CN103467751A - Extraction method of humic acid from alcohol dreg solution fermentation sludge - Google Patents
Extraction method of humic acid from alcohol dreg solution fermentation sludge Download PDFInfo
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- CN103467751A CN103467751A CN2013103916157A CN201310391615A CN103467751A CN 103467751 A CN103467751 A CN 103467751A CN 2013103916157 A CN2013103916157 A CN 2013103916157A CN 201310391615 A CN201310391615 A CN 201310391615A CN 103467751 A CN103467751 A CN 103467751A
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Abstract
The invention discloses an extraction method of humic acid from alcohol dreg solution fermentation sludge. According to the extraction method disclosed by the invention, the alcohol dreg solution fermentation sludge is taken as a raw material, and the humic acid is extracted from the alcohol dreg solution fermentation sludge through oxidation, deodorization, alkali dissolution, carboxymethylation, acid neutralization, drying and other processes. The extraction method has the characteristics of high productivity and high product purity and further has great agricultural fertilizer balance and synergy. According to the extraction method disclosed by the invention, the alcohol dreg solution fermentation sludge is for the first time taken as the raw material for producing the humic acid, so that production raw material channels of the humic acid are expanded, and the comprehensive utilization efficiency of the alcohol dreg solution fermentation sludge is simultaneously improved.
Description
Technical field
The invention belongs to chemical industry and waste ' s reclamation technical field, be specifically related to the extracting method of humic acids in a kind of alcohol tank liquid fermented sludge.
Background technology
Vinasse are the poor liquid after ethanol is manufactured in farm crop fermentations, and concentration is high, quantity is large, nontoxic, nutritious.General domestic it fully utilize to the following technique of use, at first vinasse are separated and obtain poor slag and poor liquid, poor slag drying is removed the moisture in poor slag, makes dried egg white feed of high quality and at a reasonable price.Alcohol tank liquid is carried out to biogas anaerobic fermentation and prepare biogas, for resident living fuel, also can be used as industrial raw material simultaneously.Natural pond liquid after biogas fermentation is separated, obtained fermented sludge (alcohol tank liquid fermented sludge), will be made efficient organic fertilizer after drying sludge.After drying sludge, organic matter, nitrogen (in the nitrogen element), phosphorus are (with P
2o
5meter), potassium is (with K
2the O meter) average content is greater than respectively 40%, 4%, 6%, 0.5%, almost equal with nitrogen in rapeseed cake, potassium content (4.6%, 1.4%), the content of phosphorus, far away higher than the content (2.5%) of phosphorus in rapeseed cake, is also the fertilizer that a kind of nutrient content is higher.
Make efficient organic fertilizer after drying sludge and have two its a large amount of uses of problems affect, the one, the content of nitrogen, phosphorus, potassium is lower, reach the required amount of crop growth, and the sludge quantity used is very large, and manpower and accumulating expense are higher.If mud directly is spiked in composite fertilizer, can make the outward appearance blackout of composite fertilizer, frowziness, simultaneously due to the water absorbability of mud, can affect the production technique of composite fertilizer, and composite fertilizer easily gets damp.The 2nd, the stink of mud is larger, uses inconvenient.
Essential substance as fertilizer in mud is the humic acid substance that contains carboxyl, hydroxyl isoreactivity group wherein, and they can play the effect of Balance Absorption, maintenance moisture, improvement soil, Promoting plant growth in soil to plant.
Humic acids is the fertile poiser of a kind of industrial chemicals commonly used, agriculture and synergistic agent, is mainly derived from brown coal and peat.Humic acids is the natural organic substance of element of the first species's complexity, extensively be present in weathered coal, brown coal, it is a kind of mixture of natural macromolecular aromatic hydroxy-carboxylic, the various active group had (carboxyl, phenolic hydroxyl group, alcoholic extract hydroxyl group, methoxyl group etc.) is given its several functions, as acidity, wetting ability, cationic exchange, complex ability reach higher adsorptive power etc.The application of humic acids is very extensive, relates to the every field such as industry, agricultural, medicine, herding, environmental protection, wherein, in industrial application, is mainly as tackiness agent, in agriculture application, as composite fertilizer's nutrient balance agent in the preparation at moulded coal.After humic acids is added to agriculture fertilizer, the one, can improve utilization rate of fertilizer, the N in common fertilizer, P, K nutrient are not easy to be absorbed fully by crop.Add after humic acids the utilization ratio that can increase substantially N, P, K.The 2nd, strengthen anti-adversity, humic acids can dwindle the opening degree of blade face pore, reduces the moisture evaporation, makes plants and soil keep more moisture, has unique drought resisting, cold-resistant, resistance against diseases.The 3rd, hormesis, humic acids has mobilizing function, can increase oxidase activity and Metabolic activity in plant materials, thus Promoting plant growth.The 4th, improvement soil, the calcium in humic acids in colloid and soil, magnesium form cotton-shaped gel, can improve the structure of soil, improve absorption, the exchange capacity of soil, regulate the pH value, reach soil acid-base equilibrium.Therefore humic acids has good DEVELOPMENT PROSPECT and using value.
The raw material of making now humic acids is all brown coal, peat, and the operational path of employing is the technique of caustic soda dissolving-sour neutralization precipitation.
First use contained humic acids in caustic soda soln extracting brown coal, mud coal, the humic acids sodium salt of generation is soluble in water.Its chemical equation is:
R-(COOH)n+nNaOH→R-(COONa)n+nH
2O
After filtration, use sour neutralization filtrate, be settled out humic acids, after filtration, obtain the humic acids product after oven dry.It is that raw material extracts that the preparation method of above-mentioned humic acids be take brown coal, peat.
Summary of the invention
For better utilised alcohol tank liquid fermented sludge, overcome the existing defect of utilizing approach to exist, improve the utility value of alcohol tank liquid fermented sludge.The invention provides a kind of method of extracting humic acids from the alcohol tank liquid fermented sludge.
For achieving the above object, the method for extracting humic acids from the alcohol tank liquid fermented sludge of the present invention comprises the following steps:
(1) raw material is processed
By the alcohol tank liquid fermentation sludge dewatering, make its solid content be greater than 20%;
(2) oxidation, deodorization are processed
Mud solution is heated to 20-60
0c, under agitation by ozonizer, pass into the ozone that accounts for amount of solid 0.5%-5% in mud (calculating by the scale passed into) or add the superoxol that the mass percent concentration that accounts for amount of solid 1%-5% in mud is 30% or add the peracetic acid soln that the mass percent concentration that accounts for amount of solid 0.5%-5% in mud is 30%, reaction times 30-120 minute; Its oxidation, deodorising process are used ozone, hydrogen peroxide or Peracetic Acid as oxygenant.Its usage quantity is calculated and is respectively by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids:
Ozone: 0.5-5 kilogram (calculating by the scale passed into)
Hydrogen peroxide (30%): 1-5 kilogram
Peracetic Acid (30%): 0.5-5 kilogram
(3) molten, the carboxymethylation of alkali is processed
The alkaline matters such as the sodium hydroxide of solid matter quality 5%-20%, sodium carbonate, ammoniacal liquor add mud in the mud solution after peroxidation, deodorization are processed in; Then the sodium chloroacetate reaction 30-120 minute that adds solid matter quality 0.1%-3% in mud; Filter after reaction, remove impurity, collect solution; In the molten process of alkali, use sodium hydroxide, sodium carbonate, ammoniacal liquor as the molten reagent of alkali; Its usage quantity is calculated and is respectively by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids:
Sodium hydroxide: 5-20 kilogram
Sodium carbonate: 5-20 kilogram
Ammoniacal liquor (25%): 5-30 kilogram;
In the carboxymethylation process, use sodium chloroacetate as carboxymethylation reagent, its usage quantity is calculated and is added sodium chloroacetate 0.1-3 kilogram by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids.
(4) neutralization, precipitation
Use in sulfuric acid, hydrochloric acid and solution that above filtration is collected afterwards, regulate pH value and be less than 7, standing, filter the collecting precipitation thing after precipitation, throw out to be dried, pulverizing, be packaged to be the humic acids product.
The present invention utilizes the alcohol tank liquid fermented sludge as raw material,, carboxymethylation molten by oxidation, deodorization, alkali, acid neutralization, the technique such as dry are extracted humic acids from the alcohol tank liquid fermented sludge, have the advantages that productive rate is high, product purity is high, there is the fertile balance of good agriculture and synergism.
The present invention is usingd the alcohol tank liquid fermented sludge first as the raw material production humic acids, has widened the raw materials for production channel of humic acids.Also improved the comprehensive utilization ratio of alcohol tank liquid fermented sludge simultaneously.
Embodiment
The method of extracting humic acids from the alcohol tank liquid fermented sludge of the present invention comprises the following steps:
(1) raw material is processed
By the alcohol tank liquid fermentation sludge dewatering, make its solid content be greater than 20%;
(2) oxidation, deodorization are processed
Organic content large (being greater than 40%) in the alcohol tank liquid fermented sludge, complex structure, contain a large amount of hydroxyls, carboxyl, aldehyde radical.Wherein carboxyl is water-soluble large, and the strongest to complexing and the balanced capacity of soil, chemical fertilizer, so productive rate and quality product in order to increase humic acids, need to change hydroxyl, aldehyde radical wherein into carboxyl, can use the organic matter in ozone, peroxide oxidation mud, make hydroxyl, aldehyde compound generate humic acid substance.Simultaneously because oxidation has reduced the content of aldehyde, thereby reduce the stink in mud;
Mud solution is heated to 20-60
0c, under agitation by ozonizer, pass into the ozone that accounts for amount of solid 0.5%-5% in mud (calculating by the scale passed into) or add the superoxol that the mass percent concentration that accounts for amount of solid 1%-5% in mud is 30% or add the peracetic acid soln that the mass percent concentration that accounts for amount of solid 0.5%-5% in mud is 30%, reaction times 30-120 minute; Its oxidation, deodorising process are used ozone, hydrogen peroxide or Peracetic Acid as oxygenant.Its usage quantity is calculated and is respectively by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids:
Ozone: 0.5-5 kilogram (calculating by the scale passed into)
Hydrogen peroxide (30%): 1-5 kilogram
Peracetic Acid (30%): 0.5-5 kilogram
(3) molten, the carboxylated processing of alkali
The molten process of alkali is in order to dissolve the humic acids in mud, and some other impurity can not dissolve, and then by filtration, removes impurity.Contain a large amount of oxy-compound in organic matter due to mud, not only influential to productive rate, also influential to the purity of product.In order to increase productive rate, improve the content of carboxyl in product, use sodium chloroacetate to process, make carboxymethyl replace part of hydroxyl and generate humic acid substance.
The alkaline matters such as the sodium hydroxide of solid matter quality 5%-20%, sodium carbonate, ammoniacal liquor add mud in the mud solution after peroxidation, deodorization are processed in.Then the sodium chloroacetate reaction 30-120 minute that adds solid matter quality 0.1%-3% in mud.Filter after reaction, remove impurity, collect solution.In the carboxymethylation process, use sodium chloroacetate as carboxymethylation reagent, its usage quantity is calculated and is respectively by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids:
Sodium hydroxide: 5-20 kilogram
Sodium carbonate: 5-20 kilogram
Ammoniacal liquor (25%): 5-30 kilogram;
In the carboxymethylation process, use sodium chloroacetate as carboxymethylation reagent, its usage quantity is calculated and is added sodium chloroacetate 0.1-3 kilogram by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids.
(4) neutralization, precipitation
Use in sulfuric acid, hydrochloric acid and solution that above filtration is collected afterwards, regulate pH value and be less than 7, standing, filter the collecting precipitation thing after precipitation, throw out to be dried, pulverizing, be packaged to be the humic acids product.
Be below specific embodiments of the invention, but the invention is not restricted to these examples:
Embodiment 1:
Add 2 tons of the alcohol tank liquid fermented sludge solution that solid masses concentration is 30% in reactor, stir, heat up, controlling temperature is 40 ℃; Pass into ozone 20 minutes by ozonizer in reactor.Reaction adds 50 kilograms, sodium hydroxide after finishing in reactor, adds 6 kilograms of sodium chloroacetates after dissolve complete, reacts 60 minutes, after reacting completely, filters, and removes contamination precipitation.Then add salt acid for adjusting pH value to 6.5 in filtered liquid, standing 60 minutes, filter the collecting precipitation thing, dry, pulverize, packing, be packaged to be the humic acids product.
Embodiment 2:
Add 2 tons of the alcohol tank liquid fermented sludge solution that solid masses concentration is 30% in reactor, stir, heat up, controlling temperature is 60 ℃; Add (30%) 2 kilogram, hydrogen peroxide in reactor, react 30 minutes.Reaction adds 60 kilograms, sodium carbonate after finishing in reactor, adds 6 kilograms of sodium chloroacetates after dissolve complete, reacts 60 minutes, after reacting completely, filters, and removes contamination precipitation.Then add salt acid for adjusting pH value to 6.5 in filtered liquid, standing 60 minutes, filter the collecting precipitation thing, dry, pulverize, packing, be packaged to be the humic acids product.
Embodiment 3:
Add 2 tons of the alcohol tank liquid fermented sludge solution that solid masses concentration is 30% in reactor, stir, heat up, controlling temperature is 60 ℃; Add (30%) 2 kilogram, hydrogen peroxide in reactor, react 30 minutes.Reaction adds (25%) 100 kilogram of ammoniacal liquor after finishing in reactor, adds 6 kilograms of sodium chloroacetates after dissolve complete, reacts 60 minutes, after reacting completely, filters, and removes contamination precipitation.Then add salt acid for adjusting pH value to 6.5 in filtered liquid, standing 60 minutes, filter the collecting precipitation thing, dry, pulverize, packing, be packaged to be the humic acids product.
Claims (4)
1. the extracting method of humic acids in an alcohol tank liquid fermented sludge is characterized in that the described method of extracting humic acids from the alcohol tank liquid fermented sludge comprises the following steps:
(1) raw material is processed
By the alcohol tank liquid fermentation sludge dewatering, make its solid content be greater than 20%;
(2) oxidation, deodorization are processed
Mud solution is heated to 20-60
0c, under agitation by ozonizer, pass into the ozone that accounts for amount of solid 0.5%-5% in mud or add the superoxol that the mass percent concentration that accounts for amount of solid 1%-5% in mud is 30% or add the peracetic acid soln that the mass percent concentration that accounts for amount of solid 0.5%-5% in mud is 30%, reaction times 30-120 minute;
(3) molten, the carboxylated processing of alkali
Sodium hydroxide, sodium carbonate, the ammoniacal liquor alkaline matter of solid matter quality 5%-20% add mud in the mud solution after peroxidation, deodorization are processed in; Then the sodium chloroacetate reaction 30-120 minute that adds solid matter quality 0.1%-3% in mud; Filter after reaction, remove impurity, collect solution;
(4) neutralization, precipitation
Use in sulfuric acid, hydrochloric acid and solution that above filtration is collected afterwards, regulate pH value and be less than 7, standing, filter the collecting precipitation thing after precipitation, throw out to be dried, pulverizing, be packaged to be the humic acids product.
2. according to the extracting method of humic acids in the described alcohol tank liquid fermented sludge of claim 1, it is characterized in that: its oxidation, deodorising process are used ozone, hydrogen peroxide or Peracetic Acid as oxygenant, and its usage quantity is calculated and is respectively by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids:
Ozone: 0.5-5 kilogram
Hydrogen peroxide (30%): 1-5 kilogram
Peracetic Acid (30%): 0.5-5 kilogram.
3. according to the extracting method of humic acids in the described alcohol tank liquid fermented sludge of claim 1, it is characterized in that: in the molten process of alkali, use sodium hydroxide, sodium carbonate, ammoniacal liquor as the molten reagent of alkali, its usage quantity is calculated and is respectively by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids:
Sodium hydroxide: 5-20 kilogram
Sodium carbonate: 5-20 kilogram
Ammoniacal liquor (25%): 5-30 kilogram.
4. according to the extracting method of humic acids in the described alcohol tank liquid fermented sludge of claim 1, it is characterized in that: in the carboxymethylation process, use sodium chloroacetate as carboxymethylation reagent, its usage quantity is calculated and is added sodium chloroacetate 0.1-3 kilogram by the alcohol tank liquid fermented sludge amount containing 100 kilograms of solids.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861173A (en) * | 2015-06-02 | 2015-08-26 | 福建师范大学福清分校 | Method for extracting fulvic acid |
| CN105885061A (en) * | 2016-03-31 | 2016-08-24 | 常州大学 | Method for extracting humic acid from biogas residues of pig farm |
| CN107353415A (en) * | 2017-06-27 | 2017-11-17 | 界首市沃土生物科技有限公司 | A kind of method of river silt detritus acid high efficiency extraction |
| CN112778051A (en) * | 2021-03-05 | 2021-05-11 | 元亨启正生物科技有限公司 | Acid-alkali-adjustable high-nitrogen suspension type humic acid liquid fertilizer and preparation method thereof |
| CN115286460A (en) * | 2022-07-15 | 2022-11-04 | 贵州大学 | Method for preparing humic acid type micro-fertilizer by utilizing winery sludge and electrolytic manganese residues |
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| CN102241539A (en) * | 2010-05-11 | 2011-11-16 | 林光德 | Production method of special tea tree fertilizer |
| CN102524594A (en) * | 2012-02-14 | 2012-07-04 | 中国水产科学研究院淡水渔业研究中心 | Benthic bait biological culture medium for breeding ricefield eels and using method thereof |
| US8440241B1 (en) * | 2011-09-23 | 2013-05-14 | Paul Grady | Alcohol metabolizing assisting supplement |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102206115A (en) * | 2010-03-31 | 2011-10-05 | 于雷 | Production method for special fertilizer for fruit trees |
| CN102241539A (en) * | 2010-05-11 | 2011-11-16 | 林光德 | Production method of special tea tree fertilizer |
| US8440241B1 (en) * | 2011-09-23 | 2013-05-14 | Paul Grady | Alcohol metabolizing assisting supplement |
| CN102524594A (en) * | 2012-02-14 | 2012-07-04 | 中国水产科学研究院淡水渔业研究中心 | Benthic bait biological culture medium for breeding ricefield eels and using method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861173A (en) * | 2015-06-02 | 2015-08-26 | 福建师范大学福清分校 | Method for extracting fulvic acid |
| CN105885061A (en) * | 2016-03-31 | 2016-08-24 | 常州大学 | Method for extracting humic acid from biogas residues of pig farm |
| CN107353415A (en) * | 2017-06-27 | 2017-11-17 | 界首市沃土生物科技有限公司 | A kind of method of river silt detritus acid high efficiency extraction |
| CN112778051A (en) * | 2021-03-05 | 2021-05-11 | 元亨启正生物科技有限公司 | Acid-alkali-adjustable high-nitrogen suspension type humic acid liquid fertilizer and preparation method thereof |
| CN115286460A (en) * | 2022-07-15 | 2022-11-04 | 贵州大学 | Method for preparing humic acid type micro-fertilizer by utilizing winery sludge and electrolytic manganese residues |
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Inventor after: Jin Xiaoli Inventor after: Xie Mingsen Inventor after: Su Yurong Inventor after: Xie Haiquan Inventor after: Liu Xiaodi Inventor after: Wang Fan Inventor before: Xie Haiquan Inventor before: Jin Xiaoli Inventor before: Xie Mingsen Inventor before: Liu Xiaodi Inventor before: Wang Fan |
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