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Coal gas high-temperature methanation catalyst and preparation method thereof

A methanation catalyst, coal-to-natural gas technology, applied in physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problem that the catalyst does not have high temperature resistance and pressure resistance. and other problems, to achieve the effect of improving high temperature hydrothermal stability, long life, high activity, and reducing the amount of Ni

Inactive Publication Date: 2011-11-23
CHNA ENERGY INVESTMENT CORP LTD +2
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Patent application publication CN101380581A has prepared a methanation catalyst that can be used at a pressure of 1.0-6.0 MPa, but the use temperature is still below 500°C
Although the methanation catalyst prepared by the patent application publication CN101468311A claims to be used in many occasions including coal-to-natural gas, the catalyst in this patent application does not have the high temperature resistance and pressure resistance required by the high temperature methanation process
The coke oven gas methanation catalyst proposed by the patent application publication CN101391218A still has a large gap with the coal-to-natural gas process in terms of high temperature resistance and pressure resistance

Method used

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  • Coal gas high-temperature methanation catalyst and preparation method thereof
  • Coal gas high-temperature methanation catalyst and preparation method thereof
  • Coal gas high-temperature methanation catalyst and preparation method thereof

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preparation example Construction

[0033] In the preparation method of the present invention, the active component that comprises catalyst, the various metal elements of support, as the soluble compound of Ni, Fe, Al, Zr etc. is nitrate, sulfate, hydrochloride, these strong acid salts The aqueous solution itself is acidic and can provide free metal ions; some soluble or insoluble compounds are carbonates, oxides, hydroxides, and hydrates of oxides and their minerals, such as monohydrate alumina, trihydrate oxide Aluminum, basic zirconium carbonate, etc., can be acidified by aqueous solutions such as nitric acid, sulfuric acid, hydrochloric acid, or the aqueous solution of the above-mentioned acidic soluble compounds, so that all or part of the metal elements contained in them can be dissolved in the form of metal ions. in the water. In order to avoid residues of heteroatoms such as sulfur and chlorine, nitrates are preferred for soluble salts, nitric acid is preferred for acidification treatment, and carbonates...

Embodiment 1

[0044] Take 37.7 grams of Ni(NO 3 ) 2 ·6H 2 O, 112.5 g Al(NO 3 )3 9H 2 O, 26.8 grams of Zr(NO 3 ) 4 ·5H 2 O, 0.3 g Ir(NO 3 ) 4 , dissolved in 1000ml deionized water. Over 20 minutes, 103.2 g of ammonium bicarbonate were added slowly, followed by stirring for a further 2 hours. The suspension was filtered and washed with 2000 ml of deionized water to obtain a light green precipitate. The filter cake was dried with hot air at 120° C. for 20 hours, and roasted at 400° C. for 16 hours to obtain 32.6 grams of a roasted sample. Crushed and passed through a 100-mesh sample sieve, mixed with graphite and cellulose and pressed to obtain cylindrical (Φ3) catalyst particles. After firing at 1100°C for 3 hours, the catalyst B in the oxidation state was obtained, in which, IrO 2 The content is 0.5%.

Embodiment 2

[0046] Take 37.7 grams of Ni(NO 3 ) 2 ·6H 2 O, 112.5 g Al(NO 3 ) 3 9H 2 O and 26.8 g of Zr(NO 3 ) 4 ·5H 2 O, 20.8 g Mg(NO 3 ) 2 ·6H 2 O, dissolved in 1000ml of water to obtain a green clear solution. Take MoO 3 Content is 1.0 grams of ammonium molybdate dissolved in 250 ml of aqueous solution prepared by 103.2 grams of ammonium bicarbonate, and cocurrent precipitation with the aforementioned nitrate solution as an acidic solution. After aging for 3 hours, the precipitate was filtered and washed with 2000 ml of water. After the filter cake was dried with hot air at 120°C for 20 hours, it was crushed and passed through a 100-mesh sample sieve. After adding scallop powder, oxalic acid and water, it was extruded to obtain strip-shaped (Φ3) catalyst particles. Calcined at 400°C for 16 hours and at 1100°C for 3 hours to obtain catalyst C in oxidation state, in which MgO and MoO 3 The contents were 8.8% and 2.7%.

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Abstract

The invention discloses a coal gas high-temperature methanation catalyst and a preparation method thereof. The coal gas high-temperature methanation catalyst is prepared from a Ni or FeNi alloy as an active component, Al2O3 and ZrO2 as carriers, and one or more of metals of Mo, V, W, Ir, Cr, Mg, Ca, Y, Ce and La and / or oxides thereof, wherein the one or more of the metals and / or the oxides are utilized as auxiliary agent. The coal gas high-temperature methanation catalyst comprises: by weight, 1 to 50% of Ni or 1 to 55% of FeNi as an active component, 0.01 to 25% of one or more metals and / or oxides thereof as an auxiliary agent, and the balance Al2O3 and ZrO2 as carriers, wherein a weight ratio of Al2O3 to ZrO2 is in a range of 50 to 0.1. The coal gas high-temperature methanation catalyst has good high-temperature hydrothermal stability and high activity, and can reduce production cost and satisfy requirements of application of an adiabatic fixed bed high-temperature methanation process and other high-temperature methanation processes.

Description

technical field [0001] The invention relates to a coal-to-natural gas process, in particular to a high-temperature methanation catalyst suitable for the process and a preparation method thereof. Background technique [0002] In the 1970s and 1980s, two world energy crises occurred. The energy supply of western industrial countries was cut off and the economy stagnated. Concerns about natural gas reserves and the need to ensure a stable supply of natural gas in the future have led European and American countries to intensify research on coal-based natural gas that has been carried out for more than 30 years. During this period, many coal-to-natural gas technologies have been developed, and many projects have been planned. However, after the energy crisis, the price of crude oil has been falling all the way, and coal-to-natural gas no longer has an economic advantage. In the world, only the United States established a commercially operated coal-to-natural gas plant in 1984, ...

Claims

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Application Information

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IPC IPC(8): B01J23/883B01J23/847B01J23/888B01J23/89B01J23/86B01J23/755B01J23/78B01J23/83C07C9/04C07C1/04C10L3/08
Inventor 赵利军李克健蔺华林
Owner CHNA ENERGY INVESTMENT CORP LTD
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