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

Abstract

The invention provides a sulfur-tolerant methanation process for preparing natural gases from coke oven gases. The sulfur-tolerant methanation process comprises the steps that after carbon is replenished to the coke oven gases to form feed gases and the feed gases are compressed, a part of the feed gases enter a sulfur-tolerant slurry bed reactor from the bottom of a slurry bed reactor containing a sulfur-tolerant methanation catalyst to undergo methanation reaction, the product gases enter a gas-liquid-solid separator, the liquid and solid phases are discharged from the bottom of the separator and flow black to the sulfur-tolerant slurry bed reactor, the gas phase separated from the top of the separator and the other part of the feed gases flowing along the lateral side enter a fixed bed sulfur-tolerant methanation reactor from the bottom of a fixed bed containing a sulfur-tolerant catalyst to undergo sulfur-tolerant methanation, the tail gases are exhausted from the top and enter a heat recovery device to undergo heat exchange and then the natural gas products are obtained through purification. The sulfur-tolerant methanation process has the advantages of high energy utilization rate, low equipment investment and operating cost 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. Background technique

[0002] my country is the world's largest coke producer, coke production and a large amount of coke oven gas by-product. In addition to the production of synthetic ammonia and methanol, these coke oven gas has a surplus of about 20 billion cubic meters of coke oven gas every year, causing huge energy waste and environmental pollution. Utilizing coke oven gas for methanation to produce natural gas not only produces obvious economic and environmental benefits, but also has great impact on energy. Structural adjustments are also important.

[0003] The main components of coke oven gas are probably (volume ratio): H 2 Content 50-60%, CH 4 Content 20-28%, CO content 5.5-8.5%, CO 2 Content 2-2.5%. In addition, there are trace amounts of H 2 S, COS, HCN, NH ...

Examples

Embodiment 1

[0045] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0046] 160-200 mesh, specific surface area 280m 2 / g γ-Al 2 o 3 Calcined at 550°C for 7h, at a temperature of 25°C and a stirring speed of 200r / 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 30%: 20%: 50%, impregnate and stir for 24 hours, after standing for 10 hours, evaporate to viscous at 70°C, then put it in an oven for 24 hours at 110°C, and then grind to 160-200 mesh Place in a muffle furnace and bake at 450°C for 8 hours to obtain a precursor; the volume composition is 15%H 2 and 85%N 2 , in an atmosphere with a flow rate of 120mL / min, a two-stage temperature program was adopted, firstly the temperature was raised to 350°C at 5°C / min, and then the temperature was raised to 600°C at 2°C / min for constant temperature reduction for 12 hours to obtain a mass percentage of Mo:Ni:Al of 30 %: 20%: 50% Mo-Ni-Al slur...

Embodiment 2

[0052] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0053] 120-140 mesh, specific surface area 240m 2 / g TiO 2 Calcined at 500°C for 6h, at a temperature of 50°C and a stirring speed of 240r / min, the Mo(NO 3 ) 3 ·5H 2 O, Co(NO 3 ) 2 ·6H 2 O, Fe(NO 3 ) 3 9H 2 O, TiO 2 According to the mass percentage of Mo: Co: Fe: Ti 25%: 15%: 25%: 35% equal volume impregnation and stirring for 24 hours, after standing for 8 hours, evaporate at 90°C until viscous, then put it in an oven to dry at 130°C for 24 hours, and then grind To 120-140 mesh, place in a muffle furnace and bake at 600 ° C for 5 hours to obtain a precursor; the volume composition is 25% H 2 and 75%N 2 , in an atmosphere with a flow rate of 180mL / min, two-stage temperature programming is adopted, firstly the temperature is raised to 350°C at 8°C / min, and then the temperature is raised to 600°C at 3°C / min for constant temperature reduction for 10 hours to obtain the mass of ...

Embodiment 3

[0059] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0060] 60-80 mesh, specific surface area 150m 2 / g SiO 2 Calcined at 400°C for 4h, at a temperature of 25°C and a stirring speed of 100r / min, the W(NO 3 ) 3 ·5H 2 O, Mo(NO 3 ) 3 ·5H 2 O, La(NO 3 ) 3 ·6H 2 O, SiO 2 According to the mass percentage of W:Mo:La:Si 10%: 30%: 25%: 35% equal volume impregnation and stirring for 8 hours, after standing for 4 hours, evaporate to viscous at 60°C, then put it in an oven to dry at 80°C for 12 hours, and then grind To 60-80 mesh, place in a muffle furnace and bake at 450 ° C for 4 hours to obtain a precursor; the volume composition is 15% H 2 and 85%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 4°C / min, and then raising the temperature to 500°C at 2°C / min for 6 hours to obtain the mass percentage of W:Mo:La:Si 10%: 30%: 25%: 35% W-Mo-La-Si slurry bed...

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. Background technique

[0002] my country is the world's largest coke producer, coke production and a large amount of coke oven gas by-product. In addition to the production of synthetic ammonia and methanol, these coke oven gas has a surplus of about 20 billion cubic meters of coke oven gas every year, causing huge energy waste and environmental pollution. Utilizing coke oven gas for methanation to produce natural gas not only produces obvious economic and environmental benefits, but also has great impact on energy. Structural adjustments are also important.

[0003] The main components of coke oven gas are probably (volume ratio): H 2 Content 50-60%, CH 4 Content 20-28%, CO content 5.5-8.5%, CO 2 Content 2-2.5%. In addition, there are trace amounts of H 2 S, COS, HCN, NH ...

Examples

Embodiment 1

[0045] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0046] 160-200 mesh, specific surface area 280m 2 / g γ-Al 2 o 3 Calcined at 550°C for 7h, at a temperature of 25°C and a stirring speed of 200r / 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 30%: 20%: 50%, impregnate and stir for 24 hours, after standing for 10 hours, evaporate to viscous at 70°C, then put it in an oven for 24 hours at 110°C, and then grind to 160-200 mesh Place in a muffle furnace and bake at 450°C for 8 hours to obtain a precursor; the volume composition is 15%H 2 and 85%N 2 , in an atmosphere with a flow rate of 120mL / min, a two-stage temperature program was adopted, firstly the temperature was raised to 350°C at 5°C / min, and then the temperature was raised to 600°C at 2°C / min for constant temperature reduction for 12 hours to obtain a mass percentage of Mo:Ni:Al of 30 %: 20%: 50% Mo-Ni-Al slur...

Embodiment 2

[0052] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0053] 120-140 mesh, specific surface area 240m 2 / g TiO 2 Calcined at 500°C for 6h, at a temperature of 50°C and a stirring speed of 240r / min, the Mo(NO 3 ) 3 ·5H 2 O, Co(NO 3 ) 2 ·6H 2 O, Fe(NO 3 ) 3 9H 2 O, TiO 2 According to the mass percentage of Mo: Co: Fe: Ti 25%: 15%: 25%: 35% equal volume impregnation and stirring for 24 hours, after standing for 8 hours, evaporate at 90°C until viscous, then put it in an oven to dry at 130°C for 24 hours, and then grind To 120-140 mesh, place in a muffle furnace and bake at 600 ° C for 5 hours to obtain a precursor; the volume composition is 25% H 2 and 75%N 2 , in an atmosphere with a flow rate of 180mL / min, two-stage temperature programming is adopted, firstly the temperature is raised to 350°C at 8°C / min, and then the temperature is raised to 600°C at 3°C / min for constant temperature reduction for 10 hours to obtain the mass of ...

Embodiment 3

[0059] Preparation of Sulfur-Resistant Methanation Catalyst for Slurry Bed Coke Oven Gas:

[0060] 60-80 mesh, specific surface area 150m 2 / g SiO 2 Calcined at 400°C for 4h, at a temperature of 25°C and a stirring speed of 100r / min, the W(NO 3 ) 3 ·5H 2 O, Mo(NO 3 ) 3 ·5H 2 O, La(NO 3 ) 3 ·6H 2 O, SiO 2 According to the mass percentage of W:Mo:La:Si 10%: 30%: 25%: 35% equal volume impregnation and stirring for 8 hours, after standing for 4 hours, evaporate to viscous at 60°C, then put it in an oven to dry at 80°C for 12 hours, and then grind To 60-80 mesh, place in a muffle furnace and bake at 450 ° C for 4 hours to obtain a precursor; the volume composition is 15% H 2 and 85%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 4°C / min, and then raising the temperature to 500°C at 2°C / min for 6 hours to obtain the mass percentage of W:Mo:La:Si 10%: 30%: 25%: 35% W-Mo-La-Si slurry bed...

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