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Metal wall-supported type high-temperature synthetic gas methanation catalyst as well as preparation method and application thereof

A methanation catalyst and catalyst technology, applied in the direction of metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, chemical instrument and method, etc., can solve problems such as crushing, carrier skeleton collapse, pulverization, etc. Achieve the effects of short mass transfer distance, easy amplification and low power consumption

Active Publication Date: 2016-06-01
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Catalysts that use cordierite honeycomb ceramics as a carrier to impregnate methanation active components have appeared abroad, such as patents US4002658, GB1495127, etc., which can effectively reduce the bed resistance drop. Long-term use in the environment may cause the carrier skeleton to collapse, break or even pulverize

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Take a 30×300mm Fe-Cr-Al alloy sheet, wash and remove oil, and then heat-treat it at 1000°C for 5 hours to form a dense Al on the surface. 2 o 3 The oxide film has a weighing mass of 14.53g.

[0042] Take 34.70g of γ-Al 2 o 3 With 47.21g of AlOOH, 28.35g of Al(NO 3 ) 3 9H 2 0, adding 2g of methyl cellulose, 10ml concentration of 2wt% polyvinyl alcohol solution and 300ml concentration of 3wt% nitric acid solution, carried out wet ball milling with a high energy ball mill for 16 hours to obtain a mixed slurry with a particle size of 1.5 μm.

[0043] Adjust the pH value of the above slurry to 3.5 with 65wt% nitric acid, spray the above slurry onto the above-mentioned pretreated Fe-Cr-Al alloy sheet with a spray gun, dry it at 120°C for 12 hours, and then dry it at 3°C / min The heating rate was raised to 600° C. and maintained for 2 hours, and then naturally lowered to room temperature to obtain an Al-coated catalyst intermediate. Repeat this process once until Al 2 ...

Embodiment 2

[0046] Take a 30×300mm Fe-Cr-Al alloy sheet, wash and remove oil, and then heat-treat it at 1000°C for 3 hours to form a dense Al on the surface. 2 o 3 The oxide film has a weighing mass of 14.87g.

[0047] Take 69.63g of γ-Al 2 o 3 With 69.20g of AlOOH, 52.45g of Al(NO 3 ) 3 9H 2 O, 322.05gNi(NO 3 ) 2 .6H 2 O, 88.18gLa(NO 3 ) 3 .6H 2 O, 236ml1MZr (NO 3 ) 4 After the solutions were mixed, add 3g of methylcellulose, 15ml of 2wt% polyvinyl alcohol solution and 257ml of 3wt% nitric acid solution, and perform wet ball milling with a high-energy ball mill for 16 hours to obtain a mixed slurry with a particle size of 1.5 μm .

[0048] Adjust the pH value of the above slurry to 3.5 with 65wt% nitric acid, spray the above slurry onto the above-mentioned pretreated Fe-Cr-Al alloy sheet with a spray gun, dry it at 120°C for 12 hours, and then dry it at 1°C / min The heating rate was raised to 500° C. and maintained for 4 hours, and then naturally lowered to room temperature...

Embodiment 3

[0050] Take a 30×300mm Fe-Cr-Al alloy sheet, wash and remove oil, and then heat-treat it at 1000°C for 3 hours to form a dense Al on the surface. 2 o 3 The oxide film has a weighing mass of 14.11g.

[0051] Take 169.63g of γ-Al 2 o 3 with 1M TiO 2 Sol 5670ml, the AlOOH of 142.35g, 845.65gNi (NO 3 ) 2 .6H 2 O, 116.24gLa(NO 3 ) 3 .6H 2 O, 2000ml1MZr (NO 3 ) 4 After the solutions were mixed, add 10g of methyl cellulose, 45ml of a concentration of 2wt% polyvinyl alcohol solution and 335ml of a concentration of 3wt% nitric acid solution, and carry out wet ball milling with a high-energy ball mill for 12 hours to obtain a mixed slurry with a particle size of 1.2 μm .

[0052] Adjust the pH value of the above-mentioned slurry to 4.0 with 65wt% nitric acid, spray the above-mentioned slurry onto the above-mentioned pretreated Fe-Cr-Al alloy sheet with a spray gun, dry it at 120°C for 12 hours, and then use 1°C / min The heating rate was raised to 500°C and maintained for 4 h...

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Abstract

The invention provides a metal wall-supported type high-temperature synthetic gas methanation catalyst as well as a preparation method and application thereof. The catalyst takes nickel as a main catalytic active component, oxides and binary or ternary composite oxides of rare-earth metals Ce, La, Sm, Pr, Gd or / and transition metals Zr, Mn, Co, Y and the like as auxiliaries and a mixture of one or several of gamma-Al2O3, AlOOH, Al(NO3)3*9H2O, TiO2 and SiO2 as an actual physical carrier; all the above components are supported on Fe-Cr-Al-based alloy as a flat plate type and corrugated plate type inert carrier subjected to pre-oxidation treatment in a spraying or / and dipping way. The catalyst provided by the invention has the characteristics of good high-temperature hydrothermal stability, high active component utilization rate, high mechanical strength, good heat-conducting property, reduced reaction bed pressure, simple preparation process and the like; a modularly-assembled catalyst reaction unit is easy to amplify; the metal wall-supported type high-temperature synthetic gas methanation catalyst is particularly suitable for being applied to a complete high-temperature and high-pressure multistage cyclic synthetic gas methanation process.

Description

technical field [0001] The invention relates to a synthesis gas high-temperature methanation catalyst, in particular to a metal wall-loaded synthesis gas high-temperature methanation catalyst and a preparation method and application thereof. Background technique [0002] In recent years, my country's demand for natural gas, a clean fuel, has grown explosively, which has also led to an upsurge in research and development of coal-to-natural gas technology in my country. Techno-economic analysis shows that in some specific areas, coal-based natural gas (Substitute Natural Gas, SNG) has the advantages of high energy conversion efficiency, less water consumption, and low investment compared with other coal chemical technology routes, and is one of the preferred ways of coal conversion . One of the core key technologies of coal-to-natural gas is the complete methanation technology of syngas, that is, CO and a small amount of CO in syngas 2 with H 2 The reaction converts to meth...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/86C07C1/04C07C9/04
Inventor 王树东袁中山王胜
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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