CN103898782A - Technology for extracting cellulose from biomass raw materials - Google Patents
Technology for extracting cellulose from biomass raw materials Download PDFInfo
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- CN103898782A CN103898782A CN201210576355.6A CN201210576355A CN103898782A CN 103898782 A CN103898782 A CN 103898782A CN 201210576355 A CN201210576355 A CN 201210576355A CN 103898782 A CN103898782 A CN 103898782A
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Abstract
The invention relates to a cellulose extracting technology, and specifically relates to a technology that utilizes organic acids to extract cellulose from biomass raw materials in the presence of a hydrogen peroxide catalyst. The technology comprises the following steps: in the presence of a hydrogen peroxide catalyst, utilizing an organic acid to cook biomass raw materials, wherein the organic acid is composed of formic acid with a concentration of 70 to 95 wt% and acetic acid with a concentration of 70 to 95 wt%; extracting and screening so as to obtain screened cellulose pulp; and further bleaching the screened pulp so as to obtain the target cellulose; wherein the cellulose is dissolving pulp or industrial cellulose. The alpha-cellulose content of the cellulose obtained by the method provided by the invention is more than 90 wt%. The technology has the advantages of simple route and low energy consumption.
Description
Technical field
The present invention relates to a kind of cellulose extraction process, specifically one utilizes organic acid from biomass material, to extract cellulosic technique.
Background technology
Biomass material main component is cellulose, hemicellulose and lignin, wherein, cellulose accounts for 40% left and right, hemicellulose accounts for 25% left and right, lignin accounts for 20% left and right, the biomass material total amount being generated by photosynthesis every year on the earth exceedes 2,000 hundred million tons, and therefore living beings are renewable resources abundant, the most cheap on the earth.
Cellulose is the main component of plant cell wall.The whole world, for the cellulose of the papermaking of weaving, reaches 8,000,000 tons every year.In addition, do raw material with the cellulose of separation and purification, can manufacture artificial silk, the ether derivatives such as the ester derivatives such as cellophane and 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 social fast development, living standards of the people improve constantly, the consumption of social resources increases the natural rate of growth that has been 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, be mainly the Populus deltoides dissolving pulp that cotton linter, needlebush, leaf wood are main raw material, but due to the minimizing year by year of sown areas of cotton, also reduced year by year of cotton linter output, and the resources 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 prepared in research and development, expands the raw-material range of choice of fiber use industry, and social sustainable development is had to positive meaning.
Chinese patent CN1170031C discloses the method for a kind of mixture with formic acid and acetic acid as cooking chemical production paper pulp.This patent is in the time producing paper pulp with formic acid boiling 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, object is the hemicellulose that retains to greatest extent cellulose and part, its whole technological design is all with this end in view, and therefore this technique is for also inapplicable for extracting the technique of product take cellulose.
Summary of the invention
For this reason, technical problem to be solved by this invention is to provide a kind of process route that extracts high purity cellulose from biomass material by rational parameter setting.
For solving the problems of the technologies described above, of the present inventionly from biomass material, extract cellulosic technique, it is characterized in that, comprise the steps:
(1) after biomass material is pulverized, under the catalytic action of hydrogen peroxide, use the organic acid solution being formed by formic acid and acetic acid to carry out boiling to described raw material, control boiling temperature 120-155 ℃, solid-liquid mass ratio is 1:5-1:15, reaction time 10-60min, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time; In described organic acid solution, total acid is dense is 70-95wt%, and 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) solid that described in collection, Separation of Solid and Liquid obtains for the first time, under the catalytic action of hydrogen peroxide, use the mix acid liquor being formed by formic acid, acetic acid to carry out pickling to described solid, control pickling temperature 30-100 ℃, solid-liquid mass ratio is 1:4-1:20, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the second time; In described mix acid liquor, total acid is dense is 70-95wt%, and 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) solid that described in collection, Separation of Solid and Liquid obtains for the second time, and wash, control washing temperature is 25-90 ℃, starching dense is 1-10wt%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(4) solid that described in collection, Separation of Solid and Liquid obtains for the third time screening obtain required screened stock cellulose, after bleaching, obtain cellulose.
From biomass material, extract cellulosic technique above-mentioned, described bleaching comprises the steps:
Alkali treatment, described alkali consumption accounts for the cellulosic 1-10wt% of described screened stock, and temperature is 50-100 ℃, and extracting time 0.5-4h, starches dense 5-15wt%;
Chelating agent preliminary treatment, the consumption of described chelating agent accounts for the cellulosic 0.1-3wt% of described screened stock, and pH value is controlled between 2-4, temperature 50-80 ℃, time 0.5-4h, starches dense 3-5wt%;
Alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide accounts for the cellulosic 1-10wt% of described screened stock, and pH value is controlled between 10-12, temperature 70-120 ℃, bleaching time 1-6h, starches dense 5-15wt%; With
Acid treatment, the consumption of described acid accounts for the cellulosic 1-6wt% of described screened stock, and pH value is controlled between 2-4, temperature 30-55 ℃, time 0.5-2h, starches dense 3-6wt%.
Preferably,
In the step of described alkali treatment, described alkali consumption accounts for the cellulosic 2-5wt% of described screened stock, and temperature is 70-95 ℃, and extracting time 1-3h, starches dense 6-12wt%;
In the pretreated step of described chelating agent, the consumption of described chelating agent accounts for the cellulosic 0.1-0.5wt% of described screened stock, temperature 50-65 ℃, time 0.5-2h;
In the step of described alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide accounts for the cellulosic 1-5wt% of described screened stock, temperature 80-95 ℃, and bleaching time 2-4h, starches dense 5-10wt%; With
In described acid-treated step, temperature 30-45 ℃, time 0.5-1.5h.
Preferably, describedly from biomass material, extract cellulosic processing step and also comprise, the liquid that the liquid that described in collection, Separation of Solid and Liquid obtains for the first time and described Separation of Solid and Liquid for the second time obtain evaporates, and obtains being back to described step (1) as cooking liquor after formic acid and acetic acid steam condensation.
Preferably, describedly from biomass material, extract cellulosic processing step and also comprise, the liquid that described in collection, Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to described step (1) as cooking liquor, and the water obtaining washes water with water and is back to step (3).
Preferably, in described step (1), solid-liquid mass ratio is 1:8-1:10, reaction temperature 125-145 ℃, reaction time 20-40min; The mass ratio of acetic acid and formic acid is 1:1-1:8, and total acid is dense is 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 ℃, and solid-liquid mass ratio is 1:8-1:10.
Preferably, the washing temperature of described step (3) is 60-90 ℃, and starching dense is 4-6wt%.
Preferably, the water-washing process of described step (3) is adverse current water-washing process.
Above-mentionedly from biomass material, extract cellulosic technique, described cellulose is dissolving pulp and/or industrial fiber element.
Described biomass material can be one or more in the wooden classes such as reed, beanstalk stalk, wheat stalk, straw, maize straw, melon seed cases, bamboo chip, melon seeds bar or grass as raw material.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, the present invention, by technological parameter reasonable in design, makes whole process route not be only applicable to wooden class raw material, is also applicable to grass as raw material, and the cellulose purity obtaining is high, and wherein the content of alpha-cellulose, more than 92wt%, is up to 98wt%.
2, digestion process of the present invention carries out in airtight reaction vessel, due to the part evaporation of formic acid, acetic acid and hydrogen peroxide, makes in container, to have certain pressure, thereby has shortened the digestion time of raw material, has reduced 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 of doing in degraded raw material, owing to using separately formic acid can destroy the alpha-cellulose in cellulose, not only protect alpha-cellulose not to be destroyed so add appropriate acetic acid, and the organic solvent dissolution lignin molecule that utilizes formic acid and acetic acid to form, 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, aggravated degraded and the dissolving of lignin, and prevented the hydrolytic cleavage of fiber high polymer.
4, in technique of the present invention; all add hydrogen peroxide in boiling and acid pickling step; owing to having removed to greatest extent lignin matter adding of hydrogen peroxide in pulping process; and protect carbohydrate not to be destroyed; thereby following bleaching technique, only needs chlorine-free bleaching simply can realize the slurry of high whiteness.
5, the present invention adopts specific bleaching process to carrying out bleaching through the slurry of screening, bleaching process, and this technique 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 has realized total chlorine free bleaching, pollution-free; Again, this bleaching process has not only improved pulp brightness, and can make to remove the ash content in high ash content straw pulp, has thoroughly broken through the technical bottleneck of preparing high purity cellulose (as dissolving pulp) with high ash content grass class; Finally, this technique is destroyed very little even without destroying to cellulose, can prepare high polymerization degree cellulose.
6, boiling for the first time obtains after cellulose, 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 inner cellulose remaining a small amount of lignin is decomposed and stripping, further except delignification, in addition, 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 any preliminary treatment.
7, technique of the present invention is directly evaporated the liquid that Separation of Solid and Liquid obtains for the first time and for the second time of collecting, after the formic acid that obtains, acetic acid condensation as cooking liquor, directly the whole process route of reflow step (1) is succinct, because formic acid and acetic acid re-use as raw material, boiling efficiency to raw material is higher, for utilizing the technique of the cooking liquor circulation after boiling, although saved the step of this circulation, but realize within the identical process time, higher to the clearance of hemicellulose and lignin.
Accompanying drawing explanation
For content of the present invention is 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;
Fig. 2 is the cellulosic scanning electron microscope (SEM) photograph extracting in the embodiment of the present invention 3;
Fig. 3 is the cellulosic scanning electron microscope (SEM) photograph extracting in comparative example 3 of the present invention.
The specific embodiment
Below will by specific embodiment, the invention will be further described.
In following examples, outside specified otherwise, percentage composition used all represents quality percentage composition, i.e. " % " expression " wt% "; In described organic acid solution except a certain amount of formic acid, acetic acid, surplus is water, the gross mass of the dense nail acid of total acid described in each step and acetic acid accounts for the percentage of described organic acid solution quality, and the solid-liquid mass ratio in each step refers to the quality of solid in this each step and the mass ratio of the total liquid adding
Slurry described in each step is dense=this step in quality/this step of solid the Zhi Liang of solid and liquid with ╳ 100%
The Zhi Liang ╳ 100% of cellulosic productive rate=cellulosic quality/raw material in each embodiment.
In each embodiment, the form of the aqueous hydrogen peroxide solution of hydrogen peroxide H2O2 take mass concentration as 27% adds.For example need as calculated to add 2.7g hydrogen peroxide, 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/T 50010.7-1998, alpha-cellulose content assay method is with reference to FZ/T 50010.4-1998, polymerization degree measurement adopts Fz/T 50010.3-1998 method, ash determination adopts FZ/T 50010.5-1998 method, inhales base number and measures the FZ/T 50010.9-1998 method that adopts.
Scanning electron microscope (SEM) photograph Electronic Speculum model used is EVO18, ZEISS company of Germany of manufacturer.
Embodiment 1
In the present embodiment, first reed is smashed, being crushed to particle diameter is 2cm ~ 10cm.
The present embodiment extracts cellulosic technique from described reed, comprises the steps:
(1) by after reed comminution pretreatment, use that total acid is dense carries out boiling to reed after treatment for the formic acid of 70wt% and the organic acid solution of acetic acid, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:1, and before reed raw material, adds the hydrogen peroxide (H that accounts for reed raw material 3wt% adding
2o
2) as catalyst, control 125 ℃ of reaction temperatures, reaction 40min, solid-liquid mass ratio is 1:5, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) add total acid dense for the formic acid of 70wt% and the organic acid solution of acetic acid carry out acid elution the solid that Separation of Solid and Liquid obtains for the first time, wherein in the dense organic acid solution for 70wt% of above-mentioned total acid, added the hydrogen peroxide (H that accounts for reed raw material 3wt%
2o
2) be 1:1 as the mass ratio of catalyst and acetic acid and formic acid, controlling temperature is 80 ℃, wash time 1h, solid-liquid mass ratio is 1:4, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect for the first time and the liquid that Separation of Solid and Liquid obtains for the second time, in 50 ℃, under 1KPa, evaporate, until evaporate to dryness, using the formic acid obtaining and acetic acid vapor condensing reflux to the reactor of step (1) in as cooking liquor, for the boiling of step (1);
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 25 ℃, and starching dense is 4wt%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collect the solid that Separation of Solid and Liquid obtains for the third time, the solid obtaining is screened and obtains required screened stock cellulose, then obtain cellulose through bleaching process; Adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 98%ISO, alpha-cellulose content 96wt%, and ash content 0.02wt%, the degree of polymerization 900, inhales base number 750, productive rate 43wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH that accounts for described screened stock cellulose 2wt% to carry out alkali treatment, controlling temperature is 60 ℃, and extracting time 0.5h, 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 0.1wt% of described screened stock, and pH value is controlled between 2-4, temperature 60 C, and time 0.5h, starches dense 5wt%;
(3) after EDTA preliminary treatment, carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the cellulosic 1wt% of described screened stock again, and controls the dense 8wt% of slurry, temperature 70 C, and utilize NaOH that pH value is controlled between 10-12, bleaching time 2h;
(4) adopt the sulfuric acid that accounts for described screened stock cellulose 1wt% to carry out acid treatment, pH value is controlled between 2-4, temperature 50 C, and time 1.5h, starches dense 3wt%.
Embodiment 2
In the present embodiment, first straw is smashed, being crushed to particle diameter is 3cm ~ 5cm.
The present embodiment extracts cellulosic technique from described straw, comprises the steps:
(1) by after straw comminution pretreatment, use that total acid is dense carries out boiling to straw after treatment for the formic acid of 90wt% and the organic acid solution of acetic acid, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:8, and before straw raw material, adds the hydrogen peroxide (H that accounts for straw raw material 4wt% adding
2o
2) as catalyst, control 145 ℃ of reaction temperatures, reaction 20min, solid-liquid mass ratio is 1:8, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) add total acid dense for the formic acid of 90wt% and the organic acid solution of acetic acid carry out acid elution the solid that Separation of Solid and Liquid obtains for the first time, wherein in the dense organic acid solution for 90wt% of above-mentioned total acid, added the hydrogen peroxide (H that accounts for straw raw material 1wt%
2o
2) be 1:8 as the mass ratio of catalyst and acetic acid and formic acid, controlling temperature is 30 ℃, wash time 0.5h, solid-liquid mass ratio is 1:8, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect for the first time and the liquid that Separation of Solid and Liquid obtains for the second time, in 80 ℃, under 11kPa, evaporate, until evaporate to dryness, using the formic acid obtaining and acetic acid vapor condensing reflux to the reactor of step (1) in as cooking liquor, for the boiling of step (1);
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 40 ℃, and washing slurry is dense is 5wt%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collecting Separation of Solid and Liquid obtains for the third time the solid row filter of going forward side by side obtains required screened stock cellulose, obtains cellulose through bleaching process again; Adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 96%ISO, alpha-cellulose content 95%, and ash content 0.04%, the degree of polymerization 900, inhales base number 700, productive rate 31%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) potassium hydroxide that first described screened stock cellulose utilization is accounted for to its quality 5wt% carries out alkali treatment, and controlling temperature is 70 ℃, and extracting time 1h, starches dense 10wt%;
(2) after alkali treatment, carry out chelating agent preliminary treatment, in the present embodiment, chelating agent adopts DTPA(base pentaacetic acid), its consumption accounts for the cellulosic 0.3wt% of described screened stock, and pH value is controlled between 2-4,65 ℃ of temperature, time 1h, starches dense 4wt%;
(3) after DTPA preliminary treatment, carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the cellulosic 3wt% of described screened stock again, adopts NaOH to regulate pH value between 10-12,110 ℃ of temperature, and bleaching time 3h, starches dense 6wt%;
(4) acid treatment, the acid adopting in this step is the hydrochloric acid that accounts for described screened stock cellulose 2wt%, pH value is controlled between 2-4,55 ℃ of temperature, time 1h, starches dense 4wt%.
Embodiment 3
In the present embodiment, first bamboo chip is smashed, being crushed to length is 2 ~ 10cm, the thin slice of thick 2mm.
The present embodiment extracts cellulosic technique from described bamboo chip, comprises the steps:
(1) by after bamboo chip comminution pretreatment, use that total acid is dense carries out boiling to bamboo chip after treatment for the formic acid of 95wt% and the organic acid solution of acetic acid, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:6, and before bamboo chip raw material, adds the hydrogen peroxide (H that accounts for bamboo chip raw material 6wt% adding
2o
2) as catalyst, control 135 ℃ of reaction temperatures, reaction 60min, solid-liquid mass ratio is 1:6, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) add total acid dense for the formic acid of 95wt% and the organic acid solution of acetic acid carry out acid elution the solid that Separation of Solid and Liquid obtains for the first time, wherein in the dense organic acid solution for 95wt% of above-mentioned total acid, added the hydrogen peroxide (H that accounts for bamboo chip raw material 6wt%
2o
2) be 1:6 as the mass ratio of catalyst and acetic acid and formic acid, controlling temperature is 100 ℃, wash time 1h, solid-liquid mass ratio is 1:10, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect for the first time and the liquid that Separation of Solid and Liquid obtains for the second time, in 110 ℃, under 21KPa, carry out low-temperature reduced-pressure evaporation, until evaporate to dryness, in using the formic acid obtaining and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1);
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 60 ℃, and starching dense is 1wt%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collect Separation of Solid and Liquid obtains for the third time the solid row filter of going forward side by side and obtain required screened stock cellulose, again described screened stock bleaching process is obtained to cellulose, as shown in Figure 2, bamboo fibre form is better for its form, shows that technique is less to cellulosic destructiveness described in the present embodiment; Adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 97%ISO, alpha-cellulose content 93wt%, and ash content 0.04wt%, the degree of polymerization 800, inhales base number 700, productive rate 43wt%.
Bleaching described in the present embodiment comprises the following steps:
(1) first utilize the potassium hydroxide that accounts for its quality 8wt% to carry out alkali treatment the screened stock cellulose obtaining through screening, controlling temperature is 95 ℃, and extracting time 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 cellulosic 2wt% of described screened stock, and pH value is controlled 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 to regulate pH value between 10-12,120 ℃ of temperature, and bleaching time 4h, starches dense 10wt%;
(4) in this step, adopt the sulfuric acid that accounts for described screened stock cellulose 3wt%, control pH value between 2-4, temperature 45 C, time 2h, starches dense 5wt%.
Embodiment 4
In the present embodiment, first wheat straw is smashed, 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 that total acid is dense carries out boiling to wheat straw after treatment for the formic acid of 80wt% and the organic acid solution of acetic acid, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:12, and before raw material, adds the hydrogen peroxide (H that accounts for wheat straw raw material 1wt% adding
2o
2) as catalyst, control 120 ℃ of reaction temperatures, reaction 30min, solid-liquid mass ratio is 1:10, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) add total acid dense for the formic acid of 75wt% and the organic acid solution of acetic acid carry out acid elution the solid that Separation of Solid and Liquid obtains for the first time, wherein in the dense organic acid solution for 75wt% of above-mentioned total acid, added the hydrogen peroxide (H that accounts for wheat straw raw material 8wt%
2o
2) be 1:12 as the mass ratio of catalyst and acetic acid and formic acid, controlling temperature is 90 ℃, wash time 1h, solid-liquid mass ratio is 1:9, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect for the first time and the liquid that Separation of Solid and Liquid obtains for the second time, in 120 ℃, under 301kPa, carry out High Temperature High Pressure evaporation, until evaporate to dryness, in using the formic acid obtaining and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1);
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 80 ℃, and washing slurry is dense is 6wt%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collect Separation of Solid and Liquid obtains for the third time the solid row filter of going forward side by side and obtain required screened stock cellulose, the screened stock cellulose obtaining is bleached and obtained cellulose; Adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 95%ISO, alpha-cellulose content 94wt%, and ash content 0.03wt%, the degree of polymerization 850, inhales base number 750, productive rate 35wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH that accounts for its quality 1wt% to carry out alkali treatment the screened stock cellulose obtaining through screening, controlling temperature is 80 ℃, and extracting time 2h, starches dense 12wt%;
(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 is controlled between 2-4,80 ℃ of temperature, 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 to regulate pH value to be controlled between 10-12,95 ℃ of temperature, and bleaching time 5h, starches dense 13wt%;
(4) acid treatment, the acid adopting in this step is the hydrochloric acid that accounts for described screened stock cellulose 4wt%, pH value is controlled between 2-4,40 ℃ of temperature, time 0.5h, starches dense 6wt%.
Embodiment 5
In the present embodiment, first melon seeds bar is smashed, being crushed to particle diameter is 2-10cm.
The present embodiment extracts cellulosic technique from described melon seeds bar, comprises the steps:
(1) by after melon seeds bar comminution pretreatment, use that total acid is dense carries out boiling to melon seeds bar after treatment for the formic acid of 70wt% and the organic acid solution of acetic acid, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:16, and before raw material, adds the hydrogen peroxide (H that accounts for melon seeds bar raw material 2wt% adding
2o
2) as catalyst, control 155 ℃ of reaction temperatures, reaction 10min, solid-liquid mass ratio is 1:15, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) add total acid dense for the formic acid of 80wt% and the organic acid solution of acetic acid carry out acid elution the solid that Separation of Solid and Liquid obtains for the first time, wherein in the dense organic acid solution for 80wt% of above-mentioned total acid, added the hydrogen peroxide (H that accounts for melon seeds bar raw material 4wt%
2o
2) be 1:16 as the mass ratio of catalyst and acetic acid and formic acid, controlling temperature is 60 ℃, wash time 0.5h, solid-liquid mass ratio is 1:14, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect for the first time and the liquid that Separation of Solid and Liquid obtains for the second time, in 160 ℃, under 601kPa, evaporate, until evaporate to dryness, using the formic acid obtaining and acetic acid vapor condensing reflux to the reactor of step (1) in as cooking liquor, for the boiling of step (1);
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and carry out counter-flow water and wash, controlling washing temperature is 90 ℃, and starching dense is 8wt%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collect Separation of Solid and Liquid obtains for the third time the solid row filter of going forward side by side and obtain required screened stock cellulose, the screened stock cellulose obtaining is carried out to bleaching process and obtain cellulose; Adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 96%ISO, alpha-cellulose content 95.5wt%, and ash content 0.05wt%, the degree of polymerization 750, inhales base number 600, productive rate 38wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) will first utilize the NaOH that accounts for described screened stock cellulose 7wt% to carry out alkali treatment through the screened stock cellulose of screening, controlling temperature be 50 ℃, and extracting time 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), its consumption accounts for the cellulosic 1wt% of described screened stock, and pH value is controlled 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, adopts potassium hydroxide to regulate pH value between 10-12,85 ℃ of temperature, and bleaching time 6h, starches dense 15wt%; With
(4) acid treatment, the acid adopting in this step is nitric acid, and its consumption is the cellulosic 6wt% of described screened stock, and pH value is controlled between 2-4,35 ℃ of temperature, time 2h, starches dense 6wt%.Embodiment 6
In the present embodiment, first cotton stem is smashed, 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 that total acid is dense carries out boiling to cotton stem after treatment for the formic acid of 75wt% and the organic acid solution of acetic acid, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:19, and before raw material, adds the hydrogen peroxide (H that accounts for cotton stem raw material 8wt% adding
2o
2) as catalyst, control 140 ℃ of reaction temperatures, reaction 50min, solid-liquid mass ratio is 1:9, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
(2) add total acid dense for the formic acid of 90wt% and the organic acid solution of acetic acid carry out acid elution the solid that Separation of Solid and Liquid obtains for the first time, wherein in the dense organic acid solution for 90wt% of above-mentioned total acid, added the hydrogen peroxide (H that accounts for cotton stem raw material 5wt%
2o
2) be 1:19 as the mass ratio of catalyst and acetic acid and formic acid, controlling temperature is 40 ℃, wash time 1h, solid-liquid mass ratio is 1:20, and reactant liquor is carried out to Separation of Solid and Liquid for the second time;
(3) collect for the first time and the liquid that Separation of Solid and Liquid obtains for the second time, in 180 ℃, under 901kPa, carry out High Temperature High Pressure evaporation, until evaporate to dryness, in using the formic acid obtaining and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1);
(4) collect the solid that Separation of Solid and Liquid obtains for the second time, and wash, controlling washing temperature is 70 ℃, and starching dense is 10wt%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(5) collect the liquid that Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to the boiling for step (1) as cooking liquor in the reactor of step (1), and the water obtaining is back to step (5) and washes water with water;
(6) collect Separation of Solid and Liquid obtains for the third time the solid row filter of going forward side by side and obtain required screened stock cellulose, the screened stock cellulose obtaining is bleached and obtained cellulose; Adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 94%ISO, alpha-cellulose content 96wt%, and ash content 0.02wt%, the degree of polymerization 700, inhales base number 750, productive rate 41wt%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH that accounts for its quality 10wt% to carry out alkali treatment the screened stock cellulose obtaining through screening, controlling temperature is 100 ℃, and extracting time 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 0.5wt% of described screened stock, and pH value is controlled between 2-4,80 ℃ of temperature, and time 1.5h, starches dense 3wt%;
(3) after calgon preliminary treatment, then carry out alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide is the cellulosic 10wt% of described screened stock, and adopts NaOH control pH value between 10-12,80 ℃ of temperature, and bleaching time 2.5h, starches dense 5wt%; With
(4) acid treatment, the acid adopting in this step is the sulfuric acid of described screened stock cellulose 5wt%, pH value is controlled between 2-4,30 ℃ of temperature, time 0.5h, starches dense 6wt%.
Comparative example 1
In the present embodiment, raw material used and processing step and technological parameter and embodiment 3 are basically identical, 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, the organic acid solution that the formic acid by 95wt% adopting and 5wt% water form carries out pickling, in each step, the adding proportion of hydrogen peroxide is consistent with embodiment 3, adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 67%ISO, alpha-cellulose content 88wt%, productive rate 36%.
Comparative example 2
In the present embodiment, raw material used and processing step and technological parameter and embodiment 3 are basically identical, and its difference is, except the processing step of bleaching process, does not all add hydrogen peroxide as catalyst in each step.Adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 60%ISO, alpha-cellulose content 60wt%.
Comparative example 3
In the present embodiment, raw material used and processing step and technological parameter and embodiment 3 are basically identical, and its difference is, in step (1), the digestion time of biomass material is 80min.The cellulose that it obtains, its form as shown in Figure 3, shows that technique is larger to cellulosic destructiveness described in the present embodiment; Adopting after measured its whiteness of cellulose that the method for the present embodiment obtains is 97%ISO, alpha-cellulose content 90wt%, and ash content 0.04wt%, the degree of polymerization 600, inhales base number 700, productive rate 35wt%.
Obviously, above-described embodiment is only for example is clearly described, and the 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 giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (11)
1. from biomass material, extract a cellulosic technique, it is characterized in that, comprise the steps:
(1) after biomass material is pulverized, under the catalytic action of hydrogen peroxide, use the organic acid solution being formed by formic acid and acetic acid to carry out boiling to described raw material, control boiling temperature 120-155 ℃, solid-liquid mass ratio is 1:5-1:15, reaction time 10-60min, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the first time;
In described organic acid solution, total acid is dense is 70-95wt%, and 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) solid that described in collection, Separation of Solid and Liquid obtains for the first time, under the catalytic action of hydrogen peroxide, use the mix acid liquor being formed by formic acid, acetic acid to carry out pickling to described solid, control pickling temperature 30-100 ℃, solid-liquid mass ratio is 1:4-1:20, and the reactant liquor obtaining is carried out to Separation of Solid and Liquid for the second time;
In described mix acid liquor, total acid is dense is 70-95wt%, and 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) solid that described in collection, Separation of Solid and Liquid obtains for the second time, and wash, control washing temperature is 25-90 ℃, starching dense is 1-10wt%, and the washing slurry obtaining is carried out to Separation of Solid and Liquid for the third time;
(4) solid that described in collection, Separation of Solid and Liquid obtains for the third time screening obtain required screened stock cellulose, after bleaching, obtain cellulose.
2. according to claim 1ly from biomass material, extract cellulosic technique, it is characterized in that, described bleaching comprises the steps:
Alkali treatment, described alkali consumption accounts for the cellulosic 1-10wt% of described screened stock, and temperature is 50-100 ℃, and extracting time 0.5-4h, starches dense 5-15wt%;
Chelating agent preliminary treatment, the consumption of described chelating agent accounts for the cellulosic 0.1-3wt% of described screened stock, and pH value is controlled between 2-4, temperature 50-80 ℃, time 0.5-4h, starches dense 3-5wt%;
Alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide accounts for the cellulosic 1-10wt% of described screened stock, and pH value is controlled between 10-12, temperature 70-120 ℃, bleaching time 1-6h, starches dense 5-15wt%; With
Acid treatment, the consumption of described acid accounts for the cellulosic 1-6wt% of described screened stock, and pH value is controlled between 2-4, temperature 30-55 ℃, time 0.5-2h, starches dense 3-6wt%.
3. according to claim 2ly from biomass material, extract cellulosic technique, it is characterized in that:
In the step of described alkali treatment, described alkali consumption accounts for the cellulosic 2-5wt% of described screened stock, and temperature is 70-95 ℃, and extracting time 1-3h, starches dense 6-12wt%;
In the pretreated step of described chelating agent, the consumption of described chelating agent accounts for the cellulosic 0.1-0.5wt% of described screened stock, temperature 50-65 ℃, time 0.5-2h;
In the step of described alkaline hydrogen peroxide bleaching, the consumption of hydrogen peroxide accounts for the cellulosic 1-5wt% of described screened stock, temperature 80-95 ℃, and bleaching time 2-4h, starches dense 5-10wt%; With
In described acid-treated step, temperature 30-45 ℃, time 0.5-1.5h.
4. according to the arbitrary described cellulosic technique of extracting from biomass material of claim 1-3, it is characterized in that:
Describedly from biomass material, extract cellulosic processing step and also comprise, the liquid that the liquid that described in collection, Separation of Solid and Liquid obtains for the first time and described Separation of Solid and Liquid for the second time obtain evaporates, and obtains being back to described step (1) as cooking liquor after formic acid and acetic acid steam condensation.
5. according to the arbitrary described cellulosic technique of extracting from biomass material of claim 1-4, it is characterized in that:
Describedly from biomass material, extract cellulosic processing step and also comprise, the liquid that described in collection, Separation of Solid and Liquid obtains for the third time, carry out water, sour rectifying, the mix acid liquor obtaining is back to described step (1) as cooking liquor, and the water obtaining washes water with water and is back to step (3).
6. according to the arbitrary described cellulosic technique of extracting from biomass material of claim 1-5, it is characterized in that:
In described step (1), solid-liquid mass ratio is 1:8-1:10, reaction temperature 125-145 ℃, reaction time 20-40min;
The mass ratio of acetic acid and formic acid is 1:1-1:8, and total acid is dense is 75-95wt%,
The quality of hydrogen peroxide accounts for the 3-6wt% of biomass material.
7. according to extracting cellulosic technique described in claim 1-6 from biomass material, it is characterized in that:
Mix acid liquor described in described step (2) is identical with organic acid solution described in step (1).
8. according to claim 7ly from biomass material, extract cellulosic technique, it is characterized in that:
The pickling temperature of described step (2) is 30-90 ℃, and solid-liquid mass ratio is 1:8-1:10.
9. according to the arbitrary described cellulosic technique of extracting from biomass material of claim 1-8, it is characterized in that:
The washing temperature of described step (3) is 60-90 ℃, and starching dense is 4-6wt%.
10. according to claim 9ly from biomass material, extract cellulosic technique, it is characterized in that:
The water-washing process of described step (3) is adverse current water-washing process.
11. according to the arbitrary described cellulosic technique of extracting from biomass material of claim 1-10, it is characterized in that:
Described cellulose is dissolving pulp and/or industrial fiber element.
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