CN103553723A - Solid-phase synthesis method of phosphate-phosphite compound fertilizers - Google Patents
Solid-phase synthesis method of phosphate-phosphite compound fertilizers Download PDFInfo
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Abstract
The invention discloses a solid-phase synthesis method of phosphate-phosphite compound fertilizers. The phosphate-phosphite compound fertilizers are a group of solid-phase phosphate-phosphite compounded nitrogen-phosphorus-potassium ternary compound fertilizers as well as phosphorus-potassium binary compound fertilizers and phosphorus-ammonium binary compound fertilizers, which have antibacterial and disease prevention functions and are directly synthesized through respective solid-phase acid-base neutralization reaction between solid-phase phosphorus acid and solid-phase dipotassium phosphate, diammonium phosphate and tripotassium phosphate in mixing and kneading processes and solid-phase chemical reaction induced under the action of the high-energy mechanical force of high-speed lapping. The synthesis process is short in reaction time, low in energy consumption and free of waste gases, waste liquor and waste residues and is a cleaner production process with the characteristics of simpleness, low equipment investment and low production cost.
Description
Technical field
The invention belongs to multi-Functional Fertilizers technical field, be specifically related to a kind of method of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer.
Background technology
Phosphite is a kind of mineral compound of non-agricultural chemicals, there is obvious antibiotic disease-proof functions, be widely used in agriculture antibiotic diseases prevention, for the phosphite of agriculture sterilizing disease-preventing, be mainly water miscible potassium dihydrogen phosphite, dihydrogen phosphite ammonium and citric soluble dihydrogen phosphite calcium.
Chinese invention patent CN1826899A " application of potassium dihydrogen phosphite in preparing antibacterial foliar fertilizer " discloses: using potassium dihydrogen phosphite as foliage fertilizer, and remarkable to killing rotten mould, the Rhizoctonia cerealis of red mould, the melon and fruit of Botrytis cinerea, sharp Fusariumsp cucumber specialized form, sharp Fusariumsp watermelon specialized form, sub-chinese sorghum, sclerotinite and verticillium dahliae effect.
Chinese invention patent CN101492323B " a kind of phosphite complex fertilizer of concurrently treating soil-borne disease of tobacco " discloses: take phosphorous acid sylvite and phosphorous acid ammonium salt as main, the composite fertilizer that is aided with the concurrently treating soil-borne disease of tobacco of boric acid and available nitrogen phosphate fertilizer composition, has obvious prevention effect to tobacco bacterial wilt, black shank, tobacco root-knot.
Chinese invention patent CN102964181A " a kind of composite fertilizer of disinfecting type of preventing and treating anthrax " discloses: with phosphorous acid sylvite and Cu, Zn, Fe, Mn, B, Mo trace element, form the composite fertilizer of disinfecting type, for control, comprise cucumber anthracnose, watermelon anthrax bacteria, grape anthracnose and citrus anthracnose bacterium.
The existing method of preparing potassium dihydrogen phosphite, dihydrogen phosphite ammonium all adopts acid-base neutralisation method in liquid phase, for example: while preparing the potassium dihydrogen phosphite of crystalline state in liquid phase, will be first by the water-soluble phosphorous acid aqueous solution that is mixed with of phosphorous acid, with solution of potassium carbonate or with potassium hydroxide solution, carry out acid-base neutralisation again, by controlling pH value, make dihydrogen phosphite potassium solution, then through filtering, concentrate, the operation such as crystallization, brilliant liquid separation makes crystalline state potassium dihydrogen phosphite.The method complex manufacturing, energy consumption is high, cost is also higher.
Phosphorous acid and phosphite thereof are all unstable in air, and easy oxidized generation phosphorous acid and phosphite thereof lose the function of antibiotic diseases prevention.Particularly phosphorous acid and phosphite are more easily oxidized under liquid state and heated condition, so when liquid phase is prepared phosphite, adopt inert liq or rare gas element as stablizer, prevention phosphite is oxidized to phosphoric acid salt.
Chinese invention patent CN1142090C " production method of potassium dihydrogen phosphite " has adopted phosphorous acid aqueous solution and wet chemical, under the condition existing at stablizer, carry out acid-base neutralisation and generate dihydrogen phosphite potassium solution, more after filtration, the potassium dihydrogen phosphite of operation the makes crystalline state such as concentrated, crystallization is separated with brilliant liquid.This patent stablizer used is inert nitrogen gas, helium or inert liq liquid nitrogen, liquid helium.
Phosphite is easy to be absorbed by plants, transport, and phosphite is not oxidized in plant materials, can keep for a long time its phosphite form, and in plant materials, the lasting period is long, antibiotic protection effect is obvious.
Due to phosphite not oxidized generation phosphoric acid salt in plant materials, only have phosphoric acid salt as phosphate fertilizer, to be utilized by plant, if use separately phosphite, can cause plant to lack the problem that delayed growth appears in phosphate fertilizer.So while using phosphite, application of phosphate fertilisers simultaneously, to prevent plant for want of phosphate fertilizer and the problem of the delayed growth that produces.
On agricultural materials market, not yet there is at home the fertilizer that phosphite is compound with phosphoric acid salt, mix, use the phosphatic fertilizer that has phosphite, must phosphite and phosphate fertilizer be arranged in pairs or groups in proportion after mixing temporarily and use at the scene of using.Use inconvenience, be unfavorable for applying of this technology.Therefore, be badly in need of the nitrogen with antibiotic disease-proof functions, phosphorus, the K compound fertilizer of a kind of phosphoric acid salt of exploitation and the compound composition of phosphite, to fill up the blank in fertilizer variety.
Summary of the invention
A kind of method that the object of this invention is to provide solid phase synthesis phosphoric acid salt-phosphite complex fertilizer.
The method of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer of the present invention, by the weight ratio proportioning of 1.0:1.0 ~ 1.5:0.8 ~ 1.3, through mixing, mediate and grinding the phosphoric acid salt-phosphite complex fertilizer that directly synthesizes solid phase by phosphorous acid and dipotassium hydrogen phosphate, three kinds of crystallization powders of Secondary ammonium phosphate.
Phosphoric acid salt-the phosphite complex fertilizer of solid phase synthesis of the present invention, is mixed and is formed by potassium hydrophosphate, ammonium hydrogen phosphate salt and hydrogen phosphite sylvite, hydrogen phosphite ammonium salt, is one group of composite fertilizer with antibiotic disease-proof functions.
Above-mentioned potassium hydrophosphate, ammonium hydrogen phosphate salt, hydrogen phosphite sylvite, hydrogen phosphite ammonium salt are to take potassium primary phosphate, primary ammonium phosphate, potassium dihydrogen phosphite, dihydrogen phosphite ammonium as main, and contain dipotassium hydrogen phosphate partly, Secondary ammonium phosphate, potassium phosphite, hydrogen phosphite two ammoniums composition composite powder crystal.
The technical solution used in the present invention is specific as follows:
The raw material of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer of the present invention is: the mineral compound such as phosphorous acid, dipotassium hydrogen phosphate, Secondary ammonium phosphate, Tripotassium phosphate.
Raw materials quality of the present invention, whether special dipotassium hydrogen phosphate, Secondary ammonium phosphate, Tripotassium phosphate, phosphorous acid containing crystal water, and whether moisture absorption deliquescence, be directly to obtain the key of dry powdery product by the product that is related to solid phase synthesis.
Phosphorous acid (H
3pO
3) be phosphorous oxygen acid, clear crystal, 73.5 ℃ of fusing points.The acid intensity of phosphorous acid is than ortho-phosphoric acid (H
3pO
4) strong 5 times, suitable with the acid intensity of phosphoric acid, there are strong water absorbability and deliquescence, be exposed to and in air, be easily oxidized to ortho-phosphoric acid.
For the phosphorous acid of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, requirement is the solid phase phosphorous acid without the crystal state of moisture absorption deliquescence.
Dipotassium hydrogen phosphate (K
2hPO
4), colourless or white tetragonal spheroidal coarse particles xln, easy deliquescence, soluble in water, react acid, the pH value of 1% solution is 8.7 ~ 9.3.
For the dipotassium hydrogen phosphate of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, requirement is without moisture absorption deliquescence, without the dipotassium hydrogen phosphate xln of crystal water.
Secondary ammonium phosphate [(NH
4)
2hPO
4] water white transparency monoclinic crystal or white powder, soluble in water, react acid, the pH value of 1% solution is 7.6 ~ 8.4.
For the Secondary ammonium phosphate of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, requirement is Secondary ammonium phosphate xln or the powder without moisture absorption deliquescence.
Tripotassium phosphate (K
3pO
4), having another name called potassiumphosphate, white crystals or white particulate powder, have strong water absorbability, soluble in water, react acid,, there is severe corrosive pH value>=11.5 of 1% solution.
For the Tripotassium phosphate of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, requirement is xln or the granular powder without the Tripotassium phosphate without crystal water of moisture absorption deliquescence.
Dipotassium hydrogen phosphate, Secondary ammonium phosphate, Tripotassium phosphate are the Jia, phosphorus composite fertilizer of high density and the Dan, phosphorus composite fertilizer of high density, and potassium wherein, nitrogen, phosphorus are water-soluble, and fertilizer efficiency is fast, is applicable to various soil and crop.
The method of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer of the present invention, specifically, by the mutually collaborative solid phase synthesis novel process of solid-state soda acid neutralization reaction and powder machinery force-chemical reaction, its technical scheme is divided into four steps:
Step 1, the pre-treatment of raw material and formula rate:
1, select the lenticular phosphorous acid that hardens without deliquescence as consolidating synthetic raw material, if find, the phosphorous acid hardening must be ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition, airtight seal up for safekeeping standby.
2, raw material dipotassium hydrogen phosphate and the Secondary ammonium phosphate for the preparation of nitrogen, phosphorus, potassium Nitrogen, Phosphorus and Potassium is pre-mixed by formula rate, under relative humidity (RH) 20% ~ 30% condition, is ground into 80 ~ 100 order powders, airtight seal up for safekeeping standby.
For the preparation of raw material dipotassium hydrogen phosphate, Secondary ammonium phosphate, the Tripotassium phosphate of phosphorus, potassium binary compound fertilizer, phosphorus nitrogen binary compound fertilizer, under the condition of relative temperature (RH) 20% ~ 30%, be ground into separately 80 ~ 100 order powders respectively in advance, airtight sealing up for safekeeping, standby.
3, the formula rate of the phosphoric acid salt-phosphite complex fertilizer of each formula combination (weight ratio):
(1) by H
3pO
4with K
2hPO
4, (NH
4)
2hPO
4combination preparation N, P, K Nitrogen, Phosphorus and Potassium formula rate:
H
3PO
4：K
2HPO
4：(NH
4)
2HPO
4＝1.0：1.0~1.5：0.8~1.3；
(2) by H
3pO
4with K
2hPO
4combination preparation P, K binary compound fertilizer formula rate:
H
3PO
4：K
2HPO
4＝1.0：2.3~2.8；
(3) by H
3pO
4with (NH
4)
2hPO
4combination preparation P, N binary compound fertilizer formula rate:
H
3PO
4：?(NH
4)
2HPO
4＝1.0：1.5~2.0；
(4) by H
3pO
4with K
2hPO
4combination preparation P, K binary compound fertilizer formula rate:
H
3PO
4：K
3PO
4＝1.0：1.3~1.8。
By adjusting the formula rate of dipotassium hydrogen phosphate, Secondary ammonium phosphate, Tripotassium phosphate and phosphorous acid, produce the phosphoric acid salt-phosphite complex fertilizer of different pH values (pH4.5 ~ 8.5), in acid soil, use the phosphoric acid salt-phosphite complex fertilizer of meta-alkalescence, in alkaline soil, use the phosphoric acid salt-phosphite complex fertilizer of slant acidity, the suitable foliage fertilizer as spraying corps leaf surface of neutral phosphoric acid salt-phosphite complex fertilizer, or as rushing the fertilising of rushing of executing crop root part.
Step 2, solid-state acid-base neutralisation reaction:
Below the solid-state soda acid neutralization procedure by phosphorous acid, dipotassium hydrogen phosphate, Secondary ammonium phosphate combination preparation N, P, K Nitrogen, Phosphorus and Potassium:
Step 2 is that to utilize phosphorous acid be a kind of mineral acid of strong acidity, dipotassium hydrogen phosphate, Secondary ammonium phosphate are the features of alkaline inorganic compound, highly acid phosphorous acid is mixed by above-mentioned formula rate with alkaline dipotassium hydrogen phosphate, Secondary ammonium phosphate, while mediating, produce violent acid-base neutralisation reaction in kneader.
When acid-base neutralisation reacts, acid-base neutralisation chemical reaction can discharge reaction heat, because phosphorous acid fusing point is only 73.5 ℃, after acid-base neutralisation reaction occurs, phosphorous acid crystal is melted in its reaction heat, the phosphorous acid that is melt into " liquid " state is penetrated into dipotassium hydrogen phosphate, Secondary ammonium phosphate plane of crystal very soon, has accelerated again acid-base neutralisation reaction, and whole reaction mass becomes molten state very soon.Acid-base neutralisation reaction finishes very soon, and material is also cooled to solid-state very soon, forms dry granules shape powder under the continuous stirring of kneader.
Due to the equal easy moisture absorption deliquescence of phosphorous acid, dipotassium hydrogen phosphate, Secondary ammonium phosphate, in the environment that it is 30% ~ 40% in relative humidity (RH) that solid-state soda acid neutralization reaction requires, with the kneader of the speed of mainshaft 20 ~ 80r/min, carry out 15min ~ 30min kneading.
Phosphorous acid, dipotassium hydrogen phosphate, Secondary ammonium phosphate for solid phase synthesis phosphoric acid salt-phosphite complex fertilizer all must not have the solid crystals of moisture absorption deliquescence.Dipotassium hydrogen phosphate must be selected the dipotassium hydrogen phosphate without crystal water.If raw material used is moisture absorption deliquescence, or select the Rhodiaphos DKP that contains crystal water, the material that its acid-base neutralisation reaction obtains is pasty material or the liquid material of hygrometric state, can not obtain dry granules shape powder.
By phosphorous acid and dipotassium hydrogen phosphate, form preparation P, K binary compound fertilizer, by phosphorous acid and Secondary ammonium phosphate combination, prepare P, N binary compound fertilizer, the solid-state soda acid neutralization procedure of being prepared P, K binary compound fertilizer by phosphorous acid and Tripotassium phosphate combination, each composition independency assembly on its formula rate, identical with the technique of above-mentioned N, P, K Nitrogen, Phosphorus and Potassium on processing step.
Step 3, powder machinery force-chemical reaction:
In the material generating in step 2, both contain potassium primary phosphate, primary ammonium phosphate, potassium dihydrogen phosphite, dihydrogen phosphite ammonium, had again unreacted phosphorous acid, dipotassium hydrogen phosphate, Secondary ammonium phosphate.
Due to after the reaction of violent acid-base neutralisation finishes, the rapid cooling formation particulate state powder of temperature of charge, these materials wrap up mutually, make unreacted phosphorous acid cannot produce solid-state acid-base neutralisation with dipotassium hydrogen phosphate, Secondary ammonium phosphate again and react.
Powder machinery force-chemical reaction, powder shaped chemical substance is brought out it and under solid phase condition, is produced solid-state soda acid neutralization reaction under mechanical force.
By above-mentioned pulverulent material under the condition of relative humidity (RH) 30% ~ 40%, with the high-speed grinder of 20000 ~ 25000r/min, grind 5min ~ 15min, unreacted phosphorous acid, dipotassium hydrogen phosphate, Secondary ammonium phosphate in the material being wrapped up are mutually produced to solid state reaction, make it generate potassium primary phosphate, primary ammonium phosphate, potassium dihydrogen phosphite, dihydrogen phosphite ammonium.And the phosphoric acid salt-phosphite complex fertilizer that makes the to generate crystal that is ground into powder.
Step 4, functional nitrogen, phosphorus, potassium Nitrogen, Phosphorus and Potassium packing
By the above-mentioned packing bag with protection against the tide, choke, lucifuge function for the material making, under the condition of relative humidity (RH) 40% ~ 50%, with powder automatic packing machine, pack.
In solid phase synthesis process, the potassium primary phosphate generating, primary ammonium phosphate and potassium dihydrogen phosphite, the mutual melting of dihydrogen phosphite ammonium, wrap up mutually, due to potassium primary phosphate, primary ammonium phosphate is stable in the air, be difficult for deliquescence, potassium dihydrogen phosphite, dihydrogen phosphite ammonium is at potassium primary phosphate, under the absorption of primary ammonium phosphate is protected with parcel, air and potassium dihydrogen phosphite have been intercepted, hydrogen phosphite two ammoniums directly contact, improved stability, overcome easy deliquescence, oxidizable defect, make phosphite be difficult for oxidized generation phosphoric acid salt and lose the activity of antibiotic diseases prevention, for condition has been created in the application of phosphoric acid salt-phosphite complex fertilizer:
(1) phosphoric acid salt-phosphite complex fertilizer, can directly use as multi-Functional Fertilizers;
(2) phosphoric acid salt-phosphite complex fertilizer, can be used as antibiotic diseases prevention medicament, respectively with vitriolate of tartar, Repone K, potassium primary phosphate, ammonium sulfate, ammonium chloride, bicarbonate of ammonia, primary ammonium phosphate, the composite composition function fertilizer of urea traditional chemical fertilizer;
(3) phosphoric acid salt-phosphite complex fertilizer, can be used as antibiotic diseases prevention medicament, respectively with seaweeds fertilizer, humic-acid kind fertilizer, camellia seed meal fertilizer, amino acids fertilizer, plant vinegar composite salt fertilizer and oligosaccharide kind biologically active substance compounded combination;
(4) phosphoric acid salt-phosphite complex fertilizer, avoids combining containing inorganic salt fertilizer, the organic fertilizer of oxidisability matrix with saltpetre, ammonium nitrate, nitro humic acid class.
Remarkable advantage of the present invention is: the multiple synergistic effect of utilizing mechanical force, heating power and the chemistry of mechanical force and chemical effect, under the condition of solid phase, dipotassium hydrogen phosphate, Secondary ammonium phosphate, the Powdered crystal of tricresyl phosphite kind, through mixing, mediate, grind the directly phosphoric acid salt-phosphite complex fertilizer of synthetic solid phase.
In synthesis process of the present invention, do not need dipotassium hydrogen phosphate, Secondary ammonium phosphate, tricresyl phosphite kind material dissolution to become liquid to carry out liquid-phase chemical reaction, then through filtering, the complicated technology such as concentrated, crystallization makes the product of solid phase.
In synthesis technique of the present invention, do not need heated for controlling temperature, do not need to regulate pH, the reaction times is short, consumes energy low.
In synthesis technique of the present invention, not having waste gas, waste liquid, waste residue to produce, is that a kind of technique is simple, and facility investment is few, the process for cleanly preparing that production cost is low.
Embodiment
A method for solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, is characterized in that: the screening and requirement, formula rate and the process for solid phase synthesis that comprise raw material; Described process for solid phase synthesis is divided into the pre-treatment of raw material, solid-state soda acid neutralization reaction, powder machinery force-chemical reaction and functional complex fertilizer product packing, its preparation method be by the solid phosphorous acid of the solid phosphate of crystal state and crystal state mixing, produce the reaction of solid phase acid-base neutralisation in kneading process and under the high energy mechanical power effect of speed lapping and bringing out, produce solid state reaction, directly generate the phosphoric acid salt-phosphite complex fertilizer of solid phase; The concrete steps of the phosphoric acid salt-phosphite complex fertilizer of described solid phase synthesis are as follows:
(1) phosphoric acid salt-phosphite complex fertilizer of described solid phase synthesis is a kind of nitrogen, phosphorus, potassium Nitrogen, Phosphorus and Potassium with antibiotic disease-proof functions, by potassium primary phosphate, primary ammonium phosphate, potassium dihydrogen phosphite, dihydrogen phosphite ammonium, is compound composition of main and part dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, the hydrogen phosphite Powdered crystal of two ammoniums;
(2) solid phosphate that the raw material of the phosphoric acid salt-phosphite complex fertilizer of described solid phase synthesis is crystal state and the solid phosphorous acid of crystal state, the solid phosphate of crystal state is that the solid phosphorous acid of crystal state is the xln without the phosphorous acid of moisture absorption deliquescence without moisture absorption deliquescence, without the dipotassium hydrogen phosphate of crystal water, the xln of Secondary ammonium phosphate;
(3) formula rate of the nitrogen in described solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, phosphorus, potassium Nitrogen, Phosphorus and Potassium: be that phosphorous acid by dipotassium hydrogen phosphate, Secondary ammonium phosphate and the above-mentioned specification of quality of above-mentioned specification of quality is by the weight ratio proportioning of 1.0 ~ 1.5:0.8 ~ 1.3:1.0, wherein dipotassium hydrogen phosphate, Secondary ammonium phosphate raw material must be through pre-treatment, dipotassium hydrogen phosphate, Secondary ammonium phosphate are pre-mixed in proportion and under the condition of relative humidity 20% ~ 30%, with shredder, grind to form 80 ~ 100 object mixed powders, more in proportion with the assembly of phosphorous acid crystal;
(4) the solid-state soda acid neutralization reaction in the synthesis technique of described solid phase synthesis phosphoric acid salt-phosphite complex fertilizer: the dipotassium hydrogen phosphate that is pre-mixed grinding by above-mentioned formula rate requirement, the phosphorous acid powder that Secondary ammonium phosphate powder grinds in advance by above-mentioned formula and above-mentioned formula rate requirement is under the condition of relative humidity 20% ~ 30%, in the kneader of the speed of mainshaft 20 ~ 80r/min, first mix, then in kneader, mediate 15min ~ 30min, mixing, the phosphorous acid of kneading process middle strong acidity and weakly alkaline dipotassium hydrogen phosphate, Secondary ammonium phosphate produces violent solid phase acid-base neutralisation reaction, most material reaction generates respectively relative potassium primary phosphate, primary ammonium phosphate and potassium dihydrogen phosphite, dihydrogen phosphite ammonium, the a large amount of heat energy that discharge in reaction process, make the mutual melting of the unreacted material of reacted material and part, wrap up mutually, in kneading process, form granular mixture,
(5) the powder machinery force-chemical reaction in the synthesis technique of described solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, by the solid state reaction bringing out under mechanical force: the powder-mixed material that above-mentioned acid-base neutralisation is produced, under the condition of relative humidity 30% ~ 40%, with the high-speed grinder of 20000 ~ 25000r/min, grind 5min ~ 15min, by mutual melting, the granular mixture abrasive lapping of parcel becomes fine powder, and adjust running mechanical force effect and bring out under make the unreacted dipotassium hydrogen phosphate of part, Secondary ammonium phosphate and phosphorous acid produce solid state reaction, material is all generated with potassium primary phosphate, primary ammonium phosphate and potassium dihydrogen phosphite, dihydrogen phosphite ammonium is main, contain part dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, the Powdered crystal composition phosphoric acid salt-phosphite complex fertilizer of hydrogen phosphite two ammoniums,
(6) packing of the functional nitrogen phosphorus potassium tri compound fertilizer product that the synthesis technique of described solid phase synthesis phosphoric acid salt-phosphite complex fertilizer makes: by make with potassium primary phosphate, primary ammonium phosphate and potassium dihydrogen phosphite, dihydrogen phosphite ammonium is main, contain part dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, the functional nitrogen of the Powdered crystal composition of hydrogen phosphite two ammoniums, phosphorus, potassium Nitrogen, Phosphorus and Potassium, with thering is protection against the tide, choke, the packing bag of lucifuge function, under the condition of relative humidity 40% ~ 50%, with powder automatic packing machine, pack.
The method of described a kind of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, it is characterized in that: by changing the formula combination of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, select separately without moisture absorption deliquescence, without the dipotassium hydrogen phosphate of crystal water and phosphorous acid by the weight ratio proportioning of 2.3 ~ 2.8:1.0, apply the method for above-mentioned solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, what directly synthesize solid phase is main by potassium primary phosphate, potassium dihydrogen phosphite, the functional phosphorus, the potassium binary compound fertilizer that contain part dipotassium hydrogen phosphate, potassium phosphite composition.
The method of described a kind of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, it is characterized in that: by changing the formula combination of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer and the phosphatic material combination of passing through to change alkalescence, select separately without the Secondary ammonium phosphate of moisture absorption deliquescence and phosphorous acid by the weight ratio proportioning of 1.5 ~ 2.0:1.0, apply the method for above-mentioned solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, direct synthetic solid phase by primary ammonium phosphate, dihydrogen phosphite ammonium is main, contain part Secondary ammonium phosphate, the functional phosphorus that hydrogen phosphite two ammoniums form, nitrogen binary compound fertilizer.
The method of described a kind of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, it is characterized in that: by changing raw material variety and the formula combination of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, with alkaline without moisture absorption deliquescence, Tripotassium phosphate without crystal water substitutes weakly alkaline without moisture absorption deliquescence, the weight ratio proportioning of pressing 1.3 ~ 1.8:1.0 without dipotassium hydrogen phosphate and the phosphorous acid of crystal water, apply the method for above-mentioned solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, direct synthetic solid phase by potassium primary phosphate, potassium dihydrogen phosphite is main, contain part dipotassium hydrogen phosphate, the functional phosphorus that potassium phosphite forms, potassium binary compound fertilizer.
The method of described a kind of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, it is characterized in that: by adjusting dipotassium hydrogen phosphate, Secondary ammonium phosphate, the formula rate of Tripotassium phosphate and phosphorous acid, produce pH value and be phosphoric acid salt-phosphite complex fertilizer of 4.5 ~ 8.5, in acid soil, use the phosphoric acid salt-phosphite complex fertilizer of meta-alkalescence, in alkaline soil, use the phosphoric acid salt-phosphite complex fertilizer of slant acidity, the suitable foliage fertilizer as spraying corps leaf surface of neutral phosphoric acid salt-phosphite complex fertilizer, or as rushing the fertilising of rushing of executing crop root part.
Phosphoric acid salt-the phosphite complex fertilizer of described a kind of solid phase synthesis, it is characterized in that: in solid phase synthesis process, generate potassium primary phosphate, primary ammonium phosphate and potassium dihydrogen phosphite, the mutual melting of dihydrogen phosphite ammonium, wrap up mutually, due to potassium primary phosphate, primary ammonium phosphate is stable in the air, be difficult for deliquescence, potassium dihydrogen phosphite, dihydrogen phosphite ammonium is at potassium primary phosphate, under the absorption of primary ammonium phosphate is protected with parcel, air and potassium dihydrogen phosphite have been intercepted, hydrogen phosphite two ammoniums directly contact, improved stability, overcome easy deliquescence, oxidizable defect, make phosphite be difficult for oxidized generation phosphoric acid salt and lose the activity of antibiotic diseases prevention, for condition has been created in the application of phosphoric acid salt-phosphite complex fertilizer:
(1) phosphoric acid salt-phosphite complex fertilizer, can directly use as multi-Functional Fertilizers;
(2) phosphoric acid salt-phosphite complex fertilizer, can be used as antibiotic diseases prevention medicament, respectively with vitriolate of tartar, Repone K, potassium primary phosphate, ammonium sulfate, ammonium chloride, bicarbonate of ammonia, primary ammonium phosphate, the composite composition function fertilizer of urea traditional chemical fertilizer;
(3) phosphoric acid salt-phosphite complex fertilizer, can be used as antibiotic diseases prevention medicament, respectively with seaweeds fertilizer, humic-acid kind fertilizer, camellia seed meal fertilizer, amino acids fertilizer, plant vinegar composite salt fertilizer and oligosaccharide kind biologically active substance compounded combination;
(4) phosphoric acid salt-phosphite complex fertilizer, avoids combining containing inorganic salt fertilizer, the organic fertilizer of oxidisability matrix with saltpetre, ammonium nitrate, nitro humic acid class.
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this.
embodiment 1:the dipotassium hydrogen phosphate crystal of 130g is mixed, is ground into 80 ~ 100 order powders with the Secondary ammonium phosphate crystal of 100g under relative humidity (RH) 20% ~ 30% condition.
The phosphorous acid crystal of 100g is mixed, is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The dipotassium hydrogen phosphate of 230g, Secondary ammonium phosphate mixed powder are mixed under relative humidity (RH) 30% ~ 40% condition with the phosphorous acid powder of 100g, with the kneader of the speed of mainshaft 20 ~ 80r/min, mediate 15min ~ 30min and obtain dry granules shape powder.
By the particulate state powder of above-mentioned acquisition under relative humidity (RH) 30% ~ 40% condition, with the high shear grinding machine of 20000 ~ 25000r/min, grinding 5min ~ 15min makes and take potassium primary phosphate, primary ammonium phosphate, potassium dihydrogen phosphite, dihydrogen phosphite ammonium as main, the Powdered crystal of phosphoric acid salt-phosphite complex fertilizer that contains part dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, hydrogen phosphite two ammoniums, its product pH value is in 6.5 ~ 7.5 left and right.
By the Powdered crystal of the above-mentioned phosphoric acid salt-phosphite complex fertilizer making, the packing bag with having damp proof, choke, lucifuge function, under relative humidity (RH) 40% ~ 50% condition, packs with powder automatic packing machine.
embodiment 2:the dipotassium hydrogen phosphate crystal of 150g is mixed, is ground into 80 ~ 100 order powders with the Secondary ammonium phosphate crystal of 130g under relative humidity (RH) 20% ~ 30% condition.
The phosphorous acid crystal of 100g is mixed, is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The dipotassium hydrogen phosphate of 280g, Secondary ammonium phosphate mixed powder are mixed under relative humidity (RH) 30% ~ 40% condition with the phosphorous acid powder of 100g, with the kneader of the speed of mainshaft 20 ~ 80r/min, mediate 15min ~ 30min and obtain dry granules shape powder.
By the particulate state powder of above-mentioned acquisition under relative humidity (RH) 30% ~ 40% condition, with the high shear grinding machine of 20000 ~ 25000r/min, grinding 5min ~ 15min makes and take potassium primary phosphate, primary ammonium phosphate, potassium dihydrogen phosphite, dihydrogen phosphite ammonium as main, the Powdered crystal of phosphoric acid salt-phosphite complex fertilizer that contains more dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, hydrogen phosphite two ammoniums, its product pH value is in 7.5 ~ 8.5 left and right.
By the Powdered crystal of the above-mentioned phosphoric acid salt-phosphite complex fertilizer making, the packing bag with having damp proof, choke, lucifuge function, under relative humidity (RH) 40% ~ 50% condition, packs with powder automatic packing machine.
embodiment 3:the dipotassium hydrogen phosphate crystal of 100g is mixed, is ground into 80 ~ 100 order powders with the Secondary ammonium phosphate crystal of 80g under relative humidity (RH) 20% ~ 30% condition.
The phosphorous acid crystal of 100g is mixed, is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The dipotassium hydrogen phosphate of 180g, Secondary ammonium phosphate mixed powder are mixed under relative humidity (RH) 30% ~ 40% condition with the phosphorous acid powder of 100g, with the kneader of the speed of mainshaft 20 ~ 80r/min, mediate 15min ~ 30min and obtain dry granules shape powder.
By the particulate state powder of above-mentioned acquisition under relative humidity (RH) 30% ~ 40% condition, with the high shear grinding machine of 20000 ~ 25000r/min, grinding 5min ~ 15min makes and take potassium primary phosphate, primary ammonium phosphate, potassium dihydrogen phosphite, dihydrogen phosphite ammonium as main, the Powdered crystal of phosphoric acid salt-phosphite complex fertilizer that contains part dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, hydrogen phosphite two ammoniums, its product pH value is in 4.5 ~ 5.5 left and right.
By the Powdered crystal of the above-mentioned phosphoric acid salt-phosphite complex fertilizer making, the packing bag with having damp proof, choke, lucifuge function, under relative humidity (RH) 40% ~ 50% condition, packs with powder automatic packing machine.
embodiment 4:the dipotassium hydrogen phosphate crystal of 250g is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The phosphorous acid crystal of 100g is mixed, is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The dipotassium hydrogen phosphate mixed powder of 250g is mixed under relative humidity (RH) 30% ~ 40% condition with the phosphorous acid powder of 100g, with the kneader of the speed of mainshaft 20 ~ 80r/min, mediate 15min ~ 30min and obtain dry granules shape powder.
By the particulate state powder of above-mentioned acquisition under relative humidity (RH) 30% ~ 40% condition, with the high shear grinding machine of 20000 ~ 25000r/min, grinding 5min ~ 15min makes and take potassium primary phosphate, potassium dihydrogen phosphite as main, the Powdered crystal of phosphoric acid salt-phosphite complex fertilizer that contains part dipotassium hydrogen phosphate, potassium phosphite.
By the Powdered crystal of the above-mentioned phosphoric acid salt-phosphite complex fertilizer making, the packing bag with having damp proof, choke, lucifuge function, under relative humidity (RH) 40% ~ 50% condition, packs with powder automatic packing machine.
By adjusting the formula rate of phosphorous acid and dipotassium hydrogen phosphate, can make phosphorus, the potassium binary compound fertilizer of pH value 4.5 ~ 8.5.
embodiment 5:the Secondary ammonium phosphate crystal of 180g is mixed, is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The phosphorous acid crystal of 100g is mixed, is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The Secondary ammonium phosphate powder of 180g is mixed under relative humidity (RH) 30% ~ 40% condition with the phosphorous acid powder of 100g, with the kneader of the speed of mainshaft 20 ~ 80r/min, mediate 15min ~ 30min and obtain dry granules shape powder.
By the particulate state powder of above-mentioned acquisition under relative humidity (RH) 30% ~ 40% condition, with the high shear grinding machine of 20000 ~ 25000r/min, grinding 5min ~ 15min makes and take primary ammonium phosphate, dihydrogen phosphite ammonium as main, the Powdered crystal of phosphoric acid salt-phosphite complex fertilizer that contains part Secondary ammonium phosphate, hydrogen phosphite two ammoniums.
By the Powdered crystal of the above-mentioned phosphoric acid salt-phosphite complex fertilizer making, the packing bag with having damp proof, choke, lucifuge function, under relative humidity (RH) 40% ~ 50% condition, packs with powder automatic packing machine.
By adjusting the formula rate of phosphorous acid and Secondary ammonium phosphate, can make phosphorus, the nitrogen binary compound fertilizer of pH value 4.5 ~ 8.5.
embodiment 6:the Tripotassium phosphate crystal of 150g is mixed, is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The phosphorous acid crystal of 100g is mixed, is ground into 80 ~ 100 order powders under relative humidity (RH) 20% ~ 30% condition.
The Tripotassium phosphate powder of 150g is mixed under relative humidity (RH) 30% ~ 40% condition with the phosphorous acid powder of 100g, with the kneader of the speed of mainshaft 20 ~ 80r/min, mediate 15min ~ 30min and obtain dry granules shape powder.
By the particulate state powder of above-mentioned acquisition under relative humidity (RH) 30% ~ 40% condition, with the high shear grinding machine of 20000 ~ 25000r/min, grinding 5min ~ 15min makes and take potassium primary phosphate, potassium dihydrogen phosphite as main, the Powdered crystal of phosphoric acid salt-phosphite complex fertilizer that contains part dipotassium hydrogen phosphate, potassium phosphite, hydrogen phosphite two ammoniums.
By the Powdered crystal of the above-mentioned phosphoric acid salt-phosphite complex fertilizer making, the packing bag with having damp proof, choke, lucifuge function, under relative humidity (RH) 40% ~ 50% condition, packs with powder automatic packing machine.
By adjusting the formula rate of phosphorous acid and Tripotassium phosphate, can make phosphorus, the potassium binary compound fertilizer of pH value 4.5 ~ 8.5.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. a method for solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, is characterized in that: the screening and requirement, formula rate and the process for solid phase synthesis that comprise raw material; Described process for solid phase synthesis is divided into the pre-treatment of raw material, solid-state soda acid neutralization reaction, powder machinery force-chemical reaction and functional complex fertilizer product packing, its preparation method be by the solid phosphorous acid of the solid phosphate of crystal state and crystal state mixing, produce the reaction of solid phase acid-base neutralisation in kneading process and under the high energy mechanical power effect of speed lapping and bringing out, produce solid state reaction, directly generate the phosphoric acid salt-phosphite complex fertilizer of solid phase; The concrete steps of the phosphoric acid salt-phosphite complex fertilizer of described solid phase synthesis are as follows:
(1) phosphoric acid salt-phosphite complex fertilizer of described solid phase synthesis is a kind of nitrogen, phosphorus, potassium Nitrogen, Phosphorus and Potassium with antibiotic disease-proof functions, by potassium primary phosphate, primary ammonium phosphate, potassium dihydrogen phosphite, dihydrogen phosphite ammonium, is compound composition of main and part dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, the hydrogen phosphite Powdered crystal of two ammoniums;
(2) solid phosphate that the raw material of the phosphoric acid salt-phosphite complex fertilizer of described solid phase synthesis is crystal state and the solid phosphorous acid of crystal state, the solid phosphate of crystal state is that the solid phosphorous acid of crystal state is the xln without the phosphorous acid of moisture absorption deliquescence without moisture absorption deliquescence, without the dipotassium hydrogen phosphate of crystal water, the xln of Secondary ammonium phosphate;
(3) formula rate of the nitrogen in described solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, phosphorus, potassium Nitrogen, Phosphorus and Potassium: be that phosphorous acid by dipotassium hydrogen phosphate, Secondary ammonium phosphate and the above-mentioned specification of quality of above-mentioned specification of quality is by the weight ratio proportioning of 1.0 ~ 1.5:0.8 ~ 1.3:1.0, wherein dipotassium hydrogen phosphate, Secondary ammonium phosphate raw material must be through pre-treatment, dipotassium hydrogen phosphate, Secondary ammonium phosphate are pre-mixed in proportion and under the condition of relative humidity 20% ~ 30%, with shredder, grind to form 80 ~ 100 object mixed powders, more in proportion with the assembly of phosphorous acid crystal;
(4) the solid-state soda acid neutralization reaction in the synthesis technique of described solid phase synthesis phosphoric acid salt-phosphite complex fertilizer: the dipotassium hydrogen phosphate that is pre-mixed grinding by above-mentioned formula rate requirement, the phosphorous acid powder that Secondary ammonium phosphate powder grinds in advance by above-mentioned formula and above-mentioned formula rate requirement is under the condition of relative humidity 20% ~ 30%, in the kneader of the speed of mainshaft 20 ~ 80r/min, first mix, then in kneader, mediate 15min ~ 30min, mixing, the phosphorous acid of kneading process middle strong acidity and weakly alkaline dipotassium hydrogen phosphate, Secondary ammonium phosphate produces violent solid phase acid-base neutralisation reaction, most material reaction generates respectively relative potassium primary phosphate, primary ammonium phosphate and potassium dihydrogen phosphite, dihydrogen phosphite ammonium, the a large amount of heat energy that discharge in reaction process, make the mutual melting of the unreacted material of reacted material and part, wrap up mutually, in kneading process, form granular mixture,
(5) the powder machinery force-chemical reaction in the synthesis technique of described solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, by the solid state reaction bringing out under mechanical force: the powder-mixed material that above-mentioned acid-base neutralisation is produced, under the condition of relative humidity 30% ~ 40%, with the high-speed grinder of 20000 ~ 25000r/min, grind 5min ~ 15min, by mutual melting, the granular mixture abrasive lapping of parcel becomes fine powder, and adjust running mechanical force effect and bring out under make the unreacted dipotassium hydrogen phosphate of part, Secondary ammonium phosphate and phosphorous acid produce solid state reaction, material is all generated with potassium primary phosphate, primary ammonium phosphate and potassium dihydrogen phosphite, dihydrogen phosphite ammonium is main, contain part dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, the Powdered crystal composition phosphoric acid salt-phosphite complex fertilizer of hydrogen phosphite two ammoniums,
(6) packing of the functional nitrogen phosphorus potassium tri compound fertilizer product that the synthesis technique of described solid phase synthesis phosphoric acid salt-phosphite complex fertilizer makes: by make with potassium primary phosphate, primary ammonium phosphate and potassium dihydrogen phosphite, dihydrogen phosphite ammonium is main, contain part dipotassium hydrogen phosphate, Secondary ammonium phosphate, potassium phosphite, the functional nitrogen of the Powdered crystal composition of hydrogen phosphite two ammoniums, phosphorus, potassium Nitrogen, Phosphorus and Potassium, with thering is protection against the tide, choke, the packing bag of lucifuge function, under the condition of relative humidity 40% ~ 50%, with powder automatic packing machine, pack.
2. the method for a kind of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer according to claim 1, it is characterized in that: by changing the formula combination of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, select separately without moisture absorption deliquescence, the weight ratio proportioning of pressing 2.3 ~ 2.8:1.0 without dipotassium hydrogen phosphate and the phosphorous acid of crystal water, apply the method for above-mentioned solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, direct synthetic solid phase by potassium primary phosphate, potassium dihydrogen phosphite is main, contain part dipotassium hydrogen phosphate, the functional phosphorus that potassium phosphite forms, potassium binary compound fertilizer.
3. the method for a kind of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer according to claim 1, it is characterized in that: by changing the formula combination of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer and the phosphatic material combination of passing through to change alkalescence, select separately without the Secondary ammonium phosphate of moisture absorption deliquescence and phosphorous acid by the weight ratio proportioning of 1.5 ~ 2.0:1.0, apply the method for above-mentioned solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, direct synthetic solid phase by primary ammonium phosphate, dihydrogen phosphite ammonium is main, contain part Secondary ammonium phosphate, the functional phosphorus that hydrogen phosphite two ammoniums form, nitrogen binary compound fertilizer.
4. the method for a kind of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer according to claim 1, it is characterized in that: by changing raw material variety and the formula combination of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, with alkaline without moisture absorption deliquescence, Tripotassium phosphate without crystal water substitutes weakly alkaline without moisture absorption deliquescence, the weight ratio proportioning of pressing 1.3 ~ 1.8:1.0 without dipotassium hydrogen phosphate and the phosphorous acid of crystal water, apply the method for above-mentioned solid phase synthesis phosphoric acid salt-phosphite complex fertilizer, direct synthetic solid phase by potassium primary phosphate, potassium dihydrogen phosphite is main, contain part dipotassium hydrogen phosphate, the functional phosphorus that potassium phosphite forms, potassium binary compound fertilizer.
5. according to claim 1, 2, 3, the method of a kind of solid phase synthesis phosphoric acid salt-phosphite complex fertilizer described in 4, it is characterized in that: by adjusting dipotassium hydrogen phosphate, Secondary ammonium phosphate, the formula rate of Tripotassium phosphate and phosphorous acid, produce pH value and be phosphoric acid salt-phosphite complex fertilizer of 4.5 ~ 8.5, in acid soil, use the phosphoric acid salt-phosphite complex fertilizer of meta-alkalescence, in alkaline soil, use the phosphoric acid salt-phosphite complex fertilizer of slant acidity, the suitable foliage fertilizer as spraying corps leaf surface of neutral phosphoric acid salt-phosphite complex fertilizer, or as rushing the fertilising of rushing of executing crop root part.
6. according to claim 1, 2, 3, phosphoric acid salt-the phosphite complex fertilizer of a kind of solid phase synthesis described in 4, it is characterized in that: in solid phase synthesis process, generate potassium primary phosphate, primary ammonium phosphate and potassium dihydrogen phosphite, the mutual melting of dihydrogen phosphite ammonium, wrap up mutually, due to potassium primary phosphate, primary ammonium phosphate is stable in the air, be difficult for deliquescence, potassium dihydrogen phosphite, dihydrogen phosphite ammonium is at potassium primary phosphate, under the absorption of primary ammonium phosphate is protected with parcel, air and potassium dihydrogen phosphite have been intercepted, hydrogen phosphite two ammoniums directly contact, improved stability, overcome easy deliquescence, oxidizable defect, make phosphite be difficult for oxidized generation phosphoric acid salt and lose the activity of antibiotic diseases prevention, for condition has been created in the application of phosphoric acid salt-phosphite complex fertilizer:
(1) phosphoric acid salt-phosphite complex fertilizer, can directly use as multi-Functional Fertilizers;
(2) phosphoric acid salt-phosphite complex fertilizer, can be used as antibiotic diseases prevention medicament, respectively with vitriolate of tartar, Repone K, potassium primary phosphate, ammonium sulfate, ammonium chloride, bicarbonate of ammonia, primary ammonium phosphate, the composite composition function fertilizer of urea traditional chemical fertilizer;
(3) phosphoric acid salt-phosphite complex fertilizer, can be used as antibiotic diseases prevention medicament, respectively with seaweeds fertilizer, humic-acid kind fertilizer, camellia seed meal fertilizer, amino acids fertilizer, plant vinegar composite salt fertilizer and oligosaccharide kind biologically active substance compounded combination;
(4) phosphoric acid salt-phosphite complex fertilizer, avoids combining containing inorganic salt fertilizer, the organic fertilizer of oxidisability matrix with saltpetre, ammonium nitrate, nitro humic acid class.
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| CN106018302A (en) * | 2016-07-04 | 2016-10-12 | 云南农业大学 | Application of asparagus lettuce in qualitative and quantitative detection of rhizoctonia toxins |
| CN106672929A (en) * | 2017-01-17 | 2017-05-17 | 成都乐氏化工工程有限公司 | Method for preparing potassium dihydrogen phosphite |
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| CN115197181A (en) * | 2022-07-01 | 2022-10-18 | 中国石油化工股份有限公司 | Method for synthesizing alkali metal furoate by solid phase method |
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| CN104529644A (en) * | 2014-12-31 | 2015-04-22 | 广东福利龙复合肥有限公司 | Water soluble fertilizer with function of preventing and treating citrus dieback and preparing method thereof |
| CN106018302A (en) * | 2016-07-04 | 2016-10-12 | 云南农业大学 | Application of asparagus lettuce in qualitative and quantitative detection of rhizoctonia toxins |
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Effective date of registration: 20190329 Address after: 350108 Room 408, 10 A Building, Haixi Park, Fuzhou High-tech Zone, Fujian Province Patentee after: Fuzhou Junding Biotechnology Co.,Ltd. Address before: 350008 Room 406, Building 10, 4th District, 156 West Second Ring North Road, Gulou District, Fuzhou City, Fujian Province Patentee before: Weng Yingbing |
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Correction item: Patentee|Address Correct: Fuzhou Junding Biotechnology Co.,Ltd.|350108 Room 408, 10 A Building, Haixi Park, Fuzhou High-tech Zone, Fujian Province False: Fuzhou Junding Biotechnology Co.,Ltd.|350108 Room 408, 10 A Building, Haixi Park, Fuzhou High-tech Zone, Fujian Province Number: 16-02 Volume: 35 |
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