CN110229195B - Method for extracting rhamnose from bagasse - Google Patents
Method for extracting rhamnose from bagasse Download PDFInfo
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Abstract
The invention relates to a method for extracting rhamnose from bagasse, which takes the bagasse as a raw material, hydrolyzes the bagasse under the condition of dilute acid and then carries out enzymolysis, the obtained enzymolysis finished solution is subjected to repeated chromatographic separation to enrich the rhamnose so as to obtain rhamnose crystals, and byproducts of xylose and arabinose are produced at the same time.
Description
Technical Field
The invention relates to a method for extracting and purifying monosaccharide, in particular to a method for extracting rhamnose from bagasse, and belongs to the technical field of biomass utilization.
Background
L-rhamnose, also called 6-deoxy-L-mannose, widely exists in plant polysaccharides, glycosides, plant gums and bacterial polysaccharides, but has low content, coexists with other monosaccharides, has high extraction difficulty, belongs to rare monosaccharides, and has high market value. Rhamnose has wide application, can be used for measuring intestinal permeability, can be used as sweetener, and can be used for producing essence and flavor. In recent years, with the gradual recognition of the excellent moisture retention performance of rhamnose, the rhamnose is widely used in the cosmetic industry, the market gap is extremely large, and the price is obviously increased.
Currently, many production researches of rhamnose are reported, and the rhamnose is mainly extracted from rutin (grant No. CN 103965153B), turmeric, seaweed (application No. CN 102747169A), arabic gum (application No. CN 109384820A), (application No. CN 107417763A) sophora flower bud (grant No. CN 101891774B; application No. CN 102952108A) and other raw materials by organic solvents. Firstly, the raw materials are small in reserve, expensive and difficult to collect; secondly, the reported extraction and purification process mostly relates to organic solvent extraction, and the pollution is serious.
Bagasse is a main byproduct in the sugar industry of sugarcane, is solid plant fiber obtained after sugarcane is crushed and cane juice is extracted, is rich in cellulose, hemicellulose, pectin and other components, and belongs to agricultural solid waste. The bagasse is cheap, large in quantity and centralized, so that the comprehensive utilization is very convenient. The traditional bagasse utilization mode is biomass power generation and the like, belongs to low-value utilization, and bagasse contains 19-24% of hemicellulose and also contains abundant pectin components, so that the bagasse is an ideal rare monosaccharide production raw material.
Based on the background, if rhamnose can be extracted and separated from bagasse, the problem of high-valued utilization of the bagasse can be solved, the market gap of the rhamnose can be met to a certain extent, the price of the rhamnose can be reduced, and new raw materials and new co-production ideas in the field of rare sugars are enriched and strengthened.
Disclosure of Invention
The invention provides a method for extracting rhamnose from bagasse, aiming at the market demand of rhamnose and the current situation of bagasse utilization.
First, we analyzed the hydrolysate of bagasse, and the contents of various monosaccharides are shown in table 1.
TABLE 1 content of various monosaccharides in hydrolysate of bagasse
As can be seen from the data in table 1, the bagasse contains high contents of xylose, arabinose and glucose, and if the high contents of xylose and arabinose can be separated by a technical means and low contents of rhamnose are continuously enriched, separation and purification of rhamnose can be realized on the premise of by-producing a large amount of xylose and arabinose.
The technical scheme for solving the technical problems is as follows:
a method for extracting rhamnose from bagasse comprises the following steps:
(1) Mixing bagasse with dilute hydrochloric acid or dilute sulfuric acid, and hydrolyzing for 1-4 h at 100-130 ℃ to obtain a hydrolysate, wherein the refractive index of the hydrolysate is controlled to be 1-10%;
(2) Removing non-sugar substances: removing colloids, pigments, inorganic salts, inorganic acids and organic acids in the hydrolysate obtained in the step (1) through a non-sugar substance removing process to obtain a refined hydrolysis solution, and controlling the light transmittance of the refined hydrolysis solution to be more than or equal to 75% (1 cm cuvette, wavelength of 420 nm); the conductivity is less than or equal to 3000 mu S/cm;
(3) And (3) glucose enzymolysis: adjusting the pH = 3-7 of the refined hydrolysis solution obtained in the step (2), introducing air into the refined hydrolysis solution, stirring, controlling the air speed at 2-50 BV (the ratio of the air inlet volume to the volume of the refined hydrolysis solution) per hour, controlling the temperature at 25-55 ℃, adding an enzyme preparation into the refined hydrolysis solution, performing enzymolysis reaction for 1-48 hours, and keeping the pH constant in the enzymolysis process to obtain an enzymolysis finished solution;
(4) And (3) enzyme recovery: pumping the enzymolysis finished liquid obtained in the step (3) into an ultrafiltration system, controlling the operating pressure to be 0.1-1.0 MPa and the permeation interception ratio to be (2-5): 1, collecting the intercepted liquid and returning to the step (3), and sending the permeated liquid into a raw material tank for chromatographic separation;
(5) 1# chromatographic separation: concentrating the permeate liquid obtained in the step (4) to a refractive index of 35-50%, pumping the concentrate into a 1# chromatographic separation device, taking water as an eluent, controlling the temperature of a system to be 35-80 ℃ and the pressure of the system to be 0.1-0.5 MPa, and separating to obtain a material B rich in xylose and arabinose components and a material C rich in inorganic salt, gluconic acid (salt) and glycan, wherein the refractive index of the material B is 12-25%, the xylose purity is 65-85%, and the glucose purity is less than 5%;
(6) Refining: performing decolorization and desalination refining on the obtained material B, increasing the light transmittance to be more than 50 percent and the electric conductivity to be less than 0.5mS/cm, evaporating and concentrating until the refraction is 65-85 percent, then performing gradient cooling crystallization, and performing centrifugal separation to obtain xylose crystals and xylose mother liquor;
(7) 2# chromatographic separation: the xylose mother liquor obtained in the step (6) is pumped into a 2# chromatographic separation device after ultrafiltration and filtration, water is used as eluent, the temperature of a system is controlled to be 35-80 ℃, the pressure of the system is 0.1-0.5 MPa, D material rich in xylose and non-sugar substances and E material rich in rhamnose and arabinose are obtained through separation, the D material is returned to the step (3) for further enzymolysis of glucose in the D material, and xylose is recovered;
(8) 3# chromatographic separation: evaporating and concentrating the material E obtained in the step (7) to a refractive index of 30-60%, performing ultrafiltration and filtration, pumping into a 3# chromatographic separation device, and separating to obtain a material F rich in rhamnose and a material G rich in arabinose by using a dilute hydrochloric acid solution or water as an eluent and controlling the temperature of a system to be 35-80 ℃ and the pressure of the system to be 0.1-0.5 MPa;
(9) Refining and crystallizing: decolorizing and desalting the F material and the G material obtained in the step 8) respectively, improving the light transmittance to more than 98 percent and the electric conductivity to less than 50 mu S/cm, evaporating and concentrating to 65-85 percent of refractive index, performing gradient cooling crystallization, performing centrifugal separation to obtain rhamnose crystal and rhamnose mother liquor and arabinose crystal and arabinose mother liquor respectively, mixing the rhamnose mother liquor and the arabinose mother liquor, and returning to the step (8) for further separation;
the chromatographic column packing in the 1# chromatographic separation device, the 2# chromatographic separation device and the 3# chromatographic separation device is hydrogen type, sodium type, potassium type or calcium type cation exchange resin, wherein the chromatographic column packing in the 1# chromatographic separation device is preferably sodium type cation exchange resin, the chromatographic column packing in the 2# chromatographic separation device is preferably calcium type cation exchange resin, and the chromatographic column packing in the 3# chromatographic separation device is preferably hydrogen type cation exchange resin.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the step of removing non-sugar substances in the step (2) is a combination of at least three of the steps of solid-liquid separation, neutralization, activated carbon decolorization, membrane decolorization, electrodialysis desalination and ion exchange resin desalination, preferably a combination of solid-liquid separation-decolorization-ion exchange resin, a combination of solid-liquid separation-membrane decolorization-electrodialysis desalination and a combination of solid-liquid separation-neutralization-decolorization-ion exchange resin.
Further, the enzyme preparation in step (3) is a mixture of glucose oxidase (e.c. 1.1.3.4) and peroxidase (EC 1.11.1.7 or EC 1.11.1.6), preferably the mass ratio of glucose oxidase to peroxidase is 7.
Further, in the step (3), the amount of the enzyme preparation added is 0.5 to 3% of the soluble solid content in the purified and hydrolyzed solution, and preferably 1% of the soluble solid content in the purified and hydrolyzed solution.
Further, the ultrafiltration system in the step (4) is a ceramic membrane, an organic roll-type membrane or a hollow fiber membrane, and the molecular weight cut-off of the membrane is 1,000-150,000Da, preferably 100,000Da.
Further, the gradient cooling rate in the step (6) and the step (9) is controlled to be 0.5-1.0 ℃/h, the temperature is reduced to 35-50 ℃, preferably to 35 ℃, the cooling rate is controlled to be 1.0 ℃/h-65 ℃, and the cooling rate is controlled to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃.
Further, the bagasse is naturally stacked for more than 3 months.
Further, the desalting and refining steps in the step (6) and the step (9) are performed by ion exchange resins including a cation exchange resin 001 × 7 resin and an anion exchange resin D301 and 300C resin.
Further, the dilute hydrochloric acid refers to a hydrochloric acid solution with a mass fraction of less than 4%, and the dilute sulfuric acid refers to a sulfuric acid solution with a mass fraction of less than 5%.
The invention has the beneficial effects that: the method has the advantages that the novel bagasse raw materials are combined with the mature technologies of hydrolysis, purification and the like in the xylose production process, so that the enrichment and separation of trace rare monosaccharide-rhamnose are realized by means of the chromatographic separation technology while the xylose is extracted, the rhamnose with extremely high market value is successfully obtained, the yields of xylose and arabinose are increased, and the high-value utilization of multiple products of a single raw material is realized.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
1) Hydrolysis: mixing 100Kg of bagasse stacked for 150 days with 800Kg of dilute sulfuric acid with the mass fraction of 1.0%, controlling the hydrolysis temperature to 125 ℃, and keeping the temperature for 3 hours to obtain hydrolysate, wherein the refraction of the hydrolysate is 4.1%;
2) Removing non-sugar substances: filter-pressing the hydrolysate by a belt filter press to remove hydrolysis residues, adding powdered activated carbon into the hydrolysate, decoloring the hydrolysate until the light transmittance is 75% (1 cm cuvette, wavelength is 420 nm), and desalting by electrodialysis until the conductivity is 2500 mu S/cm;
3) And (3) glucose enzymolysis: adjusting the pH of the hydrolysis refined solution to be =3.0, stirring by using air, controlling the air speed to be 20BV (air inlet volume to liquid volume ratio) per hour, adding an enzyme preparation for enzymolysis, wherein the enzyme preparation is a mixture obtained by mixing glucose oxidase and peroxidase according to a mass ratio of 7, the adding amount is 1% of the content of soluble solids in the hydrolysis refined solution, continuously conveying air, controlling the temperature to be 30 ℃, and reacting for 24 hours to obtain an enzymolysis finished solution;
4) And (3) enzyme recovery: pumping the enzymolysis finished liquid into a macromolecular ultrafiltration system, wherein the ultrafiltration membrane is a hollow fiber membrane with the molecular weight cutoff of 100,000Da, the operating pressure is 0.8MPa, the permeation cut-off ratio is 5;
5) 1# chromatographic separation: pumping the enzymolysis liquid into a No. 1 chromatographic separation device, wherein the filler is sodium resin, the eluent is pure water, the volume ratio of the feeding to the eluent is 1.5, the system temperature is 60 ℃, the system pressure is 0.2MPa, and the refraction of the material B is separated to obtain 13.5%, wherein the xylose purity is 71%, and the glucose purity is 4.5%;
6) Refining and xylose crystallization: decolorizing the material B with activated carbon, desalting and refining with anion-cation exchange resin to improve light transmittance to 98% and conductance to 0.1mS/cm, and evaporating and concentrating to refract light to 85%; gradient cooling crystallization, cooling to 35 ℃, controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and controlling the cooling rate to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain xylose crystals and a xylose mother solution. The purity of the xylose crystal is 99.5 percent, the refraction of the xylose mother liquor is 55 percent, and the dry mass ratio of the mass of the xylose crystal to the converted mass of the xylose mother liquor is 1;
7) 2# chromatographic separation: the xylose mother liquor is ultrafiltered and filtered and then pumped into a 2# chromatographic separation device, wherein the filler is calcium resin, the eluent is pure water, the volume ratio of the fed material to the eluent is 1:5, the system temperature is 60 ℃, the system pressure is 0.2MPa, and the refraction of the D material is separated to obtain 25%, wherein the xylose purity is 73%, the rhamnose purity is 0.5%, and the arabinose purity is 2.1%; the refraction of the collected E material is 11 percent, wherein the purity of rhamnose is 16 percent, and the purity of arabinose is 79 percent; the purity of xylose is 4.5%; collecting and storing the material B.
8) And 3# chromatographic separation, namely evaporating and concentrating the material E to 55% of refraction, performing macromolecular ultrafiltration and filtration, pumping the material E into a 3# chromatographic separation device, wherein a filler is hydrogen resin, an eluant is a dilute hydrochloric acid solution with the pH =3.5, the volume ratio of the feeding to the eluant is 1: refracts light by 10 percent, wherein the purity of rhamnose is 80 percent, the purity of xylose is 13.5 percent, and the purity of arabinose is 4.5 percent; indexes of the G material are as follows: refract light by 25 percent, wherein the arabinose purity is 85 percent, the xylose purity is 0.2 percent, and the rhamnose purity is 13.7 percent;
9) Refining and crystallizing rhamnose and arabinose: and (3) respectively carrying out activated carbon decoloration and anion-cation exchange resin desalination refining on the material F and the material G in the step 8).
Lifting the material F to be transparent to 99%, conducting the material F at 30 mu S/cm, evaporating and concentrating the material F to refract light at 85%, cooling the material F to 35 ℃ in a gradient manner, controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and controlling the cooling rate to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain rhamnose crystals and rhamnose mother liquor. The purity of the rhamnose crystal is 99.1 percent, the refractive index of the rhamnose mother liquor is 53 percent, and the dry mass ratio of the quality of the rhamnose crystal to the converted quality of the rhamnose mother liquor is 1;
g material is lifted to be transparent to 98 percent, the electric conductivity is 50 mu S/cm, evaporation concentration is carried out to refract light to 80 percent, gradient temperature reduction crystallization is carried out, the temperature is reduced to 35 ℃, the temperature reduction rate is firstly controlled to be 1.0 ℃/h to 65 ℃, and the temperature reduction rate is controlled to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain arabinose crystals and arabinose mother liquor. The purity of the arabinose crystal is 99.5 percent, the arabinose mother liquor refracts the light of 56 percent, and the dry matter mass ratio of the arabinose crystal mass to the arabinose mother liquor is 1.
Example 2:
1) Hydrolysis: mixing 100Kg of fresh bagasse which is not stacked with 800Kg of dilute sulfuric acid with the mass fraction of 1.2%, controlling the hydrolysis temperature to be 115 ℃, and preserving the heat for 3 hours to obtain hydrolysate, wherein the refraction of the hydrolysate is 4.5%;
2) Removing non-sugar substances: filter-pressing the hydrolysate by a belt filter press to remove hydrolysis residues, adding powdered activated carbon into the hydrolysate, decoloring the hydrolysate until the light transmittance is 75% (1 cm cuvette, wavelength is 420 nm), and desalting by using sodium ion exchange resin until the electric conductivity is 2500 mu S/cm;
3) Glucose enzymolysis: adjusting the pH of the hydrolysis refined liquid to be =4.5, stirring by using air, controlling the air speed to be 50BV (the ratio of the air inlet volume to the liquid volume) per hour, adding an enzyme preparation for enzymolysis reaction, wherein the enzyme preparation is glucose oxidase, the addition amount of the enzyme preparation is 2.0 percent of the content of soluble solids in the hydrolysis refined liquid, continuously conveying the air, controlling the temperature to be 40 ℃, and reacting for 12 hours to obtain an enzymolysis finished liquid;
4) And (3) enzyme recovery: pumping the enzymolysis finished liquid into a macromolecular ultrafiltration system, wherein the ultrafiltration membrane is a hollow fiber membrane with the molecular weight cutoff of 100,000Da, the operation pressure is 1.0MPa, the permeation cutoff ratio is 4;
5) 1# chromatographic separation: pumping the enzymolysis liquid into a 1# chromatographic separation device, wherein a filler is potassium resin, an eluent is pure water, the volume ratio of the fed material to the eluent is 1.5, the system temperature is 80 ℃, the system pressure is 0.3MPa, and the refraction rate of the material B is 14.1 percent, wherein the xylose purity is 69 percent, and the glucose purity is 5.0 percent;
6) Refining and xylose crystallization: decolorizing the material B with activated carbon, desalting and refining with anion-cation exchange resin to improve light transmittance to 98%, conductance to 0.2mS/cm, and evaporating and concentrating to refract light to 80%; gradient cooling crystallization, cooling to 40 ℃, firstly controlling the cooling rate to be 1.0 ℃/h to 65 ℃, and controlling the cooling rate to be 0.8 ℃/h between 65 ℃ and 50 ℃; the cooling rate is controlled to be 0.5 ℃/h between 50 and 40 ℃; and (4) performing centrifugal separation to obtain xylose crystals and a xylose mother liquor. The purity of the xylose crystal is 99.6 percent, the refractive index of the xylose mother liquor is 56 percent, and the dry matter mass ratio of the mass of the xylose crystal to the converted mass of the xylose mother liquor is 1;
7) 2# chromatographic separation: the xylose mother liquor is filtered by ultrafiltration and then pumped into a 2# chromatographic separation device, the filler is calcium resin, the eluent is pure water, the volume ratio of the fed material to the eluent is 1.5, the system temperature is 60 ℃, the system pressure is 0.2MPa, and the refraction of the material D is separated to obtain 21%, wherein the xylose purity is 75%, the rhamnose purity is 0.4%, and the arabinose purity is 1.9%; the refraction of the collected E material is 9 percent, wherein the purity of rhamnose is 16 percent, and the purity of arabinose is 80 percent; the purity of xylose is 3.5%; collecting and storing the material B;
8) 3# chromatographic separation: evaporating and concentrating the material E until the refractive index is 55%, performing macromolecular ultrafiltration and filtration, pumping the material E into a 3# chromatographic separation device, wherein the filler is calcium resin, the eluent is pure water, the volume ratio of the fed material to the eluent is 1.5, the system temperature is 80 ℃, the system pressure is 0.2MPa, and the indexes of the material F are obtained by separation: refracts light by 10 percent, wherein the purity of rhamnose is 72 percent, the purity of xylose is 17.6 percent, and the purity of arabinose is 6.5 percent; indexes of the G material are as follows: refract light by 22 percent, wherein the arabinose purity is 80.1 percent, the xylose purity is 1.8 percent, and the rhamnose purity is 17.6 percent;
9) Refining and crystallizing rhamnose and arabinose: and (3) respectively carrying out activated carbon decoloration and anion-cation exchange resin desalination refining on the material F and the material G in the step 8).
Lifting the material F to be transparent to 99%, conducting the material F at 35 mu S/cm, evaporating and concentrating the material F to refract light at 85%, cooling the material F to 35 ℃ in a gradient manner, and controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and the cooling rate to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain rhamnose crystals and rhamnose mother liquor. The purity of the rhamnose crystal is 98.3 percent, the refractive index of the rhamnose mother liquor is 56 percent, and the dry mass ratio of the quality of the rhamnose crystal to the converted quality of the rhamnose mother liquor is 1;
lifting the material G to ensure that the light is transmitted to 98 percent, conducting the light at 50 mu S/cm, evaporating and concentrating the material G to ensure that the light is refracted by 80 percent, cooling the material G to 35 ℃ in a gradient manner, and controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and the cooling rate to be 0.8 ℃/h between 65 and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain arabinose crystals and arabinose mother liquor. The arabinose crystal purity is 99.5 percent, the arabinose mother liquor refracts light 56 percent, and the mass ratio of the arabinose crystal to the dry mass converted by the arabinose mother liquor is 1.
Example 3:
1) Hydrolysis: mixing 100Kg of bagasse stacked for 90 days with 900Kg of dilute sulfuric acid with the mass fraction of 1.0%, controlling the hydrolysis temperature at 100 ℃, and keeping the temperature for 4h to obtain hydrolysate, wherein the refraction of the hydrolysate is 3.8%;
2) Removing non-sugar substances: filter-pressing the hydrolysate by a belt filter press to remove hydrolysis residues, adding ammonia water into the obtained hydrolysate for neutralization until the pH is =7, adding powdered activated carbon into the hydrolysate for decolorization until the light transmittance is 75% (1 cm cuvette, wavelength is 420 nm), and desalting by electrodialysis until the conductivity is 2500 mu S/cm;
3) And (3) glucose enzymolysis: adjusting the pH of the hydrolysis refined solution to be 5.5, stirring by using air, controlling the air speed to be 30BV (the ratio of the air inlet volume to the liquid volume) per hour, adding an enzyme preparation for enzymolysis reaction, wherein the enzyme preparation is a mixture formed by mixing glucose oxidase and peroxidase according to the mass ratio of 8;
4) Enzyme recovery: pumping the enzymolysis finished liquid into a macromolecular ultrafiltration system, wherein the ultrafiltration membrane is a hollow fiber membrane with the molecular weight cutoff of 100,000Da, the operating pressure is 0.5MPa, the retention liquid is collected and stored according to the retention ratio of 2;
5) 1# chromatographic separation: pumping the enzymatic hydrolysate into a chromatographic separation device, wherein the filler is sodium resin, the eluent is pure water, the volume ratio of the fed material to the eluent is 1:4, the system temperature is 35 ℃, the system pressure is 0.5MPa, and the refractive index of the material B is 15.2 percent, wherein the xylose purity is 67 percent, and the glucose purity is 5.0 percent;
6) Refining and xylose crystallization: decolorizing the material B with activated carbon, desalting and refining with anion-cation exchange resin to improve light transmittance to 98% and conductance to 0.3mS/cm, and evaporating and concentrating to refract light to 82%; gradient cooling crystallization, cooling to 35 ℃, controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and controlling the cooling rate to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain xylose crystals and a xylose mother liquor. The purity of the xylose crystal is 99.0 percent, the refractive index of the xylose mother liquor is 56 percent, and the dry matter mass ratio of the mass of the xylose crystal to the converted mass of the xylose mother liquor is 1;
7) 2# chromatographic separation: ultrafiltering and filtering the xylose mother liquor obtained in the step (6), pumping the filtered xylose mother liquor into a 2# chromatographic separation device, wherein the filler is sodium resin, the eluent is pure water, the volume ratio of the fed material to the eluent is 1; the refraction of the collected E material is 9.5 percent, wherein the purity of rhamnose is 10.5 percent, and the purity of arabinose is 54.5 percent; the purity of xylose is 12.3%; collecting and storing the material B.
8) 3# chromatographic separation: evaporating and concentrating the material E until the refractive index is 55%, performing macromolecular ultrafiltration and filtration, pumping the material E into a 3# chromatographic separation device, wherein the filler is hydrogen resin, the eluent is dilute hydrochloric acid with the pH =4.0, the volume ratio of the feeding material to the eluent is 1.5, the system temperature is 35 ℃, the system pressure is 0.36MPa, and the index of the material F is obtained by separation: refracts light by 8 percent, wherein the purity of rhamnose is 81 percent, the purity of xylose is 13.8 percent, and the purity of arabinose is 4.3 percent; indexes of the G material are as follows: refract light by 21 percent, wherein the arabinose purity is 85 percent, the xylose purity is 0.3 percent, and the rhamnose purity is 12.6 percent;
9) Refining and crystallizing rhamnose and arabinose: and (3) respectively carrying out activated carbon decolorization and anion-cation exchange resin desalination refining on the material F and the material G in the step 8).
Lifting the material F to be transparent to 99%, conducting the material F at 45 mu S/cm, evaporating and concentrating the material F to refract light at 83%, cooling the material F to 35 ℃ in a gradient manner, controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and controlling the cooling rate to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain rhamnose crystals and rhamnose mother liquor. The purity of the rhamnose crystal is 99.0 percent, the refractive index of the rhamnose mother liquor is 53 percent, and the dry mass ratio of the quality of the rhamnose crystal to the converted quality of the rhamnose mother liquor is 1;
lifting the material G to ensure that the light is transmitted to 98 percent, conducting the light by 44 mu S/cm, evaporating and concentrating the material G to ensure that the refraction is 82 percent, cooling the material G to 35 ℃ in a gradient way, controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and controlling the cooling rate to be 0.8 ℃/h between 65 and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain arabinose crystals and arabinose mother liquor. The arabinose crystal purity is 99.3 percent, the arabinose mother liquor refracts light of 55 percent, and the mass ratio of the arabinose crystal to the dry mass converted by the arabinose mother liquor is 1.
Example 4:
1) Hydrolysis: mixing 100Kg of bagasse stacked for 360 days with 700Kg of dilute sulfuric acid with the mass fraction of 1.2%, controlling the hydrolysis temperature at 130 ℃, and keeping the temperature for 1h to obtain hydrolysate with the refraction of 4.9%;
2) Removing non-sugar substances: filter-pressing the hydrolysate by a belt filter press to remove hydrolysis residues, adding powdered activated carbon into the hydrolysate, decoloring the hydrolysate until the light transmittance is 75% (1 cm cuvette, wavelength is 420 nm), and desalting by electrodialysis until the conductivity is 2500 mu S/cm;
3) Glucose enzymolysis: adjusting the pH of the hydrolysis refined solution to be =7.0, stirring by using air, controlling the air speed to be 45BV (air inlet volume to liquid volume ratio) per hour, adding an enzyme preparation for enzymolysis, wherein the enzyme preparation is a mixture obtained by mixing glucose oxidase and peroxidase according to a mass ratio of 7, the adding amount is 0.5% of the content of soluble solids in the hydrolysis refined solution, continuously conveying the air, controlling the temperature to be 55 ℃, and reacting for 1h to obtain an enzymolysis finished solution;
4) And (3) enzyme recovery: pumping the enzymolysis finished liquid into a macromolecular ultrafiltration system, wherein the ultrafiltration membrane is a hollow fiber membrane with the molecular weight cutoff of 150,000Da, the operation pressure is 0.1MPa, the permeation cutoff ratio is 5;
5) 1# chromatographic separation: pumping the enzymolysis liquid into a 1# chromatographic separation device, wherein the filler is sodium resin, the eluent is pure water, the volume ratio of the feeding to the eluent is 1.5, the system temperature is 50 ℃, the system pressure is 0.1MPa, and the refraction of the material B is separated to obtain 13.6%, wherein the xylose purity is 70%, and the glucose purity is 4.7%;
6) Refining and xylose crystallization: decolorizing the material B with activated carbon, desalting and refining with anion-cation exchange resin to improve light transmittance to 98% and conductance to 0.3mS/cm, and evaporating and concentrating to refract light to 82%; gradient cooling crystallization, cooling to 35 ℃, controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and controlling the cooling rate to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain xylose crystals and a xylose mother liquor. The purity of the xylose crystal is 99.3 percent, the refractive index of the xylose mother liquor is 54 percent, and the dry matter mass ratio of the xylose crystal mass to the xylose mother liquor is 1;
7) 2# chromatographic separation: the xylose mother liquor obtained in the step (6) is pumped into a 2# chromatographic separation device after ultrafiltration and filtration, the filler is calcium resin, the eluant is pure water, the volume ratio of the feeding material to the eluant is 1; the refraction of the collected E material is 8.0 percent, wherein the purity of rhamnose is 16 percent, and the purity of arabinose is 81 percent; the purity of xylose is 3.5%; and collecting and storing the material B.
8) 3# chromatographic separation: evaporating and concentrating the material E to 55% of refraction, performing macromolecular ultrafiltration and filtration, pumping the material E into a 3# chromatographic separation device, wherein a filler is hydrogen resin, an eluent is a dilute hydrochloric acid solution with the pH =3.5, the volume ratio of the feeding to the eluent is 1.6, the system temperature is 50 ℃, the system pressure is 0.23MPa, and the indexes of the material F are obtained by separation: refract light by 8.0 percent, wherein the purity of rhamnose is 83 percent, the purity of xylose is 7.5 percent, and the purity of arabinose is 3.4 percent; indexes of the G material are as follows: refract light by 19 percent, wherein the arabinose purity is 87 percent, the xylose purity is 0.2 percent, and the rhamnose purity is 11.8 percent;
9) Refining and crystallizing rhamnose and arabinose: and (3) respectively carrying out activated carbon decolorization and anion-cation exchange resin desalination refining on the material F and the material G in the step 8).
Lifting the material F to be transparent to 99%, conducting the material F at 32 mu S/cm, evaporating and concentrating the material F to refract light at 85%, cooling the material F to 35 ℃ in a gradient manner, controlling the cooling rate to be 1.0 ℃/h to 65 ℃ and controlling the cooling rate to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain rhamnose crystals and rhamnose mother liquor. The purity of the rhamnose crystal is 99.5 percent, the refractive index of the rhamnose mother liquor is 51 percent, and the dry mass ratio of the quality of the rhamnose crystal to the converted quality of the rhamnose mother liquor is 1;
g material is lifted to be transparent to 98 percent, the electric conductivity is 45 mu S/cm, evaporation concentration is carried out to obtain refraction 82 percent, gradient temperature reduction crystallization is carried out, the temperature is reduced to 35 ℃, the temperature reduction rate is controlled to be 1.0 ℃/h to 65 ℃, and the temperature reduction rate is controlled to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃; and (4) performing centrifugal separation to obtain arabinose crystals and arabinose mother liquor. The arabinose crystal purity is 99.6 percent, the arabinose mother liquor refracts light by 54 percent, and the mass ratio of the arabinose crystal to the dry mass converted by the arabinose mother liquor is 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for extracting rhamnose from bagasse comprises the following steps:
(1) Mixing bagasse with dilute hydrochloric acid or dilute sulfuric acid, and hydrolyzing for 1-4 h at 100-130 ℃ to obtain a hydrolysate, wherein the refractive index of the hydrolysate is controlled to be 1-10%;
(2) Removing non-sugar substances: removing colloids, pigments, inorganic salts, inorganic acids and organic acids in the hydrolysate obtained in the step (1) through a procedure of removing non-sugar substances to obtain a refined hydrolyzed liquid, and controlling the light transmittance of the refined hydrolyzed liquid to be more than or equal to 75% at a wavelength of 420nm measured by a 1cm cuvette; the conductivity is less than or equal to 3000 mu S/cm;
(3) And (3) glucose enzymolysis: adjusting the pH = 3-7 of the hydrolysis refined liquid obtained in the step (2), introducing air into the hydrolysis refined liquid, stirring, controlling the air speed to be 2-50 BV (specific volume) of the air inlet volume per hour and the volume of the hydrolysis refined liquid, controlling the temperature to be 25-55 ℃, adding an enzyme preparation into the hydrolysis refined liquid to perform enzymolysis reaction for 1-48 h, and keeping the pH constant in the enzymolysis process to obtain an enzymolysis finished liquid;
(4) Enzyme recovery: pumping the enzymolysis finished liquid obtained in the step (3) into an ultrafiltration system, controlling the operating pressure to be 0.1-1.0 MPa and the permeation interception ratio to be (2-5): 1, collecting the intercepted liquid, returning the intercepted liquid to the step (3), and sending the permeated liquid into a raw material tank for chromatographic separation;
(5) 1# chromatographic separation: concentrating the permeate liquid obtained in the step (4) to a refractive index of 35-50%, pumping the concentrate into a 1# chromatographic separation device, taking water as an eluent, controlling the temperature of a system to be 35-80 ℃ and the pressure of the system to be 0.1-0.5 MPa, and separating to obtain a material B rich in xylose and arabinose components and a material C rich in inorganic salt, gluconic acid or gluconate and glycan, wherein the refractive index of the material B is 12-25%, the xylose purity is 65-85%, and the glucose purity is less than 5%;
(6) Refining: performing decolorization, desalination and refining on the obtained material B, increasing the light transmittance to be more than 50 percent and the electric conductivity to be less than 0.5mS/cm, evaporating and concentrating until the refractive index is 65-85 percent, performing gradient cooling crystallization, and performing centrifugal separation to obtain xylose crystals and xylose mother liquor;
(7) 2# chromatographic separation: ultrafiltering and filtering the xylose mother liquor obtained in the step (6), pumping into a 2# chromatographic separation device, taking water as an eluent, controlling the system temperature to be 35-80 ℃ and the system pressure to be 0.1-0.5 MPa, separating to obtain a material D rich in xylose and non-sugar substances and a material E rich in rhamnose and arabinose, returning the material D to the step (3) for further enzymolysis of glucose in the material D and recovering xylose;
(8) 3# chromatographic separation: evaporating and concentrating the material E obtained in the step (7) to a refractive index of 30-60%, performing ultrafiltration and filtration, pumping into a 3# chromatographic separation device, and separating to obtain a rhamnose-rich material F and an arabinose-rich material G by taking a dilute hydrochloric acid solution or water as an eluent and controlling the system temperature to be 35-80 ℃ and the system pressure to be 0.1-0.5 MPa;
(9) Refining and crystallizing: respectively decolorizing and desalting the F material and the G material obtained in the step 8), improving the light transmittance to more than 98 percent and the electric conductivity to less than 50 mu S/cm, evaporating and concentrating to 65-85 percent of refractive index, performing gradient cooling crystallization, performing centrifugal separation to respectively obtain rhamnose crystal and rhamnose mother liquor and arabinose crystal and arabinose mother liquor, mixing the rhamnose mother liquor and the arabinose mother liquor, and returning to the step (8) for further separation;
the chromatographic column packing in the 1# chromatographic separation device, the 2# chromatographic separation device and the 3# chromatographic separation device is hydrogen type, sodium type, potassium type or calcium type cation exchange resin.
2. The method according to claim 1, wherein the enzyme preparation in step (3) is a mixture of glucose oxidase and peroxidase.
3. The method according to claim 2, wherein the enzyme preparation in step (3) is glucose oxidase: the mass ratio of the peroxidase is 7.
4. The method according to any one of claims 1 to 3, wherein the enzyme preparation is added in the step (3) in an amount of 0.5 to 3% based on the soluble solid content in the hydrolysis purification solution.
5. The method according to any one of claims 1 to 3, wherein the step of removing non-sugar substances in step (2) is a combination of at least three of solid-liquid separation, neutralization, decolorization with activated carbon, membrane decolorization, desalting by electrodialysis, and desalting with ion exchange resin.
6. The method according to claim 5, wherein the step of removing the non-sugar substances in the step (2) is any one of a combination of solid-liquid separation-decoloring-ion exchange resin, a combination of solid-liquid separation-membrane decoloring-electrodialysis desalination, and a combination of solid-liquid separation-neutralization-decoloring-ion exchange resin.
7. The method according to any one of claims 1 to 3 and 6, wherein the ultrafiltration system is a ceramic membrane, an organic roll-up membrane or a hollow fiber membrane with a membrane molecular weight cut-off of 1,000 to 150,000Da.
8. The method according to any one of claims 1 to 3 and 6, wherein the gradient temperature reduction rate in the steps (6) and (9) is controlled to be 0.5-1.0 ℃/h, and the temperature is reduced to 35-50 ℃.
9. The method according to any one of claims 1 to 3 and 6, wherein the gradient cooling procedure in the steps (6) and (9) is cooling to 35 ℃, the cooling rate is controlled to be 1.0 ℃/h to 65 ℃, and the cooling rate is controlled to be 0.8 ℃/h between 65 ℃ and 45 ℃; the cooling rate is controlled to be 0.5 ℃/h between 45 and 35 ℃.
10. The method according to any one of claims 1 to 3 or 6, wherein the bagasse is naturally stacked bagasse for 3 months or more.
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