concentration, filtering
Acid.
Described urea, urea phosphate, nitrogen pool >=49%, described urea phosphate, calcium phosphate, in terms of phosphorus pentoxide, always
Phosphorus amount >=40%, described potassium sulfate, in terms of potassium oxide, general potassium amount >=34%.
The described functional form fertilizer for soil pollution, its preparation method is comprised the following steps
(1) by peat soil, diatomite, after forsterite is weighed by formula ratio, at 265 DEG C, the lower calcining 2h of nitrogen protection,
30 mesh sieves were crushed, after bagasse and oyster shell whiting mixing, with winestone acid soak 35min, drying crushed 20 mesh sieves, after calcining
Raw material mixing, vibrate 12min on the vibratory sieve of 100 times/min, obtain material 1；
(2) by urea, urea phosphate, calcium phosphate and potassium sulfate are melted under its respective fusing point respectively, are sprayed respectively
Dry, then dried each raw material is mixed in proportion, the ultrasonically treated 10min under the frequency of 25KHz obtains material 2；
(3) citric acid in heavy metal accumulation agent and 1,4-CHDM are mixed, in 55 DEG C of water bath with thermostatic control ring
Under border, 6~8h of magnetic stirrer, vacuum drying is crushed, and obtains powder 1；The surplus stock in heavy metal accumulation agent is weighed,
Mixing, crushed 20 mesh sieves, added water, the infusion 50min at 90 DEG C, added the ethanol that concentration is 70%, was flowed back at 60 DEG C
70min, reclaims ethanol, adds ethyl acetate, extracts 18h, after reclaiming ethyl acetate, adds powder 1, continues to stir to aqueous
It is 15% to measure, and 2h is stood at 8 DEG C, vacuum drying, and crushing must expect 3；
(4) 1 will be expected, material 2 expects 3, modified laterite, and heavy metal accumulation agent and modified oxalic acid mix in proportion, 100KHz's
Under frequency, ultrasonically treated 15min, by granulator granulation, drying, you can.
Experimental example
In order to further illustrate application value of the invention, inventor have chosen 6 pieces of beet experimental plots of heavy metal pollution,
One of to use common fertilizer as a control group during planting beet, another 5 pieces use the embodiment of the present invention 1~5 respectively
Used as experimental group, after testing, 6 pieces of total Zn content average values on ground are 2.58mg/kg to fertilizer, and total nickel content average value is
369.2mg/kg, total arsenic content average value enters during 179.8mg/kg, plantation to 6 pieces of total zinc of soil, total nickel, total arsenic contents
Row sampling analysis, is counted with reference to Sugarbeet Yield, as a result as shown in table 1：
Table 1
Explanation：The present invention can effectively reduce the activity of metal ion in soil, change form of the heavy metal in soil, will
Heavy metal in soil is changed into soil from available state and/or crop is difficult to the invalid state that absorbs, reduces the suction of crop heavy metal
Receive, so as to reach the purpose of repairing heavy metal in soil pollution, the number turnover of invalid state is changed into as soil remediation with available state
Judging quota, the present invention reaches more than 92.86%, conversion ratio of the present invention to soil nickel metal to the conversion ratio of zinc in soil metal
Reach more than 92.6%, the present invention reaches more than 95.2% to the conversion ratio of arsenic in soil metal, a fertilizer of the invention not only huge sum of money
Category repairing effect significantly, also with abundant nutrition, effectively facilitates the growth of crop, and by taking beet as an example, per mu yield is relative to right
According to group, 10.4~11% can be increased production, realize the double benefit of high yield and repairing heavy metal in soil.
Claims (7)
1. a kind of functional form fertilizer for soil pollution, it is characterised in that be made up of following raw material by weight：Urea
30~50, urea phosphate 20~25, calcium phosphate 15~20, potassium sulfate 25~30, peat soil 15~20, diatomite 8~12, bagasse 15
~20, forsterite 10~15, oyster shell whiting 8~12, modified laterite 20~25, heavy metal accumulation agent 15~20, modified oxalic acid 10
~20.
2. the as claimed in claim 1 functional form fertilizer for being used for soil pollution, it is characterised in that by it is following by weight
Raw material is constituted：Urea 40, urea phosphate 23, calcium phosphate 18, potassium sulfate 28, peat soil 18, diatomite 10, bagasse 18, forsterite
13rd, oyster shell whiting 10, modified laterite 23, heavy metal accumulation agent 18, modified oxalic acid 15.
3. it is used for the functional form fertilizer of soil pollution as claimed in claim 1, it is characterised in that described modified laterite, goes
Except the impurity of laterite, concentration is 25~30% 25~30min of saline sook, is pulled out, adds oxalic acid, at 85~90 DEG C, magnetic
Power agitator stirs 2.5~3h, adds 0.6~0.8 times of laterite quality of dodecyl sodium sulfate, stirs 35~40min, drags for
Go out, under conditions of 278~283 DEG C, after 45~55min of calcining, be immersed in the amidin of concentration 25~30%, 200
Ultrasonically treated 10~13min under the frequency of~230KHz, drying, crushed 20~40 mesh sieves, you can.
4. the functional form fertilizer of soil pollution is used for as claimed in claim 1, it is characterised in that described heavy metal accumulation
Agent, is made up of following raw material by weight：Earthworm powder 10~15, oyster shell whiting 15~20, Spartina alterniflora 6~9, blue algae powder 10
~15, colliery powder 25~30, frogbit 12~18, alternanthera philoxeroides 6~9, citric acid 6~12,1,4-CHDM 8~
14。
5. the functional form fertilizer of soil pollution is used for as claimed in claim 1, it is characterised in that described modified oxalic acid, will
Asparatate is mixed with 75~80% ethanol by 1: 5~6 mass ratio, constant temperature stirs 15~20min at 60~65 DEG C, plus
Enter the 40~45% of gross mass oxalic acid, under the pressure of 0.05~0.07MPa, stir 25~30min, 15 are placed at 5~7 DEG C
Ethanol is reclaimed in~18h, vacuum distillation, obtains residue, and added water stirring, and temperature is risen into 75~80 with the speed of 5~6 DEG C/min
DEG C, dodecyl sodium sulfate is added, constant temperature stirs 25~30min, then cools the temperature to 8~10 DEG C with 15~20 DEG C of speed,
1~1.5h is preserved, the oxalic acid that must be modified is dried in concentration, filtering.
6. the functional form fertilizer of soil pollution is used for as claimed in claim 1, it is characterised in that described urea, urea phosphate,
Nitrogen pool >=49%, described urea phosphate, calcium phosphate, in terms of phosphorus pentoxide, total phosphorus content >=40%, described potassium sulfate, with
Potassium oxide meter, general potassium amount >=34%.
7. the functional form fertilizer of soil pollution is used for as claimed in claim 1, it is characterised in that its preparation method includes following
Step
(1) by peat soil, diatomite, after forsterite is weighed by formula ratio, at 245~265 DEG C, the lower calcining 2 of nitrogen protection
~3h, crushed 30~40 mesh sieves, and after bagasse and oyster shell whiting mixing, with winestone 35~40min of acid soak, drying crushed 20
~40 mesh sieves, mix with the raw material after calcining, and 8~12min is vibrated on the vibratory sieve of 90~100 times/min, obtain material 1；
(2) by urea, urea phosphate, calcium phosphate and potassium sulfate are melted under its respective fusing point respectively, spray-dried separately,
Dried each raw material is mixed in proportion again, ultrasonically treated 10~12min under the frequency of 25~30KHz obtains material 2；
(3) citric acid in heavy metal accumulation agent and 1,4-CHDM are mixed, in 55~60 DEG C of water bath with thermostatic control ring
Under border, 6~8h of magnetic stirrer, vacuum drying is crushed, and obtains powder 1；The surplus stock in heavy metal accumulation agent is weighed,
Mixing, crushed 20~40 mesh sieves, added water, 45~50min of infusion at 90~100 DEG C, added the second that concentration is 70~75%
Alcohol, flow back 60~70min at 60 DEG C, reclaims ethanol, adds ethyl acetate, extracts 18~22h, after reclaiming ethyl acetate, plus
Enter powder 1, it is 15~20% to continue to stir to water content, and 2~2.5h is stood at 5~8 DEG C, is vacuum dried, and crushing must expect 3；
(4) 1 will be expected, material 2 expects 3, modified laterite, and heavy metal accumulation agent and modified oxalic acid mix in proportion, in 100~120KHz
Frequency under, ultrasonically treated 10~15min, by granulator granulation, drying, you can.
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| 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 |
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| CN103539563A (en) * | 2013-10-30 | 2014-01-29 | 安徽万利生态园林景观有限公司 | Multifunctional vegetable fertilizer and preparation method thereof |
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