CN103951516B - A kind of synergy calcium superphosphate and preparation method thereof and application - Google Patents
A kind of synergy calcium superphosphate and preparation method thereof and application Download PDFInfo
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Abstract
The invention belongs to fertilizer industry field, disclose a kind of synergy calcium superphosphate and preparation method thereof and application. The present invention utilizes the secondary hydrolysis of agricultural wastes acid hydrolysis and food processing factory's discarded object, preparation contains a large amount of low-molecular-weight organic acids, amino acid or other small organic molecule, using such material as synergist I, subsequently calcium superphosphate is added in synergist I, mix to dry and pulverize and obtain powdery sustained-release synergistic calcium superphosphate; Or synergist I, suspending agent and emulsification package film are mixed, make synergist II, subsequently calcium superphosphate is added in synergist II, after colloid mill high speed shear mixes, obtain liquid slow-release synergy calcium superphosphate. Described synergy calcium superphosphate has obviously reduced that phosphorus is adsorbed by soil colloid or by fixing chances such as iron ions, has increased the validity of phosphorus, has improved utilization rate of fertilizer. The method is simple and easy to do, saves the energy and raw material, reduces production costs. The present invention can be applicable to the agricultural production such as vegetables, fruit tree.
Description
Technical field
The invention belongs to fertilizer industry field, be specifically related to a kind of synergy calcium superphosphate and preparation method thereof and application.
Background technology
Phosphorus element is one of necessary nutrient of plant growth, and the phosphorus of most of crop element critical period of nutrition is given birth at it simultaneouslyIn earlier stage, serious if soil lacks phosphorus, will the yield and quality of crops be caused to the impact that cannot reverse. According to statistics, full generationThe agricultural soil on boundary 43% lacks phosphorus, lacks phosphorus area up to 67% in China farmland, and quick-acting phosphate fertilizer applies in soil on the other hand,Most of phosphorus is not to be present in soil with original form, but along with the difference of soil property and composition, occurs very soon anti-Should, form the phosphate compounds of ADSORPTION STATE or microsolubility as Ca2-P、Ca8The forms such as-P, Al-P, Fe-P (horse righteous army etc., 1993;Liu Jianling etc., 1996; Lu Wenlong and Zhang Fusuo, 1998; Akhtar, 2003; Xia Wenjian etc., 2008). Therefore, CropThe product that phosphorus major part forms after from phosphate fertilizer and soil reaction, instead of original phosphate fertilizer itself (Giesleretal., 2005;Berg and Joem, 2006). As: after calcium superphosphate is manured into soil, the moisture in soil diffuses into fertiliser granulates immediately,After Incongruent dissolution, generate CaHPO4Precipitation and H3PO4. Because saturated solution in fertiliser granulates and the soil body are at phosphorus concentrationThe larger gradient of upper existence (differing hundreds of to several thousand times), saturated solution outwards moves, and has Dicalcium Phosphate to form in moving process.Research finds, in moistening soil, about 20% phosphorus forms dicalcium phosphate dihydrate, and on dry soil nearly 40%Phosphorus form anhydrous dicalcium phosphate, the crop validity of phosphate fertilizer significantly declines, so cause phosphate fertilizer this season utilization rate low (Lu Rukun,1998; Coteetal., 2003). In order to improve the utilization rate of phosphate fertilizer, therefore the necessary form that exists to phosphate fertilizer is adjustedWhole, to avoid or reduce phosphate fertilizer and soil occurring directly to react, this is a behave that can significantly improve phosphate fertilizer and absorb efficiency.
Calcium superphosphate has another name called general calcium, is by sulfuric acid decomposing rock phosphate with hydrogen, makes the calcium phosphate of slightly solubility change into water miscible phosphoric acid oneCalcium, wherein the content of available phosphorus depends on the grade of raw material phosphor ore. Commodity calcium superphosphate is pale powder or particle, containsAvailable phosphorus 14%-20%, free sulfuric acid and the phosphoric acid of 3.5%-5% in addition, makes fertilizer become acid because it contains free acid, and toolBe corrosive, easily moisture absorption caking, free flowability is poor. After moisture absorption, one-lime phosphate wherein easily change into slightly solubility ferric phosphate,Aluminum phosphate, causes the validity of phosphorus to reduce; After being manured into soil, water-soluble phosphoric acid one calcium in fertilizer carries out different one-tenth in soilDivide and dissolve, and then phosphorus fixation occurs. The pH value of calcium superphosphate is lower simultaneously, generally lower than soil pH, is easily subject to soilThe impact of solution acid basic ion, thus cause solution pH value to raise fast, and pH can make available phosphorus level reduce after raising, withTime pH value quick variation also increased the chance of the fixing phosphorus of metal ion.
Chinese patent (publication number: CN101033155A) has been reported a kind of rare earth addition and has been crossed phosphorus containing the rare earth of this additiveAcid calcium and preparation method thereof, but this invention is only to add rare earth element, the form that exists of calcium superphosphate is not carried outConsider, also do not consider the problems such as phosphoric acid degeneration; Chinese patent application (publication number: CN101481273A) has been reported polypeptideCalcium superphosphate preparation method and the application in agricultural thereof, this invention is the physical mixed of calcium superphosphate and polypeptide, does not send outBiochemical reaction, and the impact of not inquiring into the validity after polypeptide is manured into soil on calcium superphosphate studies, simultaneouslyThe polypeptide price adding is more expensive, has increased cost; Chinese patent (publication number: CN101913946A) has been reported pyroligneous-containedLiquid compound fertilizer and application thereof, this invention adopts method of lixiviate by the water-soluble substance dissolves in calcium superphosphate, on the one hand phosphorusThe solubility of acid dihydride calcium is low, needs a large amount of water to dissolve, and a part of slow state phosphorus in calcium superphosphate cannot be by profit simultaneouslyWith.
Liao Zongwen etc. (2011) release in developing one literary composition of new technology with short in the thinking of nutrient availability concept, think water-solubleProperty also there is a kind of not yet available state of understanding, i.e. activated state between phosphorus and citric acid soluble phosphorus. At its patent (CN1275548A)In relate to a kind of acid-saving high-efficient phosphatic manure production method, this patent is mainly to weigh with sour consumption, not to existingActivated state proposes rational evidence, also the Synergistic Mechanisms of partially acidulated rock phosphate is not studied simultaneously.
How to increase the validity of phosphorus, the utilization rate that improves superphosphate fertilizer becomes the emphasis of people's research always. And pass throughThe form that changes calcium superphosphate strengthens the validity of phosphate fertilizer, and inquires into physical and chemical properties change after this incorporation of fertilizerin the soil (slowThe property released, resiliency) research patent report actually rare.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of synergy calcium superphosphate. LogicalCross and in calcium superphosphate, add calcium superphosphate synergist and prepare synergy calcium superphosphate with this, synergy calcium superphosphate has obviously reducedPhosphorus, by soil colloid absorption or by iron ion, calcium ion, the fixing chance of aluminium ion, increases the validity of phosphorus, has improvedUtilization rate of fertilizer. And calcium superphosphate synergist mainly utilizes food processing factory's discarded object, (the extraction discarded object of glucan, through forming sedimentPowder enzyme secondary fermentation makes) and agricultural wastes animal/vegetable proteins such as (be prepared from through acid hydrolysis) pig hairs, the two mixes,By acid hydrolysis, preparation contains a large amount of low-molecular-weight organic acids, amino acid or some other small organic molecule, as lemon againLemon acid, malic acid, glycine, glutamic acid, phenolic acid, fulvic acid etc., utilize such material as calcium superphosphate synergist.The method is simple and easy to do, saves the energy and raw material, reduces production costs. The present invention passes through to add on the basis of calcium superphosphateSynergist, forms the compound of a kind of transition state phosphorus and calcium with phosphorus in calcium superphosphate and calcium, by this transition state chemical combinationThe sign of thing, has studied the Synergistic Mechanisms of synergy calcium superphosphate, and by changing the formulation of calcium superphosphate, provides oneThere is the synergy calcium superphosphate of pH resiliency, phosphorus calcium slow release.
Another object of the present invention is to provide the preparation method of above-mentioned synergy calcium superphosphate.
A further object of the present invention is to provide the application of above-mentioned synergy calcium superphosphate.
Object of the present invention is achieved through the following technical solutions:
A kind of synergy calcium superphosphate, is made up of synergist and calcium superphosphate, wherein the mass ratio of synergist and calcium superphosphate be 1～3:7～10; Described synergist is synergist I or synergist II.
The preparation method of described synergist I, comprises the following steps:
(1) hydrolysis: by joining in the reactor that mixed acid is housed through the animal/vegetable protein of pulverizing, reactor is covered,Then be warming up to 100～120 DEG C and stir hydrolysis 6～8 hours, obtain hydrolyzate I;
(2) secondary hydrolysis: organic materials and discarded object are added in hydrolyzate I, after stirring, add hydrogen peroxide, will be anti-Answer kettle cover to live, at 80～90 DEG C, stir hydrolysis 2～3 hours, then reaction kettle cover is opened, continue stirring reaction 2～3 hours,Obtain hydrolyzate II;
(3) neutralization: regulating the pH value of hydrolyzate II with nertralizer is 3.5～4.5;
(4) chelating, synergy: in the hydrolyzate II to step (3) through neutralization, add successively synergistic matter and chelating agent,Stir, obtain synergist I.
Described in step (1), animal/vegetable protein is animal protein or vegetable protein, hair that described animal protein is animal,Internal organ, skin or angle, described vegetable protein be oil crops (peanut, soybean or rape) leaf, oil crops (peanut,Soybean or rape) stem stalk, dregs of beans, peanut meal or rapeseed dregs.
Animal/vegetable protein described in step (1) be in pig hair or ox hair more than one.
Described in step (1), animal/vegetable protein fineness is less than or equal to 60 orders.
Mixed acid described in step (1) is that 15～25wt% hydrochloric acid, 10～25wt% nitric acid and 20～30wt% sulfuric acid are by matterAmount is than being that 4～7:1～4:1～3 are mixed to get.
Mixed acid described in step (1) is that 20wt% hydrochloric acid, 20wt% nitric acid and 20wt% sulfuric acid are in mass ratio for 7:2:1 is mixedClose and obtain.
Animal/vegetable protein described in step (1) and mixed acid mass ratio are 1:1.6～2.
Organic materials described in step (2) is more than one in weathered coal, brown coal, peat, molasses powder and sodium humate.
Discarded object described in step (2) is citric acid waste, the waste liquid of sugar refinery, Gourmet Powder Factory or Alcohol Plant, sugar refinery, Gourmet Powder FactoryOr the waste residue of Alcohol Plant, the waste liquid of malic acid is prepared in microorganism fermentation, and microorganism fermentation is prepared waste liquid and the yeast of citric acid and is sent outFerment is prepared more than one in the waste liquid of glucan.
Organic materials described in step (2) and mixed acid mass ratio are 1:2～3.
Discarded object described in step (2) and mixed acid mass ratio are 1:2～3.
Hydrogen peroxide mass concentration percentage described in step (2) is 30%; Described hydrogen peroxide and organic materials mass ratio are1:20～30。
Nertralizer described in step (3) is NaOH, ammoniacal liquor, potassium hydroxide, trisodium citrate, calcium oxide and oxidationMore than one in magnesium.
Synergistic matter described in step (4) be shitosan, glucan, biochemical fulvic acid potassium, vitamin C, nucleic acid,More than one in polyglutamic acid, bentonite, diatomite and attapulgite.
Chelating agent described in step (4) is D-sorbite, mannitol, xylitol, antierythrite and ethylenediamine tetra-acetic acidMore than one in disodium (EDTA-2Na).
Synergistic matter described in step (4), chelating agent and synergist I mass ratio are 1～10:1～10:100.
The preparation method of described synergist II being for to add suspending agent, emulsification package film successively in synergist I and to mix,Thereby obtain synergist II.
Described suspending agent is hydroxyethylcellulose, carboxymethyl cellulose, polyvinyl alcohol, sodium hydroxyethyl cellulose and carboxymethylMore than one in sodium cellulosate.
Described emulsification package film is sodium alginate, potassium alginate, acrylic acid-grafted sodium alginate, Polyacrylamide Grafted seaMore than one in mosanom, polysorbas20, Tween 80, OP-10 and TX-10.
Described suspending agent, emulsification package film and synergist II mass ratio are 5～10:2～10:100.
The preparation method of described synergy calcium superphosphate, is that calcium superphosphate is joined in synergist I, mixes post-drying and pulverizesMake powdery sustained-release synergistic calcium superphosphate; Or calcium superphosphate is joined in synergist II, after high speed shear mixes, systemObtain liquid slow-release synergy calcium superphosphate.
Described high speed shear instrument is colloid mill, homogeneous instrument or high-speed shearing emulsion machine.
Described high speed shear speed is 10000～30000 revs/min; The described high speed shear time is 3～5min/L.
Described synergy calcium superphosphate is applied to agricultural production, comprises vegetables, fruit tree, flowers, industrial crops etc., executesBe that base is executed by mode, punching is executed.
The present invention is by complexing or chelated forms, and what change water-soluble calcium superphosphate exists form or character, enter after soil,By the pH of buffering calcium superphosphate, reduce calcium superphosphate by soil mineral or colloid absorption and fixing amount, thereby improve phosphate fertilizerCrop validity.
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) hydrolysis material is animal/vegetable protein, organic materials and production discarded object, and wherein major part belongs to agricultural and can utilize uselessGurry, has not only reduced these discarded objects and has piled up the environmental pressure bringing, and turns waste into wealth simultaneously, meets low-carbon economy and agricultureThe sustainable development of industry.
(2) process adopts secondary hydrolysis, and the production of amino acids production and humic acid at present is all carried out separately respectively, and this justAfter having caused hydrolysis, a large amount of residual acids needs alkali to go neutralization, thereby has reduced sour utilization rate, if simultaneously with the independent water of hydrochloric acidSeparating hair needs acid discharge in the later stage, and the pollution that this has just caused environment, has increased the weight of the formation of acid rain; The present invention is independent by secondaryHydrolysis, unite two into one, improved sour utilization rate.
(3) organic materials of hydrolysis for the second time, under acid and the double action of hydrogen peroxide, the large organic materials of molecular weight by byLittle, the active high organic substance of the molecule amount that is hydrolyzed into gradually, has utilized the once residual acid of hydrolysis on the one hand, subtracts on the other handLack the alkali needed of neutralization.
(4) adopt secondary hydrolysis, animal/vegetable protein and organic materials hydrolysis are more thorough, and contained active material is higher, simultaneously waterResidual residue after solution need not be filtered, and can directly mix with calcium superphosphate, not only improves the utilization rate of calcium superphosphate, simultaneouslyReduce production cost.
(5) nertralizer trisodium citrate, not only can in and residual acid, and its can also form with calcium, magnesium, iron etc. canMolten organic acid complex compound, has improved the validity of calcium, magnesium, iron, has also reduced phosphorus fixation simultaneously.
(6) synergist adding and chelating agent, proterties is stable, still can keep greater activity, simultaneously after drying, pulverizingAlso there is stimulating plant growth, strengthen the ability of resistance.
(7) at process aspect, adopt suspension technology, avoid Liquid Fertilizer nutrient content low, the restricted (water of material addingSeparate liquid residue filter) etc. problem, the polysaccharide suspending agent simultaneously adopting, utilizes himself characteristic to carry out stimulating plant raw on the one handGrow, have on the other hand the characteristic of stabile fertilizer, the space network structure that it is special, has effectively intercepted phosphorus and self is withCalcium, iron, the reaction of aluminium, moreover entrained active function groups energy complexing calcium, iron, aluminium and other heavy metals, thus subtractLack phosphorus fixation.
(8) on the basis of suspension technology, adopt more advanced emulsification package membrane technology, utilize the special anti-of calcium and alginateShould, add outside under the condition of high speed shearing force, can be to greatest extent that calcium superphosphate is coated, play the effect of slowly-releasing.
(9) owing to having generated a large amount of organic substances, low molecular weight organic acid in system, system has stronger buffer capacity,Its pH can be stabilized between 3.5-4.5, can not only prevent degeneration and the Incongruent dissolution of phosphorus in solid calcium superphosphate, and can delayRush the impact of soil liquid intermediate ion on calcium superphosphate pH, thereby improve phosphate fertilizer utilization efficiency.
Brief description of the drawings
Fig. 1 is the influence curves of different extracting times to calcium superphosphate pH value of solution, and wherein, SP is normal superphosphate, W1,W2, W3 are respectively the prepared synergy calcium superphosphate of embodiment 1,2,3;
Fig. 2 is the influence curve of the number of times that adds of alkali to calcium superphosphate pH value of solution changing value, and wherein SP is normal superphosphate,W1, W2, W3 are respectively the prepared synergy calcium superphosphate of embodiment 1,2,3;
Fig. 3 is the impact of solid synergy calcium superphosphate on absorbed phosphorus by crop amount, and wherein (1) is that solid synergy calcium superphosphate is to plantRoot system is inhaled the impact of phosphorus amount, and (2) are solid synergy calcium superphosphate is inhaled phosphorus amount impact on plant overground part, and (3) are solid increasingEffect calcium superphosphate plant entirety is inhaled the impact of phosphorus amount; CK is that control group (not applying fertilizer), SP are for executing normal superphosphate group, TSPFor executing synergy calcium superphosphate group, G1 for executing synergist group;
Fig. 4 is solid synergy calcium superphosphate is inhaled calcium amount influence curve to plant, and wherein (1) is solid synergy calcium superphosphate pairPlant root is inhaled the impact of calcium amount, and (2) are solid synergy calcium superphosphate is inhaled calcium amount impact on plant overground part, and (3) are for solidBody synergy calcium superphosphate is inhaled the impact of calcium amount on plant entirety; CK is that control group (not applying fertilizer), SP are for executing normal superphosphateGroup, TSP are for executing synergy calcium superphosphate group, G1 for executing synergist group;
Fig. 5 is the impact of solid synergy calcium superphosphate on root system of plant vigor; CK is that control group (not applying fertilizer), SP are common for executingCalcium superphosphate group, TSP are for executing synergy calcium superphosphate group, G1 for executing synergist group;
Fig. 6 is the impact of liquid synergy calcium superphosphate on absorbed phosphorus by crop amount, and wherein (1) is that liquid synergy calcium superphosphate is to plantRoot system is inhaled the impact of phosphorus amount, and (2) are liquid synergy calcium superphosphate is inhaled phosphorus amount impact on plant overground part; CK is clear water contrastGroup, SP is for executing normal superphosphate (1.1g/ basin) group, and T1 is applying liquid synergy calcium superphosphate (0.825g/ basin) group, T2For applying liquid synergy calcium superphosphate (0.935g/ basin) group, T3 is applying liquid synergy calcium superphosphate (1.1g/ basin) group.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) hydrolysis: will through pulverizing pig hair (order number is 60 orders) add in the reactor that mixed acid is housed, mixed acid by15wt% hydrochloric acid, 15wt% nitric acid and 20wt% sulfuric acid are the ratio composition of 4:4:2 in mass ratio, pig hair and mixed acid mass ratioFor 1:1.6, reactor is covered, be warming up to 100 DEG C, stir hydrolysis 6 hours, obtain hydrolyzate I;
(2) secondary hydrolysis: ratio adds hydrolyzate according to being 1:3 with mixed acid mass ratio respectively by molasses powder and citric acid wasteIn I, stir, continuing to add mass percent is 30% hydrogen peroxide, and hydrogen peroxide and organic materials mass ratio are 1:20,Reactor is covered, at 80 DEG C, be hydrolyzed 2 hours, reaction kettle cover is opened, continue stirring reaction 2 hours, obtain hydrolyzateⅡ；
(3) neutralization: regulating the pH value of hydrolyzate II with NaOH is 3.5;
(4) chelating, synergy: shitosan and D-sorbite are added in the hydrolyzate II that step (3) pH is 3.5, stir allEven, obtain synergist I, wherein, the mass ratio of shitosan, D-sorbite and synergist I is 1:1:100; Then to increasingIn effect agent I, add calcium superphosphate, the mass ratio of calcium superphosphate and synergist I is 1:10, mixes post-drying, pulverizing, makesSolid slow-release synergy calcium superphosphate.
Embodiment 2
(1) hydrolysis: will add in the reactor that mixed acid is housed through the ox hair (80 order) of pulverizing, mixed acid is by using 20wt%Hydrochloric acid, 25wt% nitric acid and 20wt% sulfuric acid are the ratio composition of 7:2:1 in mass ratio, and pig hair and mixed acid mass ratio are 1:1.8,Reactor is covered, be warming up to 110 DEG C, be hydrolyzed 7 hours, obtain hydrolyzate I;
(2) secondary hydrolysis: ratio adds hydrolyzate according to being 1:2 with mixed acid mass ratio respectively by weathered coal and citric acid wasteIn I, stir, continuing to add mass percent is 30% hydrogen peroxide, and hydrogen peroxide and organic materials mass ratio are 1:25,Reactor is covered, at 90 DEG C, continue hydrolysis 2.5 hours, reaction kettle cover is opened, continue stirring reaction 2 hours, obtain waterSeparate liquid II;
(3) neutralization: regulating the pH value of hydrolyzate II with NaOH and trisodium citrate is 4.0;
(4) chelating, synergy: shitosan, bentonite and D-sorbite are added in the hydrolyzate II that step (3) pH is 4.0,Stir, obtain synergist I, wherein, the mass ratio of shitosan, bentonite, D-sorbite and synergist I is 2:7:2:100; Then in synergist I, add calcium superphosphate, the mass ratio of calcium superphosphate and synergist I is 2:8, mixes rear bakingDry, pulverizing, make solid slow-release synergy calcium superphosphate.
Embodiment 3
(1) hydrolysis: add in the reactor that mixed acid is housed through the pig hair (60 order) of pulverizing, mixed acid is by 20wt% saltAcid, 20wt% nitric acid and 20wt% sulfuric acid are the ratio composition of 7:2:1 in mass ratio, and pig hair and mixed acid mass ratio are 1:2, willReactor covers, and is warming up to 120 DEG C, is hydrolyzed 8 hours, obtains hydrolyzate I;
(2) secondary hydrolysis: by the waste liquid of weathered coal and culture propagation glucan respectively according to mixed acid mass ratio be 1:2.5Ratio adds in hydrolyzate I, stirs, and continuing to add mass percent is 30% hydrogen peroxide, hydrogen peroxide and organic materialsMass ratio is 1:30, and reactor is covered, and continues hydrolysis 3 hours at 90 DEG C, and reaction kettle cover is opened, and continues stirring reaction 2Hour, obtain hydrolyzate II;
(3) neutralization: regulating the pH value of hydrolyzate II with potassium hydroxide and ammoniacal liquor is 4.5;
(4) chelating, synergy: biochemical fulvic acid potassium, bentonite, diatomite, D-sorbite and EDTA-2Na are added to stepSuddenly in the hydrolyzate II that (3) pH is 4.5, stir, obtain synergist I, wherein biochemical fulvic acid potassium, bentonite,The mass ratio of diatomite, D-sorbite, EDTA-2Na and synergist I is 1:2:7:8:2:100; Then to synergistIn I, add calcium superphosphate, the mass ratio of synergist I and calcium superphosphate is 3:7, mixes post-drying, pulverizing, makes solidSustained-release synergistic calcium superphosphate.
Embodiment 4
(1) hydrolysis: add in the reactor that mixed acid is housed through the pig hair (80 order) of pulverizing, mixed acid is by 25wt% saltAcid, 25wt% nitric acid and 20wt% sulfuric acid are the ratio composition of 7:2:1 in mass ratio, and pig hair and mixed acid mass ratio are 1:2, willReactor covers, and is warming up to 110 DEG C, is hydrolyzed 8 hours, obtains hydrolyzate I;
(2) secondary hydrolysis: ratio adds hydrolyzate according to being 1:2 with mixed acid mass ratio respectively by weathered coal and sugar refinery waste liquidIn I, stir, continuing to add mass percent is 30% hydrogen peroxide, and hydrogen peroxide and organic materials mass ratio are 1:25,Reactor is covered, at 80 DEG C, continue hydrolysis 2 hours, reaction kettle cover is opened, continue stirring reaction 2 hours, obtain waterSeparate liquid II;
(3) neutralization: regulating the pH value of hydrolyzate II with trisodium citrate and ammoniacal liquor is 4.5;
(4) chelating, synergy: biochemical fulvic acid potassium, bentonite, diatomite, D-sorbite, EDTA-2Na are added to stepSuddenly in the hydrolyzate II that (3) pH is 4.5, stir, obtain synergist I, wherein biochemical fulvic acid potassium, bentonite,The mass ratio of diatomite, D-sorbite, EDTA-2Na and synergist I is 1:2:7:2:2:100;
(5) suspension, emulsification: add successively hydroxyethylcellulose, potassium alginate and polysorbas20 in synergist I, stir mixedClose evenly, obtain synergist II, wherein hydroxyethylcellulose, sodium alginate, polysorbas20 and synergist II, mass ratio is 7:7:2:100; Then add calcium superphosphate to synergist II, the mass ratio of calcium superphosphate and synergist II is 1:10, through glueBody mill high speed shear (shear rate: 10000 revs/min, shear time: every liter 4 minutes) mix after, make liquid slow-release and increaseEffect calcium superphosphate.
Embodiment 5
(1) hydrolysis: add in the reactor that mixed acid is housed through the pig hair (60 order) of pulverizing, mixed acid is by 15wt% saltAcid, 15wt% nitric acid and 30wt% sulfuric acid are the ratio composition of 6:3:1 in mass ratio, and pig hair and mixed acid mass ratio are 1:1.6,Reactor is covered, be warming up to 120 DEG C, be hydrolyzed 7 hours, obtain hydrolyzate I;
(2) secondary hydrolysis: ratio adds according to being 1:3 with mixed acid mass ratio respectively by solid sodium humate and sugar refinery waste residueIn hydrolyzate I, stir, continuing to add mass percent is 30% hydrogen peroxide, and hydrogen peroxide and organic materials mass ratio are1:30, covers reactor, is hydrolyzed 2 hours at 80 DEG C, and reaction kettle cover is opened, and continues stirring reaction 2 hours, obtains waterSeparate liquid II;
(3) neutralization: regulating the pH value of hydrolyzate II with potassium hydroxide and ammoniacal liquor is 4.0;
(4) chelating, synergy: glucan, polyglutamic acid, bentonite, mannitol and EDTA-2Na are added to step (3)PH, in 4.0 hydrolyzate II, stirs, and obtains synergist I, wherein glucan, polyglutamic acid, bentonite, sweet dewThe mass ratio of sugar alcohol, EDTA-2Na and synergist I is 2:0.5:7:4:4:100;
(5) suspension, emulsification: add successively carboxymethyl cellulose, sodium alginate and Tween 80 in synergist I, stir mixedClose evenly, obtain synergist II, wherein, the mass ratio of carboxymethyl cellulose, sodium alginate, Tween 80 and synergist II is10:7:3:100; Then add calcium superphosphate to synergist II, the mass ratio of calcium superphosphate and synergist II is 3:7, processHomogeneous instrument high speed shear mix after (shear rate: 20000 revs/min, shear time: every liter 3 minutes), make liquid slow-releaseSynergy calcium superphosphate.
Embodiment 6
(1) hydrolysis: add in the reactor that mixed acid is housed through the pig hair (60 order) of pulverizing, mixed acid is by 25wt% saltAcid, 25wt% nitric acid and 20wt% sulfuric acid are the ratio composition of 7:2:1 in mass ratio, and pig hair and mixed acid mass ratio are 1:2, willReactor covers, and is warming up to 110 DEG C, is hydrolyzed 8 hours, obtains hydrolyzate I;
(2) secondary hydrolysis: ratio adds hydrolyzate I according to being 1:2 with mixed acid mass ratio respectively by peat and brewery's waste residueIn, stir, continuing to add mass percent is 30% hydrogen peroxide, hydrogen peroxide and organic materials mass ratio are 1:25, willReactor covers, and continues hydrolysis 2 hours at 80 DEG C, and reaction kettle cover is opened, and continues stirring reaction 2 hours, is hydrolyzedLiquid II;
(3) neutralization: regulating the pH value of hydrolyzate II with natrium citricum and ammoniacal liquor is 4.5;
(4) chelating, synergy: vitamin C, bentonite, diatomite, D-sorbite and EDTA-2Na are added to step (3)PH, in 4.5 hydrolyzate II, stirs, and obtains synergist I, wherein vitamin C, bentonite, diatomite, sorbThe mass ratio of sugar alcohol, EDTA-2Na and synergist I is 1:2:7:2:2:100;
(5) suspension, emulsification: add polyvinyl alcohol and APES (OP-10) in synergist I, stirMix, obtain synergist II, wherein, the matter of polyvinyl alcohol, APES (OP-10) and synergist IIAmount is than being 5:2:100; Then add calcium superphosphate to synergist II, the mass ratio of calcium superphosphate and synergist II is 2:8,After colloid mill high speed shear mixes (shear rate: 20000 revs/min, shear time: every liter 3 minutes), make liquidSustained-release synergistic calcium superphosphate.
Embodiment 7 solid synergy calcium superphosphate pH mechanism test I
Utilize the prepared solid synergy calcium superphosphate of above-described embodiment 1-3, represent respectively with W1, W2, W3, test arranges4 processing, for normal superphosphate (SP), synergy calcium superphosphate I (W1), synergy calcium superphosphate II (W2),Synergy calcium superphosphate III (W3), wherein SP is normal superphosphate processing, takes 1.00g, W1, W2, W3 divide another nameGet and the synergy calcium superphosphate of the quality such as SP, the 10mL that adds water, vibration 1min, measures its pH after static 5min, then centrifugal willSupernatant discards, then adds 10mL water, repeats above-mentioned steps three times. Extracting times affects as Fig. 1 institute the pH value of each solutionShow.
As seen from Figure 1, in the time of lixiviate for the first time, it is minimum that SP processes pH value, and it is the highest that W3 processes pH, illustrates and add in synergist energyWith the free acid in calcium superphosphate, suitably improve the pH value of calcium superphosphate. In four leaching process, SP processes pH simultaneouslyExcursion maximum, pH value 2.09, the W3 that risen processes pH and changes littlely, and pH value has risen 0.76, and simple mistake phosphorus is describedAcid calcium pH is subject to extraneous medium influence, and pH changes greatly, thereby causes the validity reduction of phosphorus, and W3 has good pH and delaysPunching property, can maintain the pH of calcium superphosphate leaching liquor, makes the validity of phosphorus perform to maximum.
Embodiment 8 solid synergy calcium superphosphate pH mechanism test II
Utilize the prepared solid synergy calcium superphosphate of above-described embodiment 1-3, represent respectively with W1, W2, W3, test arranges4 processing, for normal superphosphate (SP), synergy calcium superphosphate I (W1), synergy calcium superphosphate II (W2),Synergy calcium superphosphate III (W3), wherein SP is normal superphosphate processing, takes 1.00g, W1, W2, W3 divide another nameGet and the synergy calcium superphosphate of the quality such as SP, the 10mL that respectively adds water, shakes up and measures pH value, respectively add 10mmol/LKOH moltenLiquid (pH=12) 5mL, shakes up and measures pH with pH meter afterwards, continues to add 10mmol/LKOH solution (pH=12) 5mL,Shake up rear mensuration pH value, so repeat 3 times. The pH value of each solution of measuring is as shown in table 1. Simultaneously with add the pH after alkali at every turnValue deducts previous pH value, is made into the figure that pH changes, and result as shown in Figure 2. Fig. 2 is that the number of times that adds of alkali is to peroxophosphoric acidThe impact of calcium solution pH changing value, wherein ordinate is that to add the changing value of pH before and after alkali (be that △ pH=adds the pH value after alkali at every turnPH value before-Jia alkali), abscissa is the number of times (addition of each alkali is identical) that alkali adds.
As seen from Table 1, only add after distilled water, the widely different significance that reaches of pH value of each solution, wherein SP processesPH is minimum, W3 process pH the highest, illustrate add synergist can in normal superphosphate in free acid, avoided lowThe injury of pH value to root system of plant; Along with constantly adding of KOH, the pH value of system, also in continuous raising, still adds for three timesEnter the widely different significance that reaches of pH value of respectively processing after KOH. Can find from table 1 and Fig. 2, add for the third time after alkali,The pH value that SP processes rises maximum, and pH value has improved 2.28, W1, W2, W3 and improved respectively 2.05,1.90,1.37,Also show that synergy calcium superphosphate can keep out the impact of outside alkali preferably simultaneously, have stronger pH resiliency, this pH is slowThe validity that the fluctuation that punching property makes phosphorus element avoid pH causes declines, thereby improves the utilization rate of phosphorus element.
Table 1 alkalimetric titration buffer test
Note: SP is normal superphosphate processing, and W1, W2, W3 are respectively the prepared synergy calcium superphosphate processing of embodiment 1,2,3, and basic pH isOnly add the pH value of measuring after distilled water, pH is the pH value that adds for the first time solution after alkali for the first time, and pH is for adding for the second time solution after alkali for the second timePH value, pH is the pH value that adds for the third time solution after alkali for the third time. The different significant differences (p < 0.05) that represent of same row letter.
Embodiment 9 solid synergy calcium superphosphate Releasing Mechanism tests
Utilize the prepared solid synergy calcium superphosphate of above-described embodiment 1-3, represent respectively with W1, W2, W3, test arranges4 processing, are SP, W1, W2, W3, and wherein SP is normal superphosphate processing, takes 1.00g, W1, W2,W3 takes respectively the synergy calcium superphosphate with the quality such as SP, the 10mL that respectively adds water, and vibration 1min, rear centrifuging and taking supernatant is for subsequent use,And then the 10mL that adds water, vibration 1min, so repeats twice, measures the phosphorus in supernatant. It the results are shown in Table 2.
As shown in Table 2, in leaching liquor, it is the highest that SP processes phosphorus content for the first time, and it is minimum that W3 processes content, between each processing, reachesSignificant difference, illustrates that the phosphorus content adding after synergist in leaching liquor for the first time significantly reduces, and reduces maximum with W3. SimultaneouslyFor the second time, in for the third time with four leaching liquor, W3 processes phosphorus content apparently higher than SP, and the total phosphorus sum of four lixiviates is poorDifferent not remarkable, illustrate that adding synergist rear section phosphorus element is transformed into slowly-releasing state (transition state) by water-soluble state, makes lixiviate for the first timeTime phosphorus content lower than SP, along with the increase of extracting times, the phosphorus of slowly-releasing state changes to water-soluble state gradually, thereby meets after cropThe demand of phase, also shows to add the phosphorus in the unfixing calcium superphosphate of synergist, but part phosphorus is transformed into slowly-releasing simultaneouslyState.
The impact of the different extracting times of table 2 on phosphorus concentration
Note: SP is normal superphosphate processing, and W1, W2, W3 are respectively the prepared synergy calcium superphosphate processing of embodiment 1,2,3, for the first timeFor adding for the first time the concentration value of phosphorus in the centrifugal gained supernatant of distilled water, for the second time for adding for the second time phosphorus in the centrifugal gained supernatant of distilled waterConcentration value, for the third time for adding for the third time the concentration value of phosphorus in the centrifugal gained supernatant of distilled water, adds the centrifugal institute of distilled water for the 4th time the 4th timeObtain the concentration value of phosphorus in supernatant. The different letter representation significant differences of same row (p < 0.05).
Embodiment 10 solid synergy calcium superphosphate corn manure trials
Utilize the prepared solid synergy calcium superphosphate of above-described embodiment 3, represent with TSP, test arrange CK, SP, TSP,Tetra-processing of G1, wherein CK is control group (not applying fertilizer), SP for executing normal superphosphate group, TSP crosses phosphorus for executing synergyAcid calcium group, G1 are for executing synergist group, and each processing repeats for 5 times, every basin dress wind desiceted soil 1kg, and the consumption of every basin N is 150mg/kgSoil applies urea, every basin K2O consumption is that 120mg/kg soil applies potassium sulfate, and wherein SP processes and uses calcium superphosphate 1.25g/Basin, during TSP processes, in synergy calcium superphosphate and G1, the consumption of synergist is identical with calcium superphosphate consumption in SP; Exist respectively5th, within 10,15,20,25 days, measure rhizosphere soil available phosphorus and exchangeable calcium, in table 3, table 4; While measuring the 25th daySuction phosphorus, calcium amount and the improving activity of root system of plant, result is as shown in Fig. 3, Fig. 4 and Fig. 5.
Table 3 is the dynamic change of available phosphorus content in different time sections Rhizosphere Soil, and as seen from the table, fertilising can improve rhizosphereThe content of available phosphorus in soil, and As time goes on, available phosphorus content constantly declines; 5th, 10 days rhizosphere soils,It is not remarkable that calcium superphosphate processing and synergy calcium superphosphate are processed available phosphorus content difference, and possible cause is that calcium superphosphate self containsA large amount of water-soluble phosphoruses, can meet the crop demand in early stage, and since the 15th day, calcium superphosphate was processed and synergy peroxophosphoric acidCalcium is processed available phosphorus content significant difference in Rhizosphere Soil, shows that the slowly-releasing phosphorus in synergy calcium superphosphate slowly discharged in the crop later stage,It has the chelating of pH resiliency and low-molecular-weight organic matter simultaneously, can avoid the fixing fast of phosphorus element, thereby be cropLater stage continues phosphorus supply.
Table 4 is the dynamic change of exchangeable calcium content in different time sections Rhizosphere Soil, as seen from the table, and at the 5th, 10 days,Synergy calcium superphosphate is processed higher than calcium superphosphate processing and exchanging calcium content, and reaches significant difference, illustrates and adds synergistCan complexing part calcium, improve its validity; Fertilizer has the reaction of pH shock-absorbing capacity reduction phosphorus element and calcium simultaneously, and calcium is existedCrop has higher activity early stage, but at the 15th, 20,25 days, calcium superphosphate was processed and synergy calcium superphosphate is processed friendshipTranssexual calcium content difference is not remarkable, and possible cause is in calcium superphosphate, to contain a large amount of calcium sulfate, along with the growth of crop, sulphurAcid calcium is dissolved by the soil liquid gradually, has supplemented the calcium of Crop, makes difference not remarkable.
From Fig. 3, Fig. 4 and Fig. 5, fertilising can improve the absorption of corn to phosphorus and calcium, the calcium superphosphate of synergy simultaneously and excessively phosphorusAcid calcium is compared, and can significantly increase the suction phosphorus amount of corn and reach significant difference, the root system of synergy calcium superphosphate processing and groundPhosphorus amount is inhaled higher than calcium superphosphate processing by portion, improves respectively 42.4% and 65.3%, root system and the overground part of the processing of synergy calcium superphosphateInhale calcium amount higher than calcium superphosphate processing, improve respectively 70.6% and 18.1%, the calcium superphosphate of synergy simultaneously can strengthen maize root system and livePower.
Table 3 rhizosphere soil available phosphorus content (mg/kg)
Note: the different letter representation significant differences of same row (p < 0.05).
Table 4 rhizosphere soil exchangeable calcium content
Note: the different letter representation significant differences of same row (p < 0.05).
Embodiment 11 liquid synergy calcium superphosphate corn manure trials
Utilize the prepared liquid synergy calcium superphosphate of above-described embodiment 4, represent with T, test arrange CK, SP, T1, T2,These 5 processed group of T3, wherein CK is clear water contrast, and consumption is 1.1g/ basin, and SP executes normal superphosphate for punching, and consumption is 1.1g/Basin, T1, T2, T3 be for rushing applying liquid synergy calcium superphosphate, and consumption is respectively 0.825g/ basin (account for SP process 70%), 0.935g/Basin (account for SP process 85%), 1.1g/ basin (processing equivalent with SP); Each group to rush applying method identical, point three punchings are executed,Every basin fills native 5kg, and each processed group repeats for 6 times; The consumption of each processed group N is that 150mg/kg soil applies urea, K2The consumption of OFor 120mg/kg soil applies potassium sulfate, all processed group basal dressing calcium superphosphate 1.1g/ basins simultaneously, corn is transplanted in 2013.9.24,After transplanting the 10th, 15,20 days are carried out 3 punchings and are executed respectively, in 2013.10.20 results, measure the suction phosphorus amount of plant. KnotFruit as shown in Figure 6.
As shown in Figure 6, along with the increase of synergy calcium superphosphate consumption, maize root system and overground part are inhaled phosphorus amount the trend of increase.T1 process (the punching amount of executing be SP treating capacity 70%) process with SP compared with, root system and overground part are inhaled phosphorus amount indifference, explanationThe consumption of synergy calcium superphosphate 70% just can reach the effect of SP, along with the suction of the increase plant of the synergy calcium superphosphate punching amount of executingPhosphorus amount constantly increases. Illustrate that synergy calcium superphosphate can improve the utilization rate of P elements, reduce its constant concentration in soil.
Above-described embodiment is preferably embodiment of the present invention, but embodiments of the present invention are not restricted to the described embodiments,Other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify, allShould be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. a synergy calcium superphosphate, is characterized in that: be made up of synergist and calcium superphosphate, wherein synergyThe mass ratio of agent and calcium superphosphate is 1～3:7～10; Described synergist is synergist I or synergist II;
The preparation method of described synergist I, comprises the following steps:
(1) hydrolysis: will join in the reactor that mixed acid is housed through the animal/vegetable protein of pulverizing, will be anti-Answer kettle cover to live, be then warming up to 100～120 DEG C and stir hydrolysis 6～8 hours, obtain hydrolyzate I;
(2) secondary hydrolysis: organic materials and discarded object are added in hydrolyzate I, add two after stirringOxygen water, covers reactor, and at 80～90 DEG C, stir hydrolysis 2～3 hours, then reaction kettle cover is opened,Continue stirring reaction 2～3 hours, obtain hydrolyzate II; Described discarded object is citric acid waste, sugar refinery, tasteThe waste liquid of essence factory or Alcohol Plant, the waste residue of sugar refinery, Gourmet Powder Factory or Alcohol Plant, malic acid is prepared in microorganism fermentationWaste liquid, microorganism fermentation is prepared the waste liquid of citric acid and culture propagation and is prepared the one in the waste liquid of glucanAbove; Described organic materials be one in weathered coal, brown coal, peat, molasses powder and sodium humate withOn;
(3) neutralization: regulating the pH value of hydrolyzate II with nertralizer is 3.5～4.5;
(4) chelating, synergy: add successively synergistic matter in the hydrolyzate II to step (3) through neutralizationAnd chelating agent, stir, obtain synergist I; Described synergistic matter is shitosan, glucan, lifeChange one in fulvic acid potassium, vitamin C, nucleic acid, polyglutamic acid, bentonite, diatomite and attapulgiteMore than kind;
The preparation method of described synergist II adds suspending agent, emulsification package film in synergist I also successivelyMix, thereby obtain synergist II; Described suspending agent be hydroxyethylcellulose, carboxymethyl cellulose,More than one in polyvinyl alcohol, sodium hydroxyethyl cellulose and sodium carboxymethylcellulose;
Described emulsification package film is sodium alginate, potassium alginate, acrylic acid-grafted sodium alginate, polypropyleneMore than one in acid amide-grafted sodium alginate, polysorbas20, Tween 80, OP-10 and TX-10.
2. synergy calcium superphosphate according to claim 1, is characterized in that: moving described in step (1)Vegetable protein is animal protein or vegetable protein, hair, internal organ, Pi Huo that described animal protein is animalAngle, the leaf that described vegetable protein is oil crops, stem stalk, dregs of beans, peanut meal or the vegetable seed of oil cropsThe dregs of rice;
Mixed acid described in step (1) be 15～25wt% hydrochloric acid, 10～25wt% nitric acid and 20～30wt% sulfuric acid is that 4～7:1～4:1～3 are mixed to get in mass ratio;
Animal/vegetable protein described in step (1) and mixed acid mass ratio are 1:(1.6～2).
3. synergy calcium superphosphate according to claim 1, is characterized in that: described in step (2)Organic materials and mixed acid mass ratio are 1:(2～3);
Discarded object described in step (2) and mixed acid mass ratio are 1:(2～3);
Hydrogen peroxide mass concentration percentage described in step (2) is 30%; Described hydrogen peroxide and organic matterMaterial mass ratio is 1:(20～30).
4. synergy calcium superphosphate according to claim 1, is characterized in that: described in step (3)Nertralizer is the one in NaOH, ammoniacal liquor, potassium hydroxide, trisodium citrate, calcium oxide and magnesiaAbove.
5. synergy calcium superphosphate according to claim 1, is characterized in that:
Chelating agent described in step (4) is D-sorbite, mannitol, xylitol, antierythrite and secondMore than one in edetate disodium;
Synergistic matter described in step (4), chelating agent and synergist I mass ratio are (1～10): (1～10):100。
6. synergy calcium superphosphate according to claim 1, is characterized in that:
Described suspending agent, emulsification package film and synergist II mass ratio are (5～10): (2～10): 100.
7. the preparation method of synergy calcium superphosphate according to claim 1, is characterized in that: be by mistakeCalcium phosphate joins in synergist I, mixes post-drying pulverizing and makes powdery sustained-release synergistic calcium superphosphate; OrPerson joins calcium superphosphate in synergist II, after high speed shear mixes, makes liquid slow-release synergy and crosses phosphorusAcid calcium.
8. the application of synergy calcium superphosphate according to claim 1, is characterized in that: described synergyCalcium superphosphate is applied to agricultural production, comprises industrial crops.
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| CN105198560B (en) * | 2015-08-18 | 2018-11-27 | 深圳市芭田生态工程股份有限公司 | Fertilizer auxiliary agent and application |
| CN105399523A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Method for preparing coated sustained-release calcium fertilizer from waste seafood shell |
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| CN106146150B (en) * | 2016-06-30 | 2018-01-12 | 吉林贝盈生物科技有限公司 | Phosphate fertilizer synergist and preparation method thereof, phosphate fertilizer synergist powder and phosphate fertilizer |
| CN106396894A (en) * | 2016-08-30 | 2017-02-15 | 山东胜伟园林科技有限公司 | Humic acid-containing water soluble fertilizer produced by molasses alcohol fermentation liquor |
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| CN109134135A (en) * | 2018-07-03 | 2019-01-04 | 南宁市英德肥业有限责任公司 | Application of the magnesia in the adjustment of molasses humic acid type compound fertilizer's pH value |
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