CN103030815B - Comprehensive utilization technology of biomass raw materials - Google Patents
Comprehensive utilization technology of biomass raw materials Download PDFInfo
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Abstract
The invention relates to a method of comprehensively utilizing biomass raw materials, in particular to a method of comprehensively utilizing cellulose, hemicellulose and lignin in the biomass raw materials. The method comprises the steps that mixed organic acid of formic acid and acetic acid is utilized to boil the biomass raw materials by the catalytic action of hydrogen peroxide; and cellulose, lignin and hemicellulose are extracted respectively. The obtained cellulose is high in purity and can be used in the textile industry; and the comprehensive and stable proceeding of three routes improves extraction rates of the three products.
Description
Technical field
The present invention relates to a kind of method fully utilizing biomass material, specifically a kind ofly extract Mierocrystalline cellulose in biomass material, hemicellulose and xylogen and the method for further co-producing bio carbon.
Background technology
Biomass material 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 biomass material total amount that the earth is generated by photosynthesis is every year more than 2,000 hundred million tons, and therefore biomass material is renewable resources abundant, the most cheap on the earth.
Mierocrystalline cellulose is the main component of plant cell wall.The whole world, for the Mierocrystalline cellulose of papermaking of weaving, reaches 8,000,000 tons every year.In addition, raw material is done with the Mierocrystalline cellulose of separation and purification, artificial silk can be manufactured, cellulose film and the ether derivative such as the ester derivative such as nitric ether, acetic ester and methylcellulose gum, ethyl cellulose, Xylo-Mucine, for aspects such as petroleum drilling, food, ceramic glaze, daily use chemicals, synthesis of detergent, graphite product, pencil manufacture, battery, coating, building materials, decoration, mosquito-repellent incense, tobacco, papermaking, rubber, agricultural, tackiness agent, plastics, explosive, electrician and Scientific Research Equipments.
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.
Furfural, have another name called furtural, it is by the double bond of two on furan nucleus and an aldehyde radical, the chemical structure of this uniqueness, can make that it is oxidized, hydrogenation, chlorination, the reaction such as nitrated and condensation, and then generate a lot of Chemicals, so be widely used in multiple production fields such as agricultural chemicals, medicine, petrochemical industry, foodstuff additive and casting.Furfural is the vegetable fibre being rich in piperylene, and if corn cob, maize straw, straw, bagasse, cotton seed hulls, straw etc. are raw material production, its principle is that in vegetable fibre, first piperylene is hydrolyzed into pentose, and then dehydration of pentoses generates furfural.
The producing and manufacturing technique of furfural mainly contains single stage method and two step method in the world.Single stage method is that pentosan hydralysis and the reaction of dehydration of pentoses generation two, furfural once complete in same reactor; The main drawback that single stage method exists is that steam consumption is large, and furaldehyde yield is low, produces a large amount of liquid and waste slag produced etc.To be process that pentosan hydralysis in raw material and dehydration of pentoses generate furfural be two-step approach carries out at least two different reactors.Than single stage method, two step method overcomes the difficult problems such as existing furfural production feed stock conversion is low, generation processing wastewater is difficult to improvement, furfural dregs utility value is low.Along with the development of furfurol industry, and the raising of raw material requirements of comprehensive utilization, development two-step approach production technique, the Mierocrystalline cellulose in separate raw materials and hemicellulose are also used respectively, are the inevitable development trend of furfurol industry.
At present, mainly use boiling to propose hemicellulose to the extraction of three kinds of main components in biomass material, to be proposed by alkaline hydrolysis xylogen, remaining Mierocrystalline cellulose generated by cellulase again needed for the target product such as ethanol.But whole processing step is loaded down with trivial details, period will through the Decomposition of boiling and alkaline hydrolysis, also can product needed for loss to a certain degree, therefore select suitable technique under the prerequisite not destroying Mierocrystalline cellulose, hemicellulose and xylogen vigor, to greatest extent three be separated and extract the maximum focus having become this technical study.
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 mixes Posterior circle for the first step treating processes with the washing black liquid obtained; Then the mixing black liquor recycling at least 3 times is carried out organic acid, lignin products and syrup solution to reclaim.The black liquor of collection is carried out flash distillation or evaporation, obtain organic acid and concentrated black liquor, the water adding 2-10 times of volume in black liquor obtains lignin products and syrup solution, and the organic acid reclaimed then refluxes for the first step process, thus realizes the higher value application of lignocellulose raw material.But also there is following shortcoming in this patent: 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, need to add sulfuric acid in reaction process and carry out catalysis, inevitably make sulfur-bearing in the follow-up xylogen obtained; 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, collect pretreatment fluid and washings in due to be dissolved with a large amount of hemicellulose boiling generate pentose, and pentose is along with can constantly contact with organic acid in mixed solution repeatedly working cycle, there is esterification and generate ester class, this patent is for the purpose of the comprehensive utilization of biomass material, therefore whether whole piece technique can be obtained pentose separately and be paid no attention to, but for for be separated and to obtain for the purpose of pentose technique, this technique is also inapplicable; 5, 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; 6, as can be seen from specification sheets, in this technique, cellulosic extraction yield is only 38-55%, lignin extraction rate is 6-16%, and the extraction yield of whole technique is relatively low; The cellulose purity adopting this technique to extract is low, can not meet textile applications.
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.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 and pentose is not paid attention to, , although therefore this technique is by Mierocrystalline cellulose extraction and application from biomass material, but can not Mierocrystalline cellulose be realized, xylogen is separated with hemicellulose, and cellulose purity is low in the paper pulp adopting this technique to obtain, papermaking can only be used for, higher industrial requirements can not be met.
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.Although this patent in a process line by Mierocrystalline cellulose, hemicellulose and xylogen are separated, 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, in the step of its 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, highly purified Mierocrystalline cellulose is extracted for comprehensive extraction three kinds of materials and there is no directive function.
Summary of the invention
For this reason, technical problem to be solved by this invention is the integrated extraction technique route of biomass material in prior art, the problem that each component yield is low, purity is low obtained, so provide a kind of can the comprehensive utilization process of high efficiency separation lignin, Mierocrystalline cellulose and half fiber by rational parameter adjustment;
For solving the problems of the technologies described above, the comprehensive utilization process of 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 raw material, control boiling temperature 80-145 DEG C, solid-liquid mass ratio is 1:5-1:25, reaction times 10-60min, and the reaction solution obtained is carried out first time solid-liquid separation; In described organic acid solution, total acid is dense is 60-95%, and the mass ratio of described acetic acid and formic acid is 1:1-1:15, and surplus is water; Hydrogen peroxide accounts for the 1-8% of biomass material;
(2) described first time solid of obtaining of solid-liquid separation is collected, under the katalysis of hydrogen peroxide, the mix acid liquor adopting formic acid, acetic acid to be formed carries out pickling to described solid, control pickling temperature 20-60 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reaction solution obtained is carried out second time solid-liquid separation; Hydrogen peroxide accounts for the 1-3% of biomass material, and the total acid of described mix acid liquor is dense is 75-95%, and the mass ratio of acetic acid and formic acid is 1:1-1:15;
(3) collect the solid that described second time solid-liquid separation obtains, and wash, control washing temperature is 60-90 DEG C, and starching dense is 1-10%, and the washing slurry obtained is carried out third time solid-liquid separation;
(4) collect described third time solid of obtaining of solid-liquid separation screening obtains screened stock Mierocrystalline cellulose, described screened stock Mierocrystalline cellulose obtains required Mierocrystalline cellulose after bleaching;
(5) collect step first time and the liquid that obtains of second time solid-liquid separation, under 110-160 DEG C, 301-701kpa, carry out evaporation obtain formic acid and acetic acid steam and concentrated solution, the solids content of described concentrated solution is 60wt%-90wt%;
(6) concentrated solution of gained in step (5) is added organic solvent, stirs, and carry out the 4th solid-liquid separation, wherein, described organic solvent add quality be the 1-10 of described concentrated solution quality doubly;
(7) the solid thin up obtained after collecting the 4th solid-liquid separation stirs, and the solid obtained after carrying out the 5th solid-liquid separation is required xylogen through washing;
(8), after described 5th solid-liquid separation, the liquid obtained is after dehydration carburizing reagent, and carry out the 6th solid-liquid separation, the solid obtained is biological carbon, and the further rectifying of the liquid obtained obtains finished product furfural.
In the comprehensive utilization process of biomass material, described dehydration carburizing reagent, control temperature of reaction is 170-220 DEG C, reaction times 90-300min, and adding acid saline catalyst, the consumption of described acid saline catalyst is the 0.05wt%-0.5wt% of the liquid mass that the 5th time solid-liquid separation obtains.
In the comprehensive utilization process of biomass material, described dehydration carburizing reagent, control temperature of reaction is 170-190 DEG C, reaction times 90-180min.
In the comprehensive utilization process of biomass material, described acid saline catalyst is hydrosulfate, supercarbonate, hydrophosphate and dihydrogen phosphate.。
In the comprehensive utilization process of biomass material, described bleaching comprises: alkaline purification, and described alkali consumption accounts for the 1-6% of described screened stock Mierocrystalline cellulose quality, and temperature is 50-100 DEG C, and extraction times 0.5-4h starches dense 5-15%; Sequestrant pre-treatment, the quality of described sequestrant accounts for the 0.1-3% of described screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 50-80 DEG C, time 0.5-2h, starches dense 4-7%; Alkaline hydrogen peroxide bleaching, the quality of alkaline hydrogen peroxide accounts for the 3-6% of described screened stock Mierocrystalline cellulose quality, and pH value controls between 10-12, temperature 70-120 DEG C, bleaching time 1-6h, starches dense 5-20%; And acid treatment, the quality of described acid accounts for the 1%-6% of described screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 20-45 DEG C, time 0.5-3h, starches dense 3-6%.
Preferably, in the step of described alkaline purification, described alkali consumption accounts for the 2-5% of described screened stock Mierocrystalline cellulose quality, and temperature is 85-95 DEG C, and extraction times 1-3h starches dense 6-12%; The alkali reagent that described alkaline purification process is selected is sodium hydroxide and/or potassium hydroxide; State in the pretreated step of sequestrant, the quality of described sequestrant accounts for the 0.1-0.5% of described screened stock Mierocrystalline cellulose quality, temperature 50-65 DEG C, time 1.5-2h; In described sequestrant preprocessing process, the sequestrant selected is one or more in edta edta, diethyl pentetic acid DTPA, Sodium hexametaphosphate 99; In the step of described alkaline hydrogen peroxide bleaching, temperature 80-100 DEG C, bleaching time 2-4h, starch dense 5-10%; In described acid-treated step, sour consumption 2-3, temperature 30-45 DEG C, time 1.5-3h; The sour reagent that described acid treatment adopts is one or more in sulfuric acid, hydrochloric acid or nitric acid.
Preferably, also comprise in described step (5) and will the formic acid and acetic acid steam condensation that obtain be evaporated, and be back in the reactor of step (1), for the step of the boiling of step (1).
Preferably, also comprise liquid third time solid-liquid separation obtained in described step (3) and carry out water acid rectifying, the formic acid obtained and the mix acid liquor of acetic acid are back in the reactor of step (1), for the step of the boiling of step (1), and using the Water circulation that obtains in step (3) as washing water.
Preferably, the liquid also comprised the 4th time solid-liquid separation obtains in described step (6) is purified, obtaining concentration is that the purification liquid of 5-10% is back to step (6) as organic solvent, and the impurity after described purification mixes with the liquid phase that in described step (8), the 5th time solid-liquid separation obtains.
Preferably, in described step (1), solid-liquid mass ratio is 1:8-1:12, temperature of reaction 120-145 DEG C, reaction times 20-40min; The total acid of described organic acid solution is dense is 70-90%, and the mass ratio of acetic acid and formic acid is 1:1-1:8, and the quality adding hydrogen peroxide accounts for the 1-6% of biomass material quality.
Preferably, in described step (2), solid-liquid mass ratio is 1:8-1:10.
Preferably, in described step (3), starching dense is 4-6%; The water washing process of described step (3) is adverse current water washing process.
Preferably, described organic solvent add quality be the 2-5 of described concentrated solution quality doubly; Described organic solvent is ether, sherwood oil, methyl tertiary butyl ether, tetrabutyl urea or tri-tert amine.
Preferably, described Mierocrystalline cellulose is dissolving pulp and/or industrial fiber element.
Described biomass material is one or more in the wooden classes such as reed, beanstalk stalk, wheat stalk, straw, maize straw, melon seed cases, bamboo chip, melon seeds bar or grass as raw material.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, the first time of collection and the liquid that obtains of second time solid-liquid separation are directly carried out evaporation and obtain formic acid, acetic acid vapor by technique of the present invention, and be directly back to after making its condensation in the cooking reaction of the first step for recycling, and re-use as raw material due to formic acid and acetic acid, higher to the boiling efficiency of biomass, for the technique utilizing the cooking liquor after boiling 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, after the technique the first step of the present invention boiling and the pentose solution collected after acid elution directly evaporate, evaporate formic acid and acetic acid, can be used for the circulation of raw material on the one hand, also reduce the acid content in pentose solution simultaneously as far as possible, avoid esterification occurs, retain boiling to greatest extent and obtain pentose solution;
3, digestion process of the present invention carries out in airtight reaction vessel, because the part of formic acid, acetic acid and hydrogen peroxide is evaporated, makes to have certain pressure in container, thus shortens the cooking time of raw material, decrease cellulosic destruction.
4, process selection formic acid of the present invention, the common boiling biomass material of acetic acid; formic acid is as a kind of strong organic acid; urge the xylogen done in degraded raw material; alpha-cellulose in Mierocrystalline cellulose can be destroyed owing to being used alone formic acid; not only protect alpha-cellulose be not destroyed so add appropriate acetic acid; and the organic solvent dissolution lignin molecule utilizing formic acid and acetic acid to be formed; also utilize its acid boiling hemicellulose wherein, and with this by Mierocrystalline cellulose, hemicellulose and lignin separation.
5, adding hydrogen peroxide in cooking liquor of the present invention is catalyzer, makes the xylogen of biomass material middle-shallow layer and hemicellulose and HO
+ionic reaction, is constantly dissolved, and HO
+little on cellulosic impact, after for some time, HO
+ion consumption is complete, H
+the activity of ion increases greatly, makes hemicellulose and be soluble in sour xylogen to remove rapidly.Thus improve the extraction yield of xylogen.
5, after first time boiling obtains Mierocrystalline cellulose, continue to adopt the organic acid solution of formic acid, acetic acid and hydrogen peroxide composition to carry out pickling to Mierocrystalline cellulose, on the one hand the hemicellulose of Mierocrystalline cellulose internal residual and xylogen are decomposed and stripping, ensure cellulosic purity simultaneously;
6, before adding auxiliary agent precipitation xylogen, formic acid and acetic acid is evaporated, 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, ensure with the auxiliary agent of minimum dose, xylogen all to be separated out, energy efficient;
7, the liquid that solid-liquid separation obtains by this processing step carries out evaporating and purify and to dissolve xylogen wherein and pentose solution when greatly reducing direct reuse, improves the purity of xylogen.
8, the auxiliary agent added in concentrated solution, is a kind of and formic acid dissolves each other but low Polar adjuvants immiscible with water, and after adding described auxiliary agent, the lignin in concentrated solution is separated out together with wood sugar, and the lignin that recycling water is separated with wood sugar obtains highly purified lignin respectively.
9, the reaction times of described dehydration carburizing reagent is longer, and ensure the transformation efficiency of furfural, the present invention produces in the process of furfural, dehydration carburizing reagent is while preparing furfural, also obtain by product biological carbon, not only reduce environmental pollution, more income can also be created for furfural enterprise.
10, furfural is heat-sensitive substance, easy generation is polymerized and is deposited on equipment, not only affects the efficiency of equipment in the course of time, also affects the productive rate of furfural, monocalcium phosphate in acid catalysts of the present invention, potassium primary phosphate can play the effect of inhibition, effectively can prevent the polymerization of furfural.
11, the corrodibility of acid catalysts of the present invention to equipment is little, and common stainless steel can be used to carry out producing apparatus, and device fabrication cost is low, and plant investment is little.
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 this application, apart from outside specified otherwise, percentage composition used all represents mass percentage, i.e. " % " expression " wt% "; In described organic acid solution or mix acid liquor except a certain amount of formic acid, acetic acid, surplus is water, the total acid dense nail acid of organic acid solution and the total mass of acetic acid account for the percentage ratio of described organic acid solution quality, the formic acid added in the total acid dense finger acid pickling step of mix acid liquor and the total mass of acetic acid account for the percentage ratio of described mix acid liquor quality
Slurry described in each step is dense=this step in solid quality/this step in the quality and × 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.
The measuring brightness method of cellulose/paper slurry is with reference to FZ/T500107-1998, alpha-cellulose content measuring method is with reference to FZ/T500104-1998, polymerization degree measurement adopts Fz/T500103-1998 method, determination of ash adopts FZ/T500105-1998 method, inhale base number and measure employing FZ/T500109-1998 method, the measuring method GB/T3332-2004 of beating degree.
In biological carbon, the assay of fixed carbon, ash content and moisture adopts proximate analysis of coal GB/T212-2008 to measure, the mensuration of sulphur content adopts the measuring method GB/T214-2007 of full content of Sulphur in coal to measure, and the heat output determining method of biological carbon adopts the heat output determining method GB/T213-2008 of coal.Solids content adopts halogen fast tester for water content (plum Teller-Tuo benefit, model: HB43-S) to measure at 115 DEG C.The concentration of pentose or xylose solution adopts high-efficient liquid phase color instrument (model: U-3000, producer: ThermoFisher Dai An company) to measure.
In each embodiment,
Quality/(the solids content) ╳ 100% of amount × this liquid of the liquid of participation reaction of biological carbon yield=biological carbon
The Zhi Liang ╳ 100% of cellulosic productive rate=cellulosic quality/raw material.
Furfural content % in furfural yield=furfural stock solution quality × liquid/(liquid glucose quality × liquid glucose furfural content %) × 100%.
Extraction yield %=pentose solution quality × pentose sugar concentration/(in raw materials quality × raw material hemicellulose level) × 100% of hemicellulose;
Lignin extraction rate=lignin quality/the content of xylogen (in the raw materials quality × raw material) × 100%.
Embodiment 1
In the present embodiment, described biomass material is reed (mass component forms: Mierocrystalline cellulose 49.5%, hemicellulose level 22.7%, xylogen 18.9%), and first smashed by reed raw material, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The present embodiment, from the comprehensive utilization process of described biomass material, comprises the steps:
(1) by after biomass material comminution pretreatment, total acid concentration is used to be that the formic acid of 60% and the organic acid solution of acetic acid carry out boiling to the biomass material 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 biomass material, add the hydrogen peroxide (H accounting for biomass material 1%
2o
2) as catalyzer, controlling temperature of reaction 80 DEG C, reaction 10min, solid-liquid mass ratio is 1:5, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that first time solid-liquid separation obtains being added total acid concentration is that the formic acid of 75% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for biomass material 1% in the organic acid solution of 75%
2o
2) as catalyzer and the mass ratio of acetic acid and formic acid is 1:1, control temperature is 20 DEG C, washing time 1h, and 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 110 DEG C, underpressure distillation is carried out under 301kpa, the steam and the solids content that obtain formic acid and acetic acid are 60% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that described second time solid-liquid separation obtains, and wash, controlling washing temperature is 60 DEG C, and starching dense is 4%, and the washing slurry obtained is carried out third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes with water with water in step (4);
(6) solid that collection third time solid-liquid separation obtains also screens and obtains screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose obtained is carried out bleaching and obtains Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose adopting the method for the present embodiment to obtain after measured is 93%ISO, alpha-cellulose content 93%, ash content 0.02%, the polymerization degree 400, inhales base number 650, productive rate 40%.
(7) concentrated solution of gained in step (3) is added the organic solvent ether accounting for concentrated solution quality 2 times to carry out analysing xylogen, add the polarity that organic solvent ether that low polarity and water dissolves each other can reduce whole system, and xylogen is separated out, carry out the 4th solid-liquid separation, the described liquid that 4th time solid-liquid separation obtains is purified, obtain concentration be 5% purification liquid be back to step (7) as organic solvent.
(8) the solid thin up (the mass ratio 1:1 of solid and water) that obtains of described 4th solid-liquid separation, and carry out the 5th solid-liquid separation, the solid obtained is xylogen, and the extraction yield of its xylogen is 90%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 85%, the impurity phase that described pentose solution obtains after purifying with step (7) mixes, under the katalysis of sodium pyrosulfate, at 170 DEG C, carry out dehydration carburizing reagent 90min, the consumption of sodium pyrosulfate is 0.05% of pentose solution quality, after completion of the reaction, reaction solution carries out the 5th solid-liquid separation, and the liquid obtained is furfural stoste.If the purer furfural that need obtain, only need adopt the ordinary method of refining furfural in prior art, furfural stoste is refined by distillation tower.The yield that reaction terminates rear furfural is 65%.
The solid obtained after described 5th solid-liquid separation is biological carbon, and its yield is 50%, and the fixed carbon content of described biological carbon is 56% after measured, ash oontent 0.12%, sulphur content 0.1%, moisture 41%, thermal value 4126J/g.
Bleaching described in the present embodiment comprises the following steps:
(1) first the screened stock Mierocrystalline cellulose through screening is carried out alkaline purification with the sodium hydroxide accounting for screened stock Mierocrystalline cellulose quality 1%, control temperature is 50 DEG C, and extraction times 0.5h starches dense 5%;
(2) after alkaline purification, carry out sequestrant pre-treatment, in the present embodiment, sequestrant adopts EDTA, and its consumption accounts for screened stock cellulosic 0.1%, and pH value controls between 2-4, temperature 50 C, and time 0.5h starches dense 4%;
(3) after EDTA pre-treatment, carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is screened stock cellulosic 3%, and by sodium hydroxide adjust ph between 10-12, temperature 70 C, bleaching time 1h, starches dense 5%; With
(4) utilize hydrochloric acid to carry out acid treatment, hydrochloric acid consumption is screened stock cellulosic 6%, and pH value controls between 2-4, temperature 20 DEG C, and time 0.5h, starches dense 3%.
Embodiment 2
In the present embodiment, first straw (mass component forms: mass component forms: Mierocrystalline cellulose 35.8%, hemicellulose 28.6%, xylogen 14.3%) is smashed, being crushed to particle diameter is 2cm ~ 10cm.
The present embodiment, from the comprehensive utilization process of described straw, comprises the steps:
(1) by after straw comminution pretreatment, total acid concentration is used to be that the formic acid of 65% 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 1:6, and before adding straw raw material, add the hydrogen peroxide (H accounting for straw raw material 2%
2o
2) as catalyzer, controlling temperature of reaction 100 DEG C, reaction 20min, solid-liquid mass ratio is 1:8, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that first time solid-liquid separation obtains being added total acid concentration is that the formic acid of 78% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for straw raw material 2% in the organic acid solution of 78%
2o
2) as catalyzer and the mass ratio of acetic acid and formic acid is 1:3, control temperature is 25 DEG C, washing time 50min, and 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, at 130 DEG C, underpressure distillation is carried out under 580kpa, the steam and the solids content that obtain formic acid and acetic acid are 70% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that second time solid-liquid separation obtains, and wash, controlling washing temperature is 65 DEG C, and starching dense is 5%, and the washing slurry obtained is carried out third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes with water with water in step (5);
(6) solid that collection third time solid-liquid separation obtains also screens and obtains screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose obtained is carried out bleaching and obtains Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose adopting the method for the present embodiment to obtain after measured is 92%ISO, alpha-cellulose content 92.5%, ash content 0.04%, the polymerization degree 450, inhales base number 660, productive rate 23%.
(7) concentrated solution of gained in step (3) is added the organic solvent ether accounting for concentrated solution quality 5 times, and carry out the 4th solid-liquid separation, the described liquid that 4th time solid-liquid separation obtains is purified, obtain concentration be 6% purification liquid be back to step (4) as organic solvent.
(8) the solid thin up (the mass ratio 1:2 of solid and water) that obtains of described 4th solid-liquid separation, and carry out the 5th solid-liquid separation, the solid obtained is xylogen, and the extraction yield of its xylogen is 91%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 85%, the impurity phase that described pentose solution obtains after purifying with step (7) is middle mixes, under the katalysis of sodium pyrosulfate, at 180 DEG C, carry out dehydration carburizing reagent 120min, the consumption of sodium pyrosulfate is 0.45% of pentose solution quality, after completion of the reaction, reaction solution carries out the 6th solid-liquid separation, and the liquid obtained is furfural stoste.If the purer furfural that need obtain, only need adopt the ordinary method of refining furfural in prior art, furfural stoste is refined by distillation tower.The yield that reaction terminates rear furfural is 63%.
The solid obtained after described 6th solid-liquid separation is biological carbon, and its yield is 52%, and the fixed carbon content of described biological carbon is 57% after measured, ash oontent 0.13%, sulphur content 0.05%, moisture 42%, thermal value 4762J/g.
Bleaching described in the present embodiment comprises the following steps:
(1) first utilize the potassium hydroxide accounting for screened stock Mierocrystalline cellulose 2% to carry out alkaline purification the screened stock Mierocrystalline cellulose through screening, control temperature is 70 DEG C, and extraction times 1h starches dense 6%;
(2) after alkaline purification, carry out sequestrant pre-treatment, in the present embodiment, sequestrant adopts DTPA(diethyl pentetic acid, and its consumption accounts for 0.5% of screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 65 DEG C, and time 1h, starches dense 6%;
(3) after DTPA pre-treatment, carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is 4% of screened stock Mierocrystalline cellulose quality, and by sodium hydroxide adjust ph between 10-12, temperature 80 DEG C, bleaching time 2h, starches dense 10%; With
(4) utilize sulfuric acid to carry out acid treatment, in this step, the consumption of sulfuric acid is 2% sulfuric acid of screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 30 DEG C, and time 1h, starches dense 4%.
Embodiment 3
In the present embodiment, described biomass material is bamboo chip (mass component forms: Mierocrystalline cellulose 47.3%, hemicellulose 24.6%, xylogen 25.8%), and first will smash, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The comprehensive utilization process of bamboo chip described in the present embodiment, comprises the steps:
(1) by after bamboo chip 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 bamboo chip after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:8, and before adding straw raw material, add the hydrogen peroxide (H accounting for straw raw material 4%
2o
2) as catalyzer, controlling temperature of reaction 120 DEG C, reaction 30min, solid-liquid mass ratio is 1:12, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that first time solid-liquid separation obtains being added total acid concentration is that the formic acid of 80% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 3% in the organic acid solution of 80%
2o
2) as catalyzer and the mass ratio of acetic acid and formic acid is 1:6, control temperature is 40 DEG C, washing time 80min, the solid-liquid mass ratio of the solid that the organic acid solution of described 95% obtains with first time solid-liquid separation 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, at 150 DEG C, underpressure distillation is carried out under 640kpa, 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) solid that collection second time solid-liquid separation obtains also is washed, and controlling washing temperature is 75 DEG C, and starching dense is 6%, and the washing slurry obtained is carried out third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes with water with water in step (4);
(6) solid that collection third time solid-liquid separation obtains also screens and obtains screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose obtained is carried out bleaching process and obtains Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose adopting the method for the present embodiment to obtain after measured is 91.5%ISO, alpha-cellulose content 93.2%, ash content 0.03%, the polymerization degree 550, inhales base number 720, productive rate 41%.
(7) concentrated solution of gained in step (3) is added the organic solvent tri-tert amine accounting for concentrated solution quality 3 times, and carry out the 4th solid-liquid separation, the described liquid that 4th time solid-liquid separation obtains is purified, obtain concentration be 8% purification liquid be back to step (7) as organic solvent.
(8) the solid thin up (the mass ratio 1:2 of solid and water) that obtains of described 4th solid-liquid separation, and carry out the 5th solid-liquid separation, the solid obtained is xylogen, and the extraction yield of its xylogen is 92%.。
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 90%, the impurity phase that described pentose solution obtains after purifying with described step (7) mixes, under the katalysis of sodium pyrosulfate, at 190 DEG C, carry out dehydration carburizing reagent 100min, the consumption of sodium pyrosulfate is 0.5% of pentose solution, after completion of the reaction, reaction solution carries out the 6th solid-liquid separation, and the liquid obtained is furfural stoste.If the purer furfural that need obtain, only need adopt the ordinary method of refining furfural in prior art, furfural stoste is refined by distillation tower.The yield that reaction terminates rear furfural is 65%.
The solid obtained after described 6th solid-liquid separation is biological carbon, and its yield is 55%, and the fixed carbon content of described biological carbon is 59.2% after measured, ash oontent 0.14%, sulphur content 0.06%, moisture 40.5%, and thermal value is 5230J/g.
Bleaching described in the present embodiment comprises the following steps:
(1) by through screening screened stock Mierocrystalline cellulose first utilize account for screened stock Mierocrystalline cellulose quality 3% potassium hydroxide carry out alkaline purification, control temperature is 85 DEG C, and extraction times 2h starches dense 8%;
(2) after alkaline purification, carry out sequestrant pre-treatment, in the present embodiment sequestrant adopt Sodium hexametaphosphate 99, its consumption account for screened stock Mierocrystalline cellulose quality 0.3%, pH value controls between 2-4, temperature 85 DEG C, and time 1.5h, starches dense 7%;
(3) after Sodium hexametaphosphate 99 pre-treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 5% of screened stock Mierocrystalline cellulose quality, and adopts sodium hydroxide adjust ph between 10-12, temperature 85 DEG C, and bleaching time 3h, starches dense 8%; With
(4) acid treatment, the acid adopted in this step is hydrochloric acid, and its consumption is 4% of screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 35 DEG C, and time 1.5h, starches dense 5%.
Embodiment 4
In the present embodiment, described biomass material is wheat straw (mass component forms: Mierocrystalline cellulose 40.5, hemicellulose 31.9%, xylogen 15.4%), and first will smash, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The present embodiment, from the comprehensive utilization process of described wheat straw, comprises the steps:
(1) by after wheat 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 bamboo chip 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 raw material, add the hydrogen peroxide (H accounting for wheat straw raw material 6%
2o
2) as catalyzer, controlling temperature of reaction 135 DEG C, reaction 40min, solid-liquid mass ratio is 1:10, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that first time solid-liquid separation obtains being added total acid concentration is that the formic acid of 84% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for wheat straw raw material 1.5% in the organic acid solution of 84%
2o
2) as catalyzer and the mass ratio of acetic acid and formic acid is 1:9, control temperature is 45 DEG C, washing time 1h, and solid-liquid mass ratio is 1:16, 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, at 120 DEG C, underpressure distillation is carried out under 390kpa, the steam and the solids content that obtain formic acid and acetic acid are 65% concentrated solution, and using in formic acid and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor;
(4) collect the solid that second time solid-liquid separation obtains, and wash, controlling washing temperature is 85 DEG C, and starching dense is 9%, and the washing slurry obtained is carried out third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes with water with water in step (4);
(6) solid that collection third time solid-liquid separation obtains also screens and obtains screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose obtained is carried out bleaching and obtains Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose adopting the method for the present embodiment to obtain after measured is 92.5%ISO, alpha-cellulose content 92.6%, ash content 0.16%, the polymerization degree 620, inhales base number 780, productive rate 32%.
(7) concentrated solution of gained in step (3) is added the organic solvent tetrabutyl urea accounting for concentrated solution quality 6 times, and carry out the 4th solid-liquid separation, the described liquid that 4th time solid-liquid separation obtains is purified, obtain concentration be 7% purification liquid be back to step (7) as organic solvent.
(8) the solid thin up (the mass ratio 1:3 of solid and water) that obtains of described 4th solid-liquid separation, and carry out the 5th solid-liquid separation, the solid obtained is xylogen, and the extraction yield of its xylogen is 88%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 95%, the impurity phase that described pentose solution obtains after purifying with described step (7) mixes, under the katalysis of sodium pyrosulfate, at 210 DEG C, carry out dehydration carburizing reagent 140min, the consumption of sodium pyrosulfate is 0.3% of pentose solution, after completion of the reaction, reaction solution carries out the 6th solid-liquid separation, and the liquid obtained is furfural stoste.If the purer furfural that need obtain, only need adopt the ordinary method of refining furfural in prior art, furfural stoste is refined by distillation tower.The yield that reaction terminates rear furfural is 64%.
The solid obtained after described 6th solid-liquid separation is biological carbon, and its yield is 54%, and the fixed carbon content of described biological carbon is 55.8% after measured, ash oontent 0.08%, sulphur content 0.08%, moisture 44%, thermal value 5012J/g.
Bleaching described in the present embodiment comprises the following steps:
(1) by through screening screened stock Mierocrystalline cellulose first utilize account for screened stock Mierocrystalline cellulose quality 5% sodium hydroxide carry out alkaline purification, control temperature is 90 DEG C, and extraction times 3h starches dense 10%;
(2) after alkaline purification, carry out sequestrant pre-treatment, in the present embodiment, sequestrant adopts Sodium hexametaphosphate 99, and its consumption accounts for 1% of screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 70 C, and time 130min starches dense 5%;
(3) after Sodium hexametaphosphate 99 pre-treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 6% of screened stock Mierocrystalline cellulose quality, and utilizes sodium hydroxide control ph between 10-12, temperature 95 DEG C, and bleaching time 4h, starches dense 12%;
(4) utilize nitric acid to carry out acid treatment, in this step, nitric acid dosage is 1% of screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 40 DEG C, and time 2h, starches dense 6%.
Embodiment 5
In the present embodiment, described biomass material is melon seeds bar (mass component forms: hemicellulose 31.91%, xylogen 23.94%, Mierocrystalline cellulose 44.15%), and first smashed by melon seeds bar, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The present embodiment, from the comprehensive utilization process of described melon seeds bar, comprises the steps:
(1) by after melon seeds bar 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 melon seeds bar after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:13, and before adding melon seeds bar raw material, add the hydrogen peroxide (H accounting for melon seeds bar raw material 7%
2o
2) as catalyzer, controlling temperature of reaction 140 DEG C, reaction 50min, the solid-liquid mass ratio of described organic acid solution and melon seeds bar raw material is 1:20, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that first time solid-liquid separation obtains being added total acid concentration is that the formic acid of 90% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for melon seeds bar raw material 2.5% in the organic acid solution of 90%
2o
2) as catalyzer and the mass ratio of acetic acid and formic acid is 1:10, control temperature is 50 DEG C, washing time 40min, and solid-liquid mass ratio is 1:12, 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, at 160 DEG C, underpressure distillation is carried out under 510kpa, 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) collect the solid that second time solid-liquid separation obtains, and wash, controlling washing temperature is 90 DEG C, and starching dense is 10%, and the washing slurry obtained is carried out third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes with water with water in step (4);
(6) solid that collection third time solid-liquid separation obtains also screens and obtains screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose obtained is carried out bleaching and obtains Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose adopting the method for the present embodiment to obtain after measured is 91%ISO, alpha-cellulose content 94%, ash content 0.08%, the polymerization degree 660, inhales base number 620, productive rate 33%.
(7) concentrated solution of gained in step (3) is added the organic solvent methyl tertiary butyl ether accounting for concentrated solution quality 8 times, and carry out the 4th solid-liquid separation, the described liquid that 4th time solid-liquid separation obtains is purified, obtain concentration be 9% purification liquid be back to step (7) as organic solvent.
(8) the solid thin up (the mass ratio 1:7 of solid and water) that obtains of described 4th solid-liquid separation, and carry out the 5th solid-liquid separation, the solid obtained is xylogen, and the extraction yield of its xylogen is 86.7%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 92%, the impurity phase that described pentose solution obtains after purifying with described step (7) mixes, under the katalysis of sodium pyrosulfate, at 220 DEG C, carry out dehydration carburizing reagent 180min, wherein sodium pyrosulfate consumption is 0.4% of pentose solution quality, after completion of the reaction, reaction solution carries out the 6th solid-liquid separation, and the liquid obtained is furfural stoste.If the purer furfural that need obtain, only need adopt the ordinary method of refining furfural in prior art, furfural stoste is refined by distillation tower.The yield that reaction terminates rear furfural is 60%.
The solid obtained after described 6th solid-liquid separation is biological carbon, and its yield is 56%, and the fixed carbon content of described biological carbon is 49.5% after measured, ash oontent 0.06%, sulphur content 0.05%, moisture 50%, thermal value 3900J/g.
Bleaching described in the present embodiment comprises the following steps:
(1) first utilize the sodium hydroxide accounting for screened stock Mierocrystalline cellulose 6% to carry out alkaline purification the screened stock Mierocrystalline cellulose through screening, control temperature is 95 DEG C, and extraction times 4h starches dense 13%;
(2) after alkaline purification, carry out sequestrant pre-treatment, in the present embodiment, sequestrant adopts EDTA ethylenediamine tetraacetic acid (EDTA), and its consumption accounts for screened stock cellulosic 2.5%, and pH value controls between 2-4, temperature 55 DEG C, and time 100min, starches dense 6.4%;
(3) after Sodium hexametaphosphate 99 pre-treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 3.5%, and by sodium hydroxide control ph between 10-12, temperature 100 DEG C, bleaching time 6h, starches dense 15%; With
(4) utilize sulfuric acid to carry out acid treatment, in this step, sulfuric acid dosage is screened stock cellulosic 3%,
Control ph is between 2-4, and temperature 45 C, time 3h, starches dense 5.5%.
Embodiment 6
In the present embodiment, described biomass material is cotton stem (mass component forms: hemicellulose 22.1%, xylogen 23.3%, Mierocrystalline cellulose 54.5%), and first smashed by cotton stem, washing dedusting with water and being crushed to particle diameter is 0.5-20cm.
The comprehensive utilization process of cotton stem described in the present embodiment, comprises the steps:
(1) by after cotton stem 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 cotton stem 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 raw material, add the hydrogen peroxide (H accounting for cotton stem raw material 8%
2o
2) as catalyzer, controlling temperature of reaction 130 DEG C, reaction 60min, solid-liquid mass ratio is 1:25, and the reaction solution obtained is carried out first time solid-liquid separation;
(2) solid that first time solid-liquid separation obtains being added total acid concentration is that the formic acid of 95% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 3% in the organic acid solution of 95%
2o
2) as catalyzer and the mass ratio of acetic acid and formic acid is 1:15, control temperature is 60 DEG C, washing time 20min, and 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, at 140 DEG C, underpressure distillation is carried out under 701kpa, 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) collect the solid that second time solid-liquid separation obtains, and wash, controlling washing temperature is 88 DEG C, and washing slurry is dense is 1%, and the washing slurry obtained is carried out third time solid-liquid separation;
(5) collect the liquid that solid-liquid separation for the third time obtains, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes with water with water in step (4);
(6) solid that collection third time solid-liquid separation obtains also screens and obtains screened stock Mierocrystalline cellulose, the screened stock Mierocrystalline cellulose obtained is carried out bleaching and obtains Mierocrystalline cellulose; Its whiteness of Mierocrystalline cellulose adopting the method for the present embodiment to obtain after measured is 90%ISO, alpha-cellulose content 94.5%, ash content 0.1%, the polymerization degree 700, inhales base number 780, productive rate 40%.
(7) concentrated solution of gained in step (3) is added the organic solvent sherwood oil of concentrated solution quality 9 times, and carry out the 4th solid-liquid separation, the described liquid that 4th time solid-liquid separation obtains is purified, and the purification liquid obtaining 10% is back to step (4) as organic solvent.
(8) the solid thin up (the mass ratio 1:5 of solid and water) that obtains of described 4th solid-liquid separation, and carry out the 5th solid-liquid separation, the solid obtained is xylogen, and the extraction yield of its xylogen is 85%.
The liquid that (9) the 5th times solid-liquid separation obtains is pentose solution, the extraction yield of its hemicellulose is 94%, described pentose solution mixes mutually with rear residual impurity of purifying in described step (7), under the katalysis of sodium pyrosulfate, at 200 DEG C, carry out dehydration carburizing reagent 300min, sodium pyrosulfate consumption is 0.35% of pentose solution, after completion of the reaction, reaction solution carries out the 6th solid-liquid separation, and the liquid obtained is furfural stoste.If the purer furfural that need obtain, only need adopt the ordinary method of refining furfural in prior art, furfural stoste is refined by distillation tower.The yield that reaction terminates rear furfural is 62%.
The solid obtained after described 6th solid-liquid separation is biological carbon, and its yield is 60%, and the fixed carbon content of described biological carbon is 57.2% after measured, ash oontent 0.09%, sulphur content 0.05%, moisture 42%, 4923J/g.
Bleaching described in the present embodiment comprises the following steps:
(1) first utilize the sodium hydroxide accounting for screened stock Mierocrystalline cellulose 4% to carry out alkaline purification the screened stock Mierocrystalline cellulose through screening, control temperature is 100 DEG C, and extraction times 3.5h starches dense 15%;
(2) after alkaline purification, carry out sequestrant pre-treatment, in the present embodiment, sequestrant adopts Sodium hexametaphosphate 99, and its consumption accounts for screened stock cellulosic 3%, and pH value controls between 2-4, temperature 60 C, and time 2h starches dense 5.5%;
(3) after Sodium hexametaphosphate 99 pre-treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is 4.5%, and controls between 10-12 by sodium hydroxide adjust ph, temperature 120 DEG C, and bleaching time 2.5h, starches dense 20%; With
(4) utilize sulfuric acid to carry out acid treatment, in this step, sulfuric acid dosage is screened stock cellulosic 5%, and pH value controls between 2-4, temperature 25 DEG C, and time 2.5h, starches dense 4.5%.
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 (13)
1. a comprehensive utilization process for biomass material, is characterized in that, 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 raw material, control boiling temperature 80-145 DEG C, solid-liquid mass ratio is 1:5-1:25, reaction times 10-60min, and the reaction solution obtained is carried out first time solid-liquid separation;
In described organic acid solution, total acid is dense is 60-95%, and the mass ratio of described acetic acid and formic acid is 1:1-1:15, and surplus is water;
Hydrogen peroxide accounts for the 1-8% of biomass material;
(2) described first time solid of obtaining of solid-liquid separation is collected, under the katalysis of hydrogen peroxide, the mix acid liquor adopting formic acid, acetic acid to be formed carries out pickling to described solid, control pickling temperature 20-60 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reaction solution obtained is carried out second time solid-liquid separation; Hydrogen peroxide accounts for the 1-3% of biomass material, and the total acid of described mix acid liquor is dense is 75-95%, and the mass ratio of acetic acid and formic acid is 1:1-1:15;
(3) collect the solid that described second time solid-liquid separation obtains, and wash, control washing temperature is 60-90 DEG C, and starching dense is 1-10%, and the washing slurry obtained is carried out third time solid-liquid separation;
(4) collect described third time solid of obtaining of solid-liquid separation screening obtains screened stock Mierocrystalline cellulose, described screened stock Mierocrystalline cellulose obtains required Mierocrystalline cellulose after bleaching;
(5) collect step first time and the liquid that obtains of second time solid-liquid separation, under 110-160 DEG C, 301-701kPa, carry out evaporation obtain formic acid and acetic acid steam and concentrated solution, the solids content of described concentrated solution is 60wt%-90wt%;
(6) concentrated solution of gained in step (5) is added organic solvent, stirs, and carry out the 4th solid-liquid separation, wherein, described organic solvent add quality be the 1-10 of described concentrated solution quality doubly;
(7) the solid thin up obtained after collecting the 4th solid-liquid separation stirs, and the solid obtained after carrying out the 5th solid-liquid separation is required xylogen through washing;
(8), after described 5th solid-liquid separation, the liquid obtained is after dehydration carburizing reagent, and carry out the 6th solid-liquid separation, the solid obtained is biological carbon, and the further rectifying of the liquid obtained obtains finished product furfural;
Described bleaching comprises:
Alkaline purification, described alkali consumption accounts for the 1-6% of described screened stock Mierocrystalline cellulose quality, and temperature is 50-100 DEG C, and extraction times 0.5-4h starches dense 5-15%;
Sequestrant pre-treatment, the quality of described sequestrant accounts for the 0.1-3% of described screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 50-80 DEG C, and time 0.5-2 h, starches dense 4-7%;
Alkaline hydrogen peroxide bleaching, the quality of alkaline hydrogen peroxide accounts for the 3-6% of described screened stock Mierocrystalline cellulose quality, and pH value controls between 10-12, temperature 70-120 DEG C, bleaching time 1-6h, starches dense 5-20%; With
Acid treatment, the quality of described acid accounts for the 1%-6% of described screened stock Mierocrystalline cellulose quality, and pH value controls between 2-4, temperature 20-45 DEG C, and time 0.5-3 h, starches dense 3-6%.
2. the comprehensive utilization process of biomass material according to claim 1, is characterized in that:
Described dehydration carburizing reagent, control temperature of reaction is 170-220
oc, reaction times 90-300min, and add acid saline catalyst, the consumption of described acid saline catalyst is the 0.05wt%-0.5wt% of the liquid mass that the 5th time solid-liquid separation obtains.
3. the comprehensive utilization process of biomass material according to claim 2, is characterized in that:
Described dehydration carburizing reagent, control temperature of reaction is 170-190
oc, reaction times 90-180min.
4. the comprehensive utilization process of biomass material according to claim 3, is characterized in that:
Described acid saline catalyst is hydrosulfate, supercarbonate, hydrophosphate and dihydrogen phosphate.。
5. the comprehensive utilization process of biomass material according to claim 4, is characterized in that:
In the step of described alkaline purification, described alkali consumption accounts for the 2-5% of described screened stock Mierocrystalline cellulose quality, and temperature is 85-95 DEG C, and extraction times 1-3h starches dense 6-12%;
The alkali reagent that described alkaline purification process is selected is sodium hydroxide and/or potassium hydroxide;
In the pretreated step of described sequestrant, the quality of described sequestrant accounts for the 0.1-0.5% of described screened stock Mierocrystalline cellulose quality, temperature 50-65 DEG C, time 1.5-2 h;
In described sequestrant preprocessing process, the sequestrant selected is one or more in edta edta, diethyl pentetic acid DTPA, Sodium hexametaphosphate 99;
In the step of described alkaline hydrogen peroxide bleaching, temperature 80-100 DEG C, bleaching time 2-4h, starch dense 5-10%;
In described acid-treated step, sour consumption 2-3, temperature 30-45 DEG C, time 1.5-3 h;
The sour reagent that described acid treatment adopts is one or more in sulfuric acid, hydrochloric acid or nitric acid.
6., according to the comprehensive utilization process of the arbitrary described biomass material of claim 1-5, it is characterized in that:
Also comprise in described step (5) and will the formic acid and acetic acid steam condensation that obtain be evaporated, and be back in the reactor of step (1), for the step of the boiling of step (1).
7. the comprehensive utilization process of biomass material according to claim 6, is characterized in that:
Also comprise liquid third time solid-liquid separation obtained in described step (3) and carry out water acid rectifying, the formic acid obtained and the mix acid liquor of acetic acid are back in the reactor of step (1), for the step of the boiling of step (1), and using the Water circulation that obtains in step (3) as washing water.
8. the comprehensive utilization process of biomass material according to claim 7, is characterized in that:
The liquid also comprised the 4th time solid-liquid separation obtains in described step (6) is purified, obtaining concentration is that the purification liquid of 5-10% is back to step (6) as organic solvent, and the impurity after described purification mixes with the liquid phase that in described step (8), the 5th time solid-liquid separation obtains.
9. the comprehensive utilization process of biomass material according to claim 8, is characterized in that:
In described step (1), solid-liquid mass ratio is 1:8-1:12, temperature of reaction 120-145 DEG C, reaction times 20-40min;
The total acid of described organic acid solution is dense is 70-90%, and the mass ratio of acetic acid and formic acid is 1:1-1:8, and the quality adding hydrogen peroxide accounts for the 1-6% of biomass material quality.
10., according to the comprehensive utilization process of the arbitrary described biomass material of claim 7-9, it is characterized in that:
In described step (2), solid-liquid mass ratio is 1:8-1:10.
The comprehensive utilization process of 11. biomass materials according to claim 10, is characterized in that:
In described step (3), starching dense is 4-6%; The water washing process of described step (3) is adverse current water washing process.
The comprehensive utilization process of 12. biomass materials according to claim 11, is characterized in that:
Described organic solvent add quality be the 2-5 of described concentrated solution quality doubly;
Described organic solvent is ether, sherwood oil, methyl tertiary butyl ether, tetrabutyl urea or tri-tert amine.
The comprehensive utilization process of 13. biomass materials according to claim 12, is characterized in that:
Described Mierocrystalline cellulose is dissolving pulp and/or industrial fiber element.
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| CN103806318A (en) * | 2014-01-16 | 2014-05-21 | 北京林业大学 | Method for extracting cellulose from furfural residues |
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