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Preparation of hierarchically porous molecular sieve supported metal catalyst and application thereof in grease hydrodeoxygenation

A metal-loaded, catalytic hydrogenation technology, applied in the direction of molecular sieve catalysts, preparation of liquid hydrocarbon mixtures, physical/chemical process catalysts, etc., can solve the problems of high cetane number, low freezing point, poor stability, etc., and achieve high reactivity , large pore volume, strong anti-carbon effect

Inactive Publication Date: 2015-02-25
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] Aiming at the deficiencies of existing catalysts, such as poor stability, low activity, and short life of non-sulfur metal deoxidation catalysts, the present invention proposes a new catalyst, which has the ability to greatly improve catalyst activity, life, and anti-carbon deposition , to increase the content of isomerized alkanes in diesel products, with the advantages of high cetane number and low freezing point

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  • Preparation of hierarchically porous molecular sieve supported metal catalyst and application thereof in grease hydrodeoxygenation
  • Preparation of hierarchically porous molecular sieve supported metal catalyst and application thereof in grease hydrodeoxygenation
  • Preparation of hierarchically porous molecular sieve supported metal catalyst and application thereof in grease hydrodeoxygenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Example 1 Alkali Treatment of Molecular Sieves to Prepare Hierarchical HBEA Molecular Sieves

[0045] Add 4g HBEA molecular sieve and 150mL mixed alkali of sodium hydroxide and sodium carbonate (molar ratio is 3 / 7) with a total concentration of 0.3mol / L into a 250ml flask, stir magnetically in an oil bath at 90°C for 2h, and cool to room temperature , the mixture was filtered, washed to neutral, and calcined after two ammonia exchanges to prepare a hierarchical porous molecular sieve. The specific surface and pore volume data of untreated HBEA molecular sieve (ECNU-1) and alkali treated (ECNU-2) are shown in Table 1, Adsorption isotherms, as figure 1 shown. From Table 1 and figure 1 The data showed that the treated carrier had a higher outer surface (from 48 to 238m 2 g -1 ) and larger mesopore volume (from 0.18 to 0.56cm 3 g -1 ).

Embodiment 2

[0046] Example 2 Alkali Treatment of Molecular Sieves to Prepare Hierarchical Porous HZSM-5 Molecular Sieves

[0047] 4g HZSM-5 molecular sieve and 150mL total concentration of 0.5mol / L tetramethylammonium hydroxide and sodium carbonate (molar ratio is 1 / 3) mixed alkali are added in a 250mL flask, and magnetically stirred in an oil bath at 80°C for 1.5 h. After cooling down to room temperature, the mixture is filtered and washed until neutral, and after two ammonia exchanges, it is then calcined to prepare a hierarchical porous molecular sieve. The specific surface and pore volume data of HZSM-5 molecular sieve without mixed alkali treatment (ECNU-3) and mixed alkali treatment (ECNU-4) are shown in Table 1. Table 1 shows that the treated supports have higher external surface area and larger mesopore volume.

[0048] Table 1: Physicochemical properties of molecular sieves

[0049]

[0050]

Embodiment 3

[0051] Example 3 Preparation of Hierarchical Porous HBEA Supported Cobalt-Based Catalyst

[0052] 3g HBEA molecular sieves were dissolved in 30mL (2mol / L) sodium hydroxide solution and stirred at room temperature for 20 minutes. 10 g (16 wt%) of cetyltetramethylammonium bromide was added to the above mixture, stirred at room temperature for 20 minutes, and the above mixture was placed in a self-pressurized reactor for crystallization at 120° C. for 48 hours. After cooling down to room temperature, the pH of the mixture solution was adjusted to 10 with a certain concentration of hydrochloric acid solution, and the adjusted pH mixture was put into a self-pressurized reactor. Crystallize at 120°C for 48h, and finally the mixture is washed, filtered, dried and calcined. 0.98 g (0.0034 mol) of cobalt nitrate hexahydrate and 1 g of hierarchically porous HBEA molecular sieve were impregnated with magnetic stirring at room temperature, and after the solution was volatilized, it was c...

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Abstract

The invention discloses a hierarchically porous molecular sieve supported metal catalyst, a preparation method thereof and application thereof in grease hydrodeoxygenation. The catalyst comprises a hierarchically porous molecular sieve serving as a supporter and a metal supported by the hierarchically porous molecular sieve; the supporter is a micro-mesoporous composite molecular sieve; the supported metal is one or more of nano-scale transition metals Fe, Co and Ni; and the transition metal is loaded on the supporter in a manner of high supported quantity and high dispersion. The porous molecular sieve supported metal catalyst has the advantages of high activity, long service life, strong inactivation resistance, strong carbon deposition resistance and the like. The production process is simple, environmentally friendly and efficient, the catalyst has strong adaptability to grease raw materials, the quality of a diesel oil product is high, and the catalyst is low in preparation cost, is suitable for industrialized large-scale production and has a wide application prospect.

Description

technical field [0001] The invention relates to the technical field of catalysts, in particular to a preparation method of a multi-stage molecular sieve-loaded metal catalyst and its application to the conversion of oil hydrodeoxygenation into high-quality diesel oil. Background technique [0002] With the increasing demand for energy and the gradual depletion of fossil fuels, the development of renewable energy is imminent. Among them, lipid biomass is considered as a potential renewable resource, the main components are carbon, hydrogen and oxygen, and it is composed of saturated or unsaturated fatty acid glycerides and a small amount of free fatty acids. The carbon numbers of these fatty acids are distributed in the C 14 -C 18 The corresponding diesel components are consistent, so the catalytic conversion of grease into fuel oil is a new way to solve the energy crisis. [0003] At present, the technologies for the deoxygenation of fats and oils into aliphatic hydrocarb...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80C10G3/00
CPCY02P30/20
Inventor 赵晨马冰
Owner EAST CHINA NORMAL UNIV
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