CN116145458A - Comprehensive utilization method of corncob - Google Patents
Comprehensive utilization method of corncob Download PDFInfo
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- CN116145458A CN116145458A CN202310058938.8A CN202310058938A CN116145458A CN 116145458 A CN116145458 A CN 116145458A CN 202310058938 A CN202310058938 A CN 202310058938A CN 116145458 A CN116145458 A CN 116145458A
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- lignin
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- 238000000034 method Methods 0.000 title claims abstract description 47
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229920005610 lignin Polymers 0.000 claims abstract description 48
- 239000000835 fiber Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 150000007524 organic acids Chemical class 0.000 claims abstract description 26
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 24
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 17
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 17
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- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
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- 230000000704 physical effect Effects 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
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- 238000005303 weighing Methods 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 2
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- 238000009776 industrial production Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000193401 Clostridium acetobutylicum Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
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- 239000002893 slag Substances 0.000 description 1
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Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The application discloses a comprehensive utilization method of corncob. The application comprises the following steps: s1, pretreatment of corncob; s2, cleaning the obtained fiber material to be neutral, then performing low-frequency ultrasonic treatment to obtain free corn cob fibers, and mixing the free corn cob fibers with paper pulp fibers according to a certain proportion to obtain mixed pulp; fluffing, sheet making and drying the mixed pulp to obtain paper; s3, directly heating the obtained aqueous phase solution, and converting xylose into furfural under the catalysis of organic acid; s4, carrying out hydrogenation depolymerization conversion on the obtained lignin to obtain a high-value aromatic monomer compound. After pretreatment of corncob, the preparation of furfural can be realized, lignin can be utilized to prepare aromatic monomer compounds in a high-valued manner, and most importantly, fiber materials obtained through pretreatment can be matched with paper pulp for papermaking after ultrasonic treatment, so that comprehensive and efficient utilization of all components of the corncob is realized.
Description
Technical Field
The invention belongs to the crossing field of pulping and papermaking engineering and agricultural solid waste recycling, and particularly relates to a comprehensive utilization method of corncobs.
Background
By 2021, the department of agriculture reported that the planting area of chinese corn reached 42670 kilohectares (6.40 hundred megaacres), the estimated unit yield reached 6370 kg per hectare (425 kg per acre), the ratio of corncob yield to corn yield was 0.21, and in rural areas, more than 87.6% of corncobs were often utilized by direct combustion, which resulted in some waste of biomass resources. How to achieve high-value conversion of corncobs has become a focus topic on aspects of agricultural solid waste disposal.
With development of biomass resource development and utilization technologies, utilization modes of corncobs are continuously increased. For example, CN201310670125.0 realizes component separation through dilute sulfuric acid, and the clostridium acetobutylicum strain is subjected to biological fermentation to obtain n-butanol, ethanol and acetone, and the nickel ruthenium bimetallic catalyst is used for preparing ethylene glycol and 1, 2-butanediol, so that the industrialization of the method is difficult due to the cost brought by a long fermentation period (48 h-72 h) and high temperature (225 ℃ to 255 ℃). CN201110374411.3 also discloses a process for comprehensive utilization of lignocellulose biomass, in the implementation example, three-element separation and efficient extraction of corncob are realized by mixed acid liquor of formic acid/acetic acid, but the subsequent utilization and pollution problem caused by acid liquor are not mentioned. The hemicellulose content (35% -40% of hemicellulose, 32% -36% of cellulose and 17% -20% of lignin) in the corncob is obviously higher than that of other straw agricultural solid wastes, so that the corncob is favored by furfural manufacturers. The technological process for preparing furfural is divided into a one-step method and a two-step method. The prior industrial production adopts a one-step method to prepare the furfural, but the one-step method has serious bottleneck problems such as low raw material utilization rate (the yield of the furfural is about 1:10-1:15 compared with the consumption of the raw material), high energy consumption (the yield of the furfural is about 1:18-1:24 compared with the high-pressure steam), serious resource waste (the yield of the furfural is about 1:150 compared with the consumption of cooling water), low utilization rate of the waste residue of the furfural and the like. The two-step method needs to convert hemicellulose into monosaccharide through pretreatment, and then the monosaccharide is dehydrated and converted into furfural, the current two-step method process is in an experimental exploration stage, and main flow researches are focused on the development and utilization of heterogeneous catalysts because of difficult recovery of homogeneous catalysts (CN 112028861A), serious pollution and the like, but heterogeneous catalysts (CN 104230860A) such as solid acid and the like are difficult to apply to large-scale industrial production because of high cost of the catalysts.
In order to solve the problems that a large amount of corncob resources in agricultural solid waste cannot be fully utilized, corncob waste residues are wasted in the process of preparing furfural and the like, the application provides a novel corncob comprehensive utilization method.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a comprehensive utilization method of corncobs.
A comprehensive utilization method of corncob comprises the following steps:
s1 pretreatment of corncob:
1-1) preheating high-concentration organic acid, then adding corncob into the preheated organic acid, and reacting for a period of time at constant temperature under the stirring condition to obtain a pretreated material;
1-2) carrying out solid-liquid separation on the pretreated material to obtain a fiber material and a hydrolysate containing lignin and hemicellulose;
1-3) performing anti-solvent precipitation on hydrolysate containing lignin and hemicellulose to obtain lignin and aqueous phase solution containing xylose and organic acid components;
s2, cleaning the fiber material obtained in the step 1-2) to be neutral, then performing low-frequency ultrasonic treatment to obtain free corn cob fibers, and blending the free corn cob fibers with pulp fibers according to a certain proportion to obtain mixed pulp; fluffing, sheet making and drying the mixed pulp to obtain paper;
s3, directly heating the aqueous phase solution obtained in the step 1-3), and directly converting xylose into furfural under the catalysis of organic acid;
s4, carrying out hydrogenation depolymerization conversion on the lignin obtained in the step 1-3) to obtain a high-value aromatic monomer compound.
Preferably, in the step 1-1), the organic acid is preheated to 80-120 ℃, the organic acid is one of acetic acid, oxalic acid, maleic acid and p-toluenesulfonic acid, the mass percent of the organic acid is 60-90%, and the solid-liquid ratio of the corn cob to the organic acid solution is 3 (50-70) g/L.
Preferably, in the step 1-1), the stirring speed is 100-300 r/min, the reaction temperature is 80-120 ℃, and the reaction time is 15-30 min.
Preferably, in the step 1-1), the particle size of the corncob is 20-40 meshes.
Preferably, in the step 1-3), the anti-solvent precipitation is performed by using deionized water, and after the deionized water is added, the mass percentage concentration of the organic acid in the aqueous phase solution is diluted to 10% -15%.
Preferably, in the step S2, the power of the low-frequency ultrasonic treatment is 140-360W, and the ultrasonic time is 30-60S.
Preferably, in the step S2, the mass of the free corn cob fibers accounts for 5% -40% of the sum of the mass of the pulp fibers and the mass of the free corn cob fibers.
Preferably, in the step S3, the conversion temperature of the furfural is 140-180 ℃ and the conversion time is 20-50 min.
Preferably, in the step S4, the catalyst of the hydrogenation depolymerization process is Ru/C, ni/C or Pt/C, and the mass ratio of the catalyst to lignin is 1 (1-1.5).
Preferably, in the step S4, the reaction temperature of the hydrogenated depolymerization is 230-250 ℃ and the reaction time is 14-18 h.
Compared with the prior art, the invention has the following advantages:
the invention provides a comprehensive utilization method of corncob, which comprises the steps of pretreating the corncob by using a completely recyclable organic acid solvent, carrying out solid-liquid separation to obtain fiber materials and hydrolysate containing lignin and hemicellulose degradation products, and then separating high-value lignin and aqueous phase solution containing xylose and organic acid from the hydrolysate by utilizing anti-solvent precipitation;
then, aqueous phase solution containing xylose and organic acid is directly subjected to high-temperature catalytic conversion by the organic acid to prepare the platform chemical furfural, and the furfural prepared by the method avoids various polycondensation reactions (polymerization of furfural, glucose, 5-HMF and lignin to form Humins) in the traditional preparation mode of steamed furfural;
according to the invention, partial lignin is dissolved out at a relatively mild temperature (90-120 ℃) in the pretreatment stage, so that the chemical structure of the obtained lignin is superior to that of the lignin in residues after the furfural is prepared by directly steaming (150-180 ℃) in a traditional one-pot method, the lignin structure is less damaged, the utilization value is high, and the lignin can be used for preparing aromatic monomer compounds;
in addition, as the dissolved lignin and hemicellulose are dissolved in the hydrolysate after the pretreatment of the step 1-1) and the step 1-2), and only a small amount of lignin and hemicellulose components exist in the fiber material, the adhesive effect of the lignin and hemicellulose components among the fibers of the fiber material is weakened, and therefore, the fiber is easy to be subjected to fibrillation separation under the action of low-frequency ultrasound to form free fibers (figure 1), and when the free fine fibers are matched with long fibers in the paper pulp, gaps among the long fibers can be filled, more hydrogen bonding effect is increased, and indexes such as tensile strength, ring compression strength, tear resistance and the like of paper can be improved. This is different from CN1203985A, this patent is directly to transfer the direct digestion of unified pot method (150-180 ℃) and prepare the residue behind the furfural and utilize, and in one of them digestion furfural conversion process (hemicellulose is to converting xylose, xylose converts to furfural), cellulose also can take place to degrade and form glucose or 5-HMF, and simultaneously furfural and glucose, 5-HMF and lignin polymerization form the Humins, and the furfural yield reduces, and cellulose also takes place the hydrolysis in addition, and the fibre is shorter, and the filter screen of probably papermaking all filters, has directly followed the water, has increased the COD load of papermaking waste water, and lignin destruction is also more than, and the value is not utilized. In addition, the slag disclosed in CN1203985a must be subjected to secondary treatment, because lignin is not removed, fibers cannot be subjected to fibrillation separation, and pulp cannot be formed, so that slaked lime is required to be used for pulping, and cost economy is poor.
In addition, the organic acid used in the invention can be completely recovered through low-temperature crystallization, and is green and pollution-free.
In summary, after pretreatment of the corncob, the method can prepare furfural and high-value aromatic monomer compounds, and most importantly, the pretreated fiber material can be matched with paper pulp for papermaking after ultrasonic treatment, so that multiple utilization of the corncob is realized, and the economy is good.
Drawings
FIG. 1 is a chart showing the morphology of free cob fibers formed by low frequency ultrasonic treatment (ultrasonic frequency 40kHz, ultrasonic power 360W, ultrasonic time 30 s) of pretreated cob;
FIG. 2 is a graph of the physical properties of handsheets obtained in example one;
FIG. 3 is a chart showing the morphology of free cob fibers formed after low frequency ultrasonic treatment (ultrasonic frequency 40kHz, ultrasonic power 360W, ultrasonic time 30 s) of the cob pretreated in the second embodiment;
FIG. 4 is a graph of the physical properties of handsheets obtained in example two;
FIG. 5 is a GC-MS chromatogram of the lignin hydrogenated polymer obtained in example II.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
A comprehensive utilization method of corncob comprises the following steps:
s1 pretreatment of corncob:
1-1) preheating 50mL of 70% by mass maleic acid solution to 90 ℃; according to the solid-to-liquid ratio of 60:1 (g/L) weighing 3g of corncob with 20-40 meshes, adding the corncob into the preheated maleic acid solution, and heating for 60min at 90 ℃ and 500rpm to obtain a pretreated material;
1-2) immediately carrying out suction filtration on the pretreated material obtained in the step 1-1) by using a suction filtration device to carry out solid-liquid separation, so as to obtain a fiber material and hydrolysate containing lignin and hemicellulose;
1-3) adding 50mL of deionized water dropwise to the hydrolysis solution containing lignin and hemicellulose for anti-solvent precipitation to obtain lignin precipitate and an aqueous solution containing xylose and organic acid components.
S2, washing the fiber material obtained in the step 1-2) to be neutral by deionized water for a small amount for a plurality of times, then carrying out low-frequency ultrasonic treatment on the neutral fiber material, wherein the ultrasonic frequency is 40kHz, the ultrasonic power is 360W, the ultrasonic time is 30S, obtaining free corn cob fine fiber, mixing the free corn cob fine fiber with softwood pulp fiber according to the mass ratio of 0.2:0.8 to obtain mixed pulp, and at the moment, the free corn cob fine fiber accounts for 20% of the total mass of the softwood pulp fiber and the free corn cob fine fiber; and then carrying out fluffing, sheet making and drying treatment on the mixed pulp to obtain paper, wherein the paper is the handsheet. The physical properties of the handsheets were measured according to GB/T24323-2009 "measurement of physical Properties of paper laboratory sheets".
As shown in fig. 2, in the first example, the ring crush index, tear index and tensile index of the prepared handsheets were respectively: 5.94 N.m/g, 6.13 mN.m 2 /g, 17.62 N.m/g; the ring crush index, tear index, and tensile index of the handsheets prepared in this example were increased by 26.35%, 66.52%, and 33.48%, respectively, as compared to handsheets prepared with pure softwood pulp.
S3, placing 25mL of the aqueous phase solution obtained in the step 1-3) into a 75mL pressure-resistant bottle, and heating at 170 ℃ for 30min to prepare furfural. After the reaction is finished, naturally cooling the pressure-resistant bottle at room temperature, and taking a reaction product to determine the furfural yield after cooling to the room temperature, wherein the calculation formula of the furfural yield is shown as formula (1):
in the formula (1), C furfural Is the concentration of furfural in the reaction product; v is the volume of the reaction product; m is m poplar The mass of the corncob used in the system; 91.28% is the proportion of the absolute dry material of the corncob; 37.81 the mass of hemicellulose accounts for the mass percentage of the corncob raw material; 0.88 is the conversion factor of hemicellulose to xylose; 0.64 is woodConversion coefficient of sugar to furfural.
Experimental results show that the yield of the furfural reaches 63.65%.
S4, washing lignin precipitates obtained in the step 1-3) by using deionized water, dialyzing to obtain neutral lignin, freeze-drying to obtain solid lignin, respectively adding 0.1g of solid lignin, 0.0667g of Ru/C catalyst and 20mL of methanol into a 50mL stainless steel reaction kettle, sealing the stainless steel reaction kettle, repeatedly performing stamping and pressure relief by using hydrogen for 5 times, completely discharging air in the stainless steel reaction kettle, and finally keeping the hydrogen pressure at 1MPa; then heating the stainless steel reaction kettle to 230 ℃, and after reacting at constant temperature for 15 hours, finishing the reaction; and then carrying out solid-liquid separation, then taking 0.5mL of liquid phase (the liquid phase contains lignin depolymerization products), carrying out qualitative analysis by utilizing a gas chromatography-mass spectrometer (Agilent 7890A-5975C), carrying out rotary evaporation on the residual liquid phase part to obtain a solid phase substance, drying and weighing the solid phase substance at 55 ℃ overnight, and calculating the mass of residual lignin for mass balance calculation.
The yield of lignin depolymerization product in this example was calculated to be 68%.
Example 2
1-1) heating 50mL of 70% by mass p-TsOH solution to 70 ℃; according to the solid-to-liquid ratio of 60:1 (g/L) weighing 3g of corncob with 20-40 meshes, adding the corncob into the preheated p-TsOH solution, and heating for 30min at 70 ℃ and 500rpm to obtain a pretreated material;
1-2) immediately carrying out suction filtration on the pretreated material obtained in the step 1-1) by using a suction filtration device to carry out solid-liquid separation, so as to obtain a fiber material and hydrolysate containing lignin and hemicellulose;
1-3) adding 50mL of deionized water dropwise to the hydrolysis solution containing lignin and hemicellulose for anti-solvent precipitation to obtain lignin precipitate and an aqueous solution containing xylose and organic acid components.
S2, washing the fiber material obtained in the step 1-2) to be neutral by deionized water for a small amount for a plurality of times, then performing low-frequency ultrasonic treatment on the neutral fiber material to obtain free corncob fine fibers, wherein the ultrasonic frequency is 40kHz, the ultrasonic power is 360W, the ultrasonic time is 30S, then mixing the free corncob fine fibers and the softwood pulp fibers according to the mass ratio of 0.2:0.8 to obtain mixed pulp, and performing fluffing, sheet making and drying treatment on the mixed pulp to obtain paper, wherein the paper is the handsheet. The physical properties of the handsheets were measured according to GB/T24323-2009 measurement of physical Properties of paper laboratory sheets.
As shown in fig. 4, in the second example, the ring crush index, tear index and tensile index of the prepared handsheets were respectively: 2.49 N.m/g, 6.06 mN.m 2 /g, 7.46 N.m/g; the ring crush index, tear index, and tensile index of the handsheets prepared in this example two were raised by 5.08%, 0.19%, and 9.12%, respectively, as compared to handsheets prepared with pure softwood pulp.
S3, placing 25mL of the aqueous phase solution obtained in the step 1-3) into a 75mL pressure-resistant bottle, and heating for 30min at 150 ℃ to prepare furfural. After the reaction is finished, naturally cooling the pressure-resistant bottle at room temperature, and taking a reaction product to determine the furfural yield after cooling to the room temperature, wherein a calculation formula of the furfural yield is shown as a formula (1).
It is known from calculation that the yield of furfural in this example reaches 68.11%.
S4, washing the lignin precipitate obtained in the step 1-3) by deionized water, dialyzing to obtain neutral lignin, freeze-drying to obtain solid lignin, respectively adding 0.1g of solid lignin, 0.0667g of Ru/C catalyst and 20mL of methanol into a 50mL stainless steel reaction kettle, sealing the stainless steel reaction kettle, repeatedly performing punching and pressure relief by using hydrogen for 5 times, completely discharging air in the reaction kettle, and finally keeping the hydrogen pressure at 1MPa; then heating the stainless steel reaction kettle to 230 ℃, and after reacting at constant temperature for 15 hours, finishing the reaction; and then carrying out solid-liquid separation, taking 0.5mL of liquid phase (the liquid phase contains lignin depolymerization products), carrying out qualitative analysis by using an air chromatography-mass spectrometer (Agilent 7890A-5975C), carrying out rotary evaporation on the residual liquid phase to obtain a solid phase substance, drying and weighing the solid phase substance at 55 ℃ overnight, and calculating the mass of residual lignin for mass balance calculation.
It is calculated that the yield of lignin depolymerization product reaches 68% in this example.
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention without departing from the technical content of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (10)
1. A comprehensive utilization method of corncob is characterized in that: the method comprises the following steps:
s1 pretreatment of corncob:
1-1) preheating high-concentration organic acid, then adding corncob into the preheated organic acid, and reacting for a period of time at constant temperature under the stirring condition to obtain a pretreated material;
1-2) carrying out solid-liquid separation on the pretreated material to obtain a fiber material and a hydrolysate containing lignin and hemicellulose;
1-3) performing anti-solvent precipitation on hydrolysate containing lignin and hemicellulose to obtain lignin and aqueous phase solution containing xylose and organic acid components;
s2, cleaning the fiber material obtained in the step 1-2) to be neutral, then performing low-frequency ultrasonic treatment to obtain free corn cob fibers, and blending the free corn cob fibers with pulp fibers according to a certain proportion to obtain mixed pulp; sequentially carrying out fluffing, sheet making and drying treatment on the mixed pulp to obtain paper;
s3, directly heating the aqueous phase solution obtained in the step 1-3), and directly converting xylose into furfural under the catalysis of organic acid;
s4, carrying out hydrogenation depolymerization conversion on the lignin obtained in the step 1-3) to obtain an aromatic monomer compound.
2. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step 1-1), the organic acid is preheated to 80-120 ℃, the organic acid is one of acetic acid, oxalic acid, maleic acid and p-toluenesulfonic acid, the mass percent of the organic acid is 60-90%, and the solid-liquid ratio of the corncob to the organic acid solution is 3 (50-70) g/L.
3. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step 1-1), the stirring speed is 100-300 r/min, the reaction temperature is 80-120 ℃, and the reaction time is 15-30 min.
4. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step 1-1), the grain size of the corncob is 20-40 meshes.
5. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step 1-3), anti-solvent precipitation is carried out by using deionized water, and after the deionized water is added, the mass percentage concentration of the organic acid in the aqueous phase solution is diluted to 10% -15%.
6. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step S2, the power of the low-frequency ultrasonic treatment is 140-360W, and the ultrasonic time is 30-60S.
7. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step S2, the mass of the free corn cob fibers accounts for 5% -40% of the sum of the mass of the pulp fibers and the mass of the free corn cob fibers.
8. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step S3, the temperature of the conversion of the furfural is 140-180 ℃ and the conversion time is 20-50 min.
9. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step S4, the catalyst in the hydrogenation depolymerization process is Ru/C, ni/C or Pt/C, and the mass ratio of the catalyst to lignin is 1 (1-1.5).
10. The comprehensive utilization method of corncob according to claim 1, wherein the method comprises the following steps: in the step S4, the reaction temperature of the hydrogenated depolymerization is 230-250 ℃ and the reaction time is 14-18 h.
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| CN113832769A (en) * | 2021-09-06 | 2021-12-24 | 天津科技大学 | Biomass-based papermaking reinforcing agent prepared from agricultural residues as raw materials, method and application |
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| CN101555667A (en) * | 2009-05-15 | 2009-10-14 | 清华大学 | Biorefinery method of wood fiber material |
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| CN103556522A (en) * | 2013-11-06 | 2014-02-05 | 济南圣泉集团股份有限公司 | Application of corncob fibers to preparation of paper for daily use |
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