CN117884184B - Sulfonyl chloride modified lignin-based carrier loaded with iron phthalocyanine and catalytic lignin depolymerization method - Google Patents
Sulfonyl chloride modified lignin-based carrier loaded with iron phthalocyanine and catalytic lignin depolymerization methodInfo
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- CN117884184B CN117884184B CN202410031275.5A CN202410031275A CN117884184B CN 117884184 B CN117884184 B CN 117884184B CN 202410031275 A CN202410031275 A CN 202410031275A CN 117884184 B CN117884184 B CN 117884184B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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Abstract
The invention discloses a method for loading iron phthalocyanine on a sulfonyl chloride modified lignin-based carrier and catalyzing lignin depolymerization. The sulfonyl chloride modified lignin-based carrier-supported iron phthalocyanine has a repeating unit represented by the formula (1): In formula (1), the wavy line indicates that other repeating units represented by formula (1) are linked, M has a structure represented by formula (2), r=nh 2 or NO 2; The catalyst is used for catalytic oxidative depolymerization of lignin, the condition is mild, and the selectivity of phenolic substances in the product is good.
Description
Technical Field
The invention relates to the technical field of lignin catalytic depolymerization, in particular to a sulfonyl chloride modified lignin-based carrier loaded iron phthalocyanine and a method for catalyzing lignin depolymerization.
Background
The papermaking industry can discharge fishy smell and toxic black liquor, the main components of the black liquor are hemicellulose and lignin which cannot be metabolized by microorganisms, the main method for treating the papermaking black liquor is to mix and burn the concentrated black liquor with coal dust of a power plant, and the treatment method causes resource waste on one hand and air pollution on the other hand. Therefore, research, development and comprehensive utilization of lignin in papermaking black liquor become a work with important social benefit and economic benefit.
Lignin is a three-dimensional reticular phenolic polymer widely existing in the cell walls of higher plants and consists of three basic aromatic structural units, namely syringyl (S), guaiacyl (G) and hydroxyphenyl (H), wherein the three basic lignin structural units are mainly connected through C-C, C-O bonds and the like. Depolymerizing lignin to make C-C or C-O bond in its structure selectively break and produce phenols or other small molecular chemicals, so that it is an important method for implementing large-scale comprehensive utilization of lignin.
Lignin can be depolymerized by pyrolysis or liquid phase catalysis methods. In general, pyrolysis of lignin requires higher reaction temperatures (400-800 ℃) and conditions are more severe. Compared with pyrolysis, the liquid phase catalytic degradation method has the advantages of mild reaction conditions, high product selectivity and the like. In the liquid-phase catalytic degradation process of lignin, C-C or C-O bonds are broken under the action of a catalyst to form aromatic or other small molecular chemicals, and the key of the liquid-phase catalytic depolymerization of lignin is to prepare an effective catalyst.
Disclosure of Invention
The invention aims to provide a sulfonyl chloride modified lignin-based carrier loaded iron phthalocyanine and a catalytic lignin depolymerization method for realizing lignin depolymerization.
The invention adopts the following technical scheme:
a sulfonyl chloride modified lignin-based carrier-supported iron phthalocyanine having a repeating unit of formula (1):
Formula (1): ,
In formula (1), the wavy line indicates that other repeating units represented by formula (1) are linked, M has a structure represented by formula (2), r=nh 2 or NO 2, i.e., three R are the same and may be selected from NH 2 or NO 2;
Formula (2): 。
The black bolded dash in formula (2) represents a group for bonding to SO 2.
The sulfonyl chloride modified lignin-based carrier loaded iron phthalocyanine is hereinafter simply referred to as a catalyst of formula (1), and one specific structure of the catalyst of formula (1) is shown in the following structural formula.
。
A method for preparing the sulfonyl chloride modified lignin-based carrier-supported iron phthalocyanine comprises the following steps:
and (3) heating the compound shown in the formula A and the compound shown in the formula B in a DMF solvent for reaction to obtain the sulfonyl chloride modified lignin-based carrier loaded iron phthalocyanine shown in the formula (1).
Preferably, the weight ratio of the compound represented by formula A to the compound represented by formula B is 1 (1-10), and the mixture is subjected to ultrasonic treatment before the heating reaction, wherein the temperature of the heating reaction is 120 ℃.
Specifically, the total volume (ml) of DMF solvent may be 5 to 50 times the total weight (g) of the compound represented by formula A and the compound represented by formula B.
A method of catalyzing depolymerization of lignin, comprising:
placing lignin and sulfonyl chloride modified lignin-based carrier loaded iron phthalocyanine shown in a formula (1) in a mixed solvent of water and acetonitrile, adding hydrogen peroxide into the solution with the pH value of the solution being less than 5 and more than 1, heating and stirring to depolymerize the lignin.
The volume ratio of water to acetonitrile may be 6:1-1:1, and the total volume (ml) of the mixed solvent may be 50-250 times the weight (g) of lignin.
Preferably, the sulfonyl chloride modified lignin-based carrier supports iron phthalocyanine in a weight ratio of 0.5wt% to 6wt%, based on the weight of lignin.
Preferably, the sulfonyl chloride modified lignin-based carrier supports iron phthalocyanine in a weight ratio of 3.5wt% based on the weight of lignin.
Preferably, the heating temperature is 120-150 ℃ and the reaction time is 40-200min.
Preferably, the heating temperature is 135 ℃ and the reaction time is 120min, and the pH value of the solution is adjusted to 3 by sulfuric acid.
Preferably, the concentration of the hydrogen peroxide is 2.5X10 -2-20×10-2 mol/L.
Preferably, the concentration of the hydrogen peroxide is 15X 10 -2 mol/L.
Compared with the prior art, the invention has the beneficial effects that at least:
According to the invention, the novel sulfonyl chloride modified lignin-based carrier loaded iron phthalocyanine is prepared, and the catalyst is used for carrying out catalytic oxidative depolymerization on lignin, so that the condition is mild, and the selectivity of phenolic compounds in depolymerization products is good.
Drawings
FIG. 1 is a FT-IR spectrum of a compound of formula B and a catalyst of formula (1) according to an embodiment of the invention.
FIG. 2 is a BET analysis chart of the compound A and the catalyst of formula (1) of the present invention.
FIG. 3 is a graph of the analysis of catalyst content versus liquid phase product yield and phenol selectivity in an example of the present invention.
FIG. 4 is a graph of H 2O2 concentration versus liquid phase product yield and phenol selectivity for the examples of the present invention.
FIG. 5 is a graph of reaction time versus liquid phase product yield and phenol selectivity for the examples of the present invention.
FIG. 6 is a picture of the ethyl acetate soluble portion of examples 5-9 of the present invention.
FIG. 7 is a GC-MS spectrum of the ethyl acetate extract product of examples 5-9 of the present invention.
FIG. 8 is a FT-IR spectrum of an ethyl acetate extract product in examples 5-9 of the invention.
FIG. 9 is SEM image of solid residue obtained at different reaction times in example 18 of the invention.
Detailed Description
Example embodiments will now be described more fully. However, the exemplary embodiments can be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the exemplary embodiments to those skilled in the art.
In the examples, the main reagents used include potassium hydroxide (KOH, purity. Gtoreq.98%), sodium hydroxide (NaOH, purity. Gtoreq.97%), sulfuric acid (H 2SO4, concentration 98%), ferric chloride hexahydrate (FeCl 3·6H2 O), ethanol (C 2H5 OH, 99.9%), hydrogen peroxide (H 2O2), thionyl chloride (SOCl 2), 4-nitrophthalic acid (C 8H5NO6), urea (CO (NH 2)2), sodium sulfide (NaS 2·9H2 O) and N, N-dimethylformamide (C 3H7 NO), all of which are commercially available.
EXAMPLE 1 preparation of Compounds of formula A
Lignin (shown as a formula A1) in the example is recovered from papermaking black liquor, and lignin-based carbon sulfonyl chloride derivatives (compounds of the formula A) are synthesized through three steps of carbonization, sulfonation and acyl chlorination.
Specifically, carbonization of lignin is carried out in a tube furnace under the protection of N 2, lignin and KOH are put into a nickel plate according to a proportion (weight ratio is 1 (0.5-3), the embodiment is 1:2), then the nickel plate is placed in the center of the tube furnace, the tube furnace is heated to 550 ℃, the heating rate is 15 ℃ per min, and finally 90 min is kept. After the reaction was completed, the resulting black sample was washed with hot water and filtered, and then dried at 105 ℃ for 12 hours to obtain carbonized lignin. Next, the carbonized lignin described above was sulfonated in a three-necked round bottom flask under N 2 protection. The carbonized lignin and H 2SO4 are mixed in a round bottom flask according to the weight ratio of 1 (5-13), reacted for 6 hours at 150 ℃, finally a black sample (named sulfonated lignin as shown in formula A2) is obtained, washed and filtered with water, and finally dried for 12 hours at 105 ℃. Finally, the synthesis of the compound of formula a may be prepared by referring to a known method for preparing sulfonyl chloride from a sulfonic acid compound, specifically, adding the compound of formula A2 into an excessive SOCl 2 solution, reacting for 24 hours at 90 ℃, after the reaction is completed, distilling off residual SOCl 2, and washing and drying the solid product (as shown in formula a) for later use.
EXAMPLE 2 Structure of Compound of formula B
The structure of the compound of formula B is shown in the above structure, wherein r=nh 2 or NO 2, which can be prepared by known methods, and the preparation method thereof is not described in detail.
EXAMPLE 3 preparation of the catalyst of formula (1)
The compound of formula a and the compound of formula B prepared above, wherein R is NH 2 in the present example and the following examples, in a weight ratio of 1:1.2, are added to DMF solvent, the total volume (ml) of the solvent is 5 times the total weight (g) of the compound of formula a and the compound of formula B, a small amount of water (for example, the volume of water is 5% of the volume of DMF) may be added to the solvent, sonicated for 2 hours, then the mixture is stirred at 120 ℃ for 72 hours, and finally the reaction mixture is filtered off to obtain a solid, which is washed with water and acetone, and dried at 65 ℃ to obtain a black blue powder catalyst (catalyst of formula (1), R is NH 2).
EXAMPLES 4-18 catalytic oxidative depolymerization of lignin
Firstly, a proper amount of catalyst of formula (1) (weight ratio of catalyst to lignin is 0 wt% to 4.5% wt.) is dispersed in a mixed solvent of water and acetonitrile (volume ratio of both is 4:1), total volume (ml) of the mixed solvent is 100 times of weight (g) of lignin, and secondly, lignin (1 g) is added to the above mixture, and pH of the mixture is adjusted to 3.0 with sulfuric acid. Subsequently, the catalyst of formula (1) and lignin were thoroughly dispersed by shaking for 20-30min, and finally H 2O2 (the concentration of H 2O2 was 0mol/L to 20X 10 -2 mol/L based on the total volume of the mixed solvent of water and acetonitrile) was added to the reaction mixture while transferring the mixture to a 150ml reactor, and the mixture was stirred at 135℃for 40-200min. After the reaction, the solid residue and the liquid product are obtained by centrifugal separation, and the liquid product is extracted by ethyl acetate to obtain ethyl acetate soluble substances for analysis.
The specific reaction conditions in examples 4-18 are shown in Table 1.
Analysis of results:
the catalyst was analyzed for chemical functional group type by a Nicolet IS10 Fourier transform Infrared Spectroscopy (FTIR) instrument and BET surface area was measured using an N 2 adsorption/desorption isotherm (Quantachrome autosorb IQ-C analyzer). The surface structure of the catalyst was analyzed by Hitachi s-3400 Scanning Electron Microscope (SEM) (Hitachi, japan).
The depolymerization products were analyzed using an Agilent 6890A/5973N-type instrument equipped with an HP-5MS (30 m0.25mm 0.25μm) column under conditions of 40℃for 2 minutes with 2. Mu.L of sample injected into the system, followed by a 5℃/min temperature rise to 150℃for 2 minutes, followed by an 8℃/min temperature rise to 280℃for 5 minutes. Elemental composition of the product was analyzed using an Elemental Analyzer (EA).
The surface structure of the solid residue was analyzed by Hitachis-3400 scanning electron microscope.
The liquid phase product yields were calculated as follows:
Liquid phase product (wt%) =w Liquid phase product /W Lignin ×100%.
Wherein W Lignin and W Liquid phase product represent the weight of lignin and the weight of the liquid phase product, respectively.
The selectivity of a phenolic substance is expressed as the ratio of the peak area of the corresponding product to the total area of the liquid phase product.
FIG. 1 is an FT-IR spectrum of a compound of formula B and a catalyst of formula (1) according to an embodiment of the invention, with reference to FIG. 1, line a represents the compound of formula B and line B represents the catalyst of formula (1). The FT-IR spectrum of fig. 1 shows that the characteristic peak of iron phthalocyanine appears at 1320 cm -1、1120 cm-1、740 cm-1, which is due to vibration of the phthalocyanine ring. Similar characteristic bands are evident in the spectra of the catalyst of formula (1), indicating that iron phthalocyanine is bonded to the compound of formula a. A new S-N stretching vibration characteristic peak appears near 900 cm -1, indicating that iron phthalocyanine was successfully incorporated into the compound of formula A by chemical reaction.
Referring to fig. 2, line a represents the compound of formula a, line b represents the catalyst of formula (1), and table 2 shows the porous structure characterization results of the compound a and the catalyst of formula (1).
Referring to fig. 2, when P/P0 is below 0.2, a steep slope can be seen, which can confirm that the two N2 adsorption-desorption isotherms conform to the type I adsorption isotherm and the type H4 hysteresis loop, which can also confirm the presence of a large number of micropores in the sample. The specific surface area and pore structure parameters of the compounds of formula A and the catalysts of formula (1) are shown in Table 2. The catalyst sample of formula (1) exhibits a lower specific surface area and pore volume, and when iron phthalocyanine is supported on the compound of formula A, the BET specific surface area decreases from 643.67 m 2/g to 638.98 m 2/g, while the pore volume decreases from 0.337 cm 3/g to 0.291 cm 3/g. The decrease in BET surface area and pore volume may be due to some pores of the support being blocked by iron phthalocyanine.
The depolymerization efficiency of lignin and the composition and properties of the liquid phase product are affected by the reaction conditions, such as the content of catalyst, reaction time, etc. Examples 4-18 examined the effect of specific reaction conditions on lignin depolymerization efficiency.
FIG. 3 is a graph of the analysis of catalyst content versus liquid product (liquid products) yield and phenolic compound (phenols) selectivity in examples of the present invention. Most reactions are affected by the active site and basic nature of the catalyst, and based on this, the present invention employs six different catalyst concentrations (catalyst contents) of 0.0 wt%, 0.5 wt%, 1.5 wt%, 2.5 wt%, 3.5 wt%, 4.5 wt% with reference to examples 4-9. As can be seen from FIG. 3, with increasing catalyst content, both the yield of liquid phase product and the selectivity to phenols are improved over the case of no catalyst degradation. When 3.5 wt% of catalyst was used, a maximum liquid product yield of 38.94% was obtained, and the selectivity to phenols reached a maximum value of 32.58%. When the catalyst content was increased to 4.5 wt%, both the liquid product yield and the phenol selectivity were reduced.
These results indicate that the proper catalyst level has some effect on the yield of liquid product and the selectivity to phenol, which may decrease once the catalyst level exceeds the optimum.
FIG. 4 is a graph of H 2O2 concentration versus liquid product (liquid products) yield and phenol (phenols) selectivity for the examples of the present invention. Referring to example 8 and examples 10-14, H 2O2 concentrations were carried out at 135℃ C, pH 3.0.0 for 120min using six different levels of concentration （0 mol/L、2.5×10-2 mol/L、5×10-2 mol/L、10×10-2 mol/L、15×10-2 mol/L、20×10-2mol/L), using 3.5 wt% catalyst. Similar trends were also observed for the yield of liquid phase product and selectivity to phenolic compounds as the H 2O2 concentration was increased from 0 mol/L to 20X 10 -2 mol/L. As the hydrogen peroxide concentration increases from 0 mol/L to 15X 10 -2 mol/L, the liquid product yield and the phenolic compound selectivity increase with the increase of the hydrogen peroxide concentration, the yield is 38.94% at the highest and the phenolic compound selectivity is 32.58% at the concentration of H 2O2 of 15X 10 -2 mol/L. Further increasing the concentration of H 2O2, the yield change of the liquid phase product is not obvious, but the selectivity of the phenolic compound is obviously reduced.
FIG. 5 is an analytical graph of reaction time versus liquid product (liquid products) yield and phenol (phenols) selectivity in examples of the present invention, and referring to examples 8 and 15-18, it can be seen from FIG. 5 that the liquid product yield and phenol compound selectivity gradually increase as the reaction time increases to 2 hours, and both values reach maximum values when the reaction time is 2 hours, and the liquid product yield and phenol compound selectivity start to decrease as the reaction time further increases to 160 minutes and 200 minutes. When the reaction time is 200min, the yield of the liquid product and the selectivity of the phenolic compound each show the lowest value, which indicates that when the reaction time exceeds 2h, the reaction is not favored.
The reaction process and the properties of the liquid products were analyzed in examples 5-9 at 5 different catalyst concentrations (0.5 wt%, 1.5 wt%, 2.5 wt%, 3.5wt%, 4.5 wt%). Specifically, the obtained liquid product was extracted with ethyl acetate, ethyl acetate solubles were shown in FIG. 6, and the product composition was analyzed by GC-MS, and the result was shown in FIG. 7.
All samples in fig. 6 (0.5 wt%, 1.5 wt%, 2.5 wt%, 3.5wt%, 4.5 wt%, corresponding in turn to samples a through e) exhibited different colors, changing from pale yellow to dark brown as the catalyst content increased. As can be seen from FIG. 7, there are significant differences in the depolymerization products obtained using different catalyst concentrations, and the detected products mainly include phenolic compounds, esters, aldehydes, etc., and detailed information of the depolymerization products are summarized in Table 3.
As is clear from Table 3, the total integrated area was large in the chemical substances such as ethyl propionate, butyl acetate, acetosyringone, phenol, and 2, 6-bis (1, 1-dimethylethyl) -naphthalene. A relatively large proportion of 2, 4-di-tert-butylphenol is observed in the product obtained when different catalyst concentrations are selected. When the catalyst concentration is 0.5 wt%, the main compound in the product is 2, 3-dihydro-benzofuran, which accounts for 13.72% of the total integral area, and the second is ethyl propionate, which accounts for 5.54% of the total integral area, and 2, 4-di-tert-butylphenol, which accounts for 3.01% of the total integral area. When the catalyst concentration was 1.5wt%, the compound 2, 3-dihydro-benzofuran accounted for a major portion of the total integrated area, 48.16%, followed by ethyl propionate and 2, 4-di-tert-butylphenol, 17.42% and 10.12% of the total integrated area, respectively. The compounds 3-hydroxy-4-methoxybenzaldehyde and eicosane account for 5.38% and 3.09% of the total integrated area, respectively. When the catalyst concentration was 2.5 wt%, 3.5 wt% and 4.5 wt%, the total integral area occupied by the compound ethyl propionate was the largest, 65.18%, 51.59% and 59.06%, respectively, and the second was 2, 4-di-tert-butylphenol, 15.73%, 14.84% and 17.08% of the total integral area, respectively.
It is noted that as the catalyst concentration increased to 3.5wt%, the total proportion of phenolic compounds was maximized and the types of phenolic compounds varied, the resulting phenolic compounds including phenol, 2-methoxyphenol, 2, 4-di-t-butylphenol, 2, 3-dimethoxyphenol, 3, 4-dimethoxyphenol, 2, 6-dimethoxyphenol were maximized, i.e., 14.84% and 2, 6-dimethoxyphenol was 10.78% of the total integrated area. The compounds 2, 3-dimethoxyphenol and 3, 4-dimethoxyphenol occupy relatively little total integrated area and only occur at 3.5wt% of the catalyst. For 2, 4-di-tert-butylphenol, the ratio increased from 3.01% to 17.08% as the catalyst content increased from 0.5wt% to 4.5%, indicating that the catalyst promoted the production of 2, 4-di-tert-butylphenol. With respect to phenol, as the catalyst amount was increased from 0.5wt% to 4.5%, the proportion thereof was first increased from 0.16% to 4.22%, the proportion of phenol was decreased to 3.7% when the catalyst amount was 4.5wt%, no 2, 6-dimethoxyphenol was observed when the catalyst amount was 0.5wt% and 1.5wt%, the proportion of 2, 6-dimethoxyphenol was increased when the catalyst amount was increased from 2.5wt% and 3.5wt%, the proportion of 2, 6-dimethoxyphenol was respectively increased to 2.15% and 10.78%, and the proportion of 2, 6-dimethoxyphenol was decreased to 0.9% when the catalyst concentration was further increased to 4.5 wt%. The proportions of 2-methoxyphenol were 0.61%, 0.72% and 1.56% when the catalyst was used in amounts of 1.5wt%, 2.5wt% and 3.5wt%, respectively, and the proportions were reduced to 0.61% when the catalyst was further increased to 4.5%.
To further confirm the chemical functional group characteristics of the degradation products of each sample in FIG. 6, FT-IR analysis was performed, and the results are shown in FIG. 8.
As shown in fig. 8, the products have more similar chemical functional groups and the positions of the vibration peaks are substantially the same, and this result indicates that the main components of the depolymerized products are structurally similar. 3480 The broad band at cm -1 was attributed to the stretching vibration peaks of O-H, =c-H and N-H in the aromatic or aliphatic groups, indicating the presence of phenols or benzene rings in the product, the peaks at 2938 and 2841 cm -1 were attributed to the asymmetric stretching vibration of methyl, methylene C-H, indicating the presence of saturated aliphatic hydrocarbons in the product, the small and broad band near 1702 cm -1 was attributed to the stretching vibration of c=o in the ketone or carboxylic acid derivative, and the peaks near 1590 and 1505 cm -1 were attributed to the vibration of c=c bonds in the aromatic backbone, indicating that the aromatic backbone structure of lignin was well preserved in the product. Peaks at 1273 and 1120cm -1 are ascribed to Ar-O bonds of methoxyphenol.
The elemental composition of the products of examples 5-9 were analyzed and the results are shown in Table 4.
The elemental analysis results showed that the carbon content in the product was increased compared to lignin, with the highest carbon content when the catalyst was used at 3.5 wt%, the slightly increased hydrogen content compared to lignin, the reduced oxygen content compared to lignin, and the lowest oxygen content found at 21.8% in the product at 3.5 wt% catalyst. At the same time, the heat value (HHV) of the product is enhanced, the HHV of lignin is 20.5MJ/kg, the HHV value of the product is increased to 23.3-30.2MJ/kg, and the highest HHV is 30.2MJ/kg.
For example 18, the change in lignin microstructure at different depolymerization times (40 min, 80min, 120min, 150 min) was investigated by SEM analysis and the results are shown in figure 9. Fig. 9 a shows lignin, 40min corresponds to fig. 9 b, 80min corresponds to fig. 9 c, 120min corresponds to fig. 9 e, and 150min corresponds to fig. 9 f.
As can be seen from figure 9, panel a, the lignin has a relatively smooth, dense surface structure, when the reaction time is extended to 40min (panel b of figure 9), the smooth surface is slightly broken, some shallow pits are observed, a small amount of scum is deposited on the lignin surface, indicating that depolymerization of lignin is proceeding from the surface, further reaction to 80min (panel c of figure 9), surface damage is exacerbated, some deeper pits appear, and an enlarged view (panel d of figure 9) shows that more chips are found to be attached to the surface or in the pits, indicating that the main reaction at this stage is lignin depolymerization. When the reaction time was continued to be prolonged to 120min (e-chart of fig. 9), a slight caking was observed, indicating that the coupling and polycondensation reaction of the intermediate product began to become apparent with an increase in the reaction time, and when the reaction time was further increased to 150min (f-chart of fig. 9), an agglomeration phenomenon was observed, indicating that a longer time promoted the coupling and polycondensation reaction of the intermediate product.
While embodiments of the present invention have been shown and described, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that changes, modifications, substitutions and alterations may be made therein by those of ordinary skill in the art without departing from the spirit and scope of the invention, all such changes being within the scope of the appended claims.
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| 木质素氧化还原解聚研究现状;沈晓骏;黄攀丽;文甲龙;孙润仓;;化学进展;20170124(01);174-190 * |
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