CN113042056B - Method for catalyzing cellulose to be directionally converted into composite carbon source by using nickel-doped copper-aluminum hydrotalcite catalyst - Google Patents
Method for catalyzing cellulose to be directionally converted into composite carbon source by using nickel-doped copper-aluminum hydrotalcite catalyst Download PDFInfo
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- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention provides a method for catalyzing cellulose to be directionally converted into a composite carbon source by a nickel-doped copper-aluminum hydrotalcite catalyst, wherein the catalyst is a trimetal mixed oxide catalyst, copper-aluminum hydrotalcite is taken as a framework, nickel atoms are positioned on a specific copper-aluminum laminate structure, and the catalyst has rich acidic and alkaline catalytic sites. The nickel-doped copper-aluminum hydrotalcite catalyst can be used for catalyzing cellulose to be directionally converted into a composite carbon source (crude methanol, levoglucosenone and carboxylic acid are obtained by recycling). The nickel-doped copper-aluminum hydrotalcite catalyst provided by the invention has a simple preparation process, is beneficial to industrialization, and has the advantages of complete crystalline phase structure, multiple acid-base catalytic sites, high catalytic efficiency, strong anti-coking performance and good stability; the catalyst can realize the function of directionally converting into the composite carbon source when catalyzing the pyrolysis of cellulose, and improves the yield and the product value of the composite carbon source.
Description
Technical Field
The invention belongs to the technical field of novel industrial catalytic assistants, and particularly relates to a method for catalyzing cellulose to be directionally converted into a composite carbon source by a nickel-doped copper-aluminum hydrotalcite catalyst.
Background
Among various renewable energy sources, nuclear energy and large-scale hydropower have potential ecological environment risks, and regional resource restrictions such as wind energy and geothermal heat are limited and questioned in vigorous development, while biomass energy is accepted by people due to the characteristics of universality, richness, renewability and the like. The uniqueness of biomass is not only that it stores solar energy, but also that it is a renewable carbon source that can be converted into conventional solid, liquid, gaseous fuels, coal, oil, natural gas, etc. energy sources, which are substantially converted from biomass energy. The biomass energy is an important component of renewable energy, and the efficient development and utilization of the biomass energy play a very positive role in solving the problems of energy and ecological environment. Since the 70 s of the 20 th century, countries in the world, especially economically developed countries, pay high attention to the technology and actively develop researches on biomass energy application, and a lot of research achievements are obtained, so that the industrial application scale is achieved.
China has wide biomass distribution and quite abundant resources, wherein the total sowing area of crops such as rice, corn, wheat and the like reaches 1.67 hundred million hectares, and crop straw resources with the quantity which is several times larger than the grain yield are generated. However, a large amount of biomass energy including crop straws, wood chips and the like is wasted and not effectively utilized. At present, the main waste treatment modes of plastics comprise landfill, incineration and the like, and the waste of resource and energy and the pressure on the natural environment are caused under the era background of global energy shortage. Corn stalks, which are one of the most biomass solid wastes in the north, contain a large amount of carbonaceous organic matters, and the preparation of methanol by fast catalytic and fast pyrolysis of the corn stalks is one of the treatment modes with great development prospects. The catalytic fast pyrolysis is based on the original biomass fast pyrolysis process, a catalyst is added in the thermochemical conversion process, the recovery of specific products and the high recovery rate of the products in the biomass thermal cracking process are realized, and thus the possibility of one-stage type from biomass raw materials to high-value chemicals is realized.
In Chinese patent databases, patents relating to biomass pyrolysis, catalyst preparation and application include integrated method for preparing carbon-based composite material by straw carbon-based catalytic pyrolysis with patent publication number CN112063400A, method for preparing monocyclic aromatic hydrocarbon by pyrolyzing ruthenium modified molecular sieve catalytic cellulose with patent publication number CN112010725A, catalyst modification method for improving yield of hydrocarbons by catalytic pyrolysis of biomass with patent publication number CN112007687A, preparation method of MOF framework catalyst for catalytic pyrolysis of biomass with patent publication number CN111939980A, and the like. Meanwhile, although the catalysts used in the prior art, such as zeolite molecular sieves, alumina, copper catalysts and the like, obtain better methanol yield, the methanol quality is lower, the methanol contains more other condensable gases, and the catalysts are lower in stability and easy to coke and deactivate. Therefore, the improvement of the preparation method, the improvement of the product phase and the development of the catalyst of the acid-base double activity center have important significance for improving the biomass pyrolysis mechanism.
Disclosure of Invention
The invention provides a nickel-doped copper-aluminum hydrotalcite catalyst, which has the advantages of simple preparation process, contribution to industrialization, complete crystal phase structure, more acid-base catalytic sites, high catalytic efficiency, strong coking resistance and good stability; the catalyst can realize the function of directionally converting into the composite carbon source when catalyzing the pyrolysis of cellulose, and improves the yield and the product value of the composite carbon source.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
a nickel-doped copper-aluminum hydrotalcite catalyst is a three-metal mixed oxide catalyst, copper-aluminum hydrotalcite is used as a framework, and nickel atoms are positioned on a specific copper-aluminum laminate structure and have abundant acidic and alkaline catalytic sites; the nickel-doped copper-aluminum hydrotalcite catalyst is prepared by the following method:
(1) dissolving nickel nitrate, copper nitrate and aluminum nitrate in water under the stirring condition to prepare a metal salt mixed solution A, wherein the molar ratio of the copper nitrate to the aluminum nitrate is 1: 1-3: 1, and the ratio of the total molar weight of the copper nitrate and the aluminum nitrate to the molar weight of the nickel nitrate is 5: 1-10: 1;
(2) adding an alkali solution into the solution A to adjust the pH value to 9-12, and stirring to prepare a suspension A;
(3) pouring the suspension A into a reaction kettle, crystallizing at 90-120 ℃ for 18-24 h, pouring out reaction liquid after crystallization, centrifuging, washing and drying to obtain a nickel-doped copper-aluminum hydrotalcite precursor;
(4) and calcining the nickel-doped copper-aluminum hydrotalcite precursor at 350-550 ℃ in an oxygen-free environment for 0.5-3 h, and cooling to room temperature after calcination to obtain the nickel-doped copper-aluminum-nickel-doped copper-aluminum hydrotalcite catalyst.
The alkali solution in the step (2) is a sodium hydroxide solution, and the concentration is 0.01-0.05 mol/L.
The reaction kettle in the step (3) is provided with a polytetrafluoroethylene lining.
And (4) the calcining equipment in the step (4) is a tubular furnace.
And (4) the oxygen-free environment in the step (4) is a nitrogen environment.
The nickel-doped copper aluminum hydrotalcite catalyst is used for catalyzing cellulose to be directionally converted into a composite carbon source.
The method for preparing the composite carbon source by directionally transforming the cellulose comprises the following steps:
(1) mixing and grinding a nickel-doped copper-aluminum hydrotalcite catalyst and biomass into particles to obtain a biomass pyrolysis precursor, wherein the mass ratio of the nickel-doped copper-aluminum hydrotalcite catalyst to the biomass is 0.025-0.045;
(2) putting the biomass pyrolysis precursor into a high-pressure reaction kettle, and pyrolyzing under the conditions of 4-6 MPa and 200-300 ℃, wherein the pyrolysis time is 0.2-0.5 h;
(3) and after pyrolysis, condensing and recycling to obtain crude methanol, levoglucosenone and carboxylic acid, namely the composite carbon source.
The biomass in the step (1) is corn straw.
The particle size of the biomass pyrolysis precursor in the step (1) is 20-50 meshes.
Compared with the prior art, the invention has the beneficial effects that: 1. according to the invention, the hydrotalcite precursor is prepared by doping copper and aluminum with metal nickel, and then the nickel-doped copper and aluminum hydrotalcite catalyst is prepared by calcining, so that the preparation process is simple, the industrialization is simple and convenient, and the catalyst is economic and efficient and is suitable for popularization and application; 2. the nickel-doped copper-aluminum hydrotalcite catalyst provided by the invention has the structural characteristics that copper-aluminum hydrotalcite is used as a framework, and nickel atoms are positioned on a copper-aluminum laminate, so that the nickel-doped copper-aluminum hydrotalcite catalyst has the structural characteristics of high specific surface area and more acid central sites, the catalytic efficiency is obviously improved, more alkaline sites adsorb and activate coke gas generated in the pyrolysis process, the coking resistance is excellent, the product value is improved, the stability of the catalyst is also obviously improved, the catalyst can be recycled, and the production cost is reduced; 3. the nickel-doped copper-aluminum hydrotalcite catalyst provided by the invention can promote the directional conversion of cellulose into crude methanol, levoglucosenone and carboxylic acid when being used for cellulose pyrolysis, so that the artificial adjustable effect is achieved, and meanwhile, through the characteristics of the laminate structure and the chemical composition of the nickel-doped copper-aluminum hydrotalcite catalyst, the biomass achieves the effects of short pyrolysis time, high pyrolysis speed and less impurities in the prepared composite carbon source in the pyrolysis process, particularly the yield of methanol and the product phase are improved, so that the utilization rate of the biomass is improved, and the reaction mechanism of biomass pyrolysis is improved.
Drawings
FIG. 1: an XRD (X-ray diffraction) pattern of the nickel-doped copper-aluminum hydrotalcite catalyst obtained in the example 1;
FIG. 2: SEM picture of nickel doped copper aluminum hydrotalcite catalyst obtained in example 1.
Detailed Description
The invention is further described below with reference to the drawings and examples.
Example 1
The method for catalyzing cellulose to be directionally converted into the composite carbon source by the nickel-doped copper aluminum hydrotalcite catalyst in the embodiment comprises the following specific steps:
(1) dissolving nickel nitrate, copper nitrate and aluminum nitrate in water under the stirring condition to prepare a metal mixed salt solution A, wherein the molar ratio of the copper nitrate to the aluminum nitrate in the solution is 1:1, and the ratio of the total molar weight of the copper nitrate and the aluminum nitrate to the molar weight of the nickel nitrate is 5: 1;
(2) dropwise adding a sodium hydroxide solution with the concentration of 0.01mol/L into the solution A, adjusting the pH to 9, and stirring to prepare a suspension A;
(3) pouring the suspension A into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 90 ℃ for 18 hours, transferring out reaction liquid after crystallization is finished, centrifuging, washing and drying to obtain a nickel-doped copper-aluminum hydrotalcite precursor;
(4) placing the nickel-doped copper-aluminum hydrotalcite precursor in a tubular furnace, calcining for 0.5 hour at 350 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain a nickel-doped copper-aluminum hydrotalcite catalyst;
(5) mixing and grinding a nickel-doped copper-aluminum hydrotalcite catalyst and corn straws to 20 meshes according to a mass feed ratio of 25mg (nickel-doped copper-aluminum hydrotalcite catalyst)/g (biomass) to obtain a biomass pyrolysis precursor;
(6) and (2) putting the biomass pyrolysis precursor into a high-pressure reaction kettle, pyrolyzing for 0.2 hour under the reaction conditions of 4MPa and 200 ℃, and condensing and recovering to obtain crude methanol, levoglucosenone and carboxylic acid, wherein the yield of the crude methanol reaches 22.1%, the yield of the levoglucosenone reaches 8.2%, and the yield of the carboxylic acid reaches 5.3%.
Example 2
The method for catalyzing cellulose to be directionally converted into the composite carbon source by the nickel-doped copper aluminum hydrotalcite catalyst in the embodiment comprises the following specific steps:
(1) dissolving nickel nitrate, copper nitrate and aluminum nitrate in water under the stirring condition to prepare a metal mixed salt solution A, wherein the molar ratio of the copper nitrate to the aluminum nitrate in the solution is 2:1, and the ratio of the total molar weight of the copper nitrate and the aluminum nitrate to the molar weight of the nickel nitrate is 6: 1;
(2) dropwise adding a sodium hydroxide solution with the concentration of 0.02mol/L into the solution A, adjusting the pH value to 10, and stirring to prepare a suspension A;
(3) pouring the suspension A into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 100 ℃ for 20 hours, transferring out reaction liquid after crystallization is finished, centrifuging, washing and drying to obtain a nickel-doped copper-aluminum hydrotalcite precursor;
(4) placing the nickel-doped copper-aluminum hydrotalcite precursor in a tubular furnace, calcining for 1 hour at 400 ℃ in a nitrogen atmosphere, and cooling to room temperature to obtain a nickel-doped copper-aluminum hydrotalcite catalyst;
(5) mixing and grinding a nickel-doped copper-aluminum hydrotalcite catalyst and corn straws according to the mass charge ratio of 30mg (nickel-doped copper-aluminum hydrotalcite catalyst)/g (biomass) to 30 meshes to obtain a biomass pyrolysis precursor;
(6) and (2) putting the biomass pyrolysis precursor into a high-pressure reaction kettle, pyrolyzing for 0.3 hour under the reaction conditions of 5MPa and 220 ℃, and condensing and recovering to obtain crude methanol, levoglucosenone and carboxylic acid, wherein the yield of the crude methanol reaches 23.4%, the yield of the levoglucosenone is 8.7%, and the yield of the carboxylic acid is 6.8%.
Example 3
The method for catalyzing cellulose to be directionally converted into the composite carbon source by the nickel-doped copper aluminum hydrotalcite catalyst in the embodiment comprises the following specific steps:
(1) dissolving nickel nitrate, copper nitrate and aluminum nitrate in water under the stirring condition to prepare a metal mixed salt solution A, wherein the molar ratio of the copper nitrate to the aluminum nitrate in the solution is 3:1, and the ratio of the total molar weight of the copper nitrate and the aluminum nitrate to the molar weight of the nickel nitrate is 7: 1;
(2) dropwise adding a sodium hydroxide solution with the concentration of 0.03mol/L into the solution A, adjusting the pH to 11, and stirring to prepare a suspension A;
(3) pouring the suspension A into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 110 ℃ for 22 hours, transferring out reaction liquid after crystallization is finished, centrifuging, washing and drying to obtain a nickel-doped copper-aluminum hydrotalcite precursor;
(4) calcining the nickel-doped copper-aluminum hydrotalcite precursor in a tubular furnace at 450 ℃ for 1.5 hours in a nitrogen atmosphere, and cooling to room temperature to obtain a nickel-doped copper-aluminum hydrotalcite catalyst;
(5) mixing and grinding a nickel-doped copper-aluminum hydrotalcite catalyst and corn straws to 40 meshes according to the mass feed ratio of 35mg (nickel-doped copper-aluminum hydrotalcite catalyst)/g (biomass) to obtain a biomass pyrolysis precursor;
(6) and (2) putting the biomass pyrolysis precursor into a high-pressure reaction kettle, pyrolyzing for 0.4 hour under the reaction conditions of 6MPa and 240 ℃, and condensing and recovering to obtain crude methanol, levoglucosenone and carboxylic acid, wherein the yield of the crude methanol is 24.3%, the yield of the levoglucosenone is 7.9% and the yield of the carboxylic acid is 5.9%.
Example 4
The method for catalyzing cellulose to be directionally converted into the composite carbon source by the nickel-doped copper aluminum hydrotalcite catalyst in the embodiment comprises the following specific steps:
(1) dissolving nickel nitrate, copper nitrate and aluminum nitrate in water under the stirring condition to prepare a metal mixed salt solution A, wherein the molar ratio of the copper nitrate to the aluminum nitrate in the solution is 1:1, and the ratio of the total molar weight of the copper nitrate and the aluminum nitrate to the molar weight of the nickel nitrate is 9: 1;
(2) dropwise adding a sodium hydroxide solution with the concentration of 0.02mol/L into the solution A, adjusting the pH value to 12, and stirring to prepare a suspension A;
(3) pouring the suspension A into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 24 hours at 120 ℃, transferring out reaction liquid after crystallization is finished, centrifuging, washing and drying to obtain a nickel-doped copper-aluminum hydrotalcite precursor;
(4) calcining the nickel-doped copper-aluminum hydrotalcite precursor in a tubular furnace at 500 ℃ for 2.5 hours in a nitrogen atmosphere, and cooling to room temperature to obtain a nickel-doped copper-aluminum hydrotalcite catalyst;
(5) mixing and grinding a nickel-doped copper-aluminum hydrotalcite catalyst and corn straws to 50 meshes according to a mass feed ratio of 40mg (nickel-doped copper-aluminum hydrotalcite catalyst)/g (biomass) to obtain a biomass pyrolysis precursor;
(6) and (2) putting the biomass pyrolysis precursor into a high-pressure reaction kettle, pyrolyzing for 0.4 hour under the reaction conditions of 5MPa and 280 ℃, and condensing and recovering to obtain crude methanol, levoglucosenone and carboxylic acid, wherein the yield of the crude methanol reaches 21.9%, the yield of the levoglucosenone reaches 8.8%, and the yield of the carboxylic acid reaches 5.7%.
Example 5
The method for catalyzing cellulose to be directionally converted into the composite carbon source by the nickel-doped copper aluminum hydrotalcite catalyst in the embodiment comprises the following specific steps:
(1) dissolving nickel nitrate, copper nitrate and aluminum nitrate in water under the condition of stirring to prepare a metal salt mixed solution, wherein the molar ratio of the copper nitrate to the aluminum nitrate in the solution is 2:1, and the ratio of the total molar weight of the copper nitrate and the aluminum nitrate to the molar weight of the nickel nitrate is 10:1, so as to prepare a mixed salt solution A.
(2) Dropwise adding a sodium hydroxide solution with the concentration of 0.01mol/L into the solution A, adjusting the pH to 11, stirring to prepare a suspension A,
(3) pouring the suspension A into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 100 ℃ for 24 hours, transferring out reaction liquid after crystallization is finished, centrifuging, washing and drying to obtain a nickel-doped copper-aluminum hydrotalcite precursor;
(4) and (3) calcining the nickel-doped copper-aluminum hydrotalcite precursor in a tubular furnace at 550 ℃ for 3 hours in a nitrogen atmosphere, and cooling to room temperature to obtain the nickel-doped copper-aluminum-nickel-doped copper-aluminum hydrotalcite catalyst.
(5) Mixing and grinding a nickel-doped copper-aluminum hydrotalcite catalyst and corn straws to 40 meshes according to a mass charge ratio of 45mg (nickel-doped copper-aluminum hydrotalcite catalyst)/g (biomass) to obtain a biomass pyrolysis precursor;
(6) and (2) putting the biomass pyrolysis precursor into a high-pressure reaction kettle, pyrolyzing for 0.5 hour under the reaction conditions of 6MPa and 300 ℃, and condensing and recycling to obtain crude methanol, levoglucosenone and carboxylic acid, wherein the yield of the crude methanol reaches 25.8%, the yield of the levoglucosenone reaches 8.6%, and the yield of the carboxylic acid reaches 6.2%.
The XRD spectrum and SEM spectrum of the nickel-doped copper-aluminum hydrotalcite catalyst prepared in this example 1 are shown in fig. 1 and 2, respectively, and as can be seen from fig. 1 and 2, the nickel-doped copper-aluminum hydrotalcite obtained in example 1 of the present invention has a complete crystal phase structure and uniform crystal grains, and has an obvious diffraction peak of copper-aluminum hydrotalcite in phase composition, and exhibits an obvious layered structure of hydrotalcite.
With the combination of the first to fifth embodiments, the nickel-doped copper-aluminum hydrotalcite catalyst has the characteristics of high specific surface area and acid-base duality due to the structural characteristics that the copper-aluminum hydrotalcite is used as a framework and the nickel atom is located on the copper-aluminum laminate, and has more acidic sites, so that the catalytic efficiency is remarkably improved, more alkaline sites adsorb and activate coke gas generated in the pyrolysis process, and the coking resistance performance is superior, so that the product phase is improved, the stability of the catalyst is also remarkably improved, and the catalyst can be recycled and reused, and the production cost is reduced.
Meanwhile, when the nickel-doped copper-aluminum hydrotalcite catalyst prepared in the embodiments 1 to 5 is used for cellulose pyrolysis, the nickel-doped copper-aluminum hydrotalcite catalyst can be promoted to be directionally converted into crude methanol, levoglucosenone and carboxylic acid, so that the artificial adjustable effect is achieved, and the utilization rate of biomass is improved; meanwhile, when the nickel-doped copper-aluminum hydrotalcite catalyst is used for cellulose pyrolysis, the pyrolysis efficiency is high, the pyrolysis time is shortened, the reaction condition requirement is simple, the operation difficulty is reduced, the industrialization is facilitated, and the nickel-doped copper-aluminum hydrotalcite catalyst is not easy to carbonize and inactivate due to superior coking resistance, can be recycled, and reduces the production cost. Therefore, by adopting the method for catalyzing the oriented conversion of the cellulose into the composite carbon source by the nickel-doped copper-aluminum hydrotalcite catalyst, the same biomass can produce the composite carbon source with better appearance and higher yield, and the preparation process is economic and efficient and is suitable for popularization and application.
Claims (7)
1. A method for preparing a composite carbon source by utilizing a nickel-doped copper-aluminum hydrotalcite catalyst to directionally convert cellulose, wherein the nickel-doped copper-aluminum hydrotalcite catalyst is a three-metal mixed oxide catalyst, copper-aluminum hydrotalcite is taken as a framework, nickel atoms are positioned on a specific copper-aluminum laminate structure, and the copper-aluminum hydrotalcite catalyst has rich acidic and alkaline catalytic sites; the nickel-doped copper-aluminum hydrotalcite catalyst is prepared by the following method:
(1) dissolving nickel nitrate, copper nitrate and aluminum nitrate in water under the stirring condition to prepare a metal salt mixed solution A, wherein the molar ratio of the copper nitrate to the aluminum nitrate is 1: 1-3: 1, and the ratio of the total molar weight of the copper nitrate and the aluminum nitrate to the molar weight of the nickel nitrate is 5: 1-10: 1;
(2) adding an alkali solution into the solution A to adjust the pH value to 9-12, and stirring to prepare a suspension A;
(3) pouring the suspension A into a reaction kettle, crystallizing at 90-120 ℃ for 18-24 h, pouring out reaction liquid after crystallization, centrifuging, washing and drying to obtain a nickel-doped copper-aluminum hydrotalcite precursor;
(4) calcining the nickel-doped copper-aluminum hydrotalcite precursor at 350-550 ℃ in an oxygen-free environment for 0.5-3 h, and cooling to room temperature after the calcination is finished to obtain the nickel-doped copper-aluminum hydrotalcite catalyst;
the method is characterized in that: the method for preparing the composite carbon source by directionally converting the cellulose comprises the following steps:
(a) mixing and grinding a nickel-doped copper-aluminum hydrotalcite catalyst and biomass into particles to obtain a biomass pyrolysis precursor, wherein the mass ratio of the nickel-doped copper-aluminum hydrotalcite catalyst to the biomass is 0.025-0.045;
(b) putting the biomass pyrolysis precursor into a high-pressure reaction kettle, and pyrolyzing under the conditions of 4-6 MPa and 200-300 ℃, wherein the pyrolysis time is 0.2-0.5 h;
(c) and after pyrolysis, condensing and recycling to obtain crude methanol, levoglucosenone and carboxylic acid, namely the composite carbon source.
2. The method for preparing the composite carbon source by directionally converting cellulose according to claim 1, wherein: the aqueous alkali in the step (2) is a sodium hydroxide solution, and the concentration is 0.01-0.05 mol/L.
3. The method for preparing the composite carbon source by directionally converting cellulose according to claim 1, wherein: the reaction kettle in the step (3) is provided with a polytetrafluoroethylene lining.
4. The method for preparing the composite carbon source by directionally converting cellulose according to claim 1, wherein: the calcining equipment in the step (4) is a tubular furnace.
5. The method for preparing the composite carbon source by directionally converting cellulose according to claim 1, wherein: and (4) the oxygen-free environment in the step (4) is a nitrogen environment.
6. The method for preparing the composite carbon source by directionally converting cellulose according to claim 1, wherein: the biomass in the step (a) is corn straw.
7. The method for directionally converting cellulose to produce a composite carbon source as claimed in claim 1, wherein: the particle size of the biomass pyrolysis precursor in the step (a) is 20-50 meshes.
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| US8063258B2 (en) * | 2009-05-22 | 2011-11-22 | Kior Inc. | Catalytic hydropyrolysis of organophillic biomass |
| US20130079566A1 (en) * | 2011-09-27 | 2013-03-28 | Nevada, | Catalytic process for conversion of biomass into hydrocarbon fuels |
| CN110586114A (en) * | 2019-09-19 | 2019-12-20 | 天津大学 | Preparation method of copper-chromium-aluminum hydrotalcite catalyst and application of catalyst in catalytic oxidation of 5-hydroxymethylfurfural |
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