CN112844464A - Hydrodeoxygenation catalyst and preparation method and application thereof - Google Patents
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention discloses a hydrodeoxygenation catalyst, and a preparation method thereof comprises the following steps: dissolving Ni-containing inorganic salt and V-containing inorganic salt in water to obtain metal salt solution; dissolving citric acid and glycol high polymer in water to obtain an auxiliary agent solution; adding the aid solution into the metal salt solution for mixing reaction to obtain a clear and transparent solution; adding the H beta molecular sieve into the clear transparent solution under the condition of stirring to prepare a catalyst precursor loaded with Ni and V; adding the catalyst precursor into baking carbon, baking at the baking temperature of 500-530 ℃ in the atmosphere of hydrogen and nitrogen, and then activating. The catalyst of the invention can effectively catalyze the hydrodeoxygenation of biological catalyst and can obtain higher BTX yield.
Description
Technical Field
The invention belongs to the technical field of material preparation and catalysis, and particularly relates to a hydrodeoxygenation catalyst and a preparation method thereof, in particular to a catalyst for preparing light aromatic hydrocarbon by hydrodeoxygenation of bio-oil.
Background
BTX is a short name for light aromatic hydrocarbons including benzene, toluene, and xylene, and is not only a main raw material of various fine chemical products but also a main constituent of gasoline. Conventional BTX production technology is primarily accomplished by catalytic reforming of naphtha. Naphtha is one of petroleum products, and is produced by processing crude oil or chemical raw materials thereof. Since crude oil is a non-renewable resource, and in view of the importance of BTX, there is a need to find new ways to prepare BTX.
The bio-oil formed by pyrolysis of biomass is rich in aromatic compounds such as phenols, and is considered to have the potential of being converted into BTX. However, bio-oils generally have a problem of high oxygen content, which not only affects their stability, but also causes difficulties in conversion to BTX. Whereas catalytic hydrodeoxygenation is one of the most efficient ways to convert bio-oil to BTX.
The molecular sieve is used as a carrier of the bio-oil hydrodeoxygenation catalyst due to good pore channel structure and proper acidity, but the reaction is mainly saturated due to the existence of acidic sites on the surface of the molecular sieve, so that the preparation rate of BTX is not high. In view of the above, it is important to develop a catalyst which can effectively catalyze the hydrodeoxygenation of bio-oil and make the product have more BTX.
Disclosure of Invention
The invention aims to solve the problem that the yield of BTX is low when a catalyst taking a molecular sieve as a carrier catalyzes biological oil hydrodeoxygenation in the prior art, and provides a hydrodeoxygenation catalyst which takes an H beta molecular sieve as a carrier, takes Ni/V metal salt as a precursor and loads Ni/V on the H beta molecular sieve carrier.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of preparing a hydrodeoxygenation catalyst comprising the steps of:
preparing a metal salt solution: dissolving Ni-containing inorganic salt and V-containing inorganic salt in water to obtain metal salt solution;
preparing an auxiliary agent solution: dissolving citric acid and glycol high polymer in water to obtain an auxiliary agent solution;
mixing and reacting: adding the aid solution into the metal salt solution for mixing reaction to obtain a clear and transparent solution;
preparing a catalyst precursor: adding the H beta molecular sieve into the clear transparent solution under the condition of stirring to prepare a catalyst precursor loaded with Ni and V;
roasting: adding a catalyst precursor into baking carbon, and baking at the baking temperature of 500-530 ℃ in the atmosphere of hydrogen and nitrogen to obtain a baked product;
activation treatment: and activating the roasted product at 620-650 ℃ in the atmosphere of hydrogen and nitrogen.
Further, the mass ratio of the inorganic salt containing Ni to the inorganic salt containing V is (1-2): the mass ratio of the 1, H beta molecular sieve to the metal salt is (5-7): 3.
further, the inorganic salt containing Ni is nickel nitrate hexahydrate, and the inorganic salt containing V is ammonium metavanadate.
Further, the molar ratio of the citric acid to the metal salt is 1:1, the molar ratio of the ethylene glycol polymer to the metal salt is 11: 100.
Further, the atmosphere of hydrogen and nitrogen was 10% by volume of hydrogen and 90% by volume of nitrogen.
Further, the auxiliary agent solution is added into the metal salt solution in the mixing reaction, and a stirrer is used for stirring, wherein the stirring speed is 300-400 r/min, the stirring time is 15-30 min, and the temperature is 35-40 ℃.
Further, in the step of preparing the catalyst precursor, the stirring speed is 300-400 r/min, the stirring time is 10-12 h, and the temperature is 35-40 ℃.
Further, in the roasting step, the roasting time is 2.5-3 h, and the mass ratio of the catalyst precursor to the roasted charcoal is (1-8): 1; in the activation step, the activation time is 1.5-2 h.
The invention also provides a hydrodeoxygenation catalyst which is prepared by adopting the preparation method of the hydrodeoxygenation catalyst.
The invention also provides an application of the hydrodeoxygenation catalyst, and the hydrodeoxygenation catalyst is used for preparing light aromatic hydrocarbon by using the bio-oil.
Compared with the prior art, the invention has the beneficial effects that:
the molecular sieve supported Ni-V based catalyst prepared by the invention has excellent biological oil hydrodeoxygenation reaction activity, can effectively catalyze the hydrodeoxygenation of biological oil, can enable the product to have more BTX, has simple preparation process and low cost, and is convenient for industrial large-scale production.
Drawings
FIG. 1 is an ion flow diagram of a hydrodeoxygenation catalyst made by various embodiments of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by a person skilled in the art without making any inventive step are within the scope of the present invention.
A hydrodeoxygenation catalyst is prepared by adopting the following preparation method:
preparing a metal salt solution: dissolving Ni-containing inorganic salt and V-containing inorganic salt in water to obtain metal salt solution;
preparing an auxiliary agent solution: dissolving citric acid and glycol high polymer in water to obtain an auxiliary agent solution;
mixing and reacting: adding the aid solution into the metal salt solution for mixing reaction to obtain a clear and transparent solution;
preparing a catalyst precursor: adding the H beta molecular sieve into the clear transparent solution under the condition of stirring to prepare a catalyst precursor loaded with Ni and V;
roasting: roasting the catalyst precursor in the atmosphere of hydrogen and nitrogen at the roasting temperature of 500-530 ℃ to obtain a roasted product;
activation treatment: and activating the roasted product at 620-650 ℃ in the atmosphere of hydrogen and nitrogen.
As an optional embodiment, the mass ratio of the Ni-containing inorganic salt to the V-containing inorganic salt is (1-2): the mass ratio of the 1, H beta molecular sieve to the metal salt is (5-7): 3. in a further preferred embodiment, the mass ratio of H β molecular sieve to metal salt is 7: 3; the mass ratio of the Ni-containing inorganic salt to the V-containing inorganic salt is 2: 1.
as an alternative embodiment, the Ni-containing inorganic salt is nickel nitrate hexahydrate, and the V-containing inorganic salt is ammonium metavanadate.
As an alternative embodiment, the molar ratio of citric acid to metal salt is 1:1, the molar ratio of the ethylene glycol polymer to the metal salt is 11: 100. Specifically, the ethylene glycol polymer is polyethylene glycol.
As an alternative embodiment, the atmosphere of hydrogen and nitrogen is 10 volume percent hydrogen and 90 volume percent nitrogen.
As an optional implementation mode, the auxiliary agent solution is added into the metal salt solution in the mixing reaction, and a stirrer is used for stirring, wherein the stirring speed is 300-400 r/min, the stirring time is 15-30 min, and the temperature is 35-40 ℃. In a further preferred scheme, the stirring speed is 350r/min, the stirring time is 20min, and the temperature is 35 ℃.
In the step of preparing the catalyst precursor, the stirring speed is 300-400 r/min, the stirring time is 10-12 h, and the temperature is 35-40 ℃. According to a further preferred scheme, the stirring speed is 350r/min, the stirring time is 12h, and the temperature is 35 ℃.
As an optional embodiment, in the roasting step, the roasting time is 2.5-3 hours; in the activation step, the activation time is 1.5-2 h, and the mass ratio of the catalyst precursor to the baking carbon is (1-8): 1. in a further preferred scheme, the roasting time is 3 hours; in the activation step, the activation time is 2 h.
Example 1:
8.4937 g of Ni (NO)3) 6H2O and 1.9685 g NH4VO3Dissolved in 30 ml of distilled water, and stirred (35 ℃ C., 350r/min) on a stirrer for 20 minutes to obtain a metal salt solution.
9.6748 g of citric acid monohydrate and 0.3453 g of polyethylene glycol were weighed and dissolved in 20 ml of distilled water to obtain an auxiliary solution.
And slowly adding the mixed assistant solution into the metal salt solution to obtain a clear and transparent solution. Then 6g of H beta molecular sieve is added into the clear transparent solution, and the obtained mixture is placed on a stirrer (35 ℃, 350r/min) to be continuously stirred for 12H, so that the catalyst precursor loaded with Ni and V is obtained. The catalyst precursor was dried in a forced air oven at 105 ℃ for 24 h. Crushing the dried catalyst precursor, weighing 8g of the crushed catalyst precursor and putting the weighed baked carbon into a quartz tube, weighing 1g of the baked carbon and putting the baked carbon into the front end of the catalyst precursor in the quartz tube, then putting the quartz tube into an atmosphere furnace for heating, raising the temperature to 500 ℃ at the speed of 20 ℃/min and keeping the temperature for 3H, raising the temperature from 500 ℃ to 650 ℃ at the speed of 20 ℃/min and keeping the temperature for 2H, and introducing 10% H at the flow rate of 200mL/min in the heating process2/90％N2The mixed gas is used as reducing gas. And grinding and sieving the reduced catalyst to obtain the hydrodeoxygenation catalyst which is recorded as NiV/Hbeta-1/8 Vm.
Example 2:
8.4937 g of Ni (NO)3)·6H2O and 1.9685 g NH4VO3Dissolved in 30 ml of distilled water, and stirred (35 ℃ C., 350r/min) on a stirrer for 20 minutes to obtain a metal salt solution.
9.6748 g of citric acid monohydrate and 0.3453 g of polyethylene glycol were weighed and dissolved in 20 ml of distilled water to obtain an auxiliary solution.
Slowly adding the mixed assistant solution into the metal salt solution to obtain a clear solutionAnd (4) a transparent solution. Then 6g of H β molecular sieve was added to the clear transparent solution. And placing the obtained mixture on a stirrer (35 ℃, 350r/min) to continuously stir for 12h to obtain the catalyst precursor loaded with Ni and V. The catalyst precursor was dried in a forced air oven at 105 ℃ for 24 h. Crushing the dried catalyst precursor, weighing 8g of the crushed catalyst precursor and putting the weighed baked carbon into a quartz tube, weighing 2g of the baked carbon and putting the baked carbon into the front end of the catalyst precursor in the quartz tube, then putting the quartz tube into an atmosphere furnace for heating, raising the temperature to 500 ℃ at the speed of 20 ℃/min and keeping the temperature for 3H, raising the temperature from 500 ℃ to 650 ℃ at the speed of 20 ℃/min and keeping the temperature for 2H, and introducing 10% H at the flow rate of 200mL/min in the heating process2/90％N2The mixed gas is used as reducing gas. And grinding and sieving the reduced catalyst to obtain the hydrodeoxygenation catalyst which is recorded as NiV/Hbeta-1/4 Vm.
Example 3:
8.4937 g of Ni (NO)3)·6H2O and 1.9685 g NH4VO3Dissolved in 30 ml of distilled water, and stirred (35 ℃ C., 350r/min) on a stirrer for 20 minutes to obtain a metal salt solution.
9.6748 g of citric acid monohydrate and 0.3453 g of polyethylene glycol were weighed and dissolved in 20 ml of distilled water to obtain an auxiliary solution.
And slowly adding the mixed assistant solution into the metal salt solution to obtain a clear and transparent solution. Then 6g of H beta molecular sieve is added into the clear transparent solution, and the obtained mixture is placed on a stirrer (35 ℃, 350r/min) to be continuously stirred for 12H, so that the catalyst precursor loaded with Ni and V is obtained. The catalyst precursor was dried in a forced air oven at 105 ℃ for 24 h. Crushing the dried catalyst precursor, weighing 8g of the crushed catalyst precursor and putting the weighed baked carbon into a quartz tube, weighing 4g of the baked carbon and putting the baked carbon into the front end of the catalyst precursor in the quartz tube, then putting the quartz tube into an atmosphere furnace for heating, raising the temperature to 500 ℃ at the speed of 20 ℃/min and keeping the temperature for 3H, raising the temperature from 500 ℃ to 650 ℃ at the speed of 20 ℃/min and keeping the temperature for 2H, and introducing 10% H at the flow rate of 200mL/min in the heating process2/90％N2The mixed gas is used as reducing gas. And grinding and sieving the reduced catalyst to obtain the hydrodeoxygenation catalyst which is recorded as NiV/Hbeta-1/2 Vm.
Example 4
8.4937 g of Ni (NO)3)·6H2O and 1.9685 g NH4VO3Dissolved in 30 ml of distilled water, and stirred (35 ℃ C., 350r/min) on a stirrer for 20 minutes to obtain a metal salt solution.
9.6748 g of citric acid monohydrate and 0.3453 g of polyethylene glycol were weighed and dissolved in 20 ml of distilled water to obtain an auxiliary solution.
And slowly adding the mixed assistant solution into the metal salt solution to obtain a clear and transparent solution. Then 6g of H beta molecular sieve is added into the clear transparent solution, and the obtained mixture is placed on a stirrer (35 ℃, 350r/min) to be continuously stirred for 12H, so that the catalyst precursor loaded with Ni and V is obtained. The catalyst precursor was dried in a forced air oven at 105 ℃ for 24 h. Crushing the dried catalyst precursor, weighing 8g of the crushed catalyst precursor and putting the weighed 8g of the crushed carbon into a quartz tube, weighing 8g of the baked carbon and putting the weighed 8g of the baked carbon into the front end of the catalyst precursor in the quartz tube, then putting the quartz tube into an atmosphere furnace for heating, raising the temperature to 500 ℃ at the speed of 20 ℃/min and keeping the temperature for 3H, raising the temperature from 500 ℃ to 650 ℃ at the speed of 20 ℃/min and keeping the temperature for 2H, and introducing 10% H at the flow rate of 200mL/min in the heating process2/90％N2The mixed gas is used as reducing gas. And grinding and sieving the reduced catalyst to obtain the hydrodeoxygenation catalyst which is recorded as NiV/Hbeta-1/1 Vm.
Example 5
8.4937 g of Ni (NO)3)·6H2O and 1.9685 g NH4VO3Dissolved in 30 ml of distilled water, and stirred (35 ℃ C., 350r/min) on a stirrer for 20 minutes to obtain a metal salt solution.
9.6748 g of citric acid monohydrate and 0.3453 g of polyethylene glycol were weighed and dissolved in 20 ml of distilled water to obtain an auxiliary solution.
And slowly adding the mixed assistant solution into the metal salt solution to obtain a clear and transparent solution. Then 6g of H beta molecular sieve is added into the clear transparent solution, and the obtained mixture is placed on a stirrer (35 ℃, 350r/min) to be continuously stirred for 12H, so that the catalyst precursor loaded with Ni and V is obtained. The catalyst precursor was dried in a forced air oven at 105 ℃ for 24 h.Crushing the dried catalyst precursor, weighing 8g of the crushed catalyst precursor and placing the weighed baked carbon into a quartz tube, weighing 16g of the baked carbon and placing the baked carbon into the front end of the catalyst precursor in the quartz tube, then placing the quartz tube into an atmosphere furnace for heating, raising the temperature to 500 ℃ at the speed of 20 ℃/min and keeping the temperature for 3H, raising the temperature from 500 ℃ to 650 ℃ at the speed of 20 ℃/min and keeping the temperature for 2H, and introducing 10% H at the flow rate of 200mL/min in the heating process2/90％N2The mixed gas is used as reducing gas. And grinding and sieving the reduced catalyst to obtain the hydrodeoxygenation catalyst which is recorded as NiV/Hbeta-2/1 Vm.
Comparative example 1
8.4937 g of Ni (NO)3)·6H2O and 1.9685 g NH4VO3Dissolved in 30 ml of distilled water, and stirred (35 ℃ C., 350r/min) on a stirrer for 20 minutes to obtain a metal salt solution.
9.6748 g of citric acid monohydrate and 0.3453 g of polyethylene glycol were weighed and dissolved in 20 ml of distilled water to obtain an auxiliary solution.
And slowly adding the mixed assistant solution into the metal salt solution to obtain a clear and transparent solution. Then 6g of H beta molecular sieve is added into the clear transparent solution, and the obtained mixture is placed on a stirrer (35 ℃, 350r/min) to be continuously stirred for 12H, so that the catalyst precursor loaded with Ni and V is obtained. The catalyst precursor was dried in a forced air oven at 105 ℃ for 24 h. Crushing the dried catalyst precursor, weighing 8g of the crushed catalyst precursor, putting the crushed catalyst precursor into a quartz tube, putting the quartz tube into an atmosphere furnace for heating, raising the temperature to 500 ℃ at the speed of 20 ℃/min, keeping the temperature for 3H, raising the temperature from 500 ℃ to 650 ℃ at the speed of 20 ℃/min, keeping the temperature for 2H, and introducing 10% H at the flow rate of 200mL/min in the heating process2/90％N2The mixed gas is used as reducing gas. Grinding and sieving the reduced catalyst to prepare the hydrodeoxygenation catalyst which is recorded as NiV/Hbeta.
Catalyst hydrodeoxygenation Performance testing
The hydrodeoxygenation performance of the catalyst was evaluated using a micro-reaction unit (FTS-3020) equipped with a high-pressure peristaltic pump. The inner diameter of the reaction tube was 8 mm. The reaction gas is 99.995 percent pure hydrogen, the gasification temperature is 220 ℃, the reaction temperature is 320 ℃, the condensation temperature is-10 ℃, and the mass space velocity (WHSV) is 0.5. Before the reaction, 3g of the catalyst was first placed in an isothermal zone of a reaction tube and reduced with pure hydrogen for 20min at a reduction temperature of 380 ℃ and a hydrogen flow rate of 300 ml/min. When the reaction starts, guaiacol enters a gasification chamber through a high-pressure peristaltic pump at the speed of 0.018ml/min, meanwhile, pure hydrogen is introduced at the speed of 300ml/min, the gasified guaiacol and the pure hydrogen pass through a catalyst to complete the hydrodeoxygenation of the guaiacol, and a liquid product is collected after the reaction is carried out for 0.5 hour. The liquid product after reaction is diluted by about 3000 times by acetone, and 100 mul of acetophenone diluted by 1000 times by acetone is added as an internal standard. The diluted sample was subjected to qualitative and quantitative analysis by a gas chromatography mass spectrometer (GC-MS) equipped with a chromatographic column. The results are shown in FIG. 1 and Table 1.
TABLE 1 liquid yield for each example
Taking the catalysts prepared by the methods described in example 3 and comparative example 1 as examples, the molecular sieve supported Ni-V based catalyst prepared by the comparative example (i.e., NiV/H β) showed BTX yield (18.19%) under the existing guaiacol hydrodeoxygenation reaction conditions (gasification temperature: 220 ℃, reaction temperature: 320 ℃, condensation temperature: -10 ℃, pressure: atmospheric pressure, mass space velocity: 0.5). In contrast, the molecular sieve supported Ni-V based catalyst (i.e., NiV/H β -1/2Vm) with volatile as modifier prepared in example 3 gave BTX yield of 61.73% in the same reaction time. The hydrodeoxygenation reaction test data of the guaiacol show that the molecular sieve supported Ni-V based catalyst synthesized by taking biochar volatile as a modifier can effectively promote the generation of BTX. Therefore, the molecular sieve supported Ni-V based catalyst synthesized by using the biochar volatile matter as the modifier can effectively catalyze the hydrodeoxygenation of the bio-oil and can generate more BTX.
Therefore, the catalyst of the invention has high reactivity in the hydrodeoxygenation process.
The above description is only for the preferred embodiment of the present invention, but the present invention should not be limited to the embodiment and the disclosure of the drawings, and therefore, all equivalent or modifications that do not depart from the spirit of the present invention are intended to fall within the scope of the present invention.
Claims (10)
1. A preparation method of a hydrodeoxygenation catalyst is characterized by comprising the following steps of:
preparing a metal salt solution: dissolving Ni-containing inorganic salt and V-containing inorganic salt in water to obtain metal salt solution;
preparing an auxiliary agent solution: dissolving citric acid and glycol high polymer in water to obtain an auxiliary agent solution;
mixing and reacting: adding the aid solution into the metal salt solution for mixing reaction to obtain a clear and transparent solution;
preparing a catalyst precursor: adding the H beta molecular sieve into the clear transparent solution under the condition of stirring to prepare a catalyst precursor loaded with Ni and V;
roasting: adding a catalyst precursor into baking carbon, and baking at the baking temperature of 500-530 ℃ in the atmosphere of hydrogen and nitrogen to obtain a baked product;
activation treatment: and activating the roasted product at 620-650 ℃ in the atmosphere of hydrogen and nitrogen.
2. The method for producing a hydrodeoxygenation catalyst according to claim 1, characterized in that the mass ratio of the Ni-containing inorganic salt to the V-containing inorganic salt is (1 to 2): the mass ratio of the 1, H beta molecular sieve to the metal salt is (5-7): 3.
3. the method of preparing a hydrodeoxygenation catalyst as claimed in claim 1, wherein the Ni-containing inorganic salt is nickel nitrate hexahydrate, and the V-containing inorganic salt is ammonium metavanadate.
4. The method of preparing a hydrodeoxygenation catalyst as claimed in claim 1, wherein the molar ratio of citric acid to metal salt is 1:1, the molar ratio of the ethylene glycol polymer to the metal salt is 11: 100.
5. The method of claim 1, wherein the atmosphere of hydrogen and nitrogen is 10 volume percent hydrogen and 90 volume percent nitrogen.
6. The preparation method of the hydrodeoxygenation catalyst according to claim 1, characterized in that the auxiliary agent solution is added into the metal salt solution in the mixing reaction and stirred by a stirrer, wherein the stirring speed is 300-400 r/min, the stirring time is 15-30 min, and the temperature is 35-40 ℃.
7. The preparation method of the hydrodeoxygenation catalyst according to claim 1, wherein in the step of preparing the catalyst precursor, the stirring speed is 300-400 r/min, the stirring time is 10-12 h, and the temperature is 35-40 ℃.
8. The preparation method of the hydrodeoxygenation catalyst according to claim 1, wherein in the roasting step, the roasting time is 2.5-3 h, and the mass ratio of the catalyst precursor to the baked carbon is (1-8): 1; in the activation step, the activation time is 1.5-2 h.
9. A hydrodeoxygenation catalyst characterized by: the preparation method of any one of claims 1 to 8.
10. Use of a hydrodeoxygenation catalyst as claimed in claim 9, characterised in that: the hydrodeoxygenation catalyst is used for preparing light aromatic hydrocarbon by adopting bio-oil.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745401A (en) * | 2009-12-07 | 2010-06-23 | 中国科学院山西煤炭化学研究所 | Load type sulfur-tolerant methanation catalyst and preparation method and application thereof |
| CN102527388A (en) * | 2012-01-06 | 2012-07-04 | 华东理工大学 | Preparation method of catalyst for dehydrogenation and oxidization of diethanol amine |
| CN102794181A (en) * | 2011-05-27 | 2012-11-28 | 中科合成油技术有限公司 | Hydrodeoxygenation catalyst for Fischer Tropsch synthesis oil and preparation method and application of hydrodeoxygenation catalyst |
| CN104119943A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for preparing aviation kerosene from furyl oxygen-containing organic compounds by hydrogenation deoxidation |
| CN105885911A (en) * | 2016-05-03 | 2016-08-24 | 四川凯沃斯能源科技有限公司 | Bio-oil hydrodeoxygenation method |
| CN105903475A (en) * | 2016-05-03 | 2016-08-31 | 四川凯沃斯能源科技有限公司 | Hydrodeoxygenation method of bio-oil as well as catalyst and preparation method used thereby |
| CN105935589A (en) * | 2016-05-03 | 2016-09-14 | 四川凯沃斯能源科技有限公司 | Method for hydrodeoxygenation of biological oil, catalyst used in method and preparation method of catalyst |
-
2021
- 2021-01-22 CN CN202110089619.4A patent/CN112844464B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745401A (en) * | 2009-12-07 | 2010-06-23 | 中国科学院山西煤炭化学研究所 | Load type sulfur-tolerant methanation catalyst and preparation method and application thereof |
| CN102794181A (en) * | 2011-05-27 | 2012-11-28 | 中科合成油技术有限公司 | Hydrodeoxygenation catalyst for Fischer Tropsch synthesis oil and preparation method and application of hydrodeoxygenation catalyst |
| CN102527388A (en) * | 2012-01-06 | 2012-07-04 | 华东理工大学 | Preparation method of catalyst for dehydrogenation and oxidization of diethanol amine |
| CN104119943A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for preparing aviation kerosene from furyl oxygen-containing organic compounds by hydrogenation deoxidation |
| CN105885911A (en) * | 2016-05-03 | 2016-08-24 | 四川凯沃斯能源科技有限公司 | Bio-oil hydrodeoxygenation method |
| CN105903475A (en) * | 2016-05-03 | 2016-08-31 | 四川凯沃斯能源科技有限公司 | Hydrodeoxygenation method of bio-oil as well as catalyst and preparation method used thereby |
| CN105935589A (en) * | 2016-05-03 | 2016-09-14 | 四川凯沃斯能源科技有限公司 | Method for hydrodeoxygenation of biological oil, catalyst used in method and preparation method of catalyst |
Non-Patent Citations (3)
| Title |
|---|
| AQSHA AQSHA ET AL.: "Investigation of catalytic hydrodeoxygenation of anisole asbio-oil model compound over Ni-Mo/TiO2 and Ni-V/TiO2 catalysts：Synthesis, kinetic, and reaction pathways studies", 《CANADIAN SOCIETY FOR CHEMICAL ENGINEERING》 * |
| E. KANTARELIS ET AL.: "Effects of Silica-Supported Nickel and Vanadium on Liquid Products of Catalytic Steam Pyrolysis of Biomass", 《ENERGY & FUELS》 * |
| 曾鹤等: "关于添加剂在加氢精制催化剂中作用的研究进展", 《化学与黏合》 * |
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