CN102093434A - Production method of acid-soluble potassium humate - Google Patents
Production method of acid-soluble potassium humate Download PDFInfo
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- CN102093434A CN102093434A CN2011100005514A CN201110000551A CN102093434A CN 102093434 A CN102093434 A CN 102093434A CN 2011100005514 A CN2011100005514 A CN 2011100005514A CN 201110000551 A CN201110000551 A CN 201110000551A CN 102093434 A CN102093434 A CN 102093434A
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- weathered coal
- acid
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Abstract
The invention provides a production method of acid-soluble potassium humate. The production method is as follows: smashing washed and purified weathered coal to 40-80 meshes, adding the weathered coal, nitric acid and tap water in a reaction kettle in a proportion of 1:1.5:5, simultaneously adding a ferrovanadium compound catalyst which accounts for 0.5-1.5% of weathered coal amount, and closing the reaction kettle; slowly rising the temperature to 130-200 DEG C, pressurizing to 0.3-1MPa, reacting for 2-4 hours, and then adding potassium hydroxide in the separated acid-soluble potassium humate solution so as to regulate the pH value to 5.0-6.0; and concentrating the material by a triple effect evaporator until the concentration is 15-20%, drying step by step to form a particle shape, thus the finished product is obtained, wherein the content of humic acid (HA) in washed and purified weathered coal is large than or equal to 75%, and the content of ash in the washed and purified weathered coal is less than or equal to 10%. The ferrovanadium compound catalyst is prepared by the steps: adding water in oxalate for dissolving, and adding ammonium metavanadate for reaction so as to obtain a vanadyl oxalate solution; adding activated carbon for separation, recovering filter cake, drying and roasting so as to obtain an activated carbon-loaded V2O5 catalyst; dispersing the activated carbon in a FeCl3 solution, stirring, adding ammonia water for regulation, separating with a plate-frame type filter press, drying, and roasting to obtain an activated carbon-loaded Fe2O3 catalyst; and evenly mixing the two catalysts in a proportion of 1:1.
Description
Technical field
The present invention relates to the precision work of humic acids, especially choosing is carried with compound, and the solubility in acid potassium humate that this method is obtained has splendid result of use as synergistic agent, the additive of organic fertilizer.
Background technology
Humic acids (Humic Acid, write a Chinese character in simplified form HA) be the animals and plants remains, mainly be the remains of plant, through decomposition and the conversion of microorganism, and geochemical a series of process has the organic acidic material of multi-active bases such as carboxyl, hydroxyl, branch hydroxyl, quinonyl, methoxyl group with a class that accumulates.It has functions such as good physiologically active and absorption, complexing, exchange.It extensively is present in soil, lake, river, ocean and peat (claiming the peat composed of rotten mosses again), brown coal, the weathered coal.Press the nature classification, it can be divided into three major types, i.e. soil rotten phytic acid, water body humic acids and coal humic acid.China exploitation as the main products of organic matter raw material fertilizer, agricultural chemicals, veterinary drug, drought resistance agent, fodder additives are arranged with humic acids; Medicine, healthcare products, makeup; More than 100 kinds such as petroleum assistant, industrial water conditioning agent, coal water mixture stabilizing agent, store battery swelling agent, ceramic additive, easer have constituted the integral framework of China's humic-acid kind product basically.
Literature search discloses: number be the patent of 200510011310 " a kind of technology with the coal production yellow humic acid ", be that weathered coal is ground into the particle that granularity is 0.3mm, it is joined in the reactor, the nitric acid that adds 4.5mol/L then, stir, under 85 ℃ temperature condition, react stop after 1 hour the heating, remove supernatant liquor, taking precipitate joins in the reactor with water and to stir, and slowly adds concentration again and be 98% sulfuric acid, mix, temperature is under 57 ℃ condition, and standing and reacting 1 hour was cooled off 4 hours then, remove residue and get filtrate, with filter behind the clear water rinsing residue that accounts for residue weight 10-15% rinsing liquid, with filtrate and rinsing liquid mix amalgamation liquid, amalgamation liquid is concentrated, oven dry gets product.
Characteristics of the present invention are purified the weathered coal washing, and add composite catalyst and potassium hydroxide adjusting pH value, make the demand of the more approaching production of product, because the pH value of product is slightly acidic, are difficult for contaminate environment, and cost is low, has vast market prospect.
Summary of the invention
The objective of the invention is to: the production method of the solubility in acid potassium humate that provides, simple and practical, energy efficiency is different from the method that other adopt the nitric acid preparation, and the actual demand of production preferably is by the colleague is admitted.
The object of the present invention is achieved like this: a kind of production method of solubility in acid potassium humate, to select the pure weathered coal of elution to be crushed to the 40-80 order earlier, add reactor with nitric acid, tap water in the ratio of 1:1.5:5, the ferrovanadium composite catalyst that adds weathered coal amount 0.5-1.5% simultaneously, closed reactor; Slowly intensification 130-200 ℃, plus-pressure 0.3-1Mpa reacted after 2-4 hour, and the solubility in acid potassium humate solution with separation obtains adds potassium hydroxide, and regulating the pH value is 5.0-6.0; Again material is concentrated into 15-20% concentration through triple-effect evaporator, dry through substep, become microgranular, get product;
Wherein the weathered coal washing is purified: raw material sieves and is crushed to below the 0.5mm, adds water and stirs, and its coal-water ratio is 1:2-1:3; Add the dilute nitric acid solution of concentration 1-2% simultaneously, continue to stir 80-90 ℃ of intensification, reaction 50-65min gets the high-quality weathered coal through the plate and frame(type)filter press solid-liquid separation;
The wherein preparation of ferrovanadium composite catalyst:
A) 126kg oxalic acid is added in the 1000kg deionized water, heat 60-70 ℃ of dissolving, add 59kg ammonium meta-vanadate solid again, stirring reaction 20min gets oxalic acid vanadyl solution; To stir in the step solution on the 1500kg gac input, time 60min separates through plate and frame(type)filter press, reclaims filter cake; With 100-120 ℃ of dry 24h, use 500 ℃ of roasting 4h again, make activated carbon supported V
2O
5Catalyzer;
B) the 1500kg gac is distributed to the FeCl of the 0.25mol/L that 1000kg configured
3Stirring 60min in the solution, is that to regulate the pH value be 9-10 for 1% ammoniacal liquor with concentration; Separate through plate and frame(type)filter press, reclaim filter cake; With 100-120 ℃ of dry 24h, use 500 ℃ of roasting 4h again, make activated carbon supported Fe
2O
3Catalyzer;
The catalyzer that above-mentioned a, b make is even by the mixed of 1:1, promptly get the ferrovanadium composite catalyst.
Described production method is selected the pure weathered coal of elution, its HA content 〉=75%, ash oontent≤10%.
Described production method, the dry drying of tower spray-drier and the drying of fluidized bed dryer of dividing of substep.
Design of the inventive method and know-why: adopt composite catalyst and oxygenant that coal humic acid is carried out handling than the oxidative degradation of the degree of depth, macromolecular Ulmic acids is become the less humic acids of molecular weight through the chemical process oxidative cleavage, generate a large amount of stronger carboxyls of acidity at chain rupture place and the unsaturated link(age) place of humic acids molecular structure simultaneously, improve the wetting ability of humic acids molecule greatly, thereby reached the purpose that dissolves in acidic conditions.
The topmost chemical feature of humic acids is to meet alkali dissolution to meet Acid precipitation, and just the alkali extraction and acid precipitation of often saying forms sediment; But the humic acids product in agriculture practical application through regular meeting and acidic fertilizier (NH
4SO
4, NH
4H
2PO
4,K
2SO
4,NH
4Cl, NH
4NO
3Deng) being mixed for spraying drip irrigation, common like this humic acids product can be at flocculation sediment under the acidic conditions, and the clogging drip irrigation band makes the humic acids product be subjected to very big restriction in water-saving agriculture is used; While is along with the enhancing of health of people and environmental consciousness, requirement to pesticide residue index in the agricultural-food is more and more higher, the agricultural chemicals that requires to use must be a high-efficiency low-toxicity, we have developed and have had under acidic conditions the solubility in acid humic acids that can also fine dissolving be applicable to drip irrigation and agricultural chemicals for this reason, show technical progress.
Description of drawings
The present invention contrasts accompanying drawing and is described further.
Accompanying drawing 1 is a process flow diagram of the present invention;
As shown in the figure: 1-weathered coal pulverizing-2-physics washing purification (catalyzer)-3-oxidizing reaction-4-separates insoluble impurity (KOH)-5-and regulates pH value-6-concentrated spray drying-7-fluidization granulation-8-metering packing finished product.
Accompanying drawing 2 is the solvability contrast and experiment in two acid of pH condition;
As shown in the figure: this product is under pH 〉=3.0 conditions, and its solvability has just kept metastable state, and is unaffected; Common refining potassium humate need could guarantee solvability preferably under the neutrallty condition of pH 〉=7.0.
Embodiment
Comparative examples of the present invention is described further.
Embodiment
The Control essentials of method:
(1) weathered coal is purified through washing, and its HA content 〉=75%, ash content drop to≤and 10%, thus improved the oxidized activity of weathered coal, can reduce the consumption of oxygenant, improve product yield and quality.
(2) oxide compound of employing composite catalyst and oxygenant makes different simple substance catalyzer performance synergistic effects.
(3) simultaneous test: the solvability of solubility in acid potassium humate and refining potassium humate contrast under condition of different pH, see the following form.
Learnt by last table: the solubility in acid potassium humate has shown good solvability under acidic conditions, and under pH 〉=3.0 conditions, its solvability has just kept metastable state, and is unaffected; Common refining potassium humate need could guarantee solvability preferably under the neutrallty condition of pH 〉=7.0.
Operation steps:
To select the pure weathered coal of elution to be crushed to 59 orders earlier, add reactor in the ratio of 1:1.5:5, add the ferrovanadium composite catalyst of weathered coal amount 0.8% simultaneously, closed reactor with nitric acid, tap water; Slowly heat up 180 ℃, plus-pressure 0.7Mpa reacted after 3 hours, the solubility in acid potassium humate solution that separation is obtained, add potassium hydroxide, regulating the pH value is 6.0, and at this moment, the mass concentration of solution is 8%, through triple-effect evaporator material is concentrated into 20% mass concentration again, concentrated solution is pressed into tower spray-drier again and carries out drying, powdery partial desiccation thing after fluidized bed dryer further is dried to microgranularly, gets product.
The weathered coal washing is purified: raw material sieves and is crushed to below the 0.5mm, adds water and stirs, and its coal-water ratio is 1:3; Add concentration simultaneously and be 2% dilute nitric acid solution and stir, heat 85 ℃, react 60min, through pressure filter separate the high-quality weathered coal;
The preparation of ferrovanadium composite catalyst:
A) 126kg oxalic acid is added in the 1000kg deionized water, heat 70 ℃ of dissolvings, add 59kg ammonium meta-vanadate solid again, stirring reaction 20min gets oxalic acid vanadyl solution; To stir in the step solution on the 1500kg gac input, time 60min separates through pressure filter, reclaims filter cake; With 110 ℃ of dry 24h,, make activated carbon supported V with 500 ℃ of roasting 4h
2O
5Catalyzer;
B) the 1500kg gac is distributed to the FeCl of the 0.25mol/L that 1000kg configured
3Stirring 60min in the solution, is that to regulate the pH value be 9 for 1% ammoniacal liquor with concentration; Separate through pressure filter, reclaim filter cake; With 120 ℃ of dry 24h,, make activated carbon supported Fe with 500 ℃ of roasting 4h
2O
3Catalyzer;
Above-mentioned two kinds of catalyzer that make are even by the mixed of 1:1, promptly get the ferrovanadium composite catalyst.Described production method, the raw material of nitric acid of selecting for use and preparation ferrovanadium composite catalyst is the commercially available prod.
Claims (4)
1. the production method of a solubility in acid potassium humate, it is characterized in that: will select the pure weathered coal of elution to be crushed to the 40-80 order earlier, add reactor with nitric acid, tap water in the ratio of 1:1.5:5, add the ferrovanadium composite catalyst of weathered coal amount 0.5-1.5% simultaneously, closed reactor; Slowly intensification 130-200 ℃, plus-pressure 0.3-1Mpa reacted after 2-4 hour, and the solubility in acid potassium humate solution with separation obtains adds potassium hydroxide, and regulating the pH value is 5.0-6.0; Again material is concentrated into 15-20% concentration through triple-effect evaporator, dry through substep, become microgranular, get product;
Wherein the weathered coal washing is purified: raw material sieves and is crushed to below the 0.5mm, adds water and stirs, and its coal-water ratio is 1:2-1:3; Add the dilute nitric acid solution of concentration 1-2% simultaneously, continue to stir 80-90 ℃ of intensification, reaction 50-65min gets the high-quality weathered coal through the plate and frame(type)filter press solid-liquid separation;
The wherein preparation of ferrovanadium composite catalyst:
A) 126kg oxalic acid is added in the 1000kg deionized water, heat 60-70 ℃ of dissolving, add 59kg ammonium meta-vanadate solid again, stirring reaction 20min gets oxalic acid vanadyl solution; To stir in the step solution on the 1500kg gac input, time 60min separates through plate and frame(type)filter press, reclaims filter cake; With 100-120 ℃ of dry 24h, use 500 ℃ of roasting 4h again, make activated carbon supported V
2O
5Catalyzer;
B) the 1500kg gac is distributed to the FeCl of the 0.25mol/L that 1000kg configured
3Stirring 60min in the solution, is that to regulate the pH value be 9-10 for 1% ammoniacal liquor with concentration; Separate through plate and frame(type)filter press, reclaim filter cake; With 100-120 ℃ of dry 24h, use 500 ℃ of roasting 4h again, make activated carbon supported Fe
2O
3Catalyzer;
The catalyzer that above-mentioned a, b make is even by the mixed of 1:1, promptly get the ferrovanadium composite catalyst.
2. production method according to claim 1 is characterized in that: select the pure weathered coal of elution, its HA content 〉=75%, ash oontent≤10%.
3. production method according to claim 1 is characterized in that: the dry drying of tower spray-drier and the drying of fluidized bed dryer of dividing of substep.
4. production method according to claim 1 is characterized in that: the raw material of nitric acid of selecting for use and preparation ferrovanadium composite catalyst is the commercially available prod.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103937005A (en) * | 2014-04-29 | 2014-07-23 | 天津博生源肥料科技发展有限公司 | Energy-saving environment-friendly production method of agricultural soluble humic acid |
| CN104874579A (en) * | 2014-02-27 | 2015-09-02 | 沾益县浩腾新型能源科技有限公司 | Coal waste comprehensive treatment method |
| CN104945171A (en) * | 2015-07-17 | 2015-09-30 | 潍坊润华生物化工有限公司 | Organic water-soluble fertilizer capable of lowering soil acidification damage and preparation method thereof |
| CN105461758A (en) * | 2015-11-18 | 2016-04-06 | 河南理工大学 | A method of increasing a humic acid extraction ratio from brown coal |
| CN107417929A (en) * | 2017-07-26 | 2017-12-01 | 湖南科技大学 | A kind of method that lignite catalysis oxidation improves Humic Acid Production Rate |
| CN109437987A (en) * | 2019-01-07 | 2019-03-08 | 哈尔滨理工大学 | A kind of preparation method of environmental-friendly hard water resistance fulvic acid potassium |
| CN111138231A (en) * | 2019-11-19 | 2020-05-12 | 西安交大凯达新技术有限责任公司 | Humic acid-containing high-concentration liquid water-soluble fertilizer and preparation method thereof |
| CN115466137A (en) * | 2022-08-26 | 2022-12-13 | 山东农业大学 | Modified humic acid with low molecular weight and high functionality, and preparation and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874579A (en) * | 2014-02-27 | 2015-09-02 | 沾益县浩腾新型能源科技有限公司 | Coal waste comprehensive treatment method |
| CN103937005A (en) * | 2014-04-29 | 2014-07-23 | 天津博生源肥料科技发展有限公司 | Energy-saving environment-friendly production method of agricultural soluble humic acid |
| CN104945171A (en) * | 2015-07-17 | 2015-09-30 | 潍坊润华生物化工有限公司 | Organic water-soluble fertilizer capable of lowering soil acidification damage and preparation method thereof |
| CN105461758A (en) * | 2015-11-18 | 2016-04-06 | 河南理工大学 | A method of increasing a humic acid extraction ratio from brown coal |
| CN107417929A (en) * | 2017-07-26 | 2017-12-01 | 湖南科技大学 | A kind of method that lignite catalysis oxidation improves Humic Acid Production Rate |
| CN109437987A (en) * | 2019-01-07 | 2019-03-08 | 哈尔滨理工大学 | A kind of preparation method of environmental-friendly hard water resistance fulvic acid potassium |
| CN109437987B (en) * | 2019-01-07 | 2021-08-03 | 哈尔滨理工大学 | Preparation method of environment-friendly hard water-resistant potassium fulvate |
| CN111138231A (en) * | 2019-11-19 | 2020-05-12 | 西安交大凯达新技术有限责任公司 | Humic acid-containing high-concentration liquid water-soluble fertilizer and preparation method thereof |
| CN115466137A (en) * | 2022-08-26 | 2022-12-13 | 山东农业大学 | Modified humic acid with low molecular weight and high functionality, and preparation and application thereof |
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Application publication date: 20110615 |