CN102211977A - Process for producing synthetic ammonia and methanol by using coke oven gas and blast furnace gas - Google Patents
Process for producing synthetic ammonia and methanol by using coke oven gas and blast furnace gas Download PDFInfo
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- CN102211977A CN102211977A CN2011100861543A CN201110086154A CN102211977A CN 102211977 A CN102211977 A CN 102211977A CN 2011100861543 A CN2011100861543 A CN 2011100861543A CN 201110086154 A CN201110086154 A CN 201110086154A CN 102211977 A CN102211977 A CN 102211977A
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Abstract
The invention discloses a process for producing synthetic ammonia and methanol by using coke oven gas and blast furnace gas. The method is characterized in that: after hydrocarbon substances in the coke oven gas are separated, the hydrocarbon-rich coke oven gas is directly used in other purposes, carbon monoxide is continuously separated from the hydrocarbon-deficient coke oven gas, the carbon monoxide-deficient coke oven gas is directly used for synthesizing raw material gas in the later section, and the carbon monoxide-rich coke oven gas and the blast furnace gas are matched in a certain ratio for producing methanol and synthetic ammonia or purely producing liquid ammonia. The costs of the produced liquid ammonia and the produced methanol are lower than those of common ammonia prepared from coal and methanol prepared from the coke oven gas.
Description
One, technical field
The present invention relates to chemical field, is a kind of method of effectively utilizing process gas to be used to produce synthetic ammonia and methyl alcohol.
Two, background technology
For the technology that coke(oven)gas is produced methyl alcohol, the method for usually using is utilized carbon monoxide and hydrogen synthesizing methanol then for methane conversion is hydrogen and carbon monoxide.Because production technique decision, hydrogen are seriously superfluous, must be used for other products production to hydrogen or be used for generating, just can make this technology performance maximum economic benefit.Because Methane Conversion needs huge equipment and more operation energy consumption, therefore, relatively difficulty is promoted in miniaturization industry, and can only use in large-scale coking system.
For the technology that blast furnace gas gas is produced liquefied ammonia, the usual method of using is utilized nitrogen and hydrogen synthetic ammonia in the blast furnace gas then for carbon monoxide being converted into hydrogen and carbonic acid gas.Because the production technique decision, the hydrogen wretched insufficiency must separate nitrogen from blast furnace gas, just can make this technology performance economic benefit.Owing to need huge equipment of nitrogen separation process need and more operation energy consumption, therefore, relatively difficulty is promoted in miniaturization industry, the part blast furnace gas can only be mixed in the coal Ammonia Process.
Three, summary of the invention
For better reclaim effective constituent hydrogen in the coke(oven)gas and and blast furnace gas in carbon monoxide and nitrogen, the present invention utilizes the strategy of combination producing, is used to improve gas effciency.
Methane and high carbon species are the rare gas elementes of ammonia, two building-up reactionss of methyl alcohol, in order to reduce energy consumption, at first need the separating hydrocarbons component, the coke(oven)gas of rich hydrocarbon component is as other purposes, poor hydro carbons coke(oven)gas continues to separate carbon monoxide, directly as the synthetic raw gas of methyl alcohol and ammonia, rich carbon monoxide coke(oven)gas and blast furnace gas are mixed into rich carbon mono oxide mixture to poor carbon monoxide coke(oven)gas according to a certain percentage, and this gas can directly become synthetic gas as methyl alcohol and ammonia-synthesizing material gas.
Because the needs of production technique, rich carbon mono oxide mixture can be through conversion under 0.1～32.0MPa, and the carbon monodixe conversion rate is 0.5%-99.99%, becomes conversion gas, and the unstripped gas as synthesizing methanol and ammonia becomes synthetic gas again.
Because the needs of production technique, conversion gas can be through carbon dioxide separation under 0.1～32.0MPa, partly or entirely separate carbon dioxide component wherein, carbon dioxide enriched conversion gas is as other purposes, and poor carbonic acid gas conversion gas becomes synthetic gas as the unstripped gas of synthesizing methanol and ammonia.
Synthetic gas is synthesizing methanol under 2.0～32.0MPa.Gas behind the synthesizing methanol passes through pure hydrocarbonylation, pure alkanisation, copper washing process removal of carbon monoxide, carbonic acid gas after certified concentration, synthetic ammonia under 2.0～32.0MPa.
By this technology, can the hydrogen in the coke(oven)gas be made full use of.Simultaneously, carbon monoxide in the blast furnace gas gas and nitrogen can fully be utilized.
Technology of the present invention and traditional ammonia join the pure technology following characteristics of comparing:
Be not specifically designed to the gas maked coal system that produces synthetic gas; The gas maked coal process becomes hydrogen and carbon monoxide to coal.Even the gas maked coal system is arranged, can only be used to regulate hydrogen, nitrogen, the carbon monoxide concentration ratio of synthetic gas.Still be provided with the carbon monodixe conversion system.This system becomes hydrogen to carbon monoxide, but the carbon monodixe conversion rate is lower than original production technique.
Technology of the present invention and the coke(oven)gas manufacture order alcohol technology following characteristics of comparing:
Do not have methane conversion and coal-burning boiler system, methane and high carbon species become urban safety coal gas by gas delivery; Do not have the hydrogen waste, methyl alcohol synthetic remaining hydrogen is used for ammonia synthesis.
Four, embodiment
Embodiment 1: certain coke(oven)gas composition
| Component | O 2+N 2+A r | H 2 | CH 4 | CO+CO 2 | C 2+ |
| (V％) | 9 | 53 | 26 | 10 | 2 |
The poor hydro carbons composition of gas behind the separating hydrocarbons
| Component | N 2 | H 2 | CH 4 | CO | C 2+ |
| (V％) | 6.49 | 83 | 0.5 | 10 | 0.01 |
Poor carbon monoxide coke(oven)gas component behind the continuation separation carbon monoxide
| Component | N 2 | H 2 | CH 4 | CO | C 2+ |
| (V％) | 0.89 | 98 | 0.01 | 1.0 | 0.001 |
Rich carbon monoxide coke(oven)gas component
| Component | N 2 | H 2 | CH 4 | CO | C 2+ |
| (V％) | 38.2 | 2 | 2.5 | 56.0 | 0.005 |
The blast furnace gas composition
| Component | O 2 | N 2+A r | H 2 | CH 4 | CO | CO 2 |
| (V％) | 0.5 | 68 | 2 | 0.5 | 28 | 2 |
When blast furnace gas is mixed with rich carbon monoxide coke(oven)gas, by the 0.8MPa conversion, 99.9% carbon monodixe conversion is become carbonic acid gas and hydrogen then, become conversion gas.After conversion gas partly removes carbonic acid gas, become the decarburization purified gas.This purified gas mixes with poor carbon monoxide coke(oven)gas, purifies carbon monoxide and carbonic acid gas through further pure hydrocarbonylation, obtains the synthetic gas of hydrogen nitrogen ratio=3: 1 at last, and this synthetic gas all is used for synthetic ammonia.
When blast furnace gas is mixed with rich carbon monoxide coke(oven)gas, by the 0.8MPa conversion, carbon monoxide 30% is transformed into carbonic acid gas and hydrogen then, become conversion gas.Behind the conversion qi exhaustion removing carbon dioxide, become the decarburization purified gas.This purified gas mixes with poor carbon monoxide coke(oven)gas, earlier at the 4.MPa synthesizing methanol.The residual air of synthesizing methanol purifies carbon monoxide and carbonic acid gas through further methanation, obtains the synthetic gas of hydrogen nitrogen ratio=3: 1 at last, and this synthetic gas all is used for synthetic ammonia.
When blast furnace gas is mixed with rich carbon monoxide coke(oven)gas, by the 0.8MPa conversion, carbon monoxide 2.0% is transformed into carbonic acid gas and hydrogen then, become conversion gas, mix with poor carbon monoxide coke(oven)gas, earlier at the 4.MPa synthesizing methanol.The residual air of synthesizing methanol obtains the synthetic gas of hydrogen nitrogen ratio=3: 1 at last through further cleanization of copper carbon monoxide and carbonic acid gas, and this synthetic gas all is used for synthetic ammonia.
Embodiment 2: certain coke(oven)gas composition
| Component | O 2+N 2+A r | H 2 | CH 4 | CO+CO 2 | C 2+ |
| (V％) | 9 | 41 | 38 | 10 | 2 |
The poor hydro carbons composition of gas behind the separating hydrocarbons
| Component | N 2 | H 2 | CH 4 | CO | C 2+ |
| (V％) | 13.5 | 70 | 3.5 | 15 | 0.01 |
Poor carbon monoxide coke(oven)gas component behind the continuation separation carbon monoxide
| Component | N 2 | H 2 | CH 4 | CO | C 2+ |
| (V％) | 11.5 | 88 | 0.01 | 0.4 | 0.001 |
Rich carbon monoxide coke(oven)gas component
| Component | N 2 | H 2 | CH 4 | CO | C 2+ |
| (V％) | 2.2 | 2 | 9.5 | 87.0 | 0.005 |
The blast furnace gas composition
| Component | O 2 | N 2+A r | H 2 | CH 4 | CO | CO 2 |
| (V％) | 0.5 | 51 | 2 | 0.5 | 38 | 9 |
When blast furnace gas is mixed with rich carbon monoxide coke(oven)gas, by the 0.8MPa conversion, 99.9% carbon monodixe conversion is become carbonic acid gas and hydrogen then, become conversion gas.After conversion gas partly removes carbonic acid gas, become the decarburization purified gas.This purified gas mixes with poor carbon monoxide coke(oven)gas, purifies carbon monoxide and carbonic acid gas through further pure hydrocarbonylation, obtains the synthetic gas of hydrogen nitrogen ratio=3: 1 at last, and this synthetic gas all is used for synthetic ammonia.
When blast furnace gas is mixed with rich carbon monoxide coke(oven)gas, by the 0.8MPa conversion, carbon monoxide 36% is transformed into carbonic acid gas and hydrogen then, become conversion gas.Behind the conversion qi exhaustion removing carbon dioxide, become the decarburization purified gas.This purified gas mixes with poor carbon monoxide coke(oven)gas, at the 12.MPa synthesizing methanol.The residual air of synthesizing methanol purifies carbon monoxide and carbonic acid gas through further methanation, obtains the synthetic gas of hydrogen nitrogen ratio=2.8: 1 at last, and this synthetic gas all is used for synthetic ammonia.
When blast furnace gas is mixed with rich carbon monoxide coke(oven)gas, by the 2.8MPa conversion, carbon monoxide 11.0% is transformed into carbonic acid gas and hydrogen then, become conversion gas.Mix with poor carbon monoxide coke(oven)gas, earlier at the 22.MPa synthesizing methanol.The residual air of synthesizing methanol obtains the synthetic gas of hydrogen nitrogen ratio=2.6: 1 at last through further cleanization of copper carbon monoxide and carbonic acid gas, and this synthetic gas all is used for synthetic ammonia.
Claims (3)
1. technology of utilizing coke(oven)gas and blast furnace gas combination producing synthetic ammonia and methyl alcohol is characterized in that: the hydrocarbons in the coke(oven)gas is separated, and rich hydro carbons coke(oven)gas is as other purposes; Poor hydro carbons coke(oven)gas continues to separate carbon monoxide, and poor carbon monoxide coke(oven)gas is as synthetic raw gas; Rich carbon monoxide coke(oven)gas cooperates according to a certain percentage with blast furnace gas, is called rich carbon mono oxide mixture, rich carbon mono oxide mixture and poor hydrocarbon gas, all or part of combination producing methyl alcohol and the synthetic ammonia of being used for.
2. according to the described rich carbon mono oxide mixture of claim one, under 0.01-32.0MPa pressure, rich carbon mono oxide mixture is for conversion into gas through part, and the carbon monodixe conversion rate is 0.5%-99.99%, all or part of combination producing methyl alcohol and the synthetic ammonia of being used for of conversion gas.
3. according to the described conversion gas of claim two, partly or entirely separate carbon dioxide component wherein, carbon dioxide enriched conversion gas is as other purposes, all or part of combination producing methyl alcohol and the synthetic ammonia of being used for of poor carbonic acid gas conversion gas.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011198A (en) * | 2012-12-20 | 2013-04-03 | 赛鼎工程有限公司 | Process for preparing synthetic ammonia with coke-oven gas |
| CN104449920A (en) * | 2014-11-05 | 2015-03-25 | 新奥能源贸易有限公司 | Method for joint production of natural gas and liquid ammonia by using coke oven gas and blast-furnace gas |
| CN104986732A (en) * | 2015-07-03 | 2015-10-21 | 赛鼎工程有限公司 | Method for preparing synthesis gas through coke oven gas and coal gas |
| CN105000533A (en) * | 2015-07-03 | 2015-10-28 | 赛鼎工程有限公司 | Method used for producing synthesis gas from coke oven gas and coal gas |
| US20160348196A1 (en) * | 2013-12-12 | 2016-12-01 | Thyssenkrupp Ag | Method for generating synthesis gas in conjunction with a smelting works |
| CN106748655A (en) * | 2016-11-27 | 2017-05-31 | 华北理工大学 | It is a kind of efficiently to reduce integrated iron and steel works CO2The method of discharge |
| CN107215848A (en) * | 2017-06-09 | 2017-09-29 | 杨皓 | A kind of carbon black tail gas and calcium carbide stove exhaust combined production of ammonia alcohol synthesis gas process |
| CN107235473A (en) * | 2017-06-09 | 2017-10-10 | 杨皓 | A kind of carbon black tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
| CN107244651A (en) * | 2017-06-09 | 2017-10-13 | 杨皓 | A kind of blast furnace tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
| CN109368659A (en) * | 2018-11-08 | 2019-02-22 | 杨皓 | A kind of coke-stove gas and blast furnace gas manufacture ammonia synthesis gas technique |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011198A (en) * | 2012-12-20 | 2013-04-03 | 赛鼎工程有限公司 | Process for preparing synthetic ammonia with coke-oven gas |
| US20160348196A1 (en) * | 2013-12-12 | 2016-12-01 | Thyssenkrupp Ag | Method for generating synthesis gas in conjunction with a smelting works |
| US10697032B2 (en) * | 2013-12-12 | 2020-06-30 | Thyssenkrupp Ag | Method for generating synthesis gas in conjunction with a smelting works |
| CN104449920A (en) * | 2014-11-05 | 2015-03-25 | 新奥能源贸易有限公司 | Method for joint production of natural gas and liquid ammonia by using coke oven gas and blast-furnace gas |
| CN104449920B (en) * | 2014-11-05 | 2016-06-29 | 新奥能源贸易有限公司 | The method utilizing coke-stove gas and blast furnace gas Joint Production natural gas with liquefied ammonia |
| CN104986732B (en) * | 2015-07-03 | 2017-01-04 | 赛鼎工程有限公司 | Utilize the method that coke-stove gas and coal gas prepare synthesis gas |
| CN105000533A (en) * | 2015-07-03 | 2015-10-28 | 赛鼎工程有限公司 | Method used for producing synthesis gas from coke oven gas and coal gas |
| CN104986732A (en) * | 2015-07-03 | 2015-10-21 | 赛鼎工程有限公司 | Method for preparing synthesis gas through coke oven gas and coal gas |
| CN106748655A (en) * | 2016-11-27 | 2017-05-31 | 华北理工大学 | It is a kind of efficiently to reduce integrated iron and steel works CO2The method of discharge |
| CN106748655B (en) * | 2016-11-27 | 2019-10-18 | 华北理工大学 | A kind of reduction integrated iron and steel works CO2The method of discharge |
| CN107215848A (en) * | 2017-06-09 | 2017-09-29 | 杨皓 | A kind of carbon black tail gas and calcium carbide stove exhaust combined production of ammonia alcohol synthesis gas process |
| CN107235473A (en) * | 2017-06-09 | 2017-10-10 | 杨皓 | A kind of carbon black tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
| CN107244651A (en) * | 2017-06-09 | 2017-10-13 | 杨皓 | A kind of blast furnace tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
| CN109368659A (en) * | 2018-11-08 | 2019-02-22 | 杨皓 | A kind of coke-stove gas and blast furnace gas manufacture ammonia synthesis gas technique |
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