High-temperature methanation catalyst for producing natural gas through coal and preparation method of catalyst

A methanation catalyst, coal-to-natural gas technology, applied in catalyst activation/preparation, physical/chemical process catalyst, catalyst carrier, etc., can solve the problems of low thermal stability of catalyst, low thermal stability of methanation catalyst, etc. The effect of improving methanation activity and thermal stability, strong ability to store and release oxygen, high mechanical strength

Active Publication Date: 2014-04-09
SOUTHWEST RES & DESIGN INST OF CHEM IND +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Chinese patent CN 102319574 A reports a mesoporous γ-alumina modified by cerium oxide as a carrier, and oxides of transition metals iridium, lanthanum, copper, iron or alkaline earth metals magnesium and calcium as auxiliary agents for syngas methanation Catalyst; Chinese patent CN 10224 7861 A has reported a kind of coal-to-natural gas high-temperature methanation catalyst, with Ni or FeNi alloy as active component, with A1 2 o 3 and ZrO 2 As a carrier, one or more metals and/or their oxides in the group consisting of Mo, V, W, Ir, Cr,

Method used

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  • High-temperature methanation catalyst for producing natural gas through coal and preparation method of catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Embodiment 1 prepares high-temperature methanation catalyst I

[0029] (1) 2L containing 25.23g Ce(NO 3 ) 3 ·6H 2 O, 257.44g Al(NO 3 ) 3 9H 2 O and 28.51g Zr(NO 3 ) 4 The mixed aqueous solution was added to the constant temperature reaction kettle, the reaction temperature was controlled at 70°C, and 8% Na was added under the condition of electric stirring. 2 CO 3 Aqueous solution, adjust the pH value to 8.5, after constant temperature reaction for 2 hours, the slurry is washed and filtered, dried at 80°C for 8 hours, and calcined at 450°C for 6 hours to obtain CeO 2 -Al 2 o 3 -ZrO 2 Composite carrier.

[0030] (2) The above CeO 2 -Al 2 o 3 -ZrO 2 The composite carrier was dispersed in 0.5L containing 116.79g Ni(NO 3 ) 2 ·6H 2 O, 29.51g Ca(NO 3 ) 2 4H 2 O and 31.57g Cr(NO 3 ) 3 9H 2 In the nitrate solution of O, soak at 50°C for 6h, then raise the temperature to 80°C, and evaporate the slurry to dryness.

[0031] (3) The evaporated material was...

Embodiment 2

[0032] Example 2 Preparation of High Temperature Methanation Catalyst II

[0033] (1) 2L containing 30.28g Ce(NO 3 ) 3 ·6H 2 O, 183.88g Al(NO 3 ) 3 9H 2 O and 35.76g Zr(NO 3 ) 4 The mixed aqueous solution was added to the constant temperature reaction kettle, the reaction temperature was controlled at 75 ° C, and 10% Na was added under the condition of electric stirring. 2 CO 3 Aqueous solution, adjust the pH value to 8.0, after constant temperature reaction for 1.5h, the slurry is washed and filtered, dried at 80°C for 8h, and calcined at 500°C for 5h to obtain CeO 2 -Al 2 o 3 -ZrO 2 Composite carrier.

[0034] (2) The above CeO 2 -Al 2 o 3 -ZrO 2 The composite carrier was dispersed in 0.5L containing 136.25g Ni(NO 3 ) 2 ·6H 2 O, 44.87 Mg(NO 3 ) 2 ·6H 2 O and 31.57g Cr(NO 3 ) 3 9H 2 In the nitrate solution of O, soak at 60°C for 5h, then raise the temperature to 90°C, and evaporate the slurry to dryness.

[0035] (3) The evaporated material was dried...

Embodiment 3

[0036] Example 3 Preparation of High Temperature Methanation Catalyst III

[0037] (1) 2L containing 20.19g Ce(NO 3 ) 3 ·6H 2 O, 220.66g Al(NO 3 ) 3 9H 2 O and 33.01g Zr(NO 3 ) 4 The mixed aqueous solution was added to the constant temperature reactor, the reaction temperature was controlled at 75°C, and 12% Na was added under the condition of electric stirring. 2 CO 3 Aqueous solution, adjust the pH value to 8.5, after constant temperature reaction for 2 hours, the slurry is washed and filtered, dried at 80°C for 8 hours, and calcined at 500°C for 5 hours to obtain CeO 2 -Al 2 o 3 -ZrO 2 Composite carrier.

[0038] (2) The above CeO 2 -Al 2 o 3 -ZrO 2 The composite carrier was dispersed in 0.5L containing 97.32g Ni(NO 3 ) 2 ·6H 2 O, 51.28g Mg(NO 3 ) 2 ·6H 2 O and 17.68g Mn(NO 3 ) 2 4H 2 In the nitrate solution of O, soak at 40°C for 6h, then raise the temperature to 85°C, and evaporate the slurry to dryness.

[0039] (3) The evaporated material was d...

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Abstract

The invention discloses a high-temperature-resistant methanation catalyst in a process of producing natural gas through coal. The high-temperature-resistant methanation catalyst comprises a carrier, an active component and assistants, wherein the carrier is a compound of CeO2, Al2O3 and ZrO2, the active component is Ni, the first assistant is one or two of alkaline earth metal oxides CaO and MgO, and the second assistant is one or two of transition metal oxides Cr2O3 and MnO. The high-temperature-resistant methanation catalyst disclosed by the invention has the advantages that the CeO2-Al2O3-ZrO2 compound oxide is used as the carrier to endow the catalyst with high mechanical strength, large specific surface area and heat resistance; the methanation activity of the catalyst is high and the thermal stability is strong; the alkaline earth metal oxide CaO and/or MgO are/is used as the first assistant to perfect the surface acidity of the carrier and inhibit carbon deposition of the catalyst; the Cr2O3 and/or MnO are/is used as the second assistant to beneficially improve the dispersibility of NiO particles and promote NiO reduction so as to improve the activity of the catalyst.

Description

technical field [0001] The invention relates to a methanation catalyst, in particular to a high-temperature-resistant methanation catalyst in the coal-to-natural gas process and a preparation method thereof. Background technique [0002] With the completion of my country's "West-to-East Gas Transmission" and "Sichuan-to-East Gas Transmission" projects, offshore natural gas landings and coastal LNG imports continue to increase, my country's natural gas industry has entered a period of rapid development, and the consumer market has grown rapidly. In 2012, the import volume of natural gas (including liquefied natural gas) was 42.5 billion cubic meters, a year-on-year increase of 31.1%. It is estimated that in 2020, the demand for natural gas is expected to exceed 300 billion Nm 3 , the market gap will reach 90 billion Nm 3 , by then 40% will depend on imports. [0003] my country is a country that is "rich in coal, poor in oil, and low in gas". Using my country's rich coal r...

Claims

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Application Information

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IPC IPC(8): B01J23/86B01J23/889B01J32/00B01J37/03C10L3/08
Inventor 李敬邢云何洋王秀林刘玉成王洁曾凌云高振郑珩崔峰张新波冯雅晨
Owner SOUTHWEST RES & DESIGN INST OF CHEM IND
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