CN114478201A - Production process for directionally preparing guaiacol and derivatives thereof from lignin - Google Patents
Production process for directionally preparing guaiacol and derivatives thereof from lignin Download PDFInfo
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- CN114478201A CN114478201A CN202111658196.XA CN202111658196A CN114478201A CN 114478201 A CN114478201 A CN 114478201A CN 202111658196 A CN202111658196 A CN 202111658196A CN 114478201 A CN114478201 A CN 114478201A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention relates to the field of guaiacol preparation, in particular to a process for directionally and efficiently preparing guaiacol and derivatives thereof by lignin, which comprises the steps of preparing guaiacol and derivatives thereof by controlling process parameters such as reaction temperature, reaction pressure, reaction time, stirring rate and the like under the inert atmosphere by taking biochar-nickel-cerium solid compound as a catalyst and lignin as a reaction substrate in a system taking crude glycerol as a reaction medium, wherein the conversion rate of lignin is over 70 percent, the selectivity of monomer guaiacol and derivatives thereof is over 75 percent, the yield is over 52 percent, the problems of equipment corrosion, high cost caused by organic hydrogen supply solvents, complicated products, difficult separation, environmental pollution and resource waste caused by acid-base homogeneous catalysts are avoided, the catalyst can be repeatedly utilized for more than 30 times, and the process operation conditions for directionally and efficiently preparing the guaiacol and the derivatives thereof are simple, the used crude glycerol is not only used as a green solvent, but also can inhibit the coking of the catalyst and provide an in-situ hydrogen source.
Description
Technical Field
The invention relates to the field of preparation of guaiacol, in particular to a production process for directionally preparing guaiacol and derivatives thereof by lignin.
Background
In order to alleviate the fossil energy crisis, scholars aim at the renewable biomass field so as to achieve the purpose of sustainable utilization of resources. Lignocellulose in nature is mainly composed of three components: cellulose, hemicellulose and lignin. At present, cellulose and hemicellulose have been valuated to a certain extent in industry, and lignin is used as waste in the pulping and papermaking industry, cannot be efficiently utilized due to complex structure and persistent properties, and is only used as low-value energy for combustion power generation. The lignin is a high-molecular complex polymer formed by disorderly connecting 3 propane structural units of guaiacyl, p-hydroxyphenylpropyl and syringyl through C-O and C-C bonds, and because the lignin contains a large number of aromatic groups and belongs to renewable resources, the lignin is depolymerized to form a monomer with high added value, so that the value-added utilization of the lignin can be realized. Theoretically, the structural bond on lignin is destroyed, guaiacol and derivatives thereof can be prepared from guaiacyl units, and then the guaiacol and derivatives thereof are used as corresponding platform molecules to be applied to the industries of pesticide, medicine and spice, so that the value increase is realized. Because the industrial synthesis of guaiacol is produced by alkylation of downstream products which mainly depend on fossil energy, the guaiacol obtained from lignin can relieve the energy crisis to a certain extent.
The crude glycerol is a byproduct in the production process of the biodiesel, 0.1 ton of crude glycerol is accompanied by the production of each ton of biodiesel, but the crude glycerol contains a large amount of water, methanol, inorganic salt, ash and other impurities, so the purification cost is high, and the direct chemical conversion has a good application prospect.
At present, a plurality of catalytic methods are used for lignin depolymerization, such as oxidative degradation, biodegradation, hydrogenolysis and the like, but the generated products are complicated, have high oxygen content and high viscosity, are difficult to separate and purify, and hinder the next comprehensive utilization, and meanwhile, in the reaction process, an acid-base homogeneous catalyst and an organic hydrogen supply solvent are adopted, so that not only is the reaction equipment corroded, but also the generation cost is increased.
Therefore, the development of a green, environment-friendly, economic, efficient and highly selective catalyst and the simple and efficient process for synthesizing aromatic phenolic compounds are key factors for solving a series of difficult problems such as complex utilization of lignin products and the like.
Disclosure of Invention
In order to solve the defects mentioned in the background technology, the invention aims to provide a production process for directionally preparing guaiacol and derivatives thereof by lignin.
The purpose of the invention can be realized by the following technical scheme:
a production process for directionally preparing guaiacol and derivatives thereof by lignin comprises the following raw materials:
crude glycerol, inert atmosphere, biochar-nickel-cerium solid compound and lignin;
under the condition of taking crude glycerin as a reaction medium and inert atmosphere, the guaiacol and the derivatives thereof are prepared by taking biochar-nickel-cerium solid compound as a catalyst and lignin as a reaction substrate and controlling reaction temperature, reaction pressure, reaction time and stirring speed.
Further, the production process comprises the following steps:
taking 0.8-1.2 parts by mass of dried lignin, adding 0.1-0.3 part by mass of a catalyst calcined at 700 ℃, adding 26-34 parts by volume of crude glycerol, putting into an intermittent high-pressure reaction kettle, then filling 0.3-0.9MPa of high-purity inert gas, stirring for 15 minutes before heating, wherein the reaction temperature is 260-300 ℃, and the reaction time is 2-7 hours;
after the reaction is finished, rapidly putting the high-pressure reaction kettle into ice water bath or liquid nitrogen for quenching and cooling, quenching the reaction, opening the reaction kettle after the reaction kettle is cooled to normal temperature, and taking out a reaction product by using an ethyl acetate solution:
carrying out suction filtration by using a sand core funnel, separating a solid phase and a liquid phase, and repeatedly washing a solid phase product by using an ethyl acetate solvent for multiple times;
placing the solid product in a drying box at the temperature of 100-;
placing the liquid phase product in a vacuum rotary evaporator, firstly evaporating the liquid phase product to dryness at 39.5-45.5 ℃ under the condition of 100-;
and finally, collecting the absolute ethyl alcohol soluble product to perform qualitative and quantitative analysis on the product.
Further, the crude glycerol is prepared by compounding water and pure glycerol in different volume ratios, wherein the water-oil ratio is 5-9: 1.
further, the lignin: catalyst: the feeding mass ratio of the crude glycerol is 0.8-1.2: 0.1-0.3: 26 to 34.
Further, the raw material of the lignin comprises one or more of sulfate lignin, alkali lignin and bamboo lignin.
Further, the inert gas is nitrogen or argon, the reaction temperature is 260-300 ℃, the reaction pressure is 7.0-10.5 MPa, the reaction time is 2-7 h, and the stirring speed is 500-1000 r/min.
Further, the biochar-nickel-cerium composite is prepared by taking biochar as a carrier and nickel and cerium as active components, wherein the content of nickel is 1-10 wt%, and the content of cerium is 1-10 wt%, and the biochar-nickel-cerium composite is prepared by a co-impregnation method.
Further, the ethyl acetate is a separation and purification solvent, the anhydrous sodium sulfate is a purification reagent, the vacuum rotary evaporation temperature is 39.5-45.5 ℃, and the vacuum rotary evaporation speed is 100-140 rpm.
The invention has the beneficial effects that:
the method adopts a biochar carrier, commercially available nickel nitrate and cerium nitrate adopt a co-impregnation method, and a high-temperature calcination mode is adopted under an inert atmosphere to prepare the solid acid catalyst, the aim of directionally and highly selectively generating the guaiacol and the derivatives thereof is achieved by controlling the reaction temperature, the reaction pressure and the reaction time, and the problems of equipment corrosion caused by an acid-base homogeneous catalyst, high cost caused by an organic hydrogen supply solvent, complicated products, difficult separation, environmental pollution and resource waste are solved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A production process for directionally preparing guaiacol and derivatives thereof from lignin comprises the following raw materials:
crude glycerol, inert atmosphere, biochar-nickel-cerium solid compound and lignin;
in brief, under the system with crude glycerin as a reaction medium and in an inert atmosphere, the guaiacol and the derivatives thereof are prepared by controlling reaction temperature, reaction pressure, reaction time and stirring rate by using biochar-nickel-cerium solid compound as a catalyst and lignin as a reaction substrate.
Wherein:
the crude glycerol is prepared by compounding water and pure glycerol in different volume ratios, wherein the water-oil ratio is 5-9: 1;
lignin: catalyst: the feeding mass ratio of the crude glycerol is 0.8-1.2: 0.1-0.3: 26 to 34;
the raw material of the lignin comprises one or more of sulfate lignin, alkali lignin and bamboo lignin;
the inert gas is nitrogen or argon, the reaction temperature is 260-300 ℃, the reaction pressure is 7.0-10.5 MPa, the reaction time is 2-7 h, and the stirring speed is 500-1000 r/min;
the biochar-nickel-cerium composite is prepared by a co-impregnation method by taking biochar as a carrier and nickel and cerium as active components, wherein the content of nickel is 1-10 wt%, and the content of cerium is 1-10 wt%.
Specifically, the production process comprises the following steps:
taking 0.8-1.2 parts by mass of dried lignin, adding 0.1-0.3 part by mass of a catalyst calcined at 700 ℃, adding 26-34 parts by volume of crude glycerol, putting into an intermittent high-pressure reaction kettle, then filling 0.3-0.9MPa of high-purity inert gas, stirring for 15 minutes before heating, wherein the reaction temperature is 260-300 ℃, and the reaction time is 2-7 hours;
and (3) rapidly putting the high-pressure reaction kettle into ice water bath or liquid nitrogen for quenching and cooling after the reaction is finished, quenching the reaction, opening the reaction kettle after the reaction is cooled to normal temperature, and taking out a reaction product by using an ethyl acetate solution:
carrying out suction filtration by using a sand core funnel, separating a solid phase and a liquid phase, and repeatedly washing a solid phase product by using an ethyl acetate solvent for multiple times;
placing the solid product in a drying box at the temperature of 100-;
placing the liquid phase product in a vacuum rotary evaporator, firstly evaporating the liquid phase product to dryness at 39.5-45.5 ℃ under the condition of 100-;
and finally, collecting the absolute ethyl alcohol soluble product to perform qualitative and quantitative analysis on the product.
Wherein the ethyl acetate is a separation and purification solvent, the anhydrous sodium sulfate is a purification reagent, the vacuum rotary evaporation temperature is 39.5-45.5 ℃, and the vacuum rotary evaporation speed is 100-140 rpm.
Example 1:
1.0012g of bamboo lignin and 0.1038g of a catalyst calcined at 700 ℃ are placed in a 100mL high-pressure reaction kettle, and 30mL of crude glycerol (water-oil ratio 9:1) is added thereto. Then, 0.5MPa of high purity argon was charged therein. The reaction was preceded by stirring at 560rpm for 15 minutes and then at a ramp rate of 2 ℃/min from ambient temperature 24 ℃ to 280 ℃ and allowed to react at this temperature for 2 hours.
And after the reaction is finished, quickly placing the high-pressure kettle into an ice water bath or liquid nitrogen for quenching and cooling, and quenching the reaction. After the temperature is reduced to normal temperature, the reaction kettle is opened, and the ethyl acetate solution is used for taking out the reaction product.
Firstly, a sand core funnel is used for suction filtration, the solid-liquid phase is separated, and the solid-phase product is repeatedly washed by ethyl acetate solvent. Subsequently, the solid product was dried in a 105 ℃ drying oven for 12 h. And (3) placing the liquid phase product in a separating funnel, extracting with saturated NaCl solution to obtain an upper oil phase, and removing trace water and glycerol by using an excessive anhydrous sodium sulfate reagent. The liquid phase product was then placed in a vacuum rotary evaporator and first evaporated to dryness at 39.5 ℃ at 100r/min (the solvent ethyl acetate was removed). Subsequently, absolute ethyl alcohol is added into the flask, the flask is placed in an ultrasonic oscillator to be vibrated for 3-7min, and after the dissolution is finished, the solution is taken out by a disposable pipette and filtered once by an organic filter head (the absolute ethyl alcohol insoluble product is separated). The absolute ethanol soluble product was then collected for qualitative and quantitative analysis of the product. Thus obtaining the guaiacol and the derivative products thereof.
The calculation shows that the conversion rate of the lignin is over 70 percent, the selectivity of the monomer guaiacol and the derivatives thereof is over 75 percent, and the yield is over 52 percent.
Example 2:
1.0002g of bamboo lignin and 0.1028g of a 700 ℃ calcined catalyst were placed in a 100mL autoclave, to which was added 30mL of crude glycerol (water to oil ratio 8: 1). Then, 0.4MPa of high purity nitrogen was charged therein. The reaction is carried out by stirring for 15 minutes at 600rpm, then increasing the temperature from 29 ℃ to 290 ℃ at the heating rate of 3 ℃/min, and reacting for 3 hours at the temperature.
And after the reaction is finished, quickly placing the high-pressure kettle into an ice water bath or liquid nitrogen for quenching and cooling, and quenching the reaction. After the temperature is reduced to normal temperature, the reaction kettle is opened, and the ethyl acetate solution is used for taking out the reaction product.
Firstly, a sand core funnel is used for suction filtration, the solid-liquid phase is separated, and the solid-phase product is repeatedly washed by ethyl acetate solvent. Subsequently, the solid product was dried in a 110 ℃ drying oven for 15 h. And (3) placing the liquid phase product in a separating funnel, extracting with saturated NaCl solution to obtain an upper oil phase, and removing trace water and glycerol by using an excessive anhydrous sodium sulfate reagent. The liquid phase product was then placed in a vacuum rotary evaporator and first evaporated to dryness at 40.5 ℃ at 110r/min (the solvent ethyl acetate was removed). Subsequently, absolute ethyl alcohol is added into the flask, the flask is placed in an ultrasonic oscillator to be vibrated for 3-7min, and after the dissolution is finished, the solution is taken out by a disposable pipette and filtered once by an organic filter head (the absolute ethyl alcohol insoluble product is separated). The absolute ethanol soluble product was then collected for qualitative and quantitative analysis of the product. Thus obtaining the guaiacol and the derivative products thereof.
The conversion rate of lignin is over 60 percent, the selectivity of the monomer guaiacol and the derivatives thereof is over 62 percent, and the yield is over 37 percent
Example 3:
1.0026g of bamboo lignin and 0.1014g of catalyst calcined at 700 ℃ are placed in a 100mL high-pressure reaction kettle, and 30mL of crude glycerol (water-oil ratio 7:1) is added thereto. Then, 0.3MPa of high purity argon was charged therein. The reaction is carried out by stirring for 15 minutes at 1000rpm, then increasing the temperature from 27 ℃ to 260 ℃ at the heating rate of 4 ℃/min, and reacting for 4 hours at the temperature.
And after the reaction is finished, quickly placing the high-pressure kettle into an ice water bath or liquid nitrogen for quenching and cooling, and quenching the reaction. After the temperature is reduced to normal temperature, the reaction kettle is opened, and the ethyl acetate solution is used for taking out the reaction product.
Firstly, a sand core funnel is used for suction filtration, the solid-liquid phase is separated, and the solid-phase product is repeatedly washed by ethyl acetate solvent. Subsequently, the solid product was dried in a 105 ℃ drying oven for 14 h. And (3) placing the liquid phase product in a separating funnel, extracting with saturated NaCl solution to obtain an upper oil phase, and removing trace water and glycerol by using an excessive anhydrous sodium sulfate reagent. The liquid phase product was then placed in a vacuum rotary evaporator and first evaporated to dryness at 41.5 ℃ at 130r/min (the solvent ethyl acetate was removed). Subsequently, absolute ethyl alcohol is added into the flask, the flask is placed in an ultrasonic oscillator to be vibrated for 3-7min, and after the dissolution is finished, the solution is taken out by a disposable pipette and filtered once by an organic filter head (the absolute ethyl alcohol insoluble product is separated). The absolute ethanol soluble product was then collected for qualitative and quantitative analysis of the product. Thus obtaining the guaiacol and the derivative products thereof.
The calculation shows that the conversion rate of the lignin is over 58 percent, the selectivity of the monomer guaiacol and the derivatives thereof is over 68 percent, and the yield is over 39 percent.
Example 4:
1.0010g of bamboo lignin and 0.1019g of a 700 ℃ calcined catalyst were placed in a 100mL autoclave, to which was added 30mL of crude glycerol (water-to-oil ratio 6: 1). Then, 0.8MPa of high purity argon was charged therein. The reaction is preceded by stirring at 900rpm for 15 minutes and then at a rate of 2.5 ℃/min from ambient temperature 28 ℃ to 280 ℃ for 5 hours.
And after the reaction is finished, quickly placing the high-pressure kettle into an ice water bath or liquid nitrogen for quenching and cooling, and quenching the reaction. After the temperature is reduced to normal temperature, the reaction kettle is opened, and the ethyl acetate solution is used for taking out the reaction product.
Firstly, a sand core funnel is used for suction filtration, the solid-liquid phase is separated, and the solid-phase product is repeatedly washed by ethyl acetate solvent. Subsequently, the solid product was dried in a 110 ℃ drying cabinet for 17 h. And (3) placing the liquid phase product in a separating funnel, extracting with saturated NaCl solution to obtain an upper oil phase, and removing trace water and glycerol by using an excessive anhydrous sodium sulfate reagent. The liquid phase product was then placed in a vacuum rotary evaporator and first evaporated to dryness at 43.5 ℃ at 140r/min (the solvent ethyl acetate was removed). Subsequently, absolute ethyl alcohol is added into the flask, the flask is placed in an ultrasonic oscillator to be vibrated for 3-7min, and after the dissolution is finished, the solution is taken out by a disposable pipette and filtered once by an organic filter head (the absolute ethyl alcohol insoluble product is separated). The absolute ethanol soluble product was then collected for qualitative and quantitative analysis of the product. Thus obtaining the guaiacol and the derivative products thereof.
The calculation shows that the conversion rate of the lignin is over 66 percent, the selectivity of the monomer guaiacol and the derivatives thereof is over 63 percent, and the yield is over 42 percent.
Example 5:
1.0006g of bamboo lignin and 0.1001g of a 700 ℃ calcined catalyst were placed in a 100mL autoclave, to which was added 30mL of crude glycerol (water to oil ratio 5: 1). Then, 0.9MPa of high purity nitrogen was charged therein. The reaction is carried out by stirring at 800rpm for 15 minutes before reaction, then increasing the temperature from 26 ℃ to 300 ℃ at the temperature increasing rate of 5 ℃/min, and reacting for 6 hours at the temperature.
And after the reaction is finished, quickly placing the high-pressure kettle into an ice water bath or liquid nitrogen for quenching and cooling, and quenching the reaction. After the temperature is reduced to normal temperature, the reaction kettle is opened, and the ethyl acetate solution is used for taking out the reaction product.
Firstly, a sand core funnel is used for suction filtration, the solid-liquid phase is separated, and the solid-phase product is repeatedly washed by ethyl acetate solvent. Subsequently, the solid product was dried in a 105 ℃ drying oven for 16 h. And (3) placing the liquid phase product in a separating funnel, extracting with a saturated NaCl solution to obtain an upper oil phase, and removing trace water and glycerol by using an excessive anhydrous sodium sulfate reagent. The liquid phase product was then placed in a vacuum rotary evaporator and first evaporated to dryness at 44.5 ℃ at 140r/min (the solvent ethyl acetate was removed). Subsequently, absolute ethyl alcohol is added into the flask, the flask is placed in an ultrasonic oscillator to be vibrated for 3-7min, and after the dissolution is finished, the solution is taken out by a disposable pipette and filtered once by an organic filter head (the absolute ethyl alcohol insoluble product is separated). The absolute ethanol soluble product was then collected for qualitative and quantitative analysis of the product. Thus obtaining the guaiacol and the derivative products thereof.
The calculation shows that the conversion rate of lignin is over 51 percent, the selectivity of the monomer guaiacol and the derivatives thereof is over 52 percent, and the yield is over 27 percent.
Example 6:
1.0025g of bamboo lignin and 0.1021g of the 700 ℃ calcined catalyst were placed in a 100mL autoclave, to which was added 30mL of crude glycerol (water to oil ratio 7: 1). Then, 0.6MPa of high purity argon was charged therein. The reaction is carried out by stirring for 15 minutes at 700rpm, then increasing the temperature from 30 ℃ to 270 ℃ at the heating rate of 6 ℃/min, and reacting for 7 hours at the temperature.
And after the reaction is finished, quickly placing the high-pressure kettle into an ice water bath or liquid nitrogen for quenching and cooling, and quenching the reaction. After the temperature is reduced to normal temperature, the reaction kettle is opened, and the ethyl acetate solution is used for taking out the reaction product.
Firstly, a sand core funnel is used for suction filtration, the solid-liquid phase is separated, and the solid-phase product is repeatedly washed by ethyl acetate solvent. Subsequently, the solid product was dried in a 105 ℃ drying oven for 18 h. And (3) placing the liquid phase product in a separating funnel, extracting with a saturated NaCl solution to obtain an upper oil phase, and removing trace water and glycerol by using an excessive anhydrous sodium sulfate reagent. The liquid phase product was then placed in a vacuum rotary evaporator and first evaporated to dryness at 45.5 ℃ at 100r/min (the solvent ethyl acetate was removed). Subsequently, absolute ethyl alcohol is added into the flask, the flask is placed in an ultrasonic oscillator to be vibrated for 3-7min, and after the dissolution is finished, the solution is taken out by a disposable pipette and filtered once by an organic filter head (the absolute ethyl alcohol insoluble product is separated). The absolute ethanol soluble product was then collected for qualitative and quantitative analysis of the product. Thus obtaining the guaiacol and the derivative products thereof.
The calculation shows that the conversion rate of lignin is over 49 percent, the selectivity of the monomer guaiacol and the derivatives thereof is over 64 percent, and the yield is over 31 percent.
In conclusion, the method adopts a biochar carrier, and commercially available nickel nitrate and cerium nitrate adopt a co-impregnation method to prepare a solid acid catalyst in a high-temperature calcination mode under an inert atmosphere, the prepared catalyst and lignin are placed in an intermittent high-pressure reaction kettle, 30ml of crude glycerol is added, the catalytic depolymerization reaction of the lignin is carried out at a certain temperature, and the aim of directionally and selectively generating the guaiacol and the derivatives thereof is fulfilled by controlling the reaction temperature, the reaction pressure and the reaction time, wherein the lignin is bamboo lignin, and the catalyst can be recycled for more than 30 times.
The method avoids the problems of equipment corrosion caused by an acid-base homogeneous catalyst, high cost caused by an organic hydrogen supply solvent, complicated products, difficulty in separation, environmental pollution and resource waste, has simple technological operation conditions for directionally and efficiently preparing the guaiacol and the derivatives thereof, uses the crude glycerol as a green solvent, can inhibit the coking of the catalyst, and provides an in-situ hydrogen source.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (8)
1. A production process for directionally preparing guaiacol and derivatives thereof by lignin is characterized in that raw materials for production comprise:
crude glycerol, inert atmosphere, biochar-nickel-cerium solid compound and lignin;
in a system with crude glycerol as a reaction medium and in an inert atmosphere, the guaiacol and the derivatives thereof are prepared by controlling reaction temperature, reaction pressure, reaction time and stirring rate by using biochar-nickel-cerium solid compound as a catalyst and lignin as a reaction substrate.
2. The production process for directionally preparing guaiacol and derivatives thereof by lignin according to claim 1, wherein the production process comprises the following steps:
taking 0.8-1.2 parts by mass of dried lignin, adding 0.1-0.3 part by mass of a catalyst calcined at 700 ℃, adding 26-34 parts by volume of crude glycerol, putting into an intermittent high-pressure reaction kettle, then filling 0.3-0.9MPa of high-purity inert gas, stirring for 15 minutes before heating, wherein the reaction temperature is 260-300 ℃, and the reaction time is 2-7 hours;
and (3) rapidly putting the high-pressure reaction kettle into ice water bath or liquid nitrogen for quenching and cooling after the reaction is finished, quenching the reaction, opening the reaction kettle after the reaction is cooled to normal temperature, and taking out a reaction product by using an ethyl acetate solution:
carrying out suction filtration by using a sand core funnel, separating a solid phase and a liquid phase, and repeatedly washing a solid phase product by using an ethyl acetate solvent for multiple times;
placing the solid product in a drying box at the temperature of 100-;
placing the liquid phase product in a vacuum rotary evaporator, firstly evaporating the liquid phase product to dryness at 39.5-45.5 ℃ under the condition of 100-;
and finally, collecting the absolute ethyl alcohol soluble product to perform qualitative and quantitative analysis on the product.
3. The production process for directionally preparing the guaiacol and the derivatives thereof by the lignin according to claim 2, wherein the crude glycerol is prepared by compounding water and pure glycerol in different volume ratios, wherein the water-oil ratio is 5-9: 1.
4. the process for producing guaiacol and derivatives thereof according to claim 2, wherein said lignin: catalyst: the feeding mass ratio of the crude glycerol is 0.8-1.2: 0.1-0.3: 26 to 34.
5. The process for producing guaiacol and derivatives thereof according to claim 2, wherein the raw material of lignin comprises one or more of kraft lignin, alkali lignin, bamboo lignin.
6. The production process for directionally preparing the guaiacol and the derivatives thereof by the lignin according to claim 2, wherein the inert gas is nitrogen or argon, the reaction temperature is 260-300 ℃, the reaction pressure is 7.0-10.5 MPa, the reaction time is 2-7 h, and the stirring speed is 500-1000 r/min.
7. The production process for directionally preparing guaiacol and derivatives thereof from lignin as claimed in claim 2, wherein the biochar-nickel-cerium composite is prepared by a co-impregnation method by using biochar as a carrier and nickel and cerium as active components, wherein the nickel content is 1-10 wt.% and the cerium content is 1-10 wt.%.
8. The process for producing guaiacol and its derivatives from lignin according to claim 2, wherein the ethyl acetate is a separation and purification solvent, the anhydrous sodium sulfate is a purification reagent, the vacuum rotary evaporation temperature is 39.5-45.5 ℃, and the vacuum rotary evaporation speed is 100-140 rpm.
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| CN202111658196.XA CN114478201A (en) | 2021-12-30 | 2021-12-30 | Production process for directionally preparing guaiacol and derivatives thereof from lignin |
| GB2202545.6A GB2614344B (en) | 2021-12-30 | 2022-02-24 | Method for directional preparation of guaiacol and derivatives thereof from lignin |
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Citations (6)
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| CN103508857A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for depolymerizing lignin into aromatic compounds under conditions of no additional hydrogen |
| US20170189891A1 (en) * | 2014-05-28 | 2017-07-06 | The Board Of Regents For Oklahoma State University | System and method of producing a char support nickel catalyst for use in syngas production |
| CN112191254A (en) * | 2020-08-27 | 2021-01-08 | 安徽理工大学 | Catalyst and method for preparing 2-ethoxyphenol by catalytic depolymerization of lignin |
| CN112973701A (en) * | 2021-03-08 | 2021-06-18 | 安徽理工大学 | Iron-sodium carbon material catalyst and preparation method and application thereof |
| CN113004122A (en) * | 2021-03-16 | 2021-06-22 | 安徽理工大学 | Method for preparing 2, 5-dimethylphenol by selective catalytic conversion of lignin |
| CN114272932A (en) * | 2021-12-31 | 2022-04-05 | 安徽理工大学 | Nickel-cerium biochar catalyst and preparation method and application thereof |
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| CN103739457B (en) * | 2014-02-11 | 2015-07-01 | 厦门大学 | Method for synchronously preparing guaiacol and syringol from bamboo lignin |
| CN113105314B (en) * | 2020-01-13 | 2022-02-18 | 中国科学院化学研究所 | Method for preparing guaiacol by catalyzing lignin to be efficiently converted through Lewis acid |
| CN112979423B (en) * | 2021-02-18 | 2022-06-07 | 陕西科技大学 | Method for preparing guaiacol and phenol by microwave-assisted depolymerization of lignin |
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| CN103508857A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for depolymerizing lignin into aromatic compounds under conditions of no additional hydrogen |
| US20170189891A1 (en) * | 2014-05-28 | 2017-07-06 | The Board Of Regents For Oklahoma State University | System and method of producing a char support nickel catalyst for use in syngas production |
| CN112191254A (en) * | 2020-08-27 | 2021-01-08 | 安徽理工大学 | Catalyst and method for preparing 2-ethoxyphenol by catalytic depolymerization of lignin |
| CN112973701A (en) * | 2021-03-08 | 2021-06-18 | 安徽理工大学 | Iron-sodium carbon material catalyst and preparation method and application thereof |
| CN113004122A (en) * | 2021-03-16 | 2021-06-22 | 安徽理工大学 | Method for preparing 2, 5-dimethylphenol by selective catalytic conversion of lignin |
| CN114272932A (en) * | 2021-12-31 | 2022-04-05 | 安徽理工大学 | Nickel-cerium biochar catalyst and preparation method and application thereof |
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| CHEN, MQ: ""Depolymerization of Lignin to Produce Monophenols and Oligomers Using a Novel Ni/Ce-CNT Catalyst"", 《BIO RESCOURCES》, vol. 13, no. 4, pages 8025 - 8040 * |
| MINGQIANG CHEN，ET AL: ""Lignin depolymerization for aromatic compounds over Ni-Ce/biochar catalyst under aqueous-phase glycerol"", 《APPLIED ENERGY》, vol. 332, no. 15, pages 1 - 18 * |
| 陈明强等。: ""Ni-Cu/海泡石水蒸汽催化重整苯酚乙醇制氢"", 《安徽理工大学学报（自然科学版）》, vol. 37, no. 6, pages 46 - 75 * |
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| GB2614344A (en) | 2023-07-05 |
| GB202202545D0 (en) | 2022-04-13 |
| GB2614344B (en) | 2024-01-03 |
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