CN102286571A - Clean and high-efficiency production process for preparing xylose and L-arabinose - Google Patents
Clean and high-efficiency production process for preparing xylose and L-arabinose Download PDFInfo
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Abstract
The invention relates to a clean and high-efficiency production process for preparing xylose and L-arabinose and belongs to the field of application of wastes of agriculture and forestry. The production process comprises the following steps of: performing pretreatment on raw materials; hydrolyzing the raw materials in a high-temperature cooking mode; performing neutralizing treatment and performing centrifugal separation on solid slag to obtain xylose or xylooligosaccharide hydrolyzate; adding coarse enzyme solution into xylooligosaccharide solution to hydrolyze to obtain xylose solution; treating the hydrolyzate by Angle yeast; purifying by using active carbon and resin; performing recompression and concentration treatment on the purified hydrolyzate by using a mechanical vapor recompression (MVR) machine; crystallizing the concentrated solution in a gradient program cooling mode to obtain xylose products and xylose mother solution; separating the xylose mother solution by a simulated moving bed or a chromatographic separation technology to obtain a xylose phase and an L-arabinose phase; returning the xylose phase to the xylose solution to concentrate and recrystallize; reusing the xylose mother solution; performing MOVR concentration treatment on the L-arabinose phase and crystallizing in a gradient program cooling mode to obtain L-arabinose products; and reusing the L-arabinose mother solution.
Description
Technical field
The present invention relates to a kind of technology of utilizing raw material cleaner production wood sugars such as agriculture and forestry organic waste material and L-arabinose, especially raw material is obtained the wood sugar crystal through taking agriculture and forestry organic waste materials such as high temperature steaming hydrolysis process processing cotton seed hulls to obtain xylose hydrolysis fluid after the pre-treatment through microbial method removal of impurities sugar and purification process post crystallization, xylose mother liquid is through simulation moving-bed separation post crystallization acquisition wood sugar and L-arabinose crystalline method.
Background technology
The annual product that carries out photosynthesis and obtain is up to nearly 2,000 hundred million tons on the earth, be unique on the earth can ultra-large regenerated utilizability resource.Accounting in the phytomass most lignocelluloses is the abundantest, the most cheap in the world renewable resources, wherein by less than 12% that people utilized.China is a large agricultural country, and the agriculture and forestry organic waste material raw material that is rich in lignocellulose that can be used for producing wood sugar is very abundant.It's a pity that more these raw materials are dropped or burn, not only cause the huge wasting of resources, also caused the serious environmental pollution.So Research on Process of carrying out rare sugar alcohols such as wood sugar and L-arabinose, to improving china natural resources and energy utilization rate, help the farmer richness extra earning to have important and positive meaning, this research invention not only has higher direct economic benefit, and has considerable social benefit.
Wood sugar has almost zero energy value as a kind of base-material of functional nutrient, the bifidus bacillus in the activating human body enteron aisle and short its growth, the immunological competence of raising body, preventing dental caries, reducing blood-fat, the effect of reducing cholesterol and prevention intestinal cancer.The compatibleness of wood sugar and food is fine, and certain purposes is also being arranged aspect light industry, the chemical industry.
L-arabinose is a kind of additive of functional nutrient efficiently, if add 3.5% content in sucrose, can suppress the absorption of 40% sucrose, makes blood glucose value raise about 50% less.Also can suppress fat, preventing constipation promotes bifidobacterium growth, and has the effect that changes the skeletal muscle fibre composition etc.Simultaneously, L-arabinose is a kind of important medicine intermediate, is mainly used to medicine synthetic anticancer, antiviral and the treatment cardiovascular and cerebrovascular diseases, can also be as biochemical reagents, be used for the preparation of bacteria culture medium, or carry out the synthetic of spices, be widely used in food, healthcare products and field of medicaments.
In the process of hydrolysis of hemicellulose, pretreatment technology is an important link, also is one of the effect of restriction hydrolysis and important factor of economy.In order to improve hemicellulose saccharification efficient, reduce its cost, raw-material pre-treatment becomes most important to agriculture and forestry organic waste material.In whole preprocessing process, peeling off or degrading of xylogen is vital.The remaining rate of xylogen is very big to agriculture and forestry organic waste material pre-treatment cost impact, it is whole that to remove delignification very big with its cost difference of xylogen of removing 20-65%, many studies show that, as long as according to different material characteristics, the xylogen of removing 20-65% just can improve hemicellulose hydrolysis efficiency and saccharification productive rate significantly.Preconditioning technique must satisfy following condition simultaneously.1. improve the hydrolysis productive rate and the efficient of hemicellulose; 2. avoid producing generation to the inhibited by product of environment or subsequent technique; 3. avoid the degraded and the loss of carbohydrate; 4. economic feasibility is strong, uses the technique means of less energy-consumption as much as possible, to reduce the technology cost.At present, preconditioning technique mainly comprises the physics method, chemical method, biological process, and some integrated conduct methods such as physical-chemical method.
Industrial traditional hydrolysis of hemicellulose prepare wood sugar process using be the method for sulfuric acid liquid hydrolysis material, whole process of production produces and produces a large amount of waste residues in a large amount of saline sewages and the N-process, 1 ton of wood sugar saline sewage of every production quantity discharged is up to more than 300 tons, and pollutent is difficult to biochemical treatment, and environmental pollution is serious.The present invention adopts simple and practical pretreatment technology in conjunction with the high temperature steaming of clean and effective or the boiling method in conjunction with enzymolysis, the hemicellulose in the agriculture and forestry organic waste material raw material is hydrolyzed produces the technology of xylose hydrolysis fluid, substitutes the classical acid hydrolysis process.Whole production technology need not neutralization and does not have waste residue to produce, and the sewage emissions amount in hydrolytic process has obtained reducing significantly, and 1 ton of wood sugar quantity of wastewater effluent of every production is less than 50 tons.Compare saltiness with the xylose hydrolysis fluid that traditional sulfuric acid process makes and reduced by 80%.
Agriculture and forestry organic waste material is in the process of hydrolysis, the main component of hemicellulose hydrolysate is a wood sugar, has other assorted sugar such as glucose, L-arabinose in addition, and the liquid glucose viscosity that not only obtains after concentrating is very big, and the content of wood sugar is not high causes crystallization yield of xylose lower, and purity is affected.The xylose mother liquid that obtains after the crystallization is because the content of assorted sugar ratio after the process crystallization raises to some extent (especially glucose), xylose crystallization mother liquor can't continue to reply utilization, L-arabinose can't obtain effective purifying, makes that the effective constituent waste in the raw material is serious.Therefore how improving the productive rate and the crystal purity of xylose hydrolysis fluid crystalline xylose, make full use of the effective constituent in the xylose mother liquid simultaneously, reduce production costs, is a problem demanding prompt solution.There are some to utilize yeast fermentation to handle glucose in the xylose mother liquid in recent years, utilize again and simulation moving-bed wood sugar is separated the report that obtains high added value monose with L-arabinose, but because assorted sugared concentration is too high in the mother liquor, osmotic pressure is too big, influence for thalli growth and removal glucose is bigger, also needing in the fermenting process to cause with the mother liquor Macrodilution, increased the weight of the load of handling.
Summary of the invention
The present invention is directed to above problem, be chosen in before the xylose crystalline process, utilize the assorted sugar such as glucose in the yeast saccharomyces cerevisiae processing xylose hydrolysis fluid.Because the sugared concentration in the hydrolyzed solution is lower at this moment, osmotic pressure is suitable, and the assorted sugar such as glucose that thalline can fully consume are wherein grown, thereby efficiently solves the influence of assorted sugar for xylose crystalline, has increased substantially crystalline yield and purity.Simultaneously, only contain other carbohydrates of wood sugar, L-arabinose and minute quantity in the xylose mother liquid that obtains after the crystallization, can directly utilize some separation means to obtain L-arabinose.This technology has improved the productive rate of xylose product effectively, has optimized the treatment process of xylose mother liquid, has reduced production cost, makes raw material obtain more abundant reasonable use.At present in the sugar alcohol industrial production, produced the technology report of L-arabinose relevant for the xylose mother liquid crystallization, but exist the product crystallization yields low mostly, problem such as the not high and rate of recovery of product purity is low, the present invention adopts the isolating technology of simulation moving-bed separation chromatography, wood sugar in the xylose mother liquid is separated with the L-arabinose mixed system, obtain the independent two-phase liquid of wood sugar and L-arabinose respectively, whole separating technology level of automation height, simple to operate, the utilization ratio height of separating filler, the resolution of wood sugar and L-arabinose can reach more than 95%, L-arabinose after the separation carries out condensing crystal mutually again, and the yield of product and purity have all had significantly lifting.
A kind of preparation wood sugar of clean and effective and the production technique of L-arabinose is characterized in that, comprise the steps (seeing Figure of description 1):
1. the preparation wood sugar of a clean and effective and the production technique of L-arabinose is characterized in that, comprise the steps:
(1) the agriculture and forestry organic waste material raw material carries out pre-treatment and soaks pre-treatment; Described agriculture and forestry organic waste material raw material comprises: corn cob, maize straw, rice straw, jowar stalk, cotton seed hulls or bagasse;
Pre-treating technology comprises: raw-material pulverizing, dedusting, washing three process;
The employed soak solution of described immersion pre-treatment starting material is dilute sulphuric acid, dilute hydrochloric acid or rare oxalic acid, the massfraction of dilute sulphuric acid, dilute hydrochloric acid or rare oxalic acid is 0.1-0.5%, soak solution is 4-8 with the massfraction ratio of raw material: 1, the temperature of soaking is 30-100 ℃, and the time of immersion is 6-24h;
After soaking the pre-treatment end, solid-liquid separation obtains pretreated raw material, and the mode of isolated pretreated raw material by washing is regulated the pH value to 4.5-6.0, and soak solution is replied and utilized;
(2) take the method hydrolyzed hemicellulose of high temperature steaming to obtain high temperature steaming wood sugar liquid or high temperature steaming xylo-oligosaccharide liquid through the agriculture and forestry organic waste material raw material after (1) processing, specific as follows;
Pretreated agriculture and forestry organic waste material is added in the reaction unit, adds 5-20 doubly to the water of expecting dry weight admittedly; Initial pH is 5.0-6.0; Boiling 0.5-2h under 145 ℃-155 ℃ the condition; Mixing speed is 80-150rpm; Operating pressure is 0.5-1.0MPa, obtains the xylo-oligosaccharide cooking liquor;
Perhaps agriculture and forestry organic waste material raw materials such as pretreated corn cob or cotton seed hulls are added in the reaction unit, add 5-20 doubly to the water of expecting dry weight admittedly; At initial pH is 4.5-6.0; High temperature steaming 1-3h under 160-180 ℃ the condition; Mixing speed is 80-150rpm; Operating pressure is 0.6-1.2MPa, obtains the wood sugar cooking liquor;
(3) utilize milk of lime to above-mentioned high temperature steaming xylo-oligosaccharide liquid carried out neutralizing treatment to pH at 8.0-9.0, again with phosphoric acid or hydrochloric acid readjustment pH to 6.0, Plate Filtration gets supernatant liquor afterwards;
Xylo-oligosaccharide cooking liquor after the employing crude enzyme liquid that aspergillus niger produced is handled (3) carries out enzymolysis and obtains the wood sugar enzymolysis solution, and is specific as follows:
The Cha Shi substratum, 115 ℃ of sterilization 30min insert aspergillus niger, cultivate the aspergillus niger seed liquor that obtained having spore shape form in 3-4 days under 28-30 ℃ condition; The product enzymic fermentation is cultivated: sucrose 2.4g, MgSO
40.12g, K
2HPO
40.12g, KH
2PO
40.24g, FeSO
40.0012g, NaNO
30.012g, use the 100ml water dissolution, mix with the mixture of corn cob and wheat bran, the mixture of corn cob and wheat bran amounts to 100g, and corn cob and wheat bran mass ratio are 3: 7-7: 3, sterilization 30min obtains fermention medium under 115 ℃ condition;
Under the condition of aseptic technique, in the 100g fermention medium, add aspergillus niger seed liquor 10-15ml with spore shape form, add sterilized water 30-90ml, take the mode of solid state fermentation, under 30 ℃ condition, cultivated 3-4 days; After producing enzymic fermentation cultivation end, under 28-30 ℃ condition, add the vibration of 250ml water and extract solid culture 1-2h, centrifugal collection supernatant liquor is crude enzyme liquid;
Crude enzyme liquid is joined in the xylo-oligosaccharide cooking liquor, and enzymatic hydrolysis condition is temperature: 40-50 ℃, pH=5.0-5.5; Enzyme concentration 5-10ml in the 100ml cooking liquor, the xylo-oligosaccharide concentration in the cooking liquor is 1.5%, obtains wood sugar liquid after 1-2 days through enzymolysis;
Perhaps lime carbonate above-mentioned high temperature steaming wood sugar liquid that (2) are obtained carries out neutralizing treatment and transfers pH to 6.0-7.0, and Plate Filtration gets supernatant liquor;
(4) the adding microorganism is removed the assorted sugar that comprises glucose and semi-lactosi in the wood sugar liquid;
Selected microorganism is at least a of intestinal bacteria, yeast saccharomyces cerevisiae; The required nitrogenous source that ferments is at least a in yeast extract paste, yeast powder, corn steep liquor, Dried Corn Steep Liquor Powder, soybean-cake flour, ammonium sulfate, the urea;
Above-mentioned wood sugar liquid adds above-mentioned nitrogenous source and fully dissolves through after being concentrated into total sugar concentration and being 100-200g/L, and the nitrogen concentration that obtains is 10-20g/L, is mixed with fermention medium;
At glucose concn is 20-30/gL, yeast extract paste concentration is to add at least a of intestinal bacteria, yeast saccharomyces cerevisiae and Angel Yeast in the activation medium of 5-10g/L, make that at least a starting point concentration of intestinal bacteria, yeast saccharomyces cerevisiae and Angel Yeast is 1-2g/L, in 30 ℃ shaking table, rotating speed activation 2-4h with 200-300rpm, centrifugal 15min abandons supernatant liquor, the bottom cell with distilled water wash after recentrifuge 10min, collecting cell mud;
In fermention medium, add cell mud 10-20g/L, leavening temperature 25-35 ℃, fermentation rotating speed 200rpm, air flow is 1-1.5vv
-1Min
-1, fermenting, fermentation time is 6-12h;
(5) fermentation back is centrifugal, gac or polymeric adsorbent then, and perhaps both are in conjunction with wood sugar liquid is carried out purification process;
(6) carry out concentration behind the wood sugar purifying; Wood sugar content in the wood sugar liquid that obtains is 700-800g/L;
(7) take gradient programmed cooling crystalline mode to obtain xylose product and xylose crystallization mother liquor;
(8) xylose crystallization mother liquor that obtains is separated through chromatographic system, obtain wood sugar mutually with L-arabinose mutually;
(9) it is concentrated with the merging of wood sugar refined solution that the wood sugar that step (8) is obtained is back to step (6) mutually, take the mode of gradient programmed cooling to carry out crystallization, obtain wood sugar crystal and xylose mother liquid, xylose mother liquid in xylose mother liquid and the step (7) merges, enter to chromatographic fractionation system and separate repeating step (8); The L-arabinose that (8) are obtained gets L-arabinose product and L-arabinose mother liquor through concentrated, crystallization mutually, and the L-arabinose mother liquor is replied and utilized.
Wherein said agriculture and forestry organic waste material raw material comprises: corn cob, maize straw, rice straw, jowar stalk, cotton seed hulls, bagasse etc., the preferred cotton seed hulls of the present invention is a raw material.
The pre-treating technology of agriculture and forestry organic waste material raw materials such as the described cotton seed hulls of step (1) comprises: raw-material pulverizing, dedusting, washing three process.
The pretreatment technology preferred operations that described agriculture and forestry organic waste material raw materials such as cotton seed hulls after pre-treatment are taked is easy, the simple infusion method of technology is handled, the employed soak solution of wherein said immersion pre-treatment starting material is a dilute sulphuric acid, dilute hydrochloric acid or rare oxalic acid, wherein preferred rare oxalic acid soak solution, reason is that remaining oxalic acid can the mode with carbon source be utilized by Institute of Micro-biology in the fermenting process in later stage in the raw material, adopt rare oxalic acid that raw material soaking is carried out pretreated mode and not only obtained good pre-treatment result, improved the wood sugar yield of high temperature steaming, also reduced the cost of later stage to the consumption and the carbon source adding of xylose metabolism, and the difficulty of later stage desalting treatment.In used rare oxalic acid soak solution, the massfraction of oxalic acid is 0.1-0.5%, and soak solution is 4-8 with the massfraction ratio of raw material: 1, and the temperature of immersion is 30-100 ℃, the time of immersion is 6-24h.After soaking end, through the mode of Plate Filtration, the immersion system is carried out solid-liquid separation obtain pretreated raw material and soak solution, soak solution is replied and is utilized, and the mode of isolated pretreated raw material by washing is regulated raw material self pH value to approaching neutral.
Step (2) utilizes the method for agriculture and forestry organic waste material raw material production xylo-oligosaccharide cooking liquors such as high-temperature cooking process hydrolysis of corncob, cotton seed hulls to be: agriculture and forestry organic waste materials such as pretreated corn cob or cotton seed hulls are added in the reaction unit, add 5-20 doubly to the water of expecting dry weight admittedly; Initial pH is 5.0-6.0; High temperature steaming 0.5-2h under 145 ℃-155 ℃ the condition; Mixing speed is 80-150rpm; Operating pressure is 0.5-1.0MPa.
Utilize the method for high-temperature cooking process hydrolysis agriculture and forestry organic waste material raw material production wood sugar cooking liquor to be: agriculture and forestry organic waste material raw materials such as pretreated corn cob or cotton seed hulls to be added in the reaction unit, to add 5-20 doubly to the water of expecting dry weight admittedly; At initial pH is 4.5-6.0; High temperature steaming 1-3h under 160-180 ℃ the condition; Mixing speed is 80-150rpm; Operating pressure is 0.6-1.2MPa.In this operation, hemicellulose is to be wood sugar by pyrohydrolysis under the environment of little sour partial neutral.
Among the present invention, utilize that the xylo-oligosaccharide yield is 0.15-0.17g/g in the agriculture and forestry organic waste material raw material production xylo-oligosaccharide cooking liquor such as high-temperature cooking process hydrolysis cotton seed hulls, produce that the wood sugar yield is 0.20-0.22g/g in the wood sugar cooking liquor.After two kinds of high temperature steaming hydrolytic processes finished, the steam of collect discharging while hot was to the steam storage tank, can need thermal process that heat energy is provided for immersion treatment technology or other.This operation can be removed the impurity of a part of easy volatile in the cooking liquor simultaneously, as furfural, phenol, acetate, also makes cooking liquor carry out concentrating to a certain degree.The cooking liquor of collecting out after the cooling carries out (containing hydrolysis residue) next step neutralizing treatment.
Step (3) utilize milk of lime to above-mentioned high temperature steaming xylo-oligosaccharide liquid carried out neutralizing treatment to pH at 8.0-9.0, again with phosphoric acid or hydrochloric acid readjustment pH to 6.0, Plate Filtration gets supernatant liquor afterwards.Perhaps lime carbonate above-mentioned high temperature steaming wood sugar liquid that (2) are obtained carries out neutralizing treatment and transfers pH to 6.0-7.0, and Plate Filtration gets supernatant liquor;
The present invention utilizes milk of lime high temperature steaming xylo-oligosaccharide liquid to carry out neutralizing treatment, regulate the boiling mixed solution to pH at 8.0-9.0, afterwards again with about phosphoric acid or hydrochloric acid readjustment pH to 6.0.The inhibition of the some effects enzyme liquid enzymolysis efficiency of taking the neutralizing treatment cooking mixture also can remove to exist in the high temperature steaming xylo-oligosaccharide liquid.Owing to have organic toxin and metal ions such as a small amount of furfural, phenol, acetate, pigment in the xylo-oligosaccharide cooking liquor, crude enzyme liquid that next step aspergillus niger produces carried out enzymolysis acquisition wood sugar liquid have bigger influence.Therefore the present invention adopt earlier milk of lime cross in and xylo-oligosaccharide high temperature steaming liquid to pH at 8.0-9.0, this moment can not only be fully in cooking liquor in acid, and the impurity in the calcium sulfate flocks that the produces energy effective elimination xylo-oligosaccharide liquid, to realize the raising of enzymolysis efficiency.Afterwards again with about phosphoric acid or hydrochloric acid readjustment pH to 6.0,, aspergillus niger provides suitable pH environment when the enzymolysis for producing enzyme liquid.Can be increased to more than 80% through the wood sugar yield of xylo-oligosaccharide cooking liquor in enzymolysis process after this neutralizing treatment, reach the requirement of producing wood sugar liquid.
The present invention utilizes lime carbonate that high temperature steaming wood sugar liquid is carried out neutralizing treatment, regulate the boiling mixed solution to pH at 6.0-7.0.This method not only helps the suitable pH environment of later stage purifying concentration, and the calcium sulfate flocks of generation also can be removed the impurity that exists in the cooking liquor.
Cotton seed hulls waste residue after adopting plate filter with high temperature steaming and the throw out elimination in the lump that neutralization produced obtain the cooking liquor after supernatant liquor is neutralizing treatment.Concrete grammar is: the cooking mixture after will being neutralized by charging pump is pressed into filter chamber, concentrates after filtration is finished and discharges, and adds 30-50 ℃ of water 2L then, solid is washed repeated washing 2 times.
Through the xylo-oligosaccharide cooking liquor after the neutralizing treatment, the crude enzyme liquid that the preferred aspergillus niger 2349 of adding aspergillus niger is produced carries out enzymolysis to the xylo-oligosaccharide in the cooking liquor and produces wood sugar, to obtain the wood sugar enzymolysis solution.The power consumption of this technology relatively still less and makes and does not degrade completely in the high temperature steaming liquid that the further enzymolysis of xylo-oligosaccharide obtains wood sugar, improved raw material production wood sugar yield.The employed crude enzyme liquid of this process has been saved Financial cost and Environmental costs for self-control.
Xylo-oligosaccharide cooking liquor after the crude enzyme liquid that the aspergillus niger 2349 of employing high yield zytase and xylosidase is produced is handled (3) carries out enzymolysis and obtains the wood sugar enzymolysis solution.Shake-flask seed substratum: Cha Shi substratum (SODIUMNITRATE 3g, dipotassium hydrogen phosphate 1g, sal epsom 0.5g, Repone K 0.5g, ferrous sulfate 0.01g, sucrose 30g distilled water 1000ml), 115 ℃ of sterilization 30min, insert aspergillus niger 2349, cultivating the 3-4 days aspergillus niger length to the seed culture medium under 28-30 ℃ condition has spore shape form to be advisable.Producing the enzymic fermentation substratum is: sucrose 2.4g, MgSO
40.12g, K
2HPO
40.12g, KH
2PO
40.24g, FeSO
40.0012g, NaNO
30.012g, use the 100ml water dissolution, mix with the mixture of corn cob and wheat bran, the mixture of corn cob and wheat bran amounts to 100g, and corn cob and wheat bran mass ratio are 3: 7-7: 3,30min sterilizes under 115 ℃ condition.Under the condition of aseptic technique, in the 100g fermention medium, add aspergillus niger seed liquor 10-15ml with spore shape form, add sterilized water 30-90ml, take the mode of solid state fermentation, under 30 ℃ condition, cultivated 3-4 days.After producing enzymic fermentation cultivation end, under 28-30 ℃ condition, add the vibration of 250ml water and extract solid culture 1-2h, centrifugal collection supernatant liquor is crude enzyme liquid.Crude enzyme liquid is joined in the xylo-oligosaccharide cooking liquor, and enzymatic hydrolysis condition is temperature: 40-50 ℃, pH=5.0-5.5.Enzyme concentration 5-10ml in the 100ml cooking liquor, the xylo-oligosaccharide concentration in the cooking liquor is 1.5%, obtains the wood sugar enzymolysis solution after 1-2 days through enzymolysis.
Step (4) adding microorganism is removed the assorted sugar that comprises glucose and semi-lactosi in the wood sugar liquid, and wood sugar in the not metabolism wood sugar liquid and L-arabinose effective constituent, to remove the interference of the assorted sugar that influences wood sugar and the two fractional crystallization of L-arabinose.The present invention is at least a for intestinal bacteria, yeast saccharomyces cerevisiae of used bacterial classification when utilizing microbe fermentation method to handle, preferred Angel Yeast; The required nitrogenous source that ferments is at least a in yeast extract paste, yeast powder, corn steep liquor, Dried Corn Steep Liquor Powder, soybean-cake flour, ammonium sulfate, the urea, preferred yeast powder or Dried Corn Steep Liquor Powder.
Wood sugar liquid adds above-mentioned nitrogenous source and fully dissolves after being concentrated into total sugar concentration and being 100-200g/L through MVR machinery recompression high-efficiency evaporating system, and the nitrogen concentration that obtains is 10-20g/L, is mixed with fermention medium.At glucose concn is 20-30g/L, yeast extract paste concentration is to add the Angel Yeast bacterial strain in the activation medium of 5-10g/L, make that its starting point concentration is 1-2g/L, in 30 ℃ shaking table, rotating speed activation 2-4h with 200-300rpm, centrifugal 15min abandons supernatant liquor, the bottom cell with distilled water wash after recentrifuge 10min, collecting cell mud.In fermention medium, add yeast slurry 10-20g/L in fermentor tank, leavening temperature 25-35 ℃, fermentation rotating speed 200rpm, air flow 1-1.5vv
-1m
-1, fermentation volume 16L ferments, and fermentation time is 6-12h.
Step among the present invention (5) is the wood sugar liquid after handling through Angel Yeast, takes the centrifugal mode to remove thalline and insoluble substance in the treatment solution (4), obtains the wood sugar treatment solution.After isolated somatic cells adds the activation medium of fresh sterile, through the activation culture process in the step (4), change in the next batch fermention medium and reuse, many batches of formulas move in circles, and become feeble and die until cell.
The wood sugar treatment solution that obtains adopts gac or macroporous adsorbent resin or both bonded modes that it is carried out purification process.The huge active surface that Powdered Activated Carbon has, absorption impurity and pigment are removed the impurity of absorption together with gac in the lump by filtering then, reach liquid glucose purified purpose.The process of charcoal absorption impurity belongs to physical adsorption, and the organic ability of charcoal absorption is much larger than the absorption inorganic salts, and the ability of absorption macromole organic pigment is much larger than the ability of absorption small molecules organic pigment.Ion-exchange: liquid glucose by cationic exchange and anionresin after, impurity cationic in the liquid glucose and impurity negatively charged ion all are adsorbed on the ion exchange resin and are removed, and these foreign ions are the integral part of sulfuric acid in the liquid glucose, organic acid and the grey impurity that grades.Submit the hydrogen ion and the hydroxide ion that change to liquid glucose from resin and then be combined into water.Wherein a kind of mode of activated carbon treatment is, in hydrolyzed solution according to the wood sugar mass ratio be that the ratio of 10-30% adds gac, slowly stir down at 30-90 ℃, pigment, nitrogenous thing, organism and colloid in the absorption boiling liquid, 20min is to 2h in decolouring.Wood sugar liquid after the activated carbon treatment is removed the gac part through the mode of Plate Filtration, and the xylose hydrolysis fluid that obtains achromaticity and clarification is the wood sugar liquid after the activated carbon treatment.
The processing mode of the wood sugar liquid employing zwitterion resins exchange after the activated carbon treatment is removed the ion in the wood sugar liquid, and the Zeo-karb trade mark of employing is 732, is strongly acidic styrene type cation exchange resin, and exchange capacity is 4.5Mmol/g; The anionite-exchange resin trade mark that adopts is that D201 is a strong-basicity styrene series anion exchange resin, and exchange capacity is 3.7Mmol/g.732 strongly acidic styrene type cation exchange resins and D201 strong-basicity styrene series anion exchange resin are successively connected hydrolyzed solution are carried out desalting treatment.The resin column blade diameter length ratio is 1: 4-5, and the material of resin column is glass reinforced plastic or carbon steel plastics, and inlet amount is 1.2-1.6 column volume per hour, and working temperature is a room temperature, and the electric conductivity value of on-line monitoring discharging feed liquid guarantees the specific conductivity＜50 μ s/cm of discharging feed liquid.Secular use reduces ion-exchange capacity even loses, and needs according to circumstances resin to be carried out activation treatment.Activation method can be decided according to pollution condition and condition, and general positive resin is subject to Fe in softening
3+Pollute progressively dilution after the acceptable salts acid soak.Negative resin is subject to Organic pollutants, and available 10%NaCl+2-5%NaOH mixing solutions soaks or drip washing.
The wood sugar content that wood sugar liquid behind the purifying that step (6) obtains (5) carries out in the wood sugar liquid that certain concentration obtains is 700-800g/L.The concentration technology of wood sugar liquid is divided into wherein a kind of in membrane concentration and the MVR machinery recompression concentration technology or is used in combination in twos.The membrane concentration operation comprises ultrafiltration, nanofiltration, reverse osmosis three process.Ultrafiltration is to remove macromolecular impurity such as protein in the cooking liquor, pigment etc. by hollow-fibre ultrafiltration device.It is to utilize suitable nanofiltration membrane that cooking liquor is carried out selectivity to concentrate and also have partially desalted effect simultaneously concurrently that nanofiltration concentrates, to alleviate the burden of postorder ion-exchange.Consider that from the energy consumption aspect evaporation concentration energy consumption is very big on the technology, a large amount of energy consumptions is also brought environmental pollution, and nanofiltration concentrates the energy consumption that can reduce evaporation greatly, shortens the time of evaporation, improves product quality.Reverse osmosis is nanofiltration to be seen through liquid carry out the desalination recovery, replys utilization to obtain pure water, thereby saves water resources.Adopt MVR machinery recompression high-efficiency evaporating system concentration technology high temperature steaming liquid.The whole plant energy-saving effect is outstanding, starting except that driving, need not to give birth to steam in the whole evaporation process.The compressed machine compression of the steam of at first low potential temperature, temperature, pressure improve, and heat content increases, and enters the interchanger condensation then, to make full use of the latent heat of steam.Technology at first is pumped into high temperature steaming liquid in the falling-film evaporator, by the material recycle pump at the heating tube internal recycle.Initial steam is given heat with live steam outside pipe, the solution ebuillition of heated is produced secondary vapour, and the secondary vapour of generation is sucked by the turbo-charging blower fan, and after supercharging, the secondary stripping temperature improves, and enters the heating chamber circulating and evaporating as the heating thermal source.Behind normal the startup, turbo-driven compressor sucks secondary steam, becomes heating steam after supercharging, carries out circulating and evaporating continually like this.The moisture that evaporates finally becomes water of condensation and discharges.
Wood sugar concentrated solution after step (7) is handled (6) adopts gradient programmed cooling crystalline mode to obtain xylose product and xylose crystallization mother liquor; To be concentrated into the wood sugar liquid that total sugar concentration is 700-800g/L, adopt the mode crystallization of gradient programmed cooling to go out the wood sugar crystal, obtain xylose crystallization mother liquor simultaneously.It is 60-80 ℃ that the mode of gradient programmed cooling is taked initial temperature, final temperature is 20-30 ℃, 0.5-2 ℃ mode is per hour taked in cooling, adds the solid content massfraction and be 0.1% commodity wood sugar in the time of 45-55 ℃ as crystal seed, and under final temperature growing the grain 12-24h.Owing to passed through microbiological treatment before the wood sugar liquid, having removed assorted sugar such as glucose, semi-lactosi disturbs later stage product crystalline, its crystallization yield is compared with traditional product crystallization yield that contains assorted sugar such as glucose, semi-lactosi and has been improved nearly 10%, reached about 70%, crystalline purity is greater than 99%.Crystallisation process finishes after centrifugation obtains xylose mother liquid, and crystal obtains the crystalline xylose product with the washing with alcohol after drying.
The chromatographic system that utilizes in the described step (8) separates wood sugar and L-arabinose in the xylose mother liquid, obtains wood sugar and selects for use the simulated moving bed chromatography of the Zeo-karb of level of automation high the calcium type that is filled with, plumbous type or sodium type to separate with the method for L-arabinose phase mutually.Because the simulated moving bed chromatography isolation technique is carried out separating of wood sugar and L-arabinose to xylose crystallization mother liquor, whole automation technolo degree height is simple to operate, has saved the consumption of resin greatly, has reduced pollution.
The xylose crystallization mother liquor that step (7) is obtained enters the pillar that 20 2.5*50cm are housed, and having filled calcium type resin cation (R.C.) is the simulated moving bed chromatography system of sorbent material, carries out chromatographic separation.Separation temperature 60-85 ℃, xylose mother liquid charging feeding rate 300-500mL/h, pure water elution speed 1-2L/h.Collect wood sugar and L-arabinose two-phase liquid after the system balancing, biphase purity is all more than 95%, and replying yield is more than 90%; After simulated moving bed chromatography system is separated, obtain wood sugar mutually with L-arabinose two-phase liquid mutually.
The wood sugar that described step (9) obtains (8) is back to step (6) mutually and merges concentrated with the wood sugar refined solution, take the mode of gradient programmed cooling to carry out crystallization, obtain wood sugar crystal and xylose mother liquid, xylose mother liquid in xylose mother liquid and the step (7) merges, enter to chromatographic fractionation system and separate repeating step (8); The L-arabinose that (8) are obtained gets L-arabinose product and L-arabinose mother liquor through concentrated, crystallization mutually, and the L-arabinose mother liquor is replied and utilized.
Advantage of the present invention
1, the inventive method is raw material with the agriculture and forestry organic waste material, through simple and practical pretreatment technology in conjunction with the high temperature steaming of advanced clean and effective or boiling method in conjunction with enzymolysis, technology to agriculture and forestry organic waste material raw material production xylose hydrolysis fluid substitutes the classical acid hydrolysis process, the whole production technological operation is simple and safe, corrodibility to equipment is little, a large amount of acid in traditional hydrolysis process have been avoided, the consumption of alkali, and the system that obtains after handling need not neutralization and does not have waste residue to produce, sewage emissions amount in hydrolytic process has obtained reducing significantly, and 1 ton of wood sugar quantity of wastewater effluent of every production is less than 50 tons.Compare saltiness with the xylose hydrolysis fluid that traditional sulfuric acid process makes and reduced by 80%.Two kinds of hydrolyzed solutions that the present invention obtains are after microorganism and purification process, the crystallization yield and the purity of wood sugar and L-arabinose product are greatly improved, the utilization that the assorted sugar that also only contains wood sugar, L-arabinose and minute quantity in the xylose mother liquid that obtains simultaneously is more conducive to the later stage with separate, avoided the waste of raw material, made raw material obtain more abundant and utilization science.The present invention produces raw materials used wide material sources, the compact easy handling of production technique, and two kinds of products of high wood sugar of the added value of product that can obtain simultaneously and L-arabinose, whole production technology is clean and effective both, has sustainability again, meets the idea of biorefinery.
2, the present invention is by choosing specific microbial strains, wood sugar liquid after the purified processing of specific consumption, remove assorted sugar such as glucose, semi-lactosi etc. that it influences later stage wood sugar and L-arabinose purified crystals process, simultaneously do not lose wood sugar and L-arabinose, the separation of being convenient to the later stage is produced.Effectively improve and avoided in the old technology because the assorted sugared excessive concentration in the xylose mother liquid, osmotic pressure is excessive, influence for assorted sugar such as thalli growth and removal glucose is bigger, also needs in the fermenting process the mother liquor Macrodilution, has increased the weight of to handle the drawback of load.Therefore the present invention takes to utilize the assorted sugar such as glucose in the yeast processing xylose hydrolysis fluid before xylose crystalline.Because sugared concentration is lower in the xylose hydrolysis fluid, osmotic pressure is suitable, and the assorted sugar such as glucose that yeast can fully consume are wherein grown, so the clearance height of assorted sugar such as glucose and semi-lactosi.Wood sugar liquid has passed through microbiological treatment, the assorted sugar that also only contains wood sugar, L-arabinose and minute quantity in the wood sugar liquid that obtains, avoided assorted sugar such as glucose, semi-lactosi that later stage wood sugar and L-arabinose product crystalline are disturbed, the crystallization yield of later stage wood sugar and L-arabinose and purity are greatly improved.Compare with the yield of the traditional hydrolyzed solution crystalline xylose of not removing assorted sugar such as glucose, semi-lactosi and to have improved nearly 10 percentage point, reached about 70%, wood sugar crystalline purity is greater than 99%.
3, since early stage the assorted sugar in the hydrolyzed solution obtained effective removal, other sugar that only contain wood sugar, L-arabinose and minute quantity in the xylose crystallization mother liquor, the purity of wood sugar, L-arabinose effective constituent with do not take microbial method to handle to compare to have obtained tangible rising, xylose mother liquid can more effectively be used for the answer utilization in later stage, make raw material obtain more abundant and utilization science, significantly improved the utility value of xylose mother liquid.In conjunction with the simulated moving bed chromatography isolation technique xylose crystallization mother liquor is carried out separating of wood sugar and L-arabinose, whole automation technolo degree height, simple to operate, saved the consumption of resin greatly, reduced pollution.Because the purity height of two kinds of products has significantly improved product separation effect and yield in the mixed solution.The L-arabinose product with high added value that extracts from xylose mother liquid effectively reduces the production cost of L-arabinose raw material, has significantly reduced the cost of whole technology, has avoided the waste of raw material, has significantly improved economic worth.
Problems such as 4, concentration process energy consumption height, quantity of wastewater effluent be big, the present invention has developed the novel concentrated rectification process-MVR machinery recompression evaporation process of a cover, realizes the zero release and the high yield of waste water.MVR is the energy that utilizes it self secondary steam of producing again, thereby reduces a technology of the demand of the energy to external world.Its working process is the compressed machine compression of the steam of low potential temperature, and temperature, pressure improve, and heat content increases, and enters the interchanger condensation then, to make full use of the latent heat of steam.Except that opening starting, need not to give birth to steam, energy-conserving and environment-protective in the whole evaporation process.The MVR machinery recompression evaporation process that the present invention adopts replaces traditional multiple-effect evaporation concentration technology, can realize the recycling of water and the significantly reduction of energy consumption, and evaporating water per ton only needs power consumption 20 degree, and energy consumption has reduced more than 80%.This The Application of Technology has low working cost, operates steadily and characteristics that level of automation is high simultaneously.
5, the present invention produces raw materials used wide material sources, and production technique compactness, easy handling can obtain two kinds of high value added products of wood sugar and L-arabinose simultaneously, improve additional value of farm products greatly.Effectively solve the high pollution that exists in the existing industrial production wood sugar process, the not high and bigger problem of production cost of high energy consumption, the rate of recovery.Whole production technology is clean and effective both, has sustainability again, meets the idea of biorefinery, and production cost is controlled in the 60-70% of productive value simultaneously, has bigger using value.
Description of drawings
Schema of the present invention.
Embodiment
Embodiment 1
(1) pre-treatment prepares the method for wood sugar liquid in conjunction with enzymolysis in conjunction with high temperature steaming or boiling
Selecting the agriculture and forestry organic waste material cotton seed hulls is raw material.The cotton seed hulls pre-treatment comprises pulverizing, the dedusting of raw material, the three process of washing.At first to pulverize and be sieved to the order number in pulverizer be 10 purpose solid particulates to the cotton seed hulls that purchase is obtained.Then the impurity in the cotton seed hulls particle and upper layer silt dust etc. is carried out dust removal process, to alleviate back operation burden.At last the agriculture and forestry organic waste material particles such as cotton seed hulls after the dust removal process are washed protein, pigment, pectin substance, the ash of removing part in its fiber, impurity such as tannin teas.The three-procedure of pre-treatment is the quality that improves the later stage product, the important measures that reduce cost.
Carry out pre-treatment through the cotton seed hulls after the pre-treatment.The pretreatment technology selection operation is easy, the simple infusion method of technology is handled, and the employed soak solution of pre-treatment cotton seed hulls is that massfraction is 0.1% dilute sulphuric acid, and used immersion liquid is 5: 1 with the massfraction ratio of raw material, and soaking temperature is 60 ℃, and soak time is 6h.After soaking end, through the mode of Plate Filtration, the immersion system is carried out solid-liquid separation obtain pretreated raw material and soak solution, soak solution is replied and is utilized, and the mode of isolated pretreated raw material by washing is regulated raw material self pH value to approaching neutral.
(2) high-temperature cooking process production is based on the high temperature steaming wood sugar liquid of wood sugar
Add in the pyroreaction still through pre-treatment and pretreated particle cotton seed hulls 3Kg (dry weight), high temperature stainless steel reactor wherein, capacity 50L adds 10 times to the water of expecting dry weight admittedly.The anchor formula is adjustable, and rotating speed stirs, electrically heated, cooling.Airtight high pressure heating, temperature is set at 165 ℃, and 70rpm stirs, and operating pressure is about 1.0MPa, and maintains 165 ℃ of following 2h, and the time of control intensification and cooling is within 0.5h.After the boiling hydrolysis finished, high-temperature steam was expelled to storage tank from high temperature conduit; The productive rate of wood sugar is 0.20-0.22g/g in the cooking liquor, and the xylo-oligosaccharide productive rate is 0.03-0.04g/g, and the glucose productive rate is that 0.02-0.3g/g and L-arabinose productive rate are 0.01-0.02g/g (with the cotton seed hulls dry weight basis).
Utilize lime carbonate that high temperature steaming wood sugar liquid is carried out neutralizing treatment, regulate the boiling mixed solution to pH 6.0, this method not only helps the suitable pH environment of later stage purifying concentration, the calcium sulfate flocks of generation also can be removed the impurity that exists in the cooking liquor.Cotton seed hulls waste residue after adopting plate filter with high temperature steaming and the throw out elimination in the lump that neutralization produced obtain the wood sugar liquid after supernatant liquor is neutralizing treatment.Concrete grammar is: the cooking mixture after will being neutralized by charging pump is pressed into filter chamber, concentrates after filtration is finished and discharges, and adds 50 ℃ of water 5L then, and solid is washed, and repeated washing 2 times is collected filtrate and obtained wood sugar liquid.
(3) purifying of wood sugar liquid and concentration
It is 120g/l that wood sugar liquid is concentrated into total sugar concentration through MVR machinery recompression high-efficiency evaporating system.Add the 12g/l Dried Corn Steep Liquor Powder and be configured to fermention medium this moment, is driven in the 20L fermentor tank stand-by.At glucose concn is 20g/L, yeast extract paste concentration is to add Angel Yeast in the substratum of 5g/L, make that its starting point concentration is 1g/L, in 30 ℃ shaking table, rotating speed activation 2h with 200rpm, centrifugal 15min abandons supernatant liquor, the bottom yeast with distilled water wash after recentrifuge 10min, collect yeast slurry.
In fermention medium, add yeast slurry 20g/L in fermentor tank, 30 ℃ of leavening temperatures, fermentation rotating speed 200rpm, air flow 1vv
-1m
-1, fermentation volume 16L ferments.Timing sampling HPLC analyzes the wherein content of each sugar component between yeast phase, after fermentation 6h, only contains the ethanol that wood sugar, L-arabinose and glucose metabolism are produced in the fermented liquid, and the clearance of assorted sugar such as glucose stops fermentation this moment more than 98%.Through the wood sugar liquid after the yeast saccharomyces cerevisiae ATCC9080 processing, take the centrifugal mode to remove thalline and insoluble substance in the treatment solution, obtain the wood sugar treatment solution, after isolated somatic cells adds the activation medium of fresh sterile, through above-mentioned activation culture process, change in the next batch fermention medium and reuse, many batches of formulas move in circles, and become feeble and die until cell.
With 65L wood sugar treatment solution (wood sugar 20-22g/l, L-arabinose 2-3g/l) is driven in the bleacher of 100L, in hydrolyzed solution according to the wood sugar mass ratio be that 15% ratio adds gac, slowly stir decolouring 1h down at 60 ℃, pigment, nitrogenous thing, organism and colloid in the absorption boiling liquid.Wood sugar liquid after the activated carbon treatment is removed the gac part through the mode of Plate Filtration, and the xylose hydrolysis fluid that obtains achromaticity and clarification is the wood sugar liquid after the activated carbon treatment.
The processing mode of the wood sugar liquid employing zwitterion resins exchange after the activated carbon treatment is removed the ion in the wood sugar liquid.Wood sugar liquid is passed through 001*7 type Zeo-karb series connection 201*7 type anionite-exchange resin, at flow velocity 1L/h, under the condition of room temperature, the electric conductivity value of on-line monitoring discharging feed liquid, the specific conductivity＜50 μ s/cm of assurance discharging feed liquid.Through the wood sugar liquid behind gac and the ion-exchange resin purification, take the mode of MVR machinery recompression high-efficiency evaporating to carry out concentration, the total sugar concentration to wood sugar liquid is 800g/L.
(4) wood sugar and L-arabinose separates and crystallization processes
After wood sugar liquid was purified and concentrated, its initial total sugar mass concentration was 800g/L, and contain wood sugar this moment in the hydrolyzed solution mass concentration is 720g/L, and the mass concentration that contains L-arabinose is 80g/L.
What carry out that the crystallization mode of wood sugar takes is the method for gradient programmed cooling, initial temperature is 70 ℃, rate of temperature fall crystallisation by cooling according to 2 ℃/h, when treating that temperature is reduced to 50 ℃, the crystal seed of adding 0.25%, after crystal seed is educated brilliant 1h, then the rate of temperature fall according to 1.5 ℃/h continues crystallisation by cooling, be cooled to about 20 ℃, growing the grain 6h, the wood sugar crystal taking-up back of separating out is centrifugal with supernatant liquor and the concentrated fore portion merging of wood sugar liquid, repeat above-mentioned condensing crystal process, the centrifugal solid that obtains washes 2 times with dehydrated alcohol, and then 45 ℃ of drying in oven obtain the xylose crystalline product.Crystallization finishes the back and obtains wood sugar crystal and xylose crystallization mother liquor, and wherein the purity of xylose product is more than 99%, and crystallization yields is 67%.Contain the wood sugar of 210g/L and the L-arabinose of 73g/L in the xylose crystallization mother liquor.
The xylose crystallization mother liquor of above-mentioned acquisition is entered the pillar that 20 2.5*50cm are housed, and having filled calcium type resin cation (R.C.) is the simulated moving bed chromatography system of sorbent material, carries out chromatographic separation.65 ℃ of separation temperatures, feeding rate 200mL/h, pure water elution speed 1.2L/h.Collect wood sugar and L-arabinose two-phase liquid after the system balancing, biphase purity is all more than 95%, and replying yield is more than 98%.
It is 800g/L that the L-arabinose that simulation moving-bed separation is obtained adopts MVR machinery recompression high-efficiency evaporating systems to be concentrated into L-arabinose concentration down at 80 ℃, then according to the rate of temperature fall crystallisation by cooling of 2.5 ℃/h, when treating that temperature is reduced to 50 ℃, the crystal seed of adding 0.25%, after crystal seed is educated brilliant 1h, then the rate of temperature fall according to 1.5 ℃/h continues crystallisation by cooling, be cooled to about 20 ℃, growing the grain 6h, with centrifugal after the L-arabinose crystal taking-up of separating out the isolated L-arabinose of supernatant liquor and chromatographic system is merged mutually, repeat above-mentioned condensing crystal process, the centrifugal solid that obtains washes 2 times with dehydrated alcohol, and then 45 ℃ of drying in oven, the L-arabinose crystallization yields is 68%, purity is more than 99%.
Xylose mother liquid is separated the wood sugar obtain to be returned mutually and is incorporated in initial wood sugar liquid of the 4th step, adopting MVR machinery recompression high-efficiency evaporating system to be concentrated into xylose concentration is 800g/L, repeat the xylose crystalline step, obtain wood sugar crystal and xylose crystallization mother liquor, the xylose crystalline productive rate is 60%, purity is more than 99%, enter after the xylose mother liquid mixing that initial xylose crystalline of xylose mother liquid that this step obtains and the 4th step obtains simulation moving-bed separation system obtain wood sugar mutually with the L-arabinose phase, with this repeatedly.
Embodiment 2
(1) pre-treatment prepares the method for wood sugar liquid in conjunction with enzymolysis in conjunction with high temperature steaming or boiling
Selecting the agriculture and forestry organic waste material cotton seed hulls is raw material.The cotton seed hulls pre-treatment comprises pulverizing, the dedusting of raw material, the three process of washing.At first to pulverize and be sieved to the order number in pulverizer be 20 purpose solid particulates to the cotton seed hulls that purchase is obtained.Then the impurity in the cotton seed hulls particle and upper layer silt dust etc. is carried out dust removal process, to alleviate back operation burden.At last the agriculture and forestry organic waste material particles such as cotton seed hulls after the dust removal process are washed protein, pigment, pectin substance, the ash of removing part in its fiber, impurity such as tannin teas.The three-procedure of pre-treatment is the quality that improves the later stage product, the important measures that reduce cost.
Carry out pre-treatment through the cotton seed hulls after the pre-treatment.The pretreatment technology selection operation is easy, the simple infusion method of technology is handled, the employed soak solution of pre-treatment cotton seed hulls is that massfraction is 0.25% dilute sulphuric acid, used immersion liquid is 6: 1 with the massfraction ratio of raw material, and soaking temperature is 30 ℃, and soak time is 24h.After soaking end, through the mode of Plate Filtration, the immersion system is carried out solid-liquid separation obtain pretreated raw material and soak solution, soak solution is replied and is utilized, and the mode of isolated pretreated raw material by washing is regulated raw material self pH value to approaching neutral.
(2) high-temperature cooking process production high temperature steaming xylo-oligosaccharide liquid prepares wood sugar liquid in conjunction with enzymolysis
Add in the pyroreaction still through pre-treatment and pretreated particle cotton seed hulls 4.5Kg (dry weight), high temperature stainless steel reactor wherein, capacity 50L adds 8 times to the water of expecting dry weight admittedly.The anchor formula is adjustable, and rotating speed stirs, electrically heated, cooling.Airtight high pressure heating, temperature is set at 155 ℃, and 70rpm stirs, and operating pressure is about 0.8MPa, and maintains 155 ℃ of following 1h, and the time of control intensification and cooling is within 0.5h.After the boiling hydrolysis finished, high-temperature steam was expelled to storage tank from high temperature conduit; The productive rate of xylo-oligosaccharide is 0.14g/g in the cooking liquor, and the wood sugar productive rate is 0.06g/gl, and the glucose productive rate is that 0.021g/g and L-arabinose productive rate are 0.013g/g (with the cotton seed hulls dry weight basis).
The present invention utilizes milk of lime high temperature steaming xylo-oligosaccharide liquid to carry out neutralizing treatment, regulate the boiling mixed solution to pH 8.5, this moment can not only be fully in and the acid in the cooking liquor, and the impurity of the calcium sulfate flocks that produces in can effective elimination xylo-oligosaccharide liquid is with the raising of realization enzymolysis efficiency.Afterwards again with about phosphoric acid or hydrochloric acid readjustment pH to 6.0,, aspergillus niger provides suitable pH environment when the enzymolysis for producing enzyme liquid.Can be increased to more than 80% through the wood sugar yield of xylo-oligosaccharide cooking liquor in enzymolysis process after this neutralizing treatment, reach the requirement of producing wood sugar liquid.Cotton seed hulls waste residue after adopting plate filter with high temperature steaming and the throw out elimination in the lump that neutralization produced obtain the xylo-oligosaccharide cooking liquor after supernatant liquor is neutralizing treatment.Concrete grammar is: the cooking mixture after will being neutralized by charging pump is pressed into filter chamber, concentrates after filtration is finished and discharges, and adds 50 ℃ of water 5L then, and solid is washed, and repeated washing 2 times is collected filtrate and obtained the xylo-oligosaccharide cooking liquor.
Xylo-oligosaccharide cooking liquor after the crude enzyme liquid that the aspergillus niger 2349 (purchasing in Chinese industrial microbial strains preservation administrative center) of employing high yield zytase and xylosidase is produced is handled (3) carries out enzymolysis and obtains the wood sugar enzymolysis solution.The shake-flask seed substratum: the Cha Shi substratum, 115 ℃ of sterilization 30min insert aspergillus niger 2349, and cultivating the 4 days aspergillus niger length to the seed culture medium under 28 ℃ condition has spore shape form to be advisable.Producing the enzymic fermentation substratum is: sucrose 2.4g, MgSO
40.12g, K
2HPO
40.12g, KH
2PO
40.24g, FeSO
40.0012g, NaNO
30.012g with mixing with the mixture of corn cob and wheat bran after the 100ml water dissolution, the mixture of corn cob and wheat bran amounts to 100g, corn cob and wheat bran mass ratio are 6: 4, and 30min sterilizes under 115 ℃ condition.Under the condition of aseptic technique, in the 100g fermention medium, add aspergillus niger seed liquor 15ml with spore shape form, add sterilized water 60ml, take the mode of solid state fermentation, under 30 ℃ condition, cultivated 4 days.After producing enzymic fermentation cultivation end, under 28 ℃ condition, add the vibration of 250ml water and extract solid culture 2h, centrifugal collection supernatant liquor is crude enzyme liquid.Crude enzyme liquid is joined in the xylo-oligosaccharide cooking liquor, and enzymatic hydrolysis condition is a temperature: 50 ℃, and pH=5.5.Enzyme concentration 10ml in the 100ml cooking liquor, the xylo-oligosaccharide concentration in the cooking liquor is 1.5%, after 2 days, the xylo-oligosaccharide more than 80% is converted into wood sugar, obtains wood sugar liquid through enzymolysis.
(3) purifying of wood sugar liquid and concentration
It is 150g/l that wood sugar liquid is concentrated into total sugar concentration through MVR machinery recompression high-efficiency evaporating system.Add the 20g/l Dried Corn Steep Liquor Powder and be configured to fermention medium this moment, is driven in the 20L fermentor tank stand-by.At glucose concn is 30g/L, yeast extract paste concentration is to add the Angel high activity dried yeast in the substratum of 10g/L, purchase in the supermarket, Angel company produces, and makes that its starting point concentration is 2g/L, in 30 ℃ shaking table, rotating speed activation 4h with 300rpm, centrifugal 15min abandons supernatant liquor, the bottom yeast with distilled water wash after recentrifuge 10min, collect yeast slurry.
In fermention medium, add yeast slurry 10g/L in fermentor tank, 32 ℃ of leavening temperatures, fermentation rotating speed 200rpm, air flow 1.4vv
-1m
-1, fermentation volume 16L ferments.Timing sampling HPLC analyzes the wherein content of each sugar component between yeast phase, after fermentation 12h, only contains the ethanol that wood sugar, L-arabinose and glucose metabolism are produced in the fermented liquid, and the clearance of assorted sugar such as glucose stops fermentation this moment more than 98%.Through the wood sugar liquid after the processing of Angel high activity dried yeast, take the centrifugal mode to remove thalline and insoluble substance in the treatment solution, obtain the wood sugar treatment solution, after isolated somatic cells adds the activation medium of fresh sterile, through above-mentioned activation culture process, change in the next batch fermention medium and reuse, many batches of formulas move in circles, and become feeble and die until cell.
With 65L wood sugar treatment solution (wood sugar 20-22g/l, L-arabinose 2-3g/l) is driven in the bleacher of 100L, in hydrolyzed solution according to the wood sugar mass ratio be that 25% ratio adds gac, slowly stir decolouring 40min down at 30 ℃, pigment, nitrogenous thing, organism and colloid in the absorption boiling liquid.Wood sugar liquid after the activated carbon treatment is removed the gac part through the mode of Plate Filtration, and the xylose hydrolysis fluid that obtains achromaticity and clarification is the wood sugar liquid after the activated carbon treatment.
The processing mode of the wood sugar liquid employing zwitterion resins exchange after the activated carbon treatment is removed the ion in the wood sugar liquid.Wood sugar liquid is passed through 001*7 type Zeo-karb series connection 201*7 type anionite-exchange resin, at flow velocity 1L/h, under the condition of room temperature, the electric conductivity value of on-line monitoring discharging feed liquid, the specific conductivity＜50 μ s/cm of assurance discharging feed liquid.Through the wood sugar liquid behind gac and the ion-exchange resin purification, take the mode of MVR machinery recompression high-efficiency evaporating to carry out concentration, the total sugar concentration to wood sugar liquid is 700g/L.
(4) wood sugar and L-arabinose separates and crystallization processes
After wood sugar liquid was purified and concentrated, its initial total sugar mass concentration was 700g/L, and contain wood sugar this moment in the hydrolyzed solution mass concentration is 630g/L, and the mass concentration that contains L-arabinose is 70g/L.
What carry out that the crystallization mode of wood sugar takes is the method for gradient programmed cooling, initial temperature is 80 ℃, rate of temperature fall crystallisation by cooling according to 3 ℃/h, when treating that temperature is reduced to 50 ℃, the crystal seed of adding 0.1%, after crystal seed is educated brilliant 2h, then the rate of temperature fall according to 2 ℃/h continues crystallisation by cooling, be cooled to about 30 ℃, the wood sugar crystal taking-up back of separating out is centrifugal with supernatant liquor and the concentrated fore portion merging of wood sugar liquid, repeat above-mentioned condensing crystal process, the centrifugal solid that obtains washes 2 times with dehydrated alcohol, and then 45 ℃ of drying in oven obtain the xylose crystalline product.Crystallization finishes the back and obtains wood sugar crystal and xylose crystallization mother liquor, and wherein the purity of xylose product is more than 99%, and crystallization yields is 65%.Contain the wood sugar of 200g/L and the L-arabinose of 70g/L in the xylose crystallization mother liquor.
The xylose crystallization mother liquor of above-mentioned acquisition is entered the pillar that 20 2.5*50cm are housed, and the ion exchange resin of having filled plumbous type sun is the simulated moving bed chromatography system of sorbent material, carries out chromatographic separation.65 ℃ of separation temperatures, feeding rate 150mL/h, pure water elution speed 1.0L/h.Collect wood sugar and L-arabinose two-phase liquid after the system balancing, biphase purity is all more than 95%, and replying yield is more than 98%.
Adopting MVR machinery recompression high-efficiency evaporating systems to be concentrated into L-arabinose concentration down at 80 ℃ the L-arabinose of gained is 800g/L, then according to the rate of temperature fall crystallisation by cooling of 3 ℃/h, when treating that temperature is reduced to 50 ℃, the crystal seed of adding 0.1%, after crystal seed is educated brilliant 2h, then the rate of temperature fall according to 2 ℃/h continues crystallisation by cooling, be cooled to about 30 ℃, with centrifugal after the L-arabinose crystal taking-up of separating out the isolated L-arabinose of supernatant liquor and chromatographic system is merged mutually, repeat above-mentioned condensing crystal process, the centrifugal solid that obtains washes 2 times with dehydrated alcohol, and then 45 ℃ of drying in oven, the L-arabinose crystallization yields is 65%, and purity is more than 99%.
Xylose mother liquid is separated the wood sugar obtain to be returned mutually and is incorporated in initial wood sugar liquid of the 4th step, adopting MVR machinery recompression high-efficiency evaporating system to be concentrated into xylose concentration is 800g/L, repeat the xylose crystalline step, obtain wood sugar crystal and xylose crystallization mother liquor, the xylose crystalline productive rate is 60%, purity is more than 99%, enter after the xylose mother liquid mixing that initial xylose crystalline of xylose mother liquid that this step obtains and the 4th step obtains simulation moving-bed separation system obtain wood sugar mutually with the L-arabinose phase, with this repeatedly.
Claims (1)
1. the preparation wood sugar of a clean and effective and the production technique of L-arabinose is characterized in that, comprise the steps:
(1) the agriculture and forestry organic waste material raw material carries out pre-treatment and soaks pre-treatment; Described agriculture and forestry organic waste material raw material comprises: corn cob, maize straw, rice straw, jowar stalk, cotton seed hulls or bagasse;
Pre-treating technology comprises: raw-material pulverizing, dedusting, washing three process;
The employed soak solution of described immersion pre-treatment starting material is dilute sulphuric acid, dilute hydrochloric acid or rare oxalic acid, the massfraction of dilute sulphuric acid, dilute hydrochloric acid or rare oxalic acid is 0.1-0.5%, soak solution is 4-8 with the massfraction ratio of raw material: 1, the temperature of soaking is 30-100 ℃, and the time of immersion is 6-24h;
After soaking the pre-treatment end, solid-liquid separation obtains pretreated raw material, and the mode of isolated pretreated raw material by washing is regulated the pH value to 4.5-6.0, and soak solution is replied and utilized;
(2) take the method hydrolyzed hemicellulose of high temperature steaming to obtain high temperature steaming wood sugar liquid or high temperature steaming xylo-oligosaccharide liquid through the agriculture and forestry organic waste material raw material after (1) processing, specific as follows;
Pretreated agriculture and forestry organic waste material is added in the reaction unit, adds 5-20 doubly to the water of expecting dry weight admittedly; Initial pH is 5.0-6.0; Boiling 0.5-2h under 145 ℃-155 ℃ the condition; Mixing speed is 80-150rpm; Operating pressure is 0.5-1.0MPa, obtains the xylo-oligosaccharide cooking liquor;
Perhaps agriculture and forestry organic waste material raw materials such as pretreated corn cob or cotton seed hulls are added in the reaction unit, add 5-20 doubly to the water of expecting dry weight admittedly; At initial pH is 4.5-6.0; High temperature steaming 1-3h under 160-180 ℃ the condition; Mixing speed is 80-150rpm; Operating pressure is 0.6-1.2MPa, obtains the wood sugar cooking liquor;
(3) utilize milk of lime to above-mentioned high temperature steaming xylo-oligosaccharide liquid carried out neutralizing treatment to pH at 8.0-9.0, again with phosphoric acid or hydrochloric acid readjustment pH to 6.0, Plate Filtration gets supernatant liquor afterwards;
Xylo-oligosaccharide cooking liquor after the employing crude enzyme liquid that aspergillus niger produced is handled (3) carries out enzymolysis and obtains the wood sugar enzymolysis solution, and is specific as follows:
The Cha Shi substratum, 115 ℃ of sterilization 30min insert aspergillus niger, cultivate the aspergillus niger seed liquor that obtained having spore shape form in 3-4 days under 28-30 ℃ condition; The product enzymic fermentation is cultivated: sucrose 2.4g, MgSO
40.12g, K
2HPO
40.12g, KH
2PO
40.24g, FeSO
40.0012g, NaNO
30.012g, use the 100ml water dissolution, mix with the mixture of corn cob and wheat bran, the mixture of corn cob and wheat bran amounts to 100g, and corn cob and wheat bran mass ratio are 3: 7-7: 3, sterilization 30min obtains fermention medium under 115 ℃ condition;
Under the condition of aseptic technique, in the 100g fermention medium, add aspergillus niger seed liquor 10-15ml with spore shape form, add sterilized water 30-90ml, take the mode of solid state fermentation, under 30 ℃ condition, cultivated 3-4 days; After producing enzymic fermentation cultivation end, under 28-30 ℃ condition, add the vibration of 250ml water and extract solid culture 1-2h, centrifugal collection supernatant liquor is crude enzyme liquid;
Crude enzyme liquid is joined in the xylo-oligosaccharide cooking liquor, and enzymatic hydrolysis condition is temperature: 40-50 ℃, pH=5.0-5.5; Enzyme concentration 5-10ml in the 100ml cooking liquor, the xylo-oligosaccharide concentration in the cooking liquor is 1.5%, obtains wood sugar liquid after 1-2 days through enzymolysis;
The above-mentioned high temperature steaming wood sugar liquid that perhaps utilizes lime carbonate that (2) are obtained carries out neutralizing treatment and transfers pH to 6.0-7.0, and Plate Filtration gets supernatant liquor;
(4) the adding microorganism is removed the assorted sugar that comprises glucose and semi-lactosi in the wood sugar liquid;
Selected microorganism is at least a of intestinal bacteria, yeast saccharomyces cerevisiae and Angel Yeast; The required nitrogenous source that ferments is at least a in yeast extract paste, yeast powder, corn steep liquor, Dried Corn Steep Liquor Powder, soybean-cake flour, ammonium sulfate, the urea;
Above-mentioned wood sugar liquid adds above-mentioned nitrogenous source and fully dissolves through after being concentrated into total sugar concentration and being 100-200g/L, and the nitrogen concentration that obtains is 10-20g/L, is mixed with fermention medium;
At glucose concn is 20-30g/L, yeast extract paste concentration is to add at least a of intestinal bacteria, yeast saccharomyces cerevisiae in the activation medium of 5-10g/L, make that at least a starting point concentration of intestinal bacteria, yeast saccharomyces cerevisiae and Angel Yeast is 1-2g/L, in 30 ℃ shaking table, rotating speed activation 2-4h with 200-300rpm, centrifugal 15min abandons supernatant liquor, the bottom cell with distilled water wash after recentrifuge 10min, collecting cell mud;
In fermention medium, add cell mud 10-20g/L, leavening temperature 25-35 ℃, fermentation rotating speed 200rpm, air flow is 1-1.5vv
-1Min
-1, fermenting, fermentation time is 6-12h;
(5) fermentation back is centrifugal, gac or polymeric adsorbent then, and perhaps both are in conjunction with wood sugar liquid is carried out purification process;
(6) carry out concentration behind the wood sugar purifying; Wood sugar content in the wood sugar liquid that obtains is 700-800g/L;
(7) take gradient programmed cooling crystalline mode to obtain xylose product and xylose crystallization mother liquor;
(8) xylose crystallization mother liquor that obtains is separated through chromatographic system, obtain wood sugar mutually with L-arabinose mutually;
(9) it is concentrated with the merging of wood sugar refined solution that the wood sugar that step (8) is obtained is back to step (6) mutually, take the mode of gradient programmed cooling to carry out crystallization, obtain wood sugar crystal and xylose mother liquid, xylose mother liquid in xylose mother liquid and the step (7) merges, enter to chromatographic fractionation system and separate repeating step (8); The L-arabinose that (8) are obtained gets L-arabinose product and L-arabinose mother liquor through concentrated, crystallization mutually, and the L-arabinose mother liquor is replied and utilized.
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