CN103103845B - Technologies for extracting cellulose from biomass raw material and preparing biochar - Google Patents
Technologies for extracting cellulose from biomass raw material and preparing biochar Download PDFInfo
- Publication number
- CN103103845B CN103103845B CN201210574918.8A CN201210574918A CN103103845B CN 103103845 B CN103103845 B CN 103103845B CN 201210574918 A CN201210574918 A CN 201210574918A CN 103103845 B CN103103845 B CN 103103845B
- Authority
- CN
- China
- Prior art keywords
- solid
- liquid
- acid
- time
- cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a method for extracting cellulose from a biomass raw material and co-producing biochar. According to the method, under the catalytic action of hydrogen peroxide, the cellulose is extracted by stewing the biomass raw material through organic acid consisting of methanoic acid and acetic acid, pickling, washing, bleaching and the like, and the biochar can be co-produced at the same time. Due to rational technology parameters, the whole technological line is suitable for wood raw materials and grass raw materials, so that the purity of the obtained cellulose is high; and the alpha-cellulose content is above 90 percent.
Description
Technical field
The present invention relates to one from biomass material, extract cellulosic method, specifically one extracts cellulose from biomass material, and utilizes the method extracted the black liquor produced in cellulose process and prepare biological carbon.
Background technology
The biomass material of the form existence of plant, main component is cellulose, hemicellulose and lignin, wherein, cellulose accounts for about 40%, hemicellulose accounts for about 25%, lignin accounts for about 20%, and the bar thing biomass material total amount that the earth is generated by photosynthesis is every year more than 2,000 hundred million tons, and therefore plant biological raw material is renewable resource abundant, the most cheap on the earth.
Cellulose is the main component of plant cell wall.The whole world, for the cellulose of papermaking of weaving, reaches 8,000,000 tons every year.In addition, raw material is done with the cellulose of separation and purification, artificial silk can be manufactured, cellophane and the ether derivative such as the ester derivative such as nitrate, acetate and methylcellulose, ethyl cellulose, sodium carboxymethylcellulose, for aspects such as oil 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, adhesive, plastics, explosive, electrician and Scientific Research Equipments.
Due to the fast development of society, living standards of the people improve constantly, the consumption of social resources increases the natural rate of growth being far longer than resource, can not meet the needs of social sustainable development, particularly textile industry viscose glue, cellulose ether and nitrated production field raw materials resource are deficient.In existing chemical dissolving pulp, mainly cotton linter, needlebush, leaf wood are the Populus deltoides dissolving pulp of main raw material, but due to the minimizing year by year of sown areas of cotton, cotton linter output also reduces year by year, and the resource such as pin, wealthy wood, also because of factors such as ecology, environmental protection, cutting significantly reduces; Therefore, novel material and the production technology thereof of dissolving pulp are prepared in research and development, expand the raw-material range of choice that fiber uses industry, have positive meaning to the sustainable development of society.
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 broad leaf 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.The regeneration of the cooking chemical of the method is evaporated and has distilled, the mixed acid obtained returns for boiling, but do not mention the processing method of solid content, in the document in solid content containing a large amount of lignin and hemicellulose and wood sugar, a large amount of wastes certainly will be caused if directly abandoned; And the method that the document is recorded is mainly in order to obtain containing hemicellulose and cellulosic paper pulp, if want to obtain highly purified cellulose, more hemicellulose will be contained further in the solid content adopting said method to obtain, bring the more wasting of resources.
Summary of the invention
For this reason, technical problem to be solved by this invention is from biomass material, extract the problem that in cellulosic process, remaining a large amount of lignin and hemicellulose can not be utilized effectively in prior art.
Second technical problem to be solved by this invention is to provide one by technical process reasonable in design and technological parameter, thus can extract highly purified cellulose from biomass material.
For solving the problems of the technologies described above, of the present inventionly from biomass material, extracting cellulose and prepare the technique of biological carbon, comprising the steps:
(1) after biomass material being pulverized, under the catalytic action of hydrogen peroxide, the organic acid solution formed by formic acid, acetic acid is used to carry out boiling to described biomass material, control boiling temperature 90-155 DEG C, solid-liquid mass ratio is 1:5-1:20, reaction time 10-60min, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid; In described organic acid solution, the dense 60-95wt% of total acid, the mass ratio of described acetic acid and formic acid is 1:1-1:19, and surplus is water; Hydrogen peroxide accounts for the 1-8wt% of biomass material;
(2) described first time solid of obtaining of Separation of Solid and Liquid is collected, under the catalytic action of hydrogen peroxide, the mix acid liquor formed by formic acid, acetic acid is used to carry out pickling to described solid, control pickling temperature 20-90 DEG C, solid-liquid mass ratio is 1:4-1:10, and the reactant liquor obtained is carried out second time Separation of Solid and Liquid; In described mix acid liquor, the dense 60-95wt% of total acid, the mass ratio of described acetic acid and formic acid is 1:1-1:19, and surplus is water; Hydrogen peroxide accounts for the 1-8wt% of biomass material;
(3) collect the solid that described second time Separation of Solid and Liquid obtains, and wash, control washing temperature is 25-90 DEG C, and starching dense is 1-10wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(4) collect the described third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side to obtain required screened stock cellulose, obtain cellulose through bleaching;
(5) collect the liquid that Separation of Solid and Liquid and second time Separation of Solid and Liquid obtain for the first time to evaporate, be back to step (1) as cooking liquor after the formic acid obtained and acetic acid vapor condensation, the solid obtained after evaporation is biological carbon; The temperature of described evaporation is 140-190 DEG C, pressure 401-901kPa.
Above-mentionedly from biomass material, extract cellulose and prepare in the technique of biological carbon, described bleaching comprises the steps:
Chelating agent preliminary treatment, the quality of described chelating agent accounts for the cellulosic 1-3wt% of described screened stock, and pH value controls between 2-4, temperature 50-85 DEG C, time 1-4h, starches dense 3-5wt%;
Alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the cellulosic 3-9wt% of described screened stock, and pH value controls between 10-12, temperature 70-100 DEG C, bleaching time 2-5h, starches dense 5-15wt%; With
Acid treatment, the quality of described acid accounts for the cellulosic 1-6wt% of described screened stock, and pH value controls between 2-4, temperature 30-55 DEG C, time 1-4h, starches dense 3-6wt%.
Preferably, before described chelating agent preliminary treatment, carry out alkali treatment, in described alkali treatment, alkali consumption accounts for the cellulosic 1-5wt% of described screened stock, and temperature is 70-95 DEG C, and extraction times 1-4h starches dense 5-15wt%.
Preferably, in the step of described alkali treatment, described alkali consumption accounts for the cellulosic 2-3wt% of described screened stock, and temperature is 80-95 DEG C, and extraction times 1-2.5h starches dense 6-10wt%; In the pretreated step of described chelating agent, the quality of described chelating agent accounts for the cellulosic 1-2wt% of described screened stock, temperature 50-65 DEG C, time 1-2h; In the step of described alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the cellulosic 3-6wt% of described screened stock, temperature 80-95 DEG C, bleaching time 2-3h, starches dense 5-10wt%; With in described acid-treated step, temperature 30-45 DEG C, time 1.5-3h.
Preferably, describedly from biomass material, extract cellulosic processing step also comprise, collect described third time liquid of obtaining of Separation of Solid and Liquid, carry out water, sour rectifying, the mix acid liquor obtained is back to described step (1) as cooking liquor, and the water obtained washes Water circulation with water in step (3).
Preferably, in described step (1), solid-liquid mass ratio is 1:6-1:10, reaction temperature 125-145 DEG C, reaction time 20-40min; The dense 75-95wt% of total acid of described organic acid solution, the mass ratio of acetic acid and formic acid is 1:1-1:8, and hydrogen peroxide addition accounts for the 1-6wt% of biomass material quality.
Preferably, step (2) described mix acid liquor is identical with organic acid solution described in step (1).
Preferably, the pickling temperature of described step (2) is 30-90 DEG C, and solid-liquid mass ratio is 1:8-1:10.
Preferably, the washing temperature of described step (3) is 60-90 DEG C, and starching dense is 4-6wt%.
Preferably, the water-washing process of described step (3) is adverse current water-washing process.
Preferably, described cellulose is dissolving pulp and/or industrial fiber element.
Described biomass material is one or more in the careless classes such as reed, beanstalk bar, wheat straw, straw, corn stalk, melon seed cases, bamboo chip, melon seeds bar or wooden class raw material.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, the present invention is by technological parameter reasonable in design, and make whole process route not be only applicable to wooden class raw material, be also applicable to grass as raw material, the cellulose purity obtained is high, and wherein the content of alpha-cellulose is more than 90%.
2, digestion process of the present invention carries out in airtight reaction vessel, because the part of formic acid, acetic acid and hydrogen peroxide is evaporated, makes to have certain pressure in container, thus shortens the digestion time of raw material, decrease cellulosic destruction.
3, the common boiling biomass material of process selection formic acid of the present invention, acetic acid and hydrogen peroxide, formic acid is as a kind of strong organic acid, urge the lignin done in degraded raw material, alpha-cellulose in 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 cellulose, hemicellulose and lignin separation; Hydrogen peroxide add the environment that can form peroxide acid solution, exacerbate degraded and the dissolving of lignin, and prevent the hydrolytic cleavage of fiber high polymer.
4, in technique of the present invention; all hydrogen peroxide is added in boiling and acid pickling step; because adding of hydrogen peroxide in pulping process eliminates lignin matter to greatest extent; and protect carbohydrate and be not destroyed; thus following bleaching technique, only need chlorine-free bleaching simply can realize the slurry of high whiteness.
5, the present invention adopts specific bleaching process to carry out bleaching to the slurry through screening, and this technique of bleaching process first applicability is strong, is not only applicable to needlebush, leaf wood magma, and is applicable to the careless class magma such as reed, straw, cotton stalk, melon seeds bar; Secondly this technique achieves total chlorine free bleaching, pollution-free; Again, this bleaching process not only increases pulp brightness, and can make the ash content in the high ash content straw pulp of removal, thoroughly breaches the technical bottleneck preparing cellulose (as dissolving pulp) with high ash content grass class; Finally, this technique is destroyed very little even without destruction to cellulose, can prepare high polymerization degree cellulose.。
6, technique of the present invention by first time Separation of Solid and Liquid and second time Separation of Solid and Liquid after acid solution prepare biological carbon, avoid acid solution and directly discharge the environmental pollution brought, the mixed acid simultaneously obtained can also be back to step (1) as cooking liquor, improves economic benefit and the environmental benefit of enterprise.
7, adopt the organic acid solution identical with step (1) to carry out acid pickling step, make the formic acid of regeneration and acetic acid regulate the circulation that can be directly used in technique without the need to any preliminary treatment.
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 flow chart of technique of the present invention.
Detailed description of the invention
Below will the invention will be further described by specific embodiment.
In following examples, apart from outside specified otherwise, percentage composition used all represents mass percentage, i.e. " % " expression " wt% "; In described organic acid solution except a certain amount of formic acid, acetic acid, surplus is water, the acid of the dense nail of total acid described in each step and the gross mass of acetic acid account for the percentage of described organic acid solution quality, the quality that the solid-liquid mass ratio in each step refers to solid in this each step and the mass ratio of total liquid added.
Slurry described in each step is dense=this step in solid quality/this step in Zhi Liang He ╳ 100% of solid and liquid
Hydrogen peroxide H in each embodiment
2o
2be that the form of the aqueous hydrogen peroxide solution of 27% adds with mass concentration.Such as need as calculated to add 2.7g hydrogen peroxide, then corresponding should be add 10g (2.7 ÷ 0.27=10) described aqueous hydrogen peroxide solution.
The measuring brightness method of cellulose/paper slurry is with reference to FZ/T50010.7-1998, alpha-cellulose content assay method is with reference to FZ/T50010.4-1998, polymerization degree measurement adopts Fz/T50010.3-1998 method, ash determination adopts FZ/T50010.5-1998 method, inhales base number and measures employing FZ/T50010.9-1998 method.
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 sulfur content adopts the assay 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.
Embodiment 1
In the present embodiment, first smashed by reed, being crushed to particle diameter is 2-10cm.
The present embodiment extracts cellulosic technique from described reed, comprises the steps:
(1) by after reed comminution pretreatment, use total acid dense for the formic acid of 70wt% and the organic acid solution of acetic acid carry out boiling to the reed after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:1, and before adding reed raw material, add the hydrogen peroxide (H accounting for reed raw material 3wt%
2o
2) as catalyst, controlling reaction temperature 125 DEG C, reaction 60min, solid-liquid mass ratio is 1:5, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that first time Separation of Solid and Liquid obtains is added total acid is dense carries out acid elution for the formic acid of 70wt% and the organic acid solution of acetic acid, wherein above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for reed raw material 3wt% in the organic acid solution of 70wt%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 1:1, control temperature is 60 DEG C, wash time 1h, and solid-liquid mass ratio is 1:4, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 140 DEG C, high temperature evaporation is carried out under 801kPa, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 85wt%, and in described biological carbon, fixed carbon content is 60wt% after measured, ash content 0.05wt%, sulfur content 0.08wt%, moisture 39.5wt%, caloric value 4000J/g.
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 25 DEG C, and starching dense is 4wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, 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 water with water in step (5);
(6) collect the third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side and be able to required screened stock cellulose, the screened stock cellulose obtained is carried out bleaching and obtains cellulose; Its whiteness of cellulose adopting the method for the present embodiment to obtain after measured is 95%ISO, alpha-cellulose content 94wt%, ash content 0.02wt%, the degree of polymerization 900, inhales base number 500, productive rate 40wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for described screened stock cellulose 2wt% to carry out alkali treatment, control temperature is 85 DEG C, and extraction times 2.5h starches dense 8wt%;
(2) after alkali treatment, carry out chelating agent preliminary treatment, in the present embodiment, chelating agent adopts EDTA, and its consumption accounts for the cellulosic 2wt% of described screened stock, and pH value controls between 2-4, temperature 60 C, and time 3.5h starches dense 5wt%;
(3) after EDTA preliminary treatment, carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is the cellulosic 6wt% of described screened stock, and controls the dense 8wt% of slurry, temperature 70 C, and utilizes NaOH to control between 10-12 by pH value, bleaching time 2h; With
(4) adopt the sulfuric acid accounting for described screened stock cellulose 1wt% to carry out acid treatment, pH value controls between 2-4, temperature 50 C, time 1.5h, starches dense 3wt%.
Embodiment 2
In the present embodiment, first smashed by straw, being crushed to particle diameter is 2-10cm.
The present embodiment extracts cellulosic technique from described straw, comprises the steps:
(1) by after straw comminution pretreatment, use total acid dense for the formic acid of 90wt% and the organic acid solution of acetic acid carry out boiling to the straw after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:8, and before adding straw raw material, add the hydrogen peroxide (H accounting for straw raw material 4wt%
2o
2) as catalyst, controlling reaction temperature 145 DEG C, reaction 20min, solid-liquid mass ratio is 1:8, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that first time Separation of Solid and Liquid obtains is added total acid is dense carries out acid elution for the formic acid of 90wt% and the organic acid solution of acetic acid, wherein above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for straw raw material 4wt% in the organic acid solution of 90wt%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 1:8, control temperature is 20 DEG C, wash time 1h, and solid-liquid mass ratio is 1:8, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 150 DEG C, high temperature evaporation is carried out under 501kPa, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 87wt%, and in described biological carbon, fixed carbon content is 62wt% after measured, ash content 0.12wt%, sulfur content 0.05wt%, moisture 37wt%, caloric value 4600J/g.
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 40 DEG C, and starching dense is 5wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, 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 water with water in step (5);
(6) collect the third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side to obtain required screened stock cellulose, obtain cellulose through bleaching process again; Its whiteness of cellulose adopting the method for the present embodiment to obtain after measured is 92%ISO, alpha-cellulose content 94wt%, ash content 0.04wt%, the degree of polymerization 900, inhales base number 600, productive rate 28wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the potassium hydroxide accounting for its quality 5wt% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 70 DEG C, and extraction times 1h starches dense 10wt%;
(2) after alkali treatment, carry out chelating agent preliminary treatment, in the present embodiment, chelating agent adopts DTPA, and its consumption accounts for the cellulosic 1wt% of described screened stock, and pH value controls between 2-4, temperature 65 DEG C, and time 1h, starches dense 4wt%;
(3) after DTPA preliminary treatment, carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is 3wt%, surplus be potassium hydroxide adjust ph between 10-12, temperature 75 DEG C, bleaching time 3h, starches dense 6wt%; With
(4) acid treatment, the acid adopted in this step is for accounting for the sulfuric acid of described thick pulp fibres 6wt%, and pH value controls between 2-4, temperature 55 DEG C, and time 1h, starches dense 4wt%.
Embodiment 3
In the present embodiment, first smashed by bamboo chip, being crushed to length is 2 ~ 10cm, thick 2mm thin slice.
The present embodiment extracts cellulosic technique from described bamboo chip, comprises the steps:
(1) by after bamboo chip comminution pretreatment, use total acid dense for the formic acid of 95wt% and the organic acid solution of acetic acid are to carrying out boiling 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 bamboo chip raw material, add the hydrogen peroxide (H accounting for bamboo chip raw material 6wt%
2o
2) as catalyst, controlling reaction temperature 90 DEG C, reaction 40min, solid-liquid mass ratio is 1:6, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that first time Separation of Solid and Liquid obtains is added total acid is dense carries out acid elution for the formic acid of 95wt% and the organic acid solution of acetic acid, wherein above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for bamboo chip raw material 6wt% in the organic acid solution of 95wt%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 1:6, control temperature is 40 DEG C, wash time 1h, and solid-liquid mass ratio is 1:10, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 160 DEG C, high temperature evaporation is carried out under 601kPa, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 92wt%, and in described biological carbon, fixed carbon content is 60wt% after measured, ash content 0.1wt%, sulfur content 0.04wt%, moisture 38.6wt%, caloric value 5000J/g.
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 60 DEG C, and starching dense is 1wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, 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 water with water in step (5);
(6) row filter of going forward side by side obtains required screened stock cellulose, more described screened stock bleaching process is obtained cellulose; Its whiteness of cellulose adopting the method for the present embodiment to obtain after measured is 94%ISO, alpha-cellulose content 95wt%, ash content 0.04wt%, the degree of polymerization 800, inhales base number 650, productive rate 40wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the potassium hydroxide accounting for its quality 3wt% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 95 DEG C, and extraction times 3h starches dense 6wt%;
(2) after alkali treatment, carry out chelating agent preliminary treatment, in the present embodiment, chelating agent adopts calgon, and its consumption accounts for the 2wt% of slurry, and pH value controls between 2-4, temperature 70 C, and time 2h starches dense 3wt%;
(3) after calgon preliminary treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the cellulosic 5wt% of described screened stock, and adopts potassium hydroxide adjust ph between 10-12, temperature 95 DEG C, and bleaching time 4h, starches dense 10wt%; With
(4) acid treatment, the acid adopted in this step is the hydrochloric acid of 3wt%, and surplus is water, and Ph value controls between 2-4, temperature 45 C, and time 2h starches dense 5wt%.
Embodiment 4
In the present embodiment, first smashed by wheat straw, being crushed to particle diameter is 2-10cm.
The present embodiment extracts cellulosic technique from described wheat straw, comprises the steps:
(1) by after wheat straw comminution pretreatment, use total acid dense for the formic acid of 75wt% and the organic acid solution of acetic acid carry out boiling to the wheat straw after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:12, and before adding raw material, add the hydrogen peroxide (H accounting for wheat straw raw material 1wt%
2o
2) as catalyst, controlling reaction temperature 110 DEG C, reaction 30min, solid-liquid mass ratio is 1:10, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that first time Separation of Solid and Liquid obtains is added total acid is dense carries out acid elution for the formic acid of 75wt% and the organic acid solution of acetic acid, wherein above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for wheat straw raw material 1wt% in the organic acid solution of 75wt%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 1:12, control temperature is 90 DEG C, wash time 1h, and solid-liquid mass ratio is 1:9, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 170 DEG C, high temperature evaporation is carried out under 701kPa, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 88wt%, and in described biological carbon, fixed carbon content is 64wt% after measured, ash content 0.15wt%, sulfur content 0.1wt%, moisture 35wt%, caloric value 4800J/g.
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 80 DEG C, and starching dense is 6wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, 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 water with water in step (5);
(6) collect the third time solid that obtains of Separation of Solid and Liquid, this solid is screened stock cellulose, is carried out successively by the screened stock cellulose obtained screening, bleaching process obtains cellulose; Its whiteness of cellulose adopting the method for the present embodiment to obtain after measured is 92%ISO, alpha-cellulose content 93wt%, ash content 0.1wt%, the degree of polymerization 500, inhales base number 750, productive rate 34wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for its quality 1wt% to carry out alkali treatment by through screening the screened stock cellulose obtained, control temperature is 80 DEG C, and extraction times 2h starches dense 5wt%;
(2) after alkali treatment, carry out chelating agent preliminary treatment, in the present embodiment, chelating agent adopts calgon, and its consumption accounts for the cellulosic 3wt% of described screened stock, and pH value controls between 2-4, temperature 80 DEG C, and time 3h, starches dense 3wt%;
(3) after calgon preliminary treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the cellulosic 7wt% of described screened stock, and utilizes NaOH adjust ph to control between 10-12, temperature 80 DEG C, and bleaching time 5h, starches dense 13wt%; With
(4) acid treatment, the acid adopted in this step is for accounting for the hydrochloric acid of described screened stock cellulose 4wt%, and pH value controls between 2-4, temperature 40 DEG C, and time 4h, starches dense 6wt%.
Embodiment 5
In the present embodiment, first smashed by melon seeds bar, being crushed to particle diameter, to be crushed to particle diameter be 2-10cm, preferred 3-5cm.
The present embodiment extracts cellulosic technique from described melon seeds bar, comprises the steps:
(1) by after melon seeds bar comminution pretreatment, use total acid dense for the formic acid of 80wt% 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 1:4, and before adding raw material, add the hydrogen peroxide (H accounting for melon seeds bar raw material 8wt%
2o
2) as catalyst, controlling reaction temperature 155 DEG C, reaction 10min, solid-liquid mass ratio is 1:20, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that first time Separation of Solid and Liquid obtains is added total acid is dense carries out acid elution for the formic acid of 80wt% and the organic acid solution of acetic acid, wherein above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for melon seeds bar raw material 8wt% in the organic acid solution of 80wt%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 1:16, control temperature is 50 DEG C, wash time 1h, and solid-liquid mass ratio is 1:6, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 190 DEG C, high temperature evaporation is carried out under 901kPa, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 90wt%, and in described biological carbon, fixed carbon content is 62wt% after measured, ash content 0.13wt%, sulfur content 0.06wt%, moisture 37wt%, caloric value 4000J/g.
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 90 DEG C, and starching dense is 3wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, 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 water with water in step (5);
(6) collect the third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side and obtain required screened stock cellulose, the screened stock cellulose obtained is carried out bleaching process and obtains cellulose; Its whiteness of cellulose adopting the method for the present embodiment to obtain after measured is 93wt%ISO, alpha-cellulose content 93wt%, ash content 0.06wt%, the degree of polymerization 400, inhales base number 550, productive rate 38wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for described screened stock cellulose 4wt% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 75 DEG C, and extraction times 4h starches dense 15wt%;
(2) after alkali treatment, carry out chelating agent preliminary treatment, in the present embodiment, chelating agent adopts EDTA (disodium ethylene diamine tetraacetate), and its consumption accounts for the cellulosic 1wt% of described screened stock, Ph value controls between 2-4, temperature 50 C, time 4h, starches dense 3wt%;
(3) after calgon preliminary treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the cellulosic 9wt% of described screened stock, and adopt NaOH adjust ph between 10-12, temperature 85 DEG C, bleaching time 4.5h, starches dense 15wt%; With
(4) acid treatment, the acid adopted in this step is hydrochloric acid, and its consumption is that cellulosic 5wt%, the Ph value of described screened stock controls between 2-4, and temperature 35 DEG C, time 3h, starches dense 3wt%.
Embodiment 6
In the present embodiment, first smashed by cotton stem, being crushed to particle diameter for being crushed to particle diameter is 0.5-2cm.
The present embodiment extracts cellulosic technique from described cotton stem, comprises the steps:
(1) by after cotton stem comminution pretreatment, use total acid dense for the formic acid of 90wt% 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 1:19, and before adding raw material, add the hydrogen peroxide (H accounting for cotton stem raw material 1wt%
2o
2) as catalyst, controlling reaction temperature 145 DEG C, reaction 50min, solid-liquid mass ratio is 1:15, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that first time Separation of Solid and Liquid obtains is added total acid is dense carries out acid elution for the formic acid of 90wt% and the organic acid solution of acetic acid, wherein above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for wheat straw raw material 1wt% in the organic acid solution of 90wt%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 1:19, control temperature is 30 DEG C, wash time 1h, and solid-liquid mass ratio is 1:8.5, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 180 DEG C, high temperature evaporation is carried out under 401KPa, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 91wt%, and in described biological carbon, fixed carbon content is 60wt% after measured, ash content 0.08wt%, sulfur content 0.05wt%, moisture 39.7wt%, caloric value 4400J/g.
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 70 DEG C, and starching dense is 10wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, 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 water with water in step (5);
(6) collect the third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side and obtain required screened stock cellulose, the screened stock cellulose obtained is carried out bleaching and obtains cellulose; Its whiteness of cellulose adopting the method for the present embodiment to obtain after measured is 95%ISO, alpha-cellulose content 92wt%, ash content 0.05wt%, the degree of polymerization 500, inhales base number 750, productive rate 40wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first the screened stock cellulose obtained is carried out chelating agent preliminary treatment, in the present embodiment, chelating agent adopts calgon, and its consumption accounts for the cellulosic 2.5wt% of described screened stock, and pH value controls between 2-4, temperature 85 DEG C, and time 1.5h, starches dense 3wt%;
(2) after calgon preliminary treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the cellulosic 4wt% of described screened stock, and adopts potassium hydroxide control ph between 10-12, temperature 80 DEG C, and bleaching time 2.5h, starches dense 5wt%; With
(3) acid treatment, the acid adopted in this step is the sulfuric acid of described screened stock cellulose 2wt%, and pH value controls between 2-4, temperature 30 DEG C, and time 2.5h, starches dense 6wt%.
Comparative example 1
Raw material used in the present embodiment and processing step and technological parameter and embodiment 3 basically identical, its difference is, the digestion process of step (1) is under the catalytic action of hydrogen peroxide, and the organic acid solution of employing is made up of the formic acid of 95wt% and 5wt% water.The acid pickling step of its step (2) is under the catalytic action of hydrogen peroxide, the organic acid solution be made up of formic acid and the 5wt% water of 95wt% adopted carries out pickling, in each step, the adding proportion of hydrogen peroxide is consistent with embodiment 3, its whiteness of cellulose adopting the method for the present embodiment to obtain after measured is 65%ISO, alpha-cellulose content 86wt%.
Comparative example 2
Raw material used in the present embodiment and processing step and technological parameter and embodiment 3 basically identical, its difference is, except the processing step of bleaching process, does not all add hydrogen peroxide as catalyst in each step.Its whiteness of cellulose adopting the method for the present embodiment to obtain after measured is 60%ISO, alpha-cellulose content 60wt%.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. from biomass material, extract cellulose and prepare the technique of biological carbon, it is characterized in that, comprise the steps:
(1) after biomass material being pulverized, under the catalytic action of hydrogen peroxide, the organic acid solution formed by formic acid, acetic acid is used to carry out boiling to described biomass material, control boiling temperature 90-155 DEG C, solid-liquid mass ratio is 1:5-1:20, reaction time 10-60min, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
In described organic acid solution, the dense 60-95wt% of total acid, the mass ratio of described acetic acid and formic acid is 1:1-1:19, and surplus is water;
Hydrogen peroxide accounts for the 1-8wt% of biomass material;
(2) described first time solid of obtaining of Separation of Solid and Liquid is collected, under the catalytic action of hydrogen peroxide, the mix acid liquor formed by formic acid, acetic acid is used to carry out pickling to described solid, control pickling temperature 20-90 DEG C, solid-liquid mass ratio is 1:4-1:10, and the reactant liquor obtained is carried out second time Separation of Solid and Liquid;
In described mix acid liquor, the dense 60-95wt% of total acid, the mass ratio of described acetic acid and formic acid is 1:1-1:19, and surplus is water;
Hydrogen peroxide accounts for the 1-8wt% of biomass material;
(3) collect the solid that described second time Separation of Solid and Liquid obtains, and wash, control washing temperature is 25-90 DEG C, and starching dense is 1-10wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(4) collect the described third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side to obtain required screened stock cellulose, obtain cellulose through bleaching;
(5) collect the liquid that Separation of Solid and Liquid and second time Separation of Solid and Liquid obtain for the first time to evaporate, be back to step (1) as cooking liquor after the formic acid obtained and acetic acid vapor condensation, the solid obtained after evaporation is biological carbon;
The temperature of described evaporation is 140-190 DEG C, pressure 401-901kPa.
2. extract cellulose in biomass material according to claim 1 and prepare the technique of biological carbon, it is characterized in that, described bleaching comprises the steps:
Chelating agent preliminary treatment, the quality of described chelating agent accounts for the cellulosic 1-3wt% of described screened stock, and pH value controls between 2-4, temperature 50-85 DEG C, and time 1-4 h, starches dense 3-5wt%;
Alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the cellulosic 3-9wt% of described screened stock, and pH value controls between 10-12, temperature 70-100 DEG C, bleaching time 2-5h, starches dense 5-15wt%; With
Acid treatment, the quality of described acid accounts for the cellulosic 1-6wt% of described screened stock, and pH value controls between 2-4, temperature 30-55 DEG C, time 1-4h, starches dense 3-6wt%.
3. extract cellulose in biomass material according to claim 2 and prepare the technique of biological carbon, it is characterized in that, alkali treatment is carried out before described chelating agent preliminary treatment, in described alkali treatment, alkali consumption accounts for the cellulosic 1-5wt% of described screened stock, temperature is 70-95 DEG C, extraction times 1-4h, starches dense 5-15wt%.
4. according to claim 3ly from biomass material, extract cellulose and prepare the technique of biological carbon, it is characterized in that:
In the step of described alkali treatment, described alkali consumption accounts for the cellulosic 2-3wt% of described screened stock, and temperature is 80-95 DEG C, and extraction times 1-2.5h starches dense 6-10wt%;
In the pretreated step of described chelating agent, the quality of described chelating agent accounts for the cellulosic 1-2wt% of described screened stock, temperature 50-65 DEG C, time 1-2 h;
In the step of described alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the cellulosic 3-6wt% of described screened stock, temperature 80-95 DEG C, bleaching time 2-3h, starches dense 5-10wt%; With
In described acid-treated step, temperature 30-45 DEG C, time 1.5-3h.
5. described from biomass material, extract cellulose according to claim 1-4 is arbitrary and prepare the technique of biological carbon, it is characterized in that:
Describedly from biomass material, extract cellulosic processing step also comprise, collect described third time liquid of obtaining of Separation of Solid and Liquid, carry out water, sour rectifying, the mix acid liquor obtained is back to described step (1) as cooking liquor, and the water obtained washes Water circulation with water in step (3).
6. according to claim 5ly from biomass material, extract cellulose and prepare the technique of biological carbon, it is characterized in that:
In described step (1), solid-liquid mass ratio is 1:6-1:10, reaction temperature 125-145 DEG C, reaction time 20-40min;
The dense 75-95wt% of total acid of described organic acid solution, the mass ratio of acetic acid and formic acid is 1:1-1:8, and hydrogen peroxide addition accounts for the 1-6wt% of biomass material quality.
7. according to claim 6ly from biomass material, extract cellulose and prepare the technique of biological carbon, it is characterized in that:
Step (2) described mix acid liquor is identical with organic acid solution described in step (1).
8. according to claim 7ly from biomass material, extract cellulose and prepare the technique of biological carbon, it is characterized in that:
The pickling temperature of described step (2) is 30-90 DEG C, and solid-liquid mass ratio is 1:8-1:10.
9. described from biomass material, extract cellulose according to claim 6-8 is arbitrary and prepare the technique of biological carbon, it is characterized in that:
The washing temperature of described step (3) is 60-90 DEG C, and starching dense is 4-6wt%.
10. according to claim 9ly from biomass material, extract cellulose and prepare the technique of biological carbon, it is characterized in that:
Described cellulose is dissolving pulp and/or industrial fiber element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210574918.8A CN103103845B (en) | 2012-12-25 | 2012-12-25 | Technologies for extracting cellulose from biomass raw material and preparing biochar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210574918.8A CN103103845B (en) | 2012-12-25 | 2012-12-25 | Technologies for extracting cellulose from biomass raw material and preparing biochar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103103845A CN103103845A (en) | 2013-05-15 |
| CN103103845B true CN103103845B (en) | 2015-07-01 |
Family
ID=48312020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210574918.8A Active CN103103845B (en) | 2012-12-25 | 2012-12-25 | Technologies for extracting cellulose from biomass raw material and preparing biochar |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103103845B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107345372B (en) * | 2016-05-05 | 2019-05-28 | 中国农业科学院农业环境与可持续发展研究所 | A method of it is prepared based on biomass material cellulose nano-fibrous |
| CN106749688A (en) * | 2016-12-28 | 2017-05-31 | 广州市楹晟生物科技有限公司 | A kind of production method of microcrystalline cellulose |
| CN108978291B (en) * | 2017-05-31 | 2021-04-23 | 张睿哲 | Acetified pulp as well as preparation method and application thereof |
| CN111215031B (en) * | 2020-03-18 | 2022-06-14 | 重庆三峡学院 | Preparation method of high-purity biochar |
| CN117728001A (en) * | 2022-09-16 | 2024-03-19 | 济南圣泉集团股份有限公司 | Application of carbon material, biomass charcoal, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864683A (en) * | 2010-03-25 | 2010-10-20 | 清华大学 | Pretreatment method of wood fiber raw materials |
| CN102766703A (en) * | 2012-08-16 | 2012-11-07 | 天津大学 | Hydrolysis method for hemicelluloses of lignocelluloses |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI117633B (en) * | 2000-12-29 | 2006-12-29 | Chempolis Oy | Recovery and manufacture of chemicals in mass production |
-
2012
- 2012-12-25 CN CN201210574918.8A patent/CN103103845B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864683A (en) * | 2010-03-25 | 2010-10-20 | 清华大学 | Pretreatment method of wood fiber raw materials |
| CN102766703A (en) * | 2012-08-16 | 2012-11-07 | 天津大学 | Hydrolysis method for hemicelluloses of lignocelluloses |
Non-Patent Citations (1)
| Title |
|---|
| 李明飞,汤志刚,樊永明,王玲玲.有机酸制浆的研究进展.《中国造纸》.2008,第27卷(第9期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103103845A (en) | 2013-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103898782B (en) | A kind of technique extracting cellulose from biomass material | |
| CN103015243B (en) | Process for extracting cellulose from biomass raw material and preparing bio-carbon | |
| CN101613970B (en) | Method for preparing bagasse dissolving pulp and pre-extracting hemicellulose and product thereof | |
| Andrade et al. | Dissolving pulp production from sugar cane bagasse | |
| CN103030815B (en) | Comprehensive utilization technology of biomass raw materials | |
| CN103898784B (en) | A kind of comprehensive utilization process of biomass material | |
| CN103103845B (en) | Technologies for extracting cellulose from biomass raw material and preparing biochar | |
| CN101503865B (en) | Method for preparing mlcrocrystalline cellulose by corps straw | |
| CN101565906A (en) | Method for producing bamboo dissolving pulp by pre-extracting hemicellulose and product thereof | |
| CN103074790B (en) | Comprehensive utilization process of biomass raw material | |
| CN101857639B (en) | Method for preparing sodium carboxymethylcellulose from residues generated by producing biobutanol from maize straw | |
| CN101555667B (en) | Biorefinery method of wood fiber material | |
| CN102912667B (en) | A kind of method utilizing poplar slab to produce dissolving pulp | |
| CN102585247A (en) | Method for preparing lignin sulfonate by utilizing residue from enzymatic hydrolysis of lignocellulose | |
| CN103898785A (en) | Comprehensive utilization method of biomass raw material | |
| CN108997445A (en) | A kind of method that steam blasting wheat straw extracts xylose, lignin and manufacture paper pulp | |
| CN103898787B (en) | A kind of comprehensive utilization process of biomass material | |
| CN104231116A (en) | Method for preparing hemicellulose, humate and feed additive by utilizing straws | |
| CN111472186A (en) | Method for preparing high-quality crop straw dissolving pulp through hydrothermal pretreatment | |
| CN104652156A (en) | Method for preparation of lignosulfonate and cogeneration of microcrystalline cellulose from corn cob residues | |
| CN103031763B (en) | Comprehensive utilization technology of biomass raw materials | |
| CN107541975B (en) | A kind of activation method of carboxymetholcel | |
| CN103896887B (en) | Technology utilizing biomass raw materials to produce furfural | |
| CN103088686B (en) | Technology for preparing paper pulp and coproducing biochar from lignocellulose biomass | |
| CN103898783B (en) | A kind of technique being prepared paper pulp by biomass material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |