CN110241644A - A kind of method agricultural crop straw full constituent separation and comprehensively utilized - Google Patents
A kind of method agricultural crop straw full constituent separation and comprehensively utilized Download PDFInfo
- Publication number
- CN110241644A CN110241644A CN201910464672.0A CN201910464672A CN110241644A CN 110241644 A CN110241644 A CN 110241644A CN 201910464672 A CN201910464672 A CN 201910464672A CN 110241644 A CN110241644 A CN 110241644A
- Authority
- CN
- China
- Prior art keywords
- liquid
- solid
- separation
- agricultural crop
- crop straw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/003—Pulping cellulose-containing materials with organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/006—Pulping cellulose-containing materials with compounds not otherwise provided for
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/22—Other features of pulping processes
- D21C3/222—Use of compounds accelerating the pulping processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
Abstract
The present invention provides the methods of a kind of separation of agricultural crop straw full constituent and comprehensive utilization, including by smashed agricultural crop straw, under the catalytic action of dilute hydrochloric acid, using being separated by solid-liquid separation after organic acid solution boiling, filtrate is " A liquid ", and filter residue is washed to drying after neutrality, obtains crude fibre；Crude fibre is separated by solid-liquid separation again using after hydrogen peroxide treatment, filtrate is " B liquid ", and filter residue is washed to drying after neutrality, obtains cellulose；It after mixing after " A liquid " and " B liquid " is evaporated under reduced pressure respectively and adjust pH, then is separated by solid-liquid separation, filtrate is " C liquid ", and precipitating is dried to obtain lignin after being washed to neutrality；It is separated by solid-liquid separation after industrial alcohol is added after adjusting " C liquid " pH；Precipitating is washed to drying after neutrality, obtains hemicellulose.The present invention can successfully separate three kinds of cellulose, hemicellulose and lignin components in stalk, and three components have the higher rate of recovery, are truly realized the comprehensive utilization of stalk.
Description
Technical field
The invention belongs to agricultural crop straws to utilize technical field, in particular to a kind of agricultural crop straw full constituent point
From and comprehensive utilization method.
Background technique
China is large agricultural country, and all kinds of stalks generated every year are other than part is for returning to the field, herding, most on-site incineration
Or processing of rotting, not only waste of resource, also results in the problem of environmental pollutions such as haze.If can be substantially efficiently rich using this reserves
Rich renewable resource, is or is derivatized to the higher product of added value, not only solve the waste of stalk resource by stover,
Play a significant role to the sustainable development for promoting China's economy.Cellulose, hemicellulose and lignin are main groups of stalk
Point, and the close weave in of three components is difficult to be separated, and therefore, is by the key that component is converted into use value product
Its each component is pre-separated.There are still serious defect or deficiencies for the isolation technics of stalk at present: each component cannot in stalk
It is kept completely separate out, causes wastage of material；Although some separation methods can come out three components separation in the prior art,
The chemical reagent for having corrosiveness to instrument has been used in separation test, or causes to set because using corrosion-resistant or high pressure resistant equipment
Standby increased costs；Most separation methods need to introduce organic additive simultaneously, and inevitable makes subsequent obtained lignin
In contain organic reagent, influence lignin purity.
The technical problem to be solved by the present invention is to how cellulose, hemicellulose be improved on the basis of not introducing organic additive
Element and lignin recovery rate, opening up the approach of an economical and efficient for stalk utilization as energy and resources is that those skilled in the art need to solve
Certainly the problem of.
Summary of the invention
The deficiency of the present invention to solve above-mentioned technical problem provides a kind of separation of agricultural crop straw full constituent and comprehensive utilization
Method, successfully three kinds of cellulose, hemicellulose and lignin components in stalk can be separated, and three components have compared with
The high rate of recovery, organic solvent used is recyclable, is truly realized the comprehensive utilization of stalk, accomplishes " to eat stalk
It is dry to squeeze only ".
In view of this, the invention proposes the method for a kind of separation of agricultural crop straw full constituent and comprehensive utilization, feature
It is, includes the following steps:
(1) smashed agricultural crop straw is utilized into organic acid under the catalytic action of 0.05-0.2mol/L dilute hydrochloric acid
Liquid is in 70-100 DEG C of condition boiling 2-8h；Wherein solid-liquid mass ratio is 1:20；
(2) it is separated by solid-liquid separation, filtrate is " A liquid ", and filter residue is washed to drying after neutrality, obtains crude fibre；
It (3) is in the hydrogenperoxide steam generator of 2-8% by crude fibre addition mass fraction and to adjust pH value of solution be 10-12,
3-4h is reacted at 40-60 DEG C；Wherein solid-liquid mass ratio is 1:30；
(4) it is separated by solid-liquid separation, filtrate is " B liquid ", and filter residue is washed to drying after neutrality, obtains cellulose；
(5) it is mixed after being evaporated under reduced pressure " A liquid " and " B liquid " respectively, and adjusting pH of mixed is 1.5-2.0, carries out solid-liquid
Separation；Filtrate is " C liquid ", and precipitating is dried to obtain lignin after being washed to neutrality；
(6) adjusting " C liquid " pH is 12, is separated by solid-liquid separation after industrial alcohol is added；Drying after supernatant concentrate is added in precipitating, obtains
To hemicellulose.
The present invention uses organic solvent or organic solvent and inorganic acid catalyst during organic solvent pretreatment
Mixed solution can destroy the connecting key between the cellulose inside fibrous raw material, lignin and hemicellulose, to realize three groups
The separation divided.The present invention is catalyst using dilute hydrochloric acid, organic distilling using organic acid and water mixed system boiling biomass
In sour step, even if after organic acid is completely distilled off out, then dilute hydrochloric acid and the alkalinity B liquid being added thereto are neutralized, it can't draw
Lignin charing is played, influences the recovery rate of lignin, and the addition of hydrogen peroxide can form the environment of peroxide acid solution, exacerbate wood
The degradation and dissolution of quality, and prevent the hydrolytic cleavage of fiber high polymer.
Hydrogen peroxide is added in crude fibre of the invention, so that the lignin and hemicellulose of biomass material middle-shallow layer
With HO+ ionic reaction, constantly it is dissolved, and influence of the HO+ to cellulose is little, after a period of time, the consumption of HO+ ion is complete, H
The activity of+ion greatly increases, so that hemicellulose removes rapidly with the lignin for being soluble in acid, to improve lignin
Recovery rate.
The present invention improves cellulose, hemicellulose and lignin recovery rate and pure on the basis of not introducing organic additive
Degree, the approach for opening up an economical and efficient for stalk utilization as energy and resources can be successfully by cellulose, hemicellulose in stalk
Element and three kinds of components of lignin are separated, and three components have the higher rate of recovery, and organic solvent used is recyclable,
It is truly realized the comprehensive utilization of stalk, is accomplished to stalk " eating dry squeeze only ".
Further, organic acid solution includes formic acid, acetic acid and water；Wherein the volume ratio of formic acid and acetic acid is 1:2-7；Total acid
Concentration is 80-90%.
Formic acid/acetic acid mixed system can remove effectively lignin and degradation half in agricultural crop straw under certain condition
Cellulose.And the Different Effects of the arboxylic acid volume ratio rate of recovery of three components, but all may be used within the scope of this volume ratio
To realize cellulose, hemicellulose and the separation of lignin.It is contemplated that formic acid boiling point is lower, if anti-in pure formic acid system
It answers, real reaction excessive velocities, solution boiling, reaction is difficult to control.
Process selection formic acid of the invention, the common boiling biomass material of acetic acid, formic acid urge work as a kind of strong organic acid
Lignin in degradation raw material can destroy the alpha-cellulose in cellulose since formic acid is used alone, so suitable second is added
Acid not only protects alpha-cellulose not to be destroyed, but also the organic solvent dissolved lignin molecule formed using formic acid and acetic acid,
Also utilize its acid boiling hemicellulose therein.
Further, drying means is dry at 60-70 DEG C.
Further, vacuum distillation method is to distill at 50-60 DEG C.
Further, the formic acid and acetic acid steam obtained after " A liquid " described in step (5) vacuum distillation is condensed and is back to
Step (1)；The water vapour obtained after " the B liquid " vacuum distillation condenses and is back to step (5).
The present invention evaporates formic acid and acetic acid before lignin is precipitated, and the formic acid and acetic acid on the one hand steamed can be used for steaming
The circular response of step is boiled to save raw material, at the same except formic acid removal, acetic acid concentration after, guarantee that lignin is precipitated, energy saving.
Further, step (5) further includes that 12-15h is stood before being separated by solid-liquid separation.
Further, step (6) further include in separation of solid and liquid the industrial alcohol steam obtained after supernatant vacuum distillation and
Supernatant concentrate；Industrial alcohol steam condenses and is back to step (6).
Further, the volume ratio of " C liquid " and industrial alcohol is 1:2-3 in step (6).
Further, step (6) further includes that 12-15h is stood before being separated by solid-liquid separation.
Adhesive is prepared using lignin in the present invention:
Lignin is as the biological material for being uniquely capable of providing renewable compound aromatic base, next in number only to fiber
Element is the second largest natural macromolecular material, is widely present in nature, since there is fragrance in the molecular structure of lignin
Base, phenolic hydroxyl group, alcoholic extract hydroxyl group, carbon-based conjugated double bond isoreactivity group, therefore lignin can prepare phenolic resin glue for part phenol
Stick.Specific preparation flow is as follows:
Xylan is prepared using hemicellulose in the present invention:
The heteromultimer that hemicellulose is made of several different types of monosaccharide, these sugar are pentose and hexose,
Including xylose, arabinose and galactolipin etc..Hemicellulose xylan accounts for the 50% of total amount in lignum, and xylan is half
The main component of cellulose can be obtained through dilute acid hydrolysis hemicellulose.
By above technical scheme, the invention proposes the sides of a kind of separation of agricultural crop straw full constituent and comprehensive utilization
Method, this method simple process, reaction condition are mild, can efficiently separate agricultural crop straw each component, and the cellulose isolated is pure
Degree can reach 98.2%, and the cellulose rate of recovery is 92.8%, and lignin recovery rate is 85.6%, the hemicellulose rate of recovery
76.8%.This method make full use of each ingredient of stalk can as chemical products with high added-value, and organic in this method
Solvent is recyclable, greatly reduces the waste of resource, has accomplished green non-pollution, and the full constituent for realizing stalk is comprehensive
It closes and utilizes, clean, is efficient, economically utilizing agricultural wastes resource, open up an economic height for stalk utilization as energy and resources
The approach of effect.
Detailed description of the invention
Fig. 1 shows the method flow diagram of the separation of agricultural crop straw full constituent and comprehensive utilization in the present invention.
Specific embodiment
To better understand the objects, features and advantages of the present invention, with reference to the accompanying drawing and specific real
Applying mode, the present invention is further described in detail.It should be noted that in the absence of conflict, the implementation of the application
Feature in example and embodiment can be combined with each other.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, still, the present invention may be used also
To be implemented using other than the one described here other modes, therefore, protection scope of the present invention is not by described below
Specific embodiment limitation.
A kind of method for separating and comprehensively utilizing the invention proposes agricultural crop straw full constituent, this method simple process,
Reaction condition is mild, can efficiently separate agricultural crop straw each component, and the cellulose purity isolated can reach 98.2%, fiber
The plain rate of recovery is 92.8%, and lignin recovery rate is 85.6%, the hemicellulose rate of recovery 76.8%.This method keep stalk each at
Dividing can make full use of as chemical products with high added-value, and organic solvent is recyclable in this method, subtracts significantly
The waste for having lacked resource, has accomplished green non-pollution, realizes the full constituent comprehensive utilization of stalk, cleans, is efficient, economic land productivity
With agricultural wastes resource, the approach of an economical and efficient is opened up for stalk utilization as energy and resources.Its detailed process such as Fig. 1.
In each embodiment, cellulose purity measuring method:
Stalk utilizes Van Soest with cellulose, hemicellulose and lignin component content in treated sample
Method analysis measurement.
The purity calculation formula of cellulose:
The content (1) of cellulose in the purity N=sample of cellulose
The calculating of cellulose, hemicellulose and lignin recovery rate:
Each component rate of recovery calculation formula:
M (cellulose)=M1/M2 (2)
M (hemicellulose)=M3/M4 (3)
M (lignin)=M5/M6 (4)
Wherein, M1For the quality of cellulose in sample, M2For the quality of cellulose in raw material, M3Resulting solid is analysed for alcohol
Quality, M4For the quality of hemicellulose in raw material, M5Resulting solid masses is sunk for acid, M6For the quality of lignin in raw material.
Embodiment 1
It by 40 mesh sieving after corn straw smashing, cleans spare, clean corn stover 1000.0g is weighed, in 0.1mol/
Under the catalytic action of L dilute hydrochloric acid, with formic acid, acetic acid and water mixed liquid boiling above-mentioned raw materials stalk, wherein formic acid, acetic acid and water
Volume ratio is 30:60:10, controls 90 DEG C of boiling temperature, solid-liquid mass ratio 1:20, reaction time 4h；After reaction, to anti-
Liquid is answered to be separated by solid-liquid separation, filtrate is collected as " A liquid ", and solid filter residue is washed to neutrality, and 60 DEG C of dryings obtain crude fibre 445.0g.
Above-mentioned crude fibre is handled using alkaline hydrogen peroxide.Wherein, hydrogenperoxide steam generator mass fraction is 5%,
PH value of solution=12 are controlled, in 60 DEG C of reactions 3h, solid-liquid mass ratio 1:30；After reaction, reaction solution is separated by solid-liquid separation, filtrate
It is collected as " B liquid ", solid filter residue is washed to neutrality, and 60 DEG C of dryings are 376.2g to get cellulose quality is arrived.
Above-mentioned " A liquid " and " B liquid " are concentrated under reduced pressure respectively, vapo(u)rizing temperature is 50 DEG C, the formic acid distilled out, acetic acid mixture
It can be recycled with water；Above-mentioned concentrate is mixed, and adjusts pH of mixed=2.0, precipitates 12h；Then to mixed liquor from
Supernatant C liquid is collected in heart separation, and precipitating is washed to neutrality, and 60 DEG C of drying are to get to lignin 100.2g.
The industrial alcohol of its 3 times of volumes is added in supernatant C liquid pH=12 in regulating step 3, precipitates 12h；Then to above-mentioned
Solution centrifuge separation is collected supernatant and is evaporated under reduced pressure to it, and the industrial alcohol distilled out can be recycled, and supernatant concentrate adds
Enter in precipitating, and be washed to neutrality, 60 DEG C of dryings to get arrive hemicellulose 163.6g.
The cellulose purity that the present embodiment is isolated can reach 98.2%, and the cellulose rate of recovery is 92.8%, and lignin returns
Yield is 85.6%, the hemicellulose rate of recovery 76.8%.
Embodiment 2
It by 40 mesh sieving after corn straw smashing, cleans spare, clean corn stover 1000.0g is weighed, in 0.2mol/
Under the catalytic action of L dilute hydrochloric acid, with formic acid, acetic acid and water mixed liquid boiling above-mentioned raw materials stalk, wherein formic acid, acetic acid and water
Volume ratio is 30:60:10, controls 90 DEG C of boiling temperature, solid-liquid mass ratio 1:20, reaction time 4h；After reaction, to anti-
Liquid is answered to be separated by solid-liquid separation, filtrate is collected as " A liquid ", and solid filter residue is washed to neutrality, and 60 DEG C of dryings obtain crude fibre 463.0g.
Above-mentioned crude fibre is handled using alkaline hydrogen peroxide.Wherein, hydrogenperoxide steam generator mass fraction is 3%,
PH value of solution=12 are controlled, in 60 DEG C of reactions 3h, solid-liquid mass ratio 1:30；After reaction, reaction solution is separated by solid-liquid separation, filtrate
It is collected as " B liquid ", solid filter residue is washed to neutrality, and 60 DEG C of dryings are 387.1g to get cellulose quality is arrived.
Above-mentioned " A liquid " and " B liquid " are concentrated under reduced pressure respectively, vapo(u)rizing temperature is 50 DEG C, the formic acid distilled out, acetic acid mixture
It can be recycled with water；Above-mentioned concentrate is mixed, and adjusts pH of mixed=1.5, precipitates 12h；Then to mixed liquor from
Supernatant C liquid is collected in heart separation, and precipitating is washed to neutrality, and 60 DEG C of drying are to get to lignin 99.6g.
The industrial alcohol of its 3 times of volumes is added in supernatant C liquid pH=12 in regulating step 3, precipitates 12h；Then to above-mentioned
Solution centrifuge separation is collected supernatant and is evaporated under reduced pressure to it, and the industrial alcohol distilled out can be recycled, and precipitate in being washed to
Property, 60 DEG C of dryings to get arrive hemicellulose 148.9g.
The cellulose purity that the present embodiment is isolated can reach 98.9%, and the cellulose rate of recovery is 96.2%, and lignin returns
Yield is 85.1%, the hemicellulose rate of recovery 69.9%.
Embodiment 3
It by 40 mesh sieving after corn straw smashing, cleans spare, clean corn stover 1000.0g is weighed, in 0.1mol/
Under the catalytic action of L dilute hydrochloric acid, with formic acid, acetic acid and water mixed liquid boiling above-mentioned raw materials stalk, wherein formic acid, acetic acid and water
Volume ratio is 20:60:20, controls 90 DEG C of boiling temperature, solid-liquid mass ratio 1:20, reaction time 4h；After reaction, to anti-
Liquid is answered to be separated by solid-liquid separation, filtrate is collected as " A liquid ", and solid filter residue is washed to neutrality, and 60 DEG C of dryings obtain crude fibre 450.0g.
Above-mentioned crude fibre is handled using alkaline hydrogen peroxide.Wherein, hydrogenperoxide steam generator mass fraction is 5%,
PH value of solution=10 are controlled, in 60 DEG C of reactions 3h, solid-liquid mass ratio 1:30；After reaction, reaction solution is separated by solid-liquid separation, filtrate
It is collected as " B liquid ", solid filter residue is washed to neutrality, and 60 DEG C of dryings are 370.4g to get cellulose quality is arrived.
Above-mentioned " A liquid " and " B liquid " are concentrated under reduced pressure respectively, vapo(u)rizing temperature is 50 DEG C, the formic acid distilled out, acetic acid mixture
It can be recycled with water；Above-mentioned concentrate is mixed, and adjusts pH of mixed=2.0, precipitates 12h；Then to mixed liquor from
Supernatant C liquid is collected in heart separation, and precipitating is washed to neutrality, and 60 DEG C of drying are to get to lignin 89.7g.
The industrial alcohol of its 2 times of volumes is added in supernatant C liquid pH=12 in regulating step 3, precipitates 12h；Then to above-mentioned
Solution centrifuge separation is collected supernatant and is evaporated under reduced pressure to it, and the industrial alcohol distilled out can be recycled, and precipitate in being washed to
Property, 60 DEG C of dryings to get arrive hemicellulose 145.1g.
The cellulose purity that the present embodiment is isolated can reach 92.4%, and the cellulose rate of recovery is 86.0%, and lignin returns
Yield is 76.7%, the hemicellulose rate of recovery 68.1%.
Embodiment 4
It by 40 mesh sieving after corn straw smashing, cleans spare, weighs clean corn stover 1000.0g,
Under the catalytic action of 0.15mol/L dilute hydrochloric acid, with formic acid, acetic acid and water mixed liquid boiling above-mentioned raw materials stalk, wherein formic acid, second
The volume ratio of acid and water is 30:60:10, controls 70 DEG C of boiling temperature, solid-liquid mass ratio 1:20, reaction time 6h；Reaction knot
Shu Hou is separated by solid-liquid separation reaction solution, and filtrate is collected as " A liquid ", and solid filter residue is washed to neutrality, and 60 DEG C of dryings obtain crude fibre
Plain 449.2g.
Above-mentioned crude fibre is handled using alkaline hydrogen peroxide.Wherein, hydrogenperoxide steam generator mass fraction is 2%,
PH value of solution=12 are controlled, in 60 DEG C of reactions 3h, solid-liquid mass ratio 1:30；After reaction, reaction solution is separated by solid-liquid separation, filtrate
It is collected as " B liquid ", solid filter residue is washed to neutrality, and 60 DEG C of dryings are 368.6g to get cellulose quality is arrived.
Above-mentioned " A liquid " and " B liquid " are concentrated under reduced pressure respectively, vapo(u)rizing temperature is 50 DEG C, the formic acid distilled out, acetic acid mixture
It can be recycled with water；Above-mentioned concentrate is mixed, and adjusts pH of mixed=1.5, precipitates 12h；Then to mixed liquor from
Supernatant C liquid is collected in heart separation, and precipitating is washed to neutrality, and 60 DEG C of drying are to get to lignin 90.2g.
The industrial alcohol of its 2 times of volumes is added in supernatant C liquid pH=12 in regulating step 3, precipitates 12h；Then to above-mentioned
Solution centrifuge separation is collected supernatant and is evaporated under reduced pressure to it, and the industrial alcohol distilled out can be recycled, and precipitate in being washed to
Property, 60 DEG C of dryings to get arrive hemicellulose 146.8g.
The cellulose purity that the present embodiment is isolated can reach 93.3%, and the cellulose rate of recovery is 86.4%, and lignin returns
Yield is 77.1%, the hemicellulose rate of recovery 69.0%.
Embodiment 5
It by 40 mesh sieving after corn straw smashing, cleans spare, clean corn stover 1000.0g is weighed, in 0.1mol/
Under the catalytic action of L dilute hydrochloric acid, with formic acid, acetic acid and water mixed liquid boiling above-mentioned raw materials stalk, wherein formic acid, acetic acid and water
Volume ratio is 30:60:10, controls 90 DEG C of boiling temperature, solid-liquid mass ratio 1:20, reaction time 8h；After reaction, to anti-
Liquid is answered to be separated by solid-liquid separation, filtrate is collected as " A liquid ", and solid filter residue is washed to neutrality, and 60 DEG C of dryings obtain crude fibre 460.7g.
Above-mentioned crude fibre is handled using alkaline hydrogen peroxide.Wherein, hydrogenperoxide steam generator mass fraction is 8%,
PH value of solution=12 are controlled, in 50 DEG C of reactions 3h, solid-liquid mass ratio 1:30；After reaction, reaction solution is separated by solid-liquid separation, filtrate
It is collected as " B liquid ", solid filter residue is washed to neutrality, and 60 DEG C of dryings are 386.2g to get cellulose quality is arrived.
Above-mentioned " A liquid " and " B liquid " are concentrated under reduced pressure respectively, vapo(u)rizing temperature is 50 DEG C, the formic acid distilled out, acetic acid mixture
It can be recycled with water；Above-mentioned concentrate is mixed, and adjusts pH of mixed=1.5, precipitates 12h；Then to mixed liquor from
Supernatant C liquid is collected in heart separation, and precipitating is washed to neutrality, and 60 DEG C of drying are to get to lignin 99.2g.
The industrial alcohol of its 3 times of volumes is added in supernatant C liquid pH=12 in regulating step 3, precipitates 12h；Then to above-mentioned
Solution centrifuge separation is collected supernatant and is evaporated under reduced pressure to it, and the industrial alcohol distilled out can be recycled, and precipitate in being washed to
Property, 60 DEG C of dryings to get arrive hemicellulose 157.1g.
The cellulose purity that the present embodiment is isolated can reach 97.9%, and the cellulose rate of recovery is 95.0%, and lignin returns
Yield is 84.8%, the hemicellulose rate of recovery 73.8%.
Comparative example 1
It by 40 mesh sieving after corn straw smashing, cleans spare, clean corn stover 1000.0g is weighed, with formic acid, second
Acid and water mixed liquid boiling above-mentioned raw materials stalk, wherein the volume ratio of formic acid, acetic acid and water is 0:8:2, controls boiling temperature 50
DEG C, solid-liquid mass ratio 1:20, reaction time 1h；After reaction, reaction solution being separated by solid-liquid separation, filtrate is collected as " A liquid ", Gu
Body filter residue is washed to neutrality, and 60 DEG C of dryings obtain crude fibre 425.0g.
Above-mentioned crude fibre is handled using alkaline hydrogen peroxide.Wherein, hydrogenperoxide steam generator mass fraction is 1%,
PH value of solution=8 are controlled, in 30 DEG C of reactions 2h, solid-liquid mass ratio 1:30；After reaction, reaction solution is separated by solid-liquid separation, filtrate
It is collected as " B liquid ", solid filter residue is washed to neutrality, and 60 DEG C of dryings are 380.6g to get cellulose quality is arrived.
Above-mentioned " A liquid " and " B liquid " are concentrated under reduced pressure respectively, vapo(u)rizing temperature is 50 DEG C, the formic acid distilled out, acetic acid mixture
It can be recycled with water；Above-mentioned concentrate is mixed, and adjusts pH of mixed=2.5, precipitates 10h；Then to mixed liquor from
Supernatant C liquid is collected in heart separation, and precipitating is washed to neutrality, and 60 DEG C of drying are to get to lignin 22.2g.
The industrial alcohol of its 3 times of volumes is added in supernatant C liquid pH=12 in regulating step 3, precipitates 10h；Then to above-mentioned
Solution centrifuge separation is collected supernatant and is evaporated under reduced pressure to it, and the industrial alcohol distilled out can be recycled, and precipitate in being washed to
Property, 60 DEG C of dryings to get arrive hemicellulose 47.0g.
The cellulose purity that the present embodiment is isolated is 56.4%, and the cellulose rate of recovery is 53.9%, lignin recovery rate
It is 19.0%, the hemicellulose rate of recovery 22.1%.
Comparative example 2
It by 40 mesh sieving after corn straw smashing, cleans spare, clean corn stover 1000.0g is weighed, in 0.4mol/
Under the catalytic action of L dilute hydrochloric acid, with formic acid, acetic acid and water mixed liquid boiling above-mentioned raw materials stalk, wherein formic acid, acetic acid and water
Volume ratio is 60:30:10, controls 120 DEG C of boiling temperature, solid-liquid mass ratio 1:20, reaction time 1h；After reaction, right
Reaction solution is separated by solid-liquid separation, and filtrate is collected as " A liquid ", and solid filter residue is washed to neutrality, and 60 DEG C of dryings obtain crude fibre
427.9g。
Above-mentioned crude fibre is handled using alkaline hydrogen peroxide.Wherein, hydrogenperoxide steam generator mass fraction is 10%,
PH value of solution=14 are controlled, in 80 DEG C of reactions 3h, solid-liquid mass ratio 1:30；After reaction, reaction solution is separated by solid-liquid separation, filtrate
It is collected as " B liquid ", solid filter residue is washed to neutrality, and 60 DEG C of dryings are 344.6g to get cellulose quality is arrived.
Above-mentioned " A liquid " and " B liquid " are concentrated under reduced pressure respectively, vapo(u)rizing temperature is 50 DEG C, the formic acid distilled out, acetic acid mixture
It can be recycled with water；Above-mentioned concentrate is mixed, and adjusts pH of mixed=1.0, precipitates 12h；Then to mixed liquor from
Supernatant C liquid is collected in heart separation, and precipitating is washed to neutrality, and 60 DEG C of drying are to get to lignin 29.4g.
The industrial alcohol of its 3 times of volumes is added in supernatant C liquid pH=12 in regulating step 3, precipitates 12h；Then to above-mentioned
Solution centrifuge separation is collected supernatant and is evaporated under reduced pressure to it, and the industrial alcohol distilled out can be recycled, and precipitate in being washed to
Property, 60 DEG C of dryings to get arrive hemicellulose 19.8g.
The cellulose purity that the present embodiment is isolated is 74.9%, and the cellulose rate of recovery is 64.9%, lignin recovery rate
It is 25.1%, the hemicellulose rate of recovery 9.3%.
Comparative example 3
It by 40 mesh sieving after corn straw smashing, cleans spare, clean corn stover 1000.0g is weighed, with formic acid, second
Acid and water mixed liquid boiling above-mentioned raw materials stalk, wherein the volume ratio of formic acid, acetic acid and water is 30:60:10, controls boiling temperature
90 DEG C, solid-liquid mass ratio 1:20, reaction time 4h；After reaction, reaction solution being separated by solid-liquid separation, filtrate is collected as " A liquid ",
Solid filter residue is washed to neutrality, and 60 DEG C of dryings obtain crude fibre 451.6g.
Above-mentioned crude fibre is handled using alkaline hydrogen peroxide.Wherein, hydrogenperoxide steam generator mass fraction is 5%,
PH value of solution=12 are controlled, in 60 DEG C of reactions 3h, solid-liquid mass ratio 1:30；After reaction, reaction solution is separated by solid-liquid separation, filtrate
It is collected as " B liquid ", solid filter residue is washed to neutrality, and 60 DEG C of dryings are 344.4g to get cellulose quality is arrived.
Above-mentioned " A liquid " and " B liquid " are concentrated under reduced pressure respectively, vapo(u)rizing temperature is 50 DEG C, the formic acid distilled out, acetic acid mixture
It can be recycled with water；Above-mentioned concentrate is mixed, and adjusts pH of mixed=2.0, precipitates 12h；Then to mixed liquor from
Supernatant C liquid is collected in heart separation, and precipitating is washed to neutrality, and 60 DEG C of drying are to get to lignin 78.7g.
The industrial alcohol of its 3 times of volumes is added in supernatant C liquid pH=12 in regulating step 3, precipitates 12h；Then to above-mentioned
Solution centrifuge separation is collected supernatant and is evaporated under reduced pressure to it, and the industrial alcohol distilled out can be recycled, and supernatant concentrate adds
Enter in precipitating, and be washed to neutrality, 60 DEG C of dryings to get arrive hemicellulose 124.0g.
The cellulose purity that the present embodiment is isolated can reach 86.8%, and the cellulose rate of recovery is 75.1%, and lignin returns
Yield is 67.3%, the hemicellulose rate of recovery 58.2%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of method of agricultural crop straw full constituent separation and comprehensive utilization, which comprises the steps of:
(1) smashed agricultural crop straw is existed under the catalytic action of 0.05-0.2mol/L dilute hydrochloric acid using organic acid solution
70-100 DEG C of condition boiling 2-8h；Wherein solid-liquid mass ratio is 1:20；
(2) it is separated by solid-liquid separation, filtrate is " A liquid ", and filter residue is washed to drying after neutrality, obtains crude fibre；
It (3) is in the hydrogenperoxide steam generator of 2-8% by crude fibre addition mass fraction and to adjust pH value of solution be 10-12
, 3-4 h is reacted at 40-60 DEG C；Wherein solid-liquid mass ratio is 1:30；
(4) it is separated by solid-liquid separation, filtrate is " B liquid ", and filter residue is washed to drying after neutrality, obtains cellulose；
(5) by described in " A liquid " and " the B liquid " mixes after being evaporated under reduced pressure respectively, and adjusting pH of mixed is 1.5-2.0, is carried out
It is separated by solid-liquid separation；Filtrate is " C liquid ", and precipitating is dried to obtain lignin after being washed to neutrality；
(6) " C liquid " pH described in adjusting is 12, is separated by solid-liquid separation after industrial alcohol is added；Precipitating is done after supernatant concentrate is added
It is dry, obtain hemicellulose.
2. the method for a kind of agricultural crop straw full constituent separation according to claim 1 and comprehensive utilization, which is characterized in that
The organic acid solution includes formic acid, acetic acid and water；Wherein the volume ratio of the formic acid and the acetic acid is 1:2-7；Total acid concentration
For 80-90%.
3. the method for a kind of agricultural crop straw full constituent separation according to claim 1 and comprehensive utilization, which is characterized in that
The drying means is dry at 60-70 DEG C.
4. the method for a kind of agricultural crop straw full constituent separation according to claim 1 and comprehensive utilization, which is characterized in that
The vacuum distillation method is to distill at 50-60 DEG C.
5. the method for a kind of agricultural crop straw full constituent separation according to claim 2 and comprehensive utilization, which is characterized in that
The formic acid and acetic acid steam obtained after " A liquid " described in step (5) vacuum distillation condenses and is back to step (1)；" the B
The water vapour obtained after liquid " vacuum distillation condenses and is back to step (5).
6. the method for a kind of agricultural crop straw full constituent separation according to claim 1 and comprehensive utilization, which is characterized in that
Step (5) further includes standing 12-15 h before the separation of solid and liquid.
7. the method for a kind of agricultural crop straw full constituent separation according to claim 1 and comprehensive utilization, which is characterized in that
Step (6) further includes being evaporated under reduced pressure supernatant to obtain industrial alcohol steam and the supernatant concentrate in separation of solid and liquid；It is described
Industrial alcohol steam condenses and is back to step (6).
8. the method for a kind of agricultural crop straw full constituent separation according to claim 1 and comprehensive utilization, which is characterized in that
The volume ratio of " C liquid " described in step (6) and the industrial alcohol is 1:2-3.
9. the method for a kind of agricultural crop straw full constituent separation according to claim 1 and comprehensive utilization, which is characterized in that
Step (6) further includes standing 12-15 h before the separation of solid and liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910464672.0A CN110241644B (en) | 2019-05-30 | 2019-05-30 | Method for separating and comprehensively utilizing all components of crop straws |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910464672.0A CN110241644B (en) | 2019-05-30 | 2019-05-30 | Method for separating and comprehensively utilizing all components of crop straws |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110241644A true CN110241644A (en) | 2019-09-17 |
| CN110241644B CN110241644B (en) | 2021-09-17 |
Family
ID=67885462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910464672.0A Active CN110241644B (en) | 2019-05-30 | 2019-05-30 | Method for separating and comprehensively utilizing all components of crop straws |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110241644B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110924206A (en) * | 2019-12-11 | 2020-03-27 | 国际竹藤中心 | Method for cleanly separating bamboo raw material components |
| CN111035018A (en) * | 2019-12-20 | 2020-04-21 | 长沙理工大学 | Comprehensive utilization method of rice bran |
| CN111321182A (en) * | 2020-04-03 | 2020-06-23 | 安徽安生生物化工科技有限责任公司 | Pretreatment method for solid acidolysis of straw |
| CN111825961A (en) * | 2020-06-24 | 2020-10-27 | 上海昶法新材料有限公司 | Biodegradable material, raw material composition thereof, and preparation method and application thereof |
| CN111849129A (en) * | 2020-06-24 | 2020-10-30 | 上海昶法新材料有限公司 | Biodegradable material, raw material composition thereof, and preparation method and application thereof |
| CN111849534A (en) * | 2020-07-21 | 2020-10-30 | 贵州理工学院 | Method for producing biomass oil by using straws |
| CN115446069A (en) * | 2022-09-20 | 2022-12-09 | 军安绿色新材料科技(广州)有限公司 | Integrated preparation system for multi-component efficient separation of biomass |
| CN115819796A (en) * | 2022-12-29 | 2023-03-21 | 浙江科技学院 | Method for efficiently separating organic acid lignin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924468A (en) * | 2014-05-16 | 2014-07-16 | 长春工业大学 | Separation method of lignocellulose raw material ingredients |
| US20150247009A1 (en) * | 2013-08-12 | 2015-09-03 | Melvin Mitchell | Method for isolating lignin from a biomass and products provided therefrom |
| CN105507051A (en) * | 2015-11-23 | 2016-04-20 | 中国科学院青岛生物能源与过程研究所 | Efficient method for separating lignocellulosic raw material |
| CN108166293A (en) * | 2017-12-04 | 2018-06-15 | 湖南省农业科学院 | The method and its system of a kind of irradiation-plant fibrous agricultural wastes of chemical method Combined Treatment |
| CN109810232A (en) * | 2019-01-03 | 2019-05-28 | 吉林大学 | A kind of method of biomass papermaking and comprehensive utilization |
-
2019
- 2019-05-30 CN CN201910464672.0A patent/CN110241644B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150247009A1 (en) * | 2013-08-12 | 2015-09-03 | Melvin Mitchell | Method for isolating lignin from a biomass and products provided therefrom |
| CN103924468A (en) * | 2014-05-16 | 2014-07-16 | 长春工业大学 | Separation method of lignocellulose raw material ingredients |
| CN105507051A (en) * | 2015-11-23 | 2016-04-20 | 中国科学院青岛生物能源与过程研究所 | Efficient method for separating lignocellulosic raw material |
| CN108166293A (en) * | 2017-12-04 | 2018-06-15 | 湖南省农业科学院 | The method and its system of a kind of irradiation-plant fibrous agricultural wastes of chemical method Combined Treatment |
| CN109810232A (en) * | 2019-01-03 | 2019-05-28 | 吉林大学 | A kind of method of biomass papermaking and comprehensive utilization |
Non-Patent Citations (1)
| Title |
|---|
| 李聪等: "NaOH-H_2O_2溶剂体系下玉米秸秆的组分分离规律研究", 《中国粮油学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110924206A (en) * | 2019-12-11 | 2020-03-27 | 国际竹藤中心 | Method for cleanly separating bamboo raw material components |
| CN111035018A (en) * | 2019-12-20 | 2020-04-21 | 长沙理工大学 | Comprehensive utilization method of rice bran |
| CN111321182A (en) * | 2020-04-03 | 2020-06-23 | 安徽安生生物化工科技有限责任公司 | Pretreatment method for solid acidolysis of straw |
| CN111825961A (en) * | 2020-06-24 | 2020-10-27 | 上海昶法新材料有限公司 | Biodegradable material, raw material composition thereof, and preparation method and application thereof |
| CN111849129A (en) * | 2020-06-24 | 2020-10-30 | 上海昶法新材料有限公司 | Biodegradable material, raw material composition thereof, and preparation method and application thereof |
| CN111849534A (en) * | 2020-07-21 | 2020-10-30 | 贵州理工学院 | Method for producing biomass oil by using straws |
| CN115446069A (en) * | 2022-09-20 | 2022-12-09 | 军安绿色新材料科技(广州)有限公司 | Integrated preparation system for multi-component efficient separation of biomass |
| CN115819796A (en) * | 2022-12-29 | 2023-03-21 | 浙江科技学院 | Method for efficiently separating organic acid lignin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110241644B (en) | 2021-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110241644A (en) | A kind of method agricultural crop straw full constituent separation and comprehensively utilized | |
| CN105860090B (en) | The method of high activity lignin and its obtained lignin are extracted from biomass | |
| US8030039B1 (en) | Method for the production of fermentable sugars and cellulose from lignocellulosic material | |
| Yin et al. | The pretreatment of lignocelluloses with green solvent as biorefinery preprocess: a minor review | |
| US20110104773A1 (en) | Processing method for fractionally converting pennisetum hydridum into fuel ethanol with co-production of electricity generation and paper pulp | |
| JPS6214280B2 (en) | ||
| EP2336193A1 (en) | Process for the Treatment of Lignocellulosic Biomass Material | |
| CN102154876B (en) | Method for extracting and separating components in ramulus mori skin | |
| CN106702800B (en) | A method of straw lignin and hemicellulose are removed with proton type ionic liquid | |
| Škulcová et al. | Deep eutectic solvents as medium for pretreatment of biomass | |
| BR112014021929B1 (en) | PROCESS FOR PRODUCTION OF A COMPOSITION FOR USE IN SOIL APPLICATION AND PROCESS FOR SOIL CONDITIONING | |
| AU2022201150B2 (en) | Efficient Methods And Compositions For Recovery Of Products From Organic Acid Pretreatment Of Plant Materials | |
| Lee et al. | Characterization of oxalic acid pretreatment on lignocellulosic biomass using oxalic acid recovered by electrodialysis | |
| CN104164801A (en) | Method for separating and recycling cellulose, semicellulose and lignin in lignocellulosic biomass at one time | |
| US20160152779A1 (en) | Processes for producing lignin-based enzymatic hydrolysis enhancers, and compositions produced therefrom | |
| CN103131802A (en) | Process for producing xylose by lignocellulose biomass | |
| CN109826044A (en) | The separation method of cellulose, hemicellulose, lignin in cotton stalk | |
| CN108893507A (en) | A method of it is pre-processed by combination and promotes sawdust enzymatic hydrolysis | |
| CN105669879A (en) | Preparation method of xylooligosaccharide | |
| CN103898246B (en) | A kind of technique of being produced wood sugar by biomass material | |
| CN103896887B (en) | Technology utilizing biomass raw materials to produce furfural | |
| CN107986275A (en) | A kind of production method of biological activated carbon | |
| CN107488413A (en) | The extracting method of tannin extract in a kind of granatum | |
| CN103898247B (en) | A kind of technique of being produced wood sugar by biomass material | |
| US20190382431A1 (en) | Hemicellulose processing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |