CN107935814B - Method for preparing aryl oxygen-containing compound by catalytic depolymerization of bagasse lignin - Google Patents
Method for preparing aryl oxygen-containing compound by catalytic depolymerization of bagasse lignin Download PDFInfo
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Abstract
The invention relates to a method for preparing aromatic oxygen-containing compounds by catalytic depolymerization of bagasse lignin, which comprises the following steps: firstly, preparing nano layered NiMgFe hydrotalcite: secondly, preparing aromatic oxygen-containing compounds by depolymerizing bagasse lignin under the catalysis of NiMgFe nano-layered composite metal oxide solid base; thirdly, centrifugally separating out residues and hydrotalcite after the catalytic depolymerization reaction to obtain a liquid-phase crude product; and fourthly, after the liquid-phase crude product is extracted and separated, removing the extractant by a rotary evaporator to obtain a pure liquid-phase product, wherein the product is an aromatic oxygen-containing compound. The nano single-layered hydrotalcite catalyst prepared by the coprecipitation hydrothermal synthesis method has high catalytic activity on bagasse lignin, and the depolymerization rate of the bagasse lignin can reach over 90 percent.
Description
Technical Field
The invention relates to the field of efficient catalytic conversion and resource utilization of bagasse lignin, and in particular relates to a method for preparing an aromatic oxygen-containing compound by catalytic depolymerization of bagasse lignin by using nano monolayer NiMgFe hydrotalcite.
Background
In nature, lignin is the second largest biomass in addition to cellulose, and it is statistically possible to regenerate up to 5.0X 10 lignin annually10Ton. The molecular structure of the aromatic oxygen-containing compound has oxygen-containing functional groups such as phenolic hydroxyl, aldehyde group, carboxyl and the like, so that the aromatic oxygen-containing compound becomes a renewable resource for producing aromatic oxygen-containing compounds. The sugar industry produces a large amount of bagasse waste which is mainly used as fuel and the like, and due to the fact that the bagasse waste is high in oxygen content and low in calorific value, the bagasse waste is caused by direct combustion. Cellulose is separated from bagasse by a chemical conversion method, the cellulose can be used for preparing ethanol by fermentation and used as a blending component of motor gasoline, and the residual bagasse lignin is difficult to be directly converted and utilized due to complex physical structure and stable chemical properties. Therefore, the method opens up a new way for preparing high value-added chemicals by high-efficiency catalytic conversion of bagasse lignin, and has important significance for realizing high-value and resource utilization of bagasse lignin.
Current methods for converting and utilizing lignin include pyrolysis, biochemical and catalytic conversion. The catalytic conversion has higher conversion rate and product selectivity, and is a method with the most prospect in lignin utilization. In the conversion process, groups such as phenol, alcohol, ether and the like in the molecular structure of lignin are easy to randomly break bonds to generate small molecular products, the types of the products are more, high-activity and high-selectivity catalysts are developed, and selective catalytic preparation of certain chemicals can be realized by selectively activating and breaking certain chemical bonds, so that the economy is improved, and the environment-friendly conversion and utilization of the lignin are hopefully realized.
The Chinese patent publication No. CN 102875343A provides a method for preparing aromatic aldehyde compounds by catalytic degradation of lignin by using an impregnation method to prepare a supported solid acid molecular sieve catalyst, but the conversion rate of the lignin in the process is low, and the product selectivity needs to be further improved. The invention patent of China with the publication number of CN 102476980A takes tungsten as a main active component and takes transition metals such as nickel, cobalt, ruthenium, iridium, palladium, platinum, copper, iron and the like as a catalyst of a second metal active component, and the lignin is subjected to hydrogenation catalysis in a polar solvent system to convert aromatic compounds. The Chinese patent application with the publication number of CN 106632515 takes the ionic liquid as a catalyst, and the lignin in an alcohol system is catalytically degraded under the condition of inert gas, the method has simple process operation, the ionic liquid can be recycled, but the lignin degradation rate is lower than 30 percent.
Disclosure of Invention
The invention aims to provide a method for preparing an aromatic oxygen-containing compound by catalytic depolymerization of bagasse lignin, which is used for solving the problem of low utilization efficiency of bagasse waste, and converting the bagasse lignin into high-value-added chemicals such as the aromatic oxygen-containing compound by a chemical method, thereby realizing resource utilization and high-value utilization of the waste.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for preparing the aryl oxygen-containing compound by catalytic depolymerization of bagasse lignin comprises the following steps:
firstly, preparing nano layered NiMgFe hydrotalcite:
(1) respectively preparing Ni (NO) with the concentration of 0.05-2mol/L3)2Solution, Mg (NO)3)2Solution, Fe (NO)3)3The solution is evenly mixed, the molar ratio of Ni to Mg in the mixed solution is 1:10-10:1, wherein the molar fraction of Fe in the three metals of NiMgFe is 1-40%;
(2) adding a cosolvent with a volume of 1-30% of the total volume of the solution into the mixed solution, wherein the cosolvent is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, butanediol, hexanediol, glycerol, hexanehexol and starch;
(3) dropwise adding 0.1-3mol/L NaOH solution into the mixed solution obtained in the step (2) to enable the pH value of the solution to be 9-12, and stopping dropwise adding to obtain uniformly mixed feed liquid;
(4) loading the uniformly mixed feed liquid into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal synthesis at the temperature of 120-280 ℃, crystallizing for 10-36h, performing centrifugal separation to obtain a solid product, washing the solid product with deionized water until the pH of supernatant is =7, and drying at the temperature of 80-120 ℃ for 6-24h to obtain nitrate type NiMgFe nano layered hydrotalcite;
(5) roasting the obtained nitrate type NiMgFe nano layered hydrotalcite at 650 ℃ for 3-12h to obtain NiMgFe nano layered composite metal oxide solid alkali;
secondly, preparing aromatic oxygen-containing compounds by depolymerizing bagasse lignin under the catalysis of NiMgFe nano-layered composite metal oxide solid base;
thirdly, centrifugally separating out residues after the catalytic depolymerization reaction and NiMgFe nano-layered composite metal oxide solids to obtain a liquid-phase crude product;
and fourthly, after the liquid-phase crude product is extracted and separated, removing the extractant by a rotary evaporator to obtain a pure liquid-phase product, wherein the product is an aromatic oxygen-containing compound.
The method for depolymerizing bagasse lignin by using NiMgFe nano-layered composite metal oxide solid base catalysis in the scheme comprises the following steps:
(1) adding bagasse lignin and NiMgFe nano-layered composite metal oxide solid alkali into an ethanol water solution, wherein the mass ratio of the bagasse lignin to the NiMgFe nano-layered composite metal oxide solid alkali is 1:10-10:1, the volume concentration of ethanol is 10-75%, and the liquid-solid ratio is 240:1-10:1 mL/g;
(2) n is required to be adopted before reaction2Purging for 10min to remove O in the reaction system2；
(3) The reaction is carried out in a high-pressure reaction kettle, the reaction temperature is 200-350 ℃, and the reaction time is 1-24 h.
In the scheme, under the catalytic action of NiMgFe nano-layered composite metal oxide solid alkali, the depolymerization rate of bagasse lignin reaches over 90 percent.
In the scheme, the yield of the liquid-phase crude product is more than 85%, the selectivity of the liquid-phase crude product is more than 80%, and the aromatic oxygen-containing compounds comprise phenols, guaiacols, syringyl compounds, catechol compounds and methoxy aromatic compounds.
The NiMgFe nano-layered composite metal oxide solid alkali after the reaction in the scheme is 500-650 DEG in the air atmosphereoC is roasted for 4-12h to realize regeneration, and the regenerated catalyst is recycled.
The invention has the following beneficial effects:
1. the method takes the bagasse lignin as a raw material to prepare the aromatic oxygen-containing compound with high added value through catalytic depolymerization, is beneficial to high-value utilization of the bagasse lignin, and avoids resource waste.
2. The nano single-layered hydrotalcite catalyst prepared by the coprecipitation hydrothermal synthesis method has high catalytic activity on bagasse lignin, and the depolymerization rate of the bagasse lignin can reach over 90 percent. And can be recycled after oxidation and regeneration.
3. After the bagasse lignin is catalytically depolymerized, the yield of a liquid product can reach more than 85%, wherein the selectivity of the aryl oxygen-containing compound can reach more than 80%, and the phenolic compounds mainly comprise high-value-added chemicals such as phenols, guaiacols, syringyl compounds, catechol compounds, methoxy aromatic compounds and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a solid of a NiMgFe nano-layered composite metal oxide in example 1 of the present invention.
Detailed Description
The invention is further described with reference to the accompanying drawings in which:
example 1:
the method for preparing the aryl oxygen-containing compound by catalytic depolymerization of bagasse lignin comprises the following steps:
1.164g of Ni (NO) was weighed3)2•6H2O、1.536g Mg(NO3)2•6H2O、1.01g Fe(NO3)3•9H2O was dissolved in 50mL of distilled water in turn, and 5mL of an absolute ethanol solution was added thereto, followed by stirring with a magnetic stirrer for 30 minutes. Titrating the solution with 2mol/L NaOH solution, and continuing stirring the solution after the titration is finished when the pH value is =11 so as to ensure that the solution is fully and uniformly stirred. Carrying out ultrasonic treatment on the solution after the titration and stirring is finished in an ultrasonic disperser for 5 minutes, taking out the solution, putting the solution into a reaction kettle, and reacting for 24 hours at 160 ℃; and after the reaction, taking out the inner liner of the reaction kettle, and washing and centrifuging the separated lower-layer precipitate. Centrifuging for 3 min at 12000 min/r, and washing off OH in precipitate-And measuring the pH value of the washing solution by using a pH meter until the pH value of the supernatant is =7, namely the supernatant is washed clean. And drying the washed and centrifuged precipitate at 80 ℃ for 24 hours to obtain nitrate type NiMgFe nano layered hydrotalcite. And (3) putting the obtained hydrotalcite into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain the NiMgFe nano-layered composite metal oxide solid alkali, wherein a scanning electron microscope photo of the NiMgFe nano-layered composite metal oxide solid alkali is shown in figure 1.
Weighing 0.40g of the NiMgFe nano-layered composite metal oxide solid alkali and 0.60g of bagasse lignin, putting into a high-pressure reaction kettle, adding 75mL of ethanol water solution, wherein the volume concentration of ethanol is 50%, and the liquid-solid ratio is 75: 1; before reaction with N2Purge for 10min to remove O from the reactor2And reacting for 4 hours at 260 ℃. And after the reaction is finished, performing solid-liquid separation on the mixture through centrifugation, extracting the obtained liquid for 3-5 times by using ethyl acetate, further removing water from the separated extract through anhydrous magnesium sulfate, and then separating the product of the aromatic oxygen-containing compound through a rotary evaporator.
The bagasse lignin conversion was calculated to be 92.6% by weighing the mass of bagasse lignin remaining after the reaction, by collecting the liquid product. The liquid product yield was calculated to be 86.4%, and the liquid product composition was analyzed by chromatography-mass spectrometry with a selectivity of the aromatic group oxygenates of 81.3%, respectively phenols (24.2%), guaiacols (8.1%), syringyl (18.5%), catechol (17.9%) and methoxybenzene (12.6%).
Example 2:
the method for preparing the aryl oxygen-containing compound by catalytic depolymerization of bagasse lignin comprises the following steps:
1.164g of Ni (NO) was weighed3)2•6H2O、1.536g Mg(NO3)2•6H2O、1.01g Fe(NO3)3•9H2O was dissolved in 50mL of distilled water in this order, 5mL of ethylene glycol solution was added, and stirring was continued for 30 minutes by a magnetic stirrer. Titrating the solution with 2mol/L NaOH solution, and continuing stirring the solution after the titration is finished when the pH value is =10.5 so as to ensure that the solution is fully and uniformly stirred. Carrying out ultrasonic treatment on the solution after the titration and stirring is finished in an ultrasonic disperser for 5 minutes, taking out the solution, putting the solution into a reaction kettle, and reacting for 24 hours at 180 ℃; and after the reaction, taking out the inner liner of the reaction kettle, and washing and centrifuging the separated lower-layer precipitate. Centrifuging for 3 min at 12000 min/r, and washing off OH in precipitate-And measuring the pH value of the washing solution by using a pH meter until the pH value of the supernatant is =7, namely the supernatant is washed clean. And drying the washed and centrifuged precipitate at 80 ℃ for 24 hours to obtain nitrate type NiMgFe nano layered hydrotalcite. And putting the obtained hydrotalcite into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain the NiMgFe nano layered composite metal oxide solid base.
Weighing 0.50g of the NiMgFe nano-layered composite metal oxide solid alkali and 0.50g of bagasse lignin, putting into a high-pressure reaction kettle, adding 90mL of ethanol aqueous solution, wherein the volume concentration of ethanol is 50%, and the liquid-solid ratio is 90: 1; before reaction with N2Purge for 10min to remove O from the reactor2And reacting for 4 hours at 280 ℃. After the reaction is finished, the mixture isPerforming solid-liquid separation by centrifugation, extracting the obtained liquid with ethyl acetate for 3-5 times, further removing water from the separated extract by anhydrous magnesium sulfate, and separating the product of aromatic oxygen-containing compound by a rotary evaporator.
The bagasse lignin conversion was calculated to be 94.3% by weighing the mass of bagasse lignin remaining after the reaction, by collecting the liquid product. The liquid product yield was calculated to be 88.1%, and the liquid product composition was analyzed by chromatography-mass spectrometry with a selectivity of the aromatic group oxygenates of 83.6%, respectively phenols (26.1%), guaiacols (7.5%), syringyl (17.8%), catechol (15.3%) and methoxybenzene (16.9%).
Example 3:
the method for preparing the aryl oxygen-containing compound by catalytic depolymerization of bagasse lignin comprises the following steps:
1.745g of Ni (NO) were weighed out3)2•6H2O、1.536g Mg(NO3)2•6H2O、1.212g Fe(NO3)3•9H2O was dissolved in 50mL of distilled water in turn, 5mL of the starch solution was added, and stirring was continued for 30 minutes with a magnetic stirrer. Titrating the solution with 2mol/L NaOH solution, and continuing stirring the solution after the titration is finished when the pH value is =11 so as to ensure that the solution is fully and uniformly stirred. Carrying out ultrasonic treatment on the solution after the titration and stirring is finished in an ultrasonic disperser for 5 minutes, taking out the solution, putting the solution into a reaction kettle, and reacting for 18 hours at 180 ℃; and after the reaction, taking out the inner liner of the reaction kettle, and washing and centrifuging the separated lower-layer precipitate. Centrifuging for 3 min at 12000 min/r, and washing off OH in precipitate-And measuring the pH value of the washing solution by using a pH meter until the pH value of the supernatant is =7, namely the supernatant is washed clean. And drying the washed and centrifuged precipitate at 80 ℃ for 24 hours to obtain nitrate type NiMgFe nano layered hydrotalcite. And putting the obtained hydrotalcite into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain the NiMgFe nano layered composite metal oxide solid base.
Weighing 0.60g of the NiMgFe nano-layered composite metal oxide solid alkali and 0.40g of bagasse ligninPutting the mixture into a high-pressure reaction kettle, and adding 100mL of ethanol aqueous solution, wherein the volume concentration of ethanol is 50%, and the liquid-solid ratio is 100: 1; before reaction with N2Purge for 10min to remove O from the reactor2And reacting for 4 hours at 300 ℃. And after the reaction is finished, performing solid-liquid separation on the mixture through centrifugation, extracting the obtained liquid for 3-5 times by using ethyl acetate, further removing water from the separated extract liquid through anhydrous magnesium sulfate, and then separating the target product, namely the aromatic oxygen-containing compound through a rotary evaporator.
The bagasse lignin conversion was calculated to be 95.2% by weighing the mass of bagasse lignin remaining after the reaction, by collecting the liquid product. The liquid product yield was calculated to be 89.5%, and the liquid product composition was analyzed by chromatography-mass spectrometry with a selectivity of the aryl oxygenates of 85.3%, phenol (27.1%), guaiacol (8.3%), syringyl (17.9%), catechol (14.7%) and methoxybenzene (17.3%), respectively.
Claims (4)
1. A method for preparing aryl oxygen-containing compounds by catalytic depolymerization of bagasse lignin is characterized in that:
1.164g of Ni (NO) was weighed3)2•6H2O、1.536g Mg(NO3)2•6H2O、1.01g Fe(NO3)3•9H2Dissolving O in 50mL of distilled water in sequence, adding 5mL of absolute ethyl alcohol solution, and continuously stirring for 30 minutes by using a magnetic stirrer; titrating the solution with 2mol/L NaOH solution, and continuing stirring the solution after the titration is finished when the pH value is =11 so as to fully and uniformly stir the solution; carrying out ultrasonic treatment on the solution after the titration and stirring is finished in an ultrasonic disperser for 5 minutes, taking out the solution, putting the solution into a reaction kettle, and reacting for 24 hours at 160 ℃; after the reaction, taking out the inner liner of the reaction kettle, and washing and centrifuging the separated lower-layer precipitate; centrifuging for 3 min at 12000 min/r, and washing off OH in precipitate-Measuring the pH of each wash with a pH meter until the pH of the supernatant = 7; drying the washed and centrifuged precipitate at 80 ℃ for 24 hours to obtain nitrate type NiMgFe nano layered hydrotalcite(ii) a Placing the obtained hydrotalcite into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain NiMgFe nano layered composite metal oxide solid alkali;
weighing 0.40g of the NiMgFe nano-layered composite metal oxide solid alkali and 0.60g of bagasse lignin, putting into a high-pressure reaction kettle, adding 75mL of ethanol water solution, wherein the volume concentration of ethanol is 50%, and the liquid-solid ratio is 75: 1; before reaction with N2Purge for 10min to remove O from the reactor2Reacting for 4 hours at the temperature of 260 ℃; after the reaction is finished, performing solid-liquid separation on the mixture through centrifugation, extracting the obtained liquid for 3-5 times by using ethyl acetate, further removing water from the separated extract liquid through anhydrous magnesium sulfate, and then separating the product, namely the aromatic oxygen-containing compound through a rotary evaporator; the bagasse lignin conversion was 92.6%, the liquid product yield was 86.4%; the selectivity of the aromatic oxygen-containing compound is 81.3 percent, and the selectivity is 24.2 percent of phenols, 8.1 percent of guaiacols, 18.5 percent of syringyl, 17.9 percent of catechol and 12.6 percent of methoxyl benzene compounds respectively.
2. A method for preparing aryl oxygen-containing compounds by catalytic depolymerization of bagasse lignin is characterized in that:
1.164g of Ni (NO) was weighed3)2•6H2O、1.536g Mg(NO3)2•6H2O、1.01g Fe(NO3)3•9H2Dissolving O in 50mL of distilled water in sequence, adding 5mL of glycol solution, and continuously stirring for 30 minutes by using a magnetic stirrer; titrating the solution with 2mol/L NaOH solution, and continuing stirring the solution after the titration is finished when the pH value is =10.5 so as to fully and uniformly stir the solution; carrying out ultrasonic treatment on the solution after the titration and stirring is finished in an ultrasonic disperser for 5 minutes, taking out the solution, putting the solution into a reaction kettle, and reacting for 24 hours at 180 ℃; after the reaction, taking out the inner liner of the reaction kettle, and washing and centrifuging the separated lower-layer precipitate; centrifuging for 3 min at 12000 min/r, and washing off OH in precipitate-Measuring the pH of each wash with a pH meter until the pH of the supernatant = 7; drying the washed and centrifuged precipitate at 80 ℃ for 24 hours to obtain a nitrate type NiMgFe nano layerHydrotalcite-like compound; placing the obtained hydrotalcite into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain NiMgFe nano layered composite metal oxide solid alkali;
weighing 0.50g of the NiMgFe nano-layered composite metal oxide solid alkali and 0.50g of bagasse lignin, putting into a high-pressure reaction kettle, adding 90mL of ethanol aqueous solution, wherein the volume concentration of ethanol is 50%, and the liquid-solid ratio is 90: 1; before reaction with N2Purge for 10min to remove O from the reactor2Reacting for 4 hours at 280 ℃; after the reaction is finished, performing solid-liquid separation on the mixture through centrifugation, extracting the obtained liquid for 3-5 times by using ethyl acetate, further removing water from the separated extract liquid through anhydrous magnesium sulfate, and then separating the product, namely the aromatic oxygen-containing compound through a rotary evaporator; the bagasse lignin conversion was 94.3%, the liquid product yield was 88.1%; the selectivity of the aromatic oxygen-containing compound is 83.6 percent, and the selectivity is 26.1 percent of phenols, 7.5 percent of guaiacols, 17.8 percent of syringyl compounds, 15.3 percent of catechol and 16.9 percent of methoxyl benzene compounds respectively.
3. A method for preparing aryl oxygen-containing compounds by catalytic depolymerization of bagasse lignin is characterized in that:
1.745g of Ni (NO) were weighed out3)2•6H2O、1.536g Mg(NO3)2•6H2O、1.212g Fe(NO3)3•9H2Dissolving O in 50mL of distilled water in sequence, adding 5mL of starch solution, and continuously stirring for 30 minutes by using a magnetic stirrer; titrating the solution with 2mol/L NaOH solution, and continuing stirring the solution after the titration is finished when the pH value is =11 so as to fully and uniformly stir the solution; carrying out ultrasonic treatment on the solution after the titration and stirring is finished in an ultrasonic disperser for 5 minutes, taking out the solution, putting the solution into a reaction kettle, and reacting for 18 hours at 180 ℃; after the reaction, taking out the inner liner of the reaction kettle, and washing and centrifuging the separated lower-layer precipitate; centrifuging for 3 min at 12000 min/r, and washing off OH in precipitate-Measuring the pH of each wash with a pH meter until the pH of the supernatant = 7; drying the washed and centrifuged precipitate at 80 ℃ for 24 hours to obtain nitrate type NiMgFe nano layered hydrotalcite; placing the obtained hydrotalcite into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain NiMgFe nano layered composite metal oxide solid alkali;
weighing 0.60g of the NiMgFe nano-layered composite metal oxide solid alkali and 0.40g of bagasse lignin, putting into a high-pressure reaction kettle, adding 100mL of ethanol water solution, wherein the volume concentration of ethanol is 50%, and the liquid-solid ratio is 100: 1; before reaction with N2Purge for 10min to remove O from the reactor2Reacting for 4 hours at the temperature of 300 ℃; after the reaction is finished, performing solid-liquid separation on the mixture through centrifugation, extracting the obtained liquid for 3-5 times by using ethyl acetate, further removing water from the separated extract liquid through anhydrous magnesium sulfate, and then separating a target product, namely the aromatic oxygen-containing compound through a rotary evaporator; the bagasse lignin conversion rate was 95.2%, and the liquid product yield was 89.5%; the selectivity of the aryl oxygen-containing compound is 85.3 percent, and the selectivity is 27.1 percent of phenols, 8.3 percent of guaiacols, 17.9 percent of syringyl compounds, 14.7 percent of catechol and 17.3 percent of methoxyl benzene compounds respectively.
4. A process for the preparation of aryl oxygenates by catalytic depolymerization of bagasse lignin according to claim 1 or 2 or 3, characterised in that: the reacted NiMgFe nano-layered composite metal oxide solid alkali is 500-650 DEG in air atmosphereoC is roasted for 4-12h to realize regeneration, and the regenerated catalyst is recycled.
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| CN107935814B true CN107935814B (en) | 2021-05-25 |
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