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Sulfur-tolerant methanation catalyst and its preparation method

A technology for sulfur-resistant methanation and catalyst, which is applied in the field of sulfur-resistant methanation catalyst and its preparation, and can solve the problems of low methane selectivity and low CO conversion rate, etc.

Inactive Publication Date: 2012-05-23
ENN SCI & TECH DEV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Patent US4491639 mentions that adding Zr, Ce, etc. to the sulfide catalyst of V, Mo or W can enhance the stability of the catalyst. This patent clearly points out that the sulfide of the above metal is directly used as the catalyst instead of using a porous substance as a carrier. However, the use of La is not mentioned in this patent, and the conversion rate of CO obtained in this patent is still low, only 50-78% at 530 ° C, and from the perspective of the proportion of methane in its product gas, its methane Not very selective, only 70-80%

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  • Sulfur-tolerant methanation catalyst and its preparation method

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[0032] The second aspect of the present invention is the preparation method of the sulfur-tolerant methanation catalyst described in the first aspect of the present invention, which generally includes a co-impregnation step, a drying step and a calcination step. Specifically, step a is to prepare an impregnation solution, the solution contains molybdenum precursors and cobalt precursors, and at least one of zirconium precursors, cerium precursors or lanthanum precursors. Since this solution is used to impregnate the support, it is called an impregnation solution. Wherein, the solvent is water, the molybdenum precursor is a water-soluble molybdate, the cobalt precursor is a water-soluble cobalt salt, and the zirconium precursor is a water-soluble zirconium salt or a water-soluble zirconate or zirconate, The cerium precursor is a water-soluble cerium salt, and the lanthanum precursor is a water-soluble lanthanum salt.

[0033]Wherein the water-soluble molybdate is selected from...

Embodiment 1

[0054] Weigh 18.42g (NH 4 ) 6 Mo 7 o 24 4H 2 O, 9.67g Co(NO 3 ) 2 ·6H 2 O, 5.06gCe(NO 3 ) 3 ·6H 2 O was dissolved in 60mL of high-purity water, and N-diethanolamine complex stabilizer was added. 100g Al 2 o 3 (The Al 2 o 3 γ-Al 2 o 3 , its physical properties are as follows: specific surface area ≥ 200m2 / g, pore volume ≥ 0.40mL / g, water absorption ≥ 52%, bulk density 0.65-0.72g / mL, crushing strength ≥ 80N / grain, particle size 3- 5mm, the same below) was put into the prepared mixed impregnation solution, left overnight, dried naturally, then dried at 120°C for 8h, and finally calcined at 450°C for 3h to obtain the MoCoCe-a catalyst. Take 5mL catalyst for evaluation test, the results of catalyst activity evaluation and heat resistance evaluation experiment are shown in Table 1.

Embodiment 2

[0056] Weigh 18.42g (NH 4 ) 6 Mo 7 o 24 4H 2 O, 9.67g Co(NO 3 ) 2 ·6H 2 O, 5.26g ZrOCl 2 ·8H 2 O was dissolved in 60mL high-purity water, and citric acid complex stabilizer was added. 100gAl 2 o 3 Put it into the prepared mixed impregnation solution, let it stand overnight, dry it naturally, then dry it at 120°C for 8 hours, and finally calcinate it at 450°C for 3 hours to obtain the MoCoZr-a catalyst. Take 5mL catalyst for evaluation test, the results of catalyst activity evaluation and heat resistance evaluation experiment are shown in Table 1.

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Abstract

The invention relates to a sulfur-tolerant methanation catalyst and its preparation method, and relates to a sulfur-tolerant methanation catalyst which can be used under a wide operation condition particularly at high temperature and its preparation method, and the sulfur-tolerant methanation catalyst contains a carrier and an active component loaded on the carrier. The carrier is selected from alumina, silica, zirconium dioxide, active carbon or molecular sieve, the active component comprises a molybdenum oxide taken as a main active component, a cobalt oxide taken as a first auxiliary agent; and a zirconium oxide, a cerium oxide or a lanthanum oxide, or a mixture composed of at least two above oxides which is taken as a second auxiliary agent. The invention also discloses the preparation method of the sulfur-tolerant methanation catalyst which is composed of a dipping step, a drying step and a calcining step.

Description

technical field [0001] The invention relates to a methanation catalyst and a preparation method thereof, in particular to a sulfur-resistant methanation catalyst suitable for wide operating conditions, especially at high temperatures, and a preparation method thereof. Background technique [0002] As a low-carbon, high-efficiency, and safe clean energy, natural gas will account for an increasing proportion of primary energy consumption. The amount of natural gas that can be exploited is very limited, and the crisis of gas sources has caused the price of natural gas to rise nationwide. Therefore, many domestic and foreign companies and R&D institutions use coal or heavy oil and other fossil raw materials to produce natural gas, and my country has also carried out many coal-to-natural gas projects. The simple process of coal-to-natural gas is as follows: coal gasification to produce synthesis gas (CO, H 2 ), then carry out desulfurization and decarbonization and water gas sh...

Claims

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Application Information

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IPC IPC(8): B01J23/887B01J23/882C07C9/04C07C1/04
Inventor 王会芳张荣毕继诚甘中学
Owner ENN SCI & TECH DEV
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