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Coke-oven gas methanation catalyst and preparation method thereof

A catalyst, gas methane technology, applied in the direction of physical/chemical process catalysts, chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, etc., can solve complex preparation process, no sulfur resistance, thermal stability Poor performance and other problems, to achieve the effect of high methanation activity, good high temperature resistance, stable activity

Active Publication Date: 2013-05-08
WUHAN KELIN FINE CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
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Problems solved by technology

High-carbon oxides have also been studied in China. The new methanation catalyst prepared in the patent CN200710146033.7 is used for deep methanation of syngas. Its space velocity is low, the pressure is high, and the preparation process is complicated.
The coke oven gas methanation catalyst prepared in the patent CN 200810046429.9 is used for coke oven gas methanation to produce SNG. The catalyst has good activity and stability, but its disadvantages are poor high temperature resistance and large heat release in the coke oven gas methanation reaction , prone to overheating to sinter the catalyst, so the key technology is to prepare a methanation catalyst with high temperature resistance and good thermal stability
In addition to the above patented methanation catalysts, there are related literature reports, such as J105 and J106 methanation catalysts are mainly used in the synthesis of ammonia, they do not have sulfur resistance, and their thermal stability is not good, so they are not suitable for coke oven gas

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  • Coke-oven gas methanation catalyst and preparation method thereof
  • Coke-oven gas methanation catalyst and preparation method thereof
  • Coke-oven gas methanation catalyst and preparation method thereof

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preparation example Construction

[0026] The preparation method of coke oven gas methanation catalyst of the present invention can be prepared by comprising the following main steps:

[0027] (1) Grinding and mixing metatitanic acid, zirconia and silicon dioxide raw materials in proportion, adding 2% nitric acid and 3% scallop powder by mass to knead and form them, after standing for 4 hours, dry at 120°C for 3 ~4h, then roasted at 550°C for 3~5h, then raised to 800~1300°C for 6~8h, and made TiO by roasting at high temperature 2 -ZrO 2 -SiO 2 Composite oxide carrier;

[0028] (2) The active component is made into a solution in the form of nitrate, impregnated in equal volume, the dipping temperature is 50-80°C, and soaked for 4-6 hours, so that the active component is impregnated in the carrier in the form of nitrate, and then soaked at 110-120 ℃ drying for 3-4 hours, and then roasting at 350-550 ℃ for 3-5 hours; the coke oven gas methanation catalyst product is obtained.

[0029] If necessary, the second ...

Embodiment 1

[0033] Grind and mix 34.6g of metatitanic acid, 46.2g of zirconia, 69.2g of silicon dioxide, and 4.5g of scallop powder evenly, then add an appropriate amount of 2% nitric acid aqueous solution and knead it into a shape. After standing for 4 hours, dry it at 120°C for 3 hours, and then 550 ℃ calcination for 3 hours, and then raised to 1300 ℃ for 6 hours to obtain TiO 2 -ZrO 2 -SiO 2 Composite oxide support, in which TiO 2 , ZrO 2 , SiO 2 3:4:6, the pore volume is 0.5cm 3 / g, the specific surface area is 175m 2 / g, the bulk density is 0.75g / ml, which is the carrier A.

Embodiment 2

[0035] Grind and mix 43.3g of metatitanic acid, 21.4g of zirconia, 52.0g of silicon dioxide, and 3.9g of scallop powder, add an appropriate amount of 2% nitric acid aqueous solution, and knead it into a shape. After standing for 4 hours, dry it at 120°C for 3.5 hours, and then Calcined at 550°C for 3.5h, then raised to 1000°C for 7h to obtain TiO 2 -ZrO 2 -SiO 2 Composite oxide support, in which TiO 2 , ZrO 2 , SiO 2 5:3:6, the pore volume is 0.58cm 3 / g, the specific surface area is 195m 2 / g, the bulk density is 0.73g / ml, which is the carrier B.

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Abstract

The invention provides a coke-oven gas methanation catalyst and a preparation method thereof. The coke-oven gas methanation catalyst is prepared by loading a certain amount of active ingredients Ni on composite oxide TiO2-ZrO2-SiO2 serving as a carrier, and using rare-earth elements RE and metal M as aids. The catalyst has the advantages which cannot be achieved by other methanation catalysts. The catalyst has the characteristics of high low-temperature activity, sulfur resistance capacity, good high temperature resistance performance and the like, and the function of hydrocarbon cracking andgood antioxidation performance and the like and is easy to prepare.

Description

technical field [0001] The invention relates to the technical field of methanation catalysts, and is especially suitable for carbon oxides (CO, CO) in coke oven gas and other industrial raw material gases. 2 ) to carry out the catalyst required for the methanation reaction and the preparation method thereof. Background technique [0002] my country's coke output in 2009 was 353 million tons, of which 1 / 3 of production capacity was in iron and steel complexes, and 2 / 3 was in independent coking enterprises. About 400m by-product per ton of coke 3 Calculation of coke oven gas, independent enterprises produce 141.2 billion cubic meters of coke oven gas every year 3 About 20 billion m3 of coke oven gas is released every year, except for heating for personal use and civil use (as city gas), and production of synthetic ammonia or methanol. 3 , and the calorific value exceeds the amount of natural gas in the first phase of the "West-to-East Gas Pipeline". At present, my country'...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/83B01J23/889C07C9/04C07C1/04C07C1/12
Inventor 陈宗杰王国兴张先茂王泽王利勇王天元赵志杰
Owner WUHAN KELIN FINE CHEM
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