CN102827656A - Methanation method for synthesizing substitute natural gas from industrial hydrocarbon tail gas - Google Patents
Methanation method for synthesizing substitute natural gas from industrial hydrocarbon tail gas Download PDFInfo
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- CN102827656A CN102827656A CN2012103081995A CN201210308199A CN102827656A CN 102827656 A CN102827656 A CN 102827656A CN 2012103081995 A CN2012103081995 A CN 2012103081995A CN 201210308199 A CN201210308199 A CN 201210308199A CN 102827656 A CN102827656 A CN 102827656A
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Abstract
The invention discloses a methanation method for synthesizing substitute natural gas from industrial hydrocarbon tail gas. Main devices required for implementing the methanation method comprise a primary reactor, a secondary reactor, a tertiary reactor, medium pressure steam waste heat boilers, a recycle gas compressor and the like. The methanation method includes dividing pretreated industrial hydrocarbon tail gas into three sections and feeding the three sections of industrial hydrocarbon tail gas into the methanation reactors respectively; simultaneously dividing waste heat into three sections and recycling the three sections of waste heat by the waste heat boilers; and finally synthesizing the substitute natural gas with high heat value. The method provides a comprehensive utilization way for the hydrocarbon-rich industrial tail gas, the idea of circular economy is realized, and the methanation is significant in increasing economical benefits, social benefit and environmental benefit.
Description
Technical field
The invention belongs to the comprehensive utilization technique field of industrial tail gas, particularly related to a kind of to be rich in the methanation method that hydrocarbon industrial tail gas is the synthetic substitute natural gas of virgin gas.
Background technology
The a large amount of coke-oven gas of the annual every discharging of China, calcium carbide stove exhaust, blue charcoal tail gas etc. are rich in hydrocarbon industrial tail gas, not only cause the wasting of resources, and environment is caused huge pollution.Adopting above-mentioned hydrocarbon industrial tail gas is basic raw material gas, regulates through deep purifying and component, just can be used as fine fuel gas and material gas.Therefore, utilizing production substitute natural gases such as being rich in hydrocarbon tail gas, is that economic benefit or social benefit, environmental benefit are all significant.
It is the methanation method of the synthetic substitute natural gas of raw material that the present invention is intended to develop with hydrocarbon industrial tail gas; For increasing natural gas supply, satisfying the processing technology routine that demand that China increases fast Sweet natural gas has found an easy economy, also opened up new approach for the recycling of hydrocarbon industrial tail gas.Have tangible competitive edge:
(1) be the raw material production Sweet natural gas with abundant cheap hydrocarbon industrial tail gas, production cost is low, has bigger profit margin and anti-price risk ability;
(2) utilize hydrocarbon industrial tail gas resource, adopt advanced, the synthetic substitute natural gas of sophisticated Technology, meet the national energy development strategy, very important promoter action is arranged for the clean and efficient utilization that realizes coal resources;
(3) utilize the synthetic substitute natural gas technical process of hydrocarbon industrial tail gas simple, technology maturation, reliable consumes lowly, need not to be provided with air separation facility and conversion section, reduced investment;
(4) the synthetic substitute natural gas of hydrocarbon industrial tail gas can be carried out under lower pressure, compares with production methyl alcohol, dme, has saved a plurality of links; Compare with synthetic oil, the device that saves is more;
(5) unit calorific value cost of investment is low, and overall thermal efficiency is high.Transformation efficiency and selectivity are high, and the transformation efficiency of carbon monoxide and hydrogen can be near 95%;
(6) the synthetic substitute natural gas used heat utilization ratio of hydrocarbon industrial tail gas is high, and the superheated vapour of synthetic substitute natural gas used heat by-product can be used for this device turbine circulator and air compressor machine, can produce favorable economic benefit.
Summary of the invention
It is virgin gas to be rich in hydrocarbon industrial tail gas that the object of the invention provides a kind of, through the synthetic substitute natural gas of methanation reaction.
The present invention adopts following technical scheme:
The methanation method of the synthetic substitute natural gas of a kind of hydrocarbon industrial tail gas is characterized in that, is fed into first stage reactor through the primary industry exhaust temperature of desulfurizing and purifying, under the effect of catalyzer, carries out CO and H
2Between methanation reaction, the residence time of control synthetic gas, make CO reaction 50%, after the synthetic gas temperature rises to 600-650 ℃; Go out first stage reactor, successively get into vapor superheater and one section waste heat boiler, after the synthetic gas temperature is reduced to 250-300 ℃, get into second stage reactor again; The residence time of same control synthetic gas, the whole primitive reactions of CO are fallen, after the synthetic gas temperature rises to 450-500 ℃; Go out second stage reactor, get into two sections waste heat boilers, after the synthetic gas temperature is reduced to 250-300 ℃; Get into three sections reactor drums, under the effect of catalyzer, carry out CO
2And H
2Between methanation reaction, with CO
2Total overall reaction is complete, and temperature rises to 350-400 ℃, goes out three sections reactor drums; Get into three sections waste heat boilers, after temperature is reduced to 250-300 ℃, successively get into feedwater preheater again; De-salted water preheater, temperature are reduced to about 80 ℃, are cooled with circulating water at last to normal temperature; Get into gas-liquid separator, remove the phlegma in the product gas, deliver to out-of-bounds.
The import synthetic gas temperature of described first stage reactor is 260-320 ℃, and pressure is 2.5MPa.G, and the temperature out of first stage reactor synthetic gas is 600-650 ℃, and pressure is 2.48MPa.G, and the air speed of first stage reactor is 1000-1500h
-1, the vapor superheater inlet steam is the 3.82MPa.G saturation steam, and temperature out is 450 ℃, and one section waste heat boiler outlet steam is the 3.82MPa.G saturation steam.
The import synthetic gas temperature of described second stage reactor is 250-300 ℃, and pressure is 2.45MPa.G, and the temperature out of first stage reactor synthetic gas is 450-500 ℃, and pressure is 2.43MPa.G, and the air speed of second stage reactor is 1000-1500h
-1, two sections waste heat boiler outlet steam are the 3.82MPa.G saturation steam.
The import synthetic gas temperature of described three sections reactor drums is 250-300 ℃, and pressure is 2.41MPa.G, and the temperature out of first stage reactor synthetic gas is 400-450 ℃, and pressure is 2.4MPa.G, and the air speed of second stage reactor is 1000-1500h
-1, three sections waste heat boiler outlet steam are the 3.82MPa.G saturation steam.
The hot(test)-spot temperature of the methanation reaction of described first stage reactor is 650-700 ℃; The hot(test)-spot temperature of the methanation reaction of described second stage reactor is 550-600 ℃; The hot(test)-spot temperature of the methanation reaction of described three sections reactor drums is 450-500 ℃.
The intensification of described catalyzer is under the car state, and system begins after replacing with nitrogen purging.Catalyzer is dry uses nitrogen temperature, and temperature rise rate is 20-30 ℃/hour, rises to 120 ℃ of constant temperature 4 hours; The constant temperature continued rises to 250 ℃ with 20-30 ℃/hour speed, and 250 ℃ of constant temperature switched hydrogen after 2 hours, continues constant temperature 4 hours; Be warming up to 350 ℃ with 20-30 ℃/hour speed, constant temperature 4 hours is warming up to 400 ℃ with 20-30 ℃/hour speed; Constant temperature 8-12 hour, reduction finished.
The outlet temperature of described catalyst reduction should be greater than 400 ℃, and the circulation of reducing gas adopts circulation to use blower fan, and the reduction of three sections methanation catalysts should be carried out separately or connect and carry out.
Useful achievement of the present invention is:
1, the approach that hydrocarbon industrial tail gas provides a kind of comprehensive utilization is rich in the present invention, has realized circular economy concept, is that economic benefit or social benefit, environmental benefit are all significant.
2, this methanation method adopts disposable gas to pass through, and does not need the synthetic gas circulation, and conserve energy reduces reactor size.
Description of drawings
Fig. 1 is the treatment process figure of the methanation method of the synthetic substitute natural gas of hydrocarbon industrial tail gas, and wherein major equipment comprises: 1, first stage reactor; 2, second stage reactor; 3, three sections reactor drums; 4, one section waste heat boiler; 5, two sections waste heat boilers; 6, three sections waste heat boilers; 7, suphtr; 8, feedwater preheater; 9, interchanger; 10, the compressor that goes into operation; 11, the well heater that goes into operation; 12, gas-liquid separator.
Embodiment
Below in conjunction with embodiment the present invention is explained further details.
Embodiment
To be fed into first stage reactor through the primary industry tail gas of desulfurizing and purifying, under the effect of catalyzer, carry out CO and H
2Between methanation reaction, the residence time of control synthetic gas, make CO reaction 50%, after the synthetic gas temperature rises to 650 ℃; Go out first stage reactor, successively get into vapor superheater and one section waste heat boiler, after the synthetic gas temperature is reduced to 300 ℃, get into second stage reactor again; The residence time of same control synthetic gas, the whole primitive reactions of CO are fallen, after the synthetic gas temperature rises to 500 ℃; Go out second stage reactor, get into two sections waste heat boilers, after the synthetic gas temperature is reduced to 250 ℃; Get into three sections reactor drums, under the effect of catalyzer, carry out CO
2And H
2Between methanation reaction, with CO
2Total overall reaction is complete, and temperature rises to 400 ℃, goes out three sections reactor drums; Get into three sections waste heat boilers, after temperature is reduced to 250 ℃, successively get into feedwater preheater again; De-salted water preheater, temperature are reduced to about 80 ℃, are cooled with circulating water at last to normal temperature; Get into gas-liquid separator, remove the phlegma in the product gas, deliver to out-of-bounds.
The import synthetic gas temperature of first stage reactor is 260 ℃, and pressure is 2.5MPa.G, and the temperature out of first stage reactor synthetic gas is 600 ℃, and pressure is 2.48MPa.G, and the first stage reactor air speed is 1200 h
-1, the vapor superheater inlet steam is the 3.82MPa.G saturation steam, and temperature out is 450 ℃, and one section waste heat boiler outlet steam is the 3.82MPa.G saturation steam.
The import synthetic gas temperature of second stage reactor is 280 ℃, and pressure is 2.45MPa.G, and the temperature out of first stage reactor synthetic gas is 500 ℃, and pressure is 2.43MPa.G, and the air speed of second stage reactor is 1000 h
-1, it is the 3.82MPa.G saturation steam that two sections waste heat boilers go out steam.
The import synthetic gas temperature of three sections reactor drums is 300 ℃, and pressure is 2.41MPa.G, and the temperature out of first stage reactor synthetic gas is 450 ℃, and pressure is 2.4MPa.G, and the air speed of second stage reactor is 1500 h
-1, three sections waste heat boiler outlet steam are the 3.82MPa.G saturation steam.
The hot(test)-spot temperature of the methanation reaction of first stage reactor is 650 ℃; The hot(test)-spot temperature of the methanation reaction of second stage reactor is 600 ℃, and the hot(test)-spot temperature of the methanation reaction of three sections reactor drums is 500 ℃.
The intensification of described catalyzer is under the car state, and system begins after replacing with nitrogen purging.Catalyzer is dry uses nitrogen temperature, and temperature rise rate is 20 ℃/hour, rises to 120 ℃ of constant temperature 4 hours; The constant temperature continued rises to 250 ℃ with 20 ℃/hour speed, and 250 ℃ of constant temperature switched hydrogen after 2 hours, continues constant temperature 4 hours; Be warming up to 350 ℃ with 20 ℃/hour speed, constant temperature 4 hours is warming up to 400 ℃ with 20 ℃/hour speed; Constant temperature 8-12 hour, reduction finished.
Claims (7)
1. the methanation method of the synthetic substitute natural gas of hydrocarbon industrial tail gas is characterized in that, will be fed into first stage reactor through the primary industry exhaust temperature of desulfurizing and purifying, under the effect of catalyzer, carries out CO and H
2Between methanation reaction, the residence time of control synthetic gas, make CO reaction 50%, after the synthetic gas temperature rises to 600-650 ℃; Go out first stage reactor, successively get into vapor superheater and one section waste heat boiler, after the synthetic gas temperature is reduced to 250-300 ℃, get into second stage reactor again; The residence time of same control synthetic gas, the whole primitive reactions of CO are fallen, after the synthetic gas temperature rises to 450-500 ℃; Go out second stage reactor, get into two sections waste heat boilers, after the synthetic gas temperature is reduced to 250-300 ℃; Get into three sections reactor drums, under the effect of catalyzer, carry out CO
2And H
2Between methanation reaction, with CO
2Total overall reaction is complete, and temperature rises to 350-400 ℃, goes out three sections reactor drums; Get into three sections waste heat boilers, after temperature is reduced to 250-300 ℃, successively get into feedwater preheater again; De-salted water preheater, temperature are reduced to about 80 ℃, are cooled with circulating water at last to normal temperature; Get into gas-liquid separator, remove the phlegma in the product gas, deliver to out-of-bounds.
2. the methanation method of the synthetic substitute natural gas of hydrocarbon industrial tail gas according to claim 1; It is characterized in that; The import synthetic gas temperature of described first stage reactor is 260-320 ℃, and pressure is 2.5MPa.G, and the temperature out of first stage reactor synthetic gas is 600-650 ℃; Pressure is 2.48MPa.G, and the air speed of first stage reactor is 1000-1500h
-1, the vapor superheater inlet steam is the 3.82MPa.G saturation steam, and temperature out is 450 ℃, and one section waste heat boiler outlet steam is the 3.82MPa.G saturation steam.
3. the methanation method of the synthetic substitute natural gas of hydrocarbon industrial tail gas according to claim 1; It is characterized in that; The import synthetic gas temperature of described second stage reactor is 250-300 ℃, and pressure is 2.45MPa.G, and the temperature out of first stage reactor synthetic gas is 450-500 ℃; Pressure is 2.43MPa.G, and the air speed of second stage reactor is 1000-1500h
-1, two sections waste heat boiler outlet steam are the 3.82MPa.G saturation steam.
4. the methanation method of the synthetic substitute natural gas of hydrocarbon industrial tail gas according to claim 1; It is characterized in that; The import synthetic gas temperature of described three sections reactor drums is 250-300 ℃, and pressure is 2.41MPa.G, and the temperature out of first stage reactor synthetic gas is 400-450 ℃; Pressure is 2.4MPa.G, and the air speed of second stage reactor is 1000-1500h
-1, three sections waste heat boiler outlet steam are the 3.82MPa.G saturation steam.
5. the methanation method of the synthetic substitute natural gas of hydrocarbon industrial tail gas according to claim 1 is characterized in that the hot(test)-spot temperature of the methanation reaction of described first stage reactor is 650-700 ℃; The hot(test)-spot temperature of the methanation reaction of described second stage reactor is 550-600 ℃; The hot(test)-spot temperature of the methanation reaction of described three sections reactor drums is 450-500 ℃.
6. the methanation method of the synthetic substitute natural gas of hydrocarbon industrial tail gas according to claim 1 is characterized in that the intensification of described catalyzer is under the car state, and system begins after replacing with nitrogen purging; Catalyzer is dry uses nitrogen temperature, and temperature rise rate is 20-30 ℃/hour, rises to 120 ℃ of constant temperature 4 hours; The constant temperature continued rises to 250 ℃ with 20-30 ℃/hour speed, and 250 ℃ of constant temperature switched hydrogen after 2 hours, continues constant temperature 4 hours; Be warming up to 350 ℃ with 20-30 ℃/hour speed, constant temperature 4 hours is warming up to 400 ℃ with 20-30 ℃/hour speed; Constant temperature 8-12 hour, reduction finished.
7. the methanation method of the synthetic substitute natural gas of hydrocarbon industrial tail gas according to claim 6; It is characterized in that; The outlet temperature of described catalyst reduction should be greater than 400 ℃; The circulation of reducing gas adopts circulation to use blower fan, and the reduction of three sections methanation catalysts should be carried out separately or connect and carry out.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031706A (en) * | 2014-05-27 | 2014-09-10 | 顾君尧 | Method for preparing natural gas by use of tail gas of calcium carbide furnace, and production device using same |
| CN105368514A (en) * | 2014-08-26 | 2016-03-02 | 大唐国际化工技术研究院有限公司 | Method and device for producing synthetic natural gas |
| CN105838461A (en) * | 2015-01-13 | 2016-08-10 | 中国科学院大连化学物理研究所 | Methanation technology of synthetic gas for synthetic natural gas |
| CN106582894A (en) * | 2015-10-16 | 2017-04-26 | 内蒙古大唐国际克什克腾煤制天然气有限责任公司 | Methanation catalyst heating reduction method |
| CN107406780A (en) * | 2015-03-03 | 2017-11-28 | 庄信万丰戴维科技有限公司 | method for producing substitute natural gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104031706A (en) * | 2014-05-27 | 2014-09-10 | 顾君尧 | Method for preparing natural gas by use of tail gas of calcium carbide furnace, and production device using same |
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| CN106582894A (en) * | 2015-10-16 | 2017-04-26 | 内蒙古大唐国际克什克腾煤制天然气有限责任公司 | Methanation catalyst heating reduction method |
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Application publication date: 20121219 |