CN1436895A - Comprehensive utilization method of pulping potash black liquor in paper-making process - Google Patents
Comprehensive utilization method of pulping potash black liquor in paper-making process Download PDFInfo
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- CN1436895A CN1436895A CN 02104838 CN02104838A CN1436895A CN 1436895 A CN1436895 A CN 1436895A CN 02104838 CN02104838 CN 02104838 CN 02104838 A CN02104838 A CN 02104838A CN 1436895 A CN1436895 A CN 1436895A
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Abstract
The comprehensive utilization method of pulping potash black liquor in paper-making process can eliminate pollution, low pollution treating cost and result in high economic benefit. The method includes extracting pulp-making black liquor, neutralizing its alkali with H3OP4 and HNO3 to prepare liquid fertilizer; regulating nutrients, pH regulation and fermentation to produce alcohol or feed protein, mixing the residue with other fertilizer, trace elements, organic matter, etc. to prepare composite fertilizer; adding azotobacteria, phosphate decomposing bacteria, etc. and fermentation to prepare liquid biological fertilizer or inoculating agent; and solid-liquid separation to prepare liquid fertilizer, solid fertilizer or composite fertilizer.
Description
Technical field
The present invention relates to the method for comprehensive utilization and the fertilizer production method of the processing of paper-making pulping black liquor, particularly pulping potash black liquor.
Background technology
Make process of pulp with alkaline aqueous solution processing plant fiber material and be called soda pulping process.Outside the present soda pulping process delime method, employed alkaline chemical mainly is the soda class, as: NaOH, Na
2S, Na
2CO
3Deng.
After the soda pulping process, there are 50% fibrous raw material and most alkaline matter to be dissolved in the cooking liquor approximately, become black liquor.Black liquor is the pollution sources of paper industry maximum, domestic and international large-scale papermaking enterprise all is to carry out black liquor treatment and alkali recovery with the traditional combustion method at present, this has not only significantly reduced the consumption of caustic soda and akali sulphide in the slurrying, also is to carry out comprehensive utilization, reduces the important measures of polluting.
But, tradition alkali recovery technology equipment complexity, investment are greatly, it is reported one the cover soda recovery unit generally need invest more than 3,000 ten thousand yuans, and its day-to-day operation expense is also very high, the cost that the paper plant of daily output 75～100t slurry reclaims alkali is up to 2671 yuan/t alkali, and the market price of NaOH only is 1800 a yuan/t alkali.Therefore the numerous all unable alkali that carries out of little factory of China reclaims at present, but with directly discharging or discharging after diluting of black liquor, causes the especially severe contamination in waters of environment.The a large amount of middle-size and small-size papermaking enterprise shutdown and bankruptcy of China have been caused because of a black liquor treatment difficult problem at present.Reclaim even carry out alkali, when burning, not only burnt the organic matter of preciousness in the black liquor, also can produce a large amount of pernicious gases simultaneously, cause secondary pollution with firing method.Therefore to the research and the comprehensive utilization of black liquor treatment, just become current paper industry problem anxious to be solved.
The history of black liquor of pulp making as fertilizer sources research for a long time, but owing to contain a large amount of sodium ions in the soda black liquor of pulp making, sodium is not the necessary nutrient of plant, and sodium ion enters and can cause that the salinization of soil and soil physico-chemical property worsen, and widely apply so its black liquor of pulp making and lignin fail to become fertilizer always behind the soil.And other alkali reclaiming method, as the hot method of hydrolysis, electroosmose process, counter-infiltration platen press, SO
2Acid-precipitation method, L
B-1It is also not mature enough that alkali is analysed methods such as method, ultrafiltrationmembrane process, all can not thoroughly solve the governing problem of black liquor of pulp making at present.
In order to solve the governing problem of black liquor of pulp making, also the someone has proposed all schemes of pulping potash and black liquor utilization.Because of potassium is the necessary a great number of elements of plant, so the black liquor behind the pulping potash can be made all kinds fertilizer.As being: CN86104368A at publication number, CN1167853A, the application number that the Chinese invention patent ublic specification of application of CN1206761A and the inventor submit in the recent period is: in 01143095.8 the application for a patent for invention, illustrated that not only potash replaces the possibility of soda slurrying, and proposed to utilize pulping potash black liquor to produce several schemes of fertilizer.The method of the sylvite that comprises potash, potassium sulfate and lignin sulfonic acid potassium has been proposed to reclaim in pulping potash black liquor by measures such as concentrated, oxidation, burning, dissolvings as inventor in the scheme of CN86104368A.The sylvite that reclaims has multiple use, and an example is to be used for fertilizer.But this recovery method is more loaded down with trivial details, and being used for fertilizer cost can be too high.In the scheme of CN1167853A, the inventor has proposed a kind of method of potash-black liquor recovery pulping, it comprises carries out boiling, washing, acidifying, causticization operation to plant fiber material, the cooking liquor of preparing in the cooking process adopts potash as main steaming preparation, adopt the water seal circulation theory, by black liquor of pulp making and cleaning solution being carried out in succession after acidifying and causticization handle, isolate sediment and clear liquid, sediment (being mainly lignin) can be used as compoiste fertilizer or other purposes that contains potassium, and clear liquid is used for preparing again cooking liquor.But what this invention was advocated mainly is the circulating pulp-making utilization of potash, rather than the fertilizer of potassium utilizes again.In the scheme of CN1206761A, the inventor has proposed a kind of potassium hydroxide straw pulp paper making process, black liquid need not carry out complicated processing as pollution sources in this technology, but directly dispatches from the factory through the compoiste fertilizer that concentrates, potassium, nitrogen, phosphorus are rich in conduct after neutralization, preparation, dry, the packing.The inventor has proposed a kind of method of utilizing pulping potash black liquor to produce fertilizer in this scheme, and method is simple, and cost is low, promotes easily, and the improvement that solves the potash black liquor is had certain meaning.But in this scheme since the inventor in and the acid of black liquor alkalescence do not offer some clarification on, therefore can make the fertilizer that utilizes this method to produce occur some problems qualitatively, and its cost is improved, as when with in sulfuric acid and the hydrochloric acid and the time, make and introduce a large amount of useless and harmful chlorion and sulfate ions in the fertilizer, and fertilizer cost is improved.This method does not make full use of the glycan class material in the black liquor and other low molecule type organic matter simultaneously, and the fertilizer variety of production is more single and elementary, contains a large amount of organic substances that do not become thoroughly decomposed etc. in the fertilizer, and using at that time may be not unfavorable to crop.
Above-mentioned pulping potash is made fertilizer with its black liquor of pulp making, solves the various technical schemes of the pollution control of black liquor of pulp making, up to the present all fails effectively to promote, and this has reflected the deficiency of these schemes to a certain extent, as: 1. cost is too high; 2. its quality of the fertilizer of making and fertilizer efficiency are not good enough; 3. utilize mode few, kind is single, is difficult to handle in one way for a large amount of black liquor of numerous paper plants.Therefore, have only the method for utilizing of seeking more potash black liquor, reducing cost just to make pulping potash and potash black liquor treatment and comprehensive utilization be promoted, and produces certain economic benefits.
The application number that is proposed before this by the inventor is 01145502.0, name is called the Chinese invention patent application of " utilizing the acid and alkali substance materials to process vegetal to produce the method for fertilizer ", its principle mainly is the residual alkaline degradation lignin that utilizes in the pulping potash black liquor, promotes that organic matter becomes thoroughly decomposed so that produce organic fertilizer fast.
The present invention is based on following thinking:
Plant fiber material is mainly formed with cellulose, hemicellulose, lignin, and the average content of these three kinds of compositions is respectively in broad-leaved wood: 45%, 34%, 21%; In needle timber, be respectively: 43%, 28%, 29%.The content of nitric acid ethanol cellulose, poly-pentose (hemicellulose), lignin is generally in the straw or like vegetable, straw stem stalk: 36%, 24%, 27%; Wheat straw stem stalk: 40%, 25%, 22%; Reed: 44%, 21%, 21%; Bagasse: 42%, 23%, 19%; Mao bamboon: 45%, 21%, 30%.The purpose of slurrying is the lignin that will dissolve in the fibrous raw material, and cellulose is not damaged and dissociates pulping each other, extracting cellulose to greatest extent, and hemicellulose is dissolved in the cooking liquor by basic hydrolysis and alkaline peeling reaction in digestion process and partly precipitated or be adsorbed in the paper pulp.Fibrous raw material is generally about 50% through the pulp yield after the boiling, wherein be mainly outside the cellulose, also contain lignin and the absorption that does not remove on a small quantity or be deposited in hemicellulose on the cellulose, about in addition 50% fibrous raw material is dissolved in after the boiling in the cooking liquor, becomes the organic matter in the cooking liquor, after organic matter is analyzed in the cooking liquor, show, about 40% is lignin in the organic matter, and about 10% is the volatilization acids, and about 50% is glycan and catabolite thereof.Though do not wish that when alkaline boiling cellulose is damaged, but in fact some chemical reactions have also taken place in cellulose, its reaction mechanism mainly is: cellulose is by β-1 by many glucose molecules, the polysaccharide of 4 glucoside combinations, more stable to alkali generally speaking, but cellulose also can be degraded by modes such as alkaline peeling reaction and basic hydrolysises in alkaline digestion process.In alkaline peeling reaction, the glucose reducing end group is to the alkali instability, under high temperature, highly basic condition on the cellulose, become the fructose terminal groups earlier, become the mutation saccharic acid then, split away off from strand, so constantly carry out, the degree of polymerization of cellulose molecular chain is constantly reduced; Basic hydrolysis, be cellulose molecular chain under the effect of high temperature, highly basic, because of hydrolysis is ruptured, become two even a plurality of short molecular chain behind the long molecular chain rupture of a glucose, cellulosic degree of polymerization is reduced, and the peeling reaction chance is increased.The reaction mechanism of hemicellulose in alkaline cooking liquor mainly is: the hemicellulose molecule is not made up of a kind of glycosyl, and its molecular structure more complicated has main chain that side chain is arranged.And the contained hemicellulose of careless class, leaf wood and needlebush is also different.Hemicellulose in the straw fiber raw material mainly is poly-4-oxygen-methyl glucoside tail acid-arabinose-wood sugar; Hemicellulose mainly is poly-4-oxygen-methyl glucoside tail acid-wood sugar in the leaf wood; Hemicellulose in the needlebush mainly is polydextrose-mannose, and a spot of D-xylan class is also arranged.The common ground of various hemicelluloses is that strand is short, and side chain is arranged, and some base is unstable especially to alkali, so it is just than easier dissolving of cellulose and generation alkaline bleach liquor degradation.Its reactive mode has: 1. the alkalescence dissolving of chemical change does not take place, and wherein a part can precipitate and be adsorbed by fiber; 2. equally with cellulose carry out peeling reaction and basic hydrolysis; 3. deacetylation generates acetate, takes off the glucuronic acid base and forms salt, and demethylation becomes methyl alcohol; 4. the alkaline bleach liquor degradation product of carbohydrate can further become propyl ester and hydroxy acid (saccharinic acid and lactic acid), also has formic acid.Therefore cellulose is the same with hemicellulose in alkaline cooking all can be damaged, its final catabolite mainly is organic acids such as mutation saccharic acid, lactic acid, formic acid, acetic acid, if it is improper that conditions of cooking is grasped, the degraded of cellulose and hemicellulose will be very serious, pulp yield is reduced, and these organic acids also will consume a large amount of alkali in digestion process this is that we are undesirable.But cellulose and hemicellulose are when carrying out degradation reaction, also carrying out a reaction that opposes with peeling reaction, be cessation reaction, at present also there are some effective measures can reduce the degraded of glycan class in addition as far as possible, particularly cellulosic degraded, and xylan class hemicellulose has bigger alkali resistance than the hemicellulose of other type, a part is attracted on the cellulose when alkaline boiling, a part is dissolved in the black liquor, add to also have some not cellulose and cellulosic half catabolites of defecation in the black liquor, therefore make still to have a certain amount of glycan class material of not degrading fully in the black liquor.Especially in leaf wood and straw pulp black liquor, have a large amount of xylan class hemicelluloses and some residual cellulose and cellulosic half catabolite.These glycan class materials have all removed lignin substantially, be easy to by acid hydrolysis, or, make xylan class hemicellulose become monose such as wood sugar by cellulose and hemicellulose decomposer or its enzyme preparation degrades, make cellulose and half catabolite thereof become glucose etc.The objective of the invention is in the lignin and potassium in making full use of pulping potash black liquor, make full use of glycan and the catabolite thereof that is dissolved in the pulping potash black liquor by microbial fermentation mode, with the comprehensive utilization that reaches black liquor of pulp making and the zero-emission of black liquor of pulp making.
Multiple microorganism can utilize glucose and wood sugar to carry out alcoholic fermentation, as: saccharomyces cerevisiae, fission yeast, fermentation single cell bacterium etc. can utilize glucose to carry out alcoholic fermentation; A kind of candida utili, pipe capsule yeast, shehatae candida, the hot anaerobic bacteria of ethanol, Mucor, fusarium etc. can utilize wood sugar etc. to carry out alcoholic fermentation.Therefore, can carry out alcoholic fermentation with above-mentioned bacterium after with diluted acid or enzyme hemicellulose and residual cellulose and cellulosic half catabolite being hydrolyzed, or can produce the microorganism of cellulose and hemicellulase with above-mentioned bacterium and some, as Mixed culture such as some wood mould (this wood of lining is mould, koning trichoderma, Trichoderma viride), carry out alcoholic fermentation; And some Clostridium thermocellums etc. also but DIRECT UTILIZATION OF CELLULOSE, cellobiose etc. carry out alcoholic fermentation, some clostridium thermosaccharolyticums etc. can directly utilize xylan and wood sugar etc. to carry out alcoholic fermentation, but not only DIRECT UTILIZATION OF CELLULOSE and hexasaccharide material also can utilize hemicellulose and pentose class material etc. to carry out alcoholic fermentation to some hot hydrosulphuric acid clostridiums etc.; Various compoiste fertilizers are made in fermentation again after fermentation residue liquid behind the distilled spirit can be mixed with organic and other nutrient.
Multiple glycan class material, organic acid and other low molecule organic matter also can be used for cultivating fermenting and producing feed mycoprotein such as cellulomonas cartae, molten fiber cupreum, koning trichoderma, Trichoderma viride, Paecilomyces varioti, Aspergillus oryzae, some heat-resisting actinomyces; Or with co-incubation such as above-mentioned bacterium and Candida, geotrichum candidum production feed mycoprotein; Fermentation again after fermentation residue liquid behind the extraction feed mycoprotein can be mixed with organic and other nutrient also can be made into various organic composite fertilizers.
Soil beneficial microbes such as multiple nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria can utilize glucose, wood sugar, mannose, arabinose, various organic acid and other low molecule organic matter etc. as carbon source and energy breeding and fixed nitrogen simultaneously, therefore can utilize the potash black liquor to carry out the cultivation of mentioned microorganism, or, produce high-quality bio-feritlizer and bio-fertilizer Inoculant with some cellulose and hemicellulose bacterium or its enzyme preparation and mentioned microorganism co-incubation.
With spentsulfiteliquor also is that acid polishing effluent and prehydrolysis waste liquid fermenting and producing alcohol, D-sorbite, fodder yeast, furfural, wood sugar, xylitol, trihydroxy glutaric acid etc. have been used for actual production.Because present soda pulping process mainly is to utilize soda such as NaOH, black liquor is strong basicity after the slurrying, and is too high with its sodium salt content of acid neutralization back, because the hyperosmosis of sodium salt and sodium can't carry out biofermentation and fertilizer production to the murder by poisoning of soil etc.And substitute soda slurrying, and use H with potash
3PO
4And HNO
3In and behind the residual alkali in the black liquor, sodium salt wherein becomes sylvite, and has introduced plant and the necessary nitrogen phosphorus potassium three big elements of microorganism, can become the comprehensive fertilizer of nutrient, and do not contain in the fertilizer unnecessary invalid and the SO of certain harm arranged
4 -2And Cl
-1, overcome K
2SO
4, problem such as the physiological phenomenon of chemical potash fertilizer such as KCL and salt damage; If again black liquor pH, salinity and various trace element and carbon source material etc. are suitably allocated, also can become the good culture medium of multiple microorganism, be used for various fermentations and bio-feritlizer production.
I am another patent of application in the recent period: " utilizing the acid and alkali substance materials to process vegetal to produce the method for fertilizer " (application number: 01145502.0), need a large amount of bio-fertilizer liquid inoculation agent when producing organic/inorganic/bio-fertilizer, need the obtaining liq culture medium when producing liquid bio fertilizer, need a large amount of water, inorganic salts especially potassium phosphate and glucide, and utilize the liquid inoculation agent of this patent production just can be connected with my enforcement of last patent.
It is reported that potassium resource in the world is abundanter, explored commercial reserves is 200 * 10
8T K
2More than the O.1987/1988 year in the world the sylvite total output reach 3150.8 * 10
4T, but wherein 2735 * 10
4T directly uses as potash fertilizer.Utilize in the mode this, this precious resources of potassium refines, processes through human exploitation, only through once utilizing (directly as fertilizer sources) just to return in nature again, this mode of utilizing is too simple, do not reach the recycling of resource, is actually uneconomical not environmental protection.
Substitute the soda pulping and paper-making with potash, the black liquor that produces is used for microbial fermentation earlier, be used further to produce fertilizer, not only make valuable potassium resource reach the repeatedly purpose of recycling, and the glycan class material in the black liquor is also utilized, lignin in the black liquor both can be used as binding agent or the excipient that organic fertilizer also can be used as fertilizer, and lignin also can be used for other field simultaneously.Though the price of potash is higher than soda, but pulping potash black liquor need not be administered, and can carry out recycling, small investment, cost are low, not only produced paper pulp, but also can pass through the sale of alcohol, feed mycoprotein, fertilizer and the exploitation of lignin product, obtain further profit, non-secondary pollution, therefore overall benefit is considerable, especially be fit to the Joint Production of medium and small papermaking enterprise, and reach the production nearby of fertilizer and sale nearby, solve surplus rural labor force's employment and agricultural wastes simultaneously and utilize problem.
Along with development of times, people's life style, the mode of production and the mode of thinking are all changing, and the mode of production of agricultural is also changing, and to extensively using chemical fertilizer, the consumption of chemical fertilizer is increasing from a past applications of farmyard manure.It is reported, the 1950's, China began to execute chemical nitrogen fertilizer, begin to execute chemical phosphatic ferfilizer the sixties, the mid-1970s begins to use chemical potash fertilizer, generally uses the n-p-k three elements composite chemical fertilizer nineties, and green agriculture and organic agriculture are risen gradually at present, agricultural is to the wilderness demand of bio-fertilizer and fertilizer, for substituting soda with potash in the pulp industry, and utilize this black liquor of pulp making to make bio-fertilizer and fertilizer, providing may.
Summary of the invention
Technical problem to be solved by this invention is the black liquor treatment of paper industry, and pollution abatement reduces the pollution treatment cost and produces good economic benefit.
Its special character of the technical solution used in the present invention is: extract pulping potash black liquor, use H
3PO
4And/or HNO
3Wherein alkali is neutralized, make liquid fertilizer.
Pulping potash black liquor refers in the paper-making pulping process to comprise KOH, K
2S, K
2CO
3The black liquor that extracts after with variety of way slurrying such as chemical method, half chemical method and chemical mechanical pulpings Deng potash class chemical substance.According to the kind of producing fertilizer and the needs of processing and utilization mode thereafter, can in and before or after the residual alkali of black liquor black liquor is carried out suitably concentrating or dilution, in and the acid of the residual alkali of black liquor be H
3PO
4Or HNO
3Or both are used, and making its pH is 4～9, and best pH is 6～7, just becomes the liquid fertilizer that contains two or three a great number of elements.
Since contain a certain amount of glycan class material, organic acid substance and other low molecular compound in the aforesaid liquid fertilizer, very unfortunate without fully oxidation, fermentation and utilization; And direct as fertilizer sources, can produce some reducing substanceses harmful during improper use to crop; This fertilizer moisture height simultaneously, active ingredient is low, the cost of transportation height.Therefore preferably carry out making fertilizer efficiency and the higher fertilizer of quality after following further utilization and the processing.
One of scheme of further utilizing and processing is: described liquid fertilizer carries out alcoholic fermentation after nutrient allotment and pH adjustment; Fermentation residue liquid remaining behind the distilled spirit is made composite fertilizer through adding nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or organic (fertilizer) and/or pulping potash black liquor and/or microbial inoculum after fermentation.
The further allotment of described nutrient, comprise and add the required inorganic salts of microorganism, organic carbon source, vitamin, organic nitrogen or the like, after can measuring the nutrient in the described liquid fertilizer, carry out suitably concentrating or dilution, as organic carbon source deficiencies such as original glycan, can suitably add the screenings that filters out behind some pulp washings and thin assorted fiber, comprise fibroid sediment in the waste water etc.When carrying out alcoholic fermentation, in the most handy phosphoric acid and the residual alkali in the black liquor, or cooperate a small amount of nitric acid with the alcoholic fermentation bacterium, and mainly with additional nitrogens such as ammonium salt or urea.
Can carry out acid hydrolysis to the glycan class material in the black liquor with diluted acid earlier before the alcoholic fermentation, or direct incoming fiber plain and hemicellulose decomposer or its enzyme preparation and alcoholic fermentation bacterium co-incubation, carry out alcoholic fermentation.
Multiple microorganism can utilize glucose and wood sugar to carry out alcoholic fermentation, as: saccharomyces cerevisiae, fission yeast, fermentation single cell bacterium or the like can utilize glucose to carry out alcoholic fermentation; A kind of candida utili, pipe capsule yeast, shehatae candida, the hot anaerobic bacteria of ethanol, Mucor, fusarium or the like can utilize wood sugar etc. to carry out alcoholic fermentation.Therefore, can carry out alcoholic fermentation with above-mentioned bacterium after with diluted acid or enzyme cellulose and hemicellulose being hydrolyzed; Or directly can produce the microorganism of cellulose and hemicellulase with above-mentioned bacterium and some without acid hydrolysis, as some wood mould (this wood of lining is mould, koning trichoderma, Trichoderma viride) or the like Mixed culture, carry out alcoholic fermentation; Or directly carry out alcoholic fermentation with Clostridium thermocellum, clostridium thermosaccharolyticum, hot hydrosulphuric acid clostridium or the like.
The fermentation residue liquid that alcohol is removed in distillation after the alcoholic fermentation can be made into composite fertilizer through adding nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or organic (fertilizer) and/or pulping potash black liquor and/or the laggard one-step fermentation of microbial inoculum.
Commercially available various chemical fertilizer and chemicals before described nitrogenous fertilizer, phosphate fertilizer, the micro-feeling the pulse with the finger-tip;
Organic (fertilizer) comprises the various vegetable wastes of industrial or agricultural, as: the waste residue of plant straw, wood chip, sugar refinery and animal wastes or the like.
Microbial inoculum is a kind of bacterium or several bacterium of nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria and other soil beneficial microbe etc., or cooperates cellulose and hemicellulose decomposer etc. again.Nitrogen-fixing bacteria, as: azotobacter chroococcum, azotobacter vinelandii, Bei Shi nitrogen-fixing bacteria, India Bei Shi nitrogen-fixing bacteria, ditch millet nitrogen-fixing bacteria, De Shi Bai Yelinke Salmonella, aerogenesis Klebsiella, produce sour Klebsiella, grass livings Erwinia, Friedlander, enterobacter cloacae, Alcaligenes faecalis, life fat azospirillum, Azospirillum brasilense, bacillus polymyxa, bacillus licheniformis or the like; Phosphate solubilizing bacteria, as: bacillus megaterium, bacillus cereus, bacillus pumilus, phosphorus decomposing fungi, pseudomonad or the like; Potassium solubilizing bacteria, as: colloid bacillus cereus, Bacillus circulans or the like; The soil beneficial microbe comprises some actinomyces, light and bacterium or the like; Cellulose and hemicellulose decomposer are as: various wood mould (this wood of lining is mould, koning trichoderma, Trichoderma viride) and cellulomonas cartae, molten fiber cupreum, Paecilomyces varioti, Aspergillus oryzae, some actinomyces or the like.
Further two of the scheme of processing and utilization are: described liquid fertilizer carries out the fermentation of feed mycoprotein after the further adjustment of nutrient allotment and pH condition; Fermentation residue liquid remaining behind the extraction feed mycoprotein is made composite fertilizer through adding nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or organic (fertilizer) and/or pulping potash black liquor and/or microbial inoculum after fermentation.
Described nutrient allotment, comprise and add the required inorganic salts of microorganism, organic carbon source, vitamin, organic nitrogen or the like, after can measuring the nutrient in the described liquid fertilizer, carry out suitably concentrating or dilution, as organic carbon source deficiencies such as original glycan, can suitably add the screenings that filters out behind some pulp washings and thin assorted fiber, comprise fibroid sediment in the waste water etc.In carrying out feed mycoprotein the most handy phosphoric acid of when fermentation and the residual alkali in the black liquor, or cooperate a small amount of nitric acid, and mainly with additional nitrogens such as ammonium salt or urea.
Cellulomonas cartae, molten fiber cupreum, wood are mould, Paecilomyces varioti, Aspergillus oryzae, some actinomyces or the like can utilize cellulose and multiple hemicellulose and some organic acids and other low molecule organic matter fermenting and producing feed mycoprotein, or produce the feed mycoprotein with bacterium co-incubation such as above-mentioned bacterium and Candida, geotrichum candidums.
Fermentation residue liquid behind the extraction feed mycoprotein is made composite fertilizer through adding nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or organic (fertilizer) and/or pulping potash black liquor and/or microbial inoculum after fermentation.
Described nitrogenous fertilizer, phosphate fertilizer, trace element, organic matter (fertilizer), microbial inoculum etc. are identical with composite fertilizer's manufacturing in the scheme one.
Further three of processing and the scheme utilized are: described liquid fertilizer is after nutrient allotment and pH are whole, insert a kind of bacterium or several bacterium of nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria and other soil beneficial microbe etc., or cooperate co-fermentation after cellulose and hemicellulose decomposer or its enzyme preparation again, make liquid bio fertilizer or bio-fertilizer Inoculant.
Described nutrient allotment, comprise the required inorganic salts of microorganism, organic carbon source, vitamin or the like, after can measuring the nutrient in the described liquid fertilizer, carry out suitably concentrating or dilution, as organic carbon source deficiencies such as original glycan, can suitably add the screenings that filters out behind some pulp washings and thin assorted fiber, comprise fibroid sediment in the waste water etc., even glucose sugar.Carry out nitrogen-fixing bacteria when cultivating in the most handy phosphoric acid and the residual alkali in the black liquor, and without nitric acid, giving full play to the nitrogen fixation of nitrogen-fixing bacteria, and reaching the purpose of producing nitrogenous fertilizer with phosphorus potash fertilizer.
Described nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria, soil beneficial microbe, cellulose and hemicellulose decomposer etc. are identical with the bacterial classification of composite fertilizer's manufacturing in the scheme one; Enzyme preparation comprises cellulase and hemicellulase.
Further four of the scheme of processing and utilization are: described liquid fertilizer carries out Separation of Solid and Liquid, and liquid partly becomes liquid fertilizer; Solid portion is mainly rugose wood element etc.
Described liquid fertilizer becomes solid fertilizer after evaporation drying; Or described liquid fertilizer is after nutrient allotment and pH adjustment, insert a kind of bacterium or several bacterium of nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria and other soil beneficial microbe etc., or cooperate co-fermentation after cellulose and hemicellulose decomposer or its enzyme preparation again, make liquid bio fertilizer or bio-fertilizer Inoculant.
Described nutrient allotment, comprise and add the required inorganic salts of microorganism, organic carbon source, vitamin or the like, after can measuring the nutrient in the described liquid fertilizer, carry out suitably concentrating or dilution, as organic carbon source deficiencies such as original glycan, can suitably add the screenings and the thin fiber etc. of mixing that filter out behind some pulp washings, even glucose sugar.Carry out nitrogen-fixing bacteria when cultivating in the most handy phosphoric acid and the residual alkali in the black liquor, and without nitric acid, giving full play to the nitrogen fixation of nitrogen-fixing bacteria, and reaching the purpose of producing nitrogenous fertilizer with phosphorus potash fertilizer.
Described nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria, soil beneficial microbe, cellulose and hemicellulose decomposer etc. are identical with the bacterial classification of composite fertilizer's manufacturing in the scheme one; Enzyme preparation comprises cellulase and hemicellulase.
Described solid portion after Separation of Solid and Liquid, its main component is a rugose wood element etc., adds granulation after nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or fertilizer and/or the microbial inoculum, drying again, makes composite fertilizer.
Commercially available various chemical fertilizer and chemicals before described nitrogenous fertilizer, phosphate fertilizer, the micro-feeling the pulse with the finger-tip; Organic (fertilizer) comprises the various vegetable wastes of industrial or agricultural, as: plant straw, wood chip and the animal wastes etc. of becoming thoroughly decomposed; Microbial inoculum is a kind of bacterium or several bacterium of nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria and other soil beneficial microbe etc., or cooperates cellulose and hemicellulose decomposer etc. again, and concrete bacterial classification is identical with the bacterial classification of composite fertilizer's manufacturing in the scheme one.
Further five of the scheme of processing and utilization are: described liquid fertilizer adds nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or organic (fertilizer) and/or microbial inoculum after fermentation again after concentrating, granulation, drying are made composite fertilizer.
Concentrate can in and before or after the residual alkali of black liquor, and can adopt various device, for middle-size and small-size factory, need only with conventional long tube film-rising evaporator, black liquor is concentrated to solid content about 30%, and then be mixed with the organic or unfermentable fertilizer of other drying, make moisture be about 50%～60%, or add necessary nutrient after fermentation again.With highly concentrated, even bone dry is compared after concentrating, and this half-dried method that concentrates the organic fermentation that is mixed again can be saved the energy that is consumed when concentrating, and equipment is simple, invests little.Can certainly use miscellaneous equipment and method, and improve concentrating degree.
Described fermentation comprises the nature fermentation reactor system, fermentation in composting device, in fermentation cylinder for fermentation etc., the bacterial classification of fermentation can natural strain fermentation, or with artificial bacteria fermentation.Described nitrogenous fertilizer, phosphate fertilizer, trace element, organic matter (fertilizer), microbial inoculum etc. are identical with composite fertilizer's manufacturing in the scheme one.
Liquid bio fertilizer made in the scheme three and four of described further processing and utilization also can be made dry bacterium powder further through low temperature drying; Or through freeze-drying, as: vacuum freeze-drying, make the freeze-drying microbial inoculum; Or use adsorbents adsorb, make solid fungicide; Or further be mixed with other fertilizer, make biological compound fertilizer.
Described adsorbent, as: the peat composed of rotten mosses, vermiculite, peat, kaolin, grass meal or their mixture or the like; The described fertilizer that is mixed that is used to make biological compound fertilizer is various chemical fertilizer and fertilizer etc.
Above-mentioned various solid fertilizer is further made fertilizer after the granulation.
Fertilizer after the described granulation also can be bulk, bar-shaped or ball shape etc.
Beneficial effect of the present invention is:
1, the present invention extracts the black liquor of pulp making that substitutes soda with potash, uses H again
3PO
4Or HNO
3Or both cooperate in and the residual alkali in the black liquor, the necessary nitrogen phosphorus potassium of plant and microorganism three big elements have been introduced in the black liquor, and having generated sylvite such as a large amount of potassium phosphates, potassium nitrate, alkali lignin potassium and multiple organic acid potassium, these sylvite itself are exactly the potash fertilizer of high-quality, only use H when neutralizing residual alkali simultaneously
3PO
4And HNO
3And without H
2SO
4And HCL, it is unnecessary invalid and the SO of certain harm arranged not contain in the fertilizer
4 -2And Cl
-1, overcome K
2SO
4, problems such as the physiological phenomenon of chemical potash fertilizer such as KCL and salt damage, also can reduce the cost of the residual alkaline consumption of neutralization with acid.
2, the present invention has made full use of lignin and potassium element in the potash black liquor not only in the mode of utilizing of fertilizer, but also has made full use of glycan class material and the catabolite thereof in the black liquor with multiple fermentation mode.
3, the present invention not only can produce various biological organic fertilizers by black liquor by the comprehensive utilization of potash black liquor, can also produce alcohol, feed mycoprotein etc. by microbial fermentation mode simultaneously, has widened the mode of utilizing of potash black liquor.
4, the present invention is better than inventing inorganic potash fertilizer and the composite organic-inorganic fertilizer of producing with other with its fertilizer efficiency of various biological organic fertilizers of microbial fermentation processes production, and biological organic fertilizer is wide in variety, purposes is wide, has adapted to the demand of present green agriculture and organic agriculture development to bio-feritlizer.
5, the present invention is more complete to the utilization of black liquor, and can produce better economic benefit.
Specific implementation method for example
Embodiment 1
1, extracts pulping potash black liquor.
2, with phosphoric acid neutralize its alkalescence to pH be 5.5～6.5.
3, by dilution, potassium phosphate content in the method regulator solution such as concentrate and append to about 4g/L, the content of carbon source class materials such as glycan is about 20g/L extremely, adds urea 1.5g/L again, CaCO
32.0g/L, MgO.6H
2O1.0g/L, yeast extract 2.0g/L, polypeptide 5.0g/L, cysteine hydrochloride 0.5g/L.
4, insert Clostridium thermocellum (Clostridium thermocellum), clostridium thermosaccharolyticum (Clostridium thermosaccharolyticum), hot hydrosulphuric acid clostridium (Clostridiumthermohydrosul furicum), in 60 ℃ of stir culture, produce alcohol in fermentation tank.
5, become to mix and stir material after the straw of residue liquid behind the distilled spirit and pulverizing mixes and stirs, its total solid-to-liquid ratio is that both moisture was about 50%～60% about 1: 1 (w/w), ferments in the composting device of packing into, gets fertilizer.
6, the fertilizer after the fermentation is equipped with 5% calcium magnesium phosphate again, and 4% urea and azotobacterin make the living bacteria count of fertilizer reach every gram dry weight fertilizer more than 0.3 hundred million, and biological organic complex fertilizer is made in granulation, low temperature drying.
Embodiment 2
1, extracts pulping potash black liquor.
2, be about 6 with phosphoric acid its alkalescence that neutralizes to pH, precipitation is removed the part lignin.
3, by dilution, potassium phosphate content in the method regulator solution such as concentrate and append to about 5g/L, the content of carbon source materials such as glycan is about 30g/L extremely, adds urea 5.0g/L again, CaCO
32.0g/L, MgO.6H
2O1.0g/L, yeast extract 2.0g/L.
4, regulate pH to 5.5, insert molten fiber cupreum (Chaetomiumcellulolyticum), carry out the air agitation fermentation, production feed mycoprotein in 37 ℃ with fermentation tank.
5, filtering fermentation liquor goes out mycelium, can be used as the feed mycoprotein after washing, the drying.
6, the lignin that is settled out is joined in the residue liquid that extracts behind the feed mycoprotein, regulate its potassium phosphate content to about 10g/L with described liquid fertilizer, and add urea content to 10g/L, the straw that adds pulverizing again mixes and stirs and becomes to mix and stir material, its total solid-to-liquid ratio is about 1: 1, be that moisture content is about 50%～60%, aerobic fementation in the solid-state fermentation tank of packing into.
7, fertilizer granulation, the drying after the fermentation made fertilizer.
Embodiment 3
1, extracts pulping potash black liquor.
2, with phosphoric acid neutralize its alkalescence to pH be about 7.
3, by dilution, potassium phosphate content in the method regulator solution such as concentrate and append to about 4g/L, the content of carbon source materials such as glycan is about 30g/L extremely, adds CaCL again
20.02g/L, MgSO
4.7H
2O0.2g/L, NaMoO
4.2H
2O0.002g/L, yeast extract 0.4g/L.
4, insert Friedlander, bacillus polymyxa, bacillus megaterium, colloid bacillus cereus, Trichoderma viride, about 72 hours, become liquid bio fertilizer or bio-fertilizer Inoculant in 30 ℃ of stirring venting cultivation with fermentation tank.
5, this bio-fertilizer Inoculant is used for embodiment 1 biological compound fertilizer manufacturing, can be made into biological organic complex fertilizer.
6, this liquid bio fertilizer adsorbs with the peat composed of rotten mosses just becomes solid fungicide.
Embodiment 4
1, extracts pulping potash black liquor.
2, be about 7 with phosphoric acid its alkalescence that neutralizes to pH, precipitation is removed the rugose wood element.
3, remove liquid behind the delignification by dilution, potassium phosphate content in the method regulator solution such as concentrate and append to about 4g/L, the content of carbon source materials such as glycan is about 20g/L extremely, adds CaCL again
20.02g/L, MgSO
4.7H
2O0.2g/L, NaMoO
4.2H
2O0.002g/L, yeast extract 0.4g/L.
4, insert Friedlander, bacillus polymyxa, bacillus megaterium, colloid bacillus cereus, Trichoderma viride, stir venting cultivation about 72 hours, become liquid bio fertilizer or bio-fertilizer Inoculant in 30 ℃ of fermentation tanks.
5, this bio-fertilizer Inoculant is used for embodiment 1 biological compound fertilizer manufacturing, can be made into biological organic complex fertilizer.
6, this liquid bio fertilizer can be made into dry bacterium powder through low temperature drying.
7, excessive moisture is removed in the lignin squeezing that is settled out, and urea is pulverized with beater grinder, joins in the lignin, and addition is 15% of a lignin dry weight, mixes thoroughly.
8, granulation, drying are made composite fertilizer.
Embodiment 5
1, extracts pulping potash black liquor.
2, with phosphoric acid neutralize its alkalescence to pH be about 7, be settled out a part of lignin.
3, with conventional long tube film-rising evaporator will neutralize alkalescence afterwards and the black liquor vaporizing that is settled out the part lignin be concentrated to about 30%, again the lignin that is settled out is joined in this black liquor.
4, in above-mentioned neutralization alkalescence and the black liquor that concentrated, add dry straw powder again, and be equipped with 1% urea, 1% CaCO
30.2% MgO, 0.06% yeast extract is mixed thoroughly, making its total solid-to-liquid ratio is about 1: 1, be that moisture is about 50%～60%, insert Friedlander, bacillus polymyxa, bacillus megaterium, colloid bacillus cereus, Trichoderma viride etc. again, in solid-state fermentation tank, stir the venting cultivation fermentation in 30 ℃.
5, the fertilizer after the fermentation is made biological organic fertilizer through granulation, low temperature drying.
Embodiment 6
1, extracts pulping potash black liquor.
2, with conventional long tube film-rising evaporator black liquor vaporizing is concentrated to about 30%,
3, with phosphoric acid neutralize its alkalescence to pH be about 7.
4, add dry cow dung again in the black liquor that above-mentioned warp concentrates and neutralization is alkaline, making its total solid-to-liquid ratio is that promptly moisture is about 50%～60% about 1: 1 (w/w), and is equipped with 5% urea, aerobic fementation in installation for fermenting.
5, the fertilizer after the fermentation is made fertilizer through granulation, drying.
Claims (18)
1, the method for comprehensive utilization of pulping potash black liquor in the paper technology is characterized in that: extract pulping potash black liquor, use H
3PO
4Wherein alkali is neutralized, make liquid fertilizer.
2, the method for comprehensive utilization of pulping potash black liquor in the paper technology is characterized in that: extract pulping potash black liquor, use HNO
3Wherein alkali is neutralized, make liquid fertilizer.
3, the method for comprehensive utilization of pulping potash black liquor in the paper technology is characterized in that: extract pulping potash black liquor, use H
3PO
4And HNO
3Wherein alkali is neutralized, make liquid fertilizer.
4, as claim 1,2 or 3 described methods, it is characterized in that: described liquid fertilizer carries out alcoholic fermentation after nutrient allotment and pH adjustment; Fermentation residue liquid remaining behind the distilled spirit is made composite fertilizer through adding nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or organic (fertilizer) and/or pulping potash black liquor and/or microbial inoculum after fermentation.
5, as claim 1,2 or 3 described methods, it is characterized in that: described liquid fertilizer carries out the fermentation of feed mycoprotein after nutrient allotment and pH adjustment; Fermentation residue liquid remaining behind the extraction feed mycoprotein is made composite fertilizer through adding nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or organic (fertilizer) and/or pulping potash black liquor and/or microbial inoculum after fermentation.
6, as claim 1,2 or 3 described methods, it is characterized in that: described liquid fertilizer is after nutrient allotment and pH adjustment, insert a kind of bacterium or several bacterium of nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria and other soil beneficial microbe etc., or cooperate co-fermentation after cellulose and hemicellulose decomposer or its enzyme preparation again, make liquid bio fertilizer or bio-fertilizer Inoculant.
7, as claim 1,2 or 3 described methods, it is characterized in that: described liquid fertilizer carries out Separation of Solid and Liquid, and liquid partly becomes liquid fertilizer.
8, method as claimed in claim 7 is characterized in that: described liquid fertilizer becomes solid fertilizer after evaporation drying; Or described liquid fertilizer is after nutrient allotment and pH adjustment, insert a kind of bacterium or several bacterium of nitrogen-fixing bacteria, phosphate solubilizing bacteria, potassium solubilizing bacteria and other soil beneficial microbe etc., or cooperate co-fermentation after cellulose and hemicellulose decomposer or its enzyme preparation again, make liquid bio fertilizer or bio-fertilizer Inoculant.
9, the method for stating as claim 7 is characterized in that: described solid portion after Separation of Solid and Liquid, granulation after adding nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or fertilizer and/or the microbial inoculum, drying are made composite fertilizer.
10, profit requires 1,2 or 3 described methods, it is characterized in that: described liquid fertilizer adds nitrogenous fertilizer and/or phosphate fertilizer and/or trace element and/or organic (fertilizer) and/or microbial inoculum after fermentation again after concentrating, granulation, drying are made composite fertilizer.
11, method as claimed in claim 6 is characterized in that: described liquid bio fertilizer is made dry bacterium powder after low temperature drying.
12, method as claimed in claim 6 is characterized in that: described liquid bio fertilizer is made the freeze-drying microbial inoculum after freeze-drying.
13, method as claimed in claim 6 is characterized in that: described liquid bio fertilizer is made solid fungicide after adsorbents adsorb.
14, method as claimed in claim 6 is characterized in that: after described liquid bio fertilizer and other fertilizer are mixed, make biological compound fertilizer.
15, method as claimed in claim 8 is characterized in that: described liquid bio fertilizer is made dry bacterium powder after low temperature drying.
16, method as claimed in claim 8 is characterized in that: described liquid bio fertilizer is made the freeze-drying microbial inoculum after freeze-drying.
17, method as claimed in claim 8 is characterized in that: described liquid bio fertilizer is made solid fungicide after adsorbents adsorb.
18, method as claimed in claim 8 is characterized in that: after described liquid bio fertilizer and other fertilizer are mixed, make biological compound fertilizer.
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| CN 02104838 CN1436895A (en) | 2002-02-09 | 2002-02-09 | Comprehensive utilization method of pulping potash black liquor in paper-making process |
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|---|---|---|---|
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| CN101210182B (en) * | 2006-12-25 | 2010-05-19 | 山东泉林纸业有限责任公司 | Method for producing soil restoring agent by using straw slurry black liquor |
| CN101209878B (en) * | 2006-12-25 | 2010-08-18 | 山东泉林纸业有限责任公司 | Production technology of plant growth regulator type fertilizer adhesive |
| CN101210395B (en) * | 2006-12-25 | 2010-09-15 | 山东泉林纸业有限责任公司 | Method for treating straw slurry black liquor by using ammonium sulfite method |
| CN101209932B (en) * | 2006-12-25 | 2011-10-12 | 山东泉林纸业有限责任公司 | Method for producing fulvic acids fertilizer by using alkaline process black liquor |
| CN102442859A (en) * | 2010-10-12 | 2012-05-09 | 上海绿乐生物科技有限公司 | Method for producing compound microbial fertilizer with microbial inoculum permeation and adsorption method |
| CN105967840A (en) * | 2016-03-17 | 2016-09-28 | 安徽凤阳德诚科技有限公司 | A microbial fertilizer promoting root nodule growth for soybean and a preparing method thereof |
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| CN101210182B (en) * | 2006-12-25 | 2010-05-19 | 山东泉林纸业有限责任公司 | Method for producing soil restoring agent by using straw slurry black liquor |
| CN101209878B (en) * | 2006-12-25 | 2010-08-18 | 山东泉林纸业有限责任公司 | Production technology of plant growth regulator type fertilizer adhesive |
| CN101210395B (en) * | 2006-12-25 | 2010-09-15 | 山东泉林纸业有限责任公司 | Method for treating straw slurry black liquor by using ammonium sulfite method |
| CN101209932B (en) * | 2006-12-25 | 2011-10-12 | 山东泉林纸业有限责任公司 | Method for producing fulvic acids fertilizer by using alkaline process black liquor |
| CN102442859A (en) * | 2010-10-12 | 2012-05-09 | 上海绿乐生物科技有限公司 | Method for producing compound microbial fertilizer with microbial inoculum permeation and adsorption method |
| CN102442859B (en) * | 2010-10-12 | 2013-06-19 | 上海绿乐生物科技有限公司 | Method for producing compound microbial fertilizer with microbial inoculum permeation and adsorption method |
| CN105967840A (en) * | 2016-03-17 | 2016-09-28 | 安徽凤阳德诚科技有限公司 | A microbial fertilizer promoting root nodule growth for soybean and a preparing method thereof |
| CN106592312A (en) * | 2016-12-21 | 2017-04-26 | 厦门大学 | Method for recovering solid alkali from pulping yellow liquid for coproduction of organic ammonium quick-acting fertilizer and slow release fertilizer |
| CN106592312B (en) * | 2016-12-21 | 2018-05-18 | 厦门大学 | The method for recycling slurrying yellow liquor solid base coproduction organic ammonium quick-acting fertilizer and slow-release fertilizer |
| CN106882909A (en) * | 2017-04-19 | 2017-06-23 | 卢松 | Administer the environment-protective process of xanthan gum fermentation waste water |
| CN106882909B (en) * | 2017-04-19 | 2019-12-10 | 内蒙古阜丰生物科技有限公司 | Environment-friendly process for treating xanthan gum fermentation wastewater |
| CN107434751A (en) * | 2017-08-04 | 2017-12-05 | 山东森博生物科技有限公司 | A kind of method that biological organic carbon fertilizer is produced using black liquor of pulp making |
| CN107558284A (en) * | 2017-08-31 | 2018-01-09 | 南京工业大学 | A kind of method that lignin co-production phosphorus potassium complex fertilizer is extracted using fermenting cellulosic ethanol residue as raw material |
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