CN108821940A - A kind of method of rice straw Efficient Conversion xylitol - Google Patents
A kind of method of rice straw Efficient Conversion xylitol Download PDFInfo
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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Abstract
The invention discloses a kind of methods of rice straw Efficient Conversion xylitol, are related to field of biotechnology.The hemicellulose Efficient Conversion steamed in quick-fried rice straw is xylose using water-boiling method and acid hydrolysis of microwave method by the present invention, xylose is xylitol by recycling catalytic hydrogenation method, the present invention has the characteristics that high conversion yield, high product purity, low loss late, and method simple practical, suitable for handling a large amount of rice straw, for the efficient utilization of rice straw, the economic benefit for increasing Rice Cropping provides completely new thinking, has broad application prospects.
Description
Technical field
The present invention relates to field of biotechnology, in particular to a kind of method of rice straw Efficient Conversion xylitol.
Background technique
Rice straw is a kind of important agricultural resource, can be used for animal and fowl fodder, paper making raw material, construction material, biomass
The energy and organic fertilizer material etc..China's Rice Cropping is with a long history, cultivated area is up to 30,000,000 hectares, and rice straw resource is rich
It is rich.Data shows about 200,000,000 tons of yield of rice straw of China year, and rice straw, will increasingly as a kind of important living resources
Mostly it is utilized.Currently, rice straw using main or mechanical returning to the field, but power consumption is big, and equipment twines grass, and it is serious to stop up mud, makees
Industry effect is poor, seriously affects the utilization of rice straw resource, there is also the rotten period is long for rice straw returning to the field, it is difficult to play organic
The utilization efficiency of matter, in order to save farming season, many areas handle rice straw using the method for on-site incineration, not only waste money
Source also causes serious environmental pollution, is unfavorable for the sustainable development of ecology, and therefore, research makes full use of the place of rice straw
Reason technology is very urgent.
Xylose is highly important monosaccharide substance, has a series of advantage, for example sugariness is high but heat is low, Ke Yigai
The living environment of microorganism in philanthropist's body promotes the proliferation and growth of beneficial bacterium in human body intestinal canal, improves the immunity etc. of human body.
Studies have shown that xylose can also promote absorption of the human body to calcium.Since xylose has the characteristics that sugariness is high but heat is low, Ke Yijin
It is possible to meet the needs of people are to sweets, it is special for group especially for diabetes etc., be in great demand, in recent years its
It has a wide range of applications in fields such as food and medicines.
In this cellulose in rice straw, there is a large amount of xylose structure units, and main two kinds of wood of discovery are poly- at present
Sugar, respectively araboxylan and Arabic glucuronic acid xylan, the former is primarily present in gramineae plant.Rice
There is D- xylose structure units abundant in stalk, take certain method degradation of hemicellulose that can obtain these D- wood
Sugar, currently used method mainly have acid-hydrolysis method, microwave-assisted acid-hydrolysis method and enzymatic isolation method.
Microwave Water solution is a kind of fast degradation method to receive much attention in recent years, with high-efficient, low energy consumption, heating is equal
Even, at low cost, good selective.Microwave heating food processing, the drying of wood and in terms of have
It is widely applied.Furthermore microwave heating can also be used in resolution, synthesis etc..Under microwave action, the orientation of polar molecule with
The variation of external electric field and change, so as to cause the warm-up movement and intermolecular interaction of molecule, produce and be similar to
The effect of friction, to convert microwave field energy to the thermal energy of medium.From common heating by it is outer and in heating method it is different, it is micro-
Wave method eliminates heat transfer, is heated in a manner of inside-out.When handling agricultural-forestry biomass raw material with microwave method, raw material
Middle hydrone absorbs microwave energy, and deep layer heats and increases transient temperature, causes raw material mix that fracture occurs to play quickly
The advantages of effect of degradation, microwave-assisted acid-hydrolysis method has both acid hydrolyzation and Microwave Water solution, when can not only greatly shorten hydrolysis
Between, also make xylose yield high, hydrolysising by-product is few.
Xylitol is the intermediate product of xylose metabolism, belongs to five-state controller.Xylitol has a series of advantageous properties,
The fields such as food, medicine and chemical industry have a wide range of applications, and also increasingly attract attention in recent years.The sweet tea of xylitol
Degree is similar with sucrose, and refrigerant mouthfeel can be generated when edible, there is many advantages, such as its thermostabilization as food additives
Property is good, and food colour will not be made to deepen, will not destroy the nutritional ingredient of food, and has than traditional sucrose sweetener longer
Shelf-life.Xylitol also has anti-caries, otitis, fatty liver, improves liver function, inhibits the growth of oral bacteria, make to damage
The calcification and exciting salivary secretion and other effects again of the tooth of wound.The U.S. regards xylitol as generally recognized as safe substance, allow beverage,
It is used in food and medicine etc..
The higher value application of hemicellulose is the important topic of hemicellulose research field a few days ago.But utilize hemicellulose
In xylan conversion xylitol there is also many problems, such as:1, hydrolysis of hemicellulose conversion wood how is improved as far as possible
The yield of sugar；2, hydrolyzate purifying process optimizes, and improves purification efficiency, drops the loss late of sill sugar；3, xylose how is improved to turn
Turn to the conversion ratio of xylitol.
Summary of the invention
The technical problems to be solved by the invention：For the skill currently with hemicellulose conversion xylitol in rice straw
Art problem, the present invention are efficiently converted into xylitol using rice straw, improve xylitol yield, purity, reduce loss late.
In order to solve the above technical problems, the present invention provides technical solution below：
A kind of method of rice straw Efficient Conversion xylitol includes following operating procedure：
(1) prepared by raw material：Rice straw is cut into the segment of 4~10cm, the rice straw sheared is put into Steam explosive machine,
Under the pressure condition of 1.8MPa, pops after 10~15min of pressure maintaining and steam quick-fried rice straw to get to required raw material；
(2) separation of hemicellulose：Boiling is carried out to quick-fried rice straw is steamed with boiling water bath, steams the matter of quick-fried rice straw and water
Amount is than being 1:15~1:30,0.6~1.5h of boiling, then 5000rpm is centrifuged 15min and is separated by solid-liquid separation, same condition, then
0.6~1.5h of boiling, and 5000rpm centrifugation 15min centrifugation is separated by solid-liquid separation, and centrifugate will be mixed twice, and be obtained enrichment half
The water cooking liquid of cellulose；
(3) remaining solid in step (2) is collected, 2~8mL of sulfuric acid is added in every gram of solid, microwave power 800~
900W carries out sour water solution 18~for 24 hours under the conditions of 95~105 DEG C, and 5000rpm is centrifuged 15min and is separated by solid-liquid separation after the completion of hydrolysis,
Collect supernatant；
(4) water cooking liquid in step (2) is subjected to sour water solution, 2~4mL of sulfuric acid is added in every milliliter of water cooking liquid, in microwave 500
~800W hydrolyzes 8~12h under the conditions of 80~100 DEG C；
(5) acid is removed with the neutralization of 0.2~0.4M sodium hydroxide after merging the hydrolyzate in step (3) and (4), is then first used
D351 anion exchange resin, then carry out purified treatment with 010 cation exchange resin, using neutralizer is pressed by the way of column
Sequence is added in resin, and the volume ratio of neutralizer and resin is 0.5:1~0.9:1, and drenched respectively with the distilled water of 5 times of column volumes
It washes, collects efflux；
(6) purified hydrolyzate is concentrated by ultrafiltration, finally that the xylose isolated is molten using chromatography separating xylose
Liquid collects concentration, is placed in 4 DEG C of refrigerators for 24 hours, xylose product is obtained in a manner of crystallisation by cooling；
(7) it weighs xylose crystalline to be dissolved in strong alkali solution, the NaBH of 1.0~1.5M is added in equal volume4Strong alkali solution
In, xylose and NaBH4Molar ratio be 1:0.2~1:1, it is placed at room temperature for 15d, glacial acetic acid removes residue NaBH in solution later4,
It is dry at 90 DEG C, dry sample quality is weighed, Determination of Xylitol in sample is measured, calculates the efficiency of xylose xylitol, it is described
Strong alkali solution is the aqueous solution that the concentration that one of KOH, NaOH are prepared is 0.0125~0.025M.
Preferably, the rice straw finishes under the conditions of 20min at 105 DEG C, 100 DEG C of drying 1h；
Preferably, the sulfuric acid in the step (3) is 0.4~0.8M using concentration；Sulfuric acid in the step (4) is dense eventually
Degree is 0.3~0.5M；
Preferably, the preprocess method of the D351 anion exchange resin and 010 cation exchange resin is as follows：
(a) activated resin 30min is impregnated using 95% ethyl alcohol, dosage is 2~3 times of resin volume；
(b) 2h is impregnated with saturated sodium chloride solution after activating；
(c) using soda acid processing is carried out to resin by the way of pillar, the equal 1mol/L of the concentration of hydrochloric acid and sodium hydroxide is used
Amount is 10 times of resin volumes, is then eluted respectively with distilled water to neutrality.
Preferably, the chromatography separating xylose, using the positive silica gel of 100~200 mesh, wet method dress post, first by silica gel
It is dissolved in the n-butanol of 10 times of volumes, is then introduced into chromatographic column with glass bar, made with the proportion liquid of methanol and acetic acid ethyl ester
The separation of xylose is carried out for leacheate.
It is further preferred that the volume ratio of methanol and acetic acid ethyl ester is 1 in the proportion liquid of the methanol and acetic acid ethyl ester:2
~1:6.
The beneficial effect that the present invention obtains：
The present invention passes through the combination of cooking process and acid hydrolysis of microwave method, is efficiently converted into using hemicellulose in rice straw
Xylose optimizes hydrolyzate purifying process, and xylose Efficient Conversion is xylitol by recycling catalytic hydrogenation method, then improves xylitol
Yield, purity, reduce loss late.
Specific embodiment
Below by the description to embodiment, specific embodiments of the present invention will be described in further detail, with side
Those skilled in the art is helped to have more complete, accurate and deep understanding to inventive concept of the invention, technical solution.
Embodiment 1：
Xylitol is prepared according to the following steps：
(1) prepared by raw material：It by 10kg rice straw at 105 DEG C, finishes under the conditions of 20min, 100 DEG C of drying 1h are cut into
The rice straw sheared is put into Steam explosive machine by the segment of 7cm, under the pressure condition of 1.8MPa, is popped after pressure maintaining 12min, i.e.,
It obtains required raw material and steams quick-fried rice straw；
(2) separation of hemicellulose：Boiling is carried out to quick-fried rice straw is steamed with boiling water bath, steams the matter of quick-fried rice straw and water
Amount is than being 1:23, boiling 1h, then 5000rpm is centrifuged 15min and is separated by solid-liquid separation, same condition, then boiling 1h, and
5000rpm centrifugation 15min centrifugation is separated by solid-liquid separation, and centrifugate will be mixed twice, and be obtained the water cooking liquid of enrichment hemicellulose；
(3) remaining solid in step (2) to be collected, sulfuric acid 5mL is added in every gram of solid, and sulfuric acid is 0.6M using concentration,
Sour water solution 21h is carried out under the conditions of microwave power 850W, 100 DEG C, 5000rpm is centrifuged 15min and carries out solid-liquid point after the completion of hydrolysis
From collection supernatant；
(4) water cooking liquid in step (2) is subjected to sour water solution, sulfuric acid 3mL is added in every milliliter of water cooking liquid, and sulfuric acid is final concentration of
0.4M hydrolyzes 10h under the conditions of microwave 650W, 90 DEG C；
(5) D351 anion exchange resin and 010 cation exchange resin are pre-processed, method is as follows：
(a) activated resin 30min is impregnated using 95% ethyl alcohol, dosage is 2.5 times of resin volume；
(b) with removing ethyl alcohol is filtered after activating, 2h is impregnated with the saturated sodium chloride solution of 2 times of resin volumes；
(c) wet method dress post, using carry out alkali process after first acid by the way of pillar to resin, hydrochloric acid and sodium hydroxide it is dense
Equal 1mol/L is spent, dosage is 10 times of resin volumes, is then eluted respectively with distilled water to neutrality, flow velocity is 10mL/min.
(6) at room temperature, acid is removed with the neutralization of 0.3M sodium hydroxide after the hydrolyzate in step (3) and (4) being merged, then first
Carry out desalination purified treatment with D351 anion exchange resin, then with 010 cation exchange resin, using by the way of column will in
It is flowed through in resin in order with liquid, the volume ratio of neutralizer and resin is 0.7:1, and drenched respectively with the distilled water of 5 times of column volumes
It washes, flow velocity 6mL/min, collects efflux；
(7) purified hydrolyzate is concentrated by ultrafiltration to the 1/30 of original volume, using chromatography separating xylose, is used
Silica gel is first dissolved in the n-butanol of 10 times of volumes by the YMC forward direction silica gel of 150 mesh, wet method dress post, then introduces layer with glass bar
It analyses in column, carries out chromatographic isolation after filling column, with the 1 of methanol and acetic acid ethyl ester:3 proportion liquid carry out point of xylose as eluent
From, 50 DEG C of separation temperature, feed rate 2mL/min, elution speed 15mL/min.
(8) it will finally elute isolated xylose solution to collect, be concentrated by ultrafiltration three times, 4 DEG C of refrigerators be placed in for 24 hours, with cooling
The mode of crystallization obtains xylose.
(9) it weighs 100g xylose crystalline to be dissolved in strong alkali solution, isometric NaBH that 1.25M is added4Strong alkali solution
In, xylose and NaBH4Molar ratio be 1:0.6, it is placed at room temperature for 15d, glacial acetic acid is added to dry, title at 7.0,90 DEG C of pH value of solution
Dry sample quality is measured, Determination of Xylitol in drying sample is measured, calculates the efficiency of xylose xylitol, the strong alkali solution
For the NaOH aqueous solution of 0.019M.
Embodiment 2：
Xylitol is prepared according to the following steps：
(1) prepared by raw material：It by 10kg rice straw at 105 DEG C, finishes under the conditions of 20min, 100 DEG C of drying 1h are cut into
The rice straw sheared is put into Steam explosive machine by the segment of 10cm, under the pressure condition of 1.8MPa, is popped after pressure maintaining 15min, i.e.,
It obtains required raw material and steams quick-fried rice straw；
(2) separation of hemicellulose：Boiling is carried out to quick-fried rice straw is steamed with boiling water bath, steams the matter of quick-fried rice straw and water
Amount is than being 1:30, boiling 1.5h, then 5000rpm is centrifuged 15min and is separated by solid-liquid separation, same condition, then boiling 1.5h, and
5000rpm centrifugation 15min centrifugation is separated by solid-liquid separation, and centrifugate will be mixed twice, and be obtained the water cooking liquid of enrichment hemicellulose；
(3) remaining solid in step (2) to be collected, sulfuric acid 8mL is added in every gram of solid, and sulfuric acid is 0.8M using concentration,
Sour water solution is carried out for 24 hours under the conditions of microwave power 900W, 105 DEG C, and 5000rpm is centrifuged 15min and carries out solid-liquid point after the completion of hydrolysis
From collection supernatant；
(4) water cooking liquid in step (2) is subjected to sour water solution, sulfuric acid 4mL is added in every milliliter of water cooking liquid, and sulfuric acid is final concentration of
0.5M hydrolyzes 12h under the conditions of microwave 800W, 100 DEG C；
(5) D351 anion exchange resin and 010 cation exchange resin are pre-processed, method is as follows：
(a) activated resin 30min is impregnated using 95% ethyl alcohol, dosage is 2.5 times of resin volume；
(b) with removing ethyl alcohol is filtered after activating, 2h is impregnated with the saturated sodium chloride solution of 2 times of resin volumes；
(c) wet method dress post, using carry out alkali process after first acid by the way of pillar to resin, hydrochloric acid and sodium hydroxide it is dense
Equal 2mol/L is spent, dosage is 10 times of resin volumes, is then eluted respectively with distilled water to neutrality, flow velocity is 20mL/min.
(6) at room temperature, acid is removed with the neutralization of 0.4M sodium hydroxide after the hydrolyzate in step (3) and (4) being merged, then first
Carry out desalination purified treatment with D351 anion exchange resin, then with 010 cation exchange resin, using by the way of column will in
It is flowed through in resin in order with liquid, the volume ratio of neutralizer and resin is 0.9:1, and drenched respectively with the distilled water of 5 times of column volumes
It washes, flow velocity 15mL/min, collects efflux；
(7) purified hydrolyzate is concentrated by ultrafiltration to the 1/40 of original volume, using chromatography separating xylose, is used
Silica gel is first dissolved in the n-butanol of 10 times of volumes by the YMC forward direction silica gel of 200 mesh, wet method dress post, then introduces layer with glass bar
It analyses in column, carries out chromatographic isolation after filling column, with the 1 of methanol and acetic acid ethyl ester:6 proportion liquid carry out point of xylose as eluent
From, 65 DEG C of separation temperature, feed rate 5mL/min, elution speed 30mL/min.
(8) it will finally elute isolated xylose solution to collect, be concentrated by ultrafiltration twice, 4 DEG C of refrigerators be placed in for 24 hours, with cooling
The mode of crystallization obtains xylose product.
(9) it weighs 100g xylose crystalline to be dissolved in strong alkali solution, isometric NaBH that 1.5M is added4Strong alkali solution
In, xylose and NaBH4Molar ratio be 1:1, it is placed at room temperature for 25d, glacial acetic acid is added to dry, weighing at 7.0,90 DEG C of pH value of solution
Dry sample quality, measures Determination of Xylitol in drying sample, calculates the efficiency of xylose xylitol, and the strong alkali solution is
The NaOH aqueous solution of 0.025M.
Embodiment 3：
Xylose is prepared according to the following steps：
(1) prepared by raw material：It by 10kg rice straw at 105 DEG C, finishes under the conditions of 20min, 100 DEG C of drying 1h are cut into
The rice straw sheared is put into Steam explosive machine by the segment of 4cm, under the pressure condition of 1.8MPa, is popped after pressure maintaining 10min, i.e.,
It obtains required raw material and steams quick-fried rice straw；
(2) separation of hemicellulose：Boiling is carried out to quick-fried rice straw is steamed with boiling water bath, steams the matter of quick-fried rice straw and water
Amount is than being 1:15, boiling 0.6h, then 5000rpm is centrifuged 15min and is separated by solid-liquid separation, same condition, then boiling 0.6h, and
5000rpm centrifugation 15min centrifugation is separated by solid-liquid separation, and centrifugate will be mixed twice, and be obtained the water cooking liquid of enrichment hemicellulose；
(3) remaining solid in step (2) to be collected, sulfuric acid 2mL is added in every gram of solid, and sulfuric acid is 0.4M using concentration,
Sour water solution 18h is carried out under the conditions of microwave power 800W, 95 DEG C, 5000rpm is centrifuged 15min and carries out solid-liquid point after the completion of hydrolysis
From collection supernatant；
(4) water cooking liquid in step (2) is subjected to sour water solution, sulfuric acid 2mL is added in every milliliter of water cooking liquid, and sulfuric acid is final concentration of
0.3M hydrolyzes 8h under the conditions of microwave 500W, 80 DEG C；
(5) D351 anion exchange resin and 010 cation exchange resin are pre-processed, method is as follows：
(a) activated resin 30min is impregnated using 95% ethyl alcohol, dosage is 2.5 times of resin volume；
(b) with removing ethyl alcohol is filtered after activating, 2h is impregnated with the saturated sodium chloride solution of 2 times of resin volumes；
(c) wet method dress post, using carry out alkali process after first acid by the way of pillar to resin, hydrochloric acid and sodium hydroxide it is dense
Equal 1mol/L is spent, dosage is 10 times of resin volumes, is then eluted respectively with distilled water to neutrality, flow velocity is 10mL/min.
(6) at room temperature, acid is removed with the neutralization of 0.2M sodium hydroxide after the hydrolyzate in step (3) and (4) being merged, then first
Carry out desalination purified treatment with D351 anion exchange resin, then with 010 cation exchange resin, using by the way of column will in
It is flowed through in resin in order with liquid, the volume ratio of neutralizer and resin is 0.5:1, and drenched respectively with the distilled water of 5 times of column volumes
It washes, flow velocity 5mL/min, collects efflux；
(7) purified hydrolyzate is concentrated by ultrafiltration to the 1/20 of original volume, using chromatography separating xylose, is used
Silica gel is first dissolved in the n-butanol of 10 times of volumes by the YMC forward direction silica gel of 100 mesh, wet method dress post, then introduces layer with glass bar
It analyses in column, carries out chromatographic isolation after filling column, with the 1 of methanol and acetic acid ethyl ester:2 proportion liquid carry out point of xylose as eluent
From, 40 DEG C of separation temperature, feed rate 2mL/min, elution speed 10mL/min.
(8) it will finally elute isolated xylose solution to collect, and be concentrated by ultrafiltration once, 4 DEG C of refrigerators are placed in for 24 hours, with cooling
The mode of crystallization obtains xylose product.
(9) it weighs 100g xylose crystalline to be dissolved in strong alkali solution, isometric NaBH that 1M is added4In strong alkali solution,
Xylose and NaBH4Molar ratio be 1:0.2, it is placed at room temperature for 25d, glacial acetic acid is added to dry, weighing at 7.0,90 DEG C of pH value of solution
Dry sample quality, measures Determination of Xylitol in drying sample, calculates the efficiency of xylose xylitol, and the strong alkali solution is
The NaOH aqueous solution of 0.0125M.
The xylose yield of comparative example 1-3, method are as follows：
(1) in rice straw hemicellulose quantitative detection：
Referring to GB/T 26677.9-2005.This test method is the quick-fried rice straw water cooking liquid of steaming and 12% that will be centrifuged
(m/m) hydrochloric acid is blended, and converts furfural for the hemicellulose in sample in a manner of heat together, is then quantitatively surveyed with volumetric method
Surely the furfural content distilled is finally converted into the content of hemicellulose again.
Hemicellulose total amount/rice straw dry weight * 100% in the water cooking liquid for hemicellulose yield=be not centrifuged
(2) quantitative detection of xylose：
((HPLC) detection, it is efficient with 1100 type of Agilent for testing HPLC used in Xylose Content to high performance liquid chromatography
Liquid chromatograph, chromatographic column used is HPX-87C 300mm × 7.8mm, using ultrapure water as mobile phase, 75 DEG C of column temperature, and flow velocity
Control is in 0.6~0.8mL/min.With reference to national standard GB/T 23532-2009, the acid hydrolysis liquid after merging is measured using external standard method
The content of middle xylose.
Xylose total amount/rice straw dry weight * 100% in acid hydrolysis liquid after xylose yield=merging
Quantitative result is as follows：
The yield of 1 rice straw of table conversion xylose
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Hemicellulose yield (wt%) | 9.05 | 8.11 | 7.32 |
| Xylose yield (wt%) | 8.06 | 6.62 | 5.86 |
| Yield (%) | 89.06 | 81.63 | 80.05 |
Note：Yield is xylose yield/hemicellulose yield * 100%
For the xylose yield of embodiment 1-3 more than 80%, transformation efficiency is higher as shown in Table 1.
Xylose Content in separation product solid portion and liquid portion is measured using HPLC, it is as a result as follows：
Xylose Content in 2 separation product solid portion of table and liquid portion
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Xylose Content (wt%) in solid | 83.3 | 77.4 | 80.5 |
| Xylose Content (wt%) in liquid | 53.2 | 61.3 | 55.5 |
The xylose loss late in purification process is calculated, calculation formula is as follows：
Loss late=[1- (xylose total amount in the acid hydrolysis liquid in final product after quality/merging of pure xylose)] * 100%
Loss late result is as follows：
The loss late of xylose in 3 purification process of table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Xylose loss late (%) | 4.4 | 5.7 | 5.0 |
The quantitative detection of xylitol：
High-efficient liquid phase chromatogram HPLC detection, it is 1100 type of Agilent that HPLC used in Determination of Xylitol is tested in this chapter experiment
High performance liquid chromatograph, chromatographic column used is HPX-87C 300mmx7.8mm, using 35% second eyeball solution as mobile phase, column temperature
75 DEG C, flow control is in 0.6-0.8mL/min.With reference to national standard GB13509-2009, Determination of Xylitol is carried out using external standard method
Measurement.The xylitol standard solution for first preparing three kinds of various concentrations, weighs about 1.0g, 1.5g and 2.0g (are accurate to respectively
Then 0.0001g) xylitol standard items move it into volumetric flask, and with distilled water constant volume to 100mL.Accurately weigh again 1 to
2g (being accurate to 0.0001g) drying sample, equally with distilled water constant volume to 100mL.
Respectively by 5 μ L of xylitol standard solution sample introduction, the peak area A of record standard xylose from solutions alcohol.In standard solution
The correction factor f of xylitol is calculated by formula, and formula is as follows：
(f is the correction factor of xylitol in standard solution to f=m/A；M is the quality (g) of xylitol in standard solution；A is
The peak area of xylitol in standard solution)
Similarly, by 5 μ L of sample preparation liquid sample introduction, the peak area A of xylitol in sample is recorded；The content X of xylitol is pressed
Formula calculates, and formula is as follows：
(X is Determination of Xylitol (wt%)；F is the correction factor of xylitol in standard solution；Ai
For the peak area of xylitol in sample；Mi is sample quality (g).
Xylose is that the special rate calculation formula of xylitol is：
Xylose Content * 100% in xylitol conversion rate=Determination of Xylitol/xylose separation product solid
As a result as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Determination of Xylitol (wt%) | 79.59 | 71.46 | 74.64 |
| Xylitol conversion rate (%) | 95.55 | 92.33 | 92.72 |
In conclusion the hemicellulose Efficient Conversion in rice straw can be xylose, wood in preferred embodiment by the present invention
Sugar yield is up to 89.06%, and product purity is up to 83.3%, and xylose loss late is 4.4% in purification process, xylitol conversion rate
Up to 95.55, the present invention has the characteristics that high yield, high product purity, low loss late and high conversion, and method is simply real
With suitable for handling a large amount of rice straw, for the efficient utilization of rice straw, the economic benefit for increasing Rice Cropping is provided
Completely new thinking, has broad application prospects.
The above examples only illustrate the technical idea of the present invention, and this does not limit the scope of protection of the present invention, all
According to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within the scope of the present invention
Within；The technology that the present invention is not directed to can be realized by the prior art.
Claims (6)
1. a kind of method of rice straw Efficient Conversion xylitol, which is characterized in that include following operating procedure：
(1) prepared by raw material：Rice straw is cut into the segment of 4~10cm, the rice straw sheared is put into Steam explosive machine,
Under the pressure condition of 1.8MPa, pops after 10~15min of pressure maintaining and steam quick-fried rice straw to get to required raw material；
(2) separation of hemicellulose：Boiling is carried out to quick-fried rice straw is steamed with boiling water bath, steams the mass ratio of quick-fried rice straw and water
It is 1:15~1:30,0.6~1.5h of boiling, then 5000rpm is centrifuged 15min and is separated by solid-liquid separation, same condition, then boiling
0.6~1.5h, and 5000rpm centrifugation 15min centrifugation is separated by solid-liquid separation, and centrifugate will be mixed twice, and be obtained enrichment hemicellulose
The water cooking liquid of element；
(3) remaining solid in step (2) to be collected, 2~8mL of sulfuric acid is added in every gram of solid, in 800~900W of microwave power,
Sour water solution 18~for 24 hours is carried out under the conditions of 95~105 DEG C, 5000rpm is centrifuged 15min and is separated by solid-liquid separation after the completion of hydrolysis, collects
Supernatant；
(4) water cooking liquid in step (2) is subjected to sour water solution, 2~4mL of sulfuric acid is added in every milliliter of water cooking liquid, microwave 500~
800W hydrolyzes 8~12h under the conditions of 80~100 DEG C；
(5) acid is removed with the neutralization of 0.2~0.4M sodium hydroxide after merging the hydrolyzate in step (3) and (4), then first uses D351
Anion exchange resin, then carry out purified treatment with 010 cation exchange resin, using by the way of column by neutralizer in order
It is added in resin, the volume ratio of neutralizer and resin is 0.5:1~0.9:1, and eluted respectively with the distilled water of 5 times of column volumes,
Collect efflux；
(6) purified hydrolyzate is concentrated by ultrafiltration, and using chromatography separating xylose, is finally received the xylose solution isolated
Collection concentration, is placed in 4 DEG C of refrigerators for 24 hours, xylose product is obtained in a manner of crystallisation by cooling；
(7) it weighs xylose crystalline to be dissolved in strong alkali solution, the NaBH of 1.0~1.5M is added in equal volume4In strong alkali solution, wood
Sugar and NaBH4Molar ratio be 1:0.2~1:1, it is placed at room temperature for 15d, glacial acetic acid removes residue NaBH in solution later4, at 90 DEG C
It is dry, dry sample quality is weighed, Determination of Xylitol in sample is measured, calculates the efficiency of xylose xylitol, the strong basicity
Solution is the aqueous solution that the concentration that one of KOH, NaOH are prepared is 0.0125~0.025M.
2. one of the according to claim 1 method of rice straw Efficient Conversion xylitol, it is characterised in that：The rice straw
Stalk finishes under the conditions of 20min at 105 DEG C, 100 DEG C of drying 1h.
3. one of the according to claim 1 method of rice straw Efficient Conversion xylitol, it is characterised in that：The step
(3) it is 0.4~0.8M that the sulfuric acid in, which uses concentration,；Final concentration of 0.3~the 0.5M of sulfuric acid in the step (4).
4. one of the according to claim 1 method of rice straw Efficient Conversion xylitol, it is characterised in that：The D351 yin
The preprocess method of ion exchange resin and 010 cation exchange resin is as follows：
(a) activated resin 30min is impregnated using 95% ethyl alcohol, dosage is 2~3 times of resin volume；
(b) 2h is impregnated with saturated sodium chloride solution after activating；
(c) using soda acid processing carried out to resin by the way of pillar, the equal 1mol/L of the concentration of hydrochloric acid and sodium hydroxide, dosage is equal
For 10 times of resin volumes, then eluted respectively with distilled water to neutrality.
5. one of the according to claim 1 method of rice straw Efficient Conversion xylitol, it is characterised in that：The chromatography
Separating xylose, using the positive silica gel of 100~200 mesh, silica gel is first dissolved in the n-butanol of 10 times of volumes, so by wet method dress post
It is introduced into chromatographic column with glass bar afterwards, carries out the separation of xylose as leacheate with the proportion liquid of methanol and acetic acid ethyl ester.
6. according to the method for one of claim 5 rice straw Efficient Conversion xylitol, it is characterised in that：The methanol and
The volume ratio of methanol and acetic acid ethyl ester is 1 in the proportion liquid of acetic acid ethyl ester:2~1:6.
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