CN109485509A - The Slow-release organic fertilizer of passivation restoration of soil polluted by heavy metal and preparation and application - Google Patents
The Slow-release organic fertilizer of passivation restoration of soil polluted by heavy metal and preparation and application Download PDFInfo
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- CN109485509A CN109485509A CN201811634052.9A CN201811634052A CN109485509A CN 109485509 A CN109485509 A CN 109485509A CN 201811634052 A CN201811634052 A CN 201811634052A CN 109485509 A CN109485509 A CN 109485509A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01C—PLANTING; SOWING; FERTILISING
- A01C21/00—Methods of fertilising, sowing or planting
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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
-
- 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
-
- 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
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/36—Layered or coated, e.g. dust-preventing coatings layered or coated with sulfur
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/22—Improving land use; Improving water use or availability; Controlling erosion
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Abstract
The present invention is mainly a kind of multifunctional slow-release organic fertilizer and preparation method comprising heavy metal deactivator.The main component of fertilizer includes matured compost, chemical nitrogen fertilizer, biochemical restrainer, heavy metal-polluted soil passivating material, plant growth beneficial element, water-keeping material and coating liquid, serves as the coating for being coated on organic fertilizer particle periphery.According to parts by weight, the ratio of matured compost, chemical nitrogen fertilizer, biochemical restrainer, heavy metal passivating material, plant growth beneficial element, water-keeping material and coating liquid is 1:0.1-0.3:0.05-0.1:0.01-0.2:0.001-0.02:0.04-0.08:0.05-0. 1.Fertilizer in the present invention can reduce Heavy Metals from Polluted Soils with Heavy Metals biological effectiveness, it reduces crop and absorbs heavy metal, simultaneously, increase soil organic matter content, improve soil fertility, and plant growth and enhancing soil water-reataining fertilizer-keeping ability can be promoted, significantly increase the multiple functions such as crop disease-resistant, drought-resistant ability.
Description
Technical field
The invention belongs to organic passivation agent to repair field to heavy metal pollution of soil, is related to a kind of native using organic fertilizer realization
The method of earth heavy metal pollution reparation.The biological effectiveness of heavy metal-polluted soil can either be specifically reduced, and can be promoted
The Slow-release organic fertilizer of plant growth and enhancing soil water-reataining fertilizer-keeping ability, realizes resource circulation utilization.
Background technique
With the high speed development of industrialization and urbanization, heavy metal pollution of soil is got worse, and China's soil is dirty within 2014
Dye status investigation bulletin shows [bibliography 1: national soil pollution situation tune bulletin [EB/OL] .2014-04-17] that China is ploughed
Soil pollution point exceeding standard rate in ground is 19.4%, especially heavy-metal contaminated soil, and chemical fertilizer is excessively used and has aggravated a huge sum of money
Belong to the pollution to soil environment, if soil acidification promotes heavy metal ion validity to improve, increases the potential absorption of plant, and
It is enriched with by food chain, endangers animals and plants existence, and the situation that soil pollution shows various metals ion and deposits, soil weight
Problems of ecological security caused by metallic pollution is got worse, and influences soil ecology function and critical process, and heavy metal polluted soil
Earth have concealment, it is accumulative and be difficult to it is restorative, repair be home and abroad environment field research key points and difficulties.Soil
Pollution amelioration generally reduces the biological effectiveness of heavy metal by modes such as complexing, absorption, precipitating, redox, heavy metal-polluted
The recovery technique for contaminating soil mainly includes electric repairing technique, elution method, phytoremediation, microorganism remediation and plant-microorganism
Combined remediation technology etc., but these technologies all have the shortcomings that different degrees of such as at high cost, complicated for operation, remediation efficiency is low,
Long-time stability difference and reparation pollution are single.
Passivator reparation is a kind of method that can reduce plant absorption heavy metal ion, can be divided into inorganic and organic blunt
Agent, organic fertilizer have passivation to heavy metal as a kind of organic passivation agent, are the effective of restoration of soil polluted by heavy metal
Means, the available state that organic and inorganic passivant can reduce pollutant in soil by processes such as absorption, co-precipitation, complexings are dense
Degree, although the plant poisoning that these two types of passivator have many advantages, such as low in cost, simple process, reduce heavy metal, has respectively
Have the shortcomings that remediation efficiency is low, stability is poor, be also easy to produce secondary pollution [bibliography 2:Mahar, A., Ping, W.A.N.G.,
Ronghua,L.I.,&ZHANG,Z.(2015).Immobilization of lead and cadmium in
contaminated soil using amendments:a review.Pedosphere,25(4),555-568.].Meanwhile
If soil depletion and under by Water Stress Conditions, various heavy contaminated ion exists jointly in contaminated soil in addition,
Keep soil environment condition more severe, the interaction between pollutant can also aggravate toxicity, inhibit soil animal and microorganism
Growth and breeding and plant growth, be unfavorable for the raising and stabilization of repairing effect.Therefore, if soil nutrient, water can be improved
Slitting part is also beneficial to the transformation, passivation and biological prosthetic process of Heavy Metals, achievees the effect that get twice the result with half the effort.In addition,
Chemical fertilizer application total amount zero growth rate scheme is formulated at the beginning of 2015 and guarantees grain-production under the premise of reducing fertilizer amount in China
Total amount and quality, [bibliography 3: too, Jiang Zishao, Ma Qiang are all for space ten thousand using one of preferable alternative solution is undoubtedly for organic fertilizer
Influence [J] plant nutrient of the birch application of organic fertilizers to soil fertility and fertilizer journal, 2009,15 (05): 1057-1064].Cause
This, explore one kind can under complicated environmental condition and meanwhile reduce in heavy metal validity can improve soil moisture, nutrient again
The method of condition is most important.
Summary of the invention
Present invention aims at providing one kind using livestock excrement composting as raw material, and by organic fertilizer, chemical fertilizer, biochemical press down
Preparation, heavy metal deactivator, plant growth beneficial element, water-keeping material carry out organic assembling and to be prepared into coating multipurpose organic
The method and its reasonable application method of fertilizer, the organic fertilizer are used to remove heavy metal ions in soil under complicated environmental condition,
Removal rate is higher.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of multifunctional slow-release organic fertilizer being passivated restoration of soil polluted by heavy metal, according to parts by weight, matured compost,
Chemical nitrogen fertilizer, biochemical restrainer, heavy metal passivating material, plant growth beneficial element, water-keeping material and coating liquid ratio be
1:0.1-0.3:0.05-0.1:0.01-0.2:0.001-0.02:0.04-0.08:0.001-0.02.Proportion optimizing is 1:0.15-
0.25:0.06-0.08:0.05-0.15:0.01-0.02:0.06-0.07:0.07-0.1
The matured compost is feces of livestock and poultry and mixes with stalk that the carbon-nitrogen ratio of compost initial feed is 25-35, compost mistake
In journey weight moisture capacity control in 40%-60%, the every 3-6 days dunghills of compost overall process are primary, when temperature be gradually decrease to it is slightly higher
When 5-10 DEG C of environment temperature, it is compacted dunghill, causes anaerobic environment inside dunghill, composting treatment process is 30-40 days, decomposed heap
Fertilizer crushed 60 meshes after 40-60 DEG C of drying 2-4h, and the material by sieve is required matured compost, the feces of livestock and poultry
For pig manure, cow dung, the livestock and poultry cultivations fecaluria such as duck excrement, the stalk is the crops straw such as corn stover, rice straw, wheat stalk
Stalk.
The chemical nitrogen fertilizer is sulfur coating urea, and granular size 0.5-3mm derives from market sale.
The heavy metal passivating material include be modification biological charcoal and lime, modification biological charcoal exists from organic waste
Pyrolysis is modified after preparing charcoal under anaerobic condition, specifically, under anaerobic by debirs in Muffle furnace, temperature
Control is at 400-800 DEG C, and the heating rate from room temperature to pyrolysis temperature is 10-20 DEG C/min, and pyrolysis time 2-6h is obtained
Charcoal is ground into the powder that particle is less than 1mm.The debirs be feces of livestock and poultry or stalk, the lime be it is powdered,
From market sale.
The modification of the charcoal, method are to be prepared after inorganic acid-wash activation by charcoal, including following step
It is rapid: charcoal is added in hydrochloric acid or sulfuric acid or the nitric acid solution of 0.5-2mol/L, and is completely soaked, 180-300rpm oscillation
Then 0.5-1h impregnates 0.5-1 days, be placed in organic solvent-acetone after taking out filtering, and charcoal and acetone volume ratio are 1:
20-40 impregnates 2-3h, modification biological charcoal is obtained after filtering, drying.
The plant growth beneficial element is selenium and/or silicon, based on 1000 parts by weight of matured compost composition, dosage are as follows:
Selenium salt 0.5-10 parts by weight and/or silicon salt 0.5-10 parts by weight, selenium salt mainly include Na2SeO3Or Na2SeO4, silicon salt mainly wraps
Include Na2SiO3·9H2O or K2SiO3。
It is described have water retention property organic fertilizer in initiator be hydrogen peroxide or sodium peroxydisulfate, the crosslinking agent be peroxidating
Diisopropylbenzene (DIPB), the bentonite sieve with 100 mesh sieve.
The biochemical restrainer includes nitrification inhibitor and urease inhibitor, wherein nitrification inhibitor are as follows: wherein nitrification suppression
Preparation are as follows: one or more of dicyandiamide, 3,4- dimethyl pyrazole phosphate, chloro- 6 trichloromethyl pyridine of 2-；Urase
Inhibitor include one or both of N- butylthiophosphoric triamide, diphenylphosphoryl diamines, quinhydrones, thiophosphoryl triamide with
On.1000 number meter of matured compost by weight, dosage, nitrification inhibitor and urease inhibitor be respectively 20-40 parts by weight,
30-60 parts by weight.
The coating liquid includes talcum powder and binder, according to 1000 parts of weight compositions of matured compost, dosage are as follows: talcum
Powder 40-80 parts by weight, binder (main component is starch and xanthan gum) 10-20 parts by weight.Binder can be by sulfur coating
Urea and the granulated fertilizer of preparation mutually bond, and promote the organic fertilizer particle to form 2-6mm.
The heavy metal passivation multifunctional slow-release organic fertilizer is prepared as steps described below, and detailed process is as follows:
S1 prepares material:
1) matured compost particle is prepared；
2) charcoal is prepared；
3) modification biological charcoal is prepared；
4) preparation has the organic fertilizer of water retention property；
Preparation method are as follows:
A, polymerization reaction: water soluble starch being added in 10-30 DEG C of water and dissolved, the volume of water soluble starch and water
Than for 1:2-5, stirring while adding at room temperature uniformly, 0.5-1h is stood, matured compost (crossing 60 meshes), β-ring paste is then added
Essence, sodium carboxymethylcellulose, expanded perlite, initiator (main component is hydrogen peroxide or sodium peroxydisulfate), crosslinking agent (ingredient
For cumyl peroxide) and polymerizer (aluminium dihydrogen phosphate), after mechanical stirring is uniform, polymerization reaction is carried out at 40-80 DEG C
2-4h obtains polymerization reactant；
B, it mixes: bentonite (sieving with 100 mesh sieve) is added in Xiang Shangshu A) in gained reactant and is uniformly mixed, at 80-100 DEG C
Under reaction 0.5-2h is hydrolyzed, reaction product is sent into granulating disc after cooling, drying, crushing and is granulated, adjustment
The gradient and velocity of rotation of good disk, pelletizer parameter setting granular size are 0.5-1mm；2-4h in baking oven will be put into dry
It is dry, 30-50 DEG C of temperature, obtain having the organic fertilizer fertilizer of water retention property spare；
S2 operating procedure:
1) it prepares coating liquid: the warm water that temperature is 40-60 DEG C being added in the reactor, will be equivalent to starch weight 2-5%
Xanthan gum be added in reactor, after mixing evenly, according to parts by weight, 80-100 parts of starch are added, warm water and starch
Volume ratio is 8-10:1, stirs into uniform slurry, then the hydrogen peroxide of 6-10 part 20% is added while stirring as oxidant,
In 50-70 DEG C of oxidation 10-20min, the sodium hydroxide of 4-8 part 20% is added as paste agent, temperature is maintained at 55-65 DEG C,
Isothermal reaction 1-2h obtains binder after cooling, and entire reaction is all completed in a water bath；At room temperature by talcum powder and system
Standby binder is sufficiently mixed stirring 10-20 minutes according to claim 7 ratio, coating liquid is obtained, by 1000 weight of matured compost
Part composition meter is measured, 50-100 parts of coating liquids are added in coating machine, the starch is cornstarch；
2) fertiliser granulates are prepared: the organic fertilizer and heavy metal passivating material, biochemistry with water retention property that will be prepared in S1
Inhibitor, plant growth beneficial element, by Mixing Machine, stir 20-30 minutes at room temperature according to required ratio, are uniformly mixed
After be sent in granulating disc, open power supply, adjust the gradient and velocity of rotation of disk, setting granular size is 1-
After 2mm is granulated, granulated fertilizer being put into 2-3h in baking oven and is dried, temperature is 40-60 DEG C, the volatilization loss of nutrient is prevented,
It is spare to obtain fertiliser granulates；
3) fertiliser granulates coating: coating machine is sent into after granulated fertilizer and coated carbamide Mixing Machine are mixed 10-20 minutes
Middle spraying coating liquid, until coating liquid spraying finishes, it is blunt then to obtain the heavy metal that partial size is 2-6mm after drying at room temperature, cooling
Change multifunctional slow-release organic fertilizer particles.
The quality of total nutrient (nitrogen+phosphorus pentoxide+potassium oxide) point in multifunctional slow-release organic fertilizer prepared by the present invention
Number (to dry in terms of base) is greater than 6.5%, meets plant growth demand.
The invention patent has the following advantages
1, the present invention provides the sides for preparing a kind of multifunctional slow-release organic fertilizer for being passivated restoration of soil polluted by heavy metal
Livestock and poultry matured compost, chemical nitrogen fertilizer, heavy metal passivating material, biochemical restrainer and water-keeping material are carried out granulation preparation, energy by method
It is enough that directly heavy-metal contaminated soil is repaired.By efficiently reducing Heavy Metals in Soil Contaminated validity, heavy metal is enhanced
Passivation stability, reduce harm of the heavy metal to crop, and then reduce influence of the heavy metal pollution to ecological environment, meanwhile,
The fertility level and water holding capacity of contaminated soil can be enhanced again, promote plant growth.In addition, these passivating material sources are wide
It is general, it is low in cost, and soil acidification can be slowed down, soil texture is improved, so that the soil after repairing realizes sustainable use.
2, it is added to biochemical restrainer in its manufacture craft of organic fertilizer of the invention, biochemical restrainer can be given full play to
Change the conversion process and retention form of fertilizer nitrogen in the soil, amidonitrogen in soil can be effectively reduced and turn to ammonium nitrogen
The conversion of change and ammonium nitrogen to nitrate nitrogen improves crop and nitrogenous fertilizer is absorbed and utilized, improves utilization rate of fertilizer, can either subtract
Few nitrogen loss, and can prevent soil acidification caused by application chemical fertilizer from available heavy metal content being caused to increase.In addition, nitrification
Conversion of the ammonium nitrogen to nitrate nitrogen can be effectively reduced in inhibitor, to reduce accumulation of the crop to nitrite, especially vegetables
Plantation reduces it and endangers crop.
3, the present invention is organically combined water-keeping material and compost by the processes such as polymerization and hydrolysis, and being formed has water conservation
The organic fertilizer of performance can improve soil-crop system Water Cycle, be retained drought resisting, promote suction of the crop to nutrient
Nutrient loss in soil is received and reduced, influence of the water stress to plant growth, and carboxymethyl cellulose in water-keeping material are alleviated
Plain sodium and sodium peroxydisulfate can provide sodium element, and not only sodium can increase the solute potential in vacuole to sodium element, have to stomatal movement
Regulating and controlling effect improves plant moisture balance, improves drought-resistant ability, and can stimulate photosynthesis of plant.
4, matured compost of the invention be animal dung compost, garbage compost or biomass compost, these be mostly live or
Obsolete material in agriculture, forestry, animal husbandry and fishery production process, the compost under aerobic conditions both can solve in agriculture, forestry, animal husbandry and fishery production process
It because of the environmental problem that waste generates, and can be realized utilization of waste as resource, improve soil organic matter content and fertility water
It is flat.
5, the present invention organically combines matured compost, chemical fertilizer, heavy metal passivating material, water-keeping material, can
Enough heavy metal-passivated combined contamination soils, and getting fat, water conservation and the multiple effect for improveing soil can be played, while these materials
Combination simplify agricultural operation, reduce labour cost, energy so that passivator, organic fertilizer and chemical nitrogen fertilizer are no longer respectively applied
Efficiently solve existing soil contamination problem.
6, organic fertilizer of the invention is slow-release coating organic fertilizer, can effectively be carried out to Nutrient Transformation and release process
Regulation, can be used as base manure applied once, reduces agriculture production cost.And include plant growth beneficial element, meet crop
To the needs of microelement, crop yield and quality are improved.
7, the production process simple process of heavy-metal contaminated soil multifunctional slow-release organic fertilizer of the invention, and finished product easily pushes away
It is wide to use, there are good market prospects.
Specific embodiment
Below with reference to example, the present invention is described further:
Embodiment 1
A kind of multifunctional slow-release organic fertilizer and preparation method being passivated restoration of soil polluted by heavy metal, comprising the following steps:
(1) it prepares matured compost: corn stover being dried or dried, its weight moisture capacity 10%, crushing maize straw are made
Stalk is the segment of 2-5cm；Fresh pig dung and corn stover are mixed well, the carbon-nitrogen ratio of regulation compost initial feed is 30, compost
Weight moisture capacity control in the process is aerated turning under 60%, natural conditions, primary every turning in 4 days, altogether turning 9 times,
And adding water tariff collection dunghill weight moisture capacity is 60%, and when temperature is gradually decrease to slightly above 10 DEG C of environment temperature, compacting
Dunghill causes anaerobic environment inside dunghill, 35 days completion digest process of compost.Matured compost crushed 60 after 50 DEG C of drying 3h
Mesh, the material by sieve are required matured compost.
(2) charcoal is prepared, corn stover is pyrolyzed under anaerobic, specifically, will be crushed under anaerobic
Corn stover be placed in Muffle furnace, at 600 DEG C, heating rate is 15 DEG C/min for temperature control, and pyrolysis time 2h is obtained
Charcoal is ground into the powder that particle is less than 1mm.
(3) charcoal prepared in step (2) is passed through into hydrochloric Acid Modification, charcoal is added to the hydrochloric acid solution of 1mol/L
In, and be completely soaked, 180rpm vibrates 1h, then impregnates 1 day, it is placed in organic solvent-acetone after taking out filtering, charcoal:
Acetone volume ratio is 1:20, impregnates 2h, modification biological charcoal is obtained after filtering, drying.
(4) prepare the organic fertilizer particles of water retention property: heavy metal passivation repair multi-functional slow organic fertilizer at subpackage
Containing water-keeping material, water-keeping material and organic fertilizer are become according to weight group, 1000 parts by weight of matured compost, 10 weight of bentonite
Part, 10 parts by weight of beta-cyclodextrin, 15 parts by weight of sodium carboxymethylcellulose, 10 parts by weight of water soluble starch, 15 weight of expanded perlite
Part, 1 parts by weight of crosslinking agent, 1 parts by weight of initiator, 3 parts by weight of polymerizer are measured, the organic fertilizer that preparation has water retention property is carried out.
Preparation method are as follows:
A, polymerization reaction: water soluble starch being added in 25 DEG C of water and dissolved, the volume ratio of water soluble starch and water
It for 1:2, stirs while adding at room temperature uniformly, stands 0.5h, matured compost (crossing 60 meshes), beta-cyclodextrin, carboxylic is then added
Sodium carboxymethylcellulose pyce, expanded perlite, initiator (hydrogen peroxide or sodium peroxydisulfate), crosslinking agent (cumyl peroxide) and poly-
Mixture after mechanical stirring is uniform, polymerization reaction 3h is carried out at 60 DEG C, obtains reactant.
B, it mixes: bentonite (sieving with 100 mesh sieve) is added in Xiang Shangshu A) in gained reactant and is uniformly mixed, at 100 DEG C
Under reaction 1h is hydrolyzed, reaction product is sent into pelletizer after cooling, drying, crushing and is granulated, and pelletizer parameter is set
Setting granular size is 1mm, obtains the organic fertilizer with water retention property.
(5) it prepares coating liquid: 50 DEG C of warm water being added in glass reactor, will be equivalent to the xanthan of starch weight 4%
Glue is added in reactor, after mixing evenly, according to parts by weight, 100 parts by weight Corn starch, the body of warm water and starch is added
Product stirs into uniform slurry than being 10:1, then the hydrogen peroxide of 8 parts by weight 20% is added while stirring as oxidant,
60 DEG C of oxidation 10min, add the sodium hydroxide of 5 parts by weight 20% as paste agent, temperature is maintained at 65 DEG C, isothermal reaction
1h obtains binder after cooling, and entire reaction is all completed in a water bath.At room temperature by the binder of talcum powder and preparation
It is sufficiently mixed stirring 20 minutes according to 60:15 weight ratio, obtains coating liquid, based on 1000 parts by weight of matured compost composition,
75 parts by weight coating liquids are added in coating machine；
(6) granulated fertilizer is prepared: by the diphenylphosphoryl two of the 2- of 30 parts by weight chloro- 6 trichloromethyl pyridine and 45 parts by weight
Amine is dissolved in 37% methanol, and the volume ratio of biochemical restrainer and methanol is 1:100,50 part by weight modified charcoals, 50 weights
Measure part lime, 5 parts by weight K2SiO3With 5 parts by weight Na2SeO4, stirred 30 minutes in Mixing Machine, be sent to circle after mixing
In disk pelletizer, power supply is opened, adjusts the gradient and velocity of rotation of disk, setting granular size is that 1-2mm granulation terminates
Afterwards, granulated fertilizer is put into 2h in baking oven to dry, temperature is lower than 60 DEG C, prevents the volatilization loss of nutrient, it is standby to obtain fertiliser granulates
With.
(7) fertiliser granulates coating: by 1000 parts by weight of granulated fertilizer in step (6) and 200 parts by weight sulfur coating urea
With Mixing Machine mix after twenty minutes be sent into coating machine in spray coating liquid, until coating liquid spraying finish, then drying at room temperature,
The heavy metal that partial size is 2-6mm is obtained after cooling is passivated multifunctional slow-release organic fertilizer particles.
Embodiment 2
A kind of multifunctional slow-release organic fertilizer of passivation restoration of soil polluted by heavy metal prepared by the embodiment of the present invention 1 is pressed
It is added in heavy metal (by taking cadmium as an example) contaminated soil according to 3% dosage of rehabilitating soil dry weight, for trying soil property such as 1 institute of table
Show, turns in time.
Table 1: for trying soil property
Reparative experiment is carried out to heavy-metal contaminated soil according to organic fertilizer of the present invention in embodiment 2, table 2 has to be of the invention
Machine fertilizer and general heavy metal pollution renovation agent are to the bound residue cadmium removal rate table of comparisons in contaminated soil, general renovation agent packet
Include commercially available common organic fertilizer, charcoal and common organic fertilizer and charcoal mixing renovation agent, it is common organic in this check experiment
Fertilizer product is rotted pig manure organic fertilizer, and charcoal is derived from corn stover in 600 DEG C of pyrolysis 2h, adding proportion and external environment item
Part is identical as organic fertilizer of the present invention, and the removal rate of sampling analysis soil bound residue cadmium, is not added with any renovation agent after 1 month
Soil utilizes 0.01mol/L CaCl as blank control, bound residue cadmium2Solution (native liquor ratio is 1:5) extracts, in 180rpm
Upper machine measurement is filtered after vibrating 2h, note counts according to such as table 2 (unit %)
Table 2: organic fertilizer of the present invention and other passivator compare the removal rate (%) of bound residue cadmium
Note: different lowercases indicate, n=3 significant in 0.05 level difference
From in table 2 common organic fertilizer product and charcoal mixed phase (can to heavy metal ion for the two single administration
Extract state cadmium) removal rate variation, it is known that common organic fertilizer product and charcoal mix the passivation to cadmium element in soil
Effect does not significantly improve.
Organic fertilizer of the present invention is apparently higher than the removal of common organic fertilizer, charcoal and common organic fertilizer and charcoal mixing
Rate.It realizes and the efficient of heavy-metal contaminated soil is repaired, which is because, the modified absorption improved to heavy metal of charcoal
Ability reduces the mobility of heavy metal ion.In addition, containing macromolecular humus in organic fertilizer, by being formed surely with cadmium
Qualitative very high complex compound is to reduce the bio-available Zn concentration of cadmium.
Embodiment 3
(1) matured compost is prepared: same as Example 1.
(2) charcoal is prepared: same as Example 1.
(3) modification biological charcoal is prepared: same as Example 1.
(4) organic fertilizer particles of water retention property are prepared: same as Example 1.
(5) coating liquid is prepared: same as Example 1.
(6) granulated fertilizer is prepared: same as Example 1.
(7) fertiliser granulates coating: same as Example 1.
Organic fertilizer prepared by the present invention is added in heavy-metal contaminated soil according to 1% dosage of soil dry weight, soil
Property is as shown in table 1 in embodiment 2.It turns in time, 1 month sampling analysis heavy metal cadmium content.
Embodiment 4
(1) matured compost is prepared: same as Example 1.
(2) charcoal is prepared: same as Example 1.
(3) modification biological charcoal is prepared: same as Example 1.
(4) organic fertilizer particles of water retention property are prepared: same as Example 1.
(5) coating liquid is prepared: same as Example 1.
(6) granulated fertilizer is prepared: same as Example 1.
(7) fertiliser granulates coating: same as Example 1.
Organic fertilizer prepared by the present invention is added in heavy-metal contaminated soil according to 5% dosage of soil dry weight, soil
Property is as shown in table 1 in embodiment 2.It turns in time, 1 month sampling analysis heavy metal cadmium content.
Embodiment 5
(1) matured compost is prepared: same as Example 1.
(2) charcoal is prepared: same as Example 1.
(3) modification biological charcoal is prepared: same as Example 1.
(4) organic fertilizer particles of water retention property are prepared: same as Example 1.
(5) coating liquid is prepared: same as Example 1.
(6) granulated fertilizer is prepared: same as Example 1.
(7) fertiliser granulates coating: same as Example 1.
Organic fertilizer prepared by the present invention is added in heavy-metal contaminated soil according to 0.5% dosage of soil dry weight, soil
Earth property is as shown in table 1 in embodiment 2.It turns in time, 1 month sampling analysis heavy metal cadmium content.
Embodiment 6
(1) matured compost is prepared: same as Example 1.
(2) charcoal is prepared: same as Example 1.
(3) modification biological charcoal is prepared: same as Example 1.
(4) organic fertilizer particles of water retention property are prepared: same as Example 1.
(5) coating liquid is prepared: same as Example 1.
(6) prepare granulated fertilizer: heavy metal passivating material only adds 100 parts by weight of charcoal, other conditions and embodiment 1
It is identical.
(7) fertiliser granulates coating: same as Example 1.
The organic fertilizer of the present embodiment is added in heavy-metal contaminated soil according to 5% dosage of soil dry weight, soil
Matter is as shown in table 1 in embodiment 2.It turns in time, 1 month sampling analysis heavy metal cadmium content.
Embodiment 7
(1) matured compost is prepared: same as Example 1.
(2) charcoal is prepared: same as Example 1.
(3) modification biological charcoal is prepared: same as Example 1.
(4) organic fertilizer particles of water retention property are prepared: same as Example 1.
(5) coating liquid is prepared: same as Example 1.
(6) granulated fertilizer is prepared: same as Example 1.
(7) fertiliser granulates coating: same as Example 1.
Organic fertilizer prepared by the present invention is added in heavy-metal contaminated soil according to 10% dosage of soil dry weight, soil
Property is as shown in table 1 in embodiment 2.It turns in time, 1 month sampling analysis heavy metal cadmium content.In order to investigate different organic fertilizers
Influence of the applicating ratio to heavy metal pollution soil remediation effect, in the same time and place according to embodiment 2,3,4,5,6,7 by organic fertilizer
Soil remediation, sampling analysis measuring available Cd content after one month are carried out, note counts according to (unit %) as shown in table 3
The removal rate table of comparisons of the different organic fertilizer adding proportions of table 3 to available Cd in contaminated soil
Note: * indicates that addition embodiment 6 prepares organic fertilizer, additive amount 5%；Different lowercases are indicated in 0.05 level
Significant difference, n=3
It can be obtained by table 3, present invention difference organic fertilizer adding proportion has different effect to heavy metal pollution of soil reparation
Fruit, with the increase of adding proportion, the removal effect presentation of available Cd first increases, the trend of rear slowly reduction, and is applying
When dosage is less than 5%, with the increase of dosage, available state removal effect increasing degree is gradually decreased, and reflects passivation effect not
It can enhance with the increase of organic fertilizer application ratio of the present invention, this is because to increase soil organic for the application of excessive organic fertilizer
Carbon content enhances the mobility of heavy metal.Comprehensively consider the factors such as repairing effect and rehabilitation cost, the application of the organic fertilizer
Ratio is best between 0.5-5%.
When the organic fertilizer additive amount prepared by the embodiment 1 and embodiment 6 is 5%, repairing effect there are still difference,
Reason is in 1 organic fertilizer of embodiment containing modification biological charcoal and lime, on acid and partial neutral soil, the presence of lime
Can be improved soil pH, and the raising of soil pH leads to the adsorption site that more negative electrical charges are generated in soil, promote cadmium ion with
Cd(OH)2Or CdCO3Precipitation form exists, to reduce Cadmium in Soil bio-available Zn concentration.Biology is contained only with prepared by embodiment 6
The organic fertilizer of charcoal is compared, and the organic fertilizer addition containing lime is higher to soil pH increase rate, therefore, in acid or partial neutral weight
1 organic fertilizer of embodiment is more preferable than 6 organic fertilizer repairing effect of embodiment in metallic pollution soil.Comprehensively consider repairing effect and a huge sum of money
Belong to contaminated soil acid-base property, recommends to use in acid or partial neutral heavy-metal contaminated soil and add charcoal in the present invention simultaneously
With the organic fertilizer of lime, and add in preparation process in alkaline heavy metal contaminated soil using containing only charcoal in the present invention
Organic fertilizer.
Described above is that the feasibility example more optimized for the present invention illustrates, but case study on implementation is not limited to
Patent claim of the invention.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention, not
The changes and modifications under the premise of the principle of the invention are detached from, these changes and modifications also should belong to technical solution of the present invention protection
Range.
Claims (10)
1. being passivated the Slow-release organic fertilizer of restoration of soil polluted by heavy metal, it is characterised in that: fertilizer component includes matured compost, changes
Nitrogenous fertilizer, biochemical restrainer, heavy metal passivating material, plant growth beneficial element, water-keeping material and coated fertilizer are learned, according to weight
Number meter, matured compost, chemical nitrogen fertilizer, biochemical restrainer, heavy metal passivating material, plant growth beneficial element, water-keeping material
With coating liquid ratio 1:0.1-0.3:0.05-0.1:0.01-0.2:0.001-0.02:0.04-0.08:0.05-0. 1.Preferred 1:
0.18-0.25:0.06-0.08:0.08-0.2:0.008-0.02:0.04-0.08:0.07-0 .1.
2. according to Slow-release organic fertilizer described in claim 1, it is characterised in that: matured compost is that feces of livestock and poultry is mixed with stalk,
The carbon-nitrogen ratio of compost initial feed is 25-35, and in 40%-60%, compost overall process is every for weight moisture capacity control in composting process
Turning in 3-6 days 1 time, when temperature is gradually decrease to slightly above 5-10 DEG C of environment temperature, it is compacted dunghill, causes anaerobism inside dunghill
Environment, composting treatment process are 30-40 days, and matured compost crushed 60 meshes after 40-60 DEG C of drying 2-4h, the object after sieving
Material is required matured compost；The feces of livestock and poultry is poultry manure, and stalk is agricultural crop straw, such as wheat stalk, corn stalk
Stalk, soybean stalk, broomcorn straw etc..
3. according to Slow-release organic fertilizer described in claim 1, it is characterised in that: chemical nitrogen fertilizer is that the sulfur coating of market sale is urinated
Element, granular size 0.5-3mm；Biochemical restrainer is made of nitrification inhibitor and urease inhibitor, wherein nitrification inhibitor are as follows:
One or more of dicyandiamide, 3,4- dimethyl pyrazole phosphate, chloro- 6 trichloromethyl pyridine of 2-；Urease inhibitor packet
Include one or more of N- butylthiophosphoric triamide, diphenylphosphoryl diamines, quinhydrones, thiophosphoryl triamide；By weight
1000 number meter of matured compost, dosage, nitrification inhibitor and urease inhibitor are respectively 20-40 parts by weight, 30-60 weight
Part.
4. according to Slow-release organic fertilizer described in claim 1, it is characterised in that: heavy metal deactivator material includes modification biological
Charcoal or modification biological charcoal and pulverized limestone, by weight 1000 parts by weight meter of matured compost, modification biological charcoal and lime adding proportion are
10-100:0-100；Charcoal is pyrolyzed under anaerobic from organic waste, specifically, will be had under anaerobic
Machine waste is placed in Muffle furnace, temperature control at 400-800 DEG C, from room temperature to the heating rate of pyrolysis temperature be 10-20 DEG C/
Min, pyrolysis time 2-6h, obtained charcoal are ground into the powder that particle is less than 1mm；The debirs are feces of livestock and poultry
Or one of stalk or two kinds or more；
Modification biological charcoal is prepared after the activation of inorganic acid elution by charcoal, comprising the following steps: charcoal is added
It in the hydrochloric acid or sulfuric acid or nitric acid solution of 0.5-2mol/L, and is completely soaked, 180-300rpm vibrates 0.5-1h, then impregnates
It 0.5-1 days, being placed in organic solvent-acetone after taking out filtering, charcoal and acetone volume ratio are 1:20-40,2-3h is impregnated,
Modification biological charcoal is obtained after filtering, drying.
5. according to Slow-release organic fertilizer described in claim 1, it is characterised in that: plant growth beneficial element is selenium and/or silicon, is pressed
1000 parts by weight of matured compost composition meter, dosage are as follows: selenium salt 0.5-10 parts by weight and/or silicon salt 0.5-10 parts by weight, selenium salt
It mainly include Na2SeO3Or Na2SeO4, silicon salt mainly includes Na2SiO3·9H2O or K2SiO3。
6. according to Slow-release organic fertilizer described in claim 1, it is characterised in that: water-keeping material is bentonite, beta-cyclodextrin, carboxylic first
Base sodium cellulosate, water soluble starch, expanded perlite, crosslinking agent, initiator and polymerizer；By water-keeping material and organic fertilizer according to
Weight composition mixing, 1000 parts of matured compost, 7-15 parts of bentonite, beta-cyclodextrin 8-15,8-15 parts of sodium carboxymethylcellulose, water
8-15 parts of soluble starch, 7-15 parts of expanded perlite, 0.1-1 parts of crosslinking agent, 0.1-1 parts of initiator, 1.8-3 parts of polymerizer, into
Row preparation has the organic fertilizer of water retention property.
7. according to multifunctional slow-release organic fertilizer described in claim 1, it is characterised in that: coated fertilizer includes talcum powder and bonding
Agent, according to 1000 parts of weight compositions of matured compost, dosage are as follows: talcum powder 40-80 parts by weight, (main component is to form sediment to binder
Powder and xanthan gum) 10-20 parts by weight.
8. a kind of preparation method of any Slow-release organic fertilizer of claim 1-7, it is characterised in that: walked including following operation
Suddenly,
S1 prepares material:
1) matured compost particle is prepared；
2) charcoal is prepared；
3) modification biological charcoal is prepared；
4) preparation has the organic fertilizer of water retention property；
Preparation method are as follows:
A, polymerization reaction: water soluble starch being added in 10-30 DEG C of water and dissolved, and the volume ratio of water soluble starch and water is
1:2-5, stirs while adding uniformly at room temperature, stands 0.5-1h, be then added matured compost (cross 60 meshes), beta-cyclodextrin,
(ingredient is for sodium carboxymethylcellulose, expanded perlite, initiator (main component is hydrogen peroxide or sodium peroxydisulfate), crosslinking agent
Cumyl peroxide) and polymerizer (aluminium dihydrogen phosphate), after mechanical stirring is uniform, polymerization reaction 2- is carried out at 40-80 DEG C
4h obtains polymerization reactant；
B, it mixes: bentonite (particle sieved with 100 mesh sieve) is added in Xiang Shangshu A) in gained reactant and is uniformly mixed, in 80-100
Reaction 0.5-2h is hydrolyzed at DEG C, reaction product is sent into granulating disc after cooling, drying, crushing and is granulated, and adjusts
The gradient and velocity of rotation of whole good disk, pelletizer parameter setting granular size are 0.5-1mm；2-4h in baking oven will be put into dry
Dry, temperature is lower than 30-50 DEG C, obtains having the organic fertilizer fertilizer of water retention property spare；
S2 operating procedure:
1) it prepares coating liquid: the warm water that temperature is 40-60 DEG C being added in the reactor, will be equivalent to the Huang of starch weight 2-5%
Virgin rubber is added in reactor, after mixing evenly, according to parts by weight, 80-100 parts of starch, the volume of starch and warm water is added
Than stirring into uniform slurry for 1:8-10, then the hydrogen peroxide of 6-10 part 20% is added while stirring as oxidant,
50-70 DEG C of oxidation 10-20min adds the sodium hydroxide of 4-8 part 20% as paste agent, and temperature is maintained at 55-65 DEG C, perseverance
Temperature reaction 1-2h, obtains binder after cooling, and entire reaction is all completed in a water bath；At room temperature by talcum powder and preparation
Binder according to claim 7 ratio be sufficiently mixed stirring 10-20 minutes, coating liquid is obtained, by 1000 weight of matured compost
Part composition meter, 50-100 parts of coating liquids are added in coating machine, and the starch is cornstarch；
2) fertiliser granulates are prepared: the organic fertilizer and heavy metal passivating material, biochemical inhibition with water retention property that will be prepared in S1
Agent, plant growth beneficial element, by Mixing Machine, are stirred 20-30 minutes at room temperature, are sent after mixing according to required ratio
Enter into granulating disc, open power supply, adjust the gradient and velocity of rotation of disk, setting granular size is made for 1-2mm
After grain, granulated fertilizer is put into 2-3h in baking oven and is dried, temperature is 40-60 DEG C, prevents the volatilization loss of nutrient, obtains fertilizer
Expect that particle is spare；
3) it fertiliser granulates coating: is sent into coating machine and sprays after granulated fertilizer and coated carbamide Mixing Machine are mixed 10-20 minutes
Coating liquid is applied, until coating liquid spraying finishes, it is more that the heavy metal passivation that partial size is 2-6mm is then obtained after drying at room temperature, cooling
Functional slow-release organic fertilizer particles.
9. a kind of heavy-metal contaminated soil as claimed in claim 1 to 7 repairs Slow-release organic fertilizer or claim 8
Application of the Slow-release organic fertilizer that preparation method obtains in restoration of soil polluted by heavy metal or soil improvement.
10. stating the application of heavy metal passivation multifunctional slow-release organic fertilizer according to claim 9, it is characterised in that: described organic
When fertilizer carries out in-situ immobilization to heavy-metal contaminated soil, organic fertilizer additive amount is the 0.5-5% of contaminated soil dry weight, preferably
5%；When organic fertilizer is as soil conditioner, the additive amount of organic fertilizer is the 0.5-2% of contaminated soil dry weight.
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Application publication date: 20190319 |