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Preparation method of hydrodeoxygenation catalyst with high hydrothermal/mechanical stability

A technology of mechanical stability and deoxidation catalyst, applied in metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, molecular sieve catalyst, etc., can solve the problems of poor catalyst activity and mechanical stability, and achieve high water content. The effect of thermal/mechanical stability

Active Publication Date: 2016-03-16
HEBEI UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] The present invention mostly adopts aluminum hydroxide dry glue or pseudo-boehmite (γ-Al 2 o 3 Precursor) is a binder, thus leading to the disadvantages of poor activity and mechanical stability of the resulting catalyst in a hydrothermal environment. A method for preparing a hydrodeoxygenation catalyst with high hydrothermal / mechanical stability is provided. The method uses sol The bulk MoNi composite oxide catalyst is prepared by the gel method, and the mixed material with good hydrothermal resistance and mechanical stability is used as the binder during the molding process, so as to obtain a catalyst with high hydrothermal / mechanical stability and high activity at the same time. Bulk MoNi Composite Oxide Hydrodeoxygenation Catalyst

Method used

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  • Preparation method of hydrodeoxygenation catalyst with high hydrothermal/mechanical stability
  • Preparation method of hydrodeoxygenation catalyst with high hydrothermal/mechanical stability

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preparation example Construction

[0024] The preparation of comparative example catalyst A:

[0025] MoNi composite oxide powder was prepared according to the patent "Preparation method of large-pore bulk Ni-Mo hydrodeoxygenation catalyst" (application number: 201510173213.9). Weigh a certain amount of Mo(NO 3 ) 3 ·5H 2 O, Ni(NO 3 ) 2 ·6H 2 O, citric acid, molar ratio is Mo: Ni=0.2, molar ratio (Mo+Ni): citric acid=1.5 (wherein, the meaning of " (Mo+Ni) mol " is the molar sum of molybdenum element and nickel element ), respectively dissolved in a certain volume fraction of 50% ethanol aqueous solution, the total consumption of ethanol aqueous solution is 500mL / (Ni+Mo)mol, the above solutions are mixed evenly and the pH value of the mixed solution is regulated by 27% ammonia water with a mass fraction of 5. The mixture was magnetically stirred in a 70°C water bath until a sol was formed, ultrasonically oscillated for 25 minutes, aged at room temperature for 4 hours, and dried at 120°C to obtain a xerogel...

Embodiment 1

[0028] Weigh a certain amount of (NH 4 ) 6 Mo 7 o 24 4H 2 O, NiSO 4 ·6H 2 O, oxalic acid, molar ratio is Mo:Ni=0.4, molar ratio (Mo+Ni): oxalic acid=1.2 (wherein, the implication of " (Mo+Ni) mol " is the molar sum of molybdenum element and nickel element), Dissolve in a certain amount of aqueous ethanol solution with a volume fraction of 50%, the total consumption of the aqueous ethanol solution is 600mL / (Ni+Mo)mol, mix the above solutions evenly and adjust the pH value of the mixed solution to 4 with a mass fraction of 27% ammonia, The mixture was magnetically stirred in an 80°C water bath until a sol was formed, ultrasonically oscillated for 15 min, aged at room temperature for 3.5 h, and dried at 120°C to obtain a xerogel. The xerogel was calcined at 300°C for 3h in a nitrogen atmosphere in a tube furnace, and at 550°C for 4h in an air atmosphere in a muffle furnace to obtain MoNi composite oxide powder B.

Embodiment 2

[0030] Weigh a certain amount of H in proportion 2 MoO 4 ·H 2 O, NiCl 2 ·6H 2 O, glycolic acid, molar ratio is Mo: Ni=0.6, molar ratio (Mo+Ni): glycolic acid=1 (wherein, the implication of " (Mo+Ni) mol " is the sum of the molar number of molybdenum element and nickel element ), respectively dissolved in a certain volume fraction of 50% ethanol aqueous solution, the total consumption of ethanol aqueous solution is 700mL / (Ni+Mo)mol, the above solutions are mixed evenly and the pH value of the mixed solution is regulated by 27% ammonia water with mass fraction 3. The mixture was magnetically stirred in a 90°C water bath until a sol was formed, ultrasonically oscillated for 30min, aged at room temperature for 3h, and dried at 120°C to obtain a xerogel. The xerogel was calcined at 200°C for 4h in a nitrogen atmosphere in a tube furnace, and at 600°C for 2h in an air atmosphere in a muffle furnace to obtain MoNi composite oxide powder C.

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Abstract

The invention discloses a preparation method of a hydrodeoxygenation catalyst with high hydrothermal / mechanical stability. The preparation method comprises the following steps: (1) preparing MoNi composite oxide powder; and (2) preparing a bulk type MoNi composite oxide catalyst, namely uniformly mixing the MoNi composite oxide powder, a binder and powder of sesbaria cannabina, dropwise adding 3% dilute nitric acid, performing strip extrusion for forming, and roasting for 2-5h in a muffle furnace at the temperature being 400-800 DEG C to obtain the bulk type MoNi composite oxide catalyst, wherein the binder is selected from two or more of magnesium aluminate spinel, kieselguhr and a molecular sieve binder. In the forming process of the catalyst, the binder is prepared from a material having relatively high hydrothermal resistance and mechanical stability, so that the bulk type MoNi composite oxide hydrodeoxygenation catalyst having high hydrothermal / mechanical stability, and activity is obtained, the edgewise comprehensive strength of the bulk type catalyst can be up to 90-140N / cm, and the hydrothermal / mechanical stability of the prepared catalyst can be obviously improved.

Description

technical field [0001] The invention relates to a preparation method of a hydrodeoxygenation catalyst with high hydrothermal / mechanical stability. The catalyst is suitable for preparing biodiesel by hydrogenation and deoxygenation of animal and vegetable oils. Background technique [0002] With the decrease of non-renewable energy sources and the improvement of people's awareness of environmental protection, the importance of developing renewable and new environmentally friendly energy sources that can replace traditional fossil fuels has become increasingly prominent. Therefore, the research on the preparation of second-generation biodiesel by hydrodeoxygenation from animal and vegetable oils and fats has received extensive attention. Traditional hydrodeoxygenation catalysts are mostly transition metal-supported catalysts, but such catalysts are restricted by the specific surface area and pore volume of the carrier, and it is difficult to greatly increase the loading of ac...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/883B01J29/00C10G3/00
CPCY02P30/20
Inventor 侯凯湖徐永卫杨红建张大龙
Owner HEBEI UNIV OF TECH
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