CN1693292A - Liquid furtilizer containing humic acid multi nutritive element and mfg. method thereof - Google Patents
Liquid furtilizer containing humic acid multi nutritive element and mfg. method thereof Download PDFInfo
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- CN1693292A CN1693292A CN 200510046149 CN200510046149A CN1693292A CN 1693292 A CN1693292 A CN 1693292A CN 200510046149 CN200510046149 CN 200510046149 CN 200510046149 A CN200510046149 A CN 200510046149A CN 1693292 A CN1693292 A CN 1693292A
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Abstract
A multi-nutrient liquid fertilizer with high and durably fertility is proportionally prepared from ammonium humate, potassium humate, phosphorus humate, N-P-K humate, trace elements, sulfite as activator (or alkali or alkali-metal carbonate) and chitin solution. Its preparing process is also disclosed.
Description
Technical field
The invention belongs to the technical field of organic fertilizer, be specifically related to a kind of liquid furtilizer containing humic acid multi nutritive element and manufacture method thereof.
Background technology
Chemical fertilizer (abbreviation chemical fertilizer) can be divided into mineral manure and organic fertilizer two classes from composition; On form, then can be divided into solid fertilizer and liquid fertilizer two classes.Chemical fertilizer plays significant effect to improving crop yield, is the indispensable production factors of modern agriculture.People's life-time service inorganic fertilizer, its negative influence are that soil fertility is seriously reduced, and even, have both destroyed the acid base equilibrium of soil, have caused the appearance of problems such as soil compaction, salt moraineization; Make again that nitrate content exceeds standard quality variation in the agricultural-food.In this case, people attempt to replace inorganic fertilizer to produce non-polluted farm product with fertilizer (mainly being traditional farm manure).Really fertilizer has increasing soil fertility, improves advantages such as crop quality.But the shortcoming of fertilizer is that fertilizer efficiency is slow, the output of farm crop improves not quite, if want to improve the amount of application that output just must roll up fertilizer.And, can not satisfy the demand of modern agricultural development far away because organic manure resource is limited.
Humic acid fertilizer has remedied the deficiency of inorganic fertilizer and fertilizer preferably with its advantage, because humic acids is a kind of natural organic high molecular compound, it contains elements such as carbon, hydrogen, oxygen, nitrogen, aromatic proton, hydroxyl, carboxyl, carbonyl, quinonyl, methoxyl group isoreactivity group.These active groups have determined humic acids to have slightly acidic, wetting ability, ion exchangeable, complexing, oxidation-reduction quality and physiologically active etc., have concurrently to improve the soil and stimulate the crop growth dual function.And humic acid liquid fertilizer is compared with solid fertilizer, have more fertilizer efficiency fast, balanced in nutrition, use advantages such as easy.Therefore along with the Sustainable development of modern agriculture, the industrial scale of humic acid liquid fertilizer constantly enlarges, and its application is also increasingly extensive.The present brand of humic acid liquid fertilizer is a lot, and especially after China joined WTO, a large amount of humic acid liquid fertilizers pour in China market.There are the following problems but this class fertilizer of import is many: first cost height, price are expensive, are difficult to produce at a low price that the client of agricultural-food accepts; It two is that the concentration of nutritive ingredient is low, comparatively speaking, has just increased packing and trucking costs.
Summary of the invention
Purpose of the present invention is intended to seek a kind of better nutritivity concentration, production cost is low, nuisanceless, product are of fine quality, output is high humic acid liquid fertilizer.This product can supply all kinds farm crop: vegetables, fruit tree, flowers and plants, cereal and cash crop etc., and for the use of protecting various plantation modes such as ground, open country and soilless culture.
The invention provides a kind of liquid furtilizer containing humic acid multi nutritive element; it comprises ammonium humate; potassium humate; phosphorus humic acid phosphorus; humic acid nitrogen phosphorus potassium and various trace elements etc.; it is characterized in that being added with in addition activator sulphite; alkali or alkaline carbonate and Synergist S-421 95 deacetylation chitin (claiming soluble chitin again); the effective constituent of this fertilizer percentage ratio by weight is calculated as: humic acids 4～16; available nitrogen 5～14; available phosphorus 2～5; effective potassium 3～6; trace element zinc 0.02～0.35; manganese 0.04～0.70, copper 0～0.6, iron 0～0.7; molybdenum 0.02～0.35, deacetylation chitin 0.01～0.5.
Adding sulphite in the liquid furtilizer containing humic acid multi nutritive element is that the activator of doing humic acids uses, and it can be a S-WAT, also can be potassium sulfite or ammonium sulphite; In addition, activator also can be used alkali and alkaline carbonate, and said here alkali can be sodium hydroxide, also can be potassium hydroxide; Alkaline carbonate then can be yellow soda ash or salt of wormwood, increases the chelating constant and the solubleness of humic acids by the interaction energy of they and humic acids.
Chitin (Chitin) this as the translucent solid of white, water insoluble, ethanol and ether.It is a class polysaccharide, be by many N-acetylglucosamines with β-1, the chain-like macromolecule compound that the 4-glycosidic bond is formed by connecting, its structure is as follows:
But deacetylate after chitin and dense NaOH effect and generate chitosan (Chitosan).Chitosan is the superpolymer of glucosamine, dissolves in 2% the acetum, is called deacetylation chitin or soluble chitin again.Add the Synergist S-421 95 soluble chitin and be the synergy of utilizing it and humic acids, can increase drought-resistant moisture-preserving ability of crop and the anti-adversity ability of crop, in the effect that can also play antibacterial strong sprout in early days of plant growth.
The present invention also provides a kind of method of making above-mentioned liquid furtilizer containing humic acid multi nutritive element, it is characterized in that it is made of three process:
(1) makes the humic acids clear liquid
Calculate raw material (granularity is at 60～120 orders), NaOH, (or KOH, the Na that will be rich in humic acids by weight percentage
2CO
3, K
2CO
3); Sulphite; Urea drops in the stirring tank in 1: 0.05～0.1: 0.1～0.3: 1～3 ratio, adds the water that is equivalent to 5～20 times of humic acid materials again and reacts under 80～100 ℃ condition 1.5～5 hours, removes solid impurity through precipitation, centrifugation.
(2) make soluble chitin
Chitin is dropped in the sodium hydroxide solution of 40wt%, be incubated 1～24 hour down at 60～140 ℃, reaction generates the deacetylation chitin, and it is dissolved in the CH of 2wt%
3In the COOH solution;
(3) make many nutritive liqs of humic acids fertilizer
With humic acids clear liquid weight is that 100Kg calculates, and various raw material powder inputs are filled in the reactor of humic acids clear liquid:
Ammonium hydrogen phosphate 3～20.0Kg copper sulfate 0～1.5Kg
Potassium hydrogen phosphate 0～19.0Kg ferrous sulfate 0～2.0Kg
Sylvite 4～18Kg molybdate 0.05～0.5Kg
Manganous sulfate 0.1～2.0Kg boric acid 0.1～0.2Kg
Zinc sulfate 0.1～2.0Kg soluble chitin acetum 500～2000ml
The reactor working temperature is 15～50 ℃, when various raw material powders after stirring abundant dissolving, with acid or alkali solution being transferred to pH value again is 6～7.5.
In the above-mentioned various raw material, the raw material that is rich in humic acids can be weathered coal, brown coal or the peat composed of rotten mosses.And sylvite can be vitriolate of tartar or Repone K, and molybdate can be potassium molybdate or ammonium molybdate, and boric acid also can be Sodium Tetraborate (being borax).And adjust the used acid of fertilizer pH value can be phosphoric acid or sulfuric acid, and used alkali can be potassium hydroxide or sodium hydroxide.
Liquid furtilizer containing humic acid multi nutritive element provided by the present invention has following characteristics in use:
(1) make full use of fuel value lower, but be rich in the weathered coal brown coal of humic acids and careless carbon etc. and make raw material, activated, be used as liquid fertilizer after extracting, be that " utilization of waste material " can create great economic worth again;
(2) nutritive value is abundant, not only is rich in the three elements of nitrogen, phosphorus, potassium crop growth, and has been rich in trace elements such as zinc, manganese, iron, copper, and fertilizer efficiency was both high, and existing quick-acting has certain slow release long-acting again, and its fertilizer efficiency has the advantage of two-ways regulation;
(3) because it is a kind of liquid fertilizer that does not precipitate and do not coagulate wadding, is particularly suitable for drip irrigation and sprayer apparatus and uses;
(4) owing to added soluble chitin, can not only improve fertilizer efficiency and also make fertilizer have the special efficacy in antibacterial strong sprout, make crop have drought resisting preferably and degeneration-resistant ability.
Embodiment
Below in conjunction with embodiment content of the present invention is further described and replenishes.Draw materials because the source of humic acids mostly is nearby, can use weathered coal, brown coal; The peat composed of rotten mosses of also available northeast blackland, the content of its humic acids can be slightly variant, but this can't influence the quality of product of the present invention, and this can regulate by urea and other raw material in implementation process.
Embodiment 1
With Huo Lin river weathered coal is that raw material is made liquid furtilizer containing humic acid multi nutritive element, is undertaken by following operation;
(1) makes the humic acids clear liquid
Get Huo Lin river weathered coal (humic acids content＞50%), grinding particle size weighs 10Kg more than 60 orders; KOH1.2Kg, urea 30Kg, potassium sulfite 0.4Kg, water 100Kg drops in the stirring tank, and temperature is controlled at 100 ± 5 ℃, reacts 3 hours.Through the centrifugation formula or through natural sedimentation in 20 hours, supernatant liquid is transferred in the reactor then.
(2) make soluble chitin
The translucent powder 1000 of chitin white is restrained in the NaOH solution of the 40wt% that drops into 20Kg, stir insulation 24 hours at 60 ℃, solution is little yellow, adds the CH of 2wt% again
3COOH makes soluble chitin (being chitin) solution.
(3) make many nutritive liqs of humic acids fertilizer
In following ratio (weight ratio) various raw material powder inputs are filled in the reactor of humic acids clear liquid:
Ammonium hydrogen phosphate 10Kg boric acid 0.6Kg
Repone K 15Kg ferrous sulfate 0.5Kg
Zinc sulfate 0.4Kg ammonium molybdate 0.05Kg
Manganous sulfate 0.4Kg soluble chitin solution 1000ml
Copper sulfate 0.5Kg
Fully stir down in room temperature (20 ℃), until pH value=6.76 that the powder of all addings dissolves back mensuration solution fully, because the soda acid appropriateness needn't be allocated with soda acid again.
Percentage ratio calculating contains humic acids 16 by weight in the chemical examination aforesaid liquid, available nitrogen 10, available phosphorus 2, effective potassium 6, trace element zinc 0.35, manganese 0.4, copper 0.6, iron 0.7, molybdenum 0.02, boron 0.35, deacetylation chitin 0.5, water surplus.Quality meets predetermined standard.
Use on the brooder vegetables with these liquid fertilizers, respond well, not only volume increase obviously, and vegetables, pure taste when fruit is edible.
Embodiment 2
With brown coal is that raw material is implemented the present invention, and its technology is as follows:
(1) makes the humic acids clear liquid
The brown coal powder of humic acids content about 40% is broken to more than 100 orders heavy 15Kg; NaOH (or Na
2CO
3) 1.0Kg, urea 45Kg, S-WAT 0.2Kg at 80 ℃, reacted 5 hours in the water 180Kg input stirring tank.Through precipitation, solid impurity or insolubles are removed in centrifugation, and its clear liquid is transferred in the reactor.
(2) make soluble chitin
500 gram chitin powder are dropped in the NaOH solution of 40wt% of 20Kg,, obtain the CH that tawny liquid is put into 2wt% again 140 ℃ of thermotonuses 1 hour
3Standby in the COOH solution.
(3) make liquid furtilizer containing humic acid multi nutritive element
With the humic acids clear liquid is that 100Kg calculates, and adds following various raw materials:
Ammonium hydrogen phosphate 5Kg copper sulfate 0.2Kg
Potassium hydrogen phosphate 5Kg ferrous sulfate 0.1Kg
Vitriolate of tartar 10Kg ammonium molybdate 0.5Kg
Zinc sulfate 0.1Kg borax 0.1Kg
Manganous sulfate 0.1Kg Chitosan solution 1000ml
Fully stir at 50 ℃, to survey pH value be 8 in the dissolving back fully, and being adjusted to pH value with phosphoric acid is 7.5.
Finished product is after chemical examination, and percentage ratio calculates and contains humic acids 8 by weight, available nitrogen 5, available phosphorus 5, effective potassium 6, trace element zinc 0.02, manganese 0.04, copper 0.2, iron 0.12, molybdenum 0.35, boron 0.02, deacetylation chitin 0.01, water surplus.Up-to-standard.
Embodiment 3
With the peat composed of rotten mosses that contains humic acids 30wt% is raw material, owing to can use after the more pulverizing earlier of the peat composed of rotten mosses impurity impurity elimination.
(1) makes the humic acids clear liquid
The peat composed of rotten mosses that contains humic acids about 30% after the impurity elimination is crushed to 120 orders, heavy 25Kg; Na
2CO
32Kg, (NH4
)SO
33Kg, urea 75Kg add the water of 300Kg and together knock down in the stirring tank, and reaction is 4 hours under 90 ℃ temperature, transfer in the reactor through precipitating 24 hours with portion's clear liquid and extracting out.
(2) make soluble chitin
Chitin powder 500 is restrained in the NaOH solution of the 40wt% that throws 8Kg, reacted 3 hours down at 100 ℃, it is standby in the acetum of the 2wt% that wherein adds 22Kg again to obtain light yellow liquid.
(3) make liquid furtilizer containing humic acid multi nutritive element
With the humic acids clear liquid is that 100Kg calculates, and adds following various raw materials:
Ammonium hydrogen phosphate 15Kg ferrous phosphate 0.01Kg
Vitriolate of tartar 4Kg ammonium molybdate 0.3Kg
Zinc sulfate 0.1Kg borax 0.5Kg
Manganous sulfate 0.8Kg Chitosan solution 800ml
The reactor working temperature is 40 ℃, when various raw material powders through after stirring dissolving fully, surveying pH value and be 5 is 6 through be transferred to PH with potassium hydroxide or sodium hydroxide.
Behind chemical analysis, confirm that in aforesaid liquid fertilizer percentage ratio calculates and contains humic acids 4 by weight, available nitrogen 14, available phosphorus 3, effective potassium 3, zinc 0.02, manganese 0.70, iron 0.01, molybdenum 0.21, copper does not detect, Chitosan0.25, water surplus.Its quality also meets preassigned.
Embodiment 4
With weathered coal is raw material, and condition is close with embodiment 1 basically.
(1) makes the humic acids clear liquid
Weathered coal is ground into 100 orders, heavy 10Kg; With its same K
2CO
30.8Kg, Na
2SO
31Kg, the also common stirring tank that drops in the water of urea 30Kg adding 200Kg.Reaction is 1.5 hours under 100 ℃ of conditions, removes solid impurity through precipitation, centrifugation and obtains clear liquid.
(2) make soluble chitin
Chitin powder 800 is restrained in the NaOH solution of the 40wt% that drops into 10Kg,, obtain soluble chitin (Chitosan), add the CH of 2wt% again 80 ℃ of insulations 10 hours
3Standby in the COOH solution.
(3) make liquid furtilizer containing humic acid multi nutritive element
With humic acids clear liquid weight is that 100Kg calculates, and various raw material powder inputs are filled in the reactor of humic acids clear liquid:
Ammonium hydrogen phosphate 8Kg copper sulfate 0.1Kg
Potassium hydrogen phosphate 5Kg potassium molybdate 0.5Kg
Vitriolate of tartar 10Kg boric acid 0.5Kg
Zinc sulfate 0.2Kg Chitosan solution 800ml
Manganous sulfate 0.5Kg
The reaction working temperature is 40 ℃, surveys pH value when various raw material powders after stirring fully dissolving, and pH value is 8.5 as a result, can make liquid fertilizer through transfer to 7 with dilute sulphuric acid.
The product of present embodiment is through chemical examination, draw its effective constituent by weight percentage ratio be calculated as: humic acids 10, available nitrogen 8, available phosphorus 5, effective potassium 5, trace element zinc 0.2, manganese 0.50, copper 0.01, molybdenum 0.35, boron 0.10, deacetylation chitin 0.2, up-to-standard.
Also can enumerate more embodiment.Must be noted that when using liquid fertilizer of the present invention, look local chemical ingredients in the soil and the composition and the content of definite trace element, and correspondingly in above-mentioned three-procedure, adjust various proportion of raw materials.
The exploitation of liquid furtilizer containing humic acid multi nutritive element of the present invention is not only and is turned waste into wealth, and can increase soil fertility significantly after product of the present invention and the application of manufacture method large-scale popularization, makes the farm crop branches and leaves healthy and strong, high-output stress-resistance, and output improves.V
CIncrease with nutrition such as sugars, improved the quality of agricultural-food.Life-time service product of the present invention can also play the effect that activates and improve the soil, protect agroecological environment, so can create good social benefit and economic benefit.
Claims (9)
1. liquid furtilizer containing humic acid multi nutritive element; it includes ammonium humate; potassium humate; phosphorus humic acid phosphorus; compositions such as humic acid nitrogen phosphorus potassium and various trace elements; it is characterized in that being added with in addition activator sulphite; alkali or alkaline carbonate also add Synergist S-421 95 soluble chitin solution; the effective constituent of this fertilizer percentage ratio by weight is calculated as: humic acids 4～16; available nitrogen 5～14; available phosphorus 2～5; effective potassium 3～6; trace element zinc 0.02～0.35, manganese 0.04～0.70, copper 0～0.6; iron 0～0.7; molybdenum 0.02～0.35, boron 0.02～0.35, deacetylation chitin 0.01～0.5.
2,, it is characterized in that said activator sulphite can be potassium sulfite, also can be S-WAT or ammonium sulphite by the described liquid furtilizer containing humic acid multi nutritive element of claim 1.
3, by the described liquid furtilizer containing humic acid multi nutritive element of claim 1, the alkali that it is characterized in that said activator is sodium hydroxide or potassium hydroxide; Alkali carbonate can be yellow soda ash or salt of wormwood.
4, a kind of manufacture method by the described liquid furtilizer containing humic acid multi nutritive element of claim 1 is characterized in that it is made of following three-procedure:
(1) makes the humic acids clear liquid
The raw material powder that is rich in humic acids is broken into 60～120 purpose powder, with its same NaOH, (or KOH, Na
2CO
3, K
2CO
3); K
2SO
3(or Na
2SO
3(NH
4)
2SO
3); Urea drops in the stirring tank in 1: 0.05～0.1: 0.1～0.3: 1～3 ratio, add the water be equivalent to 5～20 times of humic acid materials again and under 80～100 ℃ condition, reacted 1.5～5 hours, through precipitation, centrifugation remove solid impurity or insolubles clear liquid;
(2) make soluble chitin
Chitin is dropped in the NaOH solution of 40wt%, be incubated 1～24 hour down at 60～140 ℃, reaction generates the deacetylation chitin, and it is dissolved in the CH of 2wt%
3In the COOH solution;
(3) make liquid furtilizer containing humic acid multi nutritive element
Calculate with humic acids clear liquid 100Kg, following various raw material powder inputs filled in the reactor of humic acids clear liquid:
Ammonium hydrogen phosphate 3～20.0Kg copper sulfate 0～1.5Kg
Potassium hydrogen phosphate 0～19.0Kg ferrous sulfate 0～2.0Kg
Sylvite 4～18Kg molybdate 0.05～0.5Kg
Manganous sulfate 0.1～2.0Kg boric acid 0.1～0.2Kg
Zinc sulfate 0.1～2.0Kg soluble chitin acetum 500～2000ml
The reactor working temperature is 15～50 ℃, when various raw material powders after stirring abundant dissolving, with acid or alkali solution being transferred to pH value again is 6～7.5.
5, by the described liquid furtilizer containing humic acid multi nutritive element manufacture method of claim 4, it is characterized in that the said raw material that is rich in humic acids can be weathered coal, brown coal or the peat composed of rotten mosses.
6, by the described liquid furtilizer containing humic acid multi nutritive element manufacture method of claim 4, it is characterized in that sylvite can be vitriolate of tartar in the raw material of said manufacturing liquid furtilizer containing humic acid multi nutritive element, also can be Repone K.
7, by the described liquid furtilizer containing humic acid multi nutritive element manufacture method of claim 4, it is characterized in that molybdate can be an ammonium molybdate in the raw material of said manufacturing liquid furtilizer containing humic acid multi nutritive element, also can be potassium molybdate.
8, by the described liquid furtilizer containing humic acid multi nutritive element manufacture method of claim 4, the acid that it is characterized in that the adjusting pH value of said manufacturing liquid furtilizer containing humic acid multi nutritive element can be phosphoric acid, also can be sulfuric acid.
9, by the described liquid furtilizer containing humic acid multi nutritive element manufacture method of claim 4, the alkali that it is characterized in that the adjusting pH value of said manufacturing liquid furtilizer containing humic acid multi nutritive element can be sodium hydroxide; Also can be potassium hydroxide.
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