CN103898782B - A kind of technique extracting cellulose from biomass material - Google Patents
A kind of technique extracting cellulose from biomass material Download PDFInfo
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- CN103898782B CN103898782B CN201210576355.6A CN201210576355A CN103898782B CN 103898782 B CN103898782 B CN 103898782B CN 201210576355 A CN201210576355 A CN 201210576355A CN 103898782 B CN103898782 B CN 103898782B
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Abstract
The present invention relates to a kind of cellulose extraction process, specifically a kind of, under the catalytic action of hydrogen peroxide, utilize the technique that organic acid extracts cellulose from biomass material.Method of the present invention is under the catalytic action of hydrogen peroxide, by formic acid that concentration is 70-95wt% and the organic acid steaming and decocting biomass material of the formation of acetic acid, extract and screen and obtain screened stock cellulose, further bleaching obtains required cellulose, and wherein said cellulose is dissolving pulp or industrial fiber element.Adopt its alpha-cellulose content of cellulose being obtained by the present invention and be more than 90wt%, and whole process route is simple, energy consumption is relatively low.
Description
Technical field
The present invention relates to a kind of cellulose extraction process, a kind of technique utilizing organic acid to extract cellulose from biomass material.
Background technology
Biomass material is mainly composed of cellulose, hemicellulose and lignin, wherein, cellulose accounts for about 40%, hemicellulose accounts for about 25%, lignin accounts for about 20%, the biomass material total amount generated by photosynthesis every year on the earth is more than 200,000,000,000 tons, and therefore biomass are Renewable resources the abundantest, 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 isolated and purified cellulose, artificial silk can be manufactured, cellophane and the ether derivative such as the esters derivative such as nitrate, acetate and methylcellulose, ethyl cellulose, sodium carboxymethyl cellulose, 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 incense, Nicotiana tabacum L., papermaking, rubber, agricultural, adhesive, plastics, explosive, electrician and Scientific Research Equipments.
Fast development due to society, living standards of the people improve constantly, consuming of social resources increases the natural rate of growth being far longer than resource, it is impossible to meeting the needs of society's sustainable development, particularly textile industry viscose glue, cellulose ether and nitrification production field raw materials resource is the deficientest.In existing chemical dissolving pulp, mainly cotton linter, needlebush, leaf wood is the Populus deltoides dissolving pulp of primary raw material, but due to the minimizing year by year of sown areas of cotton, cotton linter yield reduces the most year by year, and the resource such as pin, wealthy wood, also because of factors such as ecology, environmental protection, cutting is greatly decreased；Therefore, novel material and the production technology thereof of dissolving pulp is prepared in research and development, expands fiber and uses the raw-material range of choice of industry, and the sustainable development to society has positive meaning.
Chinese patent CN1170031C discloses the method that the mixture of a kind of formic acid and acetic acid produces paper pulp as cooking chemical.This patent is when producing paper pulp with formic acid steaming and decocting herbaceous plant and broad leaf tree, add the paper pulp that acetic acid obtains as additional cooking chemical, the method is mainly for the preparation of paper pulp, purpose is to retain cellulose and the hemicellulose of part to greatest extent, its whole technological design is all with this end in view, therefore this technique for cellulose for extract product technique for and inapplicable.
Summary of the invention
To this end, the technical problem to be solved is to arrange a kind of process route extracting high purity cellulose from biomass material of offer by rational parameter.
For solving above-mentioned technical problem, the technique extracting cellulose from biomass material of the present invention, it is characterised in that comprise the steps:
(1) after biomass material being pulverized, under the catalytic action of hydrogen peroxide, use the organic acid solution being made up of formic acid and acetic acid that described raw material is carried out steaming and decocting, control boiling temperature 120-155 DEG C, solid-liquid mass ratio is 1:5-1:15, response time 10-60min, and the reactant liquor obtained is carried out solid-liquid separation for the first time；In described organic acid solution, the dense mass ratio for 70-95wt%, described acetic acid and formic acid of total acid is 1:1-1:19, and surplus is water；Hydrogen peroxide accounts for the 1-8wt% of biomass material；
(2) solid that described first time solid-liquid separation obtains is collected, under the catalytic action of hydrogen peroxide, use the mix acid liquor being made up of formic acid, acetic acid that described solid is carried out pickling, control pickling temperature 30-100 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reactant liquor obtained carries out second time solid-liquid separation；In described mix acid liquor, the dense mass ratio for 70-95wt%, described acetic acid and formic acid of total 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 solid-liquid separation obtains, and wash, control washing temperature and be 25-90 DEG C, starch dense for 1-10wt%, and the washing slurry obtained is carried out third time solid-liquid separation；
(4) collect solid that described third time solid-liquid separation obtains and screening obtains required screened stock cellulose, obtains cellulose after bleaching.
In the above-mentioned technique extracting cellulose from biomass material, described bleaching comprises the steps:
Alkali processes, and described alkali consumption accounts for the 1-10wt% of described screened stock cellulose, and temperature is 50-100 DEG C, and extraction times 0.5-4h starches dense 5-15wt%；
Chelating agen pretreatment, the consumption of described chelating agen accounts for the 0.1-3wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 50-80 DEG C, and time 0.5-4h starches dense 3-5wt%；
Alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide accounts for the 1-10wt% of described screened stock cellulose, and pH value controls between 10-12, temperature 70-120 DEG C, and bleaching time 1-6h starches dense 5-15wt%；With
Acid treatment, the consumption of described acid accounts for the 1-6wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 30-55 DEG C, and time 0.5-2h starches dense 3-6wt%.
Preferably,
In the step that described alkali processes, described alkali consumption accounts for the 2-5wt% of described screened stock cellulose, and temperature is 70-95 DEG C, and extraction times 1-3h starches dense 6-12wt%；
In the step of described chelating agen pretreatment, the consumption of described chelating agen accounts for the 0.1-0.5wt% of described screened stock cellulose, temperature 50-65 DEG C, time 0.5-2h；
In the step of described alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide accounts for the 1-5wt% of described screened stock cellulose, temperature 80-95 DEG C, bleaching time 2-4h, starches dense 5-10wt%；With
In the step of described acid treatment, temperature 30-45 DEG C, time 0.5-1.5h.
Preferably, the described processing step extracting cellulose from biomass material also includes, collect liquid that described first time solid-liquid separation obtains and the liquid that described second time solid-liquid separation obtains is evaporated, after obtaining formic acid and acetic acid steam condensation, be back to described step (1) as cooking liquor.
Preferably, the described processing step extracting cellulose from biomass material also includes, collects the liquid that described third time solid-liquid separation obtains, and carries out water, acid rectification, 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 1:8-1:10, reaction temperature 125-145 DEG C, response time 20-40min;The mass ratio of acetic acid and formic acid is 1:1-1:8, and total acid is dense for 75-95wt%, and the quality of hydrogen peroxide accounts for the 3-6wt% of biomass material.
Preferably, mix acid liquor described in described step (2) 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, starches dense for 4-6wt%.
Preferably, the water-washing process of described step (3) is adverse current water-washing process.
The above-mentioned technique extracting cellulose from biomass material, described cellulose is dissolving pulp and/or industrial fiber element.
Described biomass material can be one or more in the wood classes such as phragmites communis, beanstalk stalk, wheat stalk, Caulis et Folium Oryzae, corn straw, melon seed cases, bamboo chip, Semen Benincasae bar or grass as raw material.
The technique scheme of the present invention has the advantage that compared to existing technology
1, the present invention is by technological parameter reasonable in design so that whole process route is applicable not only to wood class raw material, applies also for grass as raw material, and the cellulose purity obtained is high, and wherein the content of alpha-cellulose is at more than 92wt%, up to 98wt%.
2, the digestion process of the present invention is carried out in airtight reaction vessel, owing to the part of formic acid, acetic acid and hydrogen peroxide is evaporated so that have certain pressure in container, thus shorten the digestion time of raw material, decrease the destruction to cellulose.
3, process selection formic acid of the present invention, acetic acid and hydrogen peroxide common steaming and decocting biomass material; formic acid is as a kind of strong organic acid; urge the lignin made in degraded raw material; the alpha-cellulose in cellulose can be destroyed owing to being used alone formic acid; not only protect alpha-cellulose be not destroyed so adding appropriate acetic acid; and utilize formic acid and the organic solvent dissolved lignin molecule of acetic acid formation; also utilize its acid steaming and decocting hemicellulose therein, and with this by cellulose, hemicellulose and lignin separation；The addition of hydrogen peroxide can form the environment of peroxide acid solution, exacerbates degraded and the dissolving of lignin, and prevents the hydrolytic cleavage of fiber high polymer.
4, in technique of the present invention; hydrogen peroxide is all added in steaming and decocting and acid pickling step; owing in pulping process, the addition of hydrogen peroxide eliminates lignin matter to greatest extent; and protect carbohydrate and be not destroyed; thus following bleaching technique, it is only necessary to chlorine-free bleaching can realize the slurry of high whiteness simply.
5, the present invention uses specific bleaching process that the slurry through screening carries out bleaching, bleaching process, and the first suitability of this technique is strong, is applicable not only to needlebush, leaf wood oleo stock, and is applicable to the grass class oleo stock such as phragmites communis, straw, cotton stalk, Semen Benincasae 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 in removal high ash straw pulp, thoroughly breaches the technical bottleneck preparing high purity cellulose (such as dissolving pulp) with high ash grass class；Finally, cellulose is destroyed the least even without destroying by this technique, can prepare high polymerization degree cellulose.
6, after steaming and decocting obtains cellulose for the first time, formic acid, acetic acid and hydrogen peroxide carry out pickling to cellulose, on the one hand front and continued digestion process is adjusted, on the other hand a small amount of lignin of cellulose internal residual is decomposed and dissolution, remove lignin further, additionally, use the organic acid solution identical with step (1) to carry out acid pickling step so that formic acid and the acetic acid of regeneration i.e. can be directly used for the circulation of technique without any pretreatment regulation.
7, the liquid that first time and the second time solid-liquid separation of collection obtain directly is evaporated by technique of the present invention, as cooking liquor after the condensation of the formic acid that obtains, acetic acid, directly reflow step (1) whole process route is succinct, owing to formic acid and acetic acid re-use as raw material, higher to the boiling efficiency of raw material, for the technique of the cooking liquor circulation after utilizing steaming and decocting, although eliminating the step of this circulation, but achieve within the identical process time, higher to the clearance of hemicellulose and lignin.
Accompanying drawing explanation
In order to make present disclosure be more likely to be clearly understood, below according to the specific embodiment of the present invention and combine accompanying drawing, the present invention is further detailed explanation, wherein
Fig. 1 is the flow chart of technique of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the cellulose extracted in the embodiment of the present invention 3；
Fig. 3 is the scanning electron microscope (SEM) photograph of the cellulose extracted in comparative example 3 of the present invention.
Detailed description of the invention
Below will the invention will be further described by specific embodiment.
In following example, in addition to having specified otherwise, percentage composition used all represents weight/mass percentage composition, i.e. " % " expression " wt% "；In described organic acid solution in addition to a certain amount of formic acid, acetic acid, surplus is water, the gross mass of the acid of the dense fingernail of total acid described in each step and acetic acid accounts for the percent of described organic acid solution quality, and the solid-liquid mass ratio in each step refers to the mass ratio of total liquid of the quality of solid and addition in this each step
The quality and 100% of solid and liquid in quality/this step of solid is starched in dense=this step described in each step
The quality 100% of the quality/raw material of the productivity=cellulose of cellulose in each embodiment.
In each embodiment, hydrogen peroxide H2O2 adds with the form of the aqueous hydrogen peroxide solution that mass concentration is 27%.Such as be computed needing to add 2.7g hydrogen peroxide, then corresponding should be to add 10g(2.7 ÷ 0.27=10) described aqueous hydrogen peroxide solution.
The measuring brightness method of high purity cellulose/paper pulp is with reference to FZ/T50010.7-1998, alpha-cellulose content assay method is with reference to FZ/T50010.4-1998, polymerization degree measurement uses Fz/T50010.3-1998 method, determination of ash uses FZ/T50010.5-1998 method, inhales base number and measures employing FZ/T50010.9-1998 method.
Electronic Speculum model used by scanning electron microscope (SEM) photograph is EVO18, ZEISS company of Germany of manufacturer.
Embodiment 1
In the present embodiment, first being smashed by phragmites communis, being crushed to particle diameter is 2cm ~ 10cm.
The present embodiment extracts the technique of cellulose from described phragmites communis, comprises the steps:
(1) by after phragmites communis comminution pretreatment, use total acid is dense carries out steaming and decocting for the formic acid of 70wt% and the organic acid solution of acetic acid to the phragmites communis after processing, in the organic acid solution of the present embodiment, acetic acid is 1:1 with the mass ratio of formic acid, and adds the hydrogen peroxide (H accounting for phragmites communis raw material 3wt% before adding phragmites communis raw material2O2) as catalyst, control reaction temperature 125 DEG C, react 40min, solid-liquid mass ratio is 1:5, and the reactant liquor obtained carries out solid-liquid separation for the first time；
(2) solid first time solid-liquid separation obtained adds the organic acid solution of the dense formic acid for 70wt% of total acid and acetic acid and carries out acid elution, and the most above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for phragmites communis raw material 3wt% in the organic acid solution of 70wt%2O2) it is 1:1 as the mass ratio of catalyst and acetic acid with formic acid, controlling temperature is 80 DEG C, wash time 1h, and solid-liquid mass ratio is 1:4, and reactant liquor carries out second time solid-liquid separation；
(3) collect for the first time and liquid that second time solid-liquid separation obtains, in 50 DEG C, be evaporated under 1KPa, until being evaporated, using in the formic acid obtained and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the steaming and decocting of step (1)；
(4) collecting the second time solid that obtains of solid-liquid separation, and wash, controlling washing temperature is 25 DEG C, starches dense for 4wt%, and the washing slurry obtained carries out third time solid-liquid separation；
(5) collecting the liquid that third time solid-liquid separation obtains, carry out water, acid rectification, the mix acid liquor obtained is back in the reactor of step (1) be used for the steaming and decocting of step (1) as cooking liquor, and the Water circulation obtained washes with water in step (5) and uses water；
(6) collect the solid that third time solid-liquid separation obtains, carry out the solid obtained screening obtaining required screened stock cellulose, then obtain cellulose through bleaching process；Its whiteness of cellulose using the method for the present embodiment to obtain after measured is 98%ISO, alpha-cellulose content 96wt%, ash 0.02wt%, the degree of polymerization 900, inhales base number 750, productivity 43wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) carrying out alkali process first with the sodium hydroxide accounting for described screened stock cellulose 2wt%, controlling temperature is 60 DEG C, and extraction times 0.5h starches dense 8wt%；
(2) carrying out chelating agen pretreatment after alkali processes, in the present embodiment, chelating agen uses EDTA, and its consumption accounts for the 0.1wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 60 C, and time 0.5h starches dense 5wt%；
(3) carrying out alkaline hydrogen peroxide bleaching after EDTA pretreatment again, the consumption of hydrogen peroxide is the 1wt% of described screened stock cellulose, and controls to starch dense 8wt%, temperature 70 C, and utilizes sodium hydroxide to control between 10-12 by pH value, bleaching time 2h；
(4) using the sulphuric 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 being smashed by Caulis et Folium Oryzae, being crushed to particle diameter is 3cm ~ 5cm.
The present embodiment extracts the technique of cellulose from described Caulis et Folium Oryzae, comprises the steps:
(1) by after Caulis et Folium Oryzae comminution pretreatment, use total acid is dense carries out steaming and decocting for the formic acid of 90wt% and the organic acid solution of acetic acid to the Caulis et Folium Oryzae after processing, in the organic acid solution of the present embodiment, acetic acid is 1:8 with the mass ratio of formic acid, and adds the hydrogen peroxide (H accounting for straw raw material 4wt% before adding straw raw material2O2) as catalyst, control reaction temperature 145 DEG C, react 20min, solid-liquid mass ratio is 1:8, and the reactant liquor obtained carries out solid-liquid separation for the first time；
(2) solid first time solid-liquid separation obtained adds the organic acid solution of the dense formic acid for 90wt% of total acid and acetic acid and carries out acid elution, and the most above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for straw raw material 1wt% in the organic acid solution of 90wt%2O2) it is 1:8 as the mass ratio of catalyst and acetic acid with formic acid, controlling temperature is 30 DEG C, wash time 0.5h, and solid-liquid mass ratio is 1:8, and reactant liquor carries out second time solid-liquid separation；
(3) collect for the first time and liquid that second time solid-liquid separation obtains, in 80 DEG C, be evaporated under 11kPa, until being evaporated, using in the formic acid obtained and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the steaming and decocting of step (1)；
(4) collecting the second time solid that obtains of solid-liquid separation, and wash, controlling washing temperature is 40 DEG C, and washing slurry is dense for 5wt%, and the washing slurry obtained carries out third time solid-liquid separation；
(5) collecting the liquid that third time solid-liquid separation obtains, carry out water, acid rectification, the mix acid liquor obtained is back in the reactor of step (1) be used for the steaming and decocting of step (1) as cooking liquor, and the Water circulation obtained washes with water in step (5) and uses water；
(6) collect the third time solid that obtains of solid-liquid separation row filter of going forward side by side to obtain required screened stock cellulose, obtain cellulose through bleaching process again；Its whiteness of cellulose using the method for the present embodiment to obtain after measured is 96%ISO, alpha-cellulose content 95%, ash 0.04%, the degree of polymerization 900, inhales base number 700, productivity 31%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) potassium hydroxide that first described screened stock cellulose utilization accounts for its quality 5wt% carries out alkali process, and controlling temperature is 70 DEG C, and extraction times 1h starches dense 10wt%；
(2) carrying out chelating agen pretreatment after alkali processes, in the present embodiment, chelating agen uses DTPA(base pentaacetic acid), its consumption accounts for the 0.3wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 65 DEG C, and time 1h starches dense 4wt%；
(3) carrying out alkaline hydrogen peroxide bleaching after DTPA pretreatment again, the consumption of hydrogen peroxide is the 3wt% of described screened stock cellulose, use sodium hydroxide regulation pH value between 10-12, temperature 110 DEG C, bleaching time 3h, starch dense 6wt%；
(4) acid used in acid treatment, this step is the hydrochloric acid accounting for described screened stock cellulose 2wt%, and pH value controls between 2-4, temperature 55 DEG C, and time 1h starches dense 4wt%.
Embodiment 3
In the present embodiment, first bamboo chip is smashed, be crushed to a length of 2 ~ 10cm, the thin slice of thick 2mm.
The present embodiment extracts the technique of cellulose from described bamboo chip, comprises the steps:
(1) by after bamboo chip comminution pretreatment, use total acid is dense carries out steaming and decocting for the formic acid of 95wt% and the organic acid solution of acetic acid to the bamboo chip after processing, in the organic acid solution of the present embodiment, acetic acid is 1:6 with the mass ratio of formic acid, and adds the hydrogen peroxide (H accounting for bamboo chip raw material 6wt% before adding bamboo chip raw material2O2) as catalyst, control reaction temperature 135 DEG C, react 60min, solid-liquid mass ratio is 1:6, and the reactant liquor obtained carries out solid-liquid separation for the first time；
(2) solid first time solid-liquid separation obtained adds the organic acid solution of the dense formic acid for 95wt% of total acid and acetic acid and carries out acid elution, and the most 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%2O2) it is 1:6 as the mass ratio of catalyst and acetic acid with formic acid, controlling temperature is 100 DEG C, wash time 1h, and solid-liquid mass ratio is 1:10, and reactant liquor carries out second time solid-liquid separation；
(3) liquid obtained for the first time is collected with second time solid-liquid separation, in 110 DEG C, carry out low-temperature reduced-pressure evaporation under 21KPa, until being evaporated, using in the formic acid obtained and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the steaming and decocting of step (1)；
(4) collecting the second time solid that obtains of solid-liquid separation, and wash, controlling washing temperature is 60 DEG C, starches dense for 1wt%, and the washing slurry obtained carries out third time solid-liquid separation；
(5) collecting the liquid that third time solid-liquid separation obtains, carry out water, acid rectification, the mix acid liquor obtained is back in the reactor of step (1) be used for the steaming and decocting of step (1) as cooking liquor, and the Water circulation obtained washes with water in step (5) and uses water；
(6) collect the third time solid that obtains of solid-liquid separation row filter of going forward side by side and obtain required screened stock cellulose, again described screened stock bleaching process is obtained cellulose, its form, as in figure 2 it is shown, bamboo fibre form is preferable, shows that technique described in the present embodiment is less to the destructiveness of cellulose；Its whiteness of cellulose using the method for the present embodiment to obtain after measured is 97%ISO, alpha-cellulose content 93wt%, ash 0.04wt%, the degree of polymerization 800, inhales base number 700, productivity 43wt%.
Bleaching described in the present embodiment comprises the following steps:
(1) first with the potassium hydroxide accounting for its quality 8wt%, the screened stock cellulose obtained through screening being carried out alkali process, controlling temperature is 95 DEG C, and extraction times 3h starches dense 6wt%；
(2) carrying out chelating agen pretreatment after alkali processes, in the present embodiment, chelating agen uses sodium hexameta phosphate, and its consumption accounts for the 2wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 70 C, and time 2h starches dense 3wt%；
(3) after sodium hexameta phosphate pretreatment, then carrying out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the 5wt% of described screened stock cellulose, and use potassium hydroxide regulation pH value between 10-12, temperature 120 DEG C, bleaching time 4h, starch dense 10wt%；
(4) this step use account for the sulphuric acid of described screened stock cellulose 3wt%, control ph between 2-4, temperature 45 C, time 2h, starch dense 5wt%.
Embodiment 4
In the present embodiment, first being smashed by wheat straw, being crushed to particle diameter is 2-10cm.
The present embodiment extracts the technique of cellulose from described wheat straw, comprises the steps:
(1) by after wheat straw comminution pretreatment, use total acid is dense carries out steaming and decocting for the formic acid of 80wt% and the organic acid solution of acetic acid to the wheat straw after processing, in the organic acid solution of the present embodiment, acetic acid is 1:12 with the mass ratio of formic acid, and adds the hydrogen peroxide (H accounting for wheat straw raw material 1wt% before adding raw material2O2) as catalyst, control reaction temperature 120 DEG C, react 30min, solid-liquid mass ratio is 1:10, and the reactant liquor obtained carries out solid-liquid separation for the first time；
(2) solid first time solid-liquid separation obtained adds the organic acid solution of the dense formic acid for 75wt% of total acid and acetic acid and carries out acid elution, and the most above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for wheat straw raw material 8wt% in the organic acid solution of 75wt%2O2) it is 1:12 as the mass ratio of catalyst and acetic acid with formic acid, controlling temperature is 90 DEG C, wash time 1h, and solid-liquid mass ratio is 1:9, and reactant liquor carries out second time solid-liquid separation；
(3) liquid obtained for the first time is collected with second time solid-liquid separation, in 120 DEG C, carry out High Temperature High Pressure evaporation under 301kPa, until being evaporated, using in the formic acid obtained and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the steaming and decocting of step (1)；
(4) collecting the second time solid that obtains of solid-liquid separation, and wash, controlling washing temperature is 80 DEG C, and washing slurry is dense for 6wt%, and the washing slurry obtained carries out third time solid-liquid separation；
(5) collecting the liquid that third time solid-liquid separation obtains, carry out water, acid rectification, the mix acid liquor obtained is back in the reactor of step (1) be used for the steaming and decocting of step (1) as cooking liquor, and the Water circulation obtained washes with water in step (5) and uses water；
(6) collect the third time solid that obtains of solid-liquid separation 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 using the method for the present embodiment to obtain after measured is 95%ISO, alpha-cellulose content 94wt%, ash 0.03wt%, the degree of polymerization 850, inhales base number 750, productivity 35wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first with the sodium hydroxide accounting for its quality 1wt%, the screened stock cellulose obtained through screening being carried out alkali process, controlling temperature is 80 DEG C, and extraction times 2h starches dense 12wt%；
(2) carrying out chelating agen pretreatment after alkali processes, in the present embodiment, chelating agen uses sodium hexameta phosphate, and its consumption accounts for the 3wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 80 DEG C, and time 3h starches dense 3wt%；
(3) after sodium hexameta phosphate pretreatment, then carrying out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the 7wt% of described screened stock cellulose, and utilizes sodium hydroxide regulation pH value to control between 10-12, temperature 95 DEG C, and bleaching time 5h starches dense 13wt%；
(4) acid used in acid treatment, this step is the hydrochloric acid accounting for described screened stock cellulose 4wt%, and pH value controls between 2-4, temperature 40 DEG C, and time 0.5h starches dense 6wt%.
Embodiment 5
In the present embodiment, first being smashed by Semen Benincasae bar, being crushed to particle diameter is 2-10cm.
The present embodiment extracts the technique of cellulose from described Semen Benincasae bar, comprises the steps:
(1) by after Semen Benincasae bar comminution pretreatment, use total acid is dense carries out steaming and decocting for the formic acid of 70wt% and the organic acid solution of acetic acid to the Semen Benincasae bar after processing, in the organic acid solution of the present embodiment, acetic acid is 1:16 with the mass ratio of formic acid, and adds the hydrogen peroxide (H accounting for Semen Benincasae bar raw material 2wt% before adding raw material2O2) as catalyst, control reaction temperature 155 DEG C, react 10min, solid-liquid mass ratio is 1:15, and the reactant liquor obtained carries out solid-liquid separation for the first time；
(2) solid first time solid-liquid separation obtained adds the organic acid solution of the dense formic acid for 80wt% of total acid and acetic acid and carries out acid elution, and the most above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for Semen Benincasae bar raw material 4wt% in the organic acid solution of 80wt%2O2) it is 1:16 as the mass ratio of catalyst and acetic acid with formic acid, controlling temperature is 60 DEG C, wash time 0.5h, and solid-liquid mass ratio is 1:14, and reactant liquor carries out second time solid-liquid separation；
(3) collect for the first time and liquid that second time solid-liquid separation obtains, in 160 DEG C, be evaporated under 601kPa, until being evaporated, using in the formic acid obtained and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the steaming and decocting of step (1)；
(4) collecting the second time solid that obtains of solid-liquid separation, and carry out counter-flow water and wash, controlling washing temperature is 90 DEG C, starches dense for 8wt%, and the washing slurry obtained carries out third time solid-liquid separation；
(5) collecting the liquid that third time solid-liquid separation obtains, carry out water, acid rectification, the mix acid liquor obtained is back in the reactor of step (1) be used for the steaming and decocting of step (1) as cooking liquor, and the Water circulation obtained washes with water in step (5) and uses water；
(6) collect the third time solid that obtains of solid-liquid separation 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 using the method for the present embodiment to obtain after measured is 96%ISO, alpha-cellulose content 95.5wt%, ash 0.05wt%, the degree of polymerization 750, inhales base number 600, productivity 38wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first with the sodium hydroxide accounting for described screened stock cellulose 7wt%, the screened stock cellulose through screening being carried out alkali process, controlling temperature is 50 DEG C, and extraction times 4h starches dense 15wt%；
(2) carrying out chelating agen pretreatment after alkali processes, in the present embodiment, chelating agen uses EDTA(disodiumedetate), its consumption accounts for the 1wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 50 C, and time 4h starches dense 3wt%；
(3) after sodium hexameta phosphate pretreatment, then carrying out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the 9wt% of described screened stock cellulose, use potassium hydroxide regulation pH value between 10-12, temperature 85 DEG C, bleaching time 6h, starch dense 15wt%；With
(4) acid used in acid treatment, this step is nitric acid, and its consumption is the 6wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 35 DEG C, and time 2h starches dense 6wt%.Embodiment 6
In the present embodiment, first being smashed by cotton stem, being crushed to particle diameter is 0.5-2cm.
The present embodiment extracts the technique of cellulose from described cotton stem, comprises the steps:
(1) by after cotton stem comminution pretreatment, use total acid is dense carries out steaming and decocting for the formic acid of 75wt% and the organic acid solution of acetic acid to the cotton stem after processing, in the organic acid solution of the present embodiment, acetic acid is 1:19 with the mass ratio of formic acid, and adds the hydrogen peroxide (H accounting for cotton stem raw material 8wt% before adding raw material2O2) as catalyst, control reaction temperature 140 DEG C, react 50min, solid-liquid mass ratio is 1:9, and the reactant liquor obtained carries out solid-liquid separation for the first time；
(2) solid first time solid-liquid separation obtained adds the organic acid solution of the dense formic acid for 90wt% of total acid and acetic acid and carries out acid elution, and the most above-mentioned total acid is dense for adding the hydrogen peroxide (H accounting for cotton stem raw material 5wt% in the organic acid solution of 90wt%2O2) it is 1:19 as the mass ratio of catalyst and acetic acid with formic acid, controlling temperature is 40 DEG C, wash time 1h, and solid-liquid mass ratio is 1:20, and reactant liquor carries out second time solid-liquid separation；
(3) liquid obtained for the first time is collected with second time solid-liquid separation, in 180 DEG C, carry out High Temperature High Pressure evaporation under 901kPa, until being evaporated, using in the formic acid obtained and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the steaming and decocting of step (1)；
(4) collecting the second time solid that obtains of solid-liquid separation, and wash, controlling washing temperature is 70 DEG C, starches dense for 10wt%, and the washing slurry obtained carries out third time solid-liquid separation；
(5) collecting the liquid that third time solid-liquid separation obtains, carry out water, acid rectification, the mix acid liquor obtained is back in the reactor of step (1) be used for the steaming and decocting of step (1) as cooking liquor, and the Water circulation obtained washes with water in step (5) and uses water；
(6) collect the third time solid that obtains of solid-liquid separation 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 using the method for the present embodiment to obtain after measured is 94%ISO, alpha-cellulose content 96wt%, ash 0.02wt%, the degree of polymerization 700, inhales base number 750, productivity 41wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first with the sodium hydroxide accounting for its quality 10wt%, the screened stock cellulose obtained through screening being carried out alkali process, controlling temperature is 100 DEG C, and extraction times 2h starches dense 5wt%；
(2) carrying out chelating agen pretreatment after alkali processes, in the present embodiment, chelating agen uses sodium hexameta phosphate, and its consumption accounts for the 0.5wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 80 DEG C, and time 1.5h starches dense 3wt%；
(3) after sodium hexameta phosphate pretreatment, then carrying out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the 10wt% of described screened stock cellulose, and use sodium hydroxide control ph between 10-12, temperature 80 DEG C, bleaching time 2.5h, starch dense 5wt%；With
(4) sulphuric acid that acid is described screened stock cellulose 5wt% used in acid treatment, this step, pH value controls between 2-4, temperature 30 DEG C, and time 0.5h starches dense 6wt%.
Comparative example 1
Raw material used in the present embodiment and processing step and technological parameter are basically identical with embodiment 3, and 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 formic acid and the 5wt% water of 95wt%.The acid pickling step of its step (2) is under the catalytic action of hydrogen peroxide, use the formic acid by 95wt% and organic acid solution that 5wt% water forms carries out pickling, in each step, the adding proportion of hydrogen peroxide is consistent with embodiment 3, its whiteness of cellulose using the method for the present embodiment to obtain after measured is 67%ISO, alpha-cellulose content 88wt%, productivity 36%.
Comparative example 2
Raw material used in the present embodiment and processing step and technological parameter are basically identical with embodiment 3, and its difference is, in addition to the processing step of bleaching process, does not all add hydrogen peroxide as catalyst in each step.Its whiteness of cellulose using the method for the present embodiment to obtain after measured is 60%ISO, alpha-cellulose content 60wt%.
Comparative example 3
Raw material used in the present embodiment and processing step and technological parameter are basically identical with embodiment 3, and its difference is, in step (1), the digestion time of biomass material is 80min.Its cellulose obtained, its form is as it is shown on figure 3, show that technique described in the present embodiment is bigger to the destructiveness of cellulose；Its whiteness of cellulose using the method for the present embodiment to obtain after measured is 97%ISO, alpha-cellulose content 90wt%, ash 0.04wt%, the degree of polymerization 600, inhales base number 700, productivity 35wt%.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction 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 without also cannot all of embodiment be given exhaustive.And the obvious change thus extended out or variation still in the protection domain of the invention among.
Claims (10)
1. the technique extracting cellulose from biomass material, it is characterised in that comprise the steps:
(1) after biomass material being pulverized, under the catalytic action of hydrogen peroxide, use the organic acid solution being made up of formic acid and acetic acid that described raw material is carried out steaming and decocting, control boiling temperature 120-155 DEG C, solid-liquid mass ratio is 1:5-1:15, response time 10-60min, and the reactant liquor obtained is carried out solid-liquid separation for the first time；
In described organic acid solution, the dense mass ratio for 70-95wt%, described acetic acid and formic acid of total acid is 1:1-1:19, and surplus is water；
Hydrogen peroxide accounts for the 1-8wt% of biomass material；
(2) solid that described first time solid-liquid separation obtains is collected, under the catalytic action of hydrogen peroxide, use the mix acid liquor being made up of formic acid, acetic acid that described solid is carried out pickling, control pickling temperature 30-100 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reactant liquor obtained carries out second time solid-liquid separation；
In described mix acid liquor, the dense mass ratio for 70-95wt%, described acetic acid and formic acid of total 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 solid-liquid separation obtains, and wash, control washing temperature and be 25-90 DEG C, starch dense for 1-10wt%, and the washing slurry obtained is carried out third time solid-liquid separation；
(4) collect solid that described third time solid-liquid separation obtains and screening obtains required screened stock cellulose, obtains cellulose after bleaching；
Wherein, described bleaching comprises the steps:
Alkali processes, and described alkali consumption accounts for the 1-10wt% of described screened stock cellulose, and temperature is 50-100 DEG C, and extraction times 0.5-4h starches dense 5-15wt%；
Chelating agen pretreatment, the consumption of described chelating agen accounts for the 0.1-3wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 50-80 DEG C, and time 0.5-4h starches dense 3-5wt%；
Alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide accounts for the 1-10wt% of described screened stock cellulose, and pH value controls between 10-12, temperature 70-120 DEG C, and bleaching time 1-6h starches dense 5-15wt%；With
Acid treatment, the consumption of described acid accounts for the 1-6wt% of described screened stock cellulose, and pH value controls between 2-4, temperature 30-55 DEG C, and time 0.5-2h starches dense 3-6wt%.
The technique extracting cellulose from biomass material the most according to claim 1, it is characterised in that:
In the step that described alkali processes, described alkali consumption accounts for the 2-5wt% of described screened stock cellulose, and temperature is 70-95 DEG C, and extraction times 1-3h starches dense 6-12wt%；
In the step of described chelating agen pretreatment, the consumption of described chelating agen accounts for the 0.1-0.5wt% of described screened stock cellulose, temperature 50-65 DEG C, time 0.5-2h；
In the step of described alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide accounts for the 1-5wt% of described screened stock cellulose, temperature 80-95 DEG C, bleaching time 2-4h, starches dense 5-10wt%；With
In the step of described acid treatment, temperature 30-45 DEG C, time 0.5-1.5h.
The technique extracting cellulose from biomass material the most according to claim 1 and 2, it is characterised in that:
The described processing step extracting cellulose from biomass material also includes, collect liquid that described first time solid-liquid separation obtains and the liquid that described second time solid-liquid separation obtains is evaporated, after obtaining formic acid and acetic acid steam condensation, be back to described step (1) as cooking liquor.
The technique extracting cellulose from biomass material the most according to claim 3, it is characterised in that:
The described processing step extracting cellulose from biomass material also includes, collect the liquid that described third time solid-liquid separation obtains, carry out water, acid rectification, 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).
The technique extracting cellulose from biomass material the most according to claim 4, it is characterised in that:
In described step (1), solid-liquid mass ratio is 1:8-1:10, reaction temperature 125-145 DEG C, response time 20-40min；
The mass ratio of acetic acid and formic acid is 1:1-1:8, and total acid is dense for 75-95wt%,
The quality of hydrogen peroxide accounts for the 3-6wt% of biomass material.
6. according to the technique extracting cellulose from biomass material described in claim 4 or 5, it is characterised in that:
Mix acid liquor described in described step (2) is identical with organic acid solution described in step (1).
The technique extracting cellulose from biomass material the most according to claim 6, it is characterised in that:
The pickling temperature of described step (2) is 30-90 DEG C, and solid-liquid mass ratio is 1:8-1:10.
The technique extracting cellulose from biomass material the most according to claim 7, it is characterised in that:
The washing temperature of described step (3) is 60-90 DEG C, starches dense for 4-6wt%.
9. according to the technique extracting cellulose from biomass material described in claim 7 or 8, it is characterised in that:
The water-washing process of described step (3) is adverse current water-washing process.
The technique extracting cellulose from biomass material the most according to claim 9, it is characterised in that:
Described cellulose is dissolving pulp and/or industrial fiber element.
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