CN116004269A - Method for preparing hydrocarbon fuel from light phenol component in lignin depolymerization product - Google Patents
Method for preparing hydrocarbon fuel from light phenol component in lignin depolymerization product Download PDFInfo
- Publication number
- CN116004269A CN116004269A CN202211606920.9A CN202211606920A CN116004269A CN 116004269 A CN116004269 A CN 116004269A CN 202211606920 A CN202211606920 A CN 202211606920A CN 116004269 A CN116004269 A CN 116004269A
- Authority
- CN
- China
- Prior art keywords
- lignin
- hydrocarbon fuel
- light
- lignin depolymerization
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a method for preparing hydrocarbon fuel from light phenol components in lignin depolymerization products, and belongs to the technical field of biomass liquid fuel preparation. The method for preparing the hydrocarbon fuel from the lignin depolymerization product realizes the efficient extraction and the efficient hydrodeoxygenation of the light phenol components in the lignin depolymerization product to prepare the hydrocarbon fuel, has simple operation and easy realization, ensures that the extraction rate of the light phenol components can reach 92% at most, and basically does not contain the medium phenol components and the heavy phenol components in the extracted solution. The Ru/C catalyst treated by the phosphotungstic acid provided by the invention combines the special physicochemical characteristics of the phosphotungstic acid and the carbon carrier, and obtains the strong interaction between the metal component and the acid component. The catalyst has high hydrodeoxygenation reaction activity and good selectivity of hydrocarbon fuel products. In the evaluation of catalytic activity, the conversion rate of the light phenol component is close to 100%, and the highest percentage of hydrocarbon fuel can reach 88.9%.
Description
Technical Field
The invention relates to the technical field of biomass liquid fuel preparation, in particular to a method for preparing hydrocarbon fuel from light phenol components in lignin depolymerization products.
Background
Biomass energy is widely distributed in nature and renewable, and compared with petroleum resources, the biomass energy has the advantages of remarkably reducing the net emission of carbon dioxide and having huge potential in global energy supply. Meanwhile, as the agricultural large country, the annual average yield of biomass resources can reach 8.25 hundred million tons, and the objective requirement of greatly developing biomass energy is met. However, currently a large amount of biomass resources are not utilized efficiently. For example, the straw accounts for about 52% of the total biomass resources, but only 40% of the straw resources are recycled, and the rest of the straw is directly burned in the open air. This not only hinders the effective utilization of biomass resources, but also severely jeopardizes the natural environment. Biomass is considered as a carbon neutral resource, and large-scale recycling is helpful to realize the aim of reducing carbon, and the biomass can be used for preparing liquid fuel and chemicals to realize high-value application. As an important component of biomass resources, lignocellulosic biomass (including hardwood, softwood, gramineous plants, etc.) is the most potential feedstock for sustainable production of biofuels and bio-derived chemicals. Lignocellulose is a complex and valuable polymer, the main components of which include cellulose, hemicellulose and lignin. The cellulose and hemicellulose have relatively simple structures, the industrial scale utilization is realized partially, important chemicals and fuels such as 5-hydroxymethyl furfural, fuel ethanol and the like can be prepared, the lignin has a complex structure and is very stable, the conversion and utilization difficulties are high, and the lignin is generally used as a byproduct to be directly discarded or burnt off in industry, so that great waste is caused. Lignin is a complex three-dimensional high polymer formed by random bonding of three phenylpropane structural monomers (p-hydroxyphenol H unit, guaiacyl G unit and syringyl S unit) through C-O bond and C-C bond, and is the only renewable resource which exists in nature and can directly provide benzene rings. The benzene ring structure has high carbon content and high combustion heat value, and lignin has great potential for producing high-quality liquid fuel.
Lignin is of a large relative molecular weight and requires first depolymerization to relatively low molecular weight compounds for conversion to high quality liquid fuels. Lignin depolymerization mainly involves two methods: one is a chemical process and the other is a biological process. The biological depolymerization is to break the connection between lignin molecules by using auxiliaries such as enzyme, is environment-friendly and has high selectivity of target products, but has long reaction time and easy inactivation, and is difficult to be widely used in industrial production. In contrast, the chemical method has the advantages of high reaction rate, small environmental requirement and great advantage for industrial production. The liquid phase catalytic depolymerization method in the chemical method can realize the efficient depolymerization of lignin under a relatively mild condition due to the participation of a liquid phase solvent, so as to obtain the light phenol component with high yield. However, lignin depolymerization products from lignin liquid phase catalytic depolymerization processes are dissolved in a solvent and need to be extracted from the solvent if further upgrading is desired. In addition, lignin depolymerization products dissolved in the solvent comprise a medium phenol component and a heavy phenol component in addition to the light phenol component, and the medium phenol component and the heavy phenol component have relatively complex structures, unstable physicochemical properties, high utilization difficulty and can be mixed with the light phenol component to negatively influence the extraction and utilization of the light phenol component. Patent (CN 106753549B) proposes a method of extracting light phenol components from biological oil by combining rotary distillation with ethyl acetate extraction, but the process has high energy consumption, and the extraction process is complex, so that the loss of the light phenol components is unavoidable.
The light phenolic component in the lignin depolymerization product contains a certain amount of oxygen elements and unsaturated functional groups, and further upgrading is required for high-quality liquid fuel, and hydrodeoxygenation is the most common upgrading method. Hydrodeoxygenation catalysts are of a wide variety, and earlier have been studied as catalysts with metal sulfides as the active phase, including molybdenum sulfide, cobalt sulfide, and the like. Such catalysisThe catalyst generally needs to continuously add hydrogen sulfide gas into a reaction system to maintain the metal in a vulcanized state, the operation is complex, and the introduction of sulfur element also pollutes the prepared liquid fuel. The supported transition metal catalyst also has a good hydrodeoxygenation effect, wherein the nickel-based catalyst is widely used, and can realize complete hydrodeoxygenation of the oxygen-containing compound under relatively mild conditions. Noble metals have higher catalytic activities of hydrogen adsorption and hydrogen dissociation than transition metals, and have better hydrodeoxygenation reaction effects. The patent (CN 102676201A) proposes that various supported metal/solid acid catalysts are used for hydrodeoxygenation of biological oil, and the hydrodeoxygenation reaction needs to have good effect under relatively high temperature conditions (more than 250 ℃) because the activity of metal components and acid components in the catalyst is low and the interaction between the metal components and the acid components is weak. From the point of view of the metal component, patent (CN 109971505A) proposes Ru/TiO using highly dispersed Ru metal 2 The catalyst promotes the reaction effect of hydrodeoxygenation. However, hydrodeoxygenation catalysts play an important role in addition to the metal component, also in the acid component, wherein the removal of oxygen is very dependent on the catalytic action of the acid component. The metal component and the acid component are coupled together to prepare the bifunctional catalyst, so that the hydrodeoxygenation effect of the hydrodeoxygenation catalyst can be improved to a certain extent. The existing bifunctional catalyst mainly takes a load type as a main component, the interaction between a metal component and an acid component is weak, and the synergistic effect of the metal component and the acid component is difficult to fully develop.
The light phenol component in the lignin depolymerization product can be subjected to hydrodeoxygenation to obtain hydrocarbon compounds with carbon numbers between C6 and C10, vapor pressure and carbon number distribution are similar to those of gasoline components, and the octane number is quite high, so that the lignin depolymerization product is an ideal transportation fuel component. Lignin depolymerization products obtained by a liquid-phase catalytic depolymerization method of lignin not only contain light phenolic components, but also contain medium phenolic components and heavy phenolic components. The medium phenol component and the heavy phenol component are easy to generate polycondensation reaction in the hydrodeoxygenation process, and the deactivation is initiated by carbon deposition on the surface of the catalyst, so that the hydrodeoxygenation reaction is negatively influenced. The light phenol component is extracted from the complex lignin depolymerization product and then hydrodeoxygenation is carried out, so that the quality of liquid fuel can be improved, and the deactivation of a polycondensation-induced catalyst of the complex lignin depolymerization product can be prevented. In the patent (CN 109971505 a), the light phenol component is extracted by an organic solvent extraction method such as n-octane, however, the medium phenol component and the light phenol component have similar physical and chemical characteristics, are difficult to separate thoroughly, and the heavy phenol component is more or less doped with the light phenol component, which negatively affects the subsequent hydrodeoxygenation quality improvement.
Therefore, the light phenol components are thoroughly and efficiently separated from lignin depolymerization products, and the method has great significance for subsequent efficient hydrodeoxygenation.
Disclosure of Invention
The invention provides a method for preparing hydrocarbon fuel from light phenol components in lignin depolymerization products, which aims to solve the problems in the prior art.
In order to achieve the above object, an embodiment of the present invention provides a method for preparing hydrocarbon fuel from light phenolic components in lignin depolymerization products, comprising the steps of:
s1, adding water into a lignin depolymerization product, stirring and mixing, adding n-octane, performing ultrasonic treatment, standing and layering to separate the n-octane, and obtaining a solution containing light phenolic components in the lignin depolymerization product;
s2, putting the solution containing the light phenol components in the lignin depolymerization product into a high-temperature high-pressure reaction kettle, and adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction to obtain hydrocarbon fuel;
the specific process for treating the Ru/C catalyst by the phosphotungstic acid comprises the following steps: mixing Ru/C catalyst with phosphotungstic acid, heating while stirring until the phosphotungstic acid is melted, cooling, transferring into a tube furnace, calcining and reducing reaction, and cooling to obtain Ru/C catalyst after phosphotungstic acid treatment.
Further, the Ru/C catalyst is 0.1g5wt%, and the phosphotungstic acid is 10-30 wt%.
Further, the calcination reduction reaction conditions are as follows: calcining and reducing for 4 hours at 500 ℃ under the hydrogen atmosphere at the flow rate of 10 mL/min.
Further, the hydrocarbon fuel component includes one or more of naphthenes, alkyl naphthenes, benzene and alkylbenzenes.
Further, in the step S1, the ultrasonic time is 5-10 min.
Further, the reaction conditions in the step S2: the temperature is 220 ℃ to 240 ℃ and the reaction time is 4 hours, and the pressure is 1MPa under the hydrogen atmosphere.
Further, the volume ratio of the lignin depolymerization product to water is 4:4-4:8; the volume ratio of the lignin depolymerization product to the n-octane is 4:4-4:8.
Further, adding lignin raw materials into ethanol solution, adding NiCo/C catalyst, mixing uniformly, putting into a high-temperature high-pressure reaction kettle for reaction, and filtering to obtain lignin depolymerization products.
Further, the lignin raw material comprises at least one of industrial lignin, organic solvent lignin, alkali lignin and sulfonate lignin.
Further, the reaction conditions are as follows: the pressure is 3MPa, the mixture is heated to 260 ℃ under the hydrogen atmosphere, and the reaction time is 4 hours.
The invention adopts the following method to evaluate the catalytic performance: 20mL of normal octane solution for extracting light phenol components and 0.1g of Ru/C catalyst treated by phosphotungstic acid are added into a high-temperature high-pressure reaction kettle made of 50mL of 316L material, and the mixture is reacted for 4 hours under the condition of 240 ℃ and 1MPa of hydrogen atmosphere. The conversion rate of the light phenol component is close to 100%, and the highest selectivity of the hydrocarbon fuel can reach 83.9% through testing.
The scheme of the invention has the following beneficial effects:
(1) The invention provides a method for preparing hydrocarbon fuel from lignin depolymerization products, which realizes high-efficiency extraction and high-efficiency hydrodeoxygenation of light phenol components in lignin depolymerization products to prepare hydrocarbon fuel;
(2) The high-efficiency extraction of the light phenol components in the lignin depolymerization product is simple to operate and easy to realize, the highest extraction rate of the light phenol components can reach 92%, and the extracted solution basically does not contain medium phenol components and heavy phenol components;
(3) The Ru/C catalyst treated by the phosphotungstic acid provided by the invention combines the special physicochemical characteristics of the phosphotungstic acid and the carbon carrier, and obtains the strong interaction between the metal component and the acid component. The catalyst has high hydrodeoxygenation reaction activity and good selectivity of hydrocarbon fuel products. In the evaluation of catalytic activity, the conversion rate of the light phenol component is close to 100%, and the highest percentage of hydrocarbon fuel can reach 88.9%.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained from these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a transmission electron micrograph of a Ru/C catalyst treated with phosphotungstic acid obtained in example 1 of the invention and an elemental distribution diagram thereof;
FIG. 2 is a GC-MS spectrum before and after hydrodeoxygenation of the light phenolic fraction extracted in example 5 of the present invention, wherein FIG. 2a is before hydrodeoxygenation and FIG. 2b is after hydrodeoxygenation.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The invention provides a method for preparing hydrocarbon fuel by light phenol components in lignin depolymerization products.
The lignin depolymerization products were prepared as follows: adding a certain lignin raw material (including industrial lignin, organic soluble lignin, alkali lignin, sulfonate lignin and the like) into an ethanol solution, adding a NiCo/C catalyst, uniformly mixing, putting into a high-temperature high-pressure reaction kettle, filling 3MPa hydrogen, heating to 260 ℃, reacting for 4 hours (the reaction conditions are shown in reference materials Fuel,2023,333,126357.), filtering the reaction mixture after the reaction is finished, and collecting a liquid lignin depolymerization product. Lignin depolymerization products mainly consist of light phenolic components, medium phenolic components and heavy phenolic components, wherein the medium phenolic components and the heavy phenolic components have complex structures and are difficult to further convert into hydrocarbon fuels.
Example 1
(1) Taking lignin depolymerization products as raw materials, adding a certain amount of water, stirring for 5min, fully mixing, adding n-octane, performing ultrasonic treatment for 10min, and finally transferring to a separating funnel, standing and layering to separate n-octane, thereby obtaining an n-octane solution with light phenolic components extracted;
(2) Putting 20mL of the n-octane solution of the light phenolic component obtained in the step (1) into a 50mL high-temperature high-pressure reaction kettle, adding a Ru/C catalyst (see a transmission electron microscope photo and an element distribution diagram shown in figure 1) subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction, wherein the phosphotungstic acid loading amount of the catalyst is 20wt%, the catalyst consumption is 0.1g, the reaction temperature is 220 ℃, the reaction time is 4h, and the hydrogen pressure is 1MPa, so as to obtain the hydrocarbon liquid fuel.
Example 2
(1) Taking lignin depolymerization products as raw materials, adding a certain amount of water, stirring for 5min to fully mix, adding n-octane, performing ultrasonic treatment for 10min, and finally transferring to a separating funnel for standing and layering to separate n-octane, wherein the volume ratio of water to the raw materials is 4:4, so as to obtain an n-octane solution with light phenolic components extracted;
(2) Putting 20mL of the n-octane solution of the light phenolic component obtained in the step (1) into a 50mL high-temperature high-pressure reaction kettle, adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction, wherein the phosphotungstic acid loading amount of the catalyst is 20wt%, the catalyst dosage is 0.1g, the reaction temperature is 220 ℃, the reaction time is 4 hours, and the hydrogen pressure is 1MPa, so as to obtain the hydrocarbon liquid fuel.
Example 3
(1) Taking lignin depolymerization products as raw materials, adding a certain amount of water, stirring for 5min to fully mix, adding n-octane, performing ultrasonic treatment for 10min, and finally transferring to a separating funnel for standing and layering to separate n-octane, wherein the volume ratio of water to the raw materials is 4:4, and the n-octane solution with light phenolic components extracted is obtained;
(2) Putting 20mL of the n-octane solution of the light phenolic component obtained in the step (1) into a 50mL high-temperature high-pressure reaction kettle, adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction, wherein the phosphotungstic acid loading amount of the catalyst is 20wt%, the catalyst dosage is 0.1g, the reaction temperature is 220 ℃, the reaction time is 4 hours, and the hydrogen pressure is 1MPa, so as to obtain the hydrocarbon liquid fuel.
Example 4
(1) Taking lignin depolymerization products as raw materials, adding a certain amount of water, stirring for 5min to fully mix, adding n-octane, performing ultrasonic treatment for 10min, and finally transferring to a separating funnel for standing and layering to separate n-octane, wherein the volume ratio of water to the raw materials is 6:4, and the n-octane solution with light phenolic components extracted is obtained;
(2) Putting 20mL of the n-octane solution of the light phenolic component obtained in the step (1) into a 50mL high-temperature high-pressure reaction kettle, adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction, wherein the phosphotungstic acid loading amount of the catalyst is 20wt%, the catalyst dosage is 0.1g, the reaction temperature is 220 ℃, the reaction time is 4 hours, and the hydrogen pressure is 1MPa, so as to obtain the hydrocarbon liquid fuel.
Example 5
(1) Taking lignin depolymerization products as raw materials, adding a certain amount of water, stirring for 5min, fully mixing, adding n-octane, performing ultrasonic treatment for 10min, and finally transferring to a separating funnel, standing and layering to separate n-octane, thereby obtaining an n-octane solution with light phenolic components extracted;
(2) Taking 20mL of the light phenol component (see figure 2, GC-MS spectra before and after hydrodeoxygenation, wherein figure 2a is before hydrodeoxygenation, and figure 2b is after hydrodeoxygenation) obtained in the step (1), putting the n-octane solution into a 50mL high-temperature high-pressure reaction kettle with the concentration of 316L, adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction, wherein the phosphotungstic acid loading amount of the catalyst is 20wt%, the catalyst consumption is 0.1g, the reaction temperature is 220 ℃, the reaction time is 4h, and the hydrogen pressure is 1MPa, so as to obtain the hydrocarbon liquid fuel.
Example 6
(1) Taking lignin depolymerization products as raw materials, adding a certain amount of water, stirring for 5min, fully mixing, adding n-octane, performing ultrasonic treatment for 5min, and finally transferring to a separating funnel, standing and layering to separate n-octane, thereby obtaining an n-octane solution with light phenolic components extracted;
(2) Putting 20mL of the n-octane solution of the light phenolic component obtained in the step (1) into a 50mL high-temperature high-pressure reaction kettle, adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction, wherein the phosphotungstic acid loading amount of the catalyst is 30wt%, the catalyst dosage is 0.1g, the reaction temperature is 220 ℃, the reaction time is 4 hours, and the hydrogen pressure is 1MPa, so as to obtain the hydrocarbon liquid fuel.
Example 7
(1) Taking lignin depolymerization products as raw materials, adding a certain amount of water, stirring for 5min, fully mixing, adding n-octane, performing ultrasonic treatment for 5min, and finally transferring to a separating funnel, standing and layering to separate n-octane, thereby obtaining an n-octane solution with light phenolic components extracted;
(2) Putting 20mL of the n-octane solution of the light phenolic component obtained in the step (1) into a 50mL high-temperature high-pressure reaction kettle, adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction, wherein the phosphotungstic acid loading amount of the catalyst is 30wt%, the catalyst dosage is 0.1g, the reaction temperature is 240 ℃, the reaction time is 4 hours, and the hydrogen pressure is 1MPa, so as to obtain the hydrocarbon liquid fuel.
Comparative example 1
(1) Taking lignin depolymerization products as raw materials, adding n-octane, wherein the volume ratio of the n-octane to the raw materials is 4:4, carrying out ultrasonic treatment for 10min, and finally transferring to a separating funnel for standing and layering to separate the n-octane, so as to obtain an n-octane solution with light phenolic components extracted;
(2) Putting 20mL of the n-octane solution of the light phenolic component obtained in the step (1) into a 50mL high-temperature high-pressure reaction kettle, adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction, wherein the phosphotungstic acid loading amount of the catalyst is 20wt%, the catalyst dosage is 0.1g, the reaction temperature is 220 ℃, the reaction time is 4 hours, and the hydrogen pressure is 1MPa, so as to obtain the hydrocarbon liquid fuel.
Comparative example 2
(1) Taking lignin depolymerization products as raw materials, adding a certain amount of water, stirring for 5min, fully mixing, adding n-octane, performing ultrasonic treatment for 10min, and finally transferring to a separating funnel, standing and layering to separate n-octane, thereby obtaining an n-octane solution with light phenolic components extracted;
(2) Putting 20mL of the n-octane solution of the light phenolic component obtained in the step (1) into a high-temperature and high-pressure reaction kettle with the volume of 50mL of 316L, adding 0.05g of Ru/C catalyst and 0.05g of Al 2 O 3 The solid acid consumption is 0.05g, the hydrodeoxygenation reaction is carried out, the reaction temperature is 220 ℃, the reaction time is 4 hours, and the hydrogen pressure is 1MPa, so that the hydrocarbon liquid fuel is obtained.
Example 8
The amounts of the light phenolic components before and after the extraction of the n-octane solutions of comparative examples 1 to 2, examples 1 to 7, and step (1) in which the light phenolic components were extracted were characterized by GC-MS. The light phenol component in the lignin depolymerization product is extracted, the light phenol component in the n-octane is extracted, and the extraction rate is calculated by the ratio of the sum of the peak areas of the light phenol components.
As shown in Table 1, the extraction rate of the light phenol components in examples 1 to 7 was as high as 92%. From the comparison effect of comparative example 1 and example 1, it can be seen that the water added has an accelerating effect on the extraction of the light phenolic component, and the extraction rate is increased from 62% to 69%.
TABLE 1 extraction yield of light phenolic Components from lignin depolymerization products
Example 9
The amounts of hydrocarbon fuels before and after hydrodeoxygenation of the n-octane solutions from which the light phenolic components were extracted in steps (1) of comparative examples 1 to 2, examples 1 to 7 were characterized by GC-MS, and the hydrocarbon fuel components included one or more of naphthenes, alkylnaphthenes, benzene and alkylbenzenes. The percentage of the peak area of each compound of the hydrocarbon fuel in the chromatogram to the total peak area of all compounds represents the percentage of the hydrocarbon fuel.
As shown in Table 2, the percentage of hydrocarbon fuel obtained by hydrodeoxygenation reaction of the light phenol component n-octane solutions obtained in steps 1 to 7 of the present invention was increased, and the percentage of hydrocarbon fuel was as high as 88.9%. From the comparison of comparative example 1 and example 1, the percentage of hydrocarbon fuel obtained after hydrodeoxygenation reaction of the light phenol component with water extraction is 9.4% higher than that without water extraction, which is mainly because the light phenol component with water extraction does not substantially contain medium phenol component and heavy phenol component, and does not negatively affect hydrodeoxygenation reaction, thus embodying the advancement and innovation of the invention. From the comparison effect of comparative example 2 and example 1, the Ru/C catalyst hydrodeoxygenation effect after phosphotungstic acid treatment provided by the invention is better than that of Ru/C coupling Al conventionally used 2 O 3 The catalyst is mainly characterized in that the Ru/C catalyst after the phosphotungstic acid treatment provided by the invention combines the special physicochemical characteristics of the phosphotungstic acid and the carbon carrier, so that the strong interaction between the metal component and the acid component is obtained, and the hydrodeoxygenation reaction activity is greatly improved, which is incomparable with the conventional bifunctional catalyst, and the advancement and innovation of the catalyst are also embodied.
Table 2 shows the percentage of hydrocarbon fuel before and after hydrodeoxygenation
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A process for producing a hydrocarbon fuel from light phenolic components in a lignin depolymerization product comprising the steps of:
s1, adding water into a lignin depolymerization product, stirring and mixing, adding n-octane, performing ultrasonic treatment, standing and layering to separate the n-octane, and obtaining a solution containing light phenolic components in the lignin depolymerization product;
s2, putting the solution containing the light phenol components in the lignin depolymerization product into a high-temperature high-pressure reaction kettle, and adding a Ru/C catalyst subjected to phosphotungstic acid treatment for hydrodeoxygenation reaction to obtain hydrocarbon fuel;
the specific process for treating the Ru/C catalyst by the phosphotungstic acid comprises the following steps: mixing Ru/C catalyst with phosphotungstic acid, heating while stirring until the phosphotungstic acid is melted, cooling, transferring into a tube furnace, calcining and reducing reaction, and cooling to obtain Ru/C catalyst after phosphotungstic acid treatment.
2. The method for producing hydrocarbon fuel from light phenolic components in lignin depolymerization products according to claim 1 wherein the Ru/C catalyst is 0.1g5wt% and phosphotungstic acid is 10 to 30wt%.
3. The method for producing hydrocarbon fuel from light phenolic components in lignin depolymerization products according to claim 1 wherein the calcination reduction reaction conditions are: calcining and reducing for 4 hours at 500 ℃ under the hydrogen atmosphere at the flow rate of 10 mL/min.
4. The method for producing hydrocarbon fuel from light phenolic components in lignin depolymerization products according to claim 1 wherein the hydrocarbon fuel component comprises one or more of naphthenes, alkyl naphthenes, benzene and alkylbenzenes.
5. The method for preparing hydrocarbon fuel from light phenolic components in lignin depolymerization products according to claim 1 wherein the ultrasonic time in step S1 is 5-10 min.
6. The method for preparing hydrocarbon fuel from light phenolic components in lignin depolymerization products according to claim 1 wherein the reaction conditions in step S2: the temperature is 220 ℃ to 240 ℃ and the reaction time is 4 hours, and the pressure is 1MPa under the hydrogen atmosphere.
7. The method for producing hydrocarbon fuel from light phenolic components in lignin depolymerization products according to claim 1 wherein the volume ratio of lignin depolymerization products to water is 4:4 to 4:8; the volume ratio of the lignin depolymerization product to the n-octane is 4:4-4:8.
8. The method for preparing hydrocarbon fuel from light phenol components in lignin depolymerization products according to claim 1, wherein lignin raw materials are added into ethanol solution, a NiCo/C catalyst is added, and after uniform mixing, the mixture is put into a high-temperature high-pressure reaction kettle to react, and filtered, so that lignin depolymerization products are obtained.
9. The method for producing hydrocarbon fuel from light phenolic components in lignin depolymerization products according to claim 8, wherein the lignin feedstock comprises at least one of industrial lignin, organosolv lignin, alkali lignin, sulfonate lignin.
10. The method for producing hydrocarbon fuel from light phenolic components in lignin depolymerization products according to claim 8 wherein the reaction conditions are: the pressure is 3MPa, the mixture is heated to 260 ℃ under the hydrogen atmosphere, and the reaction time is 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211606920.9A CN116004269A (en) | 2022-12-14 | 2022-12-14 | Method for preparing hydrocarbon fuel from light phenol component in lignin depolymerization product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211606920.9A CN116004269A (en) | 2022-12-14 | 2022-12-14 | Method for preparing hydrocarbon fuel from light phenol component in lignin depolymerization product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116004269A true CN116004269A (en) | 2023-04-25 |
Family
ID=86031134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211606920.9A Pending CN116004269A (en) | 2022-12-14 | 2022-12-14 | Method for preparing hydrocarbon fuel from light phenol component in lignin depolymerization product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116004269A (en) |
-
2022
- 2022-12-14 CN CN202211606920.9A patent/CN116004269A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shu et al. | A review on the catalytic hydrodeoxygenation of lignin-derived phenolic compounds and the conversion of raw lignin to hydrocarbon liquid fuels | |
| Xue et al. | A review on the operating conditions of producing bio‐oil from hydrothermal liquefaction of biomass | |
| CN103620002B (en) | The hydro-thermal hydrogenation catalyst process of biomass | |
| Qamar et al. | Feasibility-to-applications of value-added products from biomass: Current trends, challenges, and prospects | |
| CN104955922B (en) | Apply water-fast catalyst that biomass by hydro-thermal hydrogenation catalyst is processed | |
| CN107602362A (en) | The method that molybdenum oxide catalyst Catalytic lignin prepares single phenols aromatic compound | |
| Li et al. | Towards the development of a novel “bamboo-refinery” concept: selective bamboo fractionation by means of a microwave-assisted, acid-catalysed, organosolv process | |
| Shen et al. | The hydrochar activation and biocrude upgrading from hydrothermal treatment of lignocellulosic biomass | |
| Nayak et al. | Novel strategies for glucose production from biomass using heteropoly acid catalyst | |
| CN113117688A (en) | MOF precursor molybdenum-nickel catalyst, preparation method thereof and application thereof in lignin degradation | |
| CN112973701B (en) | Iron-sodium carbon material catalyst and preparation method and application thereof | |
| CN102040483A (en) | Method for producing aryl compound by using lignin | |
| CN105037103B (en) | A kind of method of the efficient depolymerization of lignin | |
| CN109647441A (en) | A kind of monatomic catalyst adds the application in hydrogen aromatic compound in catalytic lignin | |
| Yue et al. | Upgrading of reed pyrolysis oil by using its biochar-based catalytic esterification and the influence of reed sources | |
| CN113145147A (en) | Supported molybdenum carbide catalyst, preparation method thereof and application of catalyst in selective production of phenol monomers by depolymerizing lignin | |
| Guo et al. | Integrated biorefinery of bamboo for fermentable sugars, native-like lignin, and furfural production by novel deep eutectic solvents treatment | |
| Yang et al. | The catalytic hydrodeoxygenation of bio-oil for upgradation from lignocellulosic biomass | |
| Liu et al. | Conversion of waste water hyacinth into high-value chemicals by iron (III) chloride under mild conditions | |
| Guo et al. | Lignin to value-added products: Research updates and prospects | |
| Rishikesh et al. | A comprehensive review on lignin obtained from agro-residues: Potential source of useful chemicals | |
| He et al. | Bio-oil upgrading via ether extraction, looped-oxide catalytic deoxygenation, and mild electrocatalytic hydrogenation techniques | |
| CN109364925A (en) | A kind of catalysis phenolic compound hydrogenation deoxidation prepares catalyst of cycloalkane and preparation method thereof | |
| CN101544910B (en) | Method for modifying bio-oil through in-situ reduction reaction and esterification reaction | |
| CN103484158B (en) | Method for preparing chemicals containing phenols and aromatic hydrocarbons from bio-oil pyrolysis lignin through catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |