CN102532204A - Clean high-value utilization method for preparing fulvic acid and fertilizers by using papermaking black liquor - Google Patents
Clean high-value utilization method for preparing fulvic acid and fertilizers by using papermaking black liquor Download PDFInfo
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Abstract
The invention relates to a clean high-value utilization method for preparing fulvic acid and fertilizers by using papermaking black liquor, which comprises the following steps of: carrying out alkaline pulping through taking various straws or woods as raw materials, concentrating and evaporating the obtained black liquor, adopting peroxyacetic acid and hydrogen dioxide solution as oxidants and fully agitating and reacting with the strong black liquor for 30-90 minutes at a temperature of 50-90 DEG C to degrade. The pH of reaction liquid is adjusted to 4-6 by acid and the reaction liquid is then subjected to solid-liquid separation to obtain fulvic acid solution. Separated precipitates are added into raw material leftovers and activated sludge for mixing to prepare organic fertilizers or are then added into the organic fertilizers to prepare organic-inorganic compound fertilizers. The papermaking black liquor can be fully subjected to resource utilization, so that not only is the pollution caused by the black liquor eliminated, but also the black liquor is converted into the fulvic acid with high value added; and meanwhile, other solid wastes produced in the papermaking process are prepared into fertilizers, so that the clean high-value utilization of waste resources is realized.
Description
Technical field
The present invention relates to the method for the recycling of trade effluent, relate in particular to the higher value application technology that black liquid prepares xanthohumic acid and fertilizer.
Technical background
China is the big country of production of paper products and consumption, and China's paper product consumption was 7,935 ten thousand tons in 2008, occupied the second place of the world.Because China's Forest Resources is poor, annual a large amount of wood pulp and the waste paper of import that needs, about 47% will rely on import in the paper overall consumption.And the annual wastewater discharge of paper industry has reached 36.7 hundred million tons, accounts for 17.0% of national emphasis statistics enterprise wastewater total emission volumn, and 159.7 ten thousand tons of COD quantity dischargeds account for 32.4% of national COD total emission volumn.Seriously polluted paper industry the sound and sustained development that influences of waste liquid.Therefore the paper industry urgent problem is to administer black liquor pollution.
The ordinary method of the processing black liquid that adopts both at home and abroad at present, mainly contains technology such as alkali recovery technology, lignin acidizing separation technology, electroosmose process, wet oxidation process, Flocculating Settling Technology.Wherein alkali recovery technology is the main method that domestic large-scale papermaking enterprise adopts, but because this technology exists the equipment input bigger, the shortcoming that operation cost is high.Major cause is the siliceous height of straw pulp black liquor, and viscosity is big, and thermal value is low, produces a large amount of water glass after the causticization, and the recovery of sodium hydroxide is low.Large-scale papermaking enterprise is suitable to be adopted so have only, but still can only keep low profit operation.
Therefore,, must fully utilize, especially will carry out high-valued utilization it for further handling a large amount of black liquids.Common method of comprehensive utilization has exploitation compoiste fertilizer, synthesizing efficient water reducer, makes the coal sulfur-fixating combustion promoter that looses, prepares composite oil-displacing agent, makes retarding water reducer etc. at present.These products are mainly used in fields such as agricultural, light industry.
The principle of black liquor and development as resource utilization is that product has the higher market requirement and higher added value is arranged.But therefore problems such as added value is low, narrow in application range, slack market, market digestion ability difference that these product ubiquities of developing at present are difficult to fall a large amount of black liquor complete digestiones.Organism in the black liquor is converted into the effective way that humic acids then is the black liquor higher value application.
Humic acids is decomposition and the conversion of plant and animal residues through mikrobe; And the formed composition of geochemical a series of process, structure, all inhomogenous multiple organic monoacid mixture of molecular size; Contain multiple functional group, extensively be present in the physical environments such as soil, coal, water body.Humic acids has increases soil fertility, enhancing crop resistance, improves effect such as quality of agricultural product, and therefore, humic acid fertilizer has broad application prospects in the Organic farming production process.
Humic acids can be divided into xanthohumic acid, ulmic acid and brown rot acid etc.Wherein xanthohumic acid is because molecular weight is little, and active high, application prospect is good, and is especially in agricultural, also higher like the value in growth regulator and the fertilizer application.Spray xanthohumic acid the stomatal conductance of plant is had the obvious suppression effect, nursery stock photosynthesis is had promoter action, can effectively stop the decline of leaf water potential.
The preparation of xanthohumic acid at present is to adopt following several method.
1. ion exchange method prepares xanthohumic acid.Xanthohumic acid in the weathered coal, mainly the metal-salt form with calcium, magnesium exists.Ion exchange method is with the H in the acid-type ion-exchange resin
+Replace the metals ion in the Xanthohumate and discharge xanthohumic acid.
2. electroosmose process prepares xanthohumic acid.The xanthohumic acid early-products is purified with electroosmose process, promptly under effect of electric field, will further separate with xanthohumic acid bonded metals ion with the complex compound form.
3. fermentation method prepares xanthohumic acid.Utilize the fermentative Production xanthohumic acid to achieve success, mainly in foliage fertilizer, be used widely.With materials such as agricultural byproduct and wood chips, be equipped with nutritive ingredients such as an amount of nitrogen, phosphorus, potassium, through biofermentation technique, obtain containing the fermentation material of xanthohumic acid, then through leaching, from fermentation material, extract and obtain.
These methods mainly are from raw materials such as brown coal, peat or biomass, to extract, and general problem is that extraction process is complicated, and the time is long, and efficient is low.
Solid substance in the black liquid, organism accounts for 65～70%, mainly is made up of xylogen and semicellulose and materials such as degradation product in various degree thereof.Xylogen is the polymer substance that is formed by phenylpropyl alcohol alkane unit, produces a large amount of middle small-molecule substances through the highly basic effect, and a lot of reactive group.Also have other organism such as carbohydrate and organic acid etc.Black liquid is carried out oxidizing reaction with strong oxidizer; Can be with the further degraded and reactive group carried out modification of xylogen and semicellulose macromole; Obtain xanthohumic acid, the treatment time is short, transformation efficiency is high, makes pollutent maximum in the paper industry realize higher value application.
Simultaneously, the middle-stage wastewater of the generation in pulp washing and bleaching process can produce a large amount of active sludge through after the biochemical treatment.The scrap stock that produce after these active sludge and the raw material pre-treatment are enormous amount but the solid waste that is very difficult to handle in the papermaking enterprise equally.If the throw out that produces in active sludge and the xanthohumic acid preparation, and the mixing of paper making raw material scrap stock are through promptly can be used to production organic solid fertilizer after the fermentation of becoming thoroughly decomposed.
The added value of xanthohumic acid in agricultural application is high, and fertilizer is widely used in the agricultural in modern times, and consumption is huge.Black liquid is converted into xanthohumic acid and fertilizer when can eliminate black liquor pollution rapidly, realizes the profit maximization of utilization of waste material, produce good economic benefit and environmental benefit.
Summary of the invention
The purpose of this invention is to provide a kind of method that is directed against the higher value application of black liquid.This method utilizes the method for chemical oxidation to handle the technology that black liquor prepares xanthohumic acid and organic fertilizer.Not only can thoroughly eliminate the pollution of black liquid, obtain higher xanthohumic acid of added value and widely used fertilizer simultaneously.
Carrying out papermaking in China with stalk is one of best mode of stalk resource realization higher value application, but must realize the cleaning recycling of whole black liquor.Since produce the minimum black digestion liquid that produces more than 10 tons of paper pulp per ton, the black liquor enormous amount, and accumulating and processing cost are high.So must take number of ways and means to its comprehensive treating process, and should can produce the product of multiple different shape, could could ensure that total system turns round efficiently in time with black liquor utilization and digestion according to the actual market needs.
Black liquor is when getting utilization, for further improving the added value of black liquor, to the staple in the black liquor---and xylogen and semicellulose adopt the method for chemical oxidation to prepare xanthohumic acid.
Peracetic Acid and H are adopted in the chemical oxidation degraded
2O
2Oxidative degradation obtains crop is had the xanthohumic acid of good stimulating growth effect.
Peracetic Acid compares H in these two kinds of strong oxidizers
2O
2Have stronger oxidisability, not only can effectively kill various viruses, and the product that obtains after the Peracetic Acid oxidation is water and carbonic acid gas, non-environmental-pollution.
For realizing greatest contamination thing---the purpose of the higher value application of black liquor and solid waste in the paper-making process, the invention provides a kind of is the method that main raw material prepares xanthohumic acid and fertilizer with the black liquid.
A kind of black liquid prepares the higher value application method of xanthohumic acid and fertilizer; It is characterized in that; Prepare xanthohumic acid and organic fertilizer with strong oxidizer chemical oxidation degraded black liquid, this method technical process is: after black liquid is carried out pre-treatment, adopt strong oxidizer to carry out the chemical oxidation degraded; Obtain xanthohumic acid after the acidifying again; Obtain xanthohumic acid solution through separating, and deposition and paper making raw material scrap stock, active sludge after separating prepare the solid organic fertilizer material, or further add mineral manure and prepare organic-inorganic composite fertilizer.
It is that raw material carries out the black liquor that alkaline process obtains that said black liquid is meant with various stalks or timber.
The pretreatment process of said black liquid is meant black liquor is carried out the concentrated black liquid that evaporation concentration to solid holdup is 30-45%.
Strong oxidizer is Peracetic Acid or H
2O
2Solution.
The volume ratio of strong oxidant solution and concentrated black liquid is 1: 7～20.
In concentrated black liquid, add strong oxidizer abundant stirring reaction under 50～90 ℃ and carried out the chemical oxidation degraded in 30～90 minutes.
The used acid of acidification step is phosphoric acid or nitric acid, reduces pH to 4～6.
Separation after the acidifying adopts high speed centrifugation or vacuum filtration that supernatant liquid xanthohumic acid solution and deposition are separated.
Said paper making raw material scrap stock are meant that the scrap stock that raw materials such as stalk or timber are obtained in the alkaline process pre-treatment are ground into the particle of 1～5mm, or the dust when collecting raw material crushing.
Described method for preparing fertilizer is the throw out after xanthohumic acid is extracted; Mix with the active sludge behind the paper making raw material scrap stock of pulverizing, the biological treatment papermaking midcourse wastewater; The fermentation of becoming thoroughly decomposed earlier; And then obtain SOLID ORGANIC fertilizer through dry and granulation, perhaps add mineral manure again and prepare organic-inorganic composite fertilizer.
The present invention has following characteristics:
1. be the pollution that feedstock production xanthohumic acid and fertilizer can thoroughly be eliminated black liquid with the black liquid, the greatest contamination thing of paper industry is got utilization, can also handle solid waste such as a large amount of scrap stock and active sludge simultaneously.
2. the added value of xanthohumic acid is high, and fertilizer is extensive in agricultural application, and demand is big, and their combination will help in time and efficiently transforming of black liquor.
3. the black liquor transform mode adopts strong oxidizer, has the efficient height, and the time is short, the characteristics that temperature is low.
4. oxygenant adopts Peracetic Acid and H
2O
2, they not only have good oxidation susceptibility, are decomposed into water, carbonic acid gas or oxygen after the reaction simultaneously, and no chemical residual has good environmental-protection function.This technology belongs to green cleaning technique.
The present invention can make paper industry the greatest contamination thing---black liquid gets utilization fully, thoroughly eliminate pollution to environment, have good benefits in environment; Simultaneously, the xanthohumic acid of the high added value for preparing with have the organic fertilizer or the organic-inorganic composite fertilizer of soil improvement action, also can produce good economic benefit, the Sustainable development of agricultural is had promoter action.
Description of drawings
Fig. 1 is a techniqueflow of the present invention.
Embodiment
Further describe the present invention below in conjunction with embodiment.
Embodiment 1:
Straw is cut into shaft-like, scrap stock are ground into the material below the 5mm fully.Straw adds sodium hydroxide and carries out boiling, and black liquor is extruded from paper pulp.Rare black liquor evaporates earlier, is concentrated into solid holdup and is 40% concentrated black liquid.In concentrated black liquid, add 30% peracetic acid soln, the volume ratio of peracetic acid soln and concentrated black liquid is 1: 20, and fully mixing constantly is stirred in 60 ℃ of following insulation reaction.Behind the question response 50 minutes, in reaction solution, add phosphoric acid, stirring and evenly mixing is regulated pH to 4.5.After leaving standstill mixed solution is carried out vacuum filtration and obtain supernatant, the collecting precipitation thing.Xanthohumic acid content is 32.4% in the supernatant.
With papermaking midcourse wastewater through biological treatment after the active sludge that obtains with separate after throw out, the scrap stock thorough mixing after pulverizing, the fermentation of becoming thoroughly decomposed earlier, the urea, monoammonium phosphate and the vitriolate of tartar that add after the pulverizing mix again.Through granulation, further after the drying, obtain organic-inorganic composite fertilizer.The total nutrient of this fertilizer is 32.7%, and organic content is 20.8%.
Embodiment 2:
Rice straw is carried out pre-treatment, obtain neat shaft-like paper making raw material, scrap stock are pulverized fully.The rice bar is carried out alkaline process, separate the black liquor that obtains and get in the preparation jar.Black liquor is carried out the concentrated black liquid of concentration and evaporation to solid holdup 35%.In concentrated black liquid, add 30% superoxol, superoxol and concentrated black liquid volume ratio be 1: 10, mix and then under 70 ℃, carried out stirring reaction 1 hour, obtain filbert liquid.In liquid, add phosphoric acid and regulate pH to 5.4.Through high speed centrifugation, the precipitate and separate in the liquid is come out.Xanthohumic acid content is 18.3% in the clarified liq.
With the active sludge behind isolated deposition and the biological treatment papermaking midcourse wastewater, and rice bar scrap stock thorough mixing, to bank up naturally and carry out fermentation maturity, the fermentation of becoming thoroughly decomposed through 18 days just can obtain organic fertilizer through super-dry and granulation again.Organic content reaches more than 45.2%, and total nutrient content has reached 5.8%.
Embodiment 3:
Cotton stalk is delivered to feeding screw through gas delivery system after being broken into the fragment of 0.5～2cm with special-purpose kibbler, gets into rotary spherical digester again and carries out boiling.The fine dust and the broken end of scrap stock that produce when raw material is handled are collected by cyclonic separator.
Cotton stalk adopts Pottasium Hydroxide to carry out boiling, and the chemical constitution of black liquor is after the boiling: solid holdup 11.2%, K
2O4.7%, N 1.2%.It is 30% concentrated black liquid that black liquor is carried out concentration and evaporation to solid holdup, in the concentrated black liquid of 8 volumes, adds the superoxol of 1 volume.Mixed solution is heated to 85 ℃, simultaneously abundant stirring reaction 50 minutes.In mixed solution, adding nitric acid adjusting pH is 4.2, produces partly precipitated this moment.Solution is carried out vacuum filtration obtain clarifying xanthohumic acid solution, xanthohumic acid content is 21.4%.
Scrap stock and active sludge thorough mixing after the filter cake that is separated to, cotton stalk handled through after 25 days become thoroughly decomposed, add urea and diammonium phosphate again, carry out granulation and drying then, obtain organic-inorganic composite fertilizer.Its staple is an organic matter 16.9%, N17.0%, P
2O
52.4%, K
2O 4.8%.
Embodiment 4:
The living poplar of speed is cut into sheet to be delivered to rotary spherical digester and carries out alkaline cooking.Handle wood pulp with acroll press washer after the boiling, it is 42% concentrated black liquid that the black digestion liquid that obtains is evaporated to concentration.In concentrated black liquid, add 30% peracetic acid soln, the ratio of peracetic acid soln and concentrated black liquid is 1: 12, behind the thorough mixing, under 65 ℃, reacts, and reacts to obtain brown liquid after 1.2 hours.In liquid, add phosphoric acid and make its pH reduce to 6.0, through high speed centrifugation, the precipitate and separate in the liquid is come out, obtain clarifying liquid, the xanthohumic acid content of liquid is 38.4%.
Active sludge and above-mentioned throw out are mixed, and the fermentation 20 days of becoming thoroughly decomposed earlier just can obtain organic fertilizer through super-dry and granulation again.Organic content reaches 55.2%, and total nutrient content reaches 6.3%.
Claims (10)
1. a black liquid prepares the higher value application method of xanthohumic acid and fertilizer; It is characterized in that; Prepare xanthohumic acid and fertilizer with strong oxidizer chemical oxidation degraded black liquid; This method technical process is: after black liquid is carried out pre-treatment, adopt strong oxidizer to carry out the chemical oxidation degraded, further again acidifying is after separation obtains xanthohumic acid solution; Deposition after separating then is mixed with SOLID ORGANIC fertilizer with scrap stock, the active sludge of paper making raw material, or adds mineral manure again and prepare organic-inorganic composite fertilizer.
2. method according to claim 1 is characterized in that, it is that raw material carries out the black liquor that alkaline process obtains that said black liquid is meant with various stalks or timber.
3. method according to claim 1 is characterized in that, said black liquid pretreatment process is meant black liquor is carried out the concentrated black liquid that evaporation concentration to solid holdup is 30-45%.
4. method according to claim 1 is characterized in that, strong oxidizer is Peracetic Acid or H2O2 solution.
5. method according to claim 1 is characterized in that, the volume ratio of strong oxidant solution and concentrated black liquid is 1: 7～20.
6. method according to claim 1 is characterized in that, in concentrated black liquid, adds strong oxidizer abundant stirring reaction under 50～90 ℃ and carries out the chemical oxidation degraded in 30～90 minutes.
7. method according to claim 1 is characterized in that, the used acid of acidification step is phosphoric acid or nitric acid, reduces pH to 4～6.
8. method according to claim 1 is characterized in that, the separation after the acidifying adopts high speed centrifugation or vacuum filtration that supernatant liquid xanthohumic acid solution and deposition are separated.
9. method according to claim 1 is characterized in that, the scrap stock of said paper making raw material are meant that the scrap stock that raw materials such as stalk or timber are obtained in the alkaline process pre-treatment are ground into the particle of 1～5mm, or the powder when collecting raw material crushing.
10. method according to claim 1; It is characterized in that; Described method for preparing fertilizer is that the throw out after xanthohumic acid is extracted mixes with the paper making raw material scrap stock of pulverizing, the active sludge of biological treatment papermaking midcourse wastewater generation, the fermentation of becoming thoroughly decomposed earlier, and then carry out drying and granulation obtains SOLID ORGANIC fertilizer; Perhaps add mineral manure again, the preparation organic-inorganic composite fertilizer.
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Cited By (12)
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|---|---|---|---|---|
| CN102603813A (en) * | 2012-02-14 | 2012-07-25 | 西北农林科技大学 | Method for producing insect-resistant fulvic acid by using tobacco waste |
| CN105601381A (en) * | 2015-12-24 | 2016-05-25 | 稼禾生物股份有限公司 | Slow-release nutritional fertilizer using black liquid as raw material and preparation method of slow-release nutritional fertilizer |
| CN105601350A (en) * | 2015-12-31 | 2016-05-25 | 南宁太美生物科技有限公司 | Method for preparing organic nutrient solution by processing and biologically fermenting organic wastes |
| CN106432368A (en) * | 2016-09-23 | 2017-02-22 | 山东农业大学 | Method of efficiently extracting fulvic acid from papermaking black liquid |
| CN107141032A (en) * | 2017-05-26 | 2017-09-08 | 沈阳环境科学研究院 | A kind of method of high concentration corn fermentation waste liquid deep dehydration |
| CN108179650A (en) * | 2017-12-05 | 2018-06-19 | 白博 | A kind of non-wood fiber wheat straw production technology using black liquor of pulp making production Yellow humic acid fertilizer |
| CN108456070A (en) * | 2018-04-09 | 2018-08-28 | 吕莉 | A kind of water-holding slow-release type nitrogenous fertilizer and preparation method thereof |
| CN109701450A (en) * | 2019-02-21 | 2019-05-03 | 天水师范学院 | It is a kind of to produce stalk-starch conversion biomass-polycarboxylic acids compound water-reducing agent process system |
| CN111549077A (en) * | 2020-05-09 | 2020-08-18 | 山东省科学院能源研究所 | Method for producing organic acid and converting methane by regulating and controlling degradation of silage straws by using black liquor |
| CN111646825A (en) * | 2020-05-21 | 2020-09-11 | 阿拉尔市中泰纺织科技有限公司 | Method for preparing organic fertilizer by using papermaking black liquor |
| CN116396110A (en) * | 2023-05-05 | 2023-07-07 | 西北农林科技大学 | Method for preparing chelate organic zinc fertilizer by using paper pulp black liquor |
| CN117430826A (en) * | 2023-08-19 | 2024-01-23 | 蚌埠星河秸秆生物科技有限公司 | Method for producing sugar and co-producing potassium fulvate and fulvic acid by using straw |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603813A (en) * | 2012-02-14 | 2012-07-25 | 西北农林科技大学 | Method for producing insect-resistant fulvic acid by using tobacco waste |
| CN105601381A (en) * | 2015-12-24 | 2016-05-25 | 稼禾生物股份有限公司 | Slow-release nutritional fertilizer using black liquid as raw material and preparation method of slow-release nutritional fertilizer |
| CN105601350A (en) * | 2015-12-31 | 2016-05-25 | 南宁太美生物科技有限公司 | Method for preparing organic nutrient solution by processing and biologically fermenting organic wastes |
| CN106432368A (en) * | 2016-09-23 | 2017-02-22 | 山东农业大学 | Method of efficiently extracting fulvic acid from papermaking black liquid |
| CN107141032A (en) * | 2017-05-26 | 2017-09-08 | 沈阳环境科学研究院 | A kind of method of high concentration corn fermentation waste liquid deep dehydration |
| CN108179650A (en) * | 2017-12-05 | 2018-06-19 | 白博 | A kind of non-wood fiber wheat straw production technology using black liquor of pulp making production Yellow humic acid fertilizer |
| CN108456070A (en) * | 2018-04-09 | 2018-08-28 | 吕莉 | A kind of water-holding slow-release type nitrogenous fertilizer and preparation method thereof |
| CN109701450A (en) * | 2019-02-21 | 2019-05-03 | 天水师范学院 | It is a kind of to produce stalk-starch conversion biomass-polycarboxylic acids compound water-reducing agent process system |
| CN109701450B (en) * | 2019-02-21 | 2021-09-14 | 天水师范学院 | Process system for producing straw-starch modified biomass-polycarboxylic acid composite water reducing agent |
| CN111549077A (en) * | 2020-05-09 | 2020-08-18 | 山东省科学院能源研究所 | Method for producing organic acid and converting methane by regulating and controlling degradation of silage straws by using black liquor |
| CN111549077B (en) * | 2020-05-09 | 2022-03-29 | 山东省科学院能源研究所 | Method for producing organic acid and converting methane by regulating and controlling degradation of silage straws by using black liquor |
| CN111646825A (en) * | 2020-05-21 | 2020-09-11 | 阿拉尔市中泰纺织科技有限公司 | Method for preparing organic fertilizer by using papermaking black liquor |
| CN116396110A (en) * | 2023-05-05 | 2023-07-07 | 西北农林科技大学 | Method for preparing chelate organic zinc fertilizer by using paper pulp black liquor |
| CN116396110B (en) * | 2023-05-05 | 2024-10-18 | 西北农林科技大学 | Method for preparing chelated organic zinc fertilizer special for wheat by using paper pulp black liquor |
| CN117430826A (en) * | 2023-08-19 | 2024-01-23 | 蚌埠星河秸秆生物科技有限公司 | Method for producing sugar and co-producing potassium fulvate and fulvic acid by using straw |
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Application publication date: 20120704 |