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A sulfur-resistant methanation process of coke oven gas instead of natural gas

A technology for sulfur-resistant methanation and natural gas replacement. It is used in the petroleum industry, gas fuel, and fuel. It can solve the problems of sulfur poisoning and deactivation, and is not resistant to sulfur. Wide range of effects of sulfur

Inactive Publication Date: 2016-03-02
SEDIN ENG
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0013] In order to overcome the shortcomings of the methanation catalyst in the existing coke oven gas production instead of natural gas process, which is not resistant to sulfur and is easily poisoned and deactivated when encountering trace amounts of sulfur, the purpose of the present invention is to provide a high energy utilization rate, low equipment investment and operating costs, and easy A process suitable for coke oven gas sulfur resistant methanation to synthesize natural gas

Method used

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  • A sulfur-resistant methanation process of coke oven gas instead of natural gas

Examples

Experimental program
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Effect test

Embodiment 1

[0048] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0049] 60-80 mesh, specific surface area 150m 2 / g γ-Al 2 o 3 Calcined at 450°C for 5h, at a temperature of 35°C and a stirring speed of 120r / min, the Mo(NO 3 ) 3 ·5H 2 O, Ni(NO 3 ) 2 ·6H 2 O, γ-Al 2 o 3 According to the mass percentage of Mo: Ni: Al 25%: 30%: 45% equal volume impregnation and stirring for 8 hours, after standing for 4 hours, evaporate at 80°C until viscous, then put it in an oven for 12 hours and dry at 110°C, and then grind to 60-80 mesh Place in a muffle furnace and bake at 550°C for 6 hours to obtain a precursor; the volume composition is 25%H 2 and 75%N 2 , in an atmosphere with a flow rate of 80mL / min, using a two-stage temperature program, first raising the temperature to 350 °C at 5 °C / min, and then raising the temperature to 550 °C at 3 °C / min for 6 hours to obtain a mass percentage of Mo:Ni:Al of 25 %: 30%: 45% Mo-Ni-Al slurry bed coke oven gas sul...

Embodiment 2

[0056] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0057] Calcinate γ-Al2O3 with 160-200 mesh and specific surface area of ​​280m2 / g at 550°C for 7h, and then mix Mo(NO3)3·5H2O, Co(NO3)2·6H2O at 30°C and stirring speed of 200r / min , Ni(NO3)2·6H2O, γ-Al2O3 according to the mass percentage of Mo: Co: Ni: Al 20%: 10%: 35%: 35% equal volume impregnation and stirring for 24h, after standing for 10h, evaporate at 70°C to viscous , and then placed in an oven for 24 hours at 100°C, and then ground to 160-200 mesh, placed in a muffle furnace and roasted at 500°C for 8 hours to obtain a precursor; the volume composition is 15% H2 and 85% N2, and the flow rate is 120mL / In the atmosphere of min, adopt two-stage temperature program, first raise the temperature to 350°C at 5°C / min, and then raise the temperature to 600°C at 2°C / min for constant temperature reduction for 12h to obtain the mass percentage of Mo:Co:Ni:Al 20%:10 %: 35%: 35% Mo-Co-Ni-Al...

Embodiment 3

[0064] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0065] Calcinate SiO2 with 80-100 mesh and specific surface area of ​​180m2 / g at 450°C for 4h. Under the conditions of temperature 25°C and stirring speed of 120r / min, Ni(NO3)2·6H2O, Co(NO3)2·6H2O, SiO2 According to the mass percentage of Ni: Co: Si 30%: 20%: 50% equal volume impregnation and stirring for 8 hours, after standing for 4 hours, evaporate to viscous at 80°C, then dry in an oven at 110°C for 12 hours, and then grind to 80-100 mesh Place in a muffle furnace and roast at 450°C for 4 hours to prepare the precursor; in an atmosphere with a volume composition of 20% H2 and 80% N2, and a flow rate of 100mL / min, use two-stage temperature programming, first at 4°C / min Raise the temperature to 350°C, then raise the temperature to 550°C at 2°C / min for constant temperature reduction for 6 hours to obtain Ni-Co-Si slurry bed coke oven gas sulfur-resistant methane with a mass percentage ...

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Abstract

The invention relates to a sulfur methanation resistant process for preparing substitute natural gas from coke-oven gas. The process comprises the steps: enabling raw material gas, which is formed through carrying out carbon supplementing on the coke-oven gas, to enter a slurry bed from the bottom of the slurry bed, carrying out methanation reaction, discharging crude product gas from the top of a slurry-bed reactor, enabling the crude product gas to enter a gas-liquid-solid separator, enabling a separated liquid-solid phase and a catalyst containing an inert medium, which is circulated at the bottom of the slurry reactor, to enter a liquid-solid separator together, discharging a solid phase separated by the liquid-solid separator from the bottom of the liquid-solid separator, and carrying out catalyst regeneration; discharging a liquid phase separated by the liquid-solid separator from the middle-upper part of the liquid-solid separator, and enabling the liquid phase to enter an inert medium storage tank; enabling a regenerated sulfur methanation resistant catalyst to enter the inert medium storage tank, mixing and then pumping a mixture into the slurry-bed reactor by a circulating pump; and purifying the crude product gas separated by the gas-liquid-solid separator, thereby preparing the natural gas. The process has the advantages of high energy source utilization ratio, low equipment investment and operating costs and easiness in operation.

Description

technical field [0001] The invention belongs to a synthetic natural gas process, in particular to a process for producing synthetic natural gas through sulfur-resistant methanation of coke oven gas. It belongs to the field of new energy utilization technology. Background technique [0002] my country is the world's largest coke producer, coke production and a large amount of coke oven gas by-product. Part of these coke oven gas is used to make methanol, synthetic ammonia and factory gas, while remote areas are discharged in vain. The current energy utilization rate of coke oven gas is about 55%. According to the characteristics of coke oven gas composition "more hydrogen and less carbon", the use of coke oven gas methanation to synthesize artificial natural gas and by-product hydrogen will have very strong economic competition It can achieve the purpose of improving the energy utilization rate of coke oven gas. At present, in addition to producing synthetic ammonia and me...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10L3/08
Inventor 曹会博崔晓曦张庆庚李晓范辉
Owner SEDIN ENG
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