CN1169976A - High concentrative non-flocculant humic acids complexed nutrient liquid and preparation thereof - Google Patents
High concentrative non-flocculant humic acids complexed nutrient liquid and preparation thereof Download PDFInfo
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- CN1169976A CN1169976A CN96108849A CN96108849A CN1169976A CN 1169976 A CN1169976 A CN 1169976A CN 96108849 A CN96108849 A CN 96108849A CN 96108849 A CN96108849 A CN 96108849A CN 1169976 A CN1169976 A CN 1169976A
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- humic acids
- humic
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- coal
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
- C05G5/23—Solutions
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- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
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Abstract
A high-concentration non-floccular nutritive liquor of humic acid complex contains such active components (wt%) as humic acid and/or xanthohunic acid (5-12), N (6-10), P2O5 (5-8), K2O (5-10), S (1-3) and trace elements including B, Mn, Mg, Cu, Fe, Zn an Mo (0.5-3.5). The total content of the effective components is 25.5-46.5%. The content of nutrients is 17.5-34.5%. The density and pH value of raw liquor are 12-1.3 g/ml and 6-7. The nutritive liquor has obvious bioactivity and effect on increasing the yield of crops.
Description
The invention belongs to liquid fertilizer, be specifically related to a kind of humic acids complexed nutrient liquid.
The patent documentation and the report of relevant humic acid liquid fertilizer (or claiming nutritive medium) are a lot, the commodity of formation that wherein have come into the market, but all there is following defective in the said products: (1) stoste is placed and was just occurred precipitation in several days, that have even all condense into piece, occur a large amount of throw outs during use behind the dilute with water again, greatly reduce action effect; (2) nutrient solution concentration is low excessively, owing to there is the defective of precipitation and flocculation, humic acid activity is low, and lyotropy and complexing are also limited, so the total nutritive ingredient of nutritive medium all is no more than 12%; (3) potential of hydrogen too high (pH>12) or low excessively (pH<2) are not all in the best use range (pH0~7) of farm crop.For solving above-mentioned drawback, the researchist has made extensive work.US 3,770, and 411 disclose a kind of method that adopts superfine grinding feed coal and the way of adjusting the pH value to make colloidal solution or suspension.Ep164,908 provide a kind of gluconic acid sodium salt that adds with the solvability of the liquid that has additional nutrients and the method for complexing.In enclose that patent application CN 103471A proposes be a kind of commodity by name " the blade face treasured ... nutritive medium; for preventing the nutritive medium precipitation; remove humic acids concentration is strengthened (reaching more than 30%); also add molasses increasing the solution denseness, and add complexing ratio and the dispersion stabilization with the raising metallic element such as complexing agent EDTA and tensio-active agent, emulsifying agent.Though aforesaid method helps to reduce precipitation or flocculation, has increased non-nutritive ingredient in nutritive medium, cause production cost to increase, active principle reduces.
The humic acids complexed nutrient liquid that the purpose of this invention is to provide a kind of high reactivity, high density, do not flocculate, production cost is lower, and the preparation method of this nutritive medium is provided.
The effective constituent of the humic acids complexed nutrient liquid that do not flocculate of the present invention is formed (weight percent):
Humic acids and (or) xanthohumic acid 5-12 N 6-10
P
2O
5 5-8 K
2O 5-10
S 1-3
Trace element B, Mn, Mg, Cu, Fe, Zn, Mo total amount 0.5-3.5%,
Total effective constituent reaches 25.5-46.5%, nutritive element content 17.5-34.5%, and stoste density is 1.2-1.3g/ml, the pH value is 6-7.
Prepare the required organic active component-humic acids of this nutritive medium and (comprise xanthohumic acid, raw material down together) is the cheap low-grade coal that nature extensively distributes, can be peat, brown coal, weathered coal, also can adopt artificial oxidation's regeneration humic acid material, its humic acids content be preferably more than 40%.
The preparation of this nutritive medium is carried out as follows:
(1) hydrolysis of humic acids, sulfonation and extraction: will be crushed to-40 orders to-80 purpose feed coals, water, alkali, sulphonating agent by 1: 5~10: 0.08~0.2: 0.05~0.15 mixed, slowly be warming up to 90~120 ℃, under this temperature, carry out humic acids simultaneously hydrolysis, sulfonation reaction and extraction 1-3 hour;
(2) solid-liquid separation: with the cooling of above-mentioned reactant, sedimentation 24-36 hour, centrifugal deslagging;
(3) complexing of nutritive element and dissolving: clarifying humic acid solution is imported complex reactor, add each nutrition component (weight percent of humic acid solution) in following ratio:
Urea 10-20 ammonium nitrate 9-20
Vitriolate of tartar 6-12 potassium primary phosphate 8-15
Borax 2-5 zinc sulfate 1-3
Manganous sulfate 1-3 ferrous sulfate 1-3
Sal epsom 0-3 copper sulfate 0-2
Ammonium molybdate 0-05 is after room temperature or about 50 ℃ abundant stirring and dissolving, with acid or adjusting PH with base to 6~7.
Described alkali can be NaOH, Na
2CO
3, KOH.
Described sulphonating agent can be NaHSO
3, Na
2SO
3, Na
2S
2O
5
Compared with the prior art the present invention has following advantage:
(1) in alkaline media simultaneously to humic acids be hydrolyzed, sulfonation and extraction, gained humic acids productive rate height, particularly owing to hydrolysis, sulfonation, a large amount of acidic groups have been increased because of (free carboxy and sulfo group), the biological activity and the wetting ability of humic acids are improved, to complexing, the sequestering power enhancing of each metal ion species.
(2) need not add any thickening material, tensio-active agent and other complex compound.The made sulfonated humic acid of present method itself is exactly a kind of good complexing agent and tensio-active agent, can form stable complexing (chelating) or organic bridged bond with metallic cation and organic ion, its solvability is increased, the stoste long storage can not precipitate or lump, even adopt during use the water dilution of high rigidity not produce flocculation for thousands of times yet.
(3) nutrient composition content height adds humic acids organic active component, and total effective constituent can reach 46.5%, and still has the dissolving potentiality.This nutritive medium can suitably be adjusted the element proportioning according to Different Crop and natural condition, makes the tailored version liquid fertilizer.
(4) solution is neutral meta-acid, is in crop optimal adaptation scope.
(5) active and fertilizer efficiency height, benefit is obvious.This nutritive medium has physiological effect concurrently and the full nutrition double effects is provided, and is applicable to various farm crop, particularly vegetables, fruit tree foliage-spray or seed soaking.Field test proves that every mu sprays about this nutritive medium 100ml at every turn, various crop yield 10-45%, input-output value ratio reach 1: 15~and 40.
Embodiment 1
In reactor, will be crushed to-60 purpose brown coal powders (containing humic acids 68.52%, xanthohumic acid 2.51%) 200Kg, caustic soda 24Kg, NaHSO
412Kg adds water 1000L, with being steam heated to 95 ℃, stirs reaction 3h down.Reactant is entered settling bowl, place 24h.Supernatant liquor is pumped into complex reactor, add ammonium nitrate 190Kg successively, urea 110Kg, potassium primary phosphate 188Kg, vitriolate of tartar 92Kg, borax 45Kg, zinc sulfate 10Kg, copper sulfate 9kg, ferrous sulfate 20Kg, manganous sulfate 15Kg, sal epsom 15kg, ammonium molybdate 1Kg, at room temperature fully stir, make whole dissolvings, transfer pH to 6.5, get the about 1795Kg of nutritive medium with sulfuric acid.This nutritive medium effective constituent (weight percent) is: humic acids 6.87, N 6.78, P
2O
55.60, K
2O 6.79, and S 1.85, and B 0.07, and Zn 0.13, and Cu 0.07, and Fe 0.23, Mu 0.02 Mg 0.02 Mo 0.03.With ZBG21005-87 and atomic absorption spectrometry check.
Embodiment 2
Get embodiment 1 humic acids intermediate liquid (not adding any nutritive element),, be used for the seed soaking test of four kinds of crops 1000 times of its dilute with waters.Taking out behind the seed soaking 24h does not have earth culture and educates, and gained the results are shown in Table 1.
Germination speed and percentage of germination (%) after the seed soaking of table 1 humic acid solution
As seen, after the humic acid solution seed soaking, germination speed of four kinds of crop seeds (a day) and percentage of germination (seven days records) are all compared according to (water logging kind) height, illustrate that humic acids has tangible biological activity.
Embodiment 3
With 500 times of embodiment 1 gained the finished product nutritive medium dilute with waters, under same soil property, same base fertilizer situation, carry out agricultural experiment.Spray 4-5 time in production phase, gained the results are shown in Table 2.
* sharp green pepper, cucumber are big boron (greenhouse) test, represent that with Kg/0.02 mu all the other are pot experiment, represent with the g/ basin.
Test-results shows, spray nutritive medium of the present invention after, various crop yields all significantly improve, generally than the high 20-45% of control group.Pea is a special case, and is too many because of working as annual rainfall, the soil humidity, and it is not enough that base fertilizer seems, and cause serious disease and pest, causes the underproduction.But behind the spray nutritious liquor, strengthened anti-adversity ability, made pea output improve 2 times.
The biological activity of embodiment 2,3 and farmland application test were undertaken by academy of agricultural sciences, Shanxi Province soil and fertilizer institute April nineteen ninety-five~November.
Claims (5)
1. humic acids complexed nutrient liquid that do not flocculate is characterized in that effective constituent consists of (weight percent): humic acids and (or) xanthohumic acid 5-12% N 6-10%
P
2O
5 5-8% K
2O 5-10%
S 1-3% trace element B, Mn, Mg, Cu, Fe, Zn, Mo total amount 0.5-3.5 stoste density are 1.2-1.3g/ml, pH value 6-7.
2. nutritive medium as claimed in claim 1 is characterized in that as the humic acids (comprising xanthohumic acid) stated can being peat, brown coal, weathered coal or artificial oxidation's coal from the cheap low-grade coal that nature extensively distributes, and its humic acids content is preferably more than 40%.
3. the preparation method of the described nutritive medium of claim 1 is characterized in that carrying out as follows:
(1) hydrolysis of humic acids, sulfonation and extraction: will be crushed to-40 orders to-80 purpose feed coals, water, alkali, sulphonating agent by 1: 5~10: 0.08~0.2: 0.05~0.15 mixed, slowly be warming up to 90~120 ℃, under this temperature, carry out humic acids simultaneously hydrolysis, sulfonation reaction and extraction 1-3 hour;
(2) solid-liquid separation: with the cooling of above-mentioned reactant, sedimentation 24-36 hour, centrifugal deslagging;
(3) complexing of nutritive element and dissolving: clarifying humic acid solution is imported complex reactor, add each nutrition component (weight percent of humic acid solution) in following ratio:
Urea 10-20 ammonium nitrate 9-20
Vitriolate of tartar 6-12 potassium primary phosphate 8-15
Borax 2-5 zinc sulfate 1-3
Manganous sulfate 1-3 ferrous sulfate 1-3
Sal epsom 0-3 copper sulfate 0-2
Ammonium molybdate 0-0.5 is after room temperature or about 50 ℃ abundant stirring and dissolving, with acid or adjusting PH with base to 6~7.
4. method as claimed in claim 3 is characterized in that described alkali can be NaOH, Na
2CO
3Or KOH.
5. method as claimed in claim 3 is characterized in that described sulphonating agent can be NaHSO
3, Na
2SO
3Or Na
2S
2O
5
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CN96108849A CN1060147C (en) | 1996-07-08 | 1996-07-08 | High concentrative non-flocculant humic acids complexed nutrient liquid and preparation thereof |
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CN96108849A CN1060147C (en) | 1996-07-08 | 1996-07-08 | High concentrative non-flocculant humic acids complexed nutrient liquid and preparation thereof |
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CN1169976A true CN1169976A (en) | 1998-01-14 |
CN1060147C CN1060147C (en) | 2001-01-03 |
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Cited By (20)
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EP0949221A1 (en) * | 1998-04-06 | 1999-10-13 | Holland Chemical International N.V. | Composition suitable as fertilizer containing sulphur as a polythionic acid compound or a salt thereof |
CN100347136C (en) * | 2006-08-07 | 2007-11-07 | 爱沃(北京)农业技术有限公司 | Microelement type composite foliage fertilizer and its preparation method |
CN101844952A (en) * | 2009-03-24 | 2010-09-29 | 甘肃省农业科学院植物保护研究所 | Formula and production method of humic acid liquid fertilizer |
CN102276300A (en) * | 2011-07-19 | 2011-12-14 | 库尔勒海荣工贸有限公司 | Full-value organic fertilizer for drop irrigation and preparation method thereof |
CN102276296A (en) * | 2011-07-19 | 2011-12-14 | 库尔勒海荣工贸有限公司 | Method for preparing water-soluble organic nitrogenous fertilizer |
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CN104446803A (en) * | 2014-12-08 | 2015-03-25 | 四川陶普唯农农化有限公司 | High-nitrogen type water-soluble fertilizer containing fulvic acid |
CN105175103A (en) * | 2015-08-04 | 2015-12-23 | 宁夏共享生物化工有限公司 | Preparation method of household gardening nutrient solution containing biochemical humic acid |
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- 1996-07-08 CN CN96108849A patent/CN1060147C/en not_active Expired - Lifetime
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EP0949221A1 (en) * | 1998-04-06 | 1999-10-13 | Holland Chemical International N.V. | Composition suitable as fertilizer containing sulphur as a polythionic acid compound or a salt thereof |
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