CN103131017B - A kind of technique extracting xylogen from lignocellulose biomass - Google Patents
A kind of technique extracting xylogen from lignocellulose biomass Download PDFInfo
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Abstract
The present invention relates to a kind of lignin extraction technique, specifically a kind of technique utilizing organic acid to extract xylogen from lignocellulose.Method of the present invention is by the mixed organic acid acidolysis lignocellulose biomass of concentration to be the formic acid of 5-90% and concentration the be acetic acid of 5-90%, extraction obtains xylogen, the extraction yield of xylogen is up to 85%, and whole operational path is simple, energy consumption is lower, and can this technique coproduction Mierocrystalline cellulose and pentose be passed through, the even product such as furfural.
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 lignocellulose.
Background technology
Xylogen is the class material be made up of the aromatic alcohol be polymerized, and is present in lignum, and Main Function carrys out sclereid wall by forming intertexture net.Xylogen, mainly between cellulosic fibre, plays resistance to compression effect.In xylophyta, xylogen accounts for 25%, is the organism that second is the abundantest in the world, is only second to Mierocrystalline cellulose.
Along with the understanding of the problems such as mankind's environmental pollution and crisis of resource deepens continuously, the character such as renewable, degradable that natural polymer has comes into one's own day by day.The resource utilization of waste and the utilization of renewable resources are the key subjects of modern economy and social development, are also the new demands proposed contemporary science and technology.At occurring in nature, the reserves of xylogen are only second to Mierocrystalline cellulose, and all regenerate with the speed of 50,000,000,000 tons every year.Pulp and paper industry will isolate about 1.4 hundred million tons of Mierocrystalline celluloses every year from plant, obtain the xylogen byproduct of about 5,000 ten thousand tons simultaneously, but up to now, the xylogen more than 95% still directly enters rivers with " black liquor " or burns after concentrating, and is seldom utilized effectively.
In fact, 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.
Lignocellulose biomass exists with the form of plant materials, 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 lignocellulose biomass total amount that the earth is generated by photosynthesis is every year more than 2,000 hundred million tons, and therefore lignocellulose biomass is renewable resources 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 evaporation, 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 acidolysis 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 evaporation 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 to be acid hydrolysis, 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 acidolysis 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.
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 lignocellulose biomass of the present invention, is characterized in that, comprise the steps:
(1) by after biomass material comminution pretreatment, the organic acid solution be made up of formic acid and acetic acid is used to carry out acidolysis to lignocellulose biomass, control temperature of reaction 70-165 DEG C, reaction 10-150min, and the reaction solution obtained is carried out first time solid-liquid separation;
In described organic acid solution, the concentration of described formic acid is 30-90%, and the concentration of acetic acid is 5-50%, and surplus is water;
(2) collect the liquid that in step (1), solid-liquid separation obtains, in 60-100 DEG C, vacuum tightness carries out underpressure distillation and concentrates under being the pressure of 0.06-0.1atm, obtain formic acid and acetic acid steam and concentrated solution;
(3) concentrated solution of gained in step (2) is added auxiliary agent dilution, 60-70 DEG C of stirring, and carry out solid-liquid separation, the solid obtained obtains required xylogen after carrying out the process of washing de-esterifying.
Also comprise in described step (2) 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 acidolysis of step (1).
Owing to having the lignin residue of small amount in hydrolysis step in Mierocrystalline cellulose residue, in order to xylogen is washed out the extraction yield increasing xylogen, technique of the present invention can also after first time solid-liquid separation, isolated liquid is re-used the organic acid solution identical with hydrolysis step and carries out pickling, and carry out solid-liquid separation, by carrying out the step of underpressure distillation after the liquid collecting of twice solid-liquid separation again, more xylogen can be extracted.
In described organic acid solution, the concentration of described formic acid is 60-80%, and the concentration of described acetic acid is 10-40%.
In described organic acid solution, the concentration ratio of described formic acid and acetic acid is 1: 1.
In described step (1), temperature of reaction is 120-150 DEG C.
In described step (1), the solid-liquid mass ratio of described organic acid solution and biomass material is 1: 5-20.
Described solid-liquid mass ratio is 1: 6-10.
In described step (1), the reaction times is 20-120min.
Also comprise in described step (1) in the solid obtained to first time solid-liquid separation and add the step that formic acid and acetic acid carry out pickling, and reaction solution is carried out second time solid-liquid separation;
Concentration and the solid-to-liquid ratio of the concentration of the formic acid that described acid pickling step adopts and acetic acid and solid-to-liquid ratio and formic acid in organic acid solution described in described hydrolysis step and acetic acid are identical.
In described step (2), described enrichment step by liquid concentration to 4-10 doubly.
In described step (3), described auxiliary agent is water.
In described step (3), the weight ratio of described auxiliary agent and described concentrated solution is 2-4: 1.
In described step (4), in described water-washing step, the mass ratio of water and described solid is 3-5: 1, and stirs 2-3h in 75-85 DEG C.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, 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 evaporation 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 acidolysis efficiency of biomass, for the technique utilizing the acid hydrolysis solution after acidolysis to circulate, although eliminate the step of this circulation, but achieve within the identical process time, higher to the extraction efficiency of each component;
2, process selection formic acid of the present invention and the common acidolysis lignocellulose biomass of acetic acid, utilize the organic extraction performance extraction xylogen wherein of formic acid and acetic acid, and utilize its acid acidolysis hemicellulose wherein, and with this by Mierocrystalline cellulose, lignin separation, the concentration of described process selection formic acid is 30% ~ 90%, the concentration of acetic acid is 5% ~ 50%, and the xylogen in biomass is extracted (15% ~ 85%) to greatest extent;
3, described optimal process formic acid concn is 60-80%, acetic acid concentration 10-40%, makes the extraction rate reached of xylogen to 65% ~ 85%.
4, after first time acidolysis obtains Mierocrystalline cellulose, adopt, with the formic acid of hydrolysis step same concentrations and acetic acid, pickling is carried out to Mierocrystalline cellulose, on the one hand a small amount of xylogen of Mierocrystalline cellulose internal residual is decomposed and stripping, ensure that xylogen extracts completely, and due to formic acid identical with hydrolysis step with the concentration of acetic acid, make the formic acid that regenerates and acetic acid regulate ratio can be directly used in the circulation of whole technique without the need to any pre-treatment;
5, before adding auxiliary agent precipitation xylogen, carry out underpressure distillation and go out formic acid and acetic acid, the formic acid steamed on the one hand and acetic acid can be used for the circulating reaction of hydrolysis 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;
6, adopt the mode of underpressure distillation, formic acid and acetic acid are steamed, ensure can realize at a lower temperature by formic acid, separated from acetic acid out, reaction conditions is gentle;
7, the weight ratio of described auxiliary agent and described concentrated solution is 2-4: 1, ensures that the amount of auxiliary with minimum realizes the precipitation of xylogen.
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 weight percentage, i.e. " % " expression " % by weight ".
For convenience of explanation, lignocellulose biomass raw material used in embodiment is once corn cob, and in fact, technique of the present invention is applicable to multiple lignocellulose biomass raw material, as bagasse, maize straw, straw, cotton seed hulls and rice husk etc.
Embodiment 1
In the present embodiment, first smashed by corn cob (mass component forms: moisture 18.73%, Mierocrystalline cellulose 39.33%, hemicellulose 30.73%, xylogen 29.94%), being crushed to particle diameter is 0.5-20cm, preferred 2-5cm.
The comprehensive utilization process of lignocellulose biomass described in the present embodiment, comprises the steps:
(1) by after biomass material comminution pretreatment, use containing concentration be the formic acid of 90% and the acetic acid of 5% and 5% the organic acid solution of water acid hydrolysis is carried out to the lignocellulose biomass after process, control temperature of reaction 70 DEG C, reaction 150min, the liquid-solid mass ratio of described organic acid solution and biomass material is 1: 6, and the reaction solution obtained is carried out first time solid-liquid separation;
The solid that above-mentioned separation obtains is added containing concentration be the formic acid of 90% and the acetic acid of 5% and 5% the organic acid solution of water carry out acid elution, temperature is 60 ~ 80 DEG C, washing time 0.5 ~ 1h, and reaction solution is carried out second time solid-liquid separation;
(2) liquid that in step (1), solid-liquid separation obtains is collected, carry out underpressure distillation to concentrate, obtain formic acid and acetic acid vapor, and concentration is original strength of fluid 4-5 concentrated solution doubly, and by the formic acid that distills out and acetic acid vapor condensing reflux in the reactor of step (1), for the acidolysis of step (1);
(3) by the concentrated solution thin up of gained in step (2), the mass ratio of described auxiliary agent and described concentrated solution is 2: 1, control 60-70 DEG C is stirred 0.5-1h, and carry out third time solid-liquid separation, the solid obtained adds water (mass ratio of water and described solid is 3: 1), and after 75-80 DEG C of stirring 2-3h carries out washing de-esterifying, obtain required xylogen;
After carrying out quadratic acid hydrolysis treatment by the corn cob raw material that aforesaid method is new to 600g, finally obtain 1.201kg hydrolytic residue (water ratio is about 85.4%), slag content of lignin is 22.50%, and lignin extraction rate is 72.96%.Obtain finished product xylogen 187g, xylogen moisture is 51%, and the productive rate of xylogen is 62.7%.
The formula of xylogen yield is as follows:
(lignin quality × (1-xylogen moisture))/content of xylogen (in corn cob quality × (the 1-corn cob moisture) corn cob) × 100%.
Embodiment 2
In the present embodiment, first smashed by corn cob (mass component forms: moisture 18.73%, Mierocrystalline cellulose 37.22%, hemicellulose 33.73%, xylogen 29.05%), being crushed to particle diameter is 0.5-20cm, preferred 2-5cm.
The comprehensive utilization process of lignocellulose biomass described in the present embodiment, comprises the steps:
(1) by after biomass material comminution pretreatment, use containing concentration be 80% formic acid and concentration be the acetic acid of 10% and the water of 10% organic acid solution to process after lignocellulose biomass carry out acid hydrolysis, control temperature of reaction 140 DEG C, reaction 60min, the mix acid liquor of described formic acid and acetic acid and the liquid-solid mass ratio of biomass material are 1: 10, and the reaction solution obtained is carried out first time solid-liquid separation;
The solid that above-mentioned separation obtains is added containing concentration be 80% formic acid and concentration be that the organic acid solution of the acetic acid of 10% and the water of 10% carries out acid elution, temperature is 60 ~ 80 DEG C, washing time 0.5 ~ 1h, and reaction solution is carried out second time solid-liquid separation;
(2) liquid that in step (1), solid-liquid separation obtains is collected, in 60-80 DEG C, vacuum tightness carry out under being the pressure of 0.06-0.1atm underpressure distillation concentrate, obtain formic acid and acetic acid vapor, and concentration is the 9-10 concentrated solution doubly of original liquid, and by the formic acid that distills out and acetic acid vapor condensing reflux in the reactor of step (1), for the acidolysis of step (1);
(3) by the concentrated solution thin up of gained in step (2), the mass ratio of water and described concentrated solution is 4: 1, control 60-70 DEG C is stirred 0.5-1h, and carry out third time solid-liquid separation, the solid obtained adds water (mass ratio of water and described solid is 5: 1), and after 80-85 DEG C of stirring 2-3h carries out washing de-esterifying, obtain required xylogen;
After carrying out quadratic acid hydrolysis treatment by the corn cob raw material that aforesaid method is new to 600g, finally obtain 1.2kg hydrolytic residue (water ratio is about 83.5%), slag content of lignin is 6.71%, and lignin extraction rate is 90.9%.Obtain finished product xylogen 204g, xylogen moisture is 42%, and the productive rate of xylogen is 81.6%.
The formula of xylogen yield is as follows:
(lignin quality × (1-xylogen moisture))/content of xylogen (in corn cob quality × (the 1-corn cob moisture) corn cob) × 100%.
Embodiment 3
In the present embodiment, first smashed by corn cob (mass component forms: moisture 16.25%, Mierocrystalline cellulose 31.45%, hemicellulose 34.77%, xylogen 33.78%), being crushed to particle diameter is 0.5-20cm, preferred 2-5cm.
The comprehensive utilization process of lignocellulose biomass described in the present embodiment, comprises the steps:
(1) by after biomass material comminution pretreatment, use containing concentration be 60% formic acid and concentration be the acetic acid of 30% and the water of 10% organic acid solution to process after lignocellulose biomass carry out acid hydrolysis, control temperature of reaction 120 DEG C, reaction 120min, the liquid-solid mass ratio of described organic acid solution and biomass material is 1: 8, and the reaction solution obtained is carried out first time solid-liquid separation;
The solid that above-mentioned separation obtains is added containing concentration be 50% formic acid and concentration be that the organic acid solution of the acetic acid of 40% and the water of 10% carries out acid elution, temperature is 60 ~ 80 DEG C, washing time 0.5 ~ 1h, and reaction solution is carried out second time solid-liquid separation;
(2) liquid that in step (1), solid-liquid separation obtains is collected, in 60-100 DEG C, vacuum tightness carry out under being the pressure of 0.06-0.1atm underpressure distillation concentrate, obtain formic acid and acetic acid vapor, and concentration is the 7-8 concentrated solution doubly of original liquid, and by the formic acid that distills out and acetic acid vapor condensing reflux in the reactor of step (1), for the acidolysis of step (1);
(3) by the concentrated solution thin up of gained in step (2), the mass ratio of described auxiliary agent and described concentrated solution is 4: 1, control 60-70 DEG C is stirred 0.5-1h, and carry out third time solid-liquid separation, the solid obtained adds water (mass ratio of water and described solid is 4: 1), and after 75-85 DEG C of stirring 2-3h carries out washing de-esterifying, obtain required xylogen;
After carrying out quadratic acid hydrolysis treatment by the corn cob raw material that aforesaid method is new to 600g, finally obtain 1.154kg hydrolytic residue (water ratio is about 82.47%), slag content of lignin is 16.99%, and lignin extraction rate is 80%.Obtain finished product xylogen 191g, xylogen moisture is 39%, and the productive rate of xylogen is 68.6%.
The formula of xylogen yield is as follows:
(lignin quality × (1-xylogen moisture))/content of xylogen (in corn cob quality × (the 1-corn cob moisture) corn cob) × 100%.
Embodiment 4
In the present embodiment, first smashed by corn cob (mass component forms: moisture 16.25%, Mierocrystalline cellulose 31.45%, hemicellulose 34.77%, xylogen 33.78%), being crushed to particle diameter is 0.5-20cm, preferred 2-5cm.
The comprehensive utilization process of lignocellulose biomass described in the present embodiment, comprises the steps:
(1) by after biomass material comminution pretreatment, use containing concentration be 70% formic acid and concentration be the acetic acid of 25% and the water of 5% organic acid solution to process after lignocellulose biomass carry out acid hydrolysis, control temperature of reaction 135 DEG C, reaction 80min, the liquid-solid mass ratio of described organic acid solution and biomass material is 1: 8, and the reaction solution obtained is carried out first time solid-liquid separation;
The solid that above-mentioned separation obtains is added containing concentration be 70% formic acid and concentration be that the organic acid solution of the acetic acid of 25% and the water of 5% carries out acid elution, temperature is 60 ~ 80 DEG C, washing time 0.5 ~ 1h, and reaction solution is carried out second time solid-liquid separation;
(2) collect the liquid that in step (1), solid-liquid separation obtains, in 70-90 DEG C, vacuum tightness carries out underpressure distillation and concentrates under being the pressure of 0.07-0.1atm, obtain formic acid and acetic acid vapor, and concentration is the 5-6 concentrated solution doubly of original liquid; And by the formic acid that distills out and acetic acid vapor condensing reflux in the reactor of step (1), for the acidolysis of step (1);
(3) by the concentrated solution thin up of gained in step (2), the mass ratio of described auxiliary agent and described concentrated solution is 3: 1, control 65-70 DEG C is stirred 0.5-1h, and carry out third time solid-liquid separation, the solid obtained adds water (mass ratio of water and described solid is 4: 1), and after 75-80 DEG C of stirring 2-3h carries out washing de-esterifying, obtain required xylogen;
After carrying out quadratic acid hydrolysis treatment by the corn cob raw material that aforesaid method is new to 600g, finally obtain 1.023kg hydrolytic residue (water ratio is about 80.49%), slag content of lignin is 23.27%, and lignin extraction rate is 93%.Obtain finished product xylogen 239g, xylogen moisture is 38%, and the productive rate of xylogen is 87.2%.
The formula of xylogen yield is as follows:
(lignin quality × (1-xylogen moisture))/content of xylogen (in corn cob quality × (the 1-corn cob moisture) corn cob) × 100%.
Embodiment 5
In the present embodiment, first smashed by corn cob (mass component forms: moisture 18.73%, Mierocrystalline cellulose 39.33%, hemicellulose 30.73%, xylogen 29.94%), being crushed to particle diameter is 0.5-20cm, preferred 2-5cm.
The comprehensive utilization process of lignocellulose biomass described in the present embodiment, comprises the steps:
(1) by after biomass material comminution pretreatment, use containing concentration be 45% formic acid and concentration be the acetic acid of 40% and the water of 15% organic acid solution to process after lignocellulose biomass carry out acid hydrolysis, control temperature of reaction 107 DEG C, reaction 20min, the liquid-solid mass ratio of described organic acid solution and biomass material is 1: 5, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) liquid that in step (1), solid-liquid separation obtains is collected, in 60-100 DEG C, vacuum tightness carry out under being the pressure of 0.06-0.1atm underpressure distillation concentrate, obtain formic acid and acetic acid vapor, and concentration is the 8-10 concentrated solution doubly of original liquid, and by the formic acid that distills out and acetic acid vapor condensing reflux in the reactor of step (1), for the acidolysis of step (1);
(3) by the concentrated solution thin up of gained in step (2), the mass ratio of described auxiliary agent and described concentrated solution is 3: 1, control 60-70 DEG C is stirred 0.5-1h, and carry out third time solid-liquid separation, the solid obtained adds water (mass ratio of water and described solid is 4: 1), and after 75-85 DEG C of stirring 2-3h carries out washing de-esterifying, obtain required xylogen;
After carrying out quadratic acid hydrolysis treatment by the corn cob raw material that aforesaid method is new to 600g, finally obtain 1.626kg hydrolytic residue (water ratio is about 84.61%), slag content of lignin is 29.94%, and lignin extraction rate is 55.53%.Obtain finished product xylogen 98g, xylogen moisture is 39%, and the productive rate of xylogen is 40.94%.
The formula of xylogen yield is as follows:
(lignin quality × (1-xylogen moisture))/content of xylogen (in corn cob quality × (the 1-corn cob moisture) corn cob) × 100%.
Embodiment 6
In the present embodiment, first corn cob (mass component forms: moisture 15.86%, Mierocrystalline cellulose 31.72%, hemicellulose 37.56%, xylogen 30.72%) is smashed, washing dedusting with water and being crushed to particle diameter is 0.5-20cm, preferred 0.5-5cm.
The comprehensive utilization process of lignocellulose biomass described in the present embodiment, comprises the steps:
(1) by after biomass material comminution pretreatment, use containing concentration be 30% formic acid and concentration be the acetic acid of 50% and the water of 20% organic acid solution to process after lignocellulose biomass carry out acid hydrolysis, control temperature of reaction 165 DEG C, reaction 10min, the mix acid liquor of described formic acid and acetic acid and the liquid-solid mass ratio of biomass material are 1: 20, and the reaction solution obtained is carried out first time solid-liquid separation;
The solid that above-mentioned separation obtains is added containing concentration be 30% formic acid and concentration be that the organic acid solution of the acetic acid of 50% and the water of 20% carries out acid elution, temperature is 60 ~ 80 DEG C, washing time 0.5 ~ 1h, and reaction solution is carried out second time solid-liquid separation;
(2) liquid that in step (1), solid-liquid separation obtains is collected, in 60-100 DEG C, vacuum tightness carry out under being the pressure of 0.06-0.1atm underpressure distillation concentrate, obtain formic acid and acetic acid vapor, and concentration is the concentrated solution of 8 ~ 10 times of original liquid, and by the formic acid that distills out and acetic acid vapor condensing reflux in the reactor of step (1), for the acidolysis of step (1);
(3) by the concentrated solution thin up of gained in step (2), the mass ratio of described auxiliary agent and described concentrated solution is 3: 1, control 60-70 DEG C is stirred 0.5-1h, and carry out third time solid-liquid separation, the solid obtained adds water (mass ratio of water and described solid is 4: 1), and after 75-85 DEG C of stirring 2-3h carries out washing de-esterifying, obtain required xylogen;
After carrying out quadratic acid hydrolysis treatment by the corn cob raw material that aforesaid method is new to 600g, finally obtain 2kg hydrolytic residue (water ratio is about 79.82%), slag content of lignin is 29.42%, and lignin extraction rate is 23.38%.Obtain finished product xylogen 40g, xylogen moisture is 43%, and the productive rate of xylogen is 14.7%.
The formula of xylogen yield is as follows:
(lignin quality × (1-xylogen moisture))/content of xylogen (in corn cob quality × (the 1-corn cob moisture) corn cob) × 100%.
Comparative example 1
The parameter of the operational path described in the present embodiment and each step is identical with embodiment 3, its difference is only in step (2), the liquid that in step (1), solid-liquid separation obtains will be collected, and this liquid circulation is inputed to the reaction kettle for reaction of step (1), and the process of repeating step (1), after repeating 3 these above-mentioned circulations, the liquid that step (2) is collected is carried out distillation and concentration, and the formic acid obtained and acetic acid steam machine concentrated solution carry out subsequent disposal according to the treatment process of step (3) and condition again.
After carrying out quadratic acid hydrolysis treatment by the corn cob raw material that aforesaid method is new to 600g, finally obtain 1.3kg hydrolytic residue (water ratio is about 81%), slag content of lignin is 23.1%, and the extraction yield of xylogen is 66.4%.Finished product xylogen is 193g, and xylogen moisture is 48%, and xylogen yield is 59.1%.
Comparative example 2
The parameter of the operational path described in the present embodiment and each step is identical with embodiment 3, after its difference is only step (2), by the direct thin up of liquid collected, separate out to greatest extent to make xylogen wherein, the mass ratio of amount of water and concentrated solution reaches 60 ~ 70: 1, and control 60-70 DEG C is stirred 0.5-1h, and carry out third time solid-liquid separation, the solid obtained adds water (mass ratio of water and described solid is 3: 1), and after 75-80 DEG C of stirring 2-3h carries out washing de-esterifying, obtain required xylogen; And the liquid deviate from after xylogen solid is carried out underpressure distillation, distill out formic acid and acetic acid steam, after condensation, be back to the acidolysis for step (1) in the reactor of step (1).
After carrying out quadratic acid hydrolysis treatment by the corn cob raw material that aforesaid method is new to 600g, finally obtain 0.963kg hydrolytic residue (water ratio is about 77.59%), slag content of lignin is 20.18%, and lignin extraction rate is 74.34%.Obtain finished product xylogen 202g, xylogen moisture is 43%, and the productive rate of xylogen is 68.14%.
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 (1)
1. from lignocellulose biomass, extract a technique for xylogen, it is characterized in that, comprise the steps:
(1) by after biomass material comminution pretreatment, use the organic acid solution be made up of formic acid and acetic acid to carry out acidolysis to lignocellulose biomass, controlling temperature of reaction is 135 DEG C, reaction 80min, and the reaction solution obtained is carried out first time solid-liquid separation; The solid-liquid mass ratio of described organic acid solution and biomass material is 1:8;
In described organic acid solution, the concentration of described formic acid is 70%, the concentration 25% of acetic acid, and surplus is water;
In the solid that first time solid-liquid separation obtains, add formic acid and acetic acid carries out pickling, temperature is 60-80 DEG C, washing time 0.5-1h, and reaction solution is carried out second time solid-liquid separation; Concentration and the solid-to-liquid ratio of the concentration of the formic acid that described acid pickling step adopts and acetic acid and solid-to-liquid ratio and formic acid in organic acid solution described in described hydrolysis step and acetic acid are identical;
(2) collect the liquid that in step (1), solid-liquid separation obtains, in 70-90 DEG C, vacuum tightness carries out underpressure distillation and concentrates under being the pressure of 0.07-0.1atm, obtain formic acid and acetic acid steam and concentrated solution; 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 acidolysis of step (1); Described enrichment step by liquid concentration to 5-6 doubly;
(3) concentrated solution of gained in step (2) is added auxiliary agent dilution, the weight ratio of described auxiliary agent and described concentrated solution is 3:1,65-70 DEG C and stirs 0.5-1h, and carries out solid-liquid separation, the solid obtained obtains required xylogen after carrying out the process of washing de-esterifying; Wherein, described auxiliary agent is water; In water-washing step, the mass ratio of water and described solid is 4:1, and stirs 2-3h in 75-80 DEG C.
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| CN106676206B (en) * | 2016-12-27 | 2021-04-20 | 齐鲁工业大学 | Method for separating high-purity cellulose, lignin and sugar from lignocellulose by organic solvent-water combined treatment |
| CN109438724A (en) * | 2018-11-27 | 2019-03-08 | 浙江华康药业股份有限公司 | The method and its application of lignin in a kind of extraction lignocellulosic |
| CN112080015B (en) * | 2020-09-22 | 2022-06-03 | 南京林业大学 | High-glycosyl high-acylation high-condensation lignin and preparation method and application thereof |
| CN113249995B (en) * | 2021-05-20 | 2023-07-04 | 青岛大学 | Clean and efficient separation method for biomass cellulose single fiber and lignin |
| CN113736831A (en) * | 2021-09-28 | 2021-12-03 | 西华大学 | Method for processing edible fungus dregs and application thereof |
| CN114920951B (en) * | 2022-05-18 | 2023-05-26 | 湖南金昌生物技术有限公司 | Extraction method of light lignin in oil tea meal and application of light lignin in sunscreen cream |
| CN115819796A (en) * | 2022-12-29 | 2023-03-21 | 浙江科技学院 | Method for efficiently separating organic acid lignin |
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