CN110157009A - A kind of preparation method of nitrogenous water-soluble humic acid - Google Patents
A kind of preparation method of nitrogenous water-soluble humic acid Download PDFInfo
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- CN110157009A CN110157009A CN201810146820.XA CN201810146820A CN110157009A CN 110157009 A CN110157009 A CN 110157009A CN 201810146820 A CN201810146820 A CN 201810146820A CN 110157009 A CN110157009 A CN 110157009A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B15/00—Organic phosphatic fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/005—Post-treatment
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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Abstract
The invention discloses a kind of methods for preparing nitrogenous water-soluble humic acid, this method is at 40-80 DEG C, 30-720 parts of urea are dissolved with 60-360 parts of water, at 60-100 DEG C with 60-360 parts of low-grade coals are counter is uniformly mixed, 0.3-5.7 parts of soluble phosphates are added, continue to be stirred to react 10-90min, then adds 3-15 parts of ammonium hydroxide and 3-9 parts of part citric acids, be stirred to react 30-120min.It is separated by solid-liquid separation, nitrogenous water-soluble humic acid solution is made.Drying prepares the nitrogenous water-soluble humic acid of solid.The raw material low-grade coal (including weathered coal, lignite, peat) that this method uses is resourceful, and production process equipment is simple, and normal pressure non high temperature reacts easily operated control；Product cost is low, water-soluble humic acid high income, good water solubility, neutral；Waste residue can be utilized directly, non-environmental-pollution.Ben Fafa makees activator using soluble phosphate, ammonium hydroxide, citric acid, improves the yield of nitrogenous water-soluble humic acid product.
Description
Technical field
The present invention relates to a kind of preparation methods of water-soluble humic acid, more particularly to a kind of preparation side of nitrogenous water-soluble humic acid
Method.
Technical background
The extraction of humic acid and dissolving technology are the key technologies for producing fulvo acid in coal, and production is mostly
The technical foundation of number humic acid leading products.The method that traditional lye extracts humic acid be based on ion exchange principle, including
The reaction of two classes: first is that extracting free humic acid by acid-base neutralization:
HA-COOH+NaOH→HA-COONa+H2O
Second is that extracting the humic acid that calcium and magnesium combines by metathesis reaction:
(HA-COO)2Ca+Na2CO3→2HA-COONa+CaCO3↓
Most of water-soluble humic acids all be unable to do without alkali (such as sodium hydroxide, potassium hydroxide, ammonium hydrogen carbonate, wherein with caustic soda
It is in the majority) extraction step, cause to joined useless or even harmful sodium ion in the product, it is only for solve the water of humic acid
Dissolubility problem adds other nutrients when then producing humic acid fertilizer again, and such " two-step method " process not only reduces
The purity and quality of product, and also improve production cost.Continuously, long-term accumulated bring unfavorable shadow to soil environment using meeting
It rings；The acid material that part humic acid product needs additionally to add to neutralize its alkalinity, increases the salinity of product, handles
It is bad that salt damage will cause to soil.
Meanwhile during with caustic alkali (especially caustic soda) extracting water-soluble humic acid, the solid slag and technique waste water of generation, by
It is higher in alkalinity, it is difficult to utilize, accumulate or pollute environment after discharging.
These problems are both the opportunity of the developing bottleneck of fulvo acid and technological innovation.
It is that the corruption that extractant extracts in low-grade coal is planted that nitrogenous water-soluble humic acid, which is using nitrogen substances such as urea and ammonium hydroxide,
Acid is fulvo acid, and the exploitation of nitrogenous water-soluble humic acid is that production cheap, nontoxic, free of contamination water-soluble humic acid in China's produces
Product open new technological approaches, also provide outlet for efficient utilize of low-grade coal.And production contains both at home and abroad so far
The method of the water-soluble humic acid product of nitrogen (ammonium humate, humic acid urea etc.) mainly has: reacting extraction corruption with low level with ammonium hydroxide
Phytic acid ammonium, the technology key reaction principle are that ion-exchange is identical as sodium humate (potassium), and product alkalinity is big, water-soluble humic acid
Recovery rate is low, and operating condition is poor.The main extractive technique of humic acid urea mainly has: solvent method, fusion method and pack etc.
Three kinds of methods, the product of currently referred to as humic acid urea is mainly the granular urea of one layer of humic acid of coating, from stricti jurise
For upper, humic acid does not react really with urea, or micro chemical reaction or physics only occur on urea surface layer
Absorption, humic acid penetrate into urea surface and form one layer of more stable coating, and the thickness of coating, compactness, micro-porosity are to fertilizer
Sustained release, synergistic effect influence greatly, so, since technical reason or production cost are relatively high, have no large scale application.
Summary of the invention
For above-mentioned defects in the prior art, the purpose of the present invention is to provide one kind with low-grade coal (including wind
Change coal, lignite and peat) it is the method that raw material prepares nitrogenous water-soluble humic acid, the raw materials used low-grade coal resource of this method is rich
Richness, it is cheap and easy to get；Working condition is mild, and equipment is simple, easy to operate；Product neutrality, good water solubility.
Realize that the technical solution of objects of the present invention is as follows:
A kind of preparation method of nitrogenous water-soluble humic acid, includes the following steps:
1), 30-720 parts of urea are dissolved at 40-80 DEG C with 60-360 parts of water；
2), by dissolved urea and 60-360 parts of low-grade coals at 60-100 DEG C after mixing, be added 0.3-
5.7 parts of phosphate, are stirred to react 10-90min, then add 3-15 parts of ammonium hydroxide and 3-9 parts of part citric acids, are stirred to react
30—120min；
3) it, is separated by solid-liquid separation after the reaction was completed, collects nitrogenous water-soluble humic acid solution, it is nitrogenous that solid is made by drying
Water-soluble humic acid product.
Wherein, the low-grade coal is one of weathered coal, lignite or peat, low-grade coal aqueous 0-50%, corruption plant
Acid content >=30% or more is crushed to 40 mesh or more.
The phosphate is the soluble phosphate of technical grade or agriculture grade.
The urea is technical grade or agriculture grade.
The ammonium hydroxide is industry or agriculture grade, and citric acid is industry or food-grade.
Nitrogenous water-soluble humic acid is prepared with method provided by the invention, main component is:
With humic acid content 45% (butt), aqueous 22.1% Xinjiang weathered coal is that solid made from raw material is nitrogenous water-soluble
For humic acid, the recovery rate 50-72% of humic acid, fulvo acid content 25-45%, nitrogen content 30-40%.
Under the conditions of 60-100 DEG C, phosphate, ammonium hydroxide and citric acid are as activator, weathered coal and urea by certain ratio
Example is reacted in water, generates nitrogenous water-soluble humic acid soluble easily in water.
It is demonstrated experimentally that under the conditions of 60-100 DEG C, when the ratio of urea and weathered coal is 0.5-3:1, reaction 60-180
When minute, humic acid is not almost extracted not come out.Under the same reaction conditions, when a certain amount of phosphate of addition, ammonium hydroxide and citric acid
When equal composite activating agents, humic acid almost all is extracted.Research has shown that metathesis reaction occurs for phosphate and humic acid
Humic acid phosphate complex is generated, the water solubility of humic acid is enhanced.In ammonium hydroxide ammonium ion have activated weathered coal humic acid with
The reaction of urea, while ammonium ion generates a certain amount of nitrogenous water-soluble humic acid-ammonium humate, citric acid in conjunction with humic acid
The humic acid in conjunction with the complexing of calcium and magnesium plasma, release calcium and magnesium in conjunction with humic acid, while the addition of ammonium hydroxide and citric acid is adjustable
PH value in section buffering reaction process, is conducive to the progress of complex reaction between humic acid and urea, promotes humic acid and urea
Reaction.
The method provided by the invention for preparing nitrogenous water-soluble humic acid has the advantages that compared with published method
1. the raw material low-grade coal that the present invention uses is resourceful；Production technology is reasonable, and equipment investment is few, the non-height of normal pressure
Temperature is easily operated；Reaction condition is easily controllable；Product cost is low, and fulvo acid recovery rate is high, good water solubility, nothing in production
Three waste discharge, waste residue can be used directly as organic fertilizer, or appropriate processing biological organic fertilizer or compound organic and inorganic fertilizer, nothing
Environmental pollution.
2. nitrogenous water-soluble humic acid product neutrality prepared by the present invention is of wide application, urea and phosphoric acid can be grafted onto
Ammonium production process is the fertilizer such as production humic acid urea, humic acid phosphate fertilizer, is the humic acid material source for producing upper fertilizer, can
Directly to prepare liquid containing humic acid water-soluble fertilizer, humic acid lotion fertilizer: and the high-quality original of production solid fertilizer containing humic acid water-soluble
Material.Also feed and raw materials of feed additives be can be used as.Avoid the limitation of the humic acid potassium sodium salt application process of strong basicity.
3. the method applicability that the present invention prepares nitrogenous water-soluble humic acid is wide, weathered coal, lignite suitable for separate sources
And peat, with Xinjiang five colours gulf weathered coal, Hami lignite, Fukang, Xinjiang area weathered coal, Inner Mongol Wuhai weathered coal, Huo Lin
River lignite is that raw material prepares nitrogenous water-soluble humic acid, all obtains good effect.
4. phosphate, ammonium hydroxide, citric acid improve the yield of humic acid, while humic acid and phosphate and ammonia as activator
Water combines and generates humic acid phosphate fertilizer, ammonium humate applies the fixation that can inhibit phosphorus in the soil and the solubization for improving humic acid.
Specific embodiment
Further illustrate how the present invention realizes below with reference to specific embodiment:
Embodiment 1
It takes 360 parts of water in reactor, 96 parts of urea is added, after 70 DEG C or so stirring and dissolvings, be added and contain humic acid
62% (butt), aqueous 15% 120 parts of Xinjiang five colours gulf weathered coal (80 mesh), is warming up to 90 DEG C or so and stirs evenly, and is added
2.4 parts of Diammonium phosphate (DAP) are stirred to react 30min, and 6 parts of ammonium hydroxide, 4 parts of citric acid is added, is stirred to react 120 minutes, are centrifugated, on
Clear liquid drying, is made nitrogenous 119 parts of the water-soluble humic acid product of solid, contains 45 parts of HA, humic acid recovery rate 71%, water-soluble corruption is planted
Acid 38% contains N 30%.
Embodiment 2
It takes 260 parts of water in reactor, 100 parts of urea is added, after 75 DEG C or so stirring and dissolvings, be added and contain humic acid
45% (butt), aqueous 22.1% 80 parts of Hami lignite (40 mesh), is warming up to 95 DEG C or so, 3 parts of ammonium polyphosphate is added,
It is stirred to react 30min, 8 parts of ammonium hydroxide, 1 part of citric acid is added, is stirred to react 150 minutes, is separated by solid-liquid separation, supernatant drying is made
Nitrogenous 101 parts of the water-soluble humic acid product of solid contains 25 parts of HA, and humic acid recovery rate 89%, fulvo acid 25% contains N
31%.
Embodiment 3
It takes 150 parts of water in reactor, 90 parts of urea is added, after 65 DEG C or so stirring and dissolvings, be added and contain humic acid
65% (butt), aqueous 15% 90 parts of Fukang, Xinjiang weathered coal (80 mesh), is warming up to 95 DEG C or so and stirs evenly, and is added 2 parts
Monoammonium phosphate after being stirred to react 40min, is added 10 parts of ammonium hydroxide, 5 parts of citric acid, is stirred to react 120 minutes, is separated by solid-liquid separation, supernatant
Liquid drying, is made nitrogenous 112 parts of the water-soluble humic acid product of solid, contains 39 parts of HA, humic acid recovery rate 78%, water-soluble corruption is planted
Acid 35% contains N 28%.
Embodiment 4
It takes 200 parts of water in reactor, 100 parts of urea is added, after 75 DEG C or so stirring and dissolvings, be added and contain humic acid
66% (butt), aqueous 20% 60 parts of Inner Mongol Wuhai weathered coal (80 mesh) are warming up to 95 DEG C or so reaction 10min, are added
0.3 part of monoammonium phosphate after being stirred to react 40min, is added 6 parts of ammonium hydroxide, 6 parts of citric acid, is stirred to react 150 minutes, is separated by solid-liquid separation,
Supernatant drying, is made nitrogenous 92 parts of the water-soluble humic acid product of solid, contains 21 parts of HA, humic acid recovery rate 67% is water-soluble rotten
Phytic acid 23% contains N 38%.
Embodiment 5
It takes 100 parts of water in reactor, 120 parts of urea is added, after 68 DEG C or so stirring and dissolvings, be added and contain humic acid
72% (butt), aqueous 20% 100 parts of Xinjiang five colours gulf weathered coal (80 mesh), is warming up to 95 DEG C or so and stirs evenly, and is added
1.5 parts of Diammonium phosphate (DAP) after being stirred to react 30min, are added 6 parts of ammonium hydroxide, 4 parts of citric acid, are stirred to react 150 minutes, are separated by solid-liquid separation,
Supernatant drying, be made nitrogenous 127 parts of the water-soluble humic acid product of solid, contain 49.5 parts of HA, humic acid recovery rate 85.9%, water
Dissolubility humic acid 39% contains N 32.3%.
Embodiment 6
It takes 120 parts of water in reactor, 80 parts of urea is added, after 70 DEG C or so stirring and dissolvings, be added and contain humic acid
50% (butt), aqueous 15% Hami lignite
80 parts of (60 mesh) is warming up to 95 DEG C or so reaction 10min, 3 parts of Diammonium phosphate (DAP) is added, are stirred to react 30min, is added
5 parts of ammonium hydroxide, 3 parts of citric acid, are stirred to react 120 minutes, are separated by solid-liquid separation, and the nitrogenous water-soluble humic acid of solid is made in supernatant drying
86 parts of product, contain 24 parts of HA, humic acid recovery rate 70%, fulvo acid 28.0% contains N 35%.
Embodiment 7
It takes 300 parts of water in reactor, 720 parts of urea is added, after 75 DEG C or so stirring and dissolvings, be added and contain humic acid
45% (butt), aqueous 22.1% 360 parts of Hami lignite (40 mesh), is warming up to 95 DEG C or so, 3 parts of polyphosphoric acids is added
Ammonium is stirred to react 30min, and 15 parts of ammonium hydroxide, 3 parts of citric acid is added, is stirred to react 150 minutes, is separated by solid-liquid separation, supernatant drying,
Be made nitrogenous 566 parts of the water-soluble humic acid product of solid, contain 102 parts of HA, humic acid recovery rate 81%, fulvo acid 18%,
Containing N 39%.
Embodiment 8
It takes 200 parts of water in reactor, 120 parts of urea is added, after 68 DEG C or so stirring and dissolvings, be added and contain humic acid
60% (butt), aqueous 18% 240 parts of Xinjiang five colours gulf weathered coal (80 mesh), is warming up to 95 DEG C or so and stirs evenly, and is added
5.6 parts of Diammonium phosphate (DAP) after being stirred to react 30min, are added 5 parts of ammonium hydroxide, 9 parts of citric acid, are stirred to react 150 minutes, are separated by solid-liquid separation,
Supernatant drying, is made nitrogenous 183 parts of the water-soluble humic acid product of solid, contains 64 parts of HA, humic acid recovery rate 54.2% is water-soluble
Property humic acid 35%, contain N 23.2%.
Embodiment 9
It takes 160 parts of water in reactor, 200 parts of urea is added, after 75 DEG C or so stirring and dissolvings, be added and contain humic acid
66% (butt), aqueous 20% 160 parts of Inner Mongol Wuhai weathered coal (80 mesh) are warming up to 95 DEG C or so reaction 10min, are added
2 parts of monoammonium phosphate after being stirred to react 40min, are added 6 parts of ammonium hydroxide, 3 parts of citric acid, are stirred to react 150 minutes, are separated by solid-liquid separation, on
Clear liquid drying, is made nitrogenous 193 parts of the water-soluble humic acid product of solid, contains 58 parts of HA, humic acid recovery rate 69% is water-soluble rotten
Phytic acid 30% contains N 31%.
Claims (6)
1. a kind of method for preparing nitrogenous water-soluble humic acid, includes the following steps:
1), 30-720 parts of urea are dissolved at 40-80 DEG C with 60-360 parts of water；
2), by dissolved urea and 60-360 parts of low-grade coals at 60-100 DEG C after mixing, be added 0.3-5.7 parts
Phosphate, is stirred to react 10-90min, then adds 3-15 parts of ammonium hydroxide and 3-9 parts of citric acids, is stirred to react 30-
120min；
3) it, is separated by solid-liquid separation after the reaction was completed, collects nitrogenous water-soluble humic acid solution, it is nitrogenous water-soluble that solid is made by drying
Humic acid product.
2. a kind of method for preparing nitrogenous water-soluble humic acid according to claim 1, it is characterised in that: the low-grade coal
For one of weathered coal, lignite and peat.
3. a kind of method for preparing nitrogenous water-soluble humic acid according to claim 2, it is characterised in that: the low-grade coal
Aqueous 0-50%, humic acid content >=30%, partial size is greater than 40 mesh.
4. a kind of method for preparing nitrogenous water-soluble humic acid according to claim 1, it is characterised in that: the phosphate is
Technical grade or agriculture grade soluble phosphate.
5. a kind of method for preparing nitrogenous water-soluble humic acid according to claim 1, it is characterised in that: the urea is work
Industry grade or agriculture grade.
6. a kind of method for preparing nitrogenous water-soluble humic acid according to claim 1, it is characterised in that: the ammonium hydroxide is work
Industry or agriculture grade, citric acid are industry or food-grade.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552529A (en) * | 2020-12-31 | 2021-03-26 | 吉林大学 | Process for extracting humic acid from weathered coal by high-pressure ammonia gas method |
| CN116965423A (en) * | 2023-09-25 | 2023-10-31 | 山西林海腐植酸科技有限公司 | Humic acid-containing green environment-friendly pesticide and preparation method thereof |
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Application publication date: 20190823 |