CN110229195A - A method of extracting rhamnose from bagasse - Google Patents
A method of extracting rhamnose from bagasse Download PDFInfo
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- CN110229195A CN110229195A CN201910517215.3A CN201910517215A CN110229195A CN 110229195 A CN110229195 A CN 110229195A CN 201910517215 A CN201910517215 A CN 201910517215A CN 110229195 A CN110229195 A CN 110229195A
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
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- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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Abstract
The method that the present invention relates to a kind of to extract rhamnose from bagasse, using bagasse as raw material, it is digested after bagasse is hydrolyzed under the conditions of diluted acid, gained enzymatic hydrolysis completes liquid and obtains sandlwood sugar crystal after multiple chromatographic isolation is enriched with rhamnose, by-product xylose and arabinose simultaneously, the present invention combines the hydrolysis in mature xylose production process with bagasse new raw material, the technologies such as purifying are while extracting xylose, the enrichment and separation of micro rare monosaccharide-rhamnose is realized by chromatographic separation technology, the high rhamnose of market value is not only successfully obtained, and also add the yield of xylose and arabinose, realize the multi-product higher value application of single raw material.
Description
Technical field
The present invention relates to a kind of method for extraction and purification of monosaccharide more particularly to a kind of sides that rhamnose is extracted from bagasse
Method belongs to the utilization technical field of biomass.
Background technique
L- rhamnose, also known as 6-deoxy-L-mannose, in the polysaccharide of plant, glucosides, natural plant gum and bacterial polysaccharides extensively
In the presence of, but content is relatively low, and coexists with other monosaccharide, and extraction difficulty is big, is consequently belonging to rare monosaccharide, market value is high.Mouse
Lee sugar it is widely used, can be used to the permeability for measuring enteron aisle, can be used as sweetener, it may also be used for production flavors and fragrances, it is edible
With.In recent years, it is widely used in cosmetic industry as the excellent performance of keeping humidity of rhamnose is gradually recognized, market lacks
Greatly, rise in price is obvious for mouth.
Currently, rhamnose PRODUCTION TRAITS report it is more, mainly from rutin (Authorization Notice No.: CN103965153 B),
Yellow ginger, seaweed (application notification number: 102747169 A of CN), Arabic gum (application notification number: 109384820 A of CN), (Shen
Please notification number: 107417763 A of CN) sophora bud (Authorization Notice No.: 101891774 B of CN；Apply for notification number: CN
102952108 A) etc. pass through organic solvent in raw materials and extract.Firstly, the reserves of above-mentioned raw materials are small, and it is expensive, collect difficulty
Greatly；Secondly, the extraction and purification process registered is related to organic solvent extraction more, it is seriously polluted.
Bagasse is the principal by product of cane sugar manufacture industry, is that solid plant of the sugarcane after broken and extract sugarcane juice is fine
Dimension belongs to agricultural solid residue rich in ingredients such as cellulose, hemicellulose and pectin.Since bagasse is cheap, amount is big, concentrates,
It is highly convenient for comprehensively utilizing.Traditional bagasse Land use systems are biomass power generations etc., belong to devalued utilization, and are contained in bagasse
Hemicellulose 19~24% contains pectin composition more abundant simultaneously, is ideal rare monosaccharide raw materials for production.
Based on the above background, if it is possible to be extracted from bagasse and isolate rhamnose, the high-valued of bagasse both may be implemented
Utilizing question, and the market has openings of rhamnose can be met to a certain extent and reduce the price of rhamnose, enrich and strengthen
The new raw material and coproduction new approaches in rare sugared field.
Summary of the invention
The status that the present invention is utilized for the market demand and bagasse of rhamnose provides one kind and extracts sandlwood from bagasse
The method of sugar.
We analyze the hydrolysate of bagasse first, and the content of various monosaccharide is as shown in table 1.
The content of various monosaccharide in the hydrolysate of 1 bagasse of table
| Monosaccharide | Content |
| Glucose | 19~21% |
| Xylose | 65~68% |
| Rhamnose | 1~2% |
| Arabinose | 8~10% |
By the data in table 1 it is found that xylose, arabinose and glucose in bagasse containing high-content, if it is possible to logical
Technological means is crossed, the xylose of high-content and arabinose are separated, and the rhamnose of low content is made to be continuously available enrichment,
Then the separation and purifying of rhamnose can be realized under the premise of a large amount of xyloses of by-product and arabinose.
The technical scheme to solve the above technical problems is that
A method of it extracting rhamnose from bagasse, includes the following steps:
(1) bagasse is mixed with dilute hydrochloric acid or dilute sulfuric acid, 1~4h is hydrolyzed under conditions of 100~130 DEG C, is hydrolyzed
Liquid, the index of refraction for controlling hydrolyzate is 1~10%；
(2) it removes nonsugar: step (1) resulting hydrolyzate is removed into glue therein through removing nonsugar process
Body, pigment, inorganic salts, inorganic acid and organic acid obtain hydrolysis refined liquid, the light transmittance >=75% (1cm of control hydrolysis refined liquid
Cuvette, wavelength 420nm)；Conductivity≤3000 μ S/cm；
(3) digest glucose: pH=3~7 of hydrolysis refined liquid obtained by regulating step (2) are passed through air stirring thereto,
The control of air gas velocity is in 2~50BV per hour (the ratio between the volume of charge volume and hydrolysis refined liquid), controlled at 25~55
DEG C, enzyme preparation is added thereto and carries out enzyme digestion reaction, reacts 1~48h, keeps pH value constant in enzymolysis process, obtain having digested
At liquid；
(4) enzyme recycles: the resulting enzymatic hydrolysis of step (3) is completed into liquid pump and enters ultrafiltration system, operating pressure for 0.1~
1.0MPa, control is through retention than being (2~5): 1, trapped fluid is collected into return step (3), permeate is sent into chromatographic isolation
Head tank；
(5) 1# chromatographic isolation: the permeate in step (4) is concentrated into after index of refraction is 35~50% and is pumped into 1# chromatography point
From device, using water as eluent, control system temperature is 35~80 DEG C, and system pressure is 0.1~0.5MPa, separates rich in wood
The B of sugar and arabinose ingredient material and the C rich in inorganic salts, gluconic acid (salt) and glycan expect, the index of refraction of B material for 12~
25%, xylose purity is 65~85%, glucose purity < 5%；
(6) it refines: gained B material is subjected to decoloration and desalting refinement, promotion light transmittance to 50% or more, conductance 0.5mS/cm
Hereinafter, being concentrated by evaporation to refractive power 65~85%, rear gradient cooling crystallization, centrifuge separation obtains xylose crystals and xylose mother liquid；
(7) 2# chromatographic isolation: being pumped into 2# chromatographic separation device for step (6) resulting xylose mother liquid after ultra-filtration filters,
Using water as eluent, control system temperature is 35~80 DEG C, and system pressure is 0.1~0.5MPa, separates rich in xylose and non-
The D of sugar substance expects and expects rich in the E of rhamnose and arabinose, and D material return step (3) is further digested grape therein
Sugar simultaneously recycles xylose；
(8) 3# chromatographic isolation: the material of E obtained in step (7) is concentrated by evaporation to index of refraction 30~60%, through ultra-filtration filters
After be pumped into 3# chromatographic separation device, using dilute hydrochloric acid solution or water as eluant, eluent, control system temperature be 35~80 DEG C, system pressure
For 0.1~0.5MPa, the F material for separating rich in rhamnose and the G material rich in arabinose；
(9) it refines and crystallizes: the material of F obtained in step 8) and G material being subjected to decoloration and desalting refinement respectively, promote light transmission
Rate is to 98% or more, and 50 μ S/cm of conductivity is hereinafter, be concentrated by evaporation to index of refraction 65~85%, gradient cooling crystallization, centrifugation point
From sandlwood sugar crystal and rhamnose mother liquor and arabinose crystal and arabinose mother liquor being obtained respectively, by gained rhamnose
Mother liquor is back in step (8) after mixing with arabinose mother liquor and further separates；
Chromatographic column filler in the 1# chromatographic separation device, 2# chromatographic separation device and 3# chromatographic separation device is hydrogen
Type, sodium form, potassium type or calcium cation exchanger resin, wherein the preferred sodium form sun of the chromatographic column filler in 1# chromatographic separation device from
Sub-exchange resin, the preferred calcium cation exchanger resin of chromatographic column filler in 2# chromatographic separation device, 3# chromatographic separation device
The preferred hydrogen type cation exchange resin of interior chromatographic column filler.
Based on the above technical solution, the present invention can do following improvement.
Further, removing nonsugar process described in step (2) be separated by solid-liquid separation, neutralize, active carbon decoloring, film it is de-
At least three kinds of combination in color, electrodialysis desalination and ion exchange resin desalination process, preferably separation of solid and liquid-decoloration-ion are handed over
Change the combination of resin, separation of solid and liquid-film decoloration-electrodialysis desalination combination and separation of solid and liquid-neutralization-decoloration-ion exchange
The combination of resin.
Further, enzyme preparation described in step (3) is glucose oxidase (E.C.1.1.3.4) and peroxidase
The mixture of (EC 1.11.1.7 or EC1.11.1.6), the preferably mass ratio of glucose oxidase and peroxidase are 7:3.
Further, the additive amount of enzyme preparation described in step (3) be hydrolyze refined liquid in soluble solids content 0.5~
3%, preferably additive amount is hydrolyze soluble solids content in refined liquid 1%.
Further, step (4) ultrafiltration system is ceramic membrane, organic rolled film or hollow-fibre membrane, and film retains molecule
Amount 1,000~150,000Da, preferably molecular cut off 100, the hollow-fibre membrane of 000Da.
Further, gradient cooling rate control described in step (6) and step (9) is cooled in 0.5~1.0 DEG C/h
35~50 DEG C, 35 DEG C are preferably cooled to, first controls and controls rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C
For 0.8 DEG C/h；It is 0.5 DEG C/h that rate of temperature fall is controlled between 45~35 DEG C.
Further, the bagasse that the bagasse is nature stacking 3 months or more.
Further, desalting refinement process described in step (6) and step (9) is carried out by ion exchange resin, described
Ion exchange resin includes cation exchange resin and anion exchange resin, and the cation exchange resin is 001*7 resin,
Anion exchange resin is D301 and 300C resin.
Further, the dilute hydrochloric acid refers to that hydrochloric acid solution of the mass fraction less than 4%, the dilute sulfuric acid refer to mass fraction
Sulfuric acid solution less than 5%.
The beneficial effects of the present invention are: combining hydrolysis, the purifying etc. in mature xylose production process with bagasse new raw material
Technology realizes the enrichment and separation of micro rare monosaccharide-rhamnose by chromatographic separation technology, no while extracting xylose
The high rhamnose of market value has only successfully been obtained, and has also added the yield of xylose and arabinose, has been realized single
The multi-product higher value application of raw material.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Specific embodiment
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
Embodiment 1:
1) it hydrolyzes: the 100Kg bagasse stacked the phase 150 days being mixed with the dilute sulfuric acid of 800Kg mass fraction 1.0%, is controlled
125 DEG C of hydrolysis temperature, soaking time 3h, obtain hydrolyzate, hydrolyzate refractive power 4.1%；
2) it removes nonsugar: above-mentioned hydrolyzate being removed into hydrolytic residue through belt filter press filters pressing, gained hydrolyzate adds
Enter powder activity carbon decoloring to light transmittance 75% (1cm cuvette, wavelength 420nm), electrodialysis desalination to 2500 μ S/ of conductivity
cm；
3) it digests glucose: above-mentioned hydrolysis refined liquid is adjusted to pH=3.0, utilize air stirring, the control of air gas velocity
In 20BV per hour (the ratio between charge volume and liquid volume), enzyme preparation is added and carries out enzyme digestion reaction, enzyme preparation is grape glycosyloxy
Change the mixture that enzyme and peroxidase 7:3 in mass ratio are mixed to get, additive amount is that soluble solids contain in hydrolysis refined liquid
The 1% of amount persistently conveys air, and 30 DEG C of temperature control, the reaction time for 24 hours, obtains enzymatic hydrolysis and completes liquid；
4) enzyme recycles: above-mentioned enzymatic hydrolysis completion liquid pump is entered into macromolecular ultrafiltration system, ultrafiltration membrane is molecular cut off 100,
The hollow-fibre membrane of 000Da, operating pressure 0.8MPa, through retention than 5:1, by trapped fluid Collection and conservation, permeate enters color
Spectrum separation head tank；
5) 1# chromatographic isolation: above-mentioned enzymolysis liquid is pumped into 1# chromatographic separation device, filler is sodium form resin, and eluant, eluent is pure
Water, charging with eluant, eluent volume ratio 1:4.5,60 DEG C of system temperature, system pressure 0.2MPa, separate B material refractive power
13.5%, wherein xylose purity 71%, glucose purity 4.5%；
6) purification and xylose crystalline: above-mentioned B is expected to carry out active carbon decoloring, anion-cation exchange resin desalting refinement, is mentioned
Light transmission is risen to 98%, conductance 0.1mS/cm, is concentrated by evaporation to refractive power 85%；Gradient cooling crystallization, is cooled to 35 DEG C, first control drop
It is 0.8 DEG C/h that rate of temperature fall is controlled between 1.0 DEG C/h to 65 DEG C, 65~45 DEG C of warm rate；Control cooling speed between 45~35 DEG C
Rate is 0.5 DEG C/h；Centrifuge separation obtains xylose crystals and xylose mother liquid.Xylose crystals purity 99.5%, xylose mother liquid refractive power
55%, xylose crystals quality is 1:0.35 with the amount of dry matter ratio that xylose mother liquid converts into；
7) 2# chromatographic isolation: above-mentioned xylose mother liquid is pumped into 2# chromatographic separation device after ultra-filtration filters, filler is calcium type
Resin, eluant, eluent are pure water, and charging and eluant, eluent volume ratio 1:5,60 DEG C of system temperature, system pressure 0.2MPa separates to obtain D
The refractive power 25% of material, wherein xylose purity 73%, rhamnose purity of 50 percent .5%, arabinose purity 2.1%；Collect gained E material
Refractive power is 11%, wherein rhamnose purity 16%, arabinose purity 79%；Xylose purity 4.5%；B is expected into Collection and conservation.
8) 3# chromatographic isolation: above-mentioned C material is concentrated by evaporation to refractive power 55%, 3# chromatography is pumped into after macromolecular ultra-filtration filters
Separator, filler are h type resin, and eluant, eluent is the dilute hydrochloric acid solution of pH=3.5, charging and eluant, eluent volume ratio 1:5,
60 DEG C of system temperature, system pressure 0.5MPa, F material index: refractive power 10% is separated to obtain, wherein rhamnose purity 80%, xylose is pure
Degree 13.5%, arabinose purity 4.5%；The index of G material: refractive power 25%, wherein arabinose purity 85%, xylose purity
0.2%, rhamnose purity 13.7%；
9) purification and rhamnose, arabinose crystallization: by above-mentioned steps 8) in F material, G material carry out respectively active carbon decoloring,
Anion-cation exchange resin desalting refinement.
F material promotes light transmission to 99%, 30 μ S/cm of conductance, is concentrated by evaporation to refractive power 85%, gradient cooling crystallization is cooled to
35 DEG C, first controlling control rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C is 0.8 DEG C/h；45~35 DEG C it
Between control rate of temperature fall be 0.5 DEG C/h；Centrifuge separation obtains sandlwood sugar crystal and rhamnose mother liquor.Rhamnose crystal purity
99.1%, rhamnose mother liquor refractive power 53%, the amount of dry matter ratio that rhamnose crystal quality and rhamnose mother liquor convert into is 1:0.31；
G material promotes light transmission to 98%, 50 μ S/cm of conductance, is concentrated by evaporation to refractive power 80%, gradient cooling crystallization is cooled to
35 DEG C, first controlling control rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C is 0.8 DEG C/h；45~35 DEG C it
Between control rate of temperature fall be 0.5 DEG C/h；Centrifuge separation obtains arabinose crystal and arabinose mother liquor.Arabinose crystal
Purity 99.5%, arabinose mother liquor refractive power 56%, the amount of dry matter ratio that rhamnose crystal quality is converted into rhamnose mother liquor are
1:0.33。
Embodiment 2:
1) it hydrolyzes: 100Kg is mixed without the fresh bagasse of stacking with the dilute sulfuric acid of 800Kg mass fraction 1.2%, control
115 DEG C of hydrolysis temperature, soaking time 3h, obtain hydrolyzate, hydrolyzate refractive power 4.5%；
2) it removes nonsugar: above-mentioned hydrolyzate being removed into hydrolytic residue through belt filter press filters pressing, gained hydrolyzate adds
Enter powder activity carbon decoloring to light transmittance 75% (1cm cuvette, wavelength 420nm), using the desalination of sodium form ion exchange resin extremely
2500 μ S/cm of conductivity；
3) it digests glucose: above-mentioned hydrolysis refined liquid is adjusted to pH=4.5, utilize air stirring, the control of air gas velocity
In 50BV per hour (the ratio between charge volume and liquid volume), enzyme preparation is added and carries out enzyme digestion reaction, enzyme preparation is grape glycosyloxy
Change enzyme, additive amount be 2.0% of soluble solids content in hydrolysis refined liquid, persistently convey air, 40 DEG C of temperature control, the reaction time
12h must be digested and be completed liquid；
4) enzyme recycles: above-mentioned enzymatic hydrolysis completion liquid pump is entered into macromolecular ultrafiltration system, ultrafiltration membrane is molecular cut off 100,
The hollow-fibre membrane of 000Da, operating pressure 1.0MPa, through retention than 4:1, by trapped fluid Collection and conservation, permeate enters color
Spectrum separation head tank；
5) 1# chromatographic isolation: above-mentioned enzymolysis liquid is pumped into 1# chromatographic separation device, filler is potassium type resin, and eluant, eluent is pure
Water, charging with eluant, eluent volume ratio 1:4.5,80 DEG C of system temperature, system pressure 0.3MPa, separate B material refractive power
14.1%, wherein xylose purity 69%, glucose purity 5.0%；
6) purification and xylose crystalline: above-mentioned B is expected to carry out active carbon decoloring, anion-cation exchange resin desalting refinement, is mentioned
Light transmission is risen to 98%, conductance 0.2mS/cm, is concentrated by evaporation to refractive power 80%；Gradient cooling crystallization, is cooled to 40 DEG C, first control drop
It is 0.8 DEG C/h that rate of temperature fall is controlled between 1.0 DEG C/h to 65 DEG C, 65~50 DEG C of warm rate；Control cooling speed between 50~40 DEG C
Rate is 0.5 DEG C/h；Centrifuge separation obtains xylose crystals and xylose mother liquid.Xylose crystals purity 99.6%, xylose mother liquid refractive power
56%, xylose crystals quality is 1:0.38 with the amount of dry matter ratio that xylose mother liquid converts into；
7) 2# chromatographic isolation: above-mentioned xylose mother liquid is pumped into 2# chromatographic separation device after ultra-filtration filters, filler is calcium type
Resin, eluant, eluent are pure water, charging and eluant, eluent volume ratio 1:5.5,60 DEG C of system temperature, system pressure 0.2MPa, separation
The refractive power 21% of D material is obtained, wherein xylose purity 75%, rhamnose purity of 50 percent .4%, arabinose purity 1.9%；Collect gained E
The refractive power of material is 9%, wherein rhamnose purity 16%, arabinose purity 80%；Xylose purity 3.5%；B is expected to collect and is protected
It deposits；
8) 3# chromatographic isolation: above-mentioned C material is concentrated by evaporation to refractive power 55%, 3# chromatography is pumped into after macromolecular ultra-filtration filters
Separator, filler are calcium type resin, and eluant, eluent is pure water, charging and eluant, eluent volume ratio 1:5.5,80 DEG C of system temperature,
System pressure 0.2MPa separates to obtain F material index: refractive power 10%, wherein rhamnose purity 72%, xylose purity 17.6%, I
The sugared purity 6.5% of uncle；The index of G material: refractive power 22%, wherein arabinose purity 80.1%, xylose purity 1.8%, rhamnose
Purity 17.6%；
9) purification and rhamnose, arabinose crystallization: by above-mentioned steps 8) in F material, G material carry out respectively active carbon decoloring,
Anion-cation exchange resin desalting refinement.
F material promotes light transmission to 99%, 35 μ S/cm of conductance, is concentrated by evaporation to refractive power 85%, gradient cooling crystallization is cooled to
35 DEG C, first controlling control rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C is 0.8 DEG C/h；45~35 DEG C it
Between control rate of temperature fall be 0.5 DEG C/h；Centrifuge separation obtains sandlwood sugar crystal and rhamnose mother liquor.Rhamnose crystal purity
98.3%, rhamnose mother liquor refractive power 56%, the amount of dry matter ratio that rhamnose crystal quality and rhamnose mother liquor convert into is 1:0.37；
G material promotes light transmission to 98%, 50 μ S/cm of conductance, is concentrated by evaporation to refractive power 80%, gradient cooling crystallization is cooled to
35 DEG C, first controlling control rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C is 0.8 DEG C/h；45~35 DEG C it
Between control rate of temperature fall be 0.5 DEG C/h；Centrifuge separation obtains arabinose crystal and arabinose mother liquor.Arabinose crystal
Purity 99.5%, arabinose mother liquor refractive power 56%, the amount of dry matter ratio that rhamnose crystal quality is converted into rhamnose mother liquor are
1:0.33。
Embodiment 3:
1) it hydrolyzes: the 100Kg bagasse stacked the phase 90 days being mixed with the dilute sulfuric acid of 900Kg mass fraction 1.0%, controls water
100 DEG C of temperature, soaking time 4h of solution obtains hydrolyzate, hydrolyzate refractive power 3.8%；
2) it removes nonsugar: above-mentioned hydrolyzate being removed into hydrolytic residue through belt filter press filters pressing, gained hydrolyzate adds
Ammonium hydroxide is neutralized to pH=7, after be added thereto powder activity carbon decoloring to light transmittance 75% (1cm cuvette, wavelength 420nm),
Electrodialysis desalination is to 2500 μ S/cm of conductivity；
3) it digests glucose: above-mentioned hydrolysis refined liquid is adjusted to pH=5.5, utilize air stirring, the control of air gas velocity
In 30BV per hour (the ratio between charge volume and liquid volume), enzyme preparation is added and carries out enzyme digestion reaction, enzyme preparation is grape glycosyloxy
Change the mixture that enzyme and peroxidase 8:2 in mass ratio are mixed, persistently conveys air, 25 DEG C of temperature control, the reaction time
48h, additive amount are hydrolyze soluble solids content in refined liquid 3.0%, must digest and complete liquid；
4) enzyme recycles: above-mentioned enzymatic hydrolysis completion liquid pump is entered into macromolecular ultrafiltration system, ultrafiltration membrane is molecular cut off 100,
The hollow-fibre membrane of 000Da, operating pressure 0.5MPa, through retention than 2:1, by trapped fluid Collection and conservation, permeate enters color
Spectrum separation head tank；
5) 1# chromatographic isolation: above-mentioned enzymolysis liquid is pumped into chromatographic separation device, filler is sodium form resin, and eluant, eluent is pure
Water, charging with eluant, eluent volume ratio 1:4,35 DEG C of system temperature, system pressure 0.5MPa, separate B material refractive power 15.2%,
Wherein xylose purity 67%, glucose purity 5.0%；
6) purification and xylose crystalline: above-mentioned B is expected to carry out active carbon decoloring, anion-cation exchange resin desalting refinement, is mentioned
Light transmission is risen to 98%, conductance 0.3mS/cm, is concentrated by evaporation to refractive power 82%；Gradient cooling crystallization, is cooled to 35 DEG C, first control drop
It is 0.8 DEG C/h that rate of temperature fall is controlled between 1.0 DEG C/h to 65 DEG C, 65~45 DEG C of warm rate；Control cooling speed between 45~35 DEG C
Rate is 0.5 DEG C/h；Centrifuge separation obtains xylose crystals and xylose mother liquid.Xylose crystals purity 99.0%, xylose mother liquid refractive power
56%, xylose crystals quality is 1:0.37 with the amount of dry matter ratio that xylose mother liquid converts into；
7) 2# chromatographic isolation: step (6) resulting xylose mother liquid is pumped into 2# chromatographic separation device after ultra-filtration filters, is filled out
Material is sodium form resin, and eluant, eluent is pure water, charging and eluant, eluent volume ratio 1:4.5,35 DEG C of system temperature, system pressure
0.26MPa, separate D material refractive power 29%, wherein xylose purity 67%, rhamnose purity 2.5%, arabinose purity
4.8%；The refractive power for collecting gained E material is 9.5%, wherein rhamnose purity 10.5%, arabinose purity 54.5%；Xylose is pure
Degree 12.3%；B is expected into Collection and conservation.
8) 3# chromatographic isolation: above-mentioned C material is concentrated by evaporation to refractive power 55%, 3# chromatography is pumped into after macromolecular ultra-filtration filters
Separator, filler are h type resin, and eluant, eluent is that the dilute hydrochloric acid of pH=4.0 is molten, charging and eluant, eluent volume ratio 1:5.5,
35 DEG C of system temperature, system pressure 0.36MPa, F material index: refractive power 8% is separated to obtain, wherein rhamnose purity 81%, xylose is pure
Degree 13.8%, arabinose purity 4.3%；The index of G material: refractive power 21%, wherein arabinose purity 85%, xylose purity
0.3%, rhamnose purity 12.6%；
9) purification and rhamnose, arabinose crystallization: by above-mentioned steps 8) in F material, G material carry out respectively active carbon decoloring,
Anion-cation exchange resin desalting refinement.
F material promotes light transmission to 99%, 45 μ S/cm of conductance, is concentrated by evaporation to refractive power 83%, gradient cooling crystallization is cooled to
35 DEG C, first controlling control rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C is 0.8 DEG C/h；45~35 DEG C it
Between control rate of temperature fall be 0.5 DEG C/h；Centrifuge separation obtains sandlwood sugar crystal and rhamnose mother liquor.Rhamnose crystal purity
99.0%, rhamnose mother liquor refractive power 53%, the amount of dry matter ratio that rhamnose crystal quality and rhamnose mother liquor convert into is 1:0.34；
G material promotes light transmission to 98%, 44 μ S/cm of conductance, is concentrated by evaporation to refractive power 82%, gradient cooling crystallization is cooled to
35 DEG C, first controlling control rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C is 0.8 DEG C/h；45~35 DEG C it
Between control rate of temperature fall be 0.5 DEG C/h；Centrifuge separation obtains arabinose crystal and arabinose mother liquor.Arabinose crystal
Purity 99.3%, arabinose mother liquor refractive power 55%, the amount of dry matter ratio that rhamnose crystal quality is converted into rhamnose mother liquor are
1:0.34。
Embodiment 4:
1) it hydrolyzes: the 100Kg bagasse stacked the phase 360 days being mixed with the dilute sulfuric acid of 700Kg mass fraction 1.2%, is controlled
130 DEG C of hydrolysis temperature, soaking time 1h, obtain hydrolyzate, hydrolyzate refractive power 4.9%；
2) it removes nonsugar: above-mentioned hydrolyzate being removed into hydrolytic residue through belt filter press filters pressing, gained hydrolyzate adds
Enter powder activity carbon decoloring to light transmittance 75% (1cm cuvette, wavelength 420nm), electrodialysis desalination to 2500 μ S/ of conductivity
cm；
3) it digests glucose: above-mentioned hydrolysis refined liquid is adjusted to pH=7.0, utilize air stirring, the control of air gas velocity
In 45BV per hour (the ratio between charge volume and liquid volume), enzyme preparation is added and carries out enzyme digestion reaction, enzyme preparation is grape glycosyloxy
Change the mixture that enzyme and peroxidase 7:3 in mass ratio are mixed to get, additive amount is that soluble solids contain in hydrolysis refined liquid
The 0.5% of amount persistently conveys air, 55 DEG C of temperature control, reaction time 1h, must digest and complete liquid；
4) enzyme recycles: above-mentioned enzymatic hydrolysis completion liquid pump is entered into macromolecular ultrafiltration system, ultrafiltration membrane is molecular cut off 150,
The hollow-fibre membrane of 000Da, operating pressure 0.1MPa, through retention than 5:1, by trapped fluid Collection and conservation, permeate enters color
Spectrum separation head tank；
5) 1# chromatographic isolation: above-mentioned enzymolysis liquid is pumped into 1# chromatographic separation device, filler is sodium form resin, and eluant, eluent is pure
Water, charging with eluant, eluent volume ratio 1:4.5,50 DEG C of system temperature, system pressure 0.1MPa, separate B material refractive power
13.6%, wherein xylose purity 70%, glucose purity 4.7%；
6) purification and xylose crystalline: above-mentioned B is expected to carry out active carbon decoloring, anion-cation exchange resin desalting refinement, is mentioned
Light transmission is risen to 98%, conductance 0.3mS/cm, is concentrated by evaporation to refractive power 82%；Gradient cooling crystallization, is cooled to 35 DEG C, first control drop
It is 0.8 DEG C/h that rate of temperature fall is controlled between 1.0 DEG C/h to 65 DEG C, 65~45 DEG C of warm rate；Control cooling speed between 45~35 DEG C
Rate is 0.5 DEG C/h；Centrifuge separation obtains xylose crystals and xylose mother liquid.Xylose crystals purity 99.3%, xylose mother liquid refractive power
54%, xylose crystals quality is 1:0.36 with the amount of dry matter ratio that xylose mother liquid converts into；
7) 2# chromatographic isolation: step (6) resulting xylose mother liquid is pumped into 2# chromatographic separation device after ultra-filtration filters, is filled out
Material is calcium type resin, and eluant, eluent is pure water, charging and eluant, eluent volume ratio 1:6,50 DEG C of system temperature, system pressure
0.1MPa, separate D material refractive power 20.5%, wherein xylose purity 77%, rhamnose purity of 50 percent .3%, arabinose purity
1.7%；The refractive power for collecting gained E material is 8.0%, wherein rhamnose purity 16%, arabinose purity 81%；Xylose purity
3.5%；B is expected into Collection and conservation.
8) 3# chromatographic isolation: above-mentioned E material is concentrated by evaporation to refractive power 55%, 3# chromatography is pumped into after macromolecular ultra-filtration filters
Separator, filler are h type resin, and eluant, eluent is the dilute hydrochloric acid solution of pH=3.5, charging and eluant, eluent volume ratio 1:6,
50 DEG C of system temperature, system pressure 0.23MPa, F material index: refractive power 8.0% is separated to obtain, wherein rhamnose purity 83%, xylose
Purity 7.5%, arabinose purity 3.4%；The index of G material: refractive power 19%, wherein arabinose purity 87%, xylose purity
0.2%, rhamnose purity 11.8%；
9) purification and rhamnose, arabinose crystallization: by above-mentioned steps 8) in F material, G material carry out respectively active carbon decoloring,
Anion-cation exchange resin desalting refinement.
F material promotes light transmission to 99%, 32 μ S/cm of conductance, is concentrated by evaporation to refractive power 85%, gradient cooling crystallization is cooled to
35 DEG C, first controlling control rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C is 0.8 DEG C/h；45~35 DEG C it
Between control rate of temperature fall be 0.5 DEG C/h；Centrifuge separation obtains sandlwood sugar crystal and rhamnose mother liquor.Rhamnose crystal purity
99.5%, rhamnose mother liquor refractive power 51%, the amount of dry matter ratio that rhamnose crystal quality and rhamnose mother liquor convert into is 1:0.30；
G material promotes light transmission to 98%, 45 μ S/cm of conductance, is concentrated by evaporation to refractive power 82%, gradient cooling crystallization is cooled to
35 DEG C, first controlling control rate of temperature fall between 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C is 0.8 DEG C/h；45~35 DEG C it
Between control rate of temperature fall be 0.5 DEG C/h；Centrifuge separation obtains arabinose crystal and arabinose mother liquor.Arabinose crystal
Purity 99.6%, arabinose mother liquor refractive power 54%, the amount of dry matter ratio that rhamnose crystal quality is converted into rhamnose mother liquor are
1:0.30。
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method for extracting rhamnose from bagasse, includes the following steps:
(1) bagasse is mixed with dilute hydrochloric acid or dilute sulfuric acid, 1~4h is hydrolyzed under conditions of 100~130 DEG C, obtain hydrolyzate, control
The index of refraction of hydrolyzate processed is 1~10%；
(2) nonsugar is removed: by step (1) resulting hydrolyzate through removing nonsugar process removing colloid therein, color
Element, inorganic salts, inorganic acid and organic acid obtain hydrolysis refined liquid, light transmittance >=75% (the 1cm colorimetric of control hydrolysis refined liquid
Ware, wavelength 420nm)；Conductivity≤3000 μ S/cm；
(3) digest glucose: pH=3~7 of hydrolysis refined liquid obtained by regulating step (2) are passed through air stirring, air thereto
Gas velocity control is in 2~50BV per hour (the ratio between the volume of charge volume and hydrolysis refined liquid), controlled at 25~55 DEG C, to
Enzyme preparation is wherein added and carries out enzyme digestion reaction, reacts 1~48h, keeps pH value constant in enzymolysis process, obtain enzymatic hydrolysis and complete liquid；
(4) enzyme recycles: the resulting enzymatic hydrolysis of step (3) being completed liquid pump and enters ultrafiltration system, operating pressure is 0.1~1.0MPa, control
System is through retention than being (2~5): 1, trapped fluid is collected into return step (3), permeate is sent into the head tank of chromatographic isolation；
(5) 1# chromatographic isolation: the permeate in step (4) is concentrated into after index of refraction is 35~50% and is pumped into 1# chromatographic isolation dress
Set, using water as eluent, control system temperature is 35~80 DEG C, and system pressure is 0.1~0.5MPa, separate rich in xylose and
The B of arabinose ingredient expects and the C rich in inorganic salts, gluconic acid (salt) and glycan expects, the index of refraction of B material for 12~
25%, xylose purity is 65~85%, glucose purity < 5%；
(6) refine: gained B material be subjected to decoloration and desalting refinement, promote light transmittance to 50% or more, conductance 0.5mS/cm with
Under, it is concentrated by evaporation to refractive power 65~85%, rear gradient cooling crystallization, centrifuge separation obtains xylose crystals and xylose mother liquid；
(7) 2# chromatographic isolation: step (6) resulting xylose mother liquid is pumped into 2# chromatographic separation device after ultra-filtration filters, with water
For eluant, eluent, control system temperature is 35~80 DEG C, and system pressure is 0.1~0.5MPa, separates rich in xylose and non-sugar
The D of matter expects and expects rich in the E of rhamnose and arabinose, and D material return step (3) is further digested glucose therein simultaneously
Recycle xylose；
(8) 3# chromatographic isolation: the material of E obtained in step (7) is concentrated by evaporation to index of refraction 30~60%, is pumped after ultra-filtration filters
Enter 3# chromatographic separation device, using dilute hydrochloric acid solution or water as eluant, eluent, control system temperature is 35~80 DEG C, and system pressure is
0.1~0.5MPa, the F material for separating rich in rhamnose and the G material rich in arabinose；
(9) it refines and crystallizes: the material of F obtained in step 8) and G material being subjected to decoloration and desalting refinement respectively, promote light transmittance extremely
Hereinafter, being concentrated by evaporation to index of refraction 65~85%, gradient cooling crystallization is centrifugated by 98% or more, 50 μ S/cm of conductivity, point
Not Huo get sandlwood sugar crystal and rhamnose mother liquor and arabinose crystal and arabinose mother liquor, by gained rhamnose mother liquor
It is further separated with being back in step (8) after the mixing of arabinose mother liquor；
Chromatographic column filler in the 1# chromatographic separation device, 2# chromatographic separation device and 3# chromatographic separation device is Hydrogen, sodium
Type, potassium type or calcium cation exchanger resin.
2. the method according to claim 1, wherein enzyme preparation described in step (3) is glucose oxidase
With the mixture of peroxidase.
3. according to the method described in claim 2, it is characterized in that, enzyme preparation described in step (3) is glucose oxidase:
The mass ratio of peroxidase is the mixture of 7:3.
4. method described in any one of claim 1 to 3, which is characterized in that the addition of enzyme preparation described in step (3)
Amount is 0.5~3% of soluble solids content in hydrolysis refined liquid.
5. method described in any one of claim 1 to 3, which is characterized in that removing non-sugar described in step (2)
Matter process be separated by solid-liquid separation, neutralize, in the decoloration of active carbon decoloring, film, electrodialysis desalination and ion exchange resin desalination process extremely
Few three kinds of combination.
6. according to the method described in claim 5, it is characterized in that, removing nonsugar process described in step (2) is solid
Liquid separation-decoloration-ion exchange resin combination, separation of solid and liquid-film decoloration-electrodialysis desalination combination and separation of solid and liquid-
Any one in neutralization-decoloration-ion exchange resin combination.
7. according to claim 1~3, method described in any one of 6, which is characterized in that the ultrafiltration system is ceramic membrane, has
Machine rolled film or hollow-fibre membrane, retaining molecular weight 1,000~150,000Da.
8. according to claim 1~3, method described in any one of 6, which is characterized in that described in step (6) and step (9)
Gradient cooling rate control in 0.5~1.0 DEG C/h, be cooled to 35~50 DEG C.
9. according to claim 1~3, method described in any one of 6, which is characterized in that described in step (6) and step (9)
Gradient cooling program be cooled to 35 DEG C, first control 1.0 DEG C/h to 65 DEG C of rate of temperature fall, 65~45 DEG C between control cooling speed
Rate is 0.8 DEG C/h；It is 0.5 DEG C/h that rate of temperature fall is controlled between 45~35 DEG C.
10. according to claim 1~3, method described in any one of 6, which is characterized in that the bagasse is that nature stacks 3
Month or more bagasse.
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