CN103088686B - Technology for preparing paper pulp and coproducing biochar from lignocellulose biomass - Google Patents
Technology for preparing paper pulp and coproducing biochar from lignocellulose biomass Download PDFInfo
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Abstract
The invention relates to a preparation method of paper pulp, and in particular relates to a method for preparing paper pulp from biomass raw material by utilizing organic acid. The method disclosed by the invention comprises the following step of cooking the biomass raw material to prepare the paper pulp by using the organic acid formed by formic acid and acetic acid under the catalytic action of hydrogen peroxide. The method for preparing the paper pulp provided by the invention is high in yield, short in cooking time and simple in bleaching technology. The lignin is furthest removed since the hydrogen peroxide is added in the pulping process, and carbohydrate is protected from being damaged so that high-whiteness sizing agent can be obtained by only requiring chlorine free bleaching simply in subsequent bleaching technology. Moreover, the obtained paper pulp is good in drainability, low in Kappa number and good in fiber characteristics. Moreover, black liquor generated in the process of producing paper pulp can be utilized for preparing biochar, the influence of pollutants discharged in the process of paper making to the environment is reduced, and the economic benefit and environmental benefit of enterprises are improved.
Description
Technical field
The present invention relates to a kind of preparation technology of paper pulp, specifically a kind of under the catalytic action of hydrogen peroxide, utilize the organic acid boiling lignocellulose biomass raw material of formic acid and acetic acid composition to prepare the technique of paper pulp, utilize the method for black liquid production biological carbon simultaneously.
Background technology
Along with the understanding of the problems such as mankind's environmental pollution and crisis of resource deepens continuously, the character such as renewable, degradable that natural polymer has comes into one's own day by day.The resource of discarded object and the utilization of renewable resource are the key subjects of modern economy and social development, are also the new demands proposed contemporary science and technology.
Lignocellulose biomass exists with the form of plant, main component is cellulose, hemicellulose and lignin, wherein, cellulose accounts for about 40%, hemicellulose accounts for about 25%, lignin accounts for about 20%, and the lignocellulose biomass total amount that the earth is generated by photosynthesis is every year more than 2,000 hundred million tons, and therefore lignocellulose biomass is renewable resource abundant, the most cheap on the earth.Cellulose is the main component of plant cell wall.The whole world, for the cellulose of papermaking of weaving, reaches 8,000,000 tons every year.Paper pulp is the base stock of papermaking, at present in order to the plant of pulping raw material mainly based on lumber fibre class.But China's timber resources far can not meet the needs of growing pulp and paper industry.In order to make up the deficiency of raw material, every year will from a considerable amount of paper pulp of external import.Therefore expand the raw material sources of paper pulp, the sustainable development for society has great importance.
Along with the paper industry development in recent years of China is rapid, corresponding pollution problem is also more and more serious, and then paper pulp papermaking industry has become water pollutions rich and influential family.The medium-sized and small enterprises of papermaking straw pulp are wherein adopted to account for 95% of sum; Due to medium-sized and small enterprises' insufficient funds, a large amount of black liquor without or slightly treatedly just enter water body, cause serious water pollutions.Therefore, paper-making black liquor is solved imperative
Chinese patent CN1170031C discloses the method for mixture as cooking chemical production paper pulp of a kind of formic acid and acetic acid.This patent is when producing paper pulp with formic acid boiling herbaceous plant and broad leaf tree, add acetic acid as additional cooking chemical, can obtain containing hemicellulose and cellulosic paper pulp, and the mix acid liquor that used cooking liquor distills out formic acid and acetic acid carries out recycle.The regeneration of the cooking chemical of the method is evaporated and has distilled, the mixed acid obtained returns for boiling, but do not mention the processing method of solid content, in the document in solid content containing a large amount of lignin and hemicellulose and wood sugar, a large amount of wastes certainly will be caused if directly abandoned.
Chinese patent CN101864683A discloses a kind of preprocess method of lignocellulose raw material, after the mixed liquor of lignin raw material and organic acid soln and catalyst mixes by this patent, carry out first step process, obtain liquid-solid mixture and carry out Separation of Solid and Liquid, obtaining pretreatment fluid and cellulose solids; Organic acid soln washing is adopted to obtain cellulose solids; The preliminary treatment black liquor obtained is mixed Posterior circle with the washing black liquid obtained and is used for first step processing procedure; The black liquor recycling at least 3 times carries out the recovery of organic acid, lignin products and syrup solution.The black liquor of collection is carried out flash distillation or evaporation, obtains organic acid and concentrated black liquor, the water adding 2-10 times of volume in black liquor obtains lignin products and syrup solution, thus realizes the higher value application of lignocellulose raw material.But this technique adopts organic acid to carry out first step catalysis with the catalyst mix taking sulfuric acid as representative, need to add sulfuric acid in course of reaction and carry out catalysis, make in follow-up black liquor containing a large amount of sulphions; The main purpose of this technique extracts cellulose, and not only containing cellulose in paper pulp, also need to comprise a certain amount of hemicellulose.Therefore, this technique be not suitable for the preparation of paper pulp.
Summary of the invention
For this reason, the object of the present invention is to provide one by rational optimum configurations, prepared the technical process of paper pulp by lignocellulose biomass.
Another object of the present invention is to the method for the black liquor co-producing bio carbon providing a kind of technical process utilizing lignocellulose biomass to prepare paper pulp to produce.
(1) after biomass material being pulverized, under the catalytic action of hydrogen peroxide, the organic acid formed by formic acid, acetic acid is utilized to carry out boiling to described raw material, control boiling temperature 90-145 DEG C, solid-liquid mass ratio is 1:5-1:20, reaction time 30-90min, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid; In described organic acid solution, total acid concentration is 60-95%, and the mass ratio of described acetic acid and formic acid is 19:1-1:1, and surplus is water; Hydrogen peroxide accounts for the 1-8% of biomass material;
(2) described first time solid of obtaining of Separation of Solid and Liquid is collected, under the catalytic action of hydrogen peroxide, the mix acid liquor adopting formic acid, acetic acid to be formed carries out pickling to described solid, control pickling temperature 20-100 DEG C, solid-liquid mass ratio is 1:4-1:10, and the reactant liquor obtained is carried out second time Separation of Solid and Liquid; In described mix acid liquor, total acid concentration is 60-95%, and the mass ratio of described acetic acid and formic acid is 19:1-1:1, and surplus is water; Hydrogen peroxide accounts for the 1-8% of biomass material;
(3) collect the solid that described second time Separation of Solid and Liquid obtains, and wash, control washing temperature is 25-90 DEG C, and starching dense is 1-10%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(4) collect the described third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side and obtain screened stock cellulose, screened stock cellulose obtains required paper pulp through bleaching;
(5) collect the liquid that Separation of Solid and Liquid and second time Separation of Solid and Liquid obtain for the first time to evaporate, be back to step (1) as cooking liquor after the formic acid obtained and acetic acid vapor condensation, the solid obtained after evaporation is biological carbon; The temperature of described evaporation is 140-190 DEG C, pressure 401-901kPa.
Described bleaching comprises the steps:
Alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the 3-11% of screened stock cellulose quality, and pH value controls between 10-12, temperature 70-100 DEG C, and bleaching time 1-6h starches dense 5-15%; With
Acid treatment, the quality of described acid accounts for the 1-6% of screened stock cellulose quality, and pH value controls between 2-4, temperature 30-55 DEG C, and time 1-4h starches dense 3-6%.
Preferably, described bleaching also comprises alkali treatment, and described alkali consumption accounts for the 0.5-5% of screened stock cellulose quality, and temperature is 70-110 DEG C, and extraction times 1-5h starches dense 5-15%;
More preferably, in the step of described alkali treatment, described alkali consumption accounts for the 2-5% of screened stock cellulose quality, and temperature is 80-100 DEG C, and extraction times 1-2.5h starches dense 6-10%; In the step of described alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the 1%-3% of screened stock cellulose quality, temperature 80-100 DEG C, and bleaching time 1-5h starches dense 5-10%; With in described acid-treated step, temperature 35-45 DEG C, time 1.5-3h.
The described processing step preparing paper pulp co-production carbon from biomass material also comprises, collect described third time liquid of obtaining of Separation of Solid and Liquid, carry out water, sour rectifying, the mix acid liquor obtained is back to described step (1) as cooking liquor, and the water obtained washes Water circulation with water in step (3).
In described step (1), solid-liquid mass ratio is 1:6-1:15, reaction temperature 105-125 DEG C, reaction time 40-70min; Total acid concentration of described organic acid solution is 70-85%, and the mass ratio of acetic acid and formic acid is 6:1-1:1, and the quality adding hydrogen peroxide accounts for the 1-4% of biomass material quality.
In described step (2), mix acid liquor is identical with organic acid solution described in described step (1).
The pickling temperature of described step (2) is 30-90 DEG C, and solid-liquid mass ratio is 1:8-1:10.
The washing temperature of described step (3) is 60-90 DEG C, and starching dense is 4%-6%;
The water-washing process of described step (3) is adverse current water-washing process.
Described biomass material is wooden class raw material or grass as raw material.
Described biomass material is one or more in the careless classes such as reed, corn stalk, wheat straw, straw, melon seed cases, melon seed cases, bamboo chip, melon seeds bar or wooden class raw material.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, the present invention is by technological parameter reasonable in design, make whole process route simple, and whole technique is not only applicable to wooden class raw material, also be applicable to grass as raw material, and the cellulosic productive rate of the screened stock obtained by biomass material is up to 50%, Kappa number 3-10, hemicellulose level 7-15%, whiteness 30-55ISO, ash content 2-15%.Good through bleaching the Pulp Drainage Properties obtained.
3, digestion process of the present invention carries out in airtight reaction vessel, because the part of formic acid, acetic acid and hydrogen peroxide is evaporated, makes to have certain pressure in container, thus shortens the digestion time of raw material, decrease cellulosic destruction.
4, the common boiling biomass material of process selection formic acid of the present invention, acetic acid and hydrogen peroxide; formic acid is as a kind of strong organic acid; urge the lignin done in degraded raw material; alpha-cellulose in cellulose can be destroyed owing to being used alone formic acid; so add appropriate acetic acid not only protect hemicellulose and alpha-cellulose is not destroyed; and the organic solvent dissolution lignin molecule utilizing formic acid and acetic acid to be formed; hydrogen peroxide add the environment that can form peroxide acid solution; exacerbate degraded and the dissolving of lignin, and prevent the hydrolytic cleavage of fiber high polymer.
5, in technique of the present invention; all hydrogen peroxide is added in boiling and acid pickling step; because adding of hydrogen peroxide in pulping process eliminates lignin matter to greatest extent, and protect cellulose and be not destroyed, thus following bleaching technique only needs simple oxygen bleaching to reach requirement.
6, the present invention adopts specific bleaching process to carry out bleaching to the slurry through screening, 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 achieves total chlorine free bleaching, pollution-free; Again, this bleaching process not only increases pulp brightness, and can make the ash content in the high ash content straw pulp of removal, and finally this technique is destroyed very little even without destruction to cellulose.
7, after first time boiling, formic acid, acetic acid and hydrogen peroxide carry out pickling to solid, on the one hand front and continued digestion process is adjusted, on the other hand a small amount of lignin of its internal residual 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 the need to any preliminary treatment.
8, the liquid that the first time of collection and second time Separation of Solid and Liquid obtain directly evaporates by technique of the present invention, as cooking liquor after the formic acid obtained, acetic acid condensation, direct reflow step (1) whole process route is succinct, because formic acid and acetic acid re-use as raw material, higher to the boiling efficiency of raw material, for the technique utilizing the cooking liquor after boiling to circulate, although eliminate the step of this circulation, but achieve within the identical process time, higher to the clearance of hemicellulose and lignin.
9, technique of the present invention by first time Separation of Solid and Liquid and second time Separation of Solid and Liquid after acid solution be used for directly preparing biological carbon, avoid acid solution and directly discharge the environmental pollution brought, improve economic benefit and the environmental benefit of enterprise.
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the flow chart of technique of the present invention.
Detailed description of the invention
Below will the invention will be further described by specific embodiment.
In following examples, apart from outside specified otherwise, percentage composition used all represents mass percentage, i.e. " % " expression " wt% "; In described organic acid solution except a certain amount of formic acid, acetic acid, surplus is water, the acid of the dense nail of total acid described in each step and the gross mass of acetic acid account for the percentage of described organic acid solution quality, the quality that the solid-liquid mass ratio in each step refers to solid in this each step and the mass ratio of total liquid added.
Slurry described in each step is dense=this step in solid quality/this step in Zhi Liang He ╳ 100% of solid and liquid
Hydrogen peroxide H in each embodiment
2o
2be that the form of the aqueous hydrogen peroxide solution of 27% adds with mass concentration.Such as need as calculated to add 2.7g hydrogen peroxide, then corresponding should be add 10g(2.7 ÷ 0.27=10) described aqueous hydrogen peroxide solution.
The measuring brightness method of cellulose/paper slurry is with reference to FZ/T50010.7-1998, alpha-cellulose content assay method is with reference to FZ/T50010.4-1998, polymerization degree measurement adopts Fz/T50010.3-1998 method, ash determination adopts FZ/T50010.5-1998 method, inhale base number and measure employing FZ/T50010.9-1998 method, the assay method GB/T3332-2004 of beating degree.
In biological carbon, the assay of fixed carbon, ash content and moisture adopts proximate analysis of coal GB/T212-2008 to measure, the mensuration of sulfur content adopts the assay method GB/T214-2007 of full content of Sulphur in coal to measure, and the heat output determining method of biological carbon adopts the heat output determining method GB/T213-2008 of coal.Solids content adopts halogen fast tester for water content (plum Teller-Tuo benefit, model: HB43-S) to measure at 115 DEG C.The concentration of pentose or xylose solution adopts high-efficient liquid phase color instrument (model: U-3000, producer: ThermoFisher Dai An company) to measure.
In each embodiment,
Quality/(the solids content) ╳ 100% of amount × this liquid of the liquid of participation reaction of biological carbon yield=biological carbon
The Zhi Liang ╳ 100% of the quality/raw material of the productive rate=paper pulp of paper pulp.
Embodiment 1
In the present embodiment, first smashed by reed, being crushed to particle diameter is 2cm ~ 10cm.The present embodiment extracts the technique of paper pulp from described reed, comprises the steps:
(1) by after reed comminution pretreatment, total acid concentration is used to be that the formic acid of 75% and the organic acid solution of acetic acid carry out boiling to the reed after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:1, and before adding reed raw material, add the hydrogen peroxide (H accounting for reed raw material 3%
2o
2) as catalyst, controlling reaction temperature 125 DEG C, reaction 30min, solid-liquid mass ratio is 1:5, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 60% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for reed raw material 3% in the organic acid solution of 60%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 1:1, temperature is 20 DEG C, wash time 1h, and solid-liquid mass ratio is 1:4, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 180 DEG C, under 801kPa, carry out high temperature evaporation, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 95%, and in described biological carbon, fixed carbon content is 60% after measured, ash content 0.1%, sulfur content 0.08%, moisture 39.8, caloric value 5200J/g.
(4) collect the solid that in step (2), Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 25 DEG C, and starching dense is 5%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) solid that in collection step (4), Separation of Solid and Liquid obtains also screening obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measuring Kappa number is 8, and hemicellulose level is 12%, whiteness 52%ISO, ash content 9%, productive rate 42%;
(6) liquid that in step (4), Separation of Solid and Liquid obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
Screened stock cellulose after screening is carried out bleaching and obtains paper pulp; Its productive rate of paper pulp adopting the method for the present embodiment to obtain after measured is 39%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for quality 0.5% to carry out alkali treatment the screened stock cellulose after screening, control temperature is 100 DEG C, and extraction times 2.5h starches dense 8%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is screened stock cellulosic 6%, and by NaOH adjust ph between 10-12, temperature 70 C, bleaching time 2h, starches dense 9%; With
(3) utilize sulfuric acid to carry out acid treatment, sulfuric acid dosage is screened stock cellulosic 4%, and pH value controls between 2-4, temperature 50 C, and time 1.5h starches dense 3%.
Embodiment 2
In the present embodiment, first smashed by corn stalk, being crushed to particle diameter is 2cm ~ 10cm.The present embodiment extracts the technique of paper pulp from described corn stalk, comprises the steps:
(1) by after cornstalk crushing preliminary treatment, total acid concentration is used to be that the formic acid of 65% and the organic acid solution of acetic acid carry out boiling to the corn stalk after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1.5:1, and add before adding corn stalk raw material account for corn stalk 4% hydrogen peroxide (H2O2) as catalyst, control reaction temperature 105 DEG C, reaction 90min, solid-liquid mass ratio is 1:6, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 70% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for corn stalk 4% in the organic acid solution of 70%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 7:1, temperature is 60 DEG C, wash time 1h, and solid-liquid mass ratio is 1:6, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 150 DEG C, under 501kPa, carry out high temperature evaporation, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 87%, and in described biological carbon, fixed carbon content is 62% after measured, ash content 0.1%, sulfur content 0.05%, moisture 37%, caloric value 4800J/g.
(4) collect the solid that in step (2), Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 55 DEG C, and starching dense is 8%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) solid that in collection step (4), Separation of Solid and Liquid obtains is carried out screening and obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measure Kappa number 6, hemicellulose level is 14%, whiteness 49%ISO, ash content 6%, productive rate 38%;
(6) liquid that in step (4), Separation of Solid and Liquid obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
Screened stock cellulose after screening is carried out bleaching and obtains paper pulp; Its productive rate of paper pulp adopting the method for the present embodiment to obtain after measured is 36%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the potassium hydroxide accounting for its quality 1% to carry out alkali treatment the screened stock cellulose after screening, control temperature is 70 DEG C, and extraction times 3h starches dense 6%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is screened stock cellulosic 3%, and utilizes potassium hydroxide control ph between 10-12, temperature 90 DEG C, and bleaching time 4h, starches dense 15%; With
(3) utilize hydrochloric acid to carry out acid treatment, hydrochloric acid consumption is screened stock cellulosic 5%, and pH value controls between 2-4, temperature 30 DEG C, time 2h, starches dense 4.5%.
Embodiment 3
In the present embodiment, first smashed by straw, being crushed to particle diameter is 2cm ~ 10cm.The present embodiment extracts the technique of paper pulp from described straw, comprises the steps:
(1) by after broken for straw preliminary treatment, total acid concentration is used to be that the formic acid of 95% and the organic acid solution of acetic acid carry out boiling to the straw after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 2:1, and before adding straw raw material, add the hydrogen peroxide (H accounting for straw raw material 1%
2o
2) as catalyst, controlling reaction temperature 90 DEG C, reaction 40min, solid-liquid mass ratio is 1:20, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 95% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 1% in the organic acid solution of 95%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 2:1, temperature is 30 DEG C, wash time 1h, and solid-liquid mass ratio is 1:9, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 170 DEG C, under 701kPa, carry out high temperature evaporation, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 93%, and in described biological carbon, fixed carbon content is 65% after measured, ash content 0.15%, sulfur content 0.1%, moisture 33%, caloric value 5200J/g.
(4) collect the solid that in step (2), Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 80 DEG C, and starching dense is 7%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) solid that in collection step (4), Separation of Solid and Liquid obtains also screening obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measure Kappa number 10, hemicellulose level is 15%, whiteness 45%ISO, ash content 11%, productive rate 45%;
(6) liquid that in step (4), Separation of Solid and Liquid obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
Screened stock cellulose after screening is carried out bleaching and obtains paper pulp; Adopt the paper pulp that the method for the present embodiment obtains after measured, its productive rate is 32%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for its quality 4% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 90 DEG C, and extraction times 5h starches dense 10%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is screened stock cellulosic 11%, and by potassium hydroxide control ph between 10-12, temperature 80 DEG C, bleaching time 1h, starches dense 5%; With
(3) adopt sulfuric acid to carry out acid treatment, its sulfuric acid dosage is screened stock cellulosic 2%, and pH value controls between 2-4, temperature 40 DEG C, and time 3h, starches dense 5.5%.
Embodiment 4
In the present embodiment, first smashed by melon seed cases, being crushed to particle diameter is 2cm ~ 10cm.
The present embodiment extracts the technique of paper pulp from described melon seed cases, comprises the steps:
(1) by after broken for melon seed cases preliminary treatment, total acid concentration is used to be that the formic acid of 70% and the organic acid solution of acetic acid carry out boiling to the melon seed cases after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 6:1, and before adding melon seed cases raw material, add the hydrogen peroxide (H accounting for melon seed cases raw material 6%
2o
2) as catalyst, controlling reaction temperature 95 DEG C, reaction 50min, solid-liquid mass ratio is 1:12, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 80% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 6% in the organic acid solution of 80%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 19:1, temperature is 100 DEG C, wash time 1h, and solid-liquid mass ratio is 1:10, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 190 DEG C, under 901kPa, carry out high temperature evaporation, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 95%, and in described biological carbon, fixed carbon content is 63% after measured, ash content 0.05%, sulfur content 0.08%, moisture 36%, caloric value 5500J/g.
(4) collect the solid that in step (2), Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 75 DEG C, and starching dense is 4%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) solid that in collection step (4), Separation of Solid and Liquid obtains also screening obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measure Kappa number 7, hemicellulose level is 10%, whiteness 50%ISO, ash content 12%, productive rate 50%;
(6) liquid that in step (4), Separation of Solid and Liquid obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
Screened stock cellulose after screening is carried out bleaching and obtains paper pulp; Adopt the paper pulp that the method for the present embodiment obtains after measured, its productive rate is 40%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the NaOH accounting for its quality 2% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 110 DEG C, and extraction times 1h starches dense 15%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is screened stock cellulosic 5%, and by NaOH control Ph value between 10-12, temperature 85 DEG C, bleaching time 5h, starches dense 10%; With
(3) utilize hydrochloric acid to carry out acid treatment, in this step, hydrochloric acid consumption is screened stock cellulosic 6%, and pH value controls between 2-4, temperature 35 DEG C, and time 2.5h, starches dense 6%.
Embodiment 5
In the present embodiment, first smashed by cotton stem, being crushed to particle diameter is 0.5-2cm.
The present embodiment extracts the technique of paper pulp from described cotton stem, comprises the steps:
(1) by after broken for cotton stem preliminary treatment, total acid concentration is used to be that the formic acid of 85% and the organic acid solution of acetic acid carry out boiling to the cotton stem after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 4:1, and add before adding cotton stem raw material account for raw material 8% hydrogen peroxide (H2O2) as catalyst, control reaction temperature 145 DEG C, reaction 70min, solid-liquid mass ratio is 1:16, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 85% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 8% in the organic acid solution of 85%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 15:1, temperature is 90 DEG C, wash time 1h, and solid-liquid mass ratio is 1:8.5, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 160 DEG C, under 601kPa, carry out high temperature evaporation, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 90%, and in described biological carbon, fixed carbon content is 64% after measured, ash content 0.15%, sulfur content 0.1%, moisture 35.5%, caloric value 5000J/g.
(4) collect the solid that in step (2), Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 90 DEG C, and starching dense is 10%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) solid that in collection step (4), Separation of Solid and Liquid obtains also screening obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measure Kappa number 3, hemicellulose level is 7%, whiteness 40%ISO, ash content 10%, productive rate 42%;
(6) liquid that in step (4), Separation of Solid and Liquid obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
Screened stock cellulose after screening is carried out bleaching and obtains paper pulp, its productive rate is 38%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is screened stock cellulosic 7%, and by potassium hydroxide control ph between 10-12, temperature 75 DEG C, bleaching time 6h, starches dense 8%; With
(2) utilize hydrochloric acid to carry out acid treatment, hydrochloric acid consumption is 1% of screened stock cellulose quality, and pH value controls between 2-4, temperature 55 DEG C, time 1h, starches dense 5%.
Embodiment 6
In the present embodiment, first smashed by bamboo chip, being crushed to length is 2 ~ 10cm, thick 2mm thin slice.
The present embodiment extracts the technique of paper pulp from described bamboo chip, comprises the steps:
(1) by after broken for bamboo chip preliminary treatment, total acid concentration is used to be that the formic acid of 60% and the organic acid solution of acetic acid carry out boiling to the bamboo chip after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 19:1, and before adding bamboo chip raw material, add the hydrogen peroxide (H of bamboo chip raw material 1%
2o
2) as catalyst, controlling reaction temperature 130 DEG C, reaction 60min, solid-liquid mass ratio is 1:8, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that above-mentioned separation obtains being added total acid concentration is that the formic acid of 95% and the organic acid solution of acetic acid carry out acid elution, and wherein above-mentioned total acid concentration is add the hydrogen peroxide (H accounting for raw material 1% in the organic acid solution of 95%
2o
2) as catalyst and the mass ratio of acetic acid and formic acid is 9:1, temperature is 70 DEG C, wash time 1h, and solid-liquid mass ratio is 1:8, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 140 DEG C, under 401kPa, carry out high temperature evaporation, until evaporate to dryness obtains biological carbon solid, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1); The yield of biological carbon described in the present embodiment is 85%, and in described biological carbon, fixed carbon content is 60% after measured, ash content 0.05%, sulfur content 0.08%, moisture 39%, caloric value 4000J/g
(4) collect the solid that in step (2), Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 60 DEG C, and starching dense is 3%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) solid that in collection step (4), Separation of Solid and Liquid obtains also screening obtains screened stock cellulose, the screened stock cellulose obtained by said process, and measuring Kappa number is 3, and hemicellulose level is 9%, whiteness 40%ISO, ash content 2%, productive rate 46%;
(6) liquid that in step (4), Separation of Solid and Liquid obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (4);
Screened stock cellulose after screening is carried out bleaching successively and obtains paper pulp; Adopt the paper pulp that the method for the present embodiment obtains after measured, its productive rate is 40%.
Described in the present embodiment, bleaching process comprises the following steps:
(1) first utilize the potassium hydroxide accounting for its quality 5% to carry out alkali treatment the screened stock cellulose through screening, control temperature is 80 DEG C, and extraction times 2h starches dense 5%;
(2) carry out alkaline hydrogen peroxide bleaching again, the consumption of hydrogen peroxide is screened stock cellulosic 10%, and by NaOH control ph between 10-12, temperature 100 DEG C, bleaching time 3h, starches dense 11%; With
(3) utilize sulfuric acid to carry out acid treatment, sulfuric acid dosage is 3% of screened stock cellulose quality, and pH value controls between 2-4, temperature 45 C, and time 4h starches dense 4%.
Comparative example 1
Raw materials used in the present embodiment, processing step and technological parameter and embodiment 1 basically identical, its difference is, except the processing step of bleaching process, does not all add hydrogen peroxide as catalyst in each step.Adopt the screened stock cellulose that method described in the present embodiment obtains, measuring Kappa number is 30.2, and hemicellulose level is 10.5%, whiteness 25%ISO, and productive rate is 40%, is 30.3% by its productive rate of paper pulp obtained after fiber bleached for the screened stock obtained.
Comparative example 2
Raw material used in the present embodiment and processing step and technological parameter and embodiment 1 basically identical, its difference is, the digestion process of step (1) is under the catalytic action of hydrogen peroxide, and the organic acid solution of employing is made up of the formic acid of 75wt% and 25wt% water.The acid pickling step of its step (2) is under the catalytic action of hydrogen peroxide, the organic acid solution be made up of formic acid and the 40wt% water of 60wt% adopted carries out pickling, in each step, the adding proportion of hydrogen peroxide is consistent with embodiment 3, adopt the screened stock cellulose that the method for the present embodiment obtains after measured, measuring Kappa number is 26.8, and hemicellulose level is 8%, whiteness 25%ISO, productive rate is 34%, is 25% by its productive rate of paper pulp obtained after fiber bleached for the screened stock obtained.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. prepared a method for paper pulp co-production carbon by biomass material, it is characterized in that, comprise the steps:
(1) after biomass material being pulverized, under the catalytic action of hydrogen peroxide, the organic acid formed by formic acid, acetic acid is utilized to carry out boiling to described raw material, control boiling temperature 90-145 DEG C, solid-liquid mass ratio is 1:5-1:20, reaction time 30-90min, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
In described organic acid solution, total acid concentration is 60-95%, and the mass ratio of described acetic acid and formic acid is 19:1-1:1, and surplus is water;
Hydrogen peroxide accounts for the 1-8% of biomass material;
(2) described first time solid of obtaining of Separation of Solid and Liquid is collected, under the catalytic action of hydrogen peroxide, the mix acid liquor adopting formic acid, acetic acid to be formed carries out pickling to described solid, control pickling temperature 20-100 DEG C, solid-liquid mass ratio is 1:4-1:10, and the reactant liquor obtained is carried out second time Separation of Solid and Liquid;
In described mix acid liquor, total acid concentration is 60-95%, and the mass ratio of described acetic acid and formic acid is 19:1-1:1, and surplus is water;
Hydrogen peroxide accounts for the 1-8% of biomass material;
(3) collect the solid that described second time Separation of Solid and Liquid obtains, and wash, control washing temperature is 25-90 DEG C, and starching dense is 1-10%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(4) collect the described third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side and obtain screened stock cellulose, screened stock cellulose obtains required paper pulp through bleaching;
(5) collect the liquid that Separation of Solid and Liquid and second time Separation of Solid and Liquid obtain for the first time to evaporate, be back to step (1) as cooking liquor after the formic acid obtained and acetic acid vapor condensation, the solid obtained after evaporation is biological carbon;
The temperature of described evaporation is 140-190 DEG C, pressure 401-901kPa.
2. the method being prepared paper pulp co-production carbon by biomass material according to claim 1, is characterized in that, described bleaching comprises the steps:
Alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the 3-11% of screened stock cellulose quality, and pH value controls between 10-12, temperature 70-100 DEG C, and bleaching time 1-6h starches dense 5-15%; With
Acid treatment, the quality of described acid accounts for the 1-6% of screened stock cellulose quality, and pH value controls between 2-4, temperature 30-55 DEG C, and time 1-4h starches dense 3-6%.
3. the method being prepared paper pulp co-production carbon by biomass material according to claim 2, is characterized in that, described bleaching also comprises the steps:
Alkali treatment, described alkali consumption accounts for the 0.5-5% of screened stock cellulose quality, and temperature is 70-110 DEG C, and extraction times 1-5h starches dense 5-15%.
4. the method being prepared paper pulp co-production carbon by biomass material according to claim 3, is characterized in that:
In the step of described alkali treatment, described alkali consumption accounts for the 2-5% of screened stock cellulose quality, and temperature is 80-100 DEG C, and extraction times 1-2.5h starches dense 6-10%;
In the step of described alkaline hydrogen peroxide bleaching, the quality of hydrogen peroxide accounts for the 1%-3% of screened stock cellulose quality, temperature 80-100 DEG C, and bleaching time 1-5h starches dense 5-10%; With
In described acid-treated step, temperature 35-45 DEG C, time 1.5-3h.
5., according to the arbitrary described method being prepared paper pulp co-production carbon by biomass material of claim 1-4, it is characterized in that:
The described method step preparing paper pulp co-production carbon from biomass material also comprises, collect described third time liquid of obtaining of Separation of Solid and Liquid, carry out water, sour rectifying, the mix acid liquor obtained is back to described step (1) as cooking liquor, and the water obtained washes Water circulation with water in step (3).
6. the method being prepared paper pulp co-production carbon by biomass material according to claim 5, is characterized in that:
In described step (1), solid-liquid mass ratio is 1:6-1:15, reaction temperature 105-125 DEG C, reaction time 40-70min;
Total acid concentration of described organic acid solution is 70-85%, and the mass ratio of acetic acid and formic acid is 6:1-1:1, and the quality adding hydrogen peroxide accounts for the 1-4% of biomass material quality.
7. the method being prepared paper pulp co-production carbon by biomass material according to claim 6, is characterized in that:
In described step (2), mix acid liquor is identical with organic acid solution described in described step (1).
8. the method being prepared paper pulp co-production carbon by biomass material according to claim 7, is characterized in that:
The pickling temperature of described step (2) is 30-90 DEG C, and solid-liquid mass ratio is 1:8-1:10.
9., according to the arbitrary described method being prepared paper pulp co-production carbon by biomass material of claim 6-8, it is characterized in that:
The washing temperature of described step (3) is 60-90 DEG C, and starching dense is 4%-6%;
The water-washing process of described step (3) is adverse current water-washing process.
10. the method being prepared paper pulp co-production carbon by biomass material according to claim 9, is characterized in that:
Described biomass material is wooden class raw material or grass as raw material.
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