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Preparation method of catalyst for synthetic gas methanation to substitute natural gas

A technology to replace natural gas and catalysts, applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., can solve problems such as waste catalyst pollution, save a lot of costs, improve The effect of utilization rate and catalyst cost reduction

Active Publication Date: 2016-07-06
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method not only utilizes the Mo, Co and alumina supports in the spent hydrotreating catalyst, but also makes full use of the Ni and V deposited on the spent hydrotreating catalyst, which solves the pollution problem of spent catalysts, saves resources and improves benefits , is technically easy to implement, and the resulting synthesis gas methanation catalyst has the characteristics of low cost, high utilization rate of metal components, good selectivity, strong anti-coking ability and good stability

Method used

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  • Preparation method of catalyst for synthetic gas methanation to substitute natural gas
  • Preparation method of catalyst for synthetic gas methanation to substitute natural gas

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Experimental program
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Effect test

Embodiment 1

[0036] The spent hydrotreating catalyst (MoCo / Al 2 o 3 ), the oil on the surface of the catalyst was removed by extraction, dried at 110°C for 8h, and the obtained catalyst was calcined at 450°C for 4h to obtain the spent catalyst after treatment (containing Mo: 12.8wt%, Co: 2.3wt%, V: 2.5wt% , Ni: 1.9wt%, Al 2 o 3 : 71.2wt%), grind the catalyst to 200 mesh (means passing through a 200 mesh sieve), weigh 100 grams of powder, add 260mL of 98wt% concentrated sulfuric acid, stir at 50°C to dissolve the solid, collect the filtrate by filtration, and pour Add 54.01g of nickel nitrate to the filtrate, stir and dissolve, then add 27.31g of citric acid (the molar ratio of citric acid to Mo in the waste agent is 1), and then add 381mL of tetraethyl orthosilicate to control the pH value of the system to 4.0. Stir at ℃ until a gel is formed, age the gel at room temperature for 8h, then dry at 110°C for 8h, and calcinate the obtained solid at 600°C for 4h to obtain catalyst precursor A...

Embodiment 2

[0038] The spent hydrotreating catalyst (MoCo / Al 2 o 3 ), the oil on the surface of the catalyst was removed by extraction, dried at 110°C for 8h, and the obtained catalyst was calcined at 450°C for 4h to obtain the spent catalyst after treatment (containing Mo: 12.8wt%, Co: 2.3wt%, V: 2.5wt% , Ni: 1.9wt%, Al 2 o 3 : 71.2wt%), grind the catalyst to 200 mesh (referring to passing through a 200 mesh sieve), weigh 100 grams of powder, add 300mL of a mixed solution of 98wt% concentrated sulfuric acid and 65wt% concentrated nitric acid, the volume ratio is 2:1, in Stir at constant temperature at 50°C to dissolve the solid, collect the filtrate by filtration, add 41.32g of nickel nitrate to the filtrate, stir and dissolve, add 40.98g of citric acid (the molar ratio of citric acid to Mo in the waste agent is 1.5), and then add normal Ethyl silicate 67mL, control the pH value of the system to 4.0, stir at 70°C until a gel is formed, age the gel at room temperature for 8h, then dry ...

Embodiment 3

[0040] The spent hydrotreating catalyst (MoCo / Al 2 o 3 ), the oil on the surface of the catalyst was removed by extraction, dried at 110°C for 8h, and the obtained catalyst was calcined at 450°C for 4h to obtain the spent catalyst after treatment (containing Mo: 12.8wt%, Co: 2.3wt%, V: 2.5wt% , Ni: 1.9wt%, Al 2 o 3 : 71.2wt%), grind the catalyst to 200 mesh (referring to passing through a 200 mesh sieve), weigh 100 grams of powder, add 450mL of a mixed solution of 35wt% concentrated hydrochloric acid and 65wt% concentrated nitric acid, and the volume ratio is 1:1. Stir at constant temperature at 50°C to dissolve the solid, collect the filtrate by filtration, add 54.01g of nickel nitrate to the filtrate, stir and dissolve, add 13.66g of citric acid (the molar ratio of citric acid to Mo in the waste agent is 0.5), and then add normal Ethyl silicate 381mL, control the pH value of the system to 4.0, stir at 70°C until a gel is formed, age the gel at room temperature for 8h, the...

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Abstract

The invention relates to a preparation method of a catalyst for synthetic gas methanation to substitute natural gas. The catalyst comprises an active ingredient, an additive and a carrier. The preparation method is as below: treating a waste residue oil hydrogenation catalyst to prepare a catalyst precursor A; reducing the catalyst precursor A in a reducing atmosphere; adding the reduced catalyst precursor A and a polyol solution into a high pressure reactor, carrying out a hydrogenation reaction, placing a reaction effluent, filtering and dying to obtain a catalyst precursor B; and dissolving an active ingredient precursor in water to obtain a solution C, then adding the catalyst precursor B, drying and calcining to obtain the catalyst. The method of the present invention not only makes full use of waste residue oil hydrogenation catalyst, saves cost, but also promotes dispersion of more active ingredients on the surface of the carrier. The method improves the utilization of the active metal, and the conversion of carbon monoxide and selectivity of products.

Description

technical field [0001] The invention relates to a method for preparing a catalyst for producing natural gas by methanation of synthetic gas, in particular to a method for preparing a supported molybdenum-based catalyst for producing natural gas by methanation of synthetic gas. Background technique [0002] Methanation refers to CO / CO 2 with H 2 Under certain temperature, pressure and catalyst action, generate CH 4 At present, this reaction is widely used in the removal of trace carbon in the synthesis of ammonia or hydrogen production, methanation of coke oven gas, and coal-to-natural gas. Methanation is an important catalytic technology, especially in fuel applications, where it can be used to increase the calorific value of gas, allowing the conversion of coke oven gas, coal or biomass to natural gas. In recent years, with the rapid development of my country's coal-based natural gas industry, methanation, one of the core technologies, has received more and more attentio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/887C07C1/04C07C9/04C10L3/08
Inventor 孙晓丹张舒冬张信伟刘继华
Owner CHINA PETROLEUM & CHEM CORP
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