CN102276760A - Method for separating and purifying hemicelluloses from agriculture and forest biomasses by gradient ethanol precipitation - Google Patents
Method for separating and purifying hemicelluloses from agriculture and forest biomasses by gradient ethanol precipitation Download PDFInfo
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Abstract
The invention discloses a method for separating and purifying hemicelluloses from agriculture and forest biomasses by gradient ethanol precipitation, comprising the following steps: taking the agriculture and forest biomasses as raw materials; using deionized water to extract sodium chlorites so as to remove lignin and using a 6-10% (wt.) KOH (potassium hydroxide) solution to extract holocellulose; and adopting a 10-90% (wt.) ethanol solution to carry out gradient precipitation on filtrates so as to obtain hemicellulose with different branch degrees. The fractional purification method is utilized to prepare the hemicellulose with the different molecular weights and the different branch degrees, and is simple in technology and easy to industrialize; the fractionally-purified hemicellulose with high homogenization degree and large molecular weight is divided into linear hemicellulose and branched hemicellulose; and the different hemicellulose which is separated and purified can be applied to different industrial fields in accordance with different requirements.
Description
Technical field
The invention belongs to the Separation of Natural Products technical field, relate to the separation purification method of hemicellulose, be specifically related to the method for a kind of gradient ethanol sedimentation separation and purification hemicellulose from agricultural-forestry biomass.
Background technology
Agricultural-forestry biomass mainly comprises agricultural stalk and forest biomass two big classes.At present, China's forest biomass resource total amount is more than 18,000,000,000 tons, and shrub is the main forest biomass resource of China, and is annual because of stump, forest thinning, pruning fruit tree and wood machining residues etc., can obtain 8～1,000,000,000 tons.These agricultural-forestry biomass are mainly used in direct burning heat production, and some is as the raw material of feed, fertilizer and pulp and paper industry, but the not enough agricultural wastes total amount of the utilization in agricultural-forestry biomass field 50%.How rationally to utilize these important green resources to have very important realistic meaning.
The agricultural-forestry biomass main ingredient is Mierocrystalline cellulose, hemicellulose and xylogen, and three's content accounts for more than 90% of biomass total amount.Renewable natural resource such as agricultural-forestry biomass are converted into chemical feedstocks or degradation material generally has dual mode: a kind of is to adopt the mode that directly transforms, the agricultural-forestry biomass total composition is converted into Industrial products, because this conversion does not need component is separated, technology is simple, can significantly reduce cost, but because each component is mixed in together, so transformation efficiency is low; Another kind is the mode that adopts indirect reformer, each component of agricultural-forestry biomass is carried out elder generation separates afterwards and transform, and this transform mode efficient height can obtain at utmost high-valued utilization, and wherein component separation and component conversion are two critical process.It is with biomass three kinds of component fibre elements, hemicellulose and lignin separation that component is separated, and the component conversion is a root a tree name biomass components constructional feature, is converted into significant fuel and material by physics, chemistry and biological method.Yet traditional separation method and technology can not be dissociated biomass components cleaning, and component conversion process efficient is low, product types is few, seriously polluted (as cellulose industry).Therefore, inquire into the agricultural-forestry biomass component and separate and purifying, will provide fundamental basis for the efficient trans-utilization of agricultural-forestry biomass renewable resources.
The polysaccharose substance of hemicellulose for being extracted from plant cell wall by water or alkaline solution, other compositions of hemicellulose and cell walls such as Mierocrystalline cellulose, xylogen, protein etc. are connected by hydrogen bond, covalent linkage and ionic linkage etc.Hemicellulose is widely used in food and non-food product industry, can be converted into chemical, as furfural, erythritol, Xylitol, ethanol and lactic acid etc.; Also can be used as viscosity modifier, jelling agent, tablet binder and wet strength additives etc.; In addition, hemicellulose has very important pharmaceutical value, can be used for producing protection ulcer, cough-relieving, irritation, medicine such as anticancer.
The separation of hemicellulose is studied very early, and has proposed many separation methods, comprises KOH, NaOH, alkaline hydrogen peroxide, Ba (OH)
2And Ca (OH)
2Deng the separation method.The advantage that alkaline process extracts hemicellulose be simple, cost is lower and good separating effect, still, the hemicellulose of separating generally is made up of a few class hemicellulose macromole, its chemical structure is difference also.For obtaining character hemicellulose component identical and the relation of studying its structure and properties with structure, also need to be further purified to separating hemicellulose, obtain the hemicellulose of different degree of substitution.
Summary of the invention
The objective of the invention is at hemicellulose separate and purifying in the problem that exists, the method for a kind of gradient ethanol sedimentation separation and purification hemicellulose from agricultural-forestry biomass is provided.Difference with the prior art of the present invention is, do not adopt the method for column chromatography that hemicellulose is carried out grading purification, but adopt alkaline solution to extract earlier, and utilize continuous Different concentrations of alcohol solution that extracting solution is carried out grading purification then, can effectively obtain the hemicellulose of different branch degree.
In order to achieve the above object, the present invention has adopted following technical scheme.
The method of gradient ethanol sedimentation separation and purification hemicellulose from agricultural-forestry biomass may further comprise the steps:
(1) will dry and be cut into the sheet of 1～3cm after the agricultural-forestry biomass peeling, grind, cross 1.0～3.0 mm aperture sieve and obtain powdered biomass, powdered biomass is extracted 6～10h with toluene and ethanol mixed solvent, 40～60 ℃ of drying 10 ~ 18h obtain the degreasing biomass;
(2) the degreasing biomass of step (1) gained are extracted 2 ~ 3h with distilled water at 50～90 ℃, cooled and filtered obtains filtrate and water-insoluble residue;
(3) the water-insoluble residue that step (2) is obtained adds in the Textone, adding pH value conditioning agent adjusting pH value is 3.0～4.0, extracts 1 ~ 4h at 50 ~ 100 ℃, and residue is washed with distilled water to neutrality, at 40 ~ 60 ℃ of down dry 16 ~ 20h, obtain holocellulose;
(4) holocellulose that step (3) is obtained extracts 8 ~ 16h with 6 ~ 10%(wt.) KOH solution at 40 ~ 60 ℃, filters, and collects filtrate, also integrates with filtrate with the washings that obtains behind the distilled water wash residue, obtains hemicellulose extract;
(5) it is 5.5 ~ 7.0 that the hemicellulose extract that step (4) is obtained adds pH value conditioning agent adjusting pH value, concentrating under reduced pressure, obtain concentrated solution, in concentrated solution, add dehydrated alcohol to alcoholic acid mass concentration and reach 10 ~ 15%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With supernatant liquid concentrating under reduced pressure once more, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 20 ~ 30%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With the supernatant liquid concentrating under reduced pressure, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 35 ~ 45%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With the supernatant liquid concentrating under reduced pressure, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 50 ~ 60%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With the supernatant liquid concentrating under reduced pressure, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 65 ~ 75%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With the supernatant liquid concentrating under reduced pressure, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 80 ~ 90%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose.
In the step of the present invention (1), toluene and alcoholic acid volume ratio are (2 ~ 4) in the described mixed solvent: 1, the mass volume ratio of described powdered biomass and mixed solvent is 1:(15 ~ 25) g/mL.
In the step of the present invention (2), the mass volume ratio of described degreasing biomass and distilled water is 1:(15 ~ 25) g/mL.
In the step of the present invention (3), the mass ratio of described water-insoluble residue and Textone is 1:(1.2 ~ 2).
In the step of the present invention (3), described pH value conditioning agent is acetate or hydrochloric acid.
In the step of the present invention (4), the mass volume ratio of described holocellulose and 6 ~ 10%(wt.) KOH solution is 1 (15 ~ 25) g/mL.
In the step of the present invention (5), described pH value conditioning agent is acetate or hydrochloric acid.
In the step of the present invention (5), the pressure of described concentrating under reduced pressure is-0.095 ~ 0.075mbar; Described centrifugal rotation speed is 3000 ~ 5000r/min; Described cryodesiccated temperature is-50 ~-40 ℃, and the time is 32 ~ 40h.。
In the step of the present invention (5), described acidifying 70%(volume fraction) ethanol is the ethanol of regulating with acetate or hydrochloric acid, described acidifying 70%(volume fraction) alcoholic acid pH value is 2 ~ 4.
The present invention compares with existing separating and purifying technology, has following advantage and beneficial effect:
(1) method technology of the present invention is simple, easy to operate, is easy to industrialization;
(2) compare method of the present invention weak point consuming time, good separating effect with general column chromatography method;
(3) the present invention adopts Different concentrations of alcohol as purified reagent, and the reagent low price easily obtains, and recyclable utilization, the utilization ratio height;
(4) by method of the present invention, can obtain the hemicellulose of different side chain degree, can be further production xylo-oligosaccharide and Xylitol high-quality raw materials is provided.
Description of drawings
Fig. 1 is the method flow diagram that the embodiment of the invention 1 adopts salix monogolica separation and purification hemicellulose.
Fig. 2 is the method flow diagram that the embodiment of the invention 2 adopts caragana microphylla Chinese Peashrub Root separation and purification hemicellulose.
Fig. 3 is that the Infrared spectroscopy of hemicellulose component F10, F20 and the F30 of the embodiment of the invention 3 gained (is called for short: FT-IR) spectrogram.
Fig. 4 is the method flow diagram that the embodiment of the invention 3 adopts longevity bamboo separation and purification hemicellulose.
Embodiment
Below in conjunction with by embodiment the present invention being further described, but the scope of protection of present invention is not limited in this.
Embodiment 1
Adopt salix monogolica, separation and purification hemicellulose therefrom, step is as shown in Figure 1.
(1) with drying and be cut into the sheet of 1cm after the salix monogolica peeling, grind, cross 1.0 mm aperture sieve, getting the dried powder of 50g is 21 toluene and ethanol extracting 6h in Soxhlet extractor with the 750mL volume ratio, and 60 ℃ of dry 16h obtain the degreasing biomass;
(2) the dewaxing biomass of 40g step (1) gained are extracted 2.5h with 600mL distilled water at 70 ℃, cooled and filtered obtains filtrate and water-insoluble residue;
(3) the water-insoluble residue that 30g step (2) is obtained adds in the 36g Textone, and adding the second acid for adjusting pH value is 3.6～3.8, extracts 2h at 75 ℃, and residue is neutral to washings 3 times with distilled water wash, and dry 16h under 60 ℃ obtains holocellulose;
(4) holocellulose that 20g step (3) is obtained extracts 12 h with the KOH solution of 300mL mass concentration 6% at 50 ℃, filter, merging filtrate is neutral with distilled water wash residue to washings, the washings that obtains is also integrated with filtrate, obtains hemicellulose extract;
(5) hemicellulose extract that step (4) is obtained is 5.5 with the second acid for adjusting pH value, concentrating under reduced pressure is to 125mL, obtain concentrated solution, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 15%, stir 3min, leave standstill 8h, 3000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70%(volume fraction) washing with alcohol,-40 ℃ of lyophilize 40h obtain hemicellulose component H
1With supernatant liquid once more concentrating under reduced pressure to 100mL, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 30%, stir 3min, leave standstill 8h, 3000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70%(volume fraction) washing with alcohol,-40 ℃ of lyophilize 40h obtain hemicellulose H
2With the supernatant liquid concentrating under reduced pressure to 80mL, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 45%, stir 3～10min, leave standstill 8h, 3000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70%(volume fraction) washing with alcohol,-40 ℃ of lyophilize 40h obtain hemicellulose H
3With the supernatant liquid concentrating under reduced pressure to 70 mL, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 60%, stir 3min, leave standstill 8h, 3000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70%(volume fraction) washing with alcohol,-40 ℃ of lyophilize 40h obtain hemicellulose H
4With the supernatant liquid concentrating under reduced pressure to 60 mL, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 75%, stir 3min, leave standstill 8h, 3000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70%(volume fraction) washing with alcohol,-40 ℃ of lyophilize 40h obtain hemicellulose H
5With the supernatant liquid concentrating under reduced pressure to 50 mL, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 90%, stir 3min, leave standstill 8h, 3000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70%(volume fraction) washing with alcohol,-40 ℃ of lyophilize 40h obtain hemicellulose H
6
Through chromatography of ions (be called for short: HPAEC), Infrared spectroscopy (be called for short: FT-IR), gel permeation chromatography (be called for short: GPC) and
1The H nucleus magnetic resonance,
13The mensuration of C nucleus magnetic resonance and two dimensional NMR, result shows, along with alcohol precipitation concentration increases at 90% o'clock from 15%, the branch degree of hemicellulose component increases, and the straight chain hemicellulose is preferentially by the ethanol sedimentation of lower concentration.
Hemicellulose is the general name of a group complex plycan, the separation method difference, and sugar is formed different.The glycan analysis result of the hemicellulose component that embodiment 1 separation obtains is as shown in table 1:
The kind and the content of monose and uronic acid in the hemicellulose component that table 1 embodiment 1 obtains
As can be seen from Table 1, from H
1To H
6, wood sugar content reduces gradually; The content of uronic acid is from 11.11%(H
1) increase to 20.84%(H
4), reduce to 7.06%(H again
6), but from H
4To H
6, the content of semi-lactosi, glucose, pectinose and rhamnosyl but significantly increases, the sedimentary hemicellulose that goes out straight chain of above data declaration low-concentration ethanol, and when alcohol concn raise, the hemicellulose that the branch degree is high is precipitated again to come out.In addition, for the glucuronic acid xylan, the ratio of uronic acid and wood sugar (is called for short: the branch degree that Uro/Xyl) can reflect xylan.As seen from Table 1, the hemicellulose component is from H
1To H
4, promptly when the ethanol mass concentration when 15% increases to 75%, the value of Uro/Xyl increases to 0.38 from 0.14, illustrates that the side chain of xylan increases.At H
5And H
6Though middle Uro/Xyl value reduces, the amount of all the other monose but increases, and the branch degree also increases.Therefore, along with the increase of ethanol mass concentration, the branch degree of hemicellulose component increases.
The weight-average molecular weight of the different hemicelluloses of table 2 (
M w ), number-average molecular weight (
M n ) and polymolecularity (
M w / M n )
By gel health chromatogram detected six kinds of salix monogolica hemicellulose components weight-average molecular weight (
M w ), number-average molecular weight (
M n ) and polymolecularity (
M w / M n ), the results are shown in Table 2.As seen from Table 2, H
2Molecular weight the highest; Along with alcohol concn increases to 30% from 15%, molecular weight is from H
155970 g/mol be increased to H
285540 g/mol; Along with alcohol concn is increased to 90% from 30%, from H
3To H
6Molecular weight reduce thereupon.
Embodiment 2
Adopt the caragana microphylla Chinese Peashrub Root, therefrom the separation and purification hemicellulose.Step as shown in Figure 2.
(1) with the peeling of shrub caragana microphylla Chinese Peashrub Root, dry and be cut into the sheet of 3cm, grind, cross 3.0 mm aperture sieve, getting the dried powder of 50g is 41 toluene and ethanol extracting 8h in Soxhlet extractor with the 1250mL volume ratio, and 50 ℃ of dry 10h obtain the degreasing biomass;
(2) the dewaxing biomass of 40g step (1) gained are extracted 3h with 1000mL distilled water at 50 ℃, cooled and filtered obtains filtrate and water-insoluble residue;
(3) the water-insoluble residue that 30g step (2) is obtained adds in the 60g Textone, adding the second acid for adjusting pH value is 3.6～3.8, extracts 1h at 100 ℃, and residue is neutral to washings 3 times with distilled water wash, dry 16h under 40 ℃ obtains holocellulose;
(4) holocellulose that 20g step (3) is obtained is that 8%KOH solution extracts 8h at 60 ℃ with the 500mL mass concentration, filter, merging filtrate is neutral with distilled water wash residue to washings, the washings that obtains is also integrated with filtrate, obtains hemicellulose extract;
(5) it is 6.0 that the hemicellulose extract that step (4) is obtained adds pH value conditioning agent adjusting pH value, concentrating under reduced pressure is to 140 mL, obtain concentrated solution, in concentrated solution, add dehydrated alcohol to alcohol concn and reach 10%, stir 10min, leave standstill 10h, 5000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70% washing with alcohol,-50 ℃ of lyophilize 32h obtain hemicellulose component F
10With supernatant liquid once more concentrating under reduced pressure to 120 mL, in concentrated solution, add dehydrated alcohol to alcohol concn and reach 20%, stir 10min, leave standstill 10h, 5000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70% washing with alcohol,-50 ℃ of lyophilize 32h obtain hemicellulose F
20With the supernatant liquid concentrating under reduced pressure to 80 mL, in concentrated solution, add dehydrated alcohol to alcohol concn and reach 35%, stir 10min, leave standstill 10h, 5000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70% washing with alcohol,-50 ℃ of lyophilize 32h obtain hemicellulose F
35With the supernatant liquid concentrating under reduced pressure to 100 mL, in concentrated solution, add dehydrated alcohol to alcohol concn and reach 50%, stir 10min, leave standstill 10h, 5000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70% washing with alcohol,-50 ℃ of lyophilize 32h obtain hemicellulose F
50With the supernatant liquid concentrating under reduced pressure to 80 mL, in concentrated solution, add dehydrated alcohol to alcohol concn and reach 70%, stir 10min, leave standstill 10h, 5000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70% washing with alcohol,-50 ℃ of lyophilize 32h obtain hemicellulose F
70With the supernatant liquid concentrating under reduced pressure to 60 mL, in concentrated solution, add dehydrated alcohol to alcohol concn and reach 80%, stir 10min, leave standstill 10h, 5000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70% washing with alcohol,-50 ℃ of lyophilize 32h obtain hemicellulose F
80
Through chromatography of ions (be called for short: HPAEC), Infrared spectroscopy (be called for short: FT-IR), gel permeation chromatography (be called for short: GPC) and
1The H nucleus magnetic resonance,
13The mensuration of C nucleus magnetic resonance is found along with the ethanol mass concentration increases to 80%, the branch degree increase of hemicellulose from 10%.The low hemicellulose preferential precipitation of branch degree is in the ethanol of lower concentration.By Different concentrations of alcohol precipitation hemicellulose, can obtain the different hemicellulose of branch degree.
The glycan analysis result of the hemicellulose component that embodiment 2 separation obtain is as shown in table 3:
The kind and the content of monose and uronic acid in the hemicellulose component that table 3 embodiment 2 obtains
As shown in Table 3, all hemicellulose components all are rich in uronic acids such as 4-O-methyl-glucuronic acid and galacturonic acid, and glucuronic acid content reaches 10.1 ~ 21.3%, and seminose then exists only in hemicellulose component F
80In.In addition, hemicellulose component F
80With other components very big-difference is arranged, show that mainly pectinose and galactose content are higher, be respectively 26.8% and 14.5%.Wood sugar content is relatively low, also contains a spot of rhamnosyl, glucose and seminose in this component.Hemicellulose component F
70In also contain 50.2% wood sugar and semi-lactosi, uronic acid and the pectinose of high level relatively.Generally, wood sugar comes from xylan backbone more, and Chang Zuowei side chain such as pectinose, semi-lactosi, glucose and uronic acid and existing, therefore, above data show, hemicellulose component F
70And F
80With the xylan is main chain, is connected with side chains such as a large amount of pectinoses, semi-lactosi, glucose, 4-O-methyl-glucuronic acid and galacturonic acid.At other four hemicellulose component F
10, F
20, F
35And F
50In, wood sugar is main monosaccharide component, accounts for 63.7～81.2%, shows that these hemicellulose components are main chain with the xylan.The content of pectinose and semi-lactosi is respectively 2.3～5.3% and 1.7 ~ 7.4%.Also have a spot of rhamnosyl and glucose in the hemicellulose component that the low-concentration ethanol precipitation obtains, its content is respectively 0.8～2.2% and 0.2～6.1%.Above result shows that low-concentration ethanol is settled out the hemicellulose main chain, and settling out of side chain needs the ethanol of high density.In addition, as can be seen from Table 3, along with the ethanol mass concentration increases to 60% from 10%, the Uro/Xyl ratio of half fibre fractionation increases gradually, show that the ethanol of lower concentration obtains the hemicellulose of straight chain, along with the increase of alcohol concn, the branch degree of gained hemicellulose component increases.
The hemicellulose component F that Fig. 3 obtains for embodiment 2
10, F
20And F
35The FT-IR spectrogram, correspond to successively the spectrum 1 ~ 3.As can be seen from Figure 3,1596 and 1411cm
-1The strong absorption peak at place is 4-
OThe peak of carboxylate salt in-methyl-glucuronic acid.Its intensity is from F
10To F
35The trend that is increase shows at hemicellulose component F
10~ F
35The content of middle uronic acid increases gradually, and this result is consistent with the sugar component analytical results.1046 cm
-1The absorption peak at place comes from the C-O-C group on the sugar unit, is the charateristic avsorption band of hemicellulose.895cm
-1The spike at place is the characteristic peak of β-glycosidic link between the sugar unit, shows that caragana microphylla Chinese Peashrub Root hemicellulose forms main chain by wood sugar by β-key.1624cm
-1The absorption peak at place is the water molecules of hemicellulose absorption.In addition, 3418cm
-1The absorption peak at place is-stretching vibration of OH that the stretching vibration peak of C-H is at 2925cm
-1Place and 2857cm
-1The place.
Embodiment 3
With Shou Zhu is raw material, therefrom the separation and purification hemicellulose.Step as shown in Figure 4.
(1) with the longevity bamboo dry and be cut into the sheet of 2cm, grind, cross 2.0 mm aperture sieve, getting the dried powder of 50g is 31 toluene and ethanol extracting 10h in Soxhlet extractor with the 1000mL volume ratio, 40 ℃ of dry 18h obtain the degreasing biomass;
(2) the dewaxing biomass of 40g step (1) gained are extracted 2h for 90 ℃ with 800mL distilled water, cooled and filtered obtains filtrate and water-insoluble residue;
(3) the water-insoluble residue that 30g step (2) is obtained adds in the 45g Textone, and adding the salt acid for adjusting pH value is 3.6～3.8, extracts 4h at 50 ℃, and residue is neutral to washings 3 times with distilled water wash, and dry 18h under 50 ℃ obtains holocellulose;
(4) holocellulose that 20g step (3) is obtained is that 10%KOH solution extracts 16 h at 40 ℃ with the 400mL mass concentration, filter, merging filtrate is neutral with distilled water wash residue to washings, the washings that obtains is also integrated with filtrate, obtains hemicellulose extract;
(5) it is 7.0 that the hemicellulose extract that step (4) is obtained adds the salt acid for adjusting pH value, concentrating under reduced pressure is to 130 mL, obtain concentrated solution, in concentrated solution, add dehydrated alcohol to alcohol concn and reach 12%, stir 6min, leave standstill 9h, 4000r/min is centrifugal, obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70% washing with alcohol,-45 ℃ of lyophilize 36h obtain hemicellulose component H
12With supernatant liquid once more concentrating under reduced pressure to 110 mL, in concentrated solution, add dehydrated alcohol to alcohol concn and reach 25%, stir 6min, leave standstill 9h, centrifugal 4000r/min obtains supernatant liquid and lower sediment, takes off layer precipitation acidifying 70% washing with alcohol,-45 ℃ of lyophilize 36h obtain hemicellulose H
25The supernatant liquid concentrating under reduced pressure to 90 mL, is added dehydrated alcohol to alcohol concn and reaches 40% in concentrated solution, stir 6min, leave standstill 9h, centrifugal 4000r/min obtains supernatant liquid and lower sediment, take off layer precipitation acidifying 70% washing with alcohol ,-45 ℃ of lyophilize 36h obtain hemicellulose H
40The supernatant liquid concentrating under reduced pressure to 70 mL, is added dehydrated alcohol to alcohol concn and reaches 55% in concentrated solution, stir 6min, leave standstill 9h, centrifugal 4000r/min obtains supernatant liquid and lower sediment, take off layer precipitation acidifying 70% washing with alcohol ,-45 ℃ of lyophilize 36h obtain hemicellulose H
55The supernatant liquid concentrating under reduced pressure to 50 mL, is added dehydrated alcohol to alcohol concn and reaches 65% in concentrated solution, stir 6min, leave standstill 9h, centrifugal 4000r/min obtains supernatant liquid and lower sediment, take off layer precipitation acidifying 70% washing with alcohol ,-45 ℃ of lyophilize 36h obtain hemicellulose H
65The supernatant liquid concentrating under reduced pressure to 30 mL, is added dehydrated alcohol to alcohol concn and reaches 85% in concentrated solution, stir 6min, leave standstill 9h, centrifugal 4000r/min obtains supernatant liquid and lower sediment, take off layer precipitation acidifying 70% washing with alcohol ,-45 ℃ of lyophilize 36h obtain hemicellulose H
85
Through chromatography of ions (be called for short: HPAEC), Infrared spectroscopy (be called for short: FT-IR), gel permeation chromatography (be called for short: GPC) and
1The H nucleus magnetic resonance,
13The mensuration of C nucleus magnetic resonance finds that along with alcohol precipitation concentration increases to 85%, the branch degree of hemicellulose increases.The low hemicellulose preferential precipitation of branch degree is in the ethanol of lower concentration.By different ethanol sedimentation hemicelluloses, can obtain the different hemicellulose of branch degree.
The glycan analysis result of the hemicellulose component that embodiment 3 separation obtain is as shown in table 4:
The kind and the content of monose and uronic acid in the hemicellulose component that table 4 embodiment 3 obtains
As shown in Table 4, the resulting caustic solubility hemicellulose of gradient ethanol sedimentation is mainly wood sugar, and content is 53.3 ~ 84.3%; Secondly be glucose, pectinose and glucuronic acid and a spot of semi-lactosi, show that longevity bamboo hemicellulose is a glucuronic acid araboxylan type polysaccharide, similar to other kind bamboo hemicellulose chemical constitutions.Usually adopt the ratio of pectinose and wood sugar (to be called for short: the straight chain and the side chain that A/X) show hemicellulose, as can be seen from Table 4, along with alcohol concn is increased to 85%, the A/X value is increased to 0.157 from 0.068 in the gained hemicellulose component, meanwhile, glucuronic acid (is called for short: G/X) also have similar rising tendency to the ratio of wood sugar, show and under the high concentration ethanol condition, be easy to be settled out the branched chain type hemicellulose, and substitution value is high more on the half fiber straight chain, solubleness is high more, and the alcohol concn of precipitation usefulness is high more.
Claims (9)
1. the method for gradient ethanol sedimentation separation and purification hemicellulose from agricultural-forestry biomass is characterized in that, may further comprise the steps:
(1) will dry and be cut into the sheet of 1～3cm after the agricultural-forestry biomass peeling, grind, cross 1.0～3.0 mm aperture sieve and obtain powdered biomass, powdered biomass is extracted 6～10h with toluene and ethanol mixed solvent, 40～60 ℃ of drying 10 ~ 18h obtain the degreasing biomass;
(2) the degreasing biomass of step (1) gained are extracted 2 ~ 3h with distilled water at 50～90 ℃, cooled and filtered obtains filtrate and water-insoluble residue;
(3) the water-insoluble residue that step (2) is obtained adds in the Textone, adding pH value conditioning agent adjusting pH value is 3.0～4.0, extracts 1 ~ 4h at 50 ~ 100 ℃, and residue is washed with distilled water to neutrality, at 40 ~ 60 ℃ of down dry 16 ~ 20h, obtain holocellulose;
(4) holocellulose that step (3) is obtained extracts 8 ~ 16h with 6 ~ 10%(wt.) KOH solution at 40 ~ 60 ℃, filters, and collects filtrate, also integrates with filtrate with the washings that obtains behind the distilled water wash residue, obtains hemicellulose extract;
(5) it is 5.5 ~ 7.0 that the hemicellulose extract that step (4) is obtained adds pH value conditioning agent adjusting pH value, concentrating under reduced pressure, obtain concentrated solution, in concentrated solution, add dehydrated alcohol to alcoholic acid mass concentration and reach 10 ~ 15%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With supernatant liquid concentrating under reduced pressure once more, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 20 ~ 30%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With the supernatant liquid concentrating under reduced pressure, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 35 ~ 45%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With the supernatant liquid concentrating under reduced pressure, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 50 ~ 60%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With the supernatant liquid concentrating under reduced pressure, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 65 ~ 75%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose; With the supernatant liquid concentrating under reduced pressure, in concentrated solution, add dehydrated alcohol to ethanol mass concentration and reach 80 ~ 90%, stir 3～10min, leave standstill 8 ~ 10h, centrifugal, obtain supernatant liquid and lower sediment, take off layer precipitation acidifying 70%(volume fraction) washing with alcohol, lyophilize obtains hemicellulose.
2. the method for separation and purification hemicellulose according to claim 1, it is characterized in that, in the step (1), toluene and alcoholic acid volume ratio are (2 ~ 4) in the described mixed solvent: 1, the mass volume ratio of described powdered biomass and mixed solvent is 1:(15 ~ 25) g/mL.
3. the method for separation and purification hemicellulose according to claim 2 is characterized in that, in the step (2), the mass volume ratio of described degreasing biomass and distilled water is 1:(15 ~ 25) g/mL.
4. the method for separation and purification hemicellulose according to claim 3 is characterized in that, in the step (3), the mass ratio of described water-insoluble residue and Textone is 1:(1.2 ~ 2).
5. the method for separation and purification hemicellulose according to claim 3 is characterized in that, in the step (3), described pH value conditioning agent is acetate or hydrochloric acid.
6. according to the method for the described separation and purification hemicellulose of one of claim 1 ~ 5, it is characterized in that in the step (4), the mass volume ratio of described holocellulose and 6 ~ 10%(wt.) KOH solution is 1 (15 ~ 25) g/mL.
7. the method for separation and purification hemicellulose according to claim 6 is characterized in that, in the step (5), described pH value conditioning agent is acetate or hydrochloric acid.
8. the method for separation and purification hemicellulose according to claim 7 is characterized in that, in the step (5), the pressure of described concentrating under reduced pressure is-0.095 ~ 0.075mbar; Described centrifugal rotation speed is 3000 ~ 5000r/min; Described cryodesiccated temperature is-50 ~-40 ℃, and the time is 32 ~ 40h.
9. the method for separation and purification hemicellulose according to claim 8, it is characterized in that, in the step (5), described acidifying 70%(volume fraction) ethanol is the ethanol of regulating with acetate or hydrochloric acid, described acidifying 70%(volume fraction) alcoholic acid pH value is 2 ~ 4.
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