CN112480182A - Preparation method of low-molecular-weight lignin and application of low-molecular-weight lignin in preparation of monophenol compounds - Google Patents
Preparation method of low-molecular-weight lignin and application of low-molecular-weight lignin in preparation of monophenol compounds Download PDFInfo
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Abstract
The invention discloses a preparation method of low molecular weight lignin and application thereof in preparing monophenol compounds, comprising the following steps: (1) putting the lignin fiber raw material into an oxidant aqueous solution, carrying out pretreatment reaction, carrying out solid-liquid separation after the reaction is finished, and collecting liquid; (2) adjusting the pH of the liquid obtained in the step (1) to 3-1.5 by using an acid solution, standing, and centrifuging to obtain a solid, namely the low-molecular-weight lignin; wherein the low molecular weight lignin has a weight average molecular weight of not more than 3800 Da. The low molecular weight lignin obtained by the method can be subjected to fast pyrolysis to prepare a monophenol product with high selectivity under the condition of low temperature with relatively low energy consumption without a catalyst.
Description
Technical Field
The invention belongs to the field of biomass resource heat conversion, and particularly relates to a preparation method of low-molecular-weight lignin and application of the low-molecular-weight lignin in preparation of monophenol compounds.
Background
With the large production and increasing demand for fossil fuels, the development of new sustainable energy sources is a necessary trend of global development. Biomass is a recyclable natural resource, abundant in reserves, and considered as the most potential fossil fuel substitute. Lignin is one of the main components of plant fiber resources, is a natural aromatic amorphous polymer, and has a content second to cellulose. Active groups such as aromatic group, methoxyl group, conjugated double bond and the like in lignin molecule are potential chemical products.
The lignin has a series of difficulties such as complex structure, chemical inertness, difficult separation and purification of conversion products and the like, so that the utilization of the lignin is limited. At present, most of lignin after biomass pretreatment is treated in a direct discharge or incineration mode, which not only causes waste, but also can seriously pollute water, soil, air and the like. Therefore, the lignin resource is reasonably and efficiently utilized, and the aromatic compound with high added value is prepared based on the characteristic that the lignin resource is rich in aromatic rings, so that the method has important significance for protecting the environment and can provide a new idea for synthesizing chemicals by using non-fossil fuels.
The conventional method for converting the lignin is to convert the lignin into phenolic chemicals by a thermochemical mode at present, and the method has the advantage of high yield of the phenolic chemicals generally in the presence of a catalyst. However, the catalyst is often high in cost, and lignin is easily carbonized and deposited on the surface of the catalyst in the pyrolysis process, so that the catalyst is easily deactivated and difficult to recover.
It is therefore desirable to provide an efficient, low energy consumption process for producing phenolic products without the need for catalyst-based refining of the pyrolyzed lignin.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of low molecular weight lignin aiming at the defects of the prior art.
The invention also aims to solve the technical problem of providing the application of the low molecular weight lignin in preparing monophenol compounds
In order to solve the first technical problem, the invention discloses a preparation method of low molecular weight lignin, namely, plant fiber resources are pretreated by an oxidant to obtain the low molecular weight lignin, and the low molecular weight lignin is extracted and dried; specifically, the method comprises the following steps:
(1) oxidation pretreatment: putting a lignin fiber raw material into an oxidant aqueous solution, carrying out pretreatment reaction, carrying out solid-liquid separation after the reaction is finished, and collecting liquid, namely the solution rich in low molecular weight lignin;
(2) extracting low-molecular lignin: adding an acid solution into the liquid obtained in the step (1) under the condition of stirring, adjusting the pH value of the solution to 3-1.5, precipitating and separating out lignin within the pH range, standing, centrifuging to obtain a solid, namely the low-molecular-weight lignin, and carrying out freeze drying or vacuum drying treatment on the solid.
Among them, the low-molecular weight lignin has a weight average molecular weight of not higher than 3800Da, preferably not higher than 3400Da, more preferably not higher than 1700Da, still more preferably not higher than 550Da, and most preferably not higher than 400 Da.
In step (1), the lignocellulosic raw material comprises herbaceous, hardwood and softwood, which contain 15-38 wt% lignin.
Wherein, the herbaceous plants include but are not limited to corn straws, wheat straws, rice straws, bagasse and the like; the hardwood includes but is not limited to poplar, eucalyptus, bamboo and the like; the cork includes, but is not limited to, fir, larch, and the like.
In the step (1), the oxidant is any one or a combination of more of acidic sodium chlorite, acidic sodium hypochlorite, laccase, peroxy acid, hydrogen peroxide and permanganate; wherein the acidic sodium chlorite and the acidic sodium hypochlorite are prepared to be acidic by using acid.
In the step (1), the mass percent of the oxidant in the oxidant aqueous solution is 1% -15%, and the pH value of the oxidant aqueous solution is 3-12.
In the step (1), the solid-to-liquid ratio of the lignin fiber raw material to the oxidant aqueous solution is 1-15% g/mL.
When the oxidizing agent is peroxy acid, sulfuric acid can be added to catalyze the reaction, and when the reaction temperature is higher than 80 ℃, sulfuric acid can not be added.
Wherein, when the oxidant is laccase, the lignin fiber raw material and the laccase are preferably subjected to pretreatment reaction in a buffer solution.
Wherein the dosage ratio of the laccase to the lignin fiber is 50U/g, wherein the laccase is purchased from sigma, and the enzyme activity is 250U/mL; wherein the buffer solution is 50mM sodium tartrate aqueous solution.
Preferably, when the oxidising agent is a laccase, the system also contains TEMPO at a concentration of 4% g/100 mL.
In the step (1), the temperature of the pretreatment reaction is 50-160 ℃, and the time is 0.5-12 h.
In the step (1), the solid obtained by solid-liquid separation contains a large amount of cellulose, and can be used for cellulose enzymolysis or used for conventional processes such as further fermentation for producing ethanol and the like.
In the step (2), the solvent includes, but is not limited to, sulfuric acid, hydrochloric acid and oxalic acid, and preferably any one or a combination of sulfuric acid, hydrochloric acid and oxalic acid.
In the step (2), the mass fraction of the acid in the acid solution is 8-36%.
In the step (2), the standing is 4-15 ℃ or 4-12 h at room temperature.
In the step (2), the centrifugation is high-speed centrifugation (6000-10000 g).
In the step (2), the low molecular weight lignin extraction operation can be performed at normal temperature, and can be performed at low temperature in order to accelerate the precipitation of lignin.
The content of the low-molecular lignin prepared by the method is higher than 80% (the determination method is NERL method).
The low molecular weight lignin prepared by the method is also within the protection scope of the invention; wherein the weight average molecular weight of the low molecular weight lignin is not higher than 3800Da, preferably not higher than 3400Da, more preferably not higher than 1700Da, even more preferably not higher than 550Da, and most preferably not higher than 400 Da.
In order to solve the second technical problem, the invention discloses the application of low molecular weight lignin in preparing monophenol compounds.
Wherein, the monophenolic compound comprises but is not limited to 2-methoxyphenol and 4-chloro-2-methoxyphenol which is a derivative thereof.
The application comprises the steps of drying the low molecular weight lignin, then placing the dried low molecular weight lignin in a pyrolysis furnace, and pyrolyzing the lignin for 10-300 s at 250-700 ℃ in a carrier gas atmosphere to obtain the monophenol compounds.
And collecting the pyrolyzed volatile products by using a condenser to obtain pyrolyzed liquid-phase products, and performing subsequent GC-MS analysis and product separation on the collected liquid-phase products.
Wherein the pyrolysis temperature has important influence on the yield of the monophenol product and the type of the monophenol product, and the pyrolysis temperature is controlled to be 250-700 ℃.
The heating rate is one of important factors influencing pyrolysis, the heating rate has great influence on the property of a pyrolysis product, and the heating rate of pyrolysis is 5-40 ℃/ms.
Wherein, the carrier in the pyrolysis process is high-purity (more than 99.8 percent) inert gas, such as helium or nitrogen, and the introduction rate of the carrier gas is 0.6-1.5 mL/min.
Wherein, GC-MS (gas-mass spectrometer) of Agilent, Shimadzu or Thermofeiser is used for GC-MS analysis of the product. The test conditions were: the separation column is DB-5, VMS5 or other capillary column. The temperature of the pipeline and the injection valve is 250 ℃ and 300 ℃, and the split ratio is 40-80: 1. Temperature rising procedure: keeping the temperature at 50 ℃ for 3min, then heating to 280 ℃ at the heating rate of 6-15 ℃/min, and keeping the temperature for 1 min. The ion source is EI, and the scanning range is 28-500 amu.
In the present invention, the molecular weights are all weight average molecular weights.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the method is simple to operate, and the process for extracting the low-molecular-weight lignin is simple and convenient. The required oxidant pretreatment process can be completed under normal pressure, and the subsequent low molecular weight precipitation step is only required to be performed under open room temperature.
(2) The method adopts the oxidant pretreatment to recover the carbohydrate component in the plant fiber to the maximum extent, and simultaneously obtains a large amount of dissolved micromolecular lignin, thereby realizing the comprehensive utilization of the three major components of the plant fiber resource.
(3) The low molecular weight lignin obtained by the method can be subjected to fast pyrolysis to prepare monophenol products with high selectivity under the condition of relatively low energy consumption and low temperature without catalysts (including alkali metal catalysts, activated carbon catalysts, zeolite catalysts or similar derivative catalysts and the like).
(4) The process used by the method can realize high-value utilization of lignin in plant resource fibers, and simultaneously, no catalyst is used, so that the cost is greatly reduced.
Drawings
FIG. 1 shows the analysis of the low molecular weight lignin pyrolysis product prepared by pretreating wheat straw with sodium chlorite.
FIG. 2 shows the lignin molecular weight (after drying) in different pre-treated supernatants.
FIG. 3 shows the liquid product yield after different pretreatments, and the monophenol product selectivity.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
In the following examples, the molecular weight of lignin was measured by Gel Permeation Chromatography (GPC) under the following conditions: a workstation: agilent 1260; and (3) analyzing the column: the Waters-Styragel HR-1 and the Waters-Styragel HR-2 are connected in series; a detector: RID; mobile phase: tetrahydrofuran; flow rate: 1 mL/min; column temperature: 35 ℃; and (3) standard substance: polystyrene standard, molecular weight range 580-. The identification of the lignin pyrolysis liquid phase product is carried out by adopting gas mass spectrometry (GC-MS), and the determination conditions are as follows: a GC workstation: agilent 7890A; MS workstation: agilent 5957C; HP-5MS column was used. The chromatographic column carrier gas is high-purity helium, and the flow rate is 1.0 mL/min. The temperature of the injection port is maintained at 280 ℃, and the split ratio is 1: 50. The column oven temperature was carried out according to the following procedure: keeping the temperature at 50 ℃ for 3min, then heating to 280 ℃ at the heating rate of 6 ℃/min, and keeping the temperature for 1 min. The ion source is EI, and the scanning range is 28-500 amu.
Example 1: sodium chlorite pretreatment of cedar to extract low molecular weight lignin and prepare monophenol product
The method comprises the steps of taking Chinese fir sawdust collected in a wood processing plant as a raw material, and firstly carrying out oxidant pretreatment. The sodium chlorite pretreatment conditions were: the mass percent concentration of sodium chlorite in the sodium chlorite aqueous solution is 7.5 percent, the pH value of the sodium chlorite aqueous solution is adjusted to 4.5 by using acetic acid, and the solid-to-liquid ratio of the cedar wood chips to the sodium chlorite aqueous solution is 1:20 g/mL. After the materials and the sodium chlorite solution are mixed evenly, the reaction solution is put under the condition of 75 ℃ for heat preservation and pretreatment for 40 min. After the treatment is finished, carrying out solid-liquid separation by using suction filtration, collecting the solid (cellulose) for subsequent bioethanol preparation, and obtaining a liquid which is a solution rich in low molecular weight lignin. The collected solution was used 8 wt% H2SO4The solution was adjusted to pH. When the pH of the solution is lower than 3, the solution is obviously turbid, and the pH is continuously adjusted to be about 2. Standing the turbid liquid at 4 ℃ for 6h, centrifuging for 10min under the condition of 8000 Xg after standing, and removing the supernatant after centrifuging to obtain a solid, namely the low-molecular-weight lignin. The solid obtained is subjected to freeze drying treatment and collected for later use. Finally, 50g of fir wood chips contain 22g of cellulose and 18.45g of lignin, and after sodium chlorite pretreatment and lignin extraction, 19.36g of cellulose and 9.1g of low molecular weight lignin (508Da) are respectively recovered, wherein the lignin purity is 84.1 percent.
A1 g sample of dried low molecular weight lignin was taken and placed in a crucible. In the temperature rise process, carrier gas is introduced into the reactor at the rate of 1.5mL/min, the temperature rise rate is 5 ℃/ms, and the pyrolysis temperature is 650 ℃. After the raw materials are pyrolyzed quickly, the pyrolysis gas is carried out of the reactor quickly by the carrier gas and enters a condensing tube for condensation. The liquid product was collected after 10s pyrolysis for GC/MS analysis. The mass of the solid carbon remained in the final crucible was 0.397g, the mass of the liquid was 0.525g, and the GC/MS results of the liquid product are shown in Table 1. Wherein the total amount of monophenol product accounts for 76.44% of all liquid phase products, and 2-methoxyphenol and its derivative 4-chloro-2-methoxyphenol are the main products and account for up to 26.58%.
TABLE 1 GC/MS analysis of China fir oxidized lignin pyrolysis liquid phase products
Example 2: original fir ball milling lignin pyrolysis to produce monophenol
A1 g sample of dried ball milled lignin (molecular weight 7350Da, from cedar wood chips) was taken and placed in a crucible. In the temperature rise process, carrier gas is introduced into the reactor at the rate of 200mL/min, the temperature rise rate is 5 ℃/ms, and the pyrolysis temperature is 650 ℃. After the raw materials are pyrolyzed quickly, the pyrolysis gas is carried out of the reactor quickly by the carrier gas and enters a condensing tube for condensation. The liquid product was collected after 10s pyrolysis for GC/MS analysis. The mass of the residual solid carbon in the final crucible is 0.541g, the mass of the liquid is 0.387g, and the GC/MS results of the liquid products are shown in Table 2. It can be seen from table 2 that the original lignin pyrolysis product is more abundant in species and less selective than the low molecular weight lignin pyrolysis product, wherein the total amount of the ball-milled lignin monophenol product accounts for 41.38% of all liquid phase products, and the monophenol product selectivity is much lower than that of the low molecular weight lignin pyrolysis product.
TABLE 2
Example 3: sodium chlorite pretreatment of wheat straw to extract low molecular weight lignin and prepare monophenol product
Wheat straw is used as a raw material, and is subjected to oxidant pretreatment. The sodium chlorite pretreatment conditions were: the mass percent concentration of sodium chlorite in the sodium chlorite aqueous solution is 7.5 percent, the pH value of the sodium chlorite aqueous solution is adjusted to 4.5 by using acetic acid, and the solid-to-liquid ratio of wheat straws to the sodium chlorite aqueous solution is 1:20 g/mL. After the materials and the sodium chlorite solution are mixed evenly, the reaction solution is put under the condition of 75 ℃ for heat preservation and pretreatment for 40 min. After the treatment is finished, carrying out solid-liquid separation by using suction filtration, collecting the solid (cellulose) for subsequent bioethanol preparation, and obtaining a liquid which is a solution rich in low molecular weight lignin. The collected solution was used 8 wt% H2SO4The solution was adjusted to pH. When the pH of the solution is lower than 3, the solution is obviously turbid, and the pH is continuously adjusted to be about 2. Standing the turbid liquid at 4 ℃ for 6h, centrifuging for 10min under 8000g after standing, discarding the supernatant to obtain a solid, namely low molecular weight lignin (482Da), and finally recovering 4.05g of low molecular weight lignin (482Da) from 50g of wheat straws after sodium chlorite pretreatment and lignin extraction, wherein the lignin purity is 84.1%.
A1 g sample of dried low molecular weight lignin was taken and placed in a crucible. In the temperature rise process, carrier gas is introduced into the reactor at the rate of 1.5mL/min, the temperature rise rate is 5 ℃/ms, and the pyrolysis temperature is set to be 300 ℃, 400 ℃, 500 ℃ and 600 ℃ respectively. After the raw materials are pyrolyzed quickly, the pyrolysis gas is carried out of the reactor quickly by the carrier gas and enters a condensing tube for condensation. The liquid product was collected after 10s pyrolysis for GC/MS analysis. The final liquid phase product yield and monophenol product selectivity results are shown in figure 1.
Example 4: method for preparing monophenol product by extracting low molecular weight lignin from fir pretreated by different oxidants and pyrolyzing
Takes fir sawdust as raw material, and respectively uses sodium hypochlorite for pretreatment and alkaline-H2O2Pretreatment, laccase-TEMPO oxidation and peracetic acid pretreat cedar wood chips.
Sodium hypochlorite pretreatment: the sodium hypochlorite solution had a mass concentration of 5 wt% and the pH was adjusted to 4.0 with acetic acid. The solid-liquid ratio of the fir wood chips to the sodium hypochlorite solution is 1:20(g/mL), the pretreatment temperature is 80 ℃, and the pretreatment time is 1 h.
basic-H2O2The pretreatment conditions are as follows: hydrogen peroxide concentration: 10 wt%, the solid-to-liquid ratio of the fir wood chips to the hydrogen peroxide is 1:20(g/mL), the pH value of the hydrogen peroxide solution is 11.5, the pretreatment temperature is 120 ℃, and the pretreatment time is 1 h.
laccase-TEMPO oxidation pretreatment conditions: substrate concentration: 1.25% g/mL, TEMPO concentration: 4% g/mL, enzyme dosage: 50U/g fir wood chips, buffer: 50mM aqueous sodium tartrate; the pH of the solution was 6.0; reaction temperature: the pretreatment time was 12h at 50 ℃.
Peroxyacetic acid pretreatment conditions: peroxyacetic acid solution (30% H)2O2The solution and 80% acetic acid solution are mixed for standby at a volume ratio of 1: 1), the working concentration of sulfuric acid is 100mM, and the solid-to-liquid ratio of the fir wood chips to the peroxyacetic acid solution is 1:10 (g/mL). The pretreatment temperature is 60 ℃, and the treatment time is 2 h.
The lignin extraction method was the same as in example 1, and the molecular weight of the dried low molecular weight lignin was measured, and the results are shown in FIG. 2. The molecular weight of lignin dissolved in the liquid after different pretreatments is respectively compared with that of ball-milling lignin and sodium chlorite-oxidized lignin, wherein the molecular weight of lignin in the liquid after sodium chlorite pretreatment and peroxyacetic acid pretreatment is the lowest, namely 508Da (example 1) and 390Da (example 4), and the molecular weight of ball-milling lignin is the highest 7350 Da; in addition, sodium hypochlorite, alkaline-H2O2And molecular weights of the laccase-TEMPO treated lignin 1620Da (example 4), 3800Da (example 4) and 3350Da (example 4), respectively.
The pyrolysis method was the same as in example 1, 6 lignins were pyrolyzed at 650 c, and GC/MS analysis was performed on the liquid products, and the results are shown in fig. 3.
Claims (10)
1. A preparation method of low molecular weight lignin is characterized by comprising the following steps:
(1) putting the lignin fiber raw material into an oxidant aqueous solution, carrying out pretreatment reaction, carrying out solid-liquid separation after the reaction is finished, and collecting liquid;
(2) adjusting the pH of the liquid obtained in the step (1) to 3-1.5 by using an acid solution, standing, and centrifuging to obtain a solid, namely the low-molecular-weight lignin;
wherein the low molecular weight lignin has a weight average molecular weight of not more than 3800 Da.
2. The method for preparing low molecular weight lignin according to claim 1, wherein in step (1), the oxidant is any one or a combination of several of acidic sodium chlorite, acidic sodium hypochlorite, laccase, peroxy acid, hydrogen peroxide and permanganate.
3. The method for preparing low molecular weight lignin according to claim 1, wherein in step (1), the solid-to-liquid ratio of the raw material of lignin fiber to the aqueous solution of oxidant is 1-15% g/mL.
4. The method for preparing low molecular weight lignin according to claim 1, wherein in the step (1), the mass percent of the oxidant in the oxidant aqueous solution is 1-15%, and the pH of the oxidant aqueous solution is 3-12.
5. The method for preparing the low molecular weight lignin according to claim 1, wherein in the step (1), the temperature of the pretreatment reaction is 50-160 ℃ and the time is 0.5-12 h.
6. The method for preparing low molecular weight lignin according to claim 1, wherein in the step (2), the standing is performed at 4-15 ℃ or at room temperature for 4-12 h.
7. Low molecular weight lignin prepared by the method of any one of claims 1 to 6; wherein the low molecular weight lignin has a weight average molecular weight of not more than 3800 Da.
8. Use of a low molecular weight lignin according to claim 7 in the preparation of monophenolic compounds.
9. The application of claim 8, wherein the low molecular weight lignin is pyrolyzed at 250-700 ℃ for 10-300 s in a carrier gas atmosphere to obtain the monophenol compounds.
10. The use according to claim 9, wherein the rate of temperature rise of the pyrolysis is 5 to 40 ℃/ms.
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| CN113293182A (en) * | 2021-05-20 | 2021-08-24 | 齐鲁工业大学 | Pretreatment method for promoting lignocellulose enzymolysis |
| CN113293182B (en) * | 2021-05-20 | 2022-11-29 | 齐鲁工业大学 | Pretreatment method for promoting lignocellulose enzymolysis |
| CN113604514A (en) * | 2021-07-09 | 2021-11-05 | 广东省科学院化工研究所 | Method for biosynthesizing phenolic acid compound by using lignin and application thereof |
| CN113604514B (en) * | 2021-07-09 | 2023-03-10 | 广东省科学院化工研究所 | Method for biosynthesizing phenolic acid compound by using lignin and application thereof |
| CN113598195A (en) * | 2021-08-06 | 2021-11-05 | 南京林业大学 | Application of small molecular lignin as plant growth regulator |
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