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Preparation of nickel-calcium-based composite catalyst and application thereof in biomass catalytic pyrolysis process

A composite catalyst and biomass technology, which is applied in the field of Ni-Ca-based composite catalysts, can solve the problems of target product selectivity, catalytic activity reduction, active center pore blockage, etc., and achieve the advantages of migration and diffusion, increased production, and high activity. Effect

Active Publication Date: 2019-09-13
ENERGY RES INST OF SHANDONG ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the disordered accumulation and aggregation of the structure often lead to the coverage of the active center and the blockage of the pores during the reaction process, so that the selectivity of the target product and the catalytic activity decrease rapidly as the reaction progresses.
In addition, with the development of nanotechnology, it has gradually shown its limitations to improve the performance of catalysts only by adjusting the chemical composition and controlling the size of nanoparticles.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Embodiment 1: a kind of Ni-Ca base composite catalyst, it is to prepare with following steps:

[0019] According to Ni 2+ : Ca 2+ : Zn 2+ Weigh 21.81g of Ni(NO 3 ) 2 ∙6H 2 O, 7.09gCa(NO 3 ) 2 ∙6H 2 O and 13.39g Zn(NO 3 ) 2 ∙6H 2 O was added with deionized water to form a 300 ml mixed solution, and 36.64gC was weighed 6 h 5 Add 300 ml of deionized water to COONa to prepare a solution, and add 8 g of NaOH to deionized water to prepare a 400 mL alkali solution with a concentration of 0.5M. Mix the salt solution and C 6 h 5 The COONa solution was poured into a four-necked flask, and the NaOH solution was added dropwise to the above mixed solution under mechanical stirring, so that the pH of the final solution was 8.0, and the resulting slurry was crystallized at 90°C for 48 hours, washed with deionized water, Centrifuge until the supernatant is neutral, dry at 80°C for 12 hours, and grind to obtain the Ni-Ca-Zn LDR precursor.

[0020] Weigh 10g of Ni-Ca-...

Embodiment 2

[0026] Embodiment 2: This embodiment is identical with embodiment 1 and repeats no more, and difference is not to add Ca(NO 3 ) 2 ∙6H 2 O, according to Ni 2+ : Zn 2+ 21.81g of Ni(NO 3 ) 2 ∙6H 2 O and 22.31g Zn(NO 3 ) 2 ∙6H 2 O. The prepared Ni-Zn catalyst still maintains a one-dimensional rod shape, with a length of about 1.8 µm and a diameter of about 130 nm. Nanoparticles are its structural units, with an average size of about 22 nm, uniformly dispersed on the surface of the nanorods. The catalyst composition and mass percentage are Ni: 10.7%, Ni 3 ZnC 0.7 : 45.3%, ZnO: 44%, no other impurity phases were found.

[0027] Catalyst evaluation was carried out under the same experimental conditions as in Example 1. It was found that the amount of gas obtained after the reaction was 456 mL / g, and the gas component was (volume percentage): H 2 : 37.17%, CO: 18.87%, CO 2 : 34.61%, CH 4 : 5.1%, C 2 -C 3 (ethylene, ethane, propane): 4.25%, of which the effective compo...

Embodiment 3

[0028] Embodiment 3: The similarities between this embodiment and Embodiment 1 will not be repeated, the difference is that the catalyst roasting atmosphere is air. The prepared Ni-Ca-Zn catalyst still maintains a one-dimensional rod shape, with a length of about 3 µm and a diameter of about 86 nm. Nanoparticles are its structural units, with an average size of about 18 nm. Agglomeration occurs. The catalyst composition and mass percentage are NiO: 51.95%, ZnO: 35.25%, CaO: 12.8%, and no other impurity phases were found.

[0029] Catalyst evaluation was carried out under the same experimental conditions as in Example 1, and it was found that the gas output obtained after the reaction was 599mL / g, wherein the components were (volume percentage): H 2 : 51.83%, CO: 19.34%, CO 2 : 15.03%, CH 4 : 8.24%, C 2 -C 3 (ethylene, ethane, propane): 5.56%, the proportion of effective components in syngas is 71.17 vol%, H 2 The / CO ratio was 2.68. Compared with Example 1, when the cal...

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Abstract

Preparation of a nickel-calcium-based composite catalyst and its application in the biomass catalytic pyrolysis process are disclosed. The preparation comprises the following steps: preparing a layered metal hydroxide precursor; and calcinating and reducing to obtain a Ni-Ca-based composite catalyst orderly assembled by nano-particles or nanosheet structural units. The application of the catalystin the biomass catalytic pyrolysis process comprises the following steps: tabletting the prepared Ni-Ca-based composite catalyst, crushing and sieving to obtain a catalyst powder with the granularitybeing 20-80 meshes; filling a fixed bed first-order reactor with a biomass material, filling a second-order reactor with the above prepared catalyst with the particle size being 20-80 meshes, introducing N2 to discharge the air in the reactors, simultaneously heating the reactors to a set temperature, letting pyrolysis steam generated by pyrolysis of the biomass material crack and reform on the surface of the Ni-Ca-based composite catalyst to obtain cracking steam, condensing the cracking steam and then drying to obtain gaseous and liquid products.

Description

technical field [0001] The invention belongs to the field of energy and chemical industry, and more specifically relates to an application method of a Ni-Ca-based composite catalyst orderedly assembled by nano-particles or nano-sheet structural elements in a biomass catalytic pyrolysis process. Background technique [0002] Biomass-based liquid fuel is a research hotspot and future development direction in the field of biomass resource conversion. From lignocellulosic biomass raw materials with complex structures and various types, they are converted into simple and uniform syngas by pyrolysis, and then assembled into liquid fuels for vehicles and aviation with ideal composition and molecular structure through a controllable process It provides a precise, controllable, and easy-to-achieve high-value utilization method for biomass resources. However, the fuel synthesis process generally requires the hydrogen-to-carbon ratio (H 2 / CO) reaches a hydrogen-rich level of 2~3 or ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/78B01J23/80B01J27/22B01J35/02C01B3/40C07C37/00C10G3/00C07C39/04B01J35/00
CPCB01J27/22B01J23/002B01J23/80B01J23/78C01B3/40C10G3/44C07C37/004B01J2523/00B01J35/40B01J2523/23B01J2523/27B01J2523/847B01J2523/31C07C39/04Y02P30/20Y02P20/52Y02E50/10
Inventor 杨双霞陈雷赵保峰孙来芝司洪宇谢新苹孟凡军
Owner ENERGY RES INST OF SHANDONG ACAD OF SCI
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