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A kind of preparation method of highly dispersed supported nickel phosphide catalyst

A supported nickel phosphide technology, applied in the direction of molecular sieve catalysts, physical/chemical process catalysts, chemical instruments and methods, etc., can solve the problems of reduced activity, uneven dispersion, large catalyst particle size, etc., and achieve good stability, Effect of improving dispersion and good HDO activity

Active Publication Date: 2021-12-31
DALIAN UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, the hydrodeoxygenation (HDO) catalysts that have been studied more are: (1) Transition metal sulfides: During the HDO reaction, the S in the transition metal sulfide catalysts is easily replaced by O in the oxygen-containing compound to form an active phase Loss of structure, leading to catalyst deactivation
In addition, the by-product water will be generated in the HDO process, and the active phase of sulfide will be oxidized by water to become sulfate, the activity will decrease, and the catalyst will be deactivated
(2) Transition metal catalysts: Transition metal Ni catalysts are widely used in the hydrogenation reaction of biomass, but metal Ni catalysts are usually deactivated due to water poisoning, catalyst sintering and carbon deposition in the HDO process.
(3) Noble metal catalysts: Noble metal catalysts have high HDO activity and selectivity, especially the selectivity of naphthenes, such as Pd, Pt, Rh, Ru, etc., but their general price is high, resources are limited, and they are easy to deposit carbon. Under the constraints of these defects, it is difficult for precious metals to be applied on a large scale in industrial production.
At present, the impregnation method is used to use Al-containing molecular sieves such as HZSM-5 and Hβ or Al 2 o 3 When the nickel phosphide catalyst is synthesized as a carrier, it is calcined at high temperature and H 2 -Al will react with phosphorus species in the catalyst precursor during the TPR process, resulting in phosphorus loss, so it is difficult to synthesize this type of supported nickel phosphide catalyst
Moreover, the catalyst particle size obtained by the impregnation method is large and the dispersion is uneven. In order to improve the reactivity of the catalyst, it is urgent to reduce its grain size and increase the degree of dispersion.

Method used

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  • A kind of preparation method of highly dispersed supported nickel phosphide catalyst
  • A kind of preparation method of highly dispersed supported nickel phosphide catalyst
  • A kind of preparation method of highly dispersed supported nickel phosphide catalyst

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Embodiment 1

[0030] The precursor was prepared by deposition and precipitation, and Ni was prepared by electroless plating. 3 P / Al 2 o 3 catalyst.

[0031] 2.6g Ni(NO 3 ) 2 ·6H 2 O was dissolved in 300 mL deionized water to make Ni(NO 3 ) 2 solution, add 2.4g Al to 240mL of this solution 2 o 3 carrier, heated to 70°C under constant stirring to form a suspension; weigh 7.6g of urea and add it to the remaining 60mL of Ni(NO 3 ) 2 Add 0.4mL of concentrated nitric acid to the solution, and add it dropwise to the above suspension at 70°C, raise the temperature to 90°C after dropping, and react for 16h. After the reaction is completed, filter with suction, wash with deionized water until the filtrate is neutral, and dry overnight in an oven at 110°C to obtain a gray-black solid, which is the precursor compound; then prepare 100 mL of acetic acid-sodium acetate buffer solution with a pH of 5.5, Then add 9.55g of sodium hypophosphite, heat up to 90°C under constant stirring, slowly add ...

Embodiment 2

[0034] 2.6g Ni(NO 3 ) 2 ·6H 2 O was dissolved in 300 mL deionized water to make Ni(NO 3 ) 2 solution, add 2.4g of HZSM-5 carrier to 240mL of the solution, and heat to 70°C under constant stirring to form a suspension; weigh 7.6g of urea and add it to the remaining 60mL of Ni(NO 3 ) 2 Add 0.4mL of concentrated nitric acid to the solution, and add it dropwise to the above suspension at 70°C, raise the temperature to 90°C after dropping, and react for 16h. After the reaction is completed, filter with suction, wash with deionized water until the filtrate is neutral, and dry overnight in an oven at 110°C to obtain a gray-black solid, which is the precursor compound; then prepare 100 mL of acetic acid-sodium acetate buffer solution with a pH of 5.5, Then add 9.55g of sodium hypophosphite, heat up to 90°C under constant stirring, slowly add 1.6g of precursor compound within 1h; after the reaction is completed, filter with suction, wash with deionized water until the filtrate is ...

Embodiment 3

[0037] 2.6g Ni(NO 3 ) 2 ·6H 2 O was dissolved in 300 mL deionized water to make Ni(NO 3 ) 2 solution, add 2.4g SiO to 240mL of this solution 2 carrier, heated to 70°C under constant stirring to form a suspension; weigh 7.6g of urea and add it to the remaining 60mL of Ni(NO 3 ) 2 Add 0.4mL of concentrated nitric acid to the solution, and add it dropwise to the above suspension at 70°C, raise the temperature to 90°C after dropping, and react for 16h. After the reaction is completed, filter with suction, wash with deionized water until the filtrate is neutral, and dry overnight in an oven at 110°C to obtain a gray-black solid, which is the precursor compound; then prepare 100 mL of acetic acid-sodium acetate buffer solution with a pH of 5.5, Then add 9.55g of sodium hypophosphite, heat up to 90°C under constant stirring, slowly add 1.6g of precursor compound within 1h; after the reaction is completed, filter with suction, wash with deionized water until the filtrate is neut...

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Abstract

The invention provides a preparation method of a supported nickel phosphide catalyst that catalyzes the hydrodeoxygenation of phenol and its derivatives. The catalyst is a supported nickel phosphide. The steps include: 1. Dissolving nickel nitrate hexahydrate in deionized water to form solution; 2. Add the carrier, stir and heat continuously; 3. Weigh urea and add it to the obtained solution, and add concentrated nitric acid; 4. Add the solution obtained in step 3 to the suspension in step 2 drop by drop, heat up after dropping, and continue the reaction 5. Suction filtration, washing with deionized water, until the filtrate is neutral, drying overnight in an oven to obtain a gray-black solid; 6. Prepare acetic acid-sodium acetate buffer solution, then add sodium hypophosphite and continue to stir and heat up, slowly Add the precursor compound; 7. After the reaction, filter with suction and wash with deionized water until the filtrate is neutral, dry in an oven overnight, heat-treat in a chemical atmosphere and anneal at lower temperature to obtain a supported nickel phosphide catalyst. The catalyst obtained by the method of the invention has good dispersion, small particle size and good HDO activity.

Description

technical field [0001] The invention relates to the technical field of catalysts, in particular to a preparation method of a highly dispersed supported nickel phosphide catalyst and its application in the reaction process of biomass oil hydrodeoxygenation. Background technique [0002] With the development of the world economy, the demand for energy has increased sharply, and oil reserves have continued to decrease. The world is facing enormous energy pressure. At the same time, the environmental pollution caused by fossil energy has always been a hot issue of concern to the world. Therefore, actively It is very important to find alternative energy sources to relieve the pressure on energy and environment. In order to achieve sustainable social and economic development, some developed countries have successively proposed legislative policies to gradually replace traditional fossil energy with renewable energy, in order to reduce human dependence on fossil fuels and reduce gr...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J27/185B01J29/46B01J35/02C10G3/00C10G45/06C10G45/12
CPCB01J27/1853B01J35/023B01J29/46C10G3/49C10G3/45C10G45/12C10G45/06B01J2229/186Y02P30/20
Inventor 王安杰遇治权李燕妮王瑶
Owner DALIAN UNIV OF TECH
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