CN103030816B - Technique for extracting lignin from biomass raw materials - Google Patents
Technique for extracting lignin from biomass raw materials Download PDFInfo
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- CN103030816B CN103030816B CN201210576219.7A CN201210576219A CN103030816B CN 103030816 B CN103030816 B CN 103030816B CN 201210576219 A CN201210576219 A CN 201210576219A CN 103030816 B CN103030816 B CN 103030816B
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- 238000000034 method Methods 0.000 title claims abstract description 77
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- 238000000926 separation method Methods 0.000 claims description 47
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Abstract
The invention relates to a technique for extracting lignin, in particular to a technique of utilizing organic acid to extract the lignin from biomass raw materials by a catalytic action of hydrogen peroxide. According to the method, the lignin is obtained by extracting the biomass raw materials boiled by organic acid formed by methanoic acid and acetic acid by the catalytic action of hydrogen peroxide; a whole technique route is simple; the energy consumption is lower; and an extraction ratio of the lignin reaches 80-90%.
Description
Technical field
The present invention relates to a kind of lignin extraction technique, specifically a kind of technique utilizing organic acid to extract xylogen from biomass material.
Background technology
Xylogen is a kind of of great value industrial chemicals, highly purified sulphur-free lignin can be used as polymeric additive and soil improvement agent, the pesticide slow-releasing agents etc. such as phenolic resin, polyurethane foam, epoxy resin, and lignin application can make its added value far above as the added value reclaiming heat after fuel combustion in these areas.At present, lignin mainly as pulping and paper-making co-production, such as Sulfite lignin, kraft lignin etc.But these lignins contain element sulphur, and simultaneously lignin purity is lower, complicated component, molecular weight distribution are wide, viscosity is low, dispersity is high, poor processability, almost do not have thermoplastic property, thus greatly limit its industrial application.Therefore, pretreatment technology that exploitation is cleaned, that effectively can improve lignocellulose raw material enzymolysis performance realizes the biorefinery of lignocellulose raw material and the key of higher value application.
With the biomass material that the form of plant materials exists, main component is Mierocrystalline cellulose, hemicellulose and xylogen, wherein, Mierocrystalline cellulose accounts for about 40%, hemicellulose accounts for about 25%, xylogen accounts for about 20%, and the biomass material total amount that the earth is generated by photosynthesis is every year more than 2,000 hundred million tons, and therefore biomass are renewable resourcess abundant, the most cheap on the earth.
Chinese patent CN101864683A discloses a kind of pretreatment process of lignocellulose raw material, after the mixed solution of xylogen raw material and organic acid soln and catalyzer mixes by this patent, carry out the first step process, obtain liquid-solid mixture and carry out solid-liquid separation, obtaining pretreatment fluid and cellulose solids; Organic acid soln washing is adopted to obtain cellulose solids; The pre-treatment black liquor obtained is mixed Posterior circle with the washing black liquid obtained and is used for the first step treating processes; The black liquor recycling at least 3 times carries out the recovery of organic acid, lignin products and syrup solution.The black liquor of collection is carried out flash distillation or distillation, obtains organic acid and concentrated black liquor, the water adding 2-10 times of volume in black liquor obtains lignin products and syrup solution, thus realizes the higher value application of lignocellulose raw material.But this patent also exists following shortcoming: 1, as can be seen from the description in specification sheets, this technique adopts organic acid to carry out the first step catalysis with the catalyst mix taking sulfuric acid as representative, needs to add catalyzer and carry out catalysis in reaction process; 2, this technique adopts organic acid and take sulfuric acid as the common boiling biomass of catalyzer of representative, in distillation organic acid step, if organic acid distillation not exclusively, then xylogen cannot be separated out completely, if after organic acid is distilled out completely, the sulfuric acid concentration then added wherein rises, and can make xylogen charing wherein, affect the extraction yield of xylogen; Although extraction and washing the fibre element all use identical organic acid in 3 whole techniques, and the pretreatment fluid of collection and washings are directly used in are circulated in the reactor of the first step, but also gather the xylogen and pentose solution that dissolve wherein in whole mixed solution in a large number, in view of the saturation ratio restriction of organic acid extraction, the degree of functioning of its mixing black liquid extraction xylogen can significantly reduce, therefore, although this step is circulating reaction, the extraction efficiency effect for entirety is also little; 4, the black liquor be mixed to get needs circulation more than 3 times to carry out distillation process again to isolate organic acid, and the concentrated solution that dilution obtains makes xylogen separate out, the black liquor of disposable process and the high number of concentrated solution can be made, not only affect processing efficiency but also be difficult to realize the continuity of technique; 5, as can be seen from specification sheets, in this technique, lignin extraction rate is only 6-16%, and the extraction yield of whole technique is relatively low.
Chinese patent CN101514349A discloses a kind of method being prepared alcohol fuel by bamboo fiber.This patent is also the mix acid liquor boiling hydrolyzed hemicellulose with formic acid and acetic acid, and separates out lignin deposit directly to adding water in the filtrate of deviating from and isolate xylogen with this and be used.Because it adopts the mixed organic acid liquid of formic acid and acetic acid as cooking liquor, therefore without the need to adding catalyzer, although Mierocrystalline cellulose, hemicellulose and xylogen are separated by this patent in a process line, but the design of this technique is also to extract Mierocrystalline cellulose as final purpose, the loss of xylogen and pentose is not considered in the design of whole piece technique; This from its formic acid concn selected be 10%, acetic acid concentration is 70% can to find out, when in organic acid solution, the content of formic acid is starkly lower than the content of acetic acid, because the acidity of acetic acid is weaker than formic acid, therefore in biomass, the degree of breaing up of cellulose skeleton is poor, can Mierocrystalline cellulose be hindered further by boiling, retain cellulose solids to greatest extent.And Given this, the dissolving extracting solution being wound in the xylogen around cellulose skeleton can be subject to larger impact, for inapplicable for the cellulosic technique being extracted as final purpose; And in the step of this technique extracting in water precipitation in separating lignin one step, can because make xylogen be difficult to all deviate from containing formic acid and acetic acid in a large number in solution, even if add water in a large number also wherein can cannot ensure that xylogen is separated out completely because of formic acid and acetic acid, xylogen is caused to lose.Obviously, this technique only emphasis considers and extracts cellulosic technique to greatest extent, for xylogen be finally extract product technique for there is no directive function.
Chinese patent CN1170031C discloses the method for mixture as cooking chemical production paper pulp of a kind of formic acid and acetic acid.This patent is when producing paper pulp with formic acid boiling herbaceous plant and deciduous tree, add acetic acid as additional cooking chemical, can obtain containing hemicellulose and cellulosic paper pulp, and the mix acid liquor that used cooking liquor distills out formic acid and acetic acid carries out recycle, and process can be carried out to remaining concentrated solution and obtain xylogen.Although the method solves in the process of boiling biomass the problem needing to add catalyzer, but because the method is mainly for the preparation of paper pulp, its objective is the hemicellulose retaining Mierocrystalline cellulose and part to greatest extent, its whole technological design is all with this end in view, and whether the loss of wherein xylogen is not paid attention to, and the treatment process do not provided for xylogen, therefore this technique for xylogen be extract product technique for and inapplicable.
" research of Milox solvent legal system bleached bamboo pulp " (Liang Fang, Liu Yakang etc., China's paper industry, 2007, 28 (4), 40-43), show a kind of solvent pulping method adopting formic acid and hydrogen peroxide as boiling pharmaceutical chemicals, to reach the effect of dissolving or softening xylogen, but aforesaid method steams slurry process for a long time at low temperatures, the existence of a large amount of formic acid destroys the carbohydrate in raw material, and due to the acetic acid of trace can be produced in raw water solution preocess, reduce the clearance of hemicellulose in raw material, if and want to isolate the acetic acid of trace in whole process from formic acid, its step is complicated, be difficult to be separated, therefore, aforesaid method is not suitable for the extraction of xylogen.
Summary of the invention
For this reason, technical problem to be solved by this invention is that providing a kind of makes lignin extraction rate and active maximized extraction process by rational optimum configurations.
For solving the problems of the technologies described above, the technique extracting xylogen from biomass material of the present invention, comprises the steps:
(1) after biomass material being pulverized, under the katalysis of hydrogen peroxide, the organic acid solution formed by formic acid, acetic acid is used to carry out boiling to described biomass material, control temperature of reaction 80-135 DEG C, reaction times 40-100min, solid-liquid mass ratio is 1:5-1:20, and the reaction solution obtained is carried out first time solid-liquid separation; In organic acid solution, total acid concentration is 70-95%, and the mass ratio of described acetic acid and formic acid is 1:1-1:20, and surplus is water; Hydrogen peroxide accounts for the 1-10% of biomass material;
(2) solid that in step (1), solid-liquid separation obtains is collected, under the katalysis of hydrogen peroxide, with the mix acid liquor that formic acid, acetic acid are formed, pickling is carried out to described solid, control pickling temperature 20-100 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reaction solution obtained is carried out second time solid-liquid separation;
(3) collect first time solid-liquid separation and the liquid that obtains of second time solid-liquid separation distill under 50-110 DEG C, 1-21kPa, obtain formic acid and acetic acid steam and concentrated solution; The solids content of described concentrated solution is 70-95%;
(4) concentrated solution of gained in step (3) is added auxiliary agent dilution, stir, and carry out third time solid-liquid separation, the solid obtained obtains required xylogen after carrying out the process of washing de-esterifying.
Preferably, also comprise in described step (3) and will the formic acid and acetic acid steam condensation that obtain be distilled, and be back in the reactor of step (1), for the step of the boiling of step (1).
Preferably, the solids content of described concentrated solution is 80-90%.
Preferably, described auxiliary agent is water; Described auxiliary agent add quality be the 2-10 of described concentrated solution quality doubly.
Preferably, described auxiliary agent add quality be the 3-6 of described concentrated solution quality doubly.
Preferably, in described step (3), the temperature of described distillation is 50-80 DEG C.
Preferably, organic acid solution described in step (1), total acid concentration is 80-90%, and the mass ratio of acetic acid and formic acid is 1:2-1:10, and the hydrogen peroxide quality added accounts for the 3-6% of biomass material quality; The boiling temperature of step (1) controls at 100-125 DEG C, and solid-liquid mass ratio is 1:6-1:10.
Preferably, described in step (2), mix acid liquor is identical with the organic acid solution of step (1).
Preferably, in described step (2), pickling temperature is 30-90 DEG C, and solid-liquid mass ratio is 1:8-1:10.
Preferably, described biomass material is grass as raw material and/or wooden class raw material.
Described biomass material is one or more in reed, beanstalk bar, wheat straw, straw, corn stalk, melon seed cases, bamboo chip, melon seeds bar.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, the present invention is by processing parameter reasonable in design, makes whole operational path not be only applicable to wooden class raw material, be also applicable to grass as raw material, and the extraction rate reached of xylogen is to 80-90%.
2, digestion process of the present invention carries out in airtight reaction vessel, because the part of formic acid, acetic acid and hydrogen peroxide is distilled, makes to have certain pressure in container, thus shortens the cooking time of raw material.
3, the common boiling biomass material of process selection formic acid of the present invention, acetic acid and hydrogen peroxide, formic acid is as a kind of strong organic acid, urge the xylogen done in degraded raw material, utilize the organic solvent dissolution lignin molecule that formic acid and acetic acid are formed, also utilize its acid boiling hemicellulose wherein, and with this by Mierocrystalline cellulose, hemicellulose and lignin separation; Hydrogen peroxide add the environment that can form peroxide acid solution, exacerbate degraded and the dissolving of xylogen, thus improve the extraction yield of xylogen.
4, the liquid that the first time of collection and second time solid-liquid separation obtain directly is carried out distillation and concentration by technique of the present invention, directly be back in the reactor of the first step for recycling after the formic acid that distillation obtains, acetic acid condensation, whole operational path is succinct, and re-use as raw material due to formic acid and acetic acid, higher to the boiling efficiency of biomass.
5, after first time boiling obtains Mierocrystalline cellulose, the mixed solution of formic acid, acetic acid and hydrogen peroxide is adopted to carry out pickling to Mierocrystalline cellulose, a small amount of xylogen of Mierocrystalline cellulose internal residual is decomposed and stripping, ensure that xylogen extracts completely, and the mixed solution to form due to formic acid, acetic acid and hydrogen peroxide in acid pickling step is identical with the peroxide organic acid solution in boiling step, the formic acid that regenerates and acetic acid is made to regulate ratio can be directly used in the circulation of whole technique without the need to any pre-treatment.
6, before adding auxiliary agent precipitation xylogen, distillation process is carried out, the formic acid steamed on the one hand and acetic acid can be used for the circulating reaction of boiling step to economize in raw materials, simultaneously except after formic acid removal, acetic acid concentration, can ensure with the auxiliary agent of minimum dose, xylogen all to be separated out, energy efficient, adopt water to separate out the method for xylogen as auxiliary agent, the lignin molecule amount obtained is evenly distributed.
7, adopt in the application and add the method that arboxylic acid mixes hydrogen peroxide and extract xylogen, the extraction xylogen of ceiling on the basis of at high temperature less destruction carbohydrate, and acid can be made when recovered acid to be better separated with water.
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the schema of technique of the present invention.
Embodiment
Below will the invention will be further described by specific embodiment.
In following examples, apart from outside specified otherwise, percentage composition used all represents mass percentage, i.e. " % " expression " wt% "; In described organic acid solution except a certain amount of formic acid, acetic acid, surplus is water, the acid of the dense nail of total acid described in each step and the total mass of acetic acid account for the percentage ratio of described organic acid solution quality, the quality that the solid-liquid mass ratio in each step refers to solid in this each step and the mass ratio of total liquid added.
Slurry described in each step is dense=this step in solid quality/this step in Zhi Liang He ╳ 100% of solid and liquid
Hydrogen peroxide H in each embodiment
2o
2be that the form of the aqueous hydrogen peroxide solution of 27% adds with mass concentration.Such as need as calculated to add 2.7g hydrogen peroxide, then corresponding should be add 10g (2.7 ÷ 0.27=10) described aqueous hydrogen peroxide solution.Solids content adopts halogen fast tester for water content (plum Teller-Tuo benefit, model: HB43-S) to measure at 115 DEG C.
Embodiment 1
In the present embodiment, first smashed by reed (content of lignin 25.10%), being crushed to particle diameter is 2-10cm.
The present embodiment extracts the technique of xylogen from described reed, comprises the steps:
(1) by after reed comminution pretreatment, total acid concentration is used to be that the formic acid of 70% and the organic acid solution of acetic acid carry out boiling to the reed after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:1, and before adding reed raw material, add the hydrogen peroxide (H accounting for reed 3%
2o
2) as catalyzer, controlling temperature of reaction 115 DEG C, reaction 55min, solid-liquid mass ratio is 1:5, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that above-mentioned separation obtains is added the acid solution identical with organic acid solution described in step (1) and carry out acid elution, wherein the add-on of hydrogen peroxide accounts for 3% of raw material, pickling temperature is 70 DEG C, washing time 1h, solid-liquid mass ratio is 1:4, and reaction solution is carried out second time solid-liquid separation;
(3) liquid that in step (1) and step (2), twice solid-liquid separation obtains is collected, in 50 DEG C, carry out distilling the steam that obtains formic acid and acetic acid under the condition of 1kpa and solids content is 70% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) concentrated solution of gained in step (3) is added the water dilution accounting for concentrated solution quality 2 times, 60-70 DEG C of stirring, and carrying out third time solid-liquid separation, the solid obtained is washed de-esterifying further and is obtained required xylogen, and the extraction yield of its xylogen is 80%.
Embodiment 2
In the present embodiment, first smashed by corn stalk (content of lignin 24.09%), being crushed to particle diameter is 2-10cm.
The present embodiment extracts the technique of xylogen from described corn stalk, comprises the steps:
(1) by after cornstalk crushing pre-treatment, total acid concentration is used to be that the formic acid of 75% and the organic acid solution of acetic acid carry out boiling to the corn stalk after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:2, and before adding corn stalk, add the hydrogen peroxide (H accounting for corn stalk raw material 2%
2o
2) as catalyzer, controlling temperature of reaction 90 DEG C, reaction 40min, solid-liquid mass ratio is 1:15, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that above-mentioned separation obtains is added the acid solution identical with organic acid solution described in step (1) and carry out acid elution, wherein the add-on of hydrogen peroxide accounts for 2% of raw material, pickling temperature is 90 DEG C, washing time 1h, solid-liquid mass ratio is 1:6, and reaction solution is carried out second time solid-liquid separation;
(3) liquid that in step (1) and step (2), twice solid-liquid separation obtains is collected, in 60 DEG C, distill under the condition of 21kpa, the steam and the solids content that obtain formic acid and acetic acid are 75% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) concentrated solution of gained in step (3) is added the water dilution accounting for concentrated solution quality 3 times, 60-70 DEG C of stirring, and carrying out third time solid-liquid separation, the solid obtained is washed de-esterifying further and is obtained required xylogen, and the extraction yield of its xylogen is 82%.
Embodiment 3
In the present embodiment, first smashed by straw (content of lignin 19.07%), being crushed to particle diameter is 2-10cm.
The present embodiment extracts the technique of xylogen from described straw, comprises the steps:
(1) by after straw comminution pretreatment, total acid concentration is used to be that the formic acid of 80% and the organic acid solution of acetic acid carry out boiling to the straw after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:6, and before adding straw raw material, add the hydrogen peroxide (H accounting for raw material 4%
2o
2) as catalyzer, controlling temperature of reaction 135 DEG C, reaction 70min, solid-liquid mass ratio is 1:10, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that above-mentioned separation obtains is added the acid solution identical with organic acid solution described in step (1) and carry out acid elution, wherein the add-on of hydrogen peroxide accounts for 4% of raw material, pickling temperature is 100 DEG C, washing time 1h, solid-liquid mass ratio is 1:8, and reaction solution is carried out second time solid-liquid separation;
(3) liquid that in step (1) and step (2), twice solid-liquid separation obtains is collected, in 110 DEG C, distill under 11kpa condition, the steam and the solids content that obtain formic acid and acetic acid are 80% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) concentrated solution of gained in step (3) is added the water dilution accounting for concentrated solution 4 times, 60-70 DEG C of stirring, and carrying out third time solid-liquid separation, the solid obtained is washed de-esterifying further and is obtained required xylogen, and the extraction yield of its xylogen is 84%.
Embodiment 4
In the present embodiment, first smashed by beanstalk bar (lignin content is 19.5%), being crushed to particle diameter is 2-10cm.
The present embodiment extracts the technique of xylogen from described beanstalk bar, comprises the steps:
(1) by after beanstalk bar comminution pretreatment, total acid concentration is used to be that the formic acid of 85% and the organic acid solution of acetic acid carry out boiling to the beanstalk bar after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:15, and before adding beans straw raw material, add the hydrogen peroxide (H accounting for beans straw raw material 6%
2o
2) as catalyzer, controlling temperature of reaction 125 DEG C, reaction 100min, solid-liquid mass ratio is 1:20, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that above-mentioned separation obtains is added the acid solution identical with organic acid solution described in step (1) and carry out acid elution, wherein the add-on of hydrogen peroxide accounts for 6% of raw material, pickling temperature is 50 DEG C, washing time 1h, solid-liquid mass ratio is 1:15, and reaction solution is carried out second time solid-liquid separation;
(3) liquid that in step (1) and step (2), twice solid-liquid separation obtains is collected, 80 DEG C, distill under 11kpa condition, the steam and the solids content that obtain formic acid and acetic acid are 85% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) concentrated solution of gained in step (3) is added the water dilution accounting for concentrated solution quality 6 times, 60-70 DEG C of stirring, and carrying out third time solid-liquid separation, the solid obtained is washed de-esterifying further and is obtained required xylogen, and the extraction yield of its xylogen is 85%.
Embodiment 5
In the present embodiment, first cotton stem (content of lignin 23.33%) is smashed.
The present embodiment extracts the technique of xylogen from described cotton stem, comprises the steps:
(1) by after cotton stem comminution pretreatment, total acid concentration is used to be that the formic acid of 90% and the organic acid solution of acetic acid carry out boiling to the cotton stem after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:10, and before adding cotton stem raw material, add the hydrogen peroxide (H accounting for raw material 10%
2o
2) as catalyzer, controlling temperature of reaction 80 DEG C, reaction 90min, solid-liquid mass ratio is 1:6, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that above-mentioned separation obtains is added the acid solution identical with organic acid solution described in step (1) and carry out acid elution, wherein the add-on of hydrogen peroxide accounts for 10% of cotton stem quality, pickling temperature is 20 DEG C, washing time 1h, solid-liquid mass ratio is 1:20, and reaction solution is carried out second time solid-liquid separation;
(3) liquid that in step (1) and step (2), twice solid-liquid separation obtains is collected, in 75 DEG C, distill under 21kpa, the steam and the solids content that obtain formic acid and acetic acid are 95% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) concentrated solution of gained in step (3) is added the water dilution accounting for concentrated solution quality 10 times, 60-70 DEG C of stirring, and carrying out third time solid-liquid separation, the solid obtained is washed de-esterifying further and is obtained required xylogen, and the extraction yield of its xylogen is 88%.
Embodiment 6
In the present embodiment, first smashed by bamboo chip (content of lignin 27.61%), being crushed to length is 2 ~ 10cm, thick 2mm thin slice.
The present embodiment extracts the technique of xylogen from described bamboo chip, comprises the steps:
(1) by after bamboo chip comminution pretreatment, total acid concentration is used to be that the formic acid of 95% and the organic acid solution of acetic acid carry out boiling to the bamboo chip after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:20, and before adding bamboo chip raw material, add the hydrogen peroxide (H accounting for bamboo chip 1%
2o
2) as catalyzer, controlling temperature of reaction 100 DEG C, reaction 65min, solid-liquid mass ratio is 1:8, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that above-mentioned separation obtains is added the acid solution identical with organic acid solution described in step (1) and carry out acid elution, wherein the add-on of hydrogen peroxide accounts for 1% of raw material, pickling temperature is 30 DEG C, washing time 1h, solid-liquid mass ratio is 1:10, and reaction solution is carried out second time solid-liquid separation;
(3) liquid that in step (1) and step (2), twice solid-liquid separation obtains is collected, in 100 DEG C, distill under 1kpa, the steam and the solids content that obtain formic acid and acetic acid are 90% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) concentrated solution of gained in step (3) is added the water dilution accounting for concentrated solution quality 8 times, 60-70 DEG C of stirring, and carrying out third time solid-liquid separation, the solid obtained is washed de-esterifying further and is obtained required xylogen, and the extraction yield of its xylogen is 90%.
Comparative example 1
The parameter of the operational path described in the present embodiment and each step is identical with embodiment 2, its difference is only in step (3), the liquid that twice solid-liquid separation obtains will to be collected in step (3), circulation inputs to step (1), and the process of repeating step (1), after repeating 3 above-mentioned circulations, the liquid that twice solid-liquid separation in step (3) obtains is carried out distillation and concentration, and the formic acid obtained and acetic acid steam concentrated solution carry out subsequent disposal according to the treatment process of step (4) and condition again.Obtain xylogen by aforesaid method, its extraction yield is 70%.
Comparative example 2
The parameter of the operational path described in the present embodiment and each step is identical with comparative example 1, and its difference is only not add hydrogen peroxide as catalyzer in each step.Obtain xylogen by method described in the present embodiment, its extraction yield is 66.2%.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. from biomass material, extract a technique for xylogen, it is characterized in that, comprise the steps:
(1) after biomass material being pulverized, under the katalysis of hydrogen peroxide, the organic acid solution formed by formic acid, acetic acid is used to carry out boiling to described biomass material, control temperature of reaction 80-135 DEG C, reaction times 40-100min, solid-liquid mass ratio is 1:5-1:20, and the reaction solution obtained is carried out first time solid-liquid separation;
In organic acid solution, total acid concentration is 70-95%, and the mass ratio of described acetic acid and formic acid is 1:1-1:20, and surplus is water;
Hydrogen peroxide accounts for the 1-10% of biomass material;
(2) solid that in step (1), solid-liquid separation obtains is collected, under the katalysis of hydrogen peroxide, with the mix acid liquor that formic acid, acetic acid are formed, pickling is carried out to described solid, control pickling temperature 20-100 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reaction solution obtained is carried out second time solid-liquid separation;
(3) collect first time solid-liquid separation and the liquid that obtains of second time solid-liquid separation distill under 50-110 DEG C, 1-21kPa, obtain formic acid and acetic acid steam and concentrated solution; The solids content of described concentrated solution is 70-95%;
(4) concentrated solution of gained in step (3) is added auxiliary agent dilution, stir, and carry out third time solid-liquid separation, the solid obtained obtains required xylogen after carrying out the process of washing de-esterifying.
2. the technique extracting xylogen from biomass material according to claim 1, is characterized in that:
Also comprise in described step (3) and will the formic acid and acetic acid steam condensation that obtain be distilled, and be back in the reactor of step (1), for the step of the boiling of step (1).
3. the technique extracting xylogen from biomass material according to claim 2, is characterized in that:
The solids content of described concentrated solution is 80-90%.
4., according to the arbitrary described technique extracting xylogen from biomass material of claim 1-3, it is characterized in that:
Described auxiliary agent is water;
Described auxiliary agent add quality be the 2-10 of described concentrated solution quality doubly.
5. the technique extracting xylogen from biomass material according to claim 4, is characterized in that:
Described auxiliary agent add quality be the 3-6 of described concentrated solution quality doubly.
6. the technique extracting xylogen from biomass material according to claim 1,2,3 or 5, is characterized in that:
In described step (3), the temperature of described distillation is 50-80 DEG C.
7. the technique extracting xylogen from biomass material according to claim 6, is characterized in that:
Organic acid solution described in step (1), total acid concentration is 80-90%, and the mass ratio of acetic acid and formic acid is 1:2-1:10, and the hydrogen peroxide quality added accounts for the 3-6% of biomass material quality;
The boiling temperature of step (1) controls at 100-125 DEG C, and solid-liquid mass ratio is 1:6-1:10.
8. the technique extracting xylogen from biomass material biomass according to claim 7, is characterized in that:
Described in step (2), mix acid liquor is identical with the organic acid solution of step (1).
9. the technique extracting xylogen from biomass material according to claim 8, is characterized in that:
In described step (2), pickling temperature is 30-90 DEG C, and solid-liquid mass ratio is 1:8-1:10.
10. the technique extracting xylogen from biomass material according to claim 9, is characterized in that:
Described biomass material is grass as raw material and/or wooden class raw material.
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| RU2601750C1 (en) * | 2015-04-28 | 2016-11-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный лесотехнический университет имени С.М. Кирова" | Method for producing water-soluble derivative of hydrolytic lignin |
| CN108221432B (en) * | 2017-12-28 | 2020-07-07 | 潍坊友容实业有限公司 | Process method for extracting cellulose from suaeda salsa |
| CN109535440B (en) * | 2018-11-26 | 2021-04-27 | 广州楹鼎生物科技有限公司 | A method for treating plant material |
| CN111019153A (en) * | 2019-11-15 | 2020-04-17 | 陕西山河生物科技有限公司 | Component separation method by bamboo formic acid method |
| CN113004538A (en) * | 2019-12-19 | 2021-06-22 | 济南圣泉集团股份有限公司 | Method for preparing high-activity lignin by using esterified lignin crude product |
| CN113004537B (en) * | 2019-12-19 | 2022-11-01 | 济南圣泉集团股份有限公司 | Method for preparing high-activity lignin by using esterified lignin crude product |
| CN111393670B (en) * | 2020-03-26 | 2022-04-05 | 齐鲁工业大学 | A kind of method for efficient extraction and separation of active lignin |
| CN112048933B (en) * | 2020-09-07 | 2022-11-15 | 齐鲁工业大学 | Method for producing chemi-mechanical pulp and semi-chemical pulp |
| CN112480182B (en) * | 2020-12-22 | 2022-09-16 | 南京林业大学 | Preparation method of low-molecular-weight lignin and application of low-molecular-weight lignin in preparation of monophenol compounds |
| CN113977729A (en) * | 2021-08-23 | 2022-01-28 | 浙江农林大学 | Method for manufacturing bamboo pencil |
| CN114753177A (en) * | 2022-03-22 | 2022-07-15 | 齐鲁工业大学 | Method for separating biomass components by ternary system |
| CN115557499B (en) * | 2022-11-23 | 2023-03-17 | 成都达奇环境科技有限公司 | Preparation method of square bamboo activated carbon and square bamboo activated carbon |
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