CN102796768A - High value integration utilization method of maize straw - Google Patents
High value integration utilization method of maize straw Download PDFInfo
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- CN102796768A CN102796768A CN2012102662341A CN201210266234A CN102796768A CN 102796768 A CN102796768 A CN 102796768A CN 2012102662341 A CN2012102662341 A CN 2012102662341A CN 201210266234 A CN201210266234 A CN 201210266234A CN 102796768 A CN102796768 A CN 102796768A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
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Abstract
The invention provides an integration utilization method of maize straws, wherein maize straws are used as the raw material for combined production of ethanol, fiber, lignin, pectin, xylose and yeast through continuous complete technology. Specifically, the degradable substances such as polysaccharide, pectin, starch, etc. in the maize straws are degraded to be a solution of soluble substances by using an acidolysis method to realize the separation of residue from the degradable substances, and then the obtained solution of soluble substances is used for fermentation to extract ethanol fuel, pectin, and xylose, and the residue obtained by separation is used to produce fiber and lignin by using an organic solvent method. The method of the invention achieves the combined production of ethanol, fiber, lignin, pectin, xylose and yeast through integration utilization of the maize straws, and thereby costs of integration utilization of the maize straws are shared, zero-emission of pollutants in the production process is realized, and the utilization efficiency of the maize straws is improved.
Description
Technical field
What the present invention relates to is a kind of treatment process of corn straw, is specifically related to a kind of corn straw combination producing ethanol, xylogen, fiber, pectin, wood sugar and yeast method utilized.
Background technology
Be the corn main producing region to the north of China the Yellow River, the corn total area reaches 2400hm
2About, the corn straw ultimate production is approximately 1.6 hundred million tons.The utilization of current corn stalk is mainly fodder grass, shaped fuel or the chopping and returning of ruminating animal, and utility value is not high.Some area then is discarded in the rotten or burning of setting fire in the edge of a field.Cause the wasting of resources, go back serious environment pollution.
The about cellulose 33% of corn straw dry-matter, xylogen 15%, semicellulose 20%, pectin 9%, crude protein 3.5%, total sugar content 10%, crude fat, mineral substance etc. other about 8.5%.Corn straw is through the acid system hydrolysis, polysaccharide degradables such as pectin, semicellulose, starch, and reducing sugar can be increased to about 20%.Wherein half fiber degradable is wood sugar, pectinose, semi-lactosi, seminose.In the above material, Mierocrystalline cellulose, xylogen, pectin, wood sugar, reducing sugar all are most valuable goods and materials.
But reducing sugar producing fuel ethyl alcohol by ferment.The a large amount of yeast of ethanol fermentation liquid output, recyclable utilization.First degree utilization is to be used for animal-feed.The high-grade utilization then is to be developed to nutritive food.Mash behind the ethanol distillation is rich in amino acid, protein and nutritive salt, can be used for plant nutrition liquid.
Mierocrystalline cellulose is the glucose long chain polymer, and purposes is very extensive, and Application Areas comprises papermaking, building materials, chemical industry, makeup, food, medicine, pottery, refractory materials, leather, tobacco or the like.Papermaking material only, China has a large population, and the soil is few, and forest is limited, and timber resources is in short supply, the paper pulp famine.3,700 ten thousand tons of annual paper pulp breach need be spent 17,000,000,000 dollars from external pulp inlet, to satisfy domestic needs.
Xylogen is the aromatic alcohol polymkeric substance, is present in the lignum of corn straw, forms the net sclereid wall that interweaves.Xylogen and verivate thereof have multiple functional, can make dispersion agent, sorbent material/strippant, petroleum recovery auxiliary agent, asphalt emulsifier.But the mixed liquefied production fluid fluid fuel of xylogen and coal.
Xylogen also is widely used in being called the road surface lignin fibre in high speed road surface, the airfield runway.Its quality standard is: content of lignin 75-80%, and about PH7.5, maximum length 1100um, mean length 45um, volume density 25-30g/L.Market outlook are good, 2800 to 4500 yuan/ton of prices.
Pectin is good emulsifying, thickening, stable and jelling agent, is widely used in fields such as food, weaving, printing and dyeing, tobacco, metallurgy.Effects such as pectin is antibiotic in addition, hemostasis, detumescence, detoxifcation, antidiarrheal, reducing blood-fat, radioprotective are a kind of good pharmaceutical prepn matrix.Pectin also is water-soluble dietary fibre, more and more receives the attention of research and processing industry.The main output of whole world pectin is from American-European countries, and Asia output is few.At present, the main raw material of extraction pectin is orange peel, lemon peel and apple residue.These raw material resources amounts are very limited, cause price for a long time up to 120,000 yuan/ton not down.
The main application of wood sugar: be used to prepare Xylitol, the purposes of Xylitol is more extensive; Be used for food, beverage as non-caloric sweetener, be applicable to obesity and diabetic subject; As bifidus bacillus acvator, accelerating agent of calcium absorption, be used to improve the protective foods of body immunity; Be applied to feed for pet; As baked goods; As high-grade color of soy sauce; Be used for aspects such as light industry, chemical industry.
Therefore, the corn straw whole body all is precious.But the utilization technology and the technology of corn straw are mainly utilized the purpose design for certain single product now.Single product utilize method, produce paper pulp or ethanol or wood sugar like corn straw, inevitable other useful component of handlebar is discarded, promptly causes a large amount of waste discharges, increases the cost of single product again.Because output is few, benefit is low, and the corn straw cost of material can not improve, and will certainly suppress the enthusiasm that corn straw is collected by peasant household, seriously restricts corn straw deep processing industrialized development.Therefore; Must consider a kind of high-efficient simple processing scheme, multiple useful matter more than the extraction, the level of comprehensive utilization and the efficient of raising corn straw; Realization is raw material with the corn straw; One cover technology co-producing ethanol, fiber, xylogen, pectin, wood sugar and yeast are realized corn main producing region growth of agricultural efficiency, increasing peasant income, promote corn planting industry and relevant processing industry Sustainable development.
Summary of the invention
The objective of the invention is for a kind of method is provided; Through the comprehensive utilization maize straw resource; Combination producing ethanol, fiber, xylogen, pectin, wood sugar and yeast; Thereby the comprehensive utilization cost of sharing corn straw is realized the production process zero release of pollutant, improves the maize straw resource utilising efficiency.
In order to reach above-mentioned purpose of the present invention, the present invention proposes following technological method:
A kind of method of comprehensive utilization of corn straw is provided, and is to be raw material with the cornstalk, through successive set technique co-producing ethanol, fiber, xylogen, pectin, wood sugar and yeast method; Specifically; Be earlier cornstalk to be utilized degradable things such as polysaccharide that acid hydrolyzation will be wherein, pectin, starch to be degraded to the soluble substance aqueous solution; The realization slag charge separates with the degradable thing; Then the soluble substance aqueous solution that obtains is used for fermented extracted alcohol fuel, pectin, wood sugar, separates the slag charge that obtains and use organic solvent method producd fibers and xylogen again.
Method of the present invention specifically may further comprise the steps:
A) be ground into length thread less than 2 centimetres behind the corn straw defoliation that will gather; Adding mass concentration is rare syrup of 4-10%, contains the sulfuric acid of 5 ‰ mass concentrations in rare syrup, and rare syrup of adding and stalk volume ratio are 2 ~ 5 ︰ 1; The mixture that obtains is processed above 80 purpose slurries; And the water-content in the control slurry rises to 70 ~ 100 ℃ below 85% with slurry temperature, keeps 25 ~ 40 minutes; Accomplish corn straw acidolysis for the first time, make the pectin in the corn straw fully dissolve the rare syrup of entering; Pulp separated is become moisture 50% the slag charge 1 and the aqueous solution 1 that is rich in pectin and syrup;
B) mass concentration that in the slag charge 1 that step a) obtains, adds 2 ~ 5 times of its volumes is rare syrup of 4-10%; The sulfuric acid that contains 5 ‰ mass concentrations in rare syrup; Soaked 15 ~ 30 minutes, and made the slag charge temperature rise to 115 ~ 125 ℃ then, kept 60 ~ 90 minutes; Accomplish the secondary acidolysis, starch, semicellulose, polysaccharide in the slag charge are fully degraded; When treating that the slag charge temperature is reduced to below 100 ℃, the pulp separated after handling is become the slag charge 2 and the aqueous solution 2 that is rich in degraded sugar;
C) slag charge 2 that step b) is obtained by volume 1 ︰ 1 adds clear water and soaks, treat that syrup fully leaches in the slag charge after, carry out slag liquid and separate, obtain syrup acid solution 1 and slag charge 3;
D) slag charge 3 that step c) is obtained adds the ethanol of 30% concentration of 5 ~ 7 times of its volumes; In slag charge 3 and alcoholic acid mixture, add the KOH catalyzer in the ratio of 1g/L again; Behind the mixing, make temperature of charge rise to 100 ℃, kept 60 ~ 90 minutes; Accomplish the alcoholysis process of slag charge 3, the xylogen in the slag charge 3 is fully degraded; Treat that temperature of charge reduces to below 50 ℃, separate obtaining slag charge 4 and lignin liquor;
E) the slag charge 4 usefulness 30% alcohol extraction residual lignin that step d) is obtained obtains extraction liquid and Mierocrystalline cellulose; Remove and recovering step d) ethanol in the lignin liquor that obtains, obtain separating out the aqueous solution that xylogen is arranged, obtain xylogen through conventional the processing again;
F) in the aqueous solution that is rich in pectin and syrup 1 that step a) obtains, adding gac decolours; The ratio that gac adds accounts for 4 ~ 7% of the described corn straw dry matter weight of step a), and the decolouring after-filtration obtains active breeze 1 and filtrating, extraordinarily goes into 95% ethanol by 1.5 of filtrate volume in the filtrating; Making pectin become floss separates out; Accomplish pectin alcohol and analyse, obtain being rich in the slurries of pectin floss, obtain solution 3 and pectin solid substance through solid-liquid separation again; Solution 3 reclaims ethanol after distillation, remain to be syrup acid solution 2;
G) aqueous solution 2 that is rich in degraded sugar with the step b) acquisition obtains mixing syrup with syrup acid solution 2 mixing that step f) obtains, and controlling wherein sugared concentration is 16 ~ 20%, mixes in the syrup at every liter to add: (the NH that generates 0.5 ~ 1.5g
4)
2SO
4Required ammoniacal liquor, the MgSO of 8 ~ 12g
4, 2 ~ 6g KH
2PO
4CaCl with 2 ~ 6g
2, add white lime again and regulate syrup pH to 4 ~ 5;
H) get few part of the syrup solution that step g) modulates; Be diluted to pol and be 2% the aqueous solution; Add saccharic alcohol Angel Yeast, the saccharic alcohol Angel Yeast of adding is 1/0,000 of the syrup total solution weight that obtains of step g), carries out yeast under the aseptic wind oxygenation condition and expands numerous 1 ~ 3 hour; The yeast that will expand then after numerous adds in the good residue syrup of step g) allotment; Fully mix; Anaerobic fermentation 20 ~ 48 hours; Detect remaining content of reducing sugar; When content of reducing sugar remains unchanged less than 0.5% also continuous 3 detections; Alcoholic fermentation finishes, and obtains viable yeast sediment and clear liquid 1, and clear liquid 1 obtains thick wine and the mash of 40%v/v through distillation;
I) mash that step h) obtains after the distillation is pressed wherein 4 ~ 7% adding gacs of dry matter weight, accomplishes the decolouring of mash, filters and obtains clear liquid 2 and active breeze 2; Remove the charged salt ion in the clear liquid 2, through concentrating, lower the temperature, add nucleus, crystallization, drying, obtain the xylose crystalline powder then; The active breeze 1 that step f) is obtained mixes with all waste thing that this step obtains, and obtains liquid fertilizer.
In the step f), the pectin solid substance that obtains further obtains pectin powder after cleaning, drying, pulverizing.
Step h) in, the thick wine that obtains can further prepare alcohol fuel through ordinary method.
Step I) the charged salt ion in the described removal clear liquid 2 is preferably accomplished through the method for IX and nanometer ultrafiltration.
Step I) all waste thing that obtains of described step comprise active breeze 2, the waste liquid that obtains when removing the charged salt ion in the clear liquid 2 and/or concentrate, waste liquid that cooling, crystallization and drying process obtain.
In the scheme of the present invention, in order further to reduce cost, improve utilization of materials, preferred in the following ways one or more:
In the step e), after mixing, the lignin liquor that earlier said extraction liquid and step d) is obtained removes and reclaims the ethanol in the mixing solutions again;
The syrup acid solution 2 that obtains after the step f) distillation is used for the acidolysis first time of step a) or the secondary acidolysis of step b);
In the ethanol that step e) or step f) reclaim one or both and step h) the thick wine that obtains of distillation merges, and is not less than 95% alcohol fuel through obtaining concentration after rectifying, the dehydration; Perhaps
Step h) viable yeast that obtains returns step h) the numerous program loop of expansion use, reuse 6 times after, recovery prepares Yeast protein feed.The method of invention can use various existing installations to accomplish; For example; In the step a); The defoliation of corn straw be ground into silk and can adopt among the ZL200910136184.3 disclosed stalk disleaf device in enormous quantities to accomplish, this machine directly breaks into length less than 2 centimetres of silks with corn straw when removing the stalk leaf; The defoliation of described corn straw is with pulverize also can proceed step by step, and wherein being ground into silk can accomplish through dividing the silk machine, and dividing a silk machine can be that screw divides a silk machine, also can be beater disintegrating machine; The preparation of said slurry can adopt paste roller mill to make, the high-density paste mill that paste roller mill preferably adopts acid resisting material to make; Step a) and b) in acidolysis can in steam-heated retort, accomplish; Step b) and c) in separate slag charge and can use the stainless steel pulp-extruding machine; Distillation in the step e) can be accomplished in still kettle; Fermentation in the step g) can be pumped material in the fermentation bag with vacuum primingpump and accomplished; Or the like.
A kind of preferred scheme of the present invention, its process flow sheet is as shown in Figure 1, and concrete steps are following:
1) corn straw of gathering can be a fresh straw, can also be the drying in the sun stalk.After raw material is transported to source mill, adopt disclosed stalk disleaf device removal corn straw leaf in enormous quantities among the ZL200910136184.3, this machine directly breaks into length less than 2 centimetres of silks with corn straw when removing the stalk leaf;
2) with 95% vitriol oil, be mixed with the rare syrup liquid that contains 5 ‰ dilute sulphuric acids with rare syrup of 4-10% concentration, use in order to slurrying; The total amount of required rare syrup liquid is prepared by 1/5 of the stalk volume of handling; The stalk treatment capacity is accomplished after 1/5, the step 17 of output) rare syrup liquid of alternative the step preparation of rare syrup that obtain, be used for slurrying;
3) with Stainless Steel Pump with step 2) rare syrup liquid or step 10) and the step 17 of preparation) rare syrup liquid pump of obtaining goes into acidproof high consistency refining machine inlet capable, form continuously current and prepare against feeding slurrying; The filamentary material of the corn straw of step 1) being processed with conveying belt; Feed from the paste roller mill opening for feed continuously; Adjustment diluted acid or rare syrup flow; Make it with the stalk volume ratio be 2 ~ 5 ︰, 1 mixtures, process through acidproof paste roller mill and surpass 80 purpose diluted acid slurries, slurry is from paste roller mill outlet row system stock tank;
4) slurry of step 3) being processed is conveyed into enamel reactor with spiral pump, and the water-content of controlling then in the slurry is no more than 85%;
5), make sulfuric acid concentration in the slurry that step 4) obtains remain on 5 ‰ aimed concn with 10% dilution heat of sulfuric acid adjustment sulfuric acid concentration;
6) after the slurry sulfuric acid concentration of treating step 5) mixed up, the off-response jar sent steam to heat, and temperature rises to 90 ℃ in jar, kept 30 minutes, accomplished an acidolysis of corn straw, made the pectin of corn straw fully dissolve the entering diluted acid;
7) the corn straw slurry after the step 6) acidolysis processing is discharged into feed bin from retort; Use the stainless steel cut pump then; Through stainless steel pipes hot slurry is sent into the stainless steel pulp-extruding machine; So far, the slurry of step 6) is separated into moisture 50% the slag charge and the aqueous solution that is rich in pectin and syrup;
8) slag charge that step 7) is obtained is by 2 steps 2 extraordinarily of its volume) rare syrup liquid of preparation, soaked 20 minutes; Pump into enamel reactor with spiral pump again, treat that slurry is filled after, the off-response jar; Feed steam, make temperature rise to 120 ℃, kept 1 hour; Accomplish the secondary acidolysis, starch, semicellulose, the polysaccharide of slag charge are fully degraded;
When 9) treating that step 8) enamel reactor temperature is reduced to below 100 ℃, the slurry after the secondary acidolysis processing is entered feed bin, send into pulp-extruding machine with the heatproof cutting pump again, the pulp separated after step 8) is handled becomes the slag charge and the aqueous solution that is rich in degraded sugar;
10) slag charge that step 9) is obtained, by volume 1 ︰ 1 adds clear water and soaks, treat that the slag charge syrup fully leaches after, with the pulp-extruding machine squeezing, obtain rare syrup and slag charge again, rare syrup is returned step 3) slurrying;
11) slag charge that step 10) is obtained is extraordinarily gone into 30% ethanol by 5 of slag charge volume, adds the KOH catalyzer in the 1g/L ratio; Behind the mixing, send into enamel reactor, the off-response jar with spiral pump; Send into steam heating, make temperature rise to 100 ℃, kept 1 hour; Accomplish the alcoholysis process of slag charge, the xylogen of slag charge is fully degraded;
12) treat slurry after the step 11) alcoholysis, temperature is reduced to below 50 ℃, and slurry is entered feed bin, pumps into pulp-extruding machine with cutting pump then, and Mierocrystalline cellulose is separated with lignin liquor;
13) slag charge that step 12) is obtained cleans with 30% ethanol earlier, cleans with clear water then, and bleaching promptly obtains Mierocrystalline cellulose;
14) with the xylogen alcohol extraction liquid distillation of step 12) and step 13) acquisition, the alcohol concn in the solution is reduced, reclaim wine liquid simultaneously; Liquid concentrator is treated the ethanol volatilization totally, separates out owing to xylogen is water insoluble, will separate out xylogen and filter, and cleaning, drying promptly obtain xylogen; The wine liquid that reclaims continues on for alcohol and analyses, or is used for distillate fuel ethanol;
15) liquid pectin that step 7) is obtained is sent in acidproof jar with acid, in adding gac with corn straw dry-matter 4 ~ 7% ratios, carries out the liquid pectin decolouring; The liquid pectin that the decolouring after-filtration obtains press 1.5 95% ethanol extraordinarily of liquid pectin volume, and completion pectin alcohol is analysed process, makes pectin become floss and separates out; To be rich in the slurries of pectin floss again, send into whizzer, syrup will be separated with pectin with cutting pump; Syrup is sent into the distiller distillation, reclaims ethanol;
16) cleaning step 15) filter the pectin solid substance that obtains, drying is pulverized, and promptly obtains pectin powder;
17) the syrup acid solution that is rich in the sugared aqueous solution of degraded and step 15) syrup distillation back acquisition that step 9) is obtained is mixed, and controls sugared concentration at 18-20%;
18) with step 17) concentration that obtains is in the syrup of 18-20%, by (the NH that generates
4)
2SO
4For the ratio of 1g/L adds ammoniacal liquor, add MgSO in the ratio of 10g/L
4, add KH in the ratio of 5g/L
2PO
4, add CaCl in the ratio of 5g/L
2, add a small amount of white lime again, the aqueous solution to pH value is adjusted to 4 to 5;
19) the syrup solution that set by step 18) modulates; Get wherein 1/1000, be diluted to pol and be 2% the aqueous solution, drop in the yeast tank; Set by step 18) 1/0,000 ratios of preparation liquid glucose are got saccharic alcohol Angel Yeast; Drop in the jar, and give rare liquid glucose oxygenation in the jar, carry out yeast and expanded numerous 2 hours with aseptic wind;
20) with step 18) aqueous solution that modulates; Pump into fermentation bag with self priming pump; Simultaneously with step 19) the numerous yeast juice of expansion; The aqueous solution with the suction fermentation bag drops in the fermentation bag; Seal fermentation bag then and carried out anaerobic fermentation 20 to 48 hours, detect remaining content of reducing sugar, when content of reducing sugar remains unchanged less than 0.5% also continuous 3 detections; Alcoholic fermentation finishes, and obtains residual sediment and wine liquid clear liquid;
21) keep step 20) residual throw out---viable yeast in the fermentation bag, be used for next liquid glucose fermentation, reuse 6 times after, treat that yeast activity descends, reclaim yeast, cleaning, drying is used to prepare Yeast protein feed;
22) extraction step 20) wine liquid clear liquid behind the fermenting-ripening; Pump into still kettle with vacuum primingpump; Through the thick wine of distillation extraction 40% (v/v), extract alcohol fuel and the mash that concentration is not less than 95% (v/v) with the wine liquid of step 14) recovery and ethanol rectifying, the dehydration of step 15) recovery again;
23) with step 22) distillation after mash, in 4 ~ 7% ratios of dry-matter in the solution, add gac, the completion mash decolouring; Filter and obtain clear liquid and active breeze;
24) with step 23) clear liquid that obtains, through yin, yang, anion-exchange column, part is removed the yin, yang ion in the solution, obtains to be rich in the solution of wood sugar;
25) with step 24) solution that obtains, through the nanometer ultrafiltration, further remove the charged salt ion of solution;
26) with step 25) xylose solution that obtains concentrates, and cooling adds nucleus, crystallization, drying obtains the xylose crystalline powder;
27) with step 26), 25), 24) waste liquid and step 23), 15) waste residue and step 24) the ion exchange column elutriant mixes, and obtains liquid fertilizer.
The present invention is that the recycling from corn straw puts forward, but can be applied to the essential substance composition stalks close with corn straw such as straw, chrysanthemum stalk, straw.
The plant haulm that the present invention proposes to be rich in corn straw etc. pectin, half fiber, fiber, xylogen, sugar, starch, polysaccharide is raw material combination producing ethanol, pectin, wood sugar, fiber and xylogen; Reclaim the technology of yeast feed; Compare with existing corn straw processing technology, following advantage arranged:
With corn straw " acid-enzyme-synchronous fermentation method " system ethanol (Lv Weimin etc., 2002; Chen Ming, 2007) and hydrolysis system pectin (Liu Huamin, 201010249450.6) and " alcoholysis-acid-precipitation method " (Tian Yihong etc.; 2012), high boiler-elutriation method (Li Mian army etc.; 2002) extract technologies such as xylogen and other stalk system wood sugar, paper pulp and compare, the straw utilization purpose of these technologies is single, and product is single; Economic benefit is also lower, also has a large amount of residuums to go out of use.Result of implementation is that stalk resource is underused, and discharges a large amount of wastes, causes secondary pollution.In actual production, can't improve cost of material, can't improve peasant household and collect stalk enthusiasm.What the present invention considered is that corn straw fully utilizes comprehensively; Even last waste liquid also is used as foliage fertilizer, there is not the residual and discharging of waste liquid of solid waste; Accomplished a kind of corn straw output multiple product, and these products all are that Chinese national economy is built goods and materials in short supply.Around this process goal, the present invention changes above-mentioned single process method, adopts the scheme of multiple degradation method coupling, sets up and improves the technical process that links up, for the utilization fully of the corn straw multiple product that dispatches from the factory has been established the method basis.Catalyzer and degradation agents select for use it finally can be converted into the salt of wormwood and the sulfuric acid of fertilizer; Solvent adopts as far as possible and can repeat to recycle the ethanol that perhaps reclaims as product, puts for the Production Flow Chart whole process is innoxious and establishes the technology basis.
Utilize " acid-enzyme process " of corn straw co-producing ethanol, tr paper pulp, Xylitol, biogas, fertilizer and fruit tree nutrient solution to compare with ability Science and Technology Ltd. in the Suzhou; What the present invention adopted is " acid-acid-alcoholysis method "; Utilize the corn straw product that dispatches from the factory; Except ethanol was identical, other products were all inequality.Other products that the present invention is produced are fiber, xylogen, pectin, wood sugar, yeast feed and liquid fertilizer.Pure fiber wherein not only can be used for tr paper pulp, can also be used for high-grade paper pulp and other filamentary materials.The economic benefit that is produced, " acid-enzyme process " but 7000 yuan of 5883 yuan of output values of every input, rate of profit is 18.99%; And 1 ton of corn straw of " acid-acid-alcoholysis method " of the present invention every processing drops into 7570 yuan, 14440 yuan of output values, rate of profit 90.75%.
Description of drawings
Fig. 1 is the schema of optimized technical scheme of the present invention.
Embodiment
Embodiment 1
With the corn straw is raw material co-producing ethanol, pectin, wood sugar, fiber, xylogen, reclaims yeast feed, and its technical process practical implementation process is following:
1, collect 2 kilograms of dried corn straws, measured moisture content is 15%, adopts disclosed stalk disleaf device removing blade in enormous quantities among the ZL200910136184.3, obtains corn straw silk 1660 grams of length less than 2cm;
2, with 95% vitriol oil; Rare syrup with 4-10% concentration is mixed with the rare syrup liquid that contains 5 ‰ dilute sulphuric acids, and the corn straw of then rare syrup liquid and step 1 being handled well is the mixed of 2:1 by volume, through acidproof mill; Corn straw is worn into 80 purpose slurries, and volume is approximately 5m
3
3, the slurry that step 2 is obtained pumps into enamel reactor, is heated to 70-100 ℃, and reaction 30min accomplishes an acidolysis, makes pectin fully be dissolved in acid solution;
4, with the slurry after an acidolysis of step 3 processing, enter feed bin, send pulp-extruding machine to cutting pump then, pectin solution is separated with slag charge;
5, in the pectin solution that step 4 obtains, add the gac of 7g/L, carry out the liquid pectin decolouring; In the liquid pectin after decolouring, add 1.5 times 95% ethanol then, accomplish pectin alcohol and analyse process, make the pectin flocculation; Separate pectin and solution with whizzer then; Pectin is cleaned, drying is pulverized again, and obtains finished product pectin powder 160 grams; Retort solution reclaims the alcoholysis that ethanol is used for subsequent technique, obtains the syrup acid solution simultaneously;
6, the syrup acid solution that step 5 is obtained is separated acquisition with step 4 slag charge mixes, and pumps into enamel reactor, and adjustment acid strength to 5 ‰ is closed enamel reactor, and input steam makes temperature rise to 120 ℃, keeps 60min, accomplishes the secondary acidolysis; Add cold water then, be cooled to below 100 ℃, the slurry with the secondary acidolysis enters feed bin;
7, the slurry that the acidolysis of step 6 secondary is obtained pumps into pulp-extruding machine, accomplishes the syrup of secondary acidolysis and separates with slag charge; Secondary acidolysis slag charge after clear water soaks again shove anhydrate, obtain slag charge in order to the subsequent technique utilization;
8, after step 7 secondary acidolysis slag charge cleans, add 30% ethanolic soln, add the KOH catalyzer in the 1g/L ratio again by solid-liquid volume ratio 1/5; Pump into enamel reactor behind the mixing, the off-response jar adds steam; Be that temperature rises to 100 ℃, accomplish alcoholysis process, make lignin dissolution and separate with Mierocrystalline cellulose;
9, after alcoholysis was accomplished, enamel reactor added cold water and is cooled to below 50 ℃, and slurry is entered feed bin; Adopt cutting pump to send into pulp-extruding machine, accomplish lignin liquor and separate with Mierocrystalline cellulose; Mierocrystalline cellulose cleans through 30% solution, is cleaning with clear water, and drying promptly obtains purified Mierocrystalline cellulose 603 grams; Mierocrystalline cellulose 30% ethanol scavenging solution is mixed with lignin liquor,, reclaim ethanol with the distiller distillation; The xylogen deposition is dry, promptly obtains lignin product 288 grams;
10, with the method that concentrates or add water, the syrup concentration to 18% of the secondary acidolysis that set-up procedure 7 obtains, pH value are about 2; Add liming after adding ammoniacal liquor and nutritive salt earlier, in the syrup acid solution, the adjustment pH to 5 about; Ammoniacal liquor and nutritive salt add-on are: by (the NH that generates
4)
2SO
4For the ratio of 1g/L adds ammoniacal liquor, add MgSO in the ratio of 10g/L
4, add KH in the ratio of 5g/L
2PO
4, add CaCl in the ratio of 5g/L
2, obtain syrup to be fermented; Get 1/1000 in the syrup of waiting to ferment, be diluted to pol and be 2% the aqueous solution, drop in the yeast tank; 1/0,000 ratios in the syrup total amount of waiting to ferment are got saccharic alcohol Angel Yeast, in dropping into jar, and give rare liquid glucose oxygenation in the jar with aseptic wind; Carry out yeast and expanded numerous 2 hours, obtain yeast juice; With the remaining aqueous sugar juice to be fermented that modulates, pump into fermentation bag then, will expand numerous yeast juice that obtains simultaneously with vacuum primingpump; The aqueous solution with the suction fermentation bag drops in the fermentation bag; Seal fermentation bag then and carried out anaerobically fermenting 30 hours, detect remaining reducing sugar content, when reducing sugar content remains unchanged less than 0.5% also continuous 3 detections; Zymamsis finishes, and obtains residual yeast sedimentation thing and wine liquid clear liquid;
11, alcohol clear liquid to the distiller that obtains of extraction step 10 distills, and extracts thick wine; Pass through rectifying, dehydration again, obtain alcohol fuel 210 grams of 95% (v/v); The yeast sedimentation thing of recovering step 10 cleans, and takes out throw out, and drying promptly obtains yeast feed 20 grams;
12, behind step 11 ethanol distillation, in the remaining mash, add gac, mash is decoloured in dry-matter 5% ratio; Solution after decolouring through male-female-anion-exchange column, through the nanometer ultrafiltration, obtains xylose solution;
13, the xylose solution that step 12 is obtained concentrates, cools off, inserts the wood sugar crystalline substance, crystallization obtains wood sugar crystalline flour 126 grams;
14, ion exchange column elutriant, gac waste residue that the xylose crystalline raffinate that step 13 is produced, step 12 produce mix, and process leaf leaven or fertilizer 921 grams;
Through above flow process, obtain crude pectin 160 grams, Mierocrystalline cellulose 603 grams, xylogen 288 grams, ethanol 210 grams, wood sugar 126 grams, yeast 20 grams and liquid fertilizer 921 grams.Be equivalent to 2 tons of corn straws of every processing, can obtain 921 kilograms of 160 kilograms of pectin, 603 kilograms of Mierocrystalline celluloses, 288 kilograms in xylogen, 210 kilograms of ethanol, 126 kilograms of wood sugars, 20 kilograms in yeast and liquid fertilizers.
Above product current market price is: 120 yuan/kilogram of pectin, 4 yuan/kilogram of Mierocrystalline celluloses, 3 yuan/kilogram in xylogen, 5 yuan/kilogram of ethanol, 24 yuan/kilogram of wood sugars, 0.5 yuan of/kilogram meter of liquid fertilizer, above each item output value is 19200 yuan, 2412 yuan, 864 yuan, 1050 yuan, 3024 yuan, 460.5 yuan.2 tons of corn straw gross output values of stalk are 27010.5 yuan.1 ton of output value of every processing is 13505.25 yuan.
Corn straw is by 400 yuan/ton, and raw materials cost is 800 yuan; 2 tons of corn straw tooling costs: electricity charge 450kw * 0.9 yuan/kwh * 1h=405 unit; Labour cost 7 people * 100 yuan=700 yuan; Fuel cost is 1802 yuan; Auxiliary material takes 2500 yuan, other, 3593 yuan, total cost is 9800 yuan.The profit of 2 tons of corn straws of processing is 17210.5 yuan (not containing other indirectly attributable expenses such as depreciation, sale, storage, transportation).
Claims (10)
1. the method for comprehensive utilization of a corn straw is to be raw material with the cornstalk, through successive set technique co-producing ethanol, fiber, xylogen, pectin, wood sugar and yeast method; Specifically; Be earlier cornstalk to be utilized degradable things such as polysaccharide that acid hydrolyzation will be wherein, pectin, starch to be degraded to the soluble substance aqueous solution; The realization slag charge separates with the degradable thing; Then the soluble substance aqueous solution that obtains is used for fermented extracted alcohol fuel, pectin, wood sugar, separates the slag charge that obtains and use organic solvent method producd fibers and xylogen again.
2. the described method of claim 1 specifically may further comprise the steps:
A) be ground into length thread less than 2 centimetres behind the corn straw defoliation that will gather; Adding mass concentration is rare syrup of 4-10%, contains the sulfuric acid of 5 ‰ mass concentrations in rare syrup, and rare syrup of adding and stalk volume ratio are 2 ~ 5 ︰ 1; The mixture that obtains is processed above 80 purpose slurries; And the water-content in the control slurry rises to 70 ~ 100 ℃ below 85% with slurry temperature, keeps 25 ~ 40 minutes; Accomplish corn straw acidolysis for the first time, make the pectin in the corn straw fully dissolve the rare syrup of entering; Pulp separated is become moisture 50% the slag charge 1 and the aqueous solution 1 that is rich in pectin and syrup;
B) mass concentration that in the slag charge 1 that step a) obtains, adds 2 ~ 5 times of its volumes is rare syrup of 4-10%; The sulfuric acid that contains 5 ‰ mass concentrations in rare syrup; Soaked 15 ~ 30 minutes, and made the slag charge temperature rise to 115 ~ 125 ℃ then, kept 60 ~ 90 minutes; Accomplish the secondary acidolysis, starch, semicellulose, polysaccharide in the slag charge are fully degraded; When treating that the slag charge temperature is reduced to below 100 ℃, the pulp separated after handling is become the slag charge 2 and the aqueous solution 2 that is rich in degraded sugar;
C) slag charge 2 that step b) is obtained by volume 1 ︰ 1 adds clear water and soaks, treat that syrup fully leaches in the slag charge after, carry out slag liquid and separate, obtain syrup acid solution 1 and slag charge 3;
D) slag charge 3 that step c) is obtained adds the ethanol of 30% concentration of 5 ~ 7 times of its volumes; In slag charge 3 and alcoholic acid mixture, add the KOH catalyzer in the ratio of 1g/L again; Behind the mixing, make temperature of charge rise to 100 ℃, kept 60 ~ 90 minutes; Accomplish the alcoholysis process of slag charge 3, the xylogen in the slag charge 3 is fully degraded; Treat that temperature of charge reduces to below 50 ℃, separate obtaining slag charge 4 and lignin liquor;
E) the slag charge 4 usefulness 30% alcohol extraction residual lignin that step d) is obtained obtains extraction liquid and Mierocrystalline cellulose; Remove and recovering step d) ethanol in the lignin liquor that obtains, obtain separating out the aqueous solution that xylogen is arranged, obtain xylogen through conventional the processing again;
F) in the aqueous solution that is rich in pectin and syrup 1 that step a) obtains, adding gac decolours; The ratio that gac adds accounts for 4 ~ 7% of the described corn straw dry matter weight of step a), and the decolouring after-filtration obtains active breeze 1 and filtrating, extraordinarily goes into 95% ethanol by 1.5 of filtrate volume in the filtrating; Making pectin become floss separates out; Accomplish pectin alcohol and analyse, obtain being rich in the slurries of pectin floss, obtain solution 3 and pectin solid substance through solid-liquid separation again; Solution 3 reclaims ethanol after distillation, remain to be syrup acid solution 2;
G) aqueous solution 2 that is rich in degraded sugar with the step b) acquisition obtains mixing syrup with syrup acid solution 2 mixing that step f) obtains, and controlling wherein sugared concentration is 16 ~ 20%, mixes in the syrup at every liter to add: (the NH that generates 0.5 ~ 1.5g
4)
2SO
4Required ammoniacal liquor, the MgSO of 8 ~ 12g
4, 2 ~ 6g KH
2PO
4CaCl with 2 ~ 6g
2, add white lime again and regulate syrup pH to 4 ~ 5;
H) get few part of the syrup solution that step g) modulates; Be diluted to pol and be 2% the aqueous solution; Add saccharic alcohol Angel Yeast, the saccharic alcohol Angel Yeast of adding is 1/0,000 of the syrup total solution weight that obtains of step g), carries out yeast under the aseptic wind oxygenation condition and expands numerous 1 ~ 3 hour; The yeast that will expand then after numerous adds in the good residue syrup of step g) allotment; Fully mix; Anaerobic fermentation 20 ~ 48 hours; Detect remaining content of reducing sugar; When content of reducing sugar remains unchanged less than 0.5% also continuous 3 detections; Alcoholic fermentation finishes, and obtains viable yeast sediment and clear liquid 1, and clear liquid 1 obtains thick wine and the mash of 40%v/v through distillation;
I) mash that step h) obtains after the distillation is pressed wherein 4 ~ 7% adding gacs of dry matter weight, accomplishes the decolouring of mash, filters and obtains clear liquid 2 and active breeze 2; Remove the charged salt ion in the clear liquid 2, through concentrating, lower the temperature, add nucleus, crystallization, drying, obtain the xylose crystalline powder then; The active breeze 1 that step f) is obtained mixes with all waste thing that this step obtains, and obtains liquid fertilizer.
3. the described method of claim 2 is characterized in that: in the step f), the pectin solid substance that obtains further through clean, dry, pulverize back acquisition pectin powder.
4. the described method of claim 2, it is characterized in that: step h), the thick wine that obtains further prepares alcohol fuel through ordinary method.
5. the described method of claim 2 is characterized in that: step I) the charged salt ion in the described removal clear liquid 2 is accomplished through the method for IX and nanometer ultrafiltration.
6. the described method of claim 2 is characterized in that: step I) all waste thing that obtains of described step comprise active breeze 2, the waste liquid that obtains when removing the charged salt ion in the clear liquid 2 and/or concentrate, waste liquid that cooling, crystallization and drying process obtain.
7. the described method of claim 2 is characterized in that: in the step e), remove and reclaim the ethanol in the mixing solutions again after the lignin liquor that earlier said extraction liquid and step d) is obtained mixes.
8. the described method of claim 2 is characterized in that: the syrup acid solution 2 that obtains after the step f) distillation is used for the acidolysis first time of step a) or the secondary acidolysis of step b).
9. the described method of claim 2 is characterized in that: one or both in the ethanol that step e) or step f) reclaim and step h) distill the thick wine merging that obtains, through obtaining the alcohol fuel more than 95% after rectifying, the dehydration; Step h) viable yeast that obtains returns step h) the numerous program loop of expansion use, reuse 6 times after, recovery prepares Yeast protein feed.
10. the described method of claim 1, concrete steps are following:
1) corn straw of gathering can be a fresh straw, can also be the drying in the sun stalk.After raw material is transported to source mill, adopt disclosed stalk disleaf device removal corn straw leaf in enormous quantities among the ZL200910136184.3, this machine directly breaks into length less than 2 centimetres of silks with corn straw when removing the stalk leaf;
2) with 95% vitriol oil, be mixed with the rare syrup liquid that contains 5 ‰ dilute sulphuric acids with rare syrup of 4-10% concentration, use in order to slurrying; The total amount of required rare syrup liquid is prepared by 1/5 of the stalk volume of handling; The stalk treatment capacity is accomplished after 1/5, the step 17 of output) rare syrup liquid of alternative the step preparation of rare syrup that obtain, be used for slurrying;
3) with Stainless Steel Pump with step 2) rare syrup liquid or step 10) and the step 17 of preparation) rare syrup liquid pump of obtaining goes into acidproof high consistency refining machine inlet capable, form continuously current and prepare against feeding slurrying; The filamentary material of the corn straw of step 1) being processed with conveying belt; Feed from the paste roller mill opening for feed continuously; Adjustment diluted acid or rare syrup flow; Make it with the stalk volume ratio be 2 ~ 5 ︰, 1 mixtures, process through acidproof paste roller mill and surpass 80 purpose diluted acid slurries, slurry is from paste roller mill outlet row system stock tank;
4) slurry of step 3) being processed is conveyed into enamel reactor with spiral pump, and the water-content of controlling then in the slurry is no more than 85%;
5), make sulfuric acid concentration in the slurry that step 4) obtains remain on 5 ‰ aimed concn with 10% dilution heat of sulfuric acid adjustment sulfuric acid concentration;
6) after the slurry sulfuric acid concentration of treating step 5) mixed up, the off-response jar sent steam to heat, and temperature rises to 90 ℃ in jar, kept 30 minutes, accomplished an acidolysis of corn straw, made the pectin of corn straw fully dissolve the entering diluted acid;
7) the corn straw slurry after the step 6) acidolysis processing is discharged into feed bin from retort; Use the stainless steel cut pump then; Through stainless steel pipes hot slurry is sent into the stainless steel pulp-extruding machine; So far, the slurry of step 6) is separated into moisture 50% the slag charge and the aqueous solution that is rich in pectin and syrup;
8) slag charge that step 7) is obtained is by 2 steps 2 extraordinarily of its volume) rare syrup liquid of preparation, soaked 20 minutes; Pump into enamel reactor with spiral pump again, treat that slurry is filled after, the off-response jar; Feed steam, make temperature rise to 120 ℃, kept 1 hour; Accomplish the secondary acidolysis, starch, semicellulose, the polysaccharide of slag charge are fully degraded;
When 9) treating that step 8) enamel reactor temperature is reduced to below 100 ℃, the slurry after the secondary acidolysis processing is entered feed bin, send into pulp-extruding machine with the heatproof cutting pump again, the pulp separated after step 8) is handled becomes the slag charge and the aqueous solution that is rich in degraded sugar;
10) slag charge that step 9) is obtained, by volume 1 ︰ 1 adds clear water and soaks, treat that the slag charge syrup fully leaches after, with the pulp-extruding machine squeezing, obtain rare syrup and slag charge again, rare syrup is returned step 3) slurrying;
11) slag charge that step 10) is obtained is extraordinarily gone into 30% ethanol by 5 of slag charge volume, adds the KOH catalyzer in the 1g/L ratio; Behind the mixing, send into enamel reactor, the off-response jar with spiral pump; Send into steam heating, make temperature rise to 100 ℃, kept 1 hour; Accomplish the alcoholysis process of slag charge, the xylogen of slag charge is fully degraded;
12) treat slurry after the step 11) alcoholysis, temperature is reduced to below 50 ℃, and slurry is entered feed bin, pumps into pulp-extruding machine with cutting pump then, and Mierocrystalline cellulose is separated with lignin liquor;
13) slag charge that step 12) is obtained cleans with 30% ethanol earlier, cleans with clear water then, and bleaching promptly obtains Mierocrystalline cellulose;
14) with the xylogen alcohol extraction liquid distillation of step 12) and step 13) acquisition, the alcohol concn in the solution is reduced, reclaim wine liquid simultaneously; Liquid concentrator is treated the ethanol volatilization totally, separates out owing to xylogen is water insoluble, will separate out xylogen and filter, and cleaning, drying promptly obtain xylogen; The wine liquid that reclaims continues on for alcohol and analyses, or is used for distillate fuel ethanol;
15) liquid pectin that step 7) is obtained is sent in acidproof jar with acid, in adding gac with corn straw dry-matter 4 ~ 7% ratios, carries out the liquid pectin decolouring; The liquid pectin that the decolouring after-filtration obtains press 1.5 95% ethanol extraordinarily of liquid pectin volume, and completion pectin alcohol is analysed process, makes pectin become floss and separates out; To be rich in the slurries of pectin floss again, send into whizzer, syrup will be separated with pectin with cutting pump; Syrup is sent into the distiller distillation, reclaims ethanol;
16) cleaning step 15) filter the pectin solid substance that obtains, drying is pulverized, and promptly obtains pectin powder;
17) the syrup acid solution that is rich in the sugared aqueous solution of degraded and step 15) syrup distillation back acquisition that step 9) is obtained is mixed, and controls sugared concentration at 18-20%;
18) with step 17) concentration that obtains is in the syrup of 18-20%, by (the NH that generates
4)
2SO
4For the ratio of 1g/L adds ammoniacal liquor, add MgSO in the ratio of 10g/L
4, add KH in the ratio of 5g/L
2PO
4, add CaCl in the ratio of 5g/L
2, add a small amount of white lime again, the aqueous solution to pH value is adjusted to 4 to 5;
19) the syrup solution that set by step 18) modulates; Get wherein 1/1000, be diluted to pol and be 2% the aqueous solution, drop in the yeast tank; Set by step 18) 1/0,000 ratios of preparation liquid glucose are got saccharic alcohol Angel Yeast; Drop in the jar, and give rare liquid glucose oxygenation in the jar, carry out yeast and expanded numerous 2 hours with aseptic wind;
20) with step 18) aqueous solution that modulates; Pump into fermentation bag with self priming pump; Simultaneously with step 19) the numerous yeast juice of expansion; The aqueous solution with the suction fermentation bag drops in the fermentation bag; Seal fermentation bag then and carried out anaerobic fermentation 20 to 48 hours, detect remaining content of reducing sugar, when content of reducing sugar remains unchanged less than 0.5% also continuous 3 detections; Alcoholic fermentation finishes, and obtains residual sediment and wine liquid clear liquid;
21) keep step 20) residual throw out---viable yeast in the fermentation bag, be used for next liquid glucose fermentation, reuse 6 times after, treat that yeast activity descends, reclaim yeast, cleaning, drying is used to prepare Yeast protein feed;
22) extraction step 20) wine liquid clear liquid behind the fermenting-ripening; Pump into still kettle with vacuum primingpump; Through the thick wine of distillation extraction 40% (v/v), extract alcohol fuel and the mash that concentration is not less than 95% (v/v) with the wine liquid of step 14) recovery and ethanol rectifying, the dehydration of step 15) recovery again;
23) with step 22) distillation after mash, in 4 ~ 7% ratios of dry-matter in the solution, add gac, the completion mash decolouring; Filter and obtain clear liquid and active breeze;
24) with step 23) clear liquid that obtains, through yin, yang, anion-exchange column, part is removed the yin, yang ion in the solution, obtains to be rich in the solution of wood sugar;
25) with step 24) solution that obtains, through the nanometer ultrafiltration, further remove the charged salt ion of solution;
26) with step 25) xylose solution that obtains concentrates, and cooling adds nucleus, crystallization, drying obtains the xylose crystalline powder;
27) with step 26), 25), 24) waste liquid and step 23), 15) waste residue and step 24) the ion exchange column elutriant mixes, and obtains liquid fertilizer.
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