Metal wall-supported synthesis gas high temperature methanation catalyst and 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 the problems of carrier skeleton collapse, crushing, pulverization, etc. Achieve the effects of short mass transfer distance, easy amplification and low power consumption

Active Publication Date: 2018-07-10
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, 322.05g Ni(NO 3 ) 2 .6H 2 O, 88.18g La(NO 3 ) 3 .6H 2 O, 236ml 1M Zr(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 temperat...

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, 845.65g Ni (NO 3 ) 2 .6H 2 O, 116.24g La(NO 3 ) 3 .6H 2 O, 2000ml 1M Zr(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 ...

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Abstract

The invention provides a metal wall-loaded synthesis gas high-temperature methanation catalyst, a preparation method and application thereof. The catalyst uses nickel as the main catalytic active component, oxides of rare earth metals Ce, La, Sm, Pr, Gd or / and transition metals Zr, Mn, Co, Y, etc., binary or ternary composite oxides as additives , with a mixture of γ‑Al2O3 and AlOOH, Al(NO3)3·9H2O, TiO2, SiO2 as the actual physical carrier, all the above components are loaded on the pre-oxidized The shape of the treatment is flat and corrugated plate on the inert carrier Fe-Cr-Al-based alloy. The catalyst provided by the invention has the characteristics of good high-temperature hydrothermal stability, high utilization rate of active components, high mechanical strength, good thermal conductivity, reduced reaction bed pressure, simple preparation process, etc., and the modularized catalyst reaction unit is easy to enlarge, It is especially suitable for application in the complete methanation process of syngas with high temperature and high pressure multi-stage circulation.

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, compared with other coal chemical technology routes, coal-to-substitute natural gas (SNG) has the advantages of high energy conversion efficiency, less water consumption, and low investment, and is the preferred way of coal conversion one. 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 methane. After the oil ...

Claims

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Application Information

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Patent Type & Authority Patents(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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