CN103896887A - Technology utilizing biomass raw materials to produce furfural - Google Patents
Technology utilizing biomass raw materials to produce furfural Download PDFInfo
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- CN103896887A CN103896887A CN201210576228.6A CN201210576228A CN103896887A CN 103896887 A CN103896887 A CN 103896887A CN 201210576228 A CN201210576228 A CN 201210576228A CN 103896887 A CN103896887 A CN 103896887A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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Abstract
The invention relates to a preparation method of furfural, and specifically relates to a method for comprehensively utilizing biomass raw materials to produce furfural. In the preparation method, a mixed organic acid composed of formic acid and acetic acid is used to cook biomass raw materials in the presence of a hydrogen peroxide catalyst so as to obtain hemicelluloses, then the hemicelluloses are subjected to a separating and extracting treatment and high-temperature high-pressure evaporation to produce furfural, and a by-product namely biocarbon is obtained at the same time. The energy consumption of the whole reaction is low, moreover, biocarbon can be produced at the same time, and thus the economic benefit and environmental benefit for entrepreneurs are improved.
Description
Technical field
The present invention relates to a kind of method of preparing furfural, specifically a kind ofly fully utilize the method that biomass material is prepared furfural co-producing bio carbon.
Background technology
Furfural, have another name called furtural, it is by two on furan nucleus two keys and an aldehyde radical, the chemical structure of this uniqueness, can make that it is oxidized, the reaction such as hydrogenation, chlorination, nitrated and condensation, and then generate a lot of Chemicals, so be widely used in multiple production fields such as agricultural chemicals, medicine, petrochemical industry, foodstuff additive and casting.
Furfural is the vegetable fibre that is rich in piperylene, and if corn cob, maize straw, straw, bagasse, cotton seed hulls, straw etc. are raw material production, its principle is that in vegetable fibre, first piperylene is hydrolyzed into pentose, and then pentose dehydration generates furfural.
The producing and manufacturing technique of furfural mainly contains single stage method and two step method in the world at present.Single stage method is that pentosan hydralysis and two reactions of pentose dehydration generation furfural once complete in same reactor; The main drawback that single stage method exists is that steam consumption is large, and furaldehyde yield is low, produces a large amount of liquid and waste slag produced etc.Two-step approach is that the process that pentosan hydralysis in raw material and pentose dehydration generate furfural is to carry out at least two different reactors.Than single stage method, two step method has overcome the difficult problems such as existing furfural production feed stock conversion is low, generation processing wastewater is difficult to administer, furfural dregs utility value is low.Along with the development of furfurol industry, and the raising of raw material requirements of comprehensive utilization, development two-step approach production technique, the Mierocrystalline cellulose in separate raw materials and hemicellulose are also used respectively, are the inevitable development trend of furfurol industry.
Biological carbon, is by organic waste, as animal excrement, and animal bone, plant roots and stems, a kind of porous carbon that wood chip and Wheat Straw etc. processes.It can protection of the environment; in view of the characteristic of its high carbon content and porous; it not only can improve soil water storage storage and support ability; microorganism in also can soil protection; it is as a carbonaceous subterranean tank; pin carbonic acid gas, finally reach the effect that increases crop yield, therefore a lot of scientists are titled with the good reputation of biological carbon " black gold ".
Chinese patent CN101864683A discloses a kind of pretreatment process of lignocellulose raw material, this patent is mixed xylogen raw material with the mixed solution of organic acid soln and catalyzer after, carry out the first step processing, obtain liquid-solid mixture and carry out solid-liquid separation, obtain pretreatment fluid and cellulose solids; Adopt organic acid soln washing to obtain cellulose solids; Adopt diluted acid or alkali to carry out second step processing and obtain cellulose solids; The pre-treatment black liquor obtaining is cycled to used in the first step treating processes after mixing with the washing black liquid obtaining; The black liquor that recycles at least 3 times carries out organic acid, lignin products and syrup solution recovery.The black liquor of collection is carried out to flash distillation or evaporation, obtain organic acid and concentrated black liquor, obtain lignin products and syrup solution to the water that adds 2-10 times of volume in black liquor, the syrup solution obtaining can be for the preparation of furfural, thereby realizes the higher value application of lignocellulose raw material.But also there is following shortcoming in this patent: 1, the description from specification sheets can be found out, this technique is to adopt organic acid and the catalyst mix taking sulfuric acid as representative to carry out the first step catalysis, needs to add catalyzer and carry out catalysis in reaction process; 2, the common boiling biomass of this process using organic acid and the catalyzer taking sulfuric acid as representative, in distillation organic acid step, still remain in final pentose solution as the sulfuric acid of catalyzer, making also needs to take out sulfate ion wherein to the processing of the pentose obtaining in subsequent step, has increased treatment step; Although extraction and washing the fibre element all use identical organic acid in 3 whole techniques, and the pretreatment fluid of collection and washings are directly used in the reactor that is circulated to the first step, dissolve xylogen and pentose solution wherein but also gathered in a large number in whole mixed solution, in view of the saturation ratio restriction of organic acid extraction, its degree of functioning of mixing black liquid extraction xylogen can significantly reduce, therefore, although this step is circulating reaction, for overall extraction efficiency effect little; 4, in the pretreatment fluid of collecting and washings due to the pentose that is dissolved with a large amount of hemicellulose boilings and generates, and pentose is along with mixed solution repeatedly can constantly contact with organic acid in working cycle, there is esterification and generate ester class, this patent is that comprehensive utilization taking lignocellulose biomass is as object, therefore whether can obtain separately pentose and pay no attention to for whole piece technique, but for obtaining pentose for the technique of object to separate, this technique is also inapplicable; 5, the black liquor being mixed to get need to circulate and carry out above evaporation process for 3 times to isolate organic acid again, and the concentrated solution that dilution obtains is separated out xylogen, can make the black liquor of disposable processing and the quantity of concentrated solution very big, not only affect processing efficiency but also be difficult to realize the continuity of technique.
Chinese patent CN101514349A discloses a kind of method of being prepared alcohol fuel by bamboo fiber.This patent is also the mix acid liquor boiling hydrolyzed hemicellulose with formic acid and acetic acid, and directly separates out xylogen precipitation to adding water in the filtrate of deviating from and isolate xylogen with this and be used.Because it adopts the mixed organic acid liquid of formic acid and acetic acid as cooking liquor, therefore without adding catalyzer, although this patent is separated Mierocrystalline cellulose, hemicellulose and xylogen in a technique circuit, but the design of this technique is to extract Mierocrystalline cellulose as final purpose, and the loss of pentose is not considered in the design of whole piece technique; And in the step of this technique extracting in water precipitation in separating lignin one step, can make xylogen be difficult to all deviate from because containing in a large number formic acid and acetic acid in solution, can dissolve and wherein cannot ensure that xylogen separates out completely because of formic acid and acetic acid even if add water in a large number also, cause and cannot separate pentose wherein completely.Obviously, this technique only emphasis has considered to extract to greatest extent cellulosic technique, for there is no directive function taking pentose for finally extracting the technique of product.
Chinese patent CN1170031C discloses the method for a kind of mixture with formic acid and acetic acid as cooking chemical production paper pulp.This patent is in the time producing paper pulp with formic acid boiling herbaceous plant and deciduous tree, add acetic acid as additional cooking chemical and without adding catalyzer, obtain containing hemicellulose and cellulosic paper pulp, and the mix acid liquor that used cooking liquor distills out formic acid and acetic acid is carried out to recycle.Although the method has solved the problem that needs to add catalyzer in the process of boiling biomass, but because the method is mainly for the preparation of paper pulp, its objective is the hemicellulose that retains to greatest extent Mierocrystalline cellulose and part, its whole technological design is all with this end in view, therefore for this technique, hemicellulose is not effectively separated and is extracted, and therefore this technique is for also inapplicable for extracting the technique of product taking pentose.
Chinese patent CN101108839A discloses a kind of system by manufacturing furol with pentose solution, the described system of preparing furfural comprises dewatering unit and distillation unit, described dewatering unit dewaters to described pentose solution, described dewatering unit comprises the dehydration reactor that at least secondary is connected mutually, and described pentose solution is carried out at least 2 grades of processed.This system has solved in existing furfural production technology the lower and with serious pollution problem of pentose Dehydration furfural yield.But the dewatering unit described in this technique is liquid phase dehydration reaction, by heat, water is converted into water vapour, and by the mobile furfural of taking out of in reaction system of water vapour, after collection vapor condensation, obtain required furfural.But owing in this technique needing water to change into water vapour, thereby need great energy consumption, provide energy although the aldehyde gas of rear first order reaction can be previous stage reaction, the energy consumption of whole technique is still larger.
Summary of the invention
For this reason, the object of the present invention is to provide a kind of energy consumption low, technique is simply prepared the technique of furfural by biomass material; And further provide a kind of technique of being prepared furfural co-producing bio carbon by biomass material.
For solving the problems of the technologies described above, technique of being produced furfural by biomass material biomass of the present invention, is characterized in that, comprises the steps:
(1) by after biomass material comminution pretreatment, under the katalysis of hydrogen peroxide, use the organic acid solution being formed by formic acid and acetic acid to carry out boiling to biomass material, control temperature of reaction 120-155 DEG C, reaction 10-90min, solid-liquid mass ratio 1:5-1:20, and the reaction solution obtaining is carried out to solid-liquid separation for the first time; In described organic acid solution, total acid is dense is 75-95wt%, and the mass ratio of described acetic acid and formic acid is 1:19-19:1, and surplus is water, and hydrogen peroxide accounts for the 0.5-6wt% of biomass material;
(2) solid that described in collection, solid-liquid separation obtains for the first time, under the katalysis of hydrogen peroxide, the mix acid liquor that adopts formic acid, acetic acid to form carries out pickling to described solid, control pickling temperature 20-100 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reaction solution obtaining is carried out to solid-liquid separation for the second time; The total acid of described mix acid liquor is dense is 50-95wt%, and hydrogen peroxide accounts for the 1-3% of biomass material;
(3) liquid that solid-liquid separation and described solid-liquid separation for the second time obtain for the first time described in collecting carries out evaporation concentration, and obtaining formic acid, acetic acid steam and solids content is 50-95wt% concentrated solution;
(4) concentrated solution of gained in step (3) is evaporated again, the gas obtaining is furfural, and solid is biological carbon.
In above-mentioned technique of being produced furfural by biomass material, the evaporation in described step (4) obtains in the step of biological carbon, and evaporation control temperature is 140-190 DEG C, and pressure is 401-901kPa.
Preferably, the evaporation in described step (4) obtains in the step of biological carbon, and evaporation reaction control temperature is 160 ~ 180 DEG C, and pressure is 501 ~ 801kpa.
Preferably, described step (3), also comprises the step that the formic acid obtaining, acetic acid steam condensing reflux are carried out to boiling for step (1).
preferably,in described step (4), the solids content of described concentrated solution is 80-90wt%.
Preferably, in described step (1), solid-liquid mass ratio is 1:6-1:10, temperature of reaction 120-145 DEG C, reaction times 20-70min; In described organic acid solution, the mass ratio of acetic acid and formic acid is 1:6-1:1.
Preferably, in described step (2), the dense 60-85% of total acid of described mix acid liquor, pickling temperature 30-90 DEG C, solid-liquid mass ratio is 1:8-1:10.
In above-mentioned technique, described biomass material is one or more in the wooden classes such as reed, beanstalk stalk, wheat stalk, straw, maize straw, melon seed cases, bamboo chip, melon seeds bar or grass as raw material.
Technique scheme of the present invention has the following advantages compared to existing technology:
1, the present invention produces in the process of furfural, and dehydration carburizing reagent, in preparing furfural, has also obtained by product biological carbon, not only reduces environmental pollution, can also create more income for furfural enterprise.
2, the present invention directly carries out concentrated solution High Temperature High Pressure evaporation and obtains furfural, and reactions steps is simple, is beneficial to large-scale application.
3, after the technique the first step of the present invention boiling and the sugar soln of collecting after acid elution directly evaporate, obtain formic acid and acetic acid, can be used on the one hand the circulation of raw material, also reduce the acid content in pentose solution simultaneously as far as possible, avoid occurring esterification, retain to greatest extent boiling and obtain pentose solution.
4, after technique of the present invention obtains evaporation formic acid, acetic acid vapor condensation, be directly back in the reactor of the first step for recycling, whole operational path is succinct, and because formic acid and acetic acid re-use as raw material, boiling efficiency to biomass is higher, for utilizing the technique of the cooking liquor circulation after boiling, although saved the step of this circulation, realize within the identical process time, half-and-half cellulosic extraction efficiency is higher.
5, the common boiling biomass material of process selection formic acid of the present invention and acetic acid; utilize the organic extraction performance of formic acid and acetic acid to extract xylogen wherein; and the destruction of utilizing the hemicellulose in acetic acid protection raw material not to be subject to formic acid; selecting the dense organic acid solution for 75-95wt% of total acid to process also profit to raw material has the dense mix acid liquor for 50-95wt% of total acid to carry out pickling, makes the hemicellulose in biomass all can be hydrolyzed to greatest extent and extract.
Brief description of the drawings
For content of the present invention is more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is the schema of technique of the present invention.
Embodiment
Below will by specific embodiment, the invention will be further described.
In following examples, outside specified otherwise, percentage composition used all represents quality percentage composition, i.e. " % " expression " wt% "; In described organic acid solution or mix acid liquor except a certain amount of formic acid, acetic acid, surplus is water, the dense nail acid of total acid of organic acid solution and the total mass of acetic acid account for the percentage ratio of described organic acid solution quality, and the formic acid adding in the dense finger acid pickling step of total acid of mix acid liquor and the total mass of acetic acid account for the percentage ratio of described mix acid liquor quality.
Slurry described in each step is dense=this step in quality/this step of solid the Zhi Liang of solid and liquid with ╳ 100%
Hydrogen peroxide H in each embodiment
2o
2the form of the aqueous hydrogen peroxide solution taking mass concentration as 27% adds.For example need as calculated to add 2.7g hydrogen peroxide, corresponding should be to add 10g(2.7 ÷ 0.27=10) described aqueous hydrogen peroxide solution.
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 sulphur content adopts the measuring 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
Embodiment 1
In the present embodiment, first reed is smashed, being crushed to particle diameter is 2-10cm.
The present embodiment is produced the technique of furfural by described reed, comprise the steps:
(1) by after the pre-treatment of reed raw material pulverizing, under the katalysis of hydrogen peroxide, use the dense organic acid solution for 85wt% of total acid to carry out boiling to reed raw material after treatment, in the present embodiment, in described organic acid solution, the mass ratio of acetic acid and formic acid is 1:19, and the quality of described hydrogen peroxide accounts for the 5wt% of described reed raw materials quality.
Control 120 DEG C of temperature of reaction, reaction 10min, solid-liquid mass ratio is 1:6, and the reaction solution obtaining is carried out to solid-liquid separation for the first time;
(2) solid that solid-liquid separation obtains for the first time being added the mix acid liquor (in this step, the mass ratio of formic acid and acetic acid is 6:1) of the total acid being formed by formic acid and acetic acid dense 85% carry out acid elution and control pickling temperature is 30 DEG C, and after 1h, reaction solution carries out solid-liquid separation for the second time; In this step, add the hydrogen peroxide that accounts for biomass material quality 1wt% in described acid solution, solid-liquid mass ratio is 1:15.
(3) collect for the first time and the liquid that solid-liquid separation obtains for the second time, at 90 DEG C, under 89kpa, carry out underpressure distillation concentrated, obtain formic acid and acetic acid vapor, and the solids content concentrated solution that is 50wt%, and by the formic acid distilling out and acetic acid vapor condensing reflux to the reactor of step (1), for the boiling of step (1);
(4) by the concentrated solution of gained in step (3) at 140 DEG C, under the pressure of 401kPa, carry out high temperature evaporation, the gas obtaining is furfural, remaining solid is biological carbon, and its yield is 70wt%, and the fixed carbon content of described biological carbon is 60wt% after measured, ash oontent 0.15wt%, sulphur content 0.1wt%, moisture 38.7wt%, thermal value 4125J/g.
Embodiment 2
In the present embodiment, first beanstalk bar is smashed, being crushed to particle diameter is 2-10cm.
The present embodiment is produced the technique of furfural by described beanstalk bar, comprise the steps:
(1) by after the pre-treatment of beanstalk bar raw material pulverizing, under the katalysis of hydrogen peroxide, use the dense organic acid solution for 80wt% of total acid to carry out boiling to beans straw raw material after treatment, in the present embodiment, in described organic acid solution, the mass ratio of acetic acid and formic acid is 3:1, and the quality of described hydrogen peroxide accounts for the 2wt% of described reed raw materials quality.
Control 155 DEG C of temperature of reaction, reaction 20min, solid-liquid mass ratio is 1:10, and the reaction solution obtaining is carried out to solid-liquid separation for the first time;
(2) solid that solid-liquid separation obtains for the first time being added the mix acid liquor (in this step, the mass ratio of formic acid and acetic acid is 1.5:1) of the total acid being formed by formic acid and acetic acid dense 80% carry out acid elution and control pickling temperature is 100 DEG C, and after pickling 40min, reaction solution carries out solid-liquid separation for the second time; In this step, add the hydrogen peroxide that accounts for biomass material quality 3wt% in described acid solution, solid-liquid mass ratio is 1:10.
(3) collect for the first time and the liquid that solid-liquid separation obtains for the second time, at 70 DEG C, it is concentrated that 55kpa carries out underpressure distillation, obtain formic acid and acetic acid vapor, and the solids content concentrated solution that is 90wt%, and by the formic acid distilling out and acetic acid vapor condensing reflux to the reactor of step (1), for the boiling of step (1);
(4) by the concentrated solution of gained in step (3) at 190 DEG C, under the pressure of 901kPa, carry out high temperature evaporation, the gas obtaining is furfural, remaining solid is biological carbon, and its yield is 75wt%, and the fixed carbon content of described biological carbon is 61wt% after measured, ash oontent 0.1wt%, sulphur content 0.05wt%, moisture 38.6wt%, thermal value 5100J/g.
Embodiment 3
In the present embodiment, first straw is smashed, being crushed to particle diameter is 2-10cm.
The present embodiment is produced the technique of furfural by described straw, comprise the steps:
(1) by after straw raw material comminution pretreatment, under the katalysis of hydrogen peroxide, use the dense organic acid solution for 95wt% of total acid to carry out boiling to straw raw material after treatment, in the present embodiment, in described organic acid solution, the mass ratio of acetic acid and formic acid is 19:1, and the quality of described hydrogen peroxide accounts for the 6wt% of described reed raw materials quality.
Control 140 DEG C of temperature of reaction, reaction 90min, solid-liquid mass ratio is 1:5, and the reaction solution obtaining is carried out to solid-liquid separation for the first time;
(2) mix acid liquor (in this step, formic acid is 10:1 with the mass ratio of acetic acid) that the solid that solid-liquid separation obtains is for the first time added to the total acid being formed with acetic acid by formic acid dense 70% with organic acid solution described in step (1) identical acid solution to carry out acid elution and control pickling temperature be 20 DEG C, after 45min, reaction solution is carried out to solid-liquid separation for the second time; In this step, add the hydrogen peroxide that accounts for biomass material quality 2.5wt% in described acid solution, solid-liquid mass ratio is 1:20.
(3) collect for the first time and the liquid that solid-liquid separation obtains for the second time, in 88 DEG C, under 90kpa, carry out underpressure distillation concentrated, obtain formic acid and acetic acid vapor, and the solids content concentrated solution that is 60wt%, and by the formic acid distilling out and acetic acid vapor condensing reflux to the reactor of step (1), for the boiling of step (1);
(4) by the concentrated solution of gained in step (3) at 180 DEG C, under the pressure of 801kPa, carry out high temperature evaporation, the gas obtaining is furfural, remaining solid is biological carbon, and its yield is 80wt%, and the fixed carbon content of described biological carbon is 65wt% after measured, ash oontent 0.12wt%, sulphur content 0.06wt%, moisture 34.2wt%, thermal value 4875J/g.
Embodiment 4
In the present embodiment, first melon seeds bar is smashed, and to be crushed to particle diameter be 2-5cm.
The present embodiment is produced the technique of furfural by described melon seeds bar, comprise the steps:
(1) by after the pre-treatment of melon seeds bar raw material pulverizing, under the katalysis of hydrogen peroxide, using total acid dense is that 90% organic acid solution carries out boiling to melon seeds bar raw material after treatment, in the present embodiment, in described organic acid solution, the mass ratio of acetic acid and formic acid is 1:3, and the quality of described hydrogen peroxide accounts for described raw materials quality 4wt%.
Control 130 DEG C of temperature of reaction, reaction 70min, solid-liquid mass ratio is 1:7, and the reaction solution obtaining is carried out to solid-liquid separation for the first time;
(2) solid that solid-liquid separation obtains for the first time being added the identical acid solution of organic acid solution described in mix acid liquor (in this step, formic acid is 11:1 with the mass ratio of the acetic acid) step (1) of the total acid being formed with acetic acid by formic acid dense 95% carry out acid elution and control pickling temperature is 60 DEG C, and after 70min, reaction solution carries out solid-liquid separation for the second time; In this step, also add the hydrogen peroxide that accounts for biomass material quality 2wt% in described acid solution, solid-liquid mass ratio is 1:4.
(3) collect for the first time and the liquid that solid-liquid separation obtains for the second time, in 78 DEG C, under 90kpa, carry out underpressure distillation concentrated, obtain formic acid and acetic acid vapor, and the solids content concentrated solution that is 85wt%, and by the formic acid distilling out and acetic acid vapor condensing reflux to the reactor of step (1), for the boiling of step (1);
(4) by the concentrated solution of gained in step (3) at 170 DEG C, under the pressure of 701kPa, carry out high temperature evaporation, the gas obtaining is furfural, remaining solid is biological carbon, and its yield is 82wt%, and the fixed carbon content of described biological carbon is 64wt% after measured, ash oontent 0.13wt%, sulphur content 0.08wt%, moisture 35.1wt%, thermal value 4623J/g.
Embodiment 5
In the present embodiment, first cotton stem is smashed, and to be crushed to particle diameter be 2-10cm.
The present embodiment is produced the technique of furfural by described cotton stem, comprise the steps:
(1) by after the pre-treatment of cotton stem raw material pulverizing, under the katalysis of hydrogen peroxide, use the organic acid solution of the dense 75wt% of total acid to carry out boiling to cotton stem raw material after treatment, in the present embodiment, in described organic acid solution, the mass ratio of acetic acid and formic acid is 1:1, and the quality of described hydrogen peroxide accounts for the 3wt% of described cotton stem raw materials quality.
Control 145 DEG C of temperature of reaction, reaction 15min, solid-liquid mass ratio is 1:20, and the reaction solution obtaining is carried out to solid-liquid separation for the first time;
(2) solid that solid-liquid separation obtains for the first time being added the mix acid liquor (in this step, the mass ratio of formic acid and acetic acid is 1:9) of the total acid being formed by formic acid and acetic acid dense 60% carry out acid elution and control pickling temperature is 90 DEG C, and after 75min, reaction solution carries out solid-liquid separation for the second time; In this step, add the hydrogen peroxide that accounts for raw materials quality 1.5wt% in described acid solution, solid-liquid mass ratio is 1:8.
(3) collect for the first time and the liquid that solid-liquid separation obtains for the second time, carry out underpressure distillation concentrated, obtain formic acid and acetic acid vapor, and the solids content concentrated solution that is 95wt%, and by the formic acid distilling out and acetic acid vapor condensing reflux to the reactor of step (1), for the boiling of step (1);
(4) by the concentrated solution of gained in step (3) at 160 DEG C, under the pressure of 601kPa, carry out high temperature evaporation, the gas obtaining is furfural, remaining solid is biological carbon, and its yield is 85wt%, and the fixed carbon content of described biological carbon is 63wt% after measured, ash oontent 0.1wt%, sulphur content 0.07wt%, moisture 30.2wt%, thermal value 4759J/g.
Embodiment 6
In the present embodiment, first bamboo chip is smashed, being crushed to length is 2 ~ 10cm, thick 2mm thin slice.
The present embodiment is produced the technique of furfural by described bamboo chip, comprise the steps:
(1) by after the pre-treatment of bamboo chip raw material pulverizing, under the katalysis of hydrogen peroxide, use the dense organic acid solution for 75wt% of total acid to carry out boiling to bamboo chip raw material after treatment, in the present embodiment, in described organic acid solution, the mass ratio of acetic acid and formic acid is 1:6, and the quality of described hydrogen peroxide accounts for described bamboo chip raw materials quality 0.5wt%.
Control 125 DEG C of temperature of reaction, reaction 20min, solid-liquid mass ratio is 1:13, and the reaction solution obtaining is carried out to solid-liquid separation for the first time;
(2) solid that solid-liquid separation obtains is for the first time added the mix acid liquor (in this step, the mass ratio of formic acid and acetic acid is 1:4.5) of the total acid being formed by formic acid and acetic acid dense 50% carry out acid elution and control 25 DEG C of pickling temperatures, after 55min, reaction solution is carried out to solid-liquid separation for the second time; In this step, add the hydrogen peroxide that accounts for biomass material quality 1wt% in described acid solution, solid-liquid mass ratio is 1:9.
(3) collect for the first time and the liquid that solid-liquid separation obtains for the second time, in 82 DEG C, under 92kpa, carry out underpressure distillation concentrated, obtain formic acid and acetic acid vapor, and the concentrated solution of solids content 80wt%, and by the formic acid distilling out and acetic acid vapor condensing reflux to the reactor of step (1), for the boiling of step (1);
(4) by the concentrated solution of gained in step (3) at 150 DEG C, under the pressure of 501kPa, carry out high temperature evaporation, the gas obtaining is furfural, remaining solid is biological carbon, and its yield is 85wt%, and the fixed carbon content of described biological carbon is 63wt% after measured, ash oontent 0.12wt%, sulphur content 0.05wt%, moisture 36.1wt%, thermal value 5214J/g.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (7)
1. a technique of being produced furfural by biomass material, is characterized in that, comprises the steps:
(1) by after biomass material comminution pretreatment, under the katalysis of hydrogen peroxide, use the organic acid solution being formed by formic acid and acetic acid to carry out boiling to biomass material, control temperature of reaction 120-155 DEG C, reaction 10-90min, solid-liquid mass ratio 1:5-1:20, and the reaction solution obtaining is carried out to solid-liquid separation for the first time;
In described organic acid solution, total acid is dense is 75-95wt%, and the mass ratio of described acetic acid and formic acid is 1:19-19:1, and surplus is water,
Hydrogen peroxide accounts for the 0.5-6wt% of biomass material;
(2) solid that described in collection, solid-liquid separation obtains for the first time, under the katalysis of hydrogen peroxide, the mix acid liquor that adopts formic acid, acetic acid to form carries out pickling to described solid, control pickling temperature 20-100 DEG C, solid-liquid mass ratio is 1:4-1:20, and the reaction solution obtaining is carried out to solid-liquid separation for the second time; The total acid of described mix acid liquor is dense is 50-95wt%, and hydrogen peroxide accounts for the 1-3% of biomass material;
(3) liquid that solid-liquid separation and described solid-liquid separation for the second time obtain for the first time described in collecting carries out evaporation concentration, and obtaining formic acid, acetic acid steam and solids content is 50-95wt% concentrated solution;
(4) concentrated solution of gained in step (3) is evaporated again, the gas obtaining is furfural, and solid is biological carbon.
2. technique of being produced furfural by biomass material according to claim 1, is characterized in that:
Evaporation in described step (4) obtains in the step of biological carbon, and evaporation control temperature is 140-190 DEG C, and pressure is 401-901kPa.
3. technique of being produced furfural by biomass material according to claim 2, is characterized in that:
Evaporation in described step (4) obtains in the step of biological carbon, and evaporation control temperature is 160 ~ 180 DEG C, and pressure is 501 ~ 801kpa.
4. according to the arbitrary described technique of producing furfural by biomass material of claim 1-5, it is characterized in that:
Described step (3), also comprises the step that the formic acid obtaining, acetic acid steam condensing reflux are carried out to boiling for step (1).
5. according to the arbitrary described technique of producing furfural by biomass material of claim 1-4, it is characterized in that:
In described step (4), the solids content of described concentrated solution is 80-90wt%.
6. according to the arbitrary described technique of producing furfural by biomass material of claim 1-5, it is characterized in that:
In described step (1), solid-liquid mass ratio is 1:6-1:10, temperature of reaction 120-145 DEG C, reaction times 20-70min;
In described organic acid solution, the mass ratio of acetic acid and formic acid is 1:6-1:1.
7. according to the arbitrary described technique of producing furfural by biomass material biomass of claim 1-6, it is characterized in that:
In described step (2), the dense 60-85% of total acid of described mix acid liquor, pickling temperature 30-90 DEG C, solid-liquid mass ratio is 1:8-1:10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315243A (en) * | 2015-09-16 | 2016-02-10 | 安庆市宜秀区永兴农机农艺综合发展专业合作社 | Method for preparing furfural through agricultural waste |
| CN108586394A (en) * | 2018-03-23 | 2018-09-28 | 中国科学院广州能源研究所 | A kind of method of biomass coproducing furfural and charcoal |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108839A (en) * | 2007-08-28 | 2008-01-23 | 济南圣泉集团股份有限公司 | System and method of manufacturing furol with pentose solution |
| CN101130530A (en) * | 2007-09-17 | 2008-02-27 | 济南圣泉集团股份有限公司 | System and method for producing furol by using agricultural and forestry castoff |
| CN101130531A (en) * | 2007-09-17 | 2008-02-27 | 济南圣泉集团股份有限公司 | System and method for producing furol with agricultural and forestry castoff |
| CN101864683A (en) * | 2010-03-25 | 2010-10-20 | 清华大学 | Pretreatment method of wood fiber raw materials |
| US20110179703A1 (en) * | 2009-09-25 | 2011-07-28 | Auburn University | Biomass to biochar conversion in subcritical water |
-
2012
- 2012-12-25 CN CN201210576228.6A patent/CN103896887B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108839A (en) * | 2007-08-28 | 2008-01-23 | 济南圣泉集团股份有限公司 | System and method of manufacturing furol with pentose solution |
| CN101130530A (en) * | 2007-09-17 | 2008-02-27 | 济南圣泉集团股份有限公司 | System and method for producing furol by using agricultural and forestry castoff |
| CN101130531A (en) * | 2007-09-17 | 2008-02-27 | 济南圣泉集团股份有限公司 | System and method for producing furol with agricultural and forestry castoff |
| US20110179703A1 (en) * | 2009-09-25 | 2011-07-28 | Auburn University | Biomass to biochar conversion in subcritical water |
| CN101864683A (en) * | 2010-03-25 | 2010-10-20 | 清华大学 | Pretreatment method of wood fiber raw materials |
Non-Patent Citations (1)
| Title |
|---|
| 李明飞等: "有机酸纸浆的研究进展", 《中国造纸》, vol. 27, no. 9, 31 December 2008 (2008-12-31), pages 56 - 61 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315243A (en) * | 2015-09-16 | 2016-02-10 | 安庆市宜秀区永兴农机农艺综合发展专业合作社 | Method for preparing furfural through agricultural waste |
| CN108586394A (en) * | 2018-03-23 | 2018-09-28 | 中国科学院广州能源研究所 | A kind of method of biomass coproducing furfural and charcoal |
| CN108586394B (en) * | 2018-03-23 | 2020-05-05 | 中国科学院广州能源研究所 | Method for co-producing furfural and biochar from biomass |
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