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Ni2P/reduced graphene oxide catalyst for hydrodeoxygenation reaction of bio-oils and preparation method thereof

A hydrodeoxygenation and catalyst technology, which is used in physical/chemical process catalysts, preparation of liquid hydrocarbon mixtures, biological raw materials, etc., can solve problems such as adverse effects of catalyst storage, easy deactivation during storage time, and inability of phosphate to be reduced. Achieve significant application value, good stability and high selectivity

Active Publication Date: 2018-10-19
XI'AN PETROLEUM UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Al 2 o 3 Strong rigidity, cheap and easy to get, widely used in industrial catalysts (Sawhill S, Layman K, Vanwyk D, et al. Thiophene hydrodesulfurization over nickel phosphidecatalysts: effect of the precursor composition and support [J]. Journal of Catalysis, 2005, 231 (2):300-313), but due to Al 2 o 3 Not an inert carrier, it has abundant L-acid centers, and AlPO will be generated on the surface when phosphide is loaded 4 , so that most of the phosphate cannot be reduced to phosphide (ClarkP.Alumina-supported molybdenum phosphide hydroprocessing catalysts[J].Journalof Catalysis,2003,218(1):78-87), it is considered unsuitable for Ni 2 P catalyst carrier
Under normal conditions (normal temperature and pressure), the longer the storage time, the easier it is to deactivate, which has an adverse effect on the preservation of the catalyst, which brings great challenges to the application of phosphide catalysts.

Method used

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  • Ni2P/reduced graphene oxide catalyst for hydrodeoxygenation reaction of bio-oils and preparation method thereof
  • Ni2P/reduced graphene oxide catalyst for hydrodeoxygenation reaction of bio-oils and preparation method thereof
  • Ni2P/reduced graphene oxide catalyst for hydrodeoxygenation reaction of bio-oils and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] In terms of catalyst, according to Ni 2 The load of P is 20%, and the molar ratio of Ni element and P element is 2:1.5, add 1.0g graphene oxide into 500mL containing 1.1409g (4.80mmol) NiCl 2 ·6H 2 O and 0.3815g (3.60mmol) NaH 2 PO 2 ·H 2 In the mixed aqueous solution of O, ultrasonically disperse at room temperature for 2 hours, then add 2 mL (32.98 mmol) of hydrazine hydrate aqueous solution with a volume fraction of 80% at 80 ° C, react at constant temperature for 4 hours, filter with suction, and wash the filter cake repeatedly with deionized water , transferred to a vacuum drying oven at 60°C to fully dry, and finally baked at 300°C for 4 hours in a nitrogen atmosphere to obtain Ni 2 P / RGO catalyst with a specific surface area of ​​181.9m 2 g -1 , the average pore diameter is 12.2nm, the pore volume is 0.55cm 3 g -1 . Depend on figure 1 It can be seen that Ni appears at 37.6°, 43.9°, 64.2°, 77.4° 2 The typical diffraction peak of P indicates that the pre...

Embodiment 2

[0024] In terms of catalyst, according to Ni 2 The load of P is 10%, and the molar ratio of Ni element and P element is 2:1.5, add 1.0g graphene oxide into 500mL containing 0.5705g (2.40mmol) NiCl 2 ·6H2 O and 0.1908g (1.80mmol) NaH 2 PO 2 ·H 2 In the mixed aqueous solution of O, ultrasonically disperse at room temperature for 2 hours, then add 2 mL (32.98 mmol) of hydrazine hydrate aqueous solution with a volume fraction of 80% at 80 ° C, react at constant temperature for 4 hours, filter with suction, and wash the filter cake repeatedly with deionized water , transferred to a vacuum drying oven at 60°C to fully dry, and finally baked at 300°C for 4 hours in a nitrogen atmosphere to obtain Ni 2 P / RGO catalyst with a specific surface area of ​​197.4m 2 g -1 , with an average pore diameter of 10.6nm and a pore volume of 0.61cm 3 g -1 .

Embodiment 3

[0026] In terms of catalyst, according to Ni 2 The load of P is 15%, and the molar ratio of Ni element and P element is 2:1.5, add 1.0g graphene oxide into 500mL containing 0.8567g (3.60mmol) NiCl 2 ·6H 2 O and 0.2861g (2.70mmol) NaH 2 PO 2 ·H 2 In the mixed aqueous solution of O, ultrasonically disperse at room temperature for 2 hours, then add 2 mL (32.98 mmol) of hydrazine hydrate aqueous solution with a volume fraction of 80% at 80 ° C, react at constant temperature for 4 hours, filter with suction, and wash the filter cake repeatedly with deionized water , transferred to a vacuum drying oven at 60°C to fully dry, and finally baked at 300°C for 4 hours in a nitrogen atmosphere to obtain Ni 2 P / RGO catalyst with a specific surface area of ​​188.2m 2 g -1 , the average pore diameter is 11.5nm, the pore volume is 0.54cm 3 g -1 .

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Abstract

The invention discloses a Ni2P / reduced graphene oxide catalyst for hydrodeoxygenation reaction of bio-oils and a preparation method thereof. Reduced graphene oxide is used as a carrier, an active component Ni2P is loaded, and based on a catalyst, the load capacity of Ni2P is 10% to 25%. The preparation condition of the catalyst is relatively mild, and the catalyst is applied to the reaction systemfor preparing toluene by hydrodeoxygenation of benzaldehyde; the conversion rate of benzaldehyde reaches 96% or above, the selectivity of toluene is close to 90%, the catalyst activity is good, the selectivity is high, and the stability is good; the cost is much lower than the cost of precious metal catalysts, and the catalyst has very significant application value.

Description

technical field [0001] The invention belongs to the technical field of catalytic hydrogenation, in particular to a Ni 2 P / reduced graphene oxide catalyst, and the preparation method of the catalyst. Background technique [0002] Hydrodeoxygenation reaction of bio-oil is the means of its hydrorefining process. According to the degree of hydrogenation, it can also be divided into two types: deep hydrodeoxygenation and mild hydrodeoxygenation. According to different hydrogenation conditions, hydrodeoxygenation can be divided into two types. The process realized by heat treatment is called thermal hydrodeoxygenation, and the process realized by catalyst action is called catalytic hydrodeoxygenation. However, the deoxygenation rate of the product obtained by thermal hydrodeoxygenation is not ideal, generally 78% to 85%. In contrast, due to the addition of catalytic hydrodeoxygenation catalysts, the deoxygenation process conditions are relatively mild, and the deoxygenation rat...

Claims

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Application Information

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IPC IPC(8): B01J27/185B01J35/10C10G3/00
CPCC10G3/45B01J27/1853B01J35/615B01J35/633B01J35/635B01J35/647Y02P30/20
Inventor 徐海升王豪丁丽芹
Owner XI'AN PETROLEUM UNIVERSITY
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