CN101973791A - Nanometer apatite phosphate fertilizer and preparation method thereof - Google Patents

Nanometer apatite phosphate fertilizer and preparation method thereof Download PDF

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CN101973791A
CN101973791A CN2010105240215A CN201010524021A CN101973791A CN 101973791 A CN101973791 A CN 101973791A CN 2010105240215 A CN2010105240215 A CN 2010105240215A CN 201010524021 A CN201010524021 A CN 201010524021A CN 101973791 A CN101973791 A CN 101973791A
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phosphate fertilizer
nano
based sols
apatite
preparation
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魏正贵
王瑜
何春建
魏巍
崔静
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Nanjing Normal University
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Nanjing Normal University
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Abstract

The invention discloses a nanometer apatite phosphate fertilizer and a preparation method thereof. The nanometer apatite phosphate fertilizer is prepared by the steps of carrying out precipitation reaction or hydro-thermal reaction on a phosphorus base solution and a calcium base solution. The nanometer apatite phosphate fertilizer comprises 33.2-100 percent by weight of nanometer hydroxylapatite with the average grain diameter of 20-50 nanometers. The solid nanometer apatite phosphate fertilizer can not cause aquatic environment pollution by running off with rain water after being fertilized into soil and can obviously increase the content of rapidly available phosphorus contained in the soil in a short time, effectively reduce the fixation of the soil on the rapidly available phosphorus and keep the content of the rapidly available phosphorus contained in the soil at an appropriate (20-40 mg/kg) level and an abundant (more than 40 mg/kg) level for a long time; in addition, the nanometer apatite phosphate fertilizer does not have bad soil ecological effect and can realize the in-situ inactivation of pollutants if fertilized into soil polluted by the pollutants, such as heavy metals and the like.

Description

A kind of nano-apatite phosphate fertilizer and preparation method thereof
Technical field
The invention belongs to the chemical fertilizers production technical field, relate to a kind of phosphate fertilizer and preparation method thereof, particularly a kind of nano-apatite phosphate fertilizer and preparation method thereof.
Background technology
Phosphorus (P) is the necessary macronutrient of crop growthing development, and some crop producing region phosphorus are limiting factors of crop growth in China.Rationally using, use phosphate fertilizer, is to improve crop yield, quality, guarantees the important factor of agriculture production benefit.There is the problem aspect two in quick-acting phosphate fertilizer in application, on the one hand this water soluble phosphorous fertilizer can enter underground water and water body, cause or increase the weight of body eutrophication, contaminate environment; On the other hand, because soil to the strong fixed action of water-soluble phosphorus, after quick-acting phosphate fertilizer are manured into soil, can be converted into invalid phosphate fertilizer in a couple of days.
In chemical fertilizer, soil agrochemistry field, existing research is attempted to reduce phosphorus fixation and loss by administering long-lasting slow phosphate fertilizer at present.The preparation of long-acting slow phosphate fertilizer mainly contains two big class methods, and class methods are to add organic and inorganic material in quick-acting phosphate fertilizer, and the passivation rapid available phosphorus discharges so that control phosphorus is plain; Another kind of method is to the insoluble phosphorus ore containing, as adding various organic and inorganic activated materials in the phosphatic rock, the activation insoluble phosphorus.So far, the long-acting slow phosphate fertilizer that these two big class methods are produced all can not be realized both effectively reducing soil to phosphorus fixation well simultaneously, effectively avoids phosphorus to shift to water body again.
The present invention proposes nano-apatite is used as phosphate fertilizer first, and a kind of preparation method of nano-apatite phosphate fertilizer is provided.Nano fertilizer difference before this, as the disclosed a kind of nanometer composite organic-inorganic fertilizer of patent CN 101186540A, disclosed a kind of nano super composite fertilizer of patent CN 101096329A and manufacture method thereof, in its manufacturing processed, nano material is only used as adhesive for granulating or sorbent material, and the present invention is used as the fertilizer principal constituent with nano material first.
Summary of the invention
The object of the invention is to provide a kind of nano-apatite phosphate fertilizer and preparation method thereof, can overcome the fixing and loss problem of the phosphorus element that exists in the quick-acting phosphate fertilizer applications, can effectively reduce soil to phosphorus fixation, can avoid phosphorus to shift again to water body, be that a kind of soil ecology effect is good, phosphorus content can long term maintenance at the phosphate fertilizer product of optimal level.
The present invention is by the following technical solutions:
A kind of preparation method of nano-apatite phosphate fertilizer may further comprise the steps:
1) the phosphorus based sols of preparation 0.1-1.67 mol/L;
2) the calcium based sols of preparation 0.1-1.67 mol/L;
3) the phosphorus based sols is mixed with P mol ratio 5:3 by Ca with the calcium based sols and regulate acidity, make mixing solutions generation precipitin reaction or hydro-thermal reaction produce nano-apatite;
4) the resulting nano-apatite of step 3) makes nano-apatite phosphate fertilizer powder through concentrated, 50-110 ℃ oven dry down.
Described phosphorus based sols is true solution or suspension liquid, and solute comprises phosphoric acid, contains calcium phosphate such as Ca (H 2PO 4) 2, CaHPO 4Or Ca 3(PO 4) 2, contain ammonium phosphoric acid salt such as NH 4H 2PO 4, (NH 4) 2HPO 4Or (NH 4) 3PO 4, contain na phosphates such as NaH 2PO 4Or Na 2HPO 4Or Na 3PO 4, perhaps contain potassium phosphoric acid salt such as KH 2PO 4, K 2HPO 4Or K 3PO 4
Described calcium based sols is calcium hydroxide, Ca (NO 3) 2Perhaps CaCl 2True solution or suspension liquid.
The hybrid mode of phosphorus based sols and calcium based sols is not limit, the phosphorus based sols can be added dropwise in the calcium based sols and generate nanometer hydroxyapatite, perhaps the calcium based sols is added dropwise in the phosphorus based sols and generates nanometer hydroxyapatite, perhaps phosphorus based sols and calcium based sols directly mix and generate nanometer hydroxyapatite after forming mixed solution.
Regulate the acidity of the mixed solution of phosphorus based sols and calcium based sols, can utilize alkaline matter or glacial acetic acid to regulate the mixed solution of phosphorus based sols, calcium based sols or phosphorus based sols and calcium based sols, regulate pH value to 9～11.
Described alkaline matter can be selected from ammoniacal liquor, NaOH, KOH or the urea of 0.1-1 mol/L.
Described nano-apatite makes by phosphorus based sols and the generation precipitin reaction of calcium based sols or hydro-thermal reaction, and the precipitin reaction equation is:
5Ca 2++3PO 4 3-+OH -=Ca 5(PO 4) 3OH
The hydro-thermal reaction reaction equation is:
3CaHPO 4+2Ca(OH) 2=Ca 5(PO 4) 3OH+3H 2O
3Ca 3(PO 4) 2+Ca(OH) 2=2Ca 5(PO 4) 3OH
The temperature of reaction of hydro-thermal reaction is 120-180 C, 24 hours reaction times.
The invention still further relates to a kind ofly, comprise that content is that 33.2%-100%, median size are the nanometer hydroxyapatite of 20-50 nanometer by the prepared nano-apatite phosphate fertilizer of aforesaid method.
Described its degree of crystallinity of nano-apatite phosphate fertilizer is very low; Its X-ray diffractogram is 26 °, 32 °, 34 °, 40 °, 47 ° and 50 ° in 2 θ values on the X-ray diffractogram and has located wide diffraction peak as shown in Figure 1.
Nano-apatite phosphate fertilizer of the present invention both can effectively reduce soil to phosphorus fixation, effectively avoided phosphorus to shift to water body again; Described phosphate fertilizer does not have bad soil ecology effect, as is applied to contaminants soil such as heavy metal, can also realize in-situ passivation to these pollutents, be a kind of novel phosphate fertilizer that saves phosphorus, environmental protection.
Compared with the prior art, the present invention has the following advantages:
1. after nano-apatite phosphate fertilizer of the present invention is manured into soil,, can run off and cause water body environment pollution with rainwater because be solid phosphate fertilizer;
2. nanometer phosphate fertilizer of the present invention can significantly increase the content of rapid available phosphorus in the soil in the short period of time; And can effectively reduce soil to phosphorus fixation, make the content of rapid available phosphorus in the soil can long term maintenance in suitable (20-40 mg/kg) or abundant (greater than 40 mg/kg) level;
3. to the nano-apatite phosphate fertilizer of the present invention of the reasonable dosage of soil application, can satisfy the needs of the different growth phases of crop to the phosphorus element; Simultaneously
4. nano-apatite phosphate fertilizer of the present invention can also be realized in-situ passivation to these pollutents as being applied to contaminants soil such as heavy metal;
5. nano-apatite phosphate fertilizer of the present invention does not have bad soil ecology effect.
Be further described content of the present invention in order better to illustrate below by specific embodiment.Protection scope of the present invention is limited by claims.
 
Description of drawings
Fig. 1 is the X-ray diffractogram of nano-apatite phosphate fertilizer of the present invention;
Fig. 2 is the transmission electron microscope photo of nano-apatite phosphate fertilizer of the present invention.
Embodiment
Embodiment one
Prepare the Ca (NO of 0.835 mol/L respectively 3) 2(NH with 0.5 mol/L 4) 2HPO 4Solution, regulating the pH value with the ammoniacal liquor of 0.1-1 mol/L is 11, is 1.67 by Ca and P mol ratio, (NH 4) 2HPO 4Solution slowly is added drop-wise to Ca (NO 3) 2In the solution, use magnetic stirrer simultaneously, the gained throw out is transferred in the tripod bottle, behind vibration 12 h, sample 110 ℃ of oven dry down, is ground with agate mortar at last in horizontal oscillator tube.
The nano-apatite phosphate fertilizer that makes, its X-ray diffractogram and transmission electron microscope photo are respectively as depicted in figs. 1 and 2.As shown in Figure 1, this nano-apatite phosphate fertilizer 2 θ values on X ray diffracting spectrum are 26 °, 32 °, 34 °, 40 °, 47 ° and 50 ° and have located wide diffraction peak.As shown in Figure 2, nano-apatite phosphate fertilizer comprises the nanometer hydroxyapatite that degree of crystallinity is very low, and median size is the 20-50 nanometer.
Under pH 4 conditions, 1 this nano-apatite phosphate fertilizer of gram can be dissolved in the NaNO that 1 L contains 0.01 mol/L fully within 2 hours 3With the electrolytical as a setting solution of the NaCl of 0.001 mol/L.
Embodiment two
Prepare the Ca (NO of 1.67 mol/L respectively 3) 2(NH with 1 mol/L 4) 2HPO 4Solution, regulating the pH value with the ammoniacal liquor of 0.1-1 mol/L is 11, is 1.67 by Ca and P mol ratio, (NH 4) 2HPO 4Solution slowly is added drop-wise to Ca (NO 3) 2In the solution, use magnetic stirrer simultaneously, the gained throw out is transferred in the tripod bottle, behind vibration 12 h, sample 110 ℃ of oven dry down, is ground with agate mortar at last in horizontal oscillator tube.
Embodiment three
Prepare the Ca (NO of 0.835 mol/L respectively 3) 2Ca (H with 0.5 mol/L 2PO 4) 2Solution, regulating the pH value with the ammoniacal liquor of 0.1-1 mol/L is 11, is 1.67 by Ca and P mol ratio, Ca (H 2PO 4) 2Solution slowly is added drop-wise to Ca (NO 3) 2In the solution, use magnetic stirrer simultaneously, the gained throw out is transferred in the tripod bottle, behind vibration 12 h, sample 110 ℃ of oven dry down, is ground with agate mortar at last in horizontal oscillator tube.
Embodiment four
Prepare the Ca (NO of 1.67 mol/L respectively 3) 2K with 1 mol/L 2HPO 4Solution, regulating the pH value with KOH is 11, is 1.67 by Ca and P mol ratio, K 2HPO 4Solution slowly is added drop-wise to Ca (NO 3) 2In the solution, use magnetic stirrer simultaneously, the gained throw out is transferred in the tripod bottle, behind vibration 12 h, sample 110 ℃ of oven dry down, is ground with agate mortar at last in horizontal oscillator tube.
Embodiment five
Preparation contains the Ca (NO of 0.835 mol/L 3) 2(NH with 0.5 mol/L 4) 2HPO 4Mixing solutions disposes 1 mol/L KOH solution, and KOH solution slowly is added drop-wise to Ca (NO 3) 2(NH 4) 2HPO 4In the mixing solutions, regulating the final pH value is 11, uses magnetic stirrer simultaneously, and the gained throw out is transferred in the tripod bottle, behind vibration 12 h, sample 110 ℃ of oven dry down, is ground with agate mortar at last in horizontal oscillator tube.
Embodiment six
Take by weighing a certain amount of CaHPO 4And Ca (OH) 2, be mixed with the CaHPO of 0.15 mol/L respectively 4Ca (OH) with 0.1 mol/L 2Suspension liquid is with CaHPO 4And Ca (OH) 2Ca/P=1.67 uniform mixing in molar ratio, and put into reactor, add a certain amount of water, and be 9 with 25% glacial acetic acid or ammoniacal liquor regulator solution pH value, sealed reactor is placed in the permanent temperature control oven then, be heated to 120 ℃, constant temperature 24 h carry out hydro-thermal reaction, treat to take out reactant after autoclave is cooled to room temperature, and are dry down at 80 ℃.
Embodiment seven
Take by weighing a certain amount of CaHPO 4And Ca (OH) 2, be mixed with the CaHPO of 0.15 mol/L respectively 4Ca (OH) with 0.1 mol/L 2Suspension liquid is with CaHPO 4And Ca (OH) 2Ca/P=1.67 uniform mixing in molar ratio, and put into reactor, add a certain amount of water, and be 9 with 25% glacial acetic acid or ammoniacal liquor regulator solution pH value, sealed reactor is placed in the permanent temperature control oven then, be heated to 180 ℃, constant temperature 24 h carry out hydro-thermal reaction, treat to take out reactant after autoclave is cooled to room temperature, and are dry down at 80 ℃.
Embodiment eight
Take by weighing a certain amount of Ca 3(PO 4) 2And Ca (OH) 2, be mixed with the CaHPO of 0.3 mol/L respectively 4Ca (OH) with 0.1 mol/L 2Suspension liquid is with Ca 3(PO 4) 2And Ca (OH) 2Ca/P=1.67 uniform mixing in molar ratio, and put into reactor, add a certain amount of water, and be 9 with 25% glacial acetic acid or ammoniacal liquor regulator solution pH value, sealed reactor is placed in the permanent temperature control oven then, be heated to 120 ℃, constant temperature 24 h carry out hydro-thermal reaction, treat to take out reactant after autoclave is cooled to room temperature, and are dry down at 80 ℃.
Make among the embodiment 1-8 shown in its table 1 composed as follows of nano-apatite phosphate fertilizer:
Table 1 nano-apatite phosphate fertilizer is formed
Embodiment The content of nanometer hydroxyapatite in the phosphate fertilizer (%, wt%)
Embodiment one 38.6 % (61.4 % are ammonium nitrate)
Embodiment two 38.6 % (61.4 % are ammonium nitrate)
Embodiment three 47.3 % (52.7 % are ammonium nitrate)
Embodiment four 33.2 % (66.8 % are saltpetre)
Embodiment five 36.2 % (34.6 for ammonium nitrate is, 29.2 % saltpetre)
Embodiment six 100?%
Embodiment seven 100?%
Embodiment eight 100?%
Embodiment nine
Apply nano-apatite phosphate fertilizer 0.5-2.1g in the table 1 to the yellowish soil of 300 g pH values 7.30 respectively, analyze the content of rapid available phosphorus in the soil, the result is as shown in table 2 below.
Table 2 is used the content of rapid available phosphorus in 1 week of the nano-apatite phosphate fertilizer back soil
Nano-apatite phosphate fertilizer Nano-apatite phosphate fertilizer add-on (g/300g soil) Nanometer hydroxyapatite content (%) in the phosphate fertilizer The content of rapid available phosphorus (mg/kg) in the soil
Embodiment four 0.5 33.2?% 22.7
Embodiment three 0.5 47.3?% 23.1
Embodiment six 0.5 100?% 22.5
Embodiment four 1.2 33.2?% 36.9
Embodiment three 1.2 47.3?% 36.4
Embodiment seven 1.2 100?% 35.8
Embodiment four 2.1 33.2?% 52.9
Embodiment three 2.1 47.3?% 53.4
Embodiment eight 2.1 100?% 53.1
As seen use nano-apatite phosphate fertilizer of the present invention, make after 1 week that the content of rapid available phosphorus reaches in the soil, and can long term maintenance in suitable (20-40 mg/kg) and (greater than the 40 mg/kg) level of enriching.
Embodiment ten
Apply nano-apatite phosphate fertilizer 1.05-2.1g in the table 1 to the yellowish soil that contains 900 mg/kg lead of 300 g pH values 7.30 respectively, make after 1 week that the content of rapid available phosphorus reaches in the soil, and can long term maintenance in suitable (20-40 mg/kg) and (greater than the 40 mg/kg) level of enriching, as shown in table 3 below; And soil MgCl 2Can extract that plumbous concentration is reduced by 31 mg/kg and long term maintenance at 21-14 mg/kg.
Table 3 is used the content of rapid available phosphorus in the leaded soil in nano-apatite phosphate fertilizer 1 week back
Nano-apatite phosphate fertilizer Nano-apatite phosphate fertilizer add-on (g/300g soil) Nanometer hydroxyapatite content (%) in the phosphate fertilizer The content of rapid available phosphorus (mg/kg) in the soil
Embodiment four 1.05 33.2?% 28.9
Embodiment three 1.05 47.3?% 29.4
Embodiment six 1.05 100?% 29.1
Embodiment four 1.5 33.2?% 38.7
Embodiment three 1.5 47.3?% 39.4
Embodiment seven 1.5 100?% 38.1
Embodiment four 2.1 33.2?% 43.1
Embodiment three 2.1 47.3?% 43.8
Embodiment eight 2.1 100?% 44.7
Embodiment 11
The nano-apatite phosphate fertilizer that makes among the embodiment 1-8, it comprises the nanometer hydroxyapatite that degree of crystallinity is very low, yellowish soil to 300 g pH values 7.30 applies 0.1-0.8 g, by analysis, the luffing of soil microbial biomass carbon is little after 6 weeks, and 192 mg/Kg by contrast vary to 176-160 mg/kg respectively.
Embodiment 12
The nano-apatite phosphate fertilizer that makes among the embodiment 1-8, it comprises the nanometer hydroxyapatite that degree of crystallinity is very low, apply 0.2-1.6 g to 300 g, pH value 7.30, the yellowish soil that contains 1600 mg/kg lead, make the microbial biomass carbon of soil be increased to 49-126 mg/kg by 32 mg/Kg of contrast respectively after 60 days.Microbial biomass nitrogen is increased to 18-79 mg/kg by 7 mg/Kg of contrast respectively, sees table 4 for details.
 
Soil microbial biomass carbon nitrogen changed after the plumbiferous yellowish soil of table 4 applied nano-apatite phosphate fertilizer
Nano-apatite phosphate fertilizer add-on (g/300g soil) Microbial biomass carbon (mg/Kg) Microbial biomass nitrogen (mg/Kg) The microbial biomass carbon-nitrogen ratio
0 32.0 7.0 4.54
0.2 49.3 17.6 2.79
0.4 73.9 35.2 2.09
0.8 118.2 59.7 1.97
1.6 125.6 79.3 1.58

Claims (10)

1. the preparation method of a nano-apatite phosphate fertilizer may further comprise the steps:
1) the phosphorus based sols of preparation 0.1-1.67 mol/L;
2) the calcium based sols of preparation 0.1-1.67 mol/L;
3) the phosphorus based sols is mixed with P mol ratio 5:3 by Ca with the calcium based sols and regulate acidity, make mixing solutions generation precipitin reaction or hydro-thermal reaction produce nano-apatite;
4) the resulting nano-apatite warp of step 3) is concentrated, 50-110 ℃ oven dry down makes nano-apatite phosphate fertilizer powder.
2. the preparation method of nano-apatite phosphate fertilizer according to claim 1, it is characterized in that the phosphorus based sols in the described step 1) is true solution or suspension liquid, solute is phosphoric acid, contains calcium phosphate, contains ammonium phosphoric acid salt, contains na phosphates or contain potassium phosphoric acid salt.
3. the preparation method of nano-apatite phosphate fertilizer according to claim 1 is characterized in that described step 2) in the calcium based sols be calcium hydroxide, Ca (NO 3) 2Perhaps CaCl 2True solution or suspension liquid.
4. the preparation method of nano-apatite phosphate fertilizer according to claim 1, it is characterized in that the hybrid mode in the described step 3), comprise the phosphorus based sols is added dropwise to the calcium based sols, perhaps the calcium based sols is added dropwise to the phosphorus based sols, perhaps the phosphorus based sols directly mixes the formation mixed solution with the calcium based sols.
5. the preparation method of nano-apatite phosphate fertilizer according to claim 1, it is characterized in that the solution adjusting acidity in the described step 3), comprise the mixed solution that utilizes alkaline matter or glacial acetic acid to regulate phosphorus based sols, calcium based sols or phosphorus based sols and calcium based sols, regulate pH value to 9～11.
6. the preparation method of nano-apatite phosphate fertilizer according to claim 5 is characterized in that described alkaline matter is ammoniacal liquor, NaOH, KOH or the urea of 0.1-1 mol/L.
7. the preparation method of nano-apatite phosphate fertilizer according to claim 1 is characterized in that the hydrothermal temperature in the described step 3) is 120-180 C, 24 hours reaction times.
8. the nano-apatite phosphate fertilizer of a method according to claim 1 preparation.
9. nano-apatite phosphate fertilizer according to claim 8 is characterized in that it is 33.2%-100% that described phosphate fertilizer comprises weight percent content, and median size is the nanometer hydroxyapatite of 20-50 nanometer.
10. nano-apatite phosphate fertilizer according to claim 8 is characterized in that being 26 °, 32 °, 34 °, 40 °, 47 ° and 50 ° in 2 θ values on the X-ray diffractogram of described nano-apatite phosphate fertilizer has located wide diffraction peak.
CN2010105240215A 2010-10-28 2010-10-28 Nanometer apatite phosphate fertilizer and preparation method thereof Pending CN101973791A (en)

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CN110156508A (en) * 2019-06-06 2019-08-23 中国科学院沈阳应用生态研究所 A kind of nanometer phosphate fertilizer and preparation method thereof that can promote a large amount of and microelement and absorbed in plant
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Application publication date: 20110216