CN101693837B - Method for recycling methanol synthesis purge gas produced by coke oven gas - Google Patents
Method for recycling methanol synthesis purge gas produced by coke oven gas Download PDFInfo
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- CN101693837B CN101693837B CN2009100757538A CN200910075753A CN101693837B CN 101693837 B CN101693837 B CN 101693837B CN 2009100757538 A CN2009100757538 A CN 2009100757538A CN 200910075753 A CN200910075753 A CN 200910075753A CN 101693837 B CN101693837 B CN 101693837B
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- gas
- coke oven
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- oven
- methanol
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Abstract
The invention relates to a method for recycling methanol synthesis purge gas produced by coke oven gas, which belongs to the technical field of organic chemical engineering and is used for solving the problem that the methanol synthesis purge gas produced by coke oven gas cannot be effectively utilized. In the technical scheme, the method comprises the following steps: recycling all methanol synthesis purge gas produced by a coke oven gas produced methanol system to a mixing tank; introducing coke oven gas to the mixing tank so that the purge gas and the coke oven gas are sufficiently mixed to form a gas mixture; and using the gas mixture as a fuel to heat a coke oven. The method has the following main advantages: 1. the purge gas is effectively utilized, thereby avoiding environment pollution caused by the dispersion or burning of the purge gas and increasing the benefit of enterprises; 2. the gas mixture burns to heat the coke oven instead of coke oven gas, therefore, the high position heating of the coke oven and the uniformity of the oven body of the coke oven are improved and the coke quality is improved while the requirement on coke oven production is met; and 3. the coke oven gas replaced by the purge gas is used for a methanol production system and used as a virgin gas for increasing the yield of methanol, thereby further increasing the income of the enterprises.
Description
Technical field
The present invention relates to a kind of gas recovery techniques, particularly coal chemical technology and utilize the methanol synthesis purge gas produced by coke oven gas recoverying and utilizing method, belong to field of chemical technology.
Background technology
Use problem at coking industry for solving coke-oven gas, part enterprise adopts and makes rational use of resources with the mode of coke-oven gas system methyl alcohol.At present coal chemical enterprise with the employing of coke-oven gas system methyl alcohol be the pressurized catalysis partial oxidation process, technological process is: with wet method, dry desulfurization, be removed to 0.1ppm to total sulfur after, contain certain methane (CH in the coke-oven gas
4), make CH
4Under the condition of catalyst action and high-temperature pressurizing, carry out oxidation with pure oxygen, CH
4Change into CO and CO
2, synthesize then, (composition is H with coke-oven gas
2: 50～60%, CO:4～9%, CO
2: 1.4～3.5%, CH
4: 19～28%, N
2: 3～12%, C
mH
n: the CO 2～4%), CO
2, H
2CO that becomes with methane conversion and CO
2Enter into synthesis system together, under the effect of certain temperature, pressure and catalyzer, make it to generate methyl alcohol gas, generate off-gas simultaneously.The problem that this ordinary method exists is: the coke(oven)gas hydrogen-carbon ratio is high, finally will inevitably produce a large amount of off-gas.Theoretical carbon ratio (the H of synthesizing methanol
2/ C) be 2, the many carbon of hydrogen be less coke-oven gas with the birth defects that transform legal system methyl alcohol, 1m usually
3Coke(oven)gas produces 0.28m approximately
3Off-gas contains H in the composition of off-gas
2, CO, CO
2, CH
4, N
2, off-gas many employings in suitability for industrialized production are diffused or are applied a torch and burn, thereby cause environmental pollution, and the fuel gas that off-gas is used for boiler is also arranged, but because the off-gas calorific value is low, operation is dangerous.
At present, some coal chemical enterprise is being developed and is being mended carbon method raising methanol output, adopts following three kinds of modes usually: 1. from other flue gas, reclaim CO
2Add to the synthetic furnace inlet, CO
2And H
2Synthesize methyl alcohol, but require CO
2The purity high technology is complicated, investment is big, it is low to produce effects; 2. directly adopt purer CO
2, but must increase the complete CO of a cover
2The gasification pressurizing device, it is also not obvious to produce effects; 3. the employing coal gasification method makes coal gasify through vapourizing furnace, and the gas of generation is mended carbon, because of the back coal gas that gasifies must carry out a series of purification, though can reach the purpose of mending carbon, investment is big, and technology is complicated, replenishes proper C O
2Gas still can produce certain off-gas.
In sum, the many carbon of coke-oven gas system methyl alcohol hydrogen will produce certain off-gas less, owing to still contain certain CO, CO in the off-gas
2, causing the minimizing methanol output is birth defects, off-gas fails to find the approach of effective utilization, causes certain loss to enterprise.
Summary of the invention
Problem to be solved by this invention is to overcome the defective of prior art and provide a kind of recovering discharging gas to mix with coke-oven gas, replaces the methanol synthetic discharged gas delayed recoverying and utilizing method of coal gas system of coke-oven gas heating coke oven.
The method of the invention is solved by following technical scheme:
A kind of methanol synthesis purge gas produced by coke oven gas recoverying and utilizing method; Its special feature is: the methanol synthetic discharged gas delayed mixing tank that all is recycled to that it is produced coke-oven gas system methyl alcohol system; Make off-gas and coke-oven gas thorough mixing formation gas mixture with feeding coke-oven gas in the mixing tank, with the above-mentioned gas mixture heating coke oven that acts as a fuel.
Above-mentioned methanol synthesis purge gas produced by coke oven gas recoverying and utilizing method, the methanol synthetic discharged gas delayed ratio that accounts for gas mixture is 10～27.6% in the said gas mixture.
Above-mentioned methanol synthesis purge gas produced by coke oven gas recoverying and utilizing method, the composition of said mixed gas is following: H
2: 58.729～62.388%, CO:7.195～7.281%, CO
2: 2.901～3.026%, CH
4: 19.607～23.792%, N
2: 4.746～5.724%, C
mH
n: 2.06～2.551%.
Above-mentioned methanol synthesis purge gas produced by coke oven gas recoverying and utilizing method, when said gas mixture was used to heat coke oven, mixture pressure was 6～9kpa.Flow is 49000～52000m
3/ h.
The problem that the inventive method fails effectively to utilize to existing methanol synthesis purge gas produced by coke oven gas is improved; Explore through the characteristic during current coke(oven)gas system methyl alcohol technology coke-oven gas is transformed, synthesizes and the research of coke-oven gas and off-gas composition, propose off-gas is carried out comprehensive utilization method.This method reclaims the off-gas that coke-oven gas system methyl alcohol produces, and the mixed gas of the suitable heating coke oven that forms with the coke-oven gas blending according to a certain percentage substitutes coke-oven gas heating coke oven with said gas mixture.The inventive method principal feature is following: 1. effectively utilize off-gas, avoid off-gas to diffuse or burn and cause environmental pollution, and can increase the performance of enterprises; 2. substitute coke-oven gas burning heating coke oven with said gas mixture, when satisfying the coke oven production requirement, can improve the homogeneity of coke oven height, improve coke quality to heating and coking furnace shaft temperature; 3. will be used to produce the methyl alcohol system with this part coke-oven gas that off-gas is replaced out,, can further increase enterprise income as the virgin gas of increase yield of methanol.Through measuring and calculating, the inventive method is applied to 200,000 tons/year coke-oven gas system methyl alcohol system, but about 30,000 tons of year increase yield of methanol year is created more than 5,000 ten thousand yuan of benefit Yue Keda.
Embodiment
Core technology of the present invention is that the off-gas that produces during with coke-oven gas system methyl alcohol all reclaims, again according to certain ratio be used for the coke oven heating after coke-oven gas mixes.
Coke-oven gas will inevitably produce a large amount of off-gas with transforming legal system methyl alcohol, and the present invention is because of can the effective recycling off-gas, can suitably increase to a certain extent to discharge tolerance, is equivalent to improve the dividing potential drop of available gas, helps improving transforming and synthetic ratio.Compare with coke-oven gas, off-gas combustion value is low and contain a certain amount of rare gas element.When coke-oven gas was used to heat coke oven, its combustion value was 17585KJ/m
3, the minimum combustion value of coke oven design requirements coke-oven gas is not less than 15910KJ/m
3, the present invention mixes coke-oven gas and off-gas according to the coke oven design requirements, and when the methanol synthetic discharged gas delayed ratio that accounts for gas mixture was 10～27.6% (volume ratios) in the said gas mixture, its combustion value was not less than 15910KJ/m
3, therefore can guarantee the normal operation of coke oven.After coke oven uses gas mixture; Total flux through increasing the coke oven heating remedies the influence that fuel combustion value reduces, and increases coke oven vault gas line pressure simultaneously, and the gas line pressure distribution is all increased to two ends; Limit producer gas flow increases, and improves and improve the temperature of limit stove.In addition, increased the content of rare gas element in the gas mixture, theoretical and coke-oven gas burning feature according to diffusion combustion; The length of flame in the time of can improving mixture combustion; Play the effect of elongating flame, improve the coke oven height, thereby improve the homogeneity of coke oven temperature to heat levels.Methanol synthetic discharged gas delayed owing in coke oven fuel, having added, displace the part coke-oven gas, this part coke-oven gas that displaces is used to produce methyl alcohol, form closed cycle.The coke-oven gas carbon containing is high, plays the effect of mending carbon simultaneously, improves the output of methyl alcohol.
According to routine techniques, methanol synthetic discharged gas delayed composition is generally: H
2: 60～80%, CO 5～21%, CO
2: 3～8%, CH
4: 0.5～4%, N
2: 2～12%, C
mH
n: 0.02～0.2% (C
mH
nRefer to remove in the gas CH
4In addition contain the C organic constituent); The composition of coke-oven gas is: H
2: 50～60%, CO:4～9%, CO
2: 1.4～3.5%, CH
4: 19～28%, N
2: 3～12%, C
mH
n: 2～4%.For guaranteeing that the low combustion value of gas mixture is not less than 15910KJ/m
3, the composition of the present invention's technology mixed gas is: H
2: 58.729～62.388%, CO:7.195～7.281%, CO
2: 2.901～3.026%, CH
4: 19.607～23.792%, N
2: 4.746～5.724%, C
mH
n: 2.06～2.551%.The methanol synthetic discharged gas delayed pressure that gets in the mixing tank is 0.015～0.02Mpa, temperature≤40 ℃; The coke-oven gas pressure that gets in the mixing tank is 0.003～0.012Mpa.
Below provide several concrete embodiment:
Embodiment 1: methanol synthesis purge gas produced by coke oven gas and coke-oven gas are introduced mixing tank, and the methanol synthetic discharged gas delayed pressure that gets in the mixing tank is 0.015Mpa, temperature≤40 ℃; The coke-oven gas pressure that gets in the mixing tank is 0.003Mpa.The wherein methanol synthetic discharged gas delayed ratio that accounts for mixed gas is 10%, and said gas mixture composition is: H
2: 58.729, CO:7.281, CO
22.901, CH
4: 23.792, N
2: 4.746, C
mH
n: 2.551.Above-mentioned mixed gas is introduced coke oven heating system, and mixture pressure is 6kPa, and flow is 49000m
3/ h, the branch flue suction force is 204Pa, coke oven vault gas line 452Pa.
Embodiment 2: methanol synthesis purge gas produced by coke oven gas and coke-oven gas are introduced mixing tank, and the methanol synthetic discharged gas delayed pressure that gets in the mixing tank is 0.018Mpa, temperature≤40 ℃, and the coke-oven gas pressure that gets in the mixing tank is 0.008Mpa.The wherein methanol synthetic discharged gas delayed ratio that accounts for mixed gas is 23.3%, and said gas mixture composition is: H
2: 61.50, CO:7.216, CO
2: 2.995, CH
4: 20.63, N
2: 5.485, C
mH
n: 2.174; Above-mentioned mixed gas is introduced coke oven heating system, and mixture pressure is 6.8kPa, and flow is 51400m
3/ h, the branch flue suction force is 211Pa, coke oven vault gas line 523Pa.
Embodiment 3: methanol synthesis purge gas produced by coke oven gas and coke-oven gas are introduced mixing tank, and the methanol synthetic discharged gas delayed pressure that gets in the mixing tank is 0.02Mpa, temperature≤40 ℃, and the coke-oven gas pressure that gets in the mixing tank is 0.012Mpa.The wherein methanol synthetic discharged gas delayed ratio that accounts for mixed gas is 27.6%, and said gas mixture composition is: H
2: 62.388, CO:7.195, CO
2: 3.026, CH
4: 19.607, N
2: 5.724, C
mH
n: 2.06; Above-mentioned mixed gas is introduced coke oven heating system, and mixture pressure is 9kPa, and flow is 52000m
3/ h, the branch flue suction force is 215Pa, coke oven vault gas line 550Pa.
Claims (2)
1. methanol synthesis purge gas produced by coke oven gas recoverying and utilizing method; It is characterized in that: the methanol synthetic discharged gas delayed mixing tank that all is recycled to that it is produced coke-oven gas system methyl alcohol system; Make off-gas and coke-oven gas thorough mixing form gas mixture with feeding coke-oven gas in the mixing tank; With the above-mentioned gas mixture heating coke oven that acts as a fuel, the methanol synthetic discharged gas delayed ratio that accounts for gas mixture is 10～27.6% in the said gas mixture, and the composition of said mixed gas is following: H
2: 58.729～62.388%, CO:7.195～7.281%, CO
2: 2.901～3.026%, CH
4: 19.607～23.792%, N
2: 4.746～5.724%, C
mH
n: 2.06～2.551%, C wherein
mH
nRefer to remove in the gas CH
4In addition contain the C organic constituent.
2. methanol synthesis purge gas produced by coke oven gas recoverying and utilizing method according to claim 1 is characterized in that: when said gas mixture was used to heat coke oven, mixture pressure was 6～9kPa; Flow is 49000～52000m
3/ h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100757538A CN101693837B (en) | 2009-10-21 | 2009-10-21 | Method for recycling methanol synthesis purge gas produced by coke oven gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100757538A CN101693837B (en) | 2009-10-21 | 2009-10-21 | Method for recycling methanol synthesis purge gas produced by coke oven gas |
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| Publication Number | Publication Date |
|---|---|
| CN101693837A CN101693837A (en) | 2010-04-14 |
| CN101693837B true CN101693837B (en) | 2012-08-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100757538A Expired - Fee Related CN101693837B (en) | 2009-10-21 | 2009-10-21 | Method for recycling methanol synthesis purge gas produced by coke oven gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105802639A (en) * | 2016-05-10 | 2016-07-27 | 中冶焦耐工程技术有限公司 | Coke dry quenching furnace diffused gas treatment method |
| CN113292394B (en) * | 2021-06-15 | 2022-04-05 | 河海大学 | Coke oven gas coupling waste incineration power generation system methyl alcohol device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2620823Y (en) * | 2003-04-30 | 2004-06-16 | 肖凤杳 | Gas and natural gas split combustion burner |
| CN101302139A (en) * | 2008-07-07 | 2008-11-12 | 西南化工研究设计院 | Method for preparing methanol using coal bed gas |
| CN101343580A (en) * | 2008-08-22 | 2009-01-14 | 四川天一科技股份有限公司 | Method for preparing methanol synthesis gas with oven gas and blast furnace gas |
| CN101549856A (en) * | 2009-05-02 | 2009-10-07 | 大连理工大学 | Separation method of comprehensively recycled hydrogen and carbon monooxide from synthesis purge gas |
-
2009
- 2009-10-21 CN CN2009100757538A patent/CN101693837B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2620823Y (en) * | 2003-04-30 | 2004-06-16 | 肖凤杳 | Gas and natural gas split combustion burner |
| CN101302139A (en) * | 2008-07-07 | 2008-11-12 | 西南化工研究设计院 | Method for preparing methanol using coal bed gas |
| CN101343580A (en) * | 2008-08-22 | 2009-01-14 | 四川天一科技股份有限公司 | Method for preparing methanol synthesis gas with oven gas and blast furnace gas |
| CN101549856A (en) * | 2009-05-02 | 2009-10-07 | 大连理工大学 | Separation method of comprehensively recycled hydrogen and carbon monooxide from synthesis purge gas |
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| CN101693837A (en) | 2010-04-14 |
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Granted publication date: 20120822 Termination date: 20211021 |