CN108976436A - A kind of stage division of lignin - Google Patents
A kind of stage division of lignin Download PDFInfo
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- CN108976436A CN108976436A CN201710405810.9A CN201710405810A CN108976436A CN 108976436 A CN108976436 A CN 108976436A CN 201710405810 A CN201710405810 A CN 201710405810A CN 108976436 A CN108976436 A CN 108976436A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
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Abstract
The present invention relates to a kind of stage divisions of lignin, the organic acid solvent of the first concentration gradient of the method and/or the aqueous dissolution lignin of alcohols solvent, it is separated by solid-liquid separation, obtained solid matter and filtrate is respectively the first fraction of lignin and the first filtrate；Water is added into the first obtained filtrate, the concentration of aqueous solution of organic acid solvent and/or alcohols solvent is adjusted to the second concentration gradient, is separated by solid-liquid separation, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate.Lignin can be divided into multistage by the method, and in each fraction lignin recovery rate it is high, environmental pollution is small, simple process, is conducive to carry out industrialized production.
Description
Technical field
The invention belongs to the separating-purifying fields of compound, are related to a kind of stage division of lignin.
Background technique
Lignin is the polymer as composed by 3 kinds of benzene oxide monomers, and depolymerization is usually the fracture of these monomer associative keys,
But the connection type between lignin monomer is extremely complex, causes during depolymerization separates, there are the fractures of associative key not
Uniform, separating the lignin molecule amount of depolymerization, there are larger differences, and polydispersity is high, and product quality is unstable in subsequent applications
It is fixed.
Commonly being classified means in industry at present mainly has ultrafiltration.Ultrafiltration is under pressure difference effect according to membrane aperture
Size separated, separating effect is preferable.But it is also deposited between the fraction isolated and the relative molecular mass that shuts off of filter membrane
In biggish difference.Ultrafiltration requires special ultrafilter and ultrafiltration membrane to be classified for certain lignin using ultrafiltration
And it is improper, because ultrafiltration membrane may be damaged because of lignin solvent.Furthermore need to consider being applicable in for membrane material using film classification
Condition, while the higher cost of film, limit application range.
106087513 A of CN discloses a kind of fractionation method of sulfate-reducing conditions, is adjusted step by step using sulfuric acid
The pH value of black liquor makes lignin deposit, its advantage is that easy to operate, required equipment and investment are less, and comprehensive production cost is low, lacks
Point is that chelating reagent is costly, and sulphate reagent dosage is larger.
Therefore, it is particularly significant to study a kind of new lignin fractionation method.
Summary of the invention
For the technical problems in the prior art, the present invention provides a kind of stage division of lignin, the method
Lignin can be divided into multistage, and in each fraction lignin purity is high, environmental pollution is small, simple process, is conducive to carry out
Industrialized production.
To reach above-mentioned technical effect, the present invention takes following technical scheme:
The present invention provides a kind of stage division of lignin, the described method comprises the following steps:
(1) with the organic acid solvent of the first concentration gradient and/or the aqueous dissolution lignin of alcohols solvent, solid-liquid point
From obtained solid matter and filtrate is respectively the first fraction of lignin and the first filtrate；
Optionally, water is added in the first filtrate that (2) are obtained to step (1), by organic acid solvent and/or alcohols solvent
Concentration of aqueous solution be adjusted to the second concentration gradient, be separated by solid-liquid separation, obtained solid matter and filtrate is respectively lignin the
Two fractions and the second filtrate.
As currently preferred technical solution, step (1) the organic acid solvent includes in formic acid, acetic acid or propionic acid
Any one or at least two combination, the combination is typical but non-limiting example has: the combination of formic acid and acetic acid, acetic acid and third
The combination of acid, the combination or formic acid of propionic acid and formic acid, the combination of acetic acid and propionic acid etc..
Preferably, step (1) described alcohols solvent includes any one in methanol, ethyl alcohol, normal propyl alcohol or isopropanol or extremely
Few two kinds of combination, the combination is typical but non-limiting example has: the combination of methanol and ethyl alcohol, ethyl alcohol and normal propyl alcohol group
Conjunction, normal propyl alcohol and the combination of isopropanol, the combination or methanol of isopropanol and methanol, the combination of ethyl alcohol and normal propyl alcohol etc..
Wherein, step (1) lignin is wooden to be prepared in lignocellulose raw material by chemical method extraction
Element.
Preferably, the lignocellulose raw material include hardwood, cork, shrub, in gramineae plant any one or extremely
Few two kinds of combination.The combination is typical but non-limiting example has: combination, poplar and the Triploid of Populus Tomentosa of wheat straw and poplar
Combination, the combination of Triploid of Populus Tomentosa and Eucalyptus, the combination of Eucalyptus and bagasse, wheat straw, poplar and the combination of Eucalyptus etc..
Preferably, step (1) first concentration gradient include 75~100wt%, 60~75wt% (be free of 75%wt),
It is any one in 50~60wt% (being free of 60wt%), 40~50wt% (being free of 50wt%) or 10~40wt% (being free of 40%)
Kind.
Wherein, can be 75% when the first concentration gradient is 75~100wt%, 78%, 80%, 82%, 85%, 88%,
90%, 92%, 95%, 98% or 100% etc.；First concentration gradient can be when being 60~75wt% (being free of 75%wt)
60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73% or 74%
Deng；First concentration gradient can be 50% when being 50~60wt% (be free of 60wt%), 51%, 52%, 53%, 54%, 55%,
56%, 57%, 58% or 59% etc.；When first concentration gradient is 40~50wt% (is free of 50wt%), can be 40%,
41%, 42%, 43%, 44%, 45%, 46%, 47%, 48% or 49% etc.；First concentration gradient is that 10~40wt% (is free of
40%) it can be 10%, 12%, 15%, 16%, 23%, 26%, 32%, 36%, 38% or 39% etc. when, but simultaneously not only limit
It is equally applicable in other unlisted numerical value in cited numerical value, above-mentioned each numberical range.
Preferably, the quality of the aqueous solution of step (1) lignin and the organic acid solvent and/or alcohols solvent
Volume ratio is 1:(50~300) g/mL, such as 1:50g/mL, 1:100g/mL, 1:150g/mL, 1:200g/mL, 1:250g/mL or
1:300g/mL etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (1) dissolution carries out under stiring.
Preferably, the stirring rate of the stirring be 50~20000rpm, as 50rpm, 100rpm, 200rpm, 500rpm,
800rpm, 1000rpm, 2000rpm, 5000rpm, 8000rpm, 10000rpm, 15000rpm or 20000rpm etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the time of the stirring be 1~200min, as 1min, 2min, 5min, 8min, 10min, 20min,
50min, 80min, 100min, 120min, 150min, 180min or 200min etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
Preferably, the method for step (1) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or
At least two combination, the combination is typical but non-limiting example has: the group of combination, centrifugation and the evaporation of filtering and centrifugation
It closes, the combination of evaporation and sedimentation, the combination or the combination of sedimentation, centrifugation and filtering etc. of sedimentation and filtering, further preferably
Filter.
As currently preferred technical solution, 60~75wt% (being free of 75%wt), 50~60wt% (are free of
60wt%), any one in 40~50wt% (being free of 50wt%) or 10~40wt% (being free of 40%).
Wherein, can be 60% when the second concentration gradient is 60~75wt% (is free of 75%wt), 61%, 62%, 63%,
64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73% or 74% etc.；Second concentration gradient be 50~
It can be 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58% or 59% when 60wt% (being free of 60wt%)
Deng；When second concentration gradient is 40~50wt% (is free of 50wt%), can be 40%, 41%, 42%, 43%, 44%,
45%, 46%, 47%, 48% or 49% etc.；Second concentration gradient can be 10% when being 10~40wt% (be free of 40%),
12%, 15%, 16%, 23%, 26%, 32%, 36%, 38% or 39% etc., it is not limited to cited numerical value, above-mentioned
Other unlisted numerical value are equally applicable in each numberical range, and the second concentration gradient is not identical as the first concentration gradient.
Preferably, after step (2) the addition water, mixed liquor is stirred.
Preferably, the stirring rate of the stirring be 50~20000rpm, as 50rpm, 100rpm, 200rpm, 500rpm,
800rpm, 1000rpm, 2000rpm, 5000rpm, 8000rpm, 10000rpm, 15000rpm or 20000rpm etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the time of the stirring be 1~200min, as 1min, 2min, 5min, 8min, 10min, 20min,
50min, 80min, 100min, 120min, 150min, 180min or 200min etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
Preferably, the method for step (2) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or
At least two combination, the combination is typical but non-limiting example has: the group of combination, centrifugation and the evaporation of filtering and centrifugation
It closes, the combination of evaporation and sedimentation, the combination or the combination of sedimentation, centrifugation and filtering etc. of sedimentation and filtering, further preferably
Filter.
As currently preferred technical solution, step (2) carries out step (3) afterwards, the second filtrate obtained to step (2)
The concentration of aqueous solution of organic acid solvent and/or alcohols solvent is adjusted to third concentration gradient by middle addition water, is separated by solid-liquid separation,
Obtained solid matter and filtrate is respectively lignin third fraction and third filtrate.
As currently preferred technical solution, step (3) the third concentration includes that 50~60wt% (is free of
60wt%), any one in 40~50wt% (being free of 50wt%) or 10~40wt% (being free of 40%).
Wherein, can be 50% when third concentration gradient is 50~60wt% (is free of 60wt%), 51%, 52%, 53%,
54%, 55%, 56%, 57%, 58% or 59% etc.；It, can be with when third concentration gradient is 40~50wt% (is free of 50wt%)
It is 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48% or 49% etc.；Third concentration gradient be 10~
It can be 10%, 12%, 15%, 16%, 23%, 26%, 32%, 36%, 38% or 39% etc. when 40wt% (being free of 40%),
It is not limited to cited numerical value, other interior unlisted numerical value of above-mentioned each numberical range are equally applicable, and third concentration
Gradient is not identical as the second concentration gradient.
Preferably, after step (3) the addition water, mixed liquor is stirred.
Preferably, the stirring rate of the stirring be 50~20000rpm, as 50rpm, 100rpm, 200rpm, 500rpm,
800rpm, 1000rpm, 2000rpm, 5000rpm, 8000rpm, 10000rpm, 15000rpm or 20000rpm etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the time of the stirring be 1~200min, as 1min, 2min, 5min, 8min, 10min, 20min,
50min, 80min, 100min, 120min, 150min, 180min or 200min etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
Preferably, the method for step (3) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or
At least two combination, the combination is typical but non-limiting example has: the group of combination, centrifugation and the evaporation of filtering and centrifugation
It closes, the combination of evaporation and sedimentation, the combination or the combination of sedimentation, centrifugation and filtering etc. of sedimentation and filtering, further preferably
Filter.
As currently preferred technical solution, step (3) carries out step (4) afterwards, the third filtrate obtained to step (4)
The concentration of aqueous solution of organic acid solvent and/or alcohols solvent is adjusted to the 4th concentration gradient by middle addition water, is separated by solid-liquid separation,
Obtained solid matter and filtrate is respectively the lignin fourth stage point and the 4th filtrate.
As currently preferred technical solution, step (4) the 4th concentration includes that 40~50wt% (is free of
50wt%) or 10~40wt% (be free of 40%).
Wherein, wherein when the 4th concentration gradient is 40~50wt% (is free of 50wt%), can be 40%, 41%,
42%, 43%, 44%, 45%, 46%, 47%, 48% or 49% etc.；4th concentration gradient is 10~40wt% (being free of 40%)
When can be 10%, 12%, 15%, 16%, 23%, 26%, 32%, 36%, 38% or 39% etc., it is not limited to listed
The numerical value of act, other unlisted numerical value are equally applicable in above-mentioned each numberical range, and the 4th concentration gradient not with third concentration
Gradient is identical.
Preferably, after step (4) the addition water, mixed liquor is stirred.
Preferably, the stirring rate of the stirring be 50~20000rpm, as 50rpm, 100rpm, 200rpm, 500rpm,
800rpm, 1000rpm, 2000rpm, 5000rpm, 8000rpm, 10000rpm, 15000rpm or 20000rpm etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the time of the stirring be 1~200min, as 1min, 2min, 5min, 8min, 10min, 20min,
50min, 80min, 100min, 120min, 150min, 180min or 200min etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
Preferably, the method for step (4) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or
At least two combination, the combination is typical but non-limiting example has: the group of combination, centrifugation and the evaporation of filtering and centrifugation
It closes, the combination of evaporation and sedimentation, the combination or the combination of sedimentation, centrifugation and filtering etc. of sedimentation and filtering, further preferably
Filter.
As currently preferred technical solution, step (4) carries out step (5) afterwards, the 4th filtrate obtained to step (4)
The concentration of aqueous solution of organic acid solvent and/or alcohols solvent is adjusted to the 5th concentration gradient by middle addition water, is separated by solid-liquid separation,
Obtained solid matter is lignin level V point.
As currently preferred technical solution, step (5) the 5th concentration gradient is 10~40% (being free of 40%),
Such as 10%, 12%, 15%, 16%, 23%, 26%, 32%, 36%, 38% or 39%, it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable, and the 5th concentration gradient is not identical as the 4th concentration gradient.
Preferably, after step (5) the addition water, mixed liquor is stirred.
Preferably, the stirring rate of the stirring be 50~20000rpm, as 50rpm, 100rpm, 200rpm, 500rpm,
800rpm, 1000rpm, 2000rpm, 5000rpm, 8000rpm, 10000rpm, 15000rpm or 20000rpm etc., but simultaneously not only
It is limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the time of the stirring be 1~200min, as 1min, 2min, 5min, 8min, 10min, 20min,
50min, 80min, 100min, 120min, 150min, 180min or 200min etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
Preferably, the method for step (5) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or
At least two combination, the combination is typical but non-limiting example has: the group of combination, centrifugation and the evaporation of filtering and centrifugation
It closes, the combination of evaporation and sedimentation, the combination or the combination of sedimentation, centrifugation and filtering etc. of sedimentation and filtering, further preferably
Filter.
As currently preferred technical solution, the described method comprises the following steps:
(1) the organic acid solvent of 75~100wt% of concentration and/or the aqueous dissolution lignin of alcohols solvent are used, Gu
Liquid separation, obtained solid matter and filtrate is respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), by the water-soluble of organic acid solvent and/or alcohols solvent
Liquid concentration is adjusted to 60~75wt% (without 75wt%), is separated by solid-liquid separation, obtained solid matter and filtrate is respectively wooden
Plain second fraction and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), by the water-soluble of organic acid solvent and/or alcohols solvent
Liquid concentration is adjusted to 50~60wt% (without 60wt%), is separated by solid-liquid separation, obtained solid matter and filtrate is respectively wooden
Plain third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (4), by the water-soluble of organic acid solvent and/or alcohols solvent
Liquid concentration is adjusted to 40~50wt% (without 50wt%), is separated by solid-liquid separation, obtained solid matter and filtrate is respectively wooden
The plain fourth stage point and the 4th filtrate；
(5) water is added in the 4th filtrate obtained to step (4), by the water-soluble of organic acid solvent and/or alcohols solvent
Liquid concentration is adjusted to 10~40wt% (without 40wt%), is separated by solid-liquid separation, and obtained solid matter is lignin level V point.
The present invention uses organic acid solvent and alcohols solvent as separation agent, for lignin, in difference
There is different solvent effects in the solvent of solubility parameter, another aspect lignin will form between solvent in course of dissolution
Hydrogen bond, powerful hydrogen bond action can also impact solubility, therefore other than the solubility parameter of solvent, the polarity of solvent
Also it will affect the solubility of lignin.Use the organic acid with opposed polarity molten according to the requirement to lignin grading effect
Agent and alcohols solvent dissolve that the lignin that can ensure is purer, free from admixture to lignin, and grading effect is more
It is good；It can make have difference molten under various concentration by adjusting the concentration of separation agent during being classified separating lignin
The lignin phase postprecipitation of the different molecular weight of Xie Du obtains.
Compared with prior art, the present invention at least has the advantages that
(1) stage division of a kind of lignin provided by the invention, the extraction of the lignin of the first isolated fraction
Rate is up to 95%；
(2) stage division of a kind of lignin provided by the invention, the recovery rate of the lignin of isolated second fraction
Up to 94%；
(3) stage division of a kind of lignin provided by the invention, the extraction of the lignin of isolated third fraction
Rate is up to 92%；
(4) stage division of a kind of lignin provided by the invention, the extraction of the lignin of the isolated fourth stage point
Rate is up to 91%；
(5) stage division of a kind of lignin provided by the invention, the extraction of the lignin of isolated level V point
Rate is up to 89%；
(6) a kind of stage division of lignin provided by the invention, the method are with organic acid or organic alcohols solvent
By normal pressure or reuse can be recovered under reduced pressure in separation agent, solvent, and treating capacity is big, hierarchical speed is fast, and overall cost is low, to ring
Border is friendly；
(7) a kind of stage division of lignin provided by the invention, the method simple process are conducive to industrial metaplasia
It produces.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of stage division of lignin, the described method comprises the following steps:
60min dissolution 100g bagasse lignin is stirred at 1000rpm with 40% acetic acid aqueous solution of 5L, filtering obtains
Solid matter is the first fraction of lignin.
It is 5000~24000 between the molecular weight area of obtained the first fraction of lignin.
Embodiment 2
A kind of stage division of lignin, the described method comprises the following steps:
(1) 60min dissolution 100g bagasse lignin is stirred at 1000rpm with 5L 40wt% acetic acid aqueous solution, filter,
Obtained solid matter and filtrate is respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to 20wt%,
60min is stirred under 1000rpm, is filtered, and obtained solid matter is the second fraction of lignin.
It is 5000~24000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 2000~5000 between molecular weight area.
Embodiment 3
A kind of stage division of lignin, the described method comprises the following steps:
(1) 60min dissolution 100g bagasse lignin is stirred at 1000rpm with 5L 50wt% acetic acid aqueous solution, filter,
Obtained solid matter and filtrate is respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to the 40%th,
60min is stirred under 1000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), acetic acid aqueous solution concentration is adjusted to 20%,
60min is stirred under 1000rpm, is filtered, and obtained solid matter is lignin third fraction.
It is 8000~24000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 5000~8000 between molecular weight area, is 2000~5000 between the molecular weight area of obtained lignin third fraction.
Embodiment 4
A kind of stage division of lignin, the described method comprises the following steps:
(1) 60min dissolution 100g bagasse lignin is stirred at 1000rpm with 60% acetic acid aqueous solution of 5L, filtering obtains
To solid matter and filtrate be respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to the 50%th,
60min is stirred under 1000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), acetic acid aqueous solution concentration is adjusted to 40%,
60min is stirred under 1000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), acetic acid aqueous solution concentration is adjusted to 20%,
60min is stirred under 1000rpm, is filtered, and obtained solid matter is the lignin fourth stage point.
It is 10000~24000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 8000~10000 between molecular weight area, is 5000~8000 between the molecular weight area of obtained lignin third fraction, obtained wood
It is 2000~5000 between the molecular weight area of the quality fourth stage point.
Embodiment 5
A kind of stage division of lignin, the described method comprises the following steps:
(1) 60min dissolution 100g bagasse lignin is stirred at 1000rpm with 75% acetic acid aqueous solution of 5L, filtering obtains
To solid matter and filtrate be respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to the 60%th,
60min is stirred under 1000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), acetic acid aqueous solution concentration is adjusted to 50%,
60min is stirred under 1000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), acetic acid aqueous solution concentration is adjusted to 40%,
60min is stirred under 1000rpm, is filtered, and obtained solid matter and filtrate is respectively the lignin fourth stage point and the 4th filtrate；
(5) water is added in the 4th filtrate obtained to step (4), acetic acid aqueous solution concentration is adjusted to 20%,
60min is stirred under 1000rpm, is filtered, and obtained solid matter is lignin level V point.
It is 15000~24000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 10000~15000 between molecular weight area, is 8000~10000 between the molecular weight area of obtained lignin third fraction, obtains
It is 5000~8000 between the molecular weight area of the lignin fourth stage point, is 2000 between the molecular weight area of obtained lignin level V point
~5000.
Embodiment 6
A kind of stage division of lignin, the described method comprises the following steps:
200min dissolution 10g RICE STRAW LIGNIN is stirred at 50rpm with 60% acetic acid aqueous solution of 3L, filtering, what is obtained consolidates
Body substance is the first fraction of lignin.
It is 14000~64000 between the molecular weight area of obtained the first fraction of lignin.
Embodiment 7
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10g RICE STRAW LIGNIN, filtering, obtained solid matter and filtrate are dissolved with 3L 50wt% acetic acid aqueous solution
Respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to 20wt%,
200min is stirred under 50rpm, is filtered, and obtained solid matter is the second fraction of lignin.
It is 11000~64000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 2000~11000 between molecular weight area.
Embodiment 8
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10g RICE STRAW LIGNIN, filtering, obtained solid matter and filtrate are dissolved with 3L 60wt% acetic acid aqueous solution
Respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to the 40%th,
200min is stirred under 50rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), acetic acid aqueous solution concentration is adjusted to 20%, in 50rpm
Lower stirring 200min, filtering, obtained solid matter are lignin third fraction.
It is 14000~64000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 7000~14000 between molecular weight area, is 2000~7000 between the molecular weight area of obtained lignin third fraction.
Embodiment 9
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10g RICE STRAW LIGNIN, filtering, obtained solid matter and filtrate point are dissolved with 75% acetic acid aqueous solution of 3L
It Wei not the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to the 60%th,
200min is stirred under 50rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), acetic acid aqueous solution concentration is adjusted to 50%, in 50rpm
Lower stirring 200min, filtering, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), acetic acid aqueous solution concentration is adjusted to 40%, in 50rpm
Lower stirring 200min, filtering, obtained solid matter are the lignin fourth stage point.
It is 30000~64000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 14000~30000 between molecular weight area, is 11000~14000 between the molecular weight area of obtained lignin third fraction, obtains
The lignin fourth stage point molecular weight area between be 2000~11000.
Embodiment 10
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10g RICE STRAW LIGNIN, filtering, obtained solid matter and filtrate point are dissolved with 75% acetic acid aqueous solution of 3L
It Wei not the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to the 60%th,
200min is stirred under 50rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), acetic acid aqueous solution concentration is adjusted to 50%, in 50rpm
Lower stirring 200min, filtering, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), acetic acid aqueous solution concentration is adjusted to 40%, in 50rpm
Lower stirring 200min, filtering, obtained solid matter and filtrate are respectively the lignin fourth stage point and the 4th filtrate；
(5) water is added in the 4th filtrate obtained to step (4), acetic acid aqueous solution concentration is adjusted to 20%, in 50rpm
Lower stirring 200min, filtering, obtained solid matter are lignin level V point.
It is 30000~64000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 14000~30000 between molecular weight area, is 11000~14000 between the molecular weight area of obtained lignin third fraction, obtains
The lignin fourth stage point molecular weight area between be 7000~11000, be between the molecular weight area of obtained lignin level V point
2000~7000.
Embodiment 11
A kind of stage division of lignin, the described method comprises the following steps:
1min dissolution 10g moso bamboo lignin is stirred at 20000rpm with 45% aqueous formic acid of 1L, filtering obtains
Solid matter is the first fraction of lignin.
It is 5000~50000 between the molecular weight area of obtained the first fraction of lignin.
Embodiment 12
A kind of stage division of lignin, the described method comprises the following steps:
(1) 1min dissolution 10g moso bamboo lignin is stirred at 20000rpm with 1L 45wt% aqueous formic acid, filtering obtains
To solid matter and filtrate be respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), aqueous formic acid concentration is adjusted to 30wt%,
1min is stirred under 20000rpm, is filtered, and obtained solid matter is the second fraction of lignin.
It is 5000~50000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 2000~5000 between molecular weight area.
Embodiment 13
A kind of stage division of lignin, the described method comprises the following steps:
(1) 1min dissolution 10g moso bamboo lignin is stirred at 20000rpm with 1L 55wt% aqueous formic acid, filtering obtains
To solid matter and filtrate be respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), aqueous formic acid concentration is adjusted to the 45%th,
1min is stirred under 20000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), aqueous formic acid concentration is adjusted to 30%,
1min is stirred under 20000rpm, is filtered, and obtained solid matter is lignin third fraction.
It is 9000~50000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 5000~9000 between molecular weight area, is 2000~5000 between the molecular weight area of obtained lignin third fraction.
Embodiment 14
A kind of stage division of lignin, the described method comprises the following steps:
(1) 1min dissolution 10g moso bamboo lignin is stirred at 20000rpm with 65% aqueous formic acid of 1L, filtering obtains
Solid matter and filtrate be respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), aqueous formic acid concentration is adjusted to the 55%th,
1min is stirred under 20000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), aqueous formic acid concentration is adjusted to 45%,
1min is stirred under 20000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), aqueous formic acid concentration is adjusted to 30%,
1min is stirred under 20000rpm, is filtered, and obtained solid matter is the lignin fourth stage point.
It is 13000~50000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 9000~13000 between molecular weight area, is 5000~9000 between the molecular weight area of obtained lignin third fraction, obtained wood
It is 2000~5000 between the molecular weight area of the quality fourth stage point.
Embodiment 15
A kind of stage division of lignin, the described method comprises the following steps:
(1) 1min dissolution 10g moso bamboo lignin is stirred at 20000rpm with 95% aqueous formic acid of 1L, filtering obtains
Solid matter and filtrate be respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), acetic acid aqueous solution concentration is adjusted to the 65%th,
1min is stirred under 20000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), aqueous formic acid concentration is adjusted to 55%,
1min is stirred under 20000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), aqueous formic acid concentration is adjusted to 45%,
1min is stirred under 20000rpm, is filtered, and obtained solid matter and filtrate is respectively the lignin fourth stage point and the 4th filtrate；
(5) water is added in the 4th filtrate obtained to step (4), aqueous formic acid concentration is adjusted to 30%,
1min is stirred under 20000rpm, is filtered, and obtained solid matter is lignin level V point.
It is 25000~50000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 13000~25000 between molecular weight area, is 9000~13000 between the molecular weight area of obtained lignin third fraction, obtains
It is 5000~9000 between the molecular weight area of the lignin fourth stage point, is 2000 between the molecular weight area of obtained lignin level V point
~5000.
Embodiment 16
A kind of stage division of lignin, the described method comprises the following steps:
30min dissolution 10g reed lignin is stirred at 2000rpm with 74% methanol aqueous solution of 1L, filtering obtains
Solid matter is the first fraction of lignin.
It is 10000~77000 between the molecular weight area of obtained the first fraction of lignin.
Embodiment 17
A kind of stage division of lignin, the described method comprises the following steps:
(1) 30min dissolution 10g reed lignin, filtering, obtained solid are stirred at 2000rpm with 1L anhydrous methanol
Substance and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to 39wt%,
30min is stirred under 2000rpm, is filtered, and obtained solid matter is the second fraction of lignin.
It is 18000~77000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 2000~18000 between molecular weight area.
Embodiment 18
A kind of stage division of lignin, the described method comprises the following steps:
(1) 30min dissolution 10g reed lignin is stirred at 2000rpm with 1L 59wt% methanol aqueous solution, filtering obtains
To solid matter and filtrate be respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 49%th,
30min is stirred under 2000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 39%,
30min is stirred under 2000rpm, is filtered, and obtained solid matter is lignin third fraction.
It is 8000~77000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 5000~8000 between molecular weight area, is 2000~5000 between the molecular weight area of obtained lignin third fraction.
Embodiment 19
A kind of stage division of lignin, the described method comprises the following steps:
(1) 30min dissolution 10g reed lignin, filtering, obtained solid are stirred at 2000rpm with 1L anhydrous methanol
Substance and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 59%th,
30min is stirred under 2000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 49%,
30min is stirred under 2000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), methanol aqueous solution concentration is adjusted to 39%,
30min is stirred under 2000rpm, is filtered, and obtained solid matter is the lignin fourth stage point.
It is 18000~77000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 8000~18000 between molecular weight area, is 5000~8000 between the molecular weight area of obtained lignin third fraction, obtained wood
It is 2000~5000 between the molecular weight area of the quality fourth stage point.
Embodiment 20
A kind of stage division of lignin, the described method comprises the following steps:
(1) 30min dissolution 10g reed lignin, filtering, obtained solid are stirred at 2000rpm with 1L anhydrous methanol
Substance and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 74%th,
30min is stirred under 2000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 59%,
30min is stirred under 2000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), methanol aqueous solution concentration is adjusted to 49%,
30min is stirred under 2000rpm, is filtered, and obtained solid matter and filtrate is respectively the lignin fourth stage point and the 4th filtrate；
(5) water is added in the 4th filtrate obtained to step (4), methanol aqueous solution concentration is adjusted to 39%,
30min is stirred under 2000rpm, 30min is stirred at 2000rpm, is filtered, obtained solid matter is lignin level V point.
It is 18000~77000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 10000~18000 between molecular weight area, is 8000~10000 between the molecular weight area of obtained lignin third fraction, obtains
It is 5000~8000 between the molecular weight area of the lignin fourth stage point, is 2000 between the molecular weight area of obtained lignin level V point
~5000.
Embodiment 21
A kind of stage division of lignin, the described method comprises the following steps:
10min dissolution 10g China fir lignin is stirred at 5000rpm with 65% methanol aqueous solution of 1L, filtering obtains
Solid matter is the first fraction of lignin.
It is 8200~19600 between the molecular weight area of obtained the first fraction of lignin.
Embodiment 22
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10min dissolution 10g China fir lignin, filtering, obtained solid are stirred at 5000rpm with 1L anhydrous methanol
Substance and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to 65wt%,
10min is stirred under 5000rpm, is filtered, and obtained solid matter is the second fraction of lignin.
It is 12000~19600 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 8200~11800 between molecular weight area.
Embodiment 23
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10min dissolution 10g China fir lignin is stirred at 5000rpm with 1L anhydrous methanol aqueous solution, filtering obtains
Solid matter and filtrate be respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 65%th,
10min is stirred under 5000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 55%,
10min is stirred under 5000rpm, is filtered, and obtained solid matter is lignin third fraction.
It is 12000~19600 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 8200~11800 between molecular weight area, is 5500~7800 between the molecular weight area of obtained lignin third fraction.
Embodiment 24
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10min dissolution 10g China fir lignin, filtering, obtained solid are stirred at 5000rpm with 1L anhydrous methanol
Substance and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 65%th,
10min is stirred under 5000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 55%,
10min is stirred under 5000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), methanol aqueous solution concentration is adjusted to 45%,
10min is stirred under 5000rpm, is filtered, and obtained solid matter is the lignin fourth stage point.
It is 12000~19600 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 8200~11800 between molecular weight area, is 5500~7800 between the molecular weight area of obtained lignin third fraction, obtained wood
It is 2500~5200 between the molecular weight area of the quality fourth stage point.
Embodiment 25
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10min dissolution 10g China fir lignin, filtering, obtained solid are stirred at 5000rpm with 1L anhydrous methanol
Substance and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 65%th,
10min is stirred under 5000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 55%,
10min is stirred under 5000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), methanol aqueous solution concentration is adjusted to 45%,
10min is stirred under 5000rpm, is filtered, and obtained solid matter and filtrate is respectively the lignin fourth stage point and the 4th filtrate；
(5) water is added in the 4th filtrate obtained to step (4), methanol aqueous solution concentration is adjusted to 15%,
10min is stirred under 5000rpm, is filtered, and obtained solid matter is lignin level V point.
It is 12000~19600 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 8200~11800 between molecular weight area, is 5500~7800 between the molecular weight area of obtained lignin third fraction, obtained wood
Be 2500~5200 between the molecular weight area of the quality fourth stage point, between the molecular weight area of obtained lignin level V point for 1000~
2300。
Embodiment 26
A kind of stage division of lignin, the described method comprises the following steps:
5min dissolution 10g poplar lignin is stirred at 10000rpm with 65% methanol aqueous solution of 1L, filtering obtains
Solid matter is the first fraction of lignin.
It is 20000~77000 between the molecular weight area of obtained the first fraction of lignin.
Embodiment 27
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10g poplar lignin, filtering, obtained solids are dissolved with stirring 5min under 1L anhydrous methanol 10000rpm
Matter and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to 65wt%,
5min is stirred under 10000rpm, is filtered, and obtained solid matter is the second fraction of lignin.
It is 45000~77000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 20000~44000 between molecular weight area.
Embodiment 28
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10g poplar lignin is dissolved with stirring 5min under 1L anhydrous methanol aqueous solution 10000rpm, filtering obtains
Solid matter and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 65%th,
5min is stirred under 10000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 55%,
5min is stirred under 10000rpm, is filtered, and obtained solid matter is lignin third fraction.
It is 45000~77000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 20000~44000 between molecular weight area, is 14200~19700 between the molecular weight area of obtained lignin third fraction.
Embodiment 29
A kind of stage division of lignin, the described method comprises the following steps:
(1) 5min dissolution 10g poplar lignin, filtering, obtained solid are stirred at 10000rpm with 1L anhydrous methanol
Substance and filtrate are respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 65%th,
5min is stirred under 10000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 55%,
5min is stirred under 10000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), methanol aqueous solution concentration is adjusted to 45%,
5min is stirred under 10000rpm, is filtered, and obtained solid matter is the lignin fourth stage point.
It is 45000~77000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 20000~44000 between molecular weight area, is 14200~19700 between the molecular weight area of obtained lignin third fraction, obtains
The lignin fourth stage point molecular weight area between be 9800~13800.
Embodiment 30
A kind of stage division of lignin, the described method comprises the following steps:
(1) 10g poplar lignin is dissolved with 1L anhydrous methanol, filtering, obtained solid matter and filtrate are respectively wood
The first fraction of quality and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), methanol aqueous solution concentration is adjusted to the 65%th,
5min is stirred under 10000rpm, is filtered, obtained solid matter and filtrate is respectively the second fraction of lignin and the second filtrate；
(3) water is added in the second filtrate obtained to step (2), methanol aqueous solution concentration is adjusted to 55%,
5min is stirred under 10000rpm, is filtered, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate；
(4) water is added in the third filtrate obtained to step (3), methanol aqueous solution concentration is adjusted to 45%,
5min is stirred under 10000rpm, is filtered, and obtained solid matter and filtrate is respectively the lignin fourth stage point and the 4th filtrate；
(5) water is added in the 4th filtrate obtained to step (4), methanol aqueous solution concentration is adjusted to 15%,
5min is stirred under 10000rpm, is filtered, and obtained solid matter is lignin level V point.
It is 45000~77000 between the molecular weight area of obtained the first fraction of lignin, obtained the second fraction of lignin
It is 20000~44000 between molecular weight area, is 14200~19700 between the molecular weight area of obtained lignin third fraction, obtains
The lignin fourth stage point molecular weight area between be 9800~13800, be between the molecular weight area of obtained lignin level V point
2300~8800.
Comparative example 1
A kind of stage division of lignin, the described method comprises the following steps:
(1) 800g bagasse lignin is packed into the vertical electric heating digester of 10L, and alkali charge 24% is (with Na2O meter), sulphidity
25%, solid-to-liquid ratio 1:5 are warming up to 165 DEG C, heating-up time 1h, keep the temperature 2-3h.Pot inner pressure is utilized after reaction, the row of collection
Then black liquor out uses filtered on buchner funnel, remove the large particulate matter in black liquor；
(2) it is 2mol/L sulfuric acid that concentration is added in the black liquor obtained to step (1), and the pH value of solution is slowly adjusted to 2, and
It is stirred continuously 1-2h, is then centrifuged for separating, obtains the first fraction of lignin.
It is 2000~24000 between the molecular weight area of obtained the first fraction of lignin.
Comparative example 2
A kind of stage division of lignin, the described method comprises the following steps:
(1) 800g bagasse lignin is packed into the vertical electric heating digester of 10L, and alkali charge 24% is (with Na2O meter), sulphidity
25%, solid-to-liquid ratio 1:5 are warming up to 165 DEG C, heating-up time 1h, keep the temperature 2-3h.Pot inner pressure is utilized after reaction, the row of collection
Then black liquor out uses filtered on buchner funnel, remove the large particulate matter in black liquor；
(2) it is 2mol/L sulfuric acid that concentration is continuously added in the black liquor in step (1), and the pH value of solution is slowly adjusted to 4,
And it is stirred continuously 1-2h, and it is then centrifuged for separation and obtains the first fraction of lignin, the liquid after collecting centrifugation；
(3) concentration is added in the liquid collected to step (2) is 2mol/L sulfuric acid, and the pH value of solution is slowly adjusted to 2, and
It is stirred continuously 1-2h, is then centrifuged for separating, obtains the second fraction of lignin.
It is 8000~24000 between the molecular weight area of obtained the first fraction of lignin, obtained the first fraction of lignin
It is 2000~8000 between molecular weight area.
Comparative example 3
A kind of stage division of lignin, the described method comprises the following steps:
(1) 800g bagasse lignin is packed into the vertical electric heating digester of 10L, and alkali charge 24% is (with Na2O meter), sulphidity
25%, solid-to-liquid ratio 1:5 are warming up to 165 DEG C, heating-up time 1h, keep the temperature 2-3h.Pot inner pressure is utilized after reaction, the row of collection
Then black liquor out uses filtered on buchner funnel, remove the large particulate matter in black liquor；
(2) it is 2mol/L sulfuric acid that concentration is continuously added in the black liquor in step (1), and the pH value of solution is slowly adjusted to 6,
And it is stirred continuously 1-2h, and it is then centrifuged for separation and obtains the first fraction of lignin, the liquid after collecting centrifugation；
(3) concentration is added in the liquid collected to step (2) is 2mol/L sulfuric acid, and the pH value of solution is slowly adjusted to 4, and
It is stirred continuously 1-2h, is then centrifuged for separating, obtains the second fraction of lignin；
(4) concentration is added in the liquid collected to step (3) is 2mol/L sulfuric acid, and the pH value of solution is slowly adjusted to 2, and
It is stirred continuously 1-2h, is then centrifuged for separating, obtains lignin third fraction.
It is 12000~24000 between the molecular weight area of obtained the first fraction of lignin, obtained the first fraction of lignin
It is 8000~12000 between molecular weight area, is 2000~8000 between the molecular weight area of obtained lignin third fraction.
It is isolated to embodiment 1-5, embodiment 6-10, embodiment 11-15, embodiment 16-20 and comparative example 1-3
Each fraction carries out gel spectrum test, obtains the recovery rate of each fraction as shown in tables 1 to 5.
Wherein, the quality for the first fraction of lignin that the first fraction recovery rate obtains for the stage division accounts in raw material should
The percentage of lignin quality between molecular weight area；Second fraction recovery rate is the second fraction of lignin that the stage division obtains
Quality account for the percentage of lignin quality between the molecular weight area in raw material；Third fraction recovery rate is that the stage division obtains
The quality of lignin third fraction account for the percentage of lignin quality between the molecular weight area in raw material；The fourth stage divides the recovery rate to be
The quality of the lignin fourth stage that the stage division obtains point accounts for the percentage of lignin quality between the molecular weight area in raw material；
The quality that the lignin level V that level V divides recovery rate to obtain for the stage division divides accounts for wooden between the molecular weight area in raw material
The percentage of quality quality.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
| Project | First fraction recovery rate/% | Second fraction recovery rate/% | Third fraction recovery rate/% |
| Comparative example 1 | 82.3 | - | - |
| Comparative example 2 | 80.7 | 79.9 | - |
| Comparative example 3 | 78.6 | 77.5 | 72.1 |
It can be seen that embodiment 1-5, embodiment 6-10, embodiment 11-15, embodiment 16-20, embodiment according to table 1-7
In 21-25 and embodiment 26-30, using lignin stage division provided by the present invention respectively to bagasse, straw, moso bamboo,
Lignin in reed, China fir and poplar is classified, the recovery rate of the recovery rate of the first fraction up to 95%, second fraction
Up to 94%, the recovery rate of third fraction is up to 92%, and for the recovery rate of the fourth stage point up to 91%, the recovery rate of level V point can
Up to 89%.Comparative example 1-3 at most only carries out three sections of classifications to bagasse lignin, and big between the molecular weight area of each fraction, cannot
Between obtaining relatively narrow molecular weight area, the recovery rate of the first fraction only up to the recovery rate of 82%, second fraction only up to 80%, and
The recovery rate of third fraction is only up to 72%.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of stage division of lignin, which is characterized in that the described method comprises the following steps:
(1) it with the organic acid solvent of the first concentration gradient and/or the aqueous dissolution lignin of alcohols solvent, is separated by solid-liquid separation,
Obtained solid matter and filtrate is respectively the first fraction of lignin and the first filtrate；
Optionally, water is added in the first filtrate that (2) are obtained to step (1), by organic acid solvent and/or the water of alcohols solvent
Solution concentration is adjusted to the second concentration gradient, is separated by solid-liquid separation, obtained solid matter and filtrate is respectively the lignin second level
Divide and the second filtrate.
2. the method according to claim 1, wherein step (1) the organic acid solvent includes formic acid, acetic acid
Any one in propionic acid or at least two combination；
Preferably, step (1) described alcohols solvent includes any one in methanol, ethyl alcohol, normal propyl alcohol or n-butanol or at least two
The combination of kind；
Preferably, the lignin is that lignocellulose raw material extracts the lignin being prepared by chemical method.
It is preferred that low, the plant fiber material is woody biolobic material or/and grass biolobic material；
Preferably, the woody biolobic material include in hardwood, cork or shrub any one or at least two combination；
Preferably, the grass biolobic material include in bagasse, bamboo, straw, wheat straw, cornstalk or reed any one or
At least two combination.
Preferably, step (1) first concentration gradient include 75~100wt%, 60~75wt% (be free of 75%wt), 50~
Any one in 60wt% (be free of 60wt%), 40~50wt% (being free of 50wt%) or 10~40wt% (being free of 40%)；
Preferably, the quality volume of the aqueous solution of step (1) lignin and the organic acid solvent and/or alcohols solvent
Than for 1:(50~300) g/mL；
Preferably, step (1) dissolution carries out under stiring；
Preferably, the stirring rate of the stirring is 50~20000rpm；
Preferably, the time of the stirring is 1~200min；
Preferably, the method for step (1) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or at least
Two kinds of combination, is further preferably filtered.
3. method according to claim 1 or 2, which is characterized in that step (2) second concentration gradient be 60~
75wt% (being free of 75%wt), 50~60wt% (being free of 60wt%), 40~50wt% (being free of 50wt%) or 10~40wt%
Any one in (be free of 40%)；
Preferably, after step (2) the addition water, mixed liquor is stirred；
Preferably, the stirring rate of the stirring is 50~20000rpm；
Preferably, the time of the stirring is 1~200min；
Preferably, the method for step (2) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or at least
Two kinds of combination, is further preferably filtered.
4. method according to claim 1-3, which is characterized in that step (2) carries out step (3) afterwards, to step
(2) water is added in the second filtrate obtained, it is dense that the concentration of aqueous solution of organic acid solvent and/or alcohols solvent is adjusted to third
Gradient is spent, is separated by solid-liquid separation, obtained solid matter and filtrate is respectively lignin third fraction and third filtrate.
5. according to the method described in claim 4, it is characterized in that, step (3) the third concentration gradient is 50~60wt%
Any one in (be free of 60wt%), 40~50wt% (being free of 50wt%) or 10~40wt% (being free of 40%)；
Preferably, after step (3) the addition water, mixed liquor is stirred；
Preferably, the stirring rate of the stirring is 50~20000rpm；
Preferably, the time of the stirring is 1~200min；
Preferably, the method for step (3) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or at least
Two kinds of combination, is further preferably filtered.
6. method according to claim 4 or 5, which is characterized in that step (3) carries out step (4) afterwards, obtains to step (4)
To third filtrate in water is added, by the concentration of aqueous solution of organic acid solvent and/or alcohols solvent be adjusted to the 4th concentration ladder
Degree is separated by solid-liquid separation, and obtained solid matter and filtrate is respectively the lignin fourth stage point and the 4th filtrate.
7. according to the method described in claim 6, it is characterized in that, step (4) the 4th concentration gradient is 40~50wt%
(being free of 50wt%) or 10~40wt% (being free of 40%)；
Preferably, after step (4) the addition water, mixed liquor is stirred；
Preferably, the stirring rate of the stirring is 4000~20000rpm；
Preferably, the time of the stirring is 1~200min；
Preferably, the method for step (4) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or at least
Two kinds of combination, is further preferably filtered.
8. method according to claim 6 or 7, which is characterized in that step (4) carries out step (5) afterwards, obtains to step (4)
To the 4th filtrate in water is added, by the concentration of aqueous solution of organic acid solvent and/or alcohols solvent be adjusted to the 5th concentration ladder
Degree is separated by solid-liquid separation, and obtained solid matter is lignin level V point.
9. according to the method described in claim 8, it is characterized in that, the 5th concentration gradient described in step (5) be 10~
40wt% is free of 40wt%；
Preferably, after step (5) the addition water, mixed liquor is stirred；
Preferably, the stirring rate of the stirring is 50~20000rpm；
Preferably, the time of the stirring is 1~200min；
Preferably, the method for step (5) described separation of solid and liquid include filtering, centrifugation, evaporation or sedimentation in any one or at least
Two kinds of combination, is further preferably filtered.
10. -9 described in any item methods according to claim 1, which is characterized in that the described method comprises the following steps:
(1) with the organic acid solvent of 75~100wt% of concentration and/or the aqueous dissolution lignin of alcohols solvent, solid-liquid point
From obtained solid matter and filtrate is respectively the first fraction of lignin and the first filtrate；
(2) water is added in the first filtrate obtained to step (1), the aqueous solution of organic acid solvent and/or alcohols solvent is dense
Degree is adjusted to 60~75wt%, is separated by solid-liquid separation, obtained solid matter and filtrate is respectively the second fraction of lignin and second
Filtrate；
(3) water is added in the second filtrate obtained to step (2), the aqueous solution of organic acid solvent and/or alcohols solvent is dense
Degree is adjusted to 50~60wt%, is separated by solid-liquid separation, obtained solid matter and filtrate is respectively lignin third fraction and third
Filtrate；
(4) water is added in the third filtrate obtained to step (4), the aqueous solution of organic acid solvent and/or alcohols solvent is dense
Degree is adjusted to 40~50wt%, is separated by solid-liquid separation, and obtained solid matter and filtrate is respectively the lignin fourth stage point and the 4th
Filtrate；
(5) water is added in the 4th filtrate obtained to step (4), the aqueous solution of organic acid solvent and/or alcohols solvent is dense
Degree is adjusted to 10~40wt%, is separated by solid-liquid separation, and obtained solid matter is lignin level V point.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109868670A (en) * | 2019-03-13 | 2019-06-11 | 内蒙古科技大学 | A kind of preprocess method reducing content of lignin in reed |
| CN109970991A (en) * | 2019-03-20 | 2019-07-05 | 华南理工大学 | It is classified the modified method of comprehensive utilization of the small fraction demethoxylation of lignin |
| CN112011068A (en) * | 2020-09-03 | 2020-12-01 | 天津科技大学 | Hydrogel for lignin classification and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109868670A (en) * | 2019-03-13 | 2019-06-11 | 内蒙古科技大学 | A kind of preprocess method reducing content of lignin in reed |
| CN109970991A (en) * | 2019-03-20 | 2019-07-05 | 华南理工大学 | It is classified the modified method of comprehensive utilization of the small fraction demethoxylation of lignin |
| CN112011068A (en) * | 2020-09-03 | 2020-12-01 | 天津科技大学 | Hydrogel for lignin classification and preparation method thereof |
| CN112011068B (en) * | 2020-09-03 | 2023-01-24 | 天津科技大学 | Hydrogel for lignin classification and preparation method thereof |
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