CN105197883A - Methanol synthesis purge gas recycling method - Google Patents
Methanol synthesis purge gas recycling method Download PDFInfo
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- CN105197883A CN105197883A CN201510601379.6A CN201510601379A CN105197883A CN 105197883 A CN105197883 A CN 105197883A CN 201510601379 A CN201510601379 A CN 201510601379A CN 105197883 A CN105197883 A CN 105197883A
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- gases
- periodic
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- purge gas
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Abstract
The invention discloses a methanol synthesis purge gas recycling method. One part of purge gas is purified through a pressure swing adsorption device after being processed, and the purified gas is used as a hydrogen raw material of a benzene hydrogenation system; the other part of purge gas is used as fuel of a combustion boiler through a pipeline after being processed. The part of purge gas serving as the hydrogen raw material is processed through the steps of conducting a steam conversion reaction on purge gas, converting carbon monoxide in purge gas into carbon dioxide and hydrogen, reforming and dissolving methyl alcohol in purge gas into carbon dioxide and hydrogen, and conducting processing through the pressure swing adsorption device, wherein a copper-based catalyst and a catalyst activating agent are added to the purge gas steam conversion reaction. Purge gas generated in the methyl alcohol production process is used for combustion or purification to generate hydrogen, hydrogen is then used as the raw material in the benzene hydrogenation system, the effective utilization rate of purge gas can be increased, and the production cost can be reduced.
Description
Technical field
The present invention relates to the treatment process of periodic off-gases in chemical field, be specially a kind of methanol-fueled CLC periodic off-gases recovery method.
Background technology
Utilize the coke(oven)gas methanol of coking by-product, on the one hand can the increasingly serious Energy situation of partial rcsponse China; On the other hand for an effective economy, environmental protection new way are opened up in numerous coking enterprise waste gas comprehensive utilization.Existing preparing methanol from coke oven gas technology, its main process be by desulfurization after coke(oven)gas transform, obtaining main component is CO, CO
2and H
2unstripped gas send into methyl alcohol synthetic reactor, and under the effect of catalyzer synthesizing methanol.From synthetic tower gas out after refrigerated separation methyl alcohol; major part sends into synthetic tower as circulation gas together with the virgin gas charging of synthetic tower; for maintaining system balancing; remainder gas is just by as methanol purge gas; at present, methanol purge gas body can be carried out burn processing by preparing methanol from coke oven gas enterprise usually.
China's Coal Chemical Industry belongs to highly energy-consuming, maximum discharge industry, by limitation of the technology, the energy conversion efficiency of coal in overall industrial chain is not high, energy consumption and Carbon emission intensity all exceed more than 10 times of national industry average level, and the development disorder of Coal Chemical Industry directly will affect the realization that national energy-saving reduces discharging overall goal.Therefore, the strict restriction that 1,000,000 tons and following ammonia from coal project and other Coal Chemical Engineering Project receive national industrial policies is produced per year.Under this industry policy, the large-scale ammonia from coal technology of megaton is developed fast.Due to coal be source synthesizing methanol device material synthesis gas in hydrogen content relatively low, cause synthesis virgin gas hydrogen-carbon ratio can not meet synthesizing methanol reaction requirement, the hydrogen partial mainly through adopting partial synthesis gas to come in supplementary synthetic gas through the operation such as low temperature shift reaction and pressure swing adsorption decarbonization in current ammonia from coal full scale plant.
In preparing methanol from coke oven gas enterprise, be the needs of adapt to economic development development, require to improve throughput.A kind of settling mode reconstructs a set of production equipment; Scale of investment is large, once methyl alcohol needs to weaken, loss of enterprise risk is high; Another kind of settling mode is the production load improving existing apparatus, but for certain coal chemical enterprise, its coke(oven)gas mean load is at 20000Nm
3/ h, synthetic tower pressure be 4.2-5.2MPa, under temperature out is the reaction conditions of 236 DEG C, methanol purge gas is 7000Nm
3/ h, wherein CO content is 2.10%, CO
2content is 4.33%, total carbon content about 6.43%.But when load reaches 34000Nm
3/ h, methanol purge gas amount is approximately 14000Nm
3/ h, the CO content at this moment in periodic off-gases is 7.43%, CO
2content is 8.56%.Carbon content in periodic off-gases is very high, also just means that the carbon loss through periodic off-gases is a lot, if the direct fire row of gas that carbon content is so high bled off, must cause the very big destruction to environment and the waste very large to the energy.
In addition, in preparing methanol from coke oven gas, in the coke(oven)gas that coking produces, sulphur content is higher, such as may at 100ppm ~ 300ppm, there is great murder by poisoning to the catalyzer of follow-up coke(oven)gas conversion, synthesizing methanol, catalyzer is lost activity, therefore, coke(oven)gas needs to carry out desulfurization process, to meet methanol-fueled CLC requirement.In production, conventional iron-manganese desulfurizer carries out desulfurization, and the iron-manganese desulfurizer of new clothes must first could use after reduction, and when carrying out reducing with coke(oven)gas, just needs coke(oven)gas greatly.Such production load just needs to reduce to very low, even stops, and changes coke oven tolerance simultaneously and is also unfavorable for that the stable of production operation carries out, add production hidden danger.
In the process that methanol-fueled CLC periodic off-gases is processed, fuel can be it can be used as, also can be purified and make highly purified hydrogen, such as in Chinese patent CN103264989A, disclose a kind of processing method of synthetic gas synthesizing methanol device release gas recovery, it is purified to periodic off-gases by reformation and pressure-variable adsorption, and then obtains highly purified hydrogen.
In this patent documentation, carrying out in water vapour transformationreation process, the catalyzer employed is CuO/ZnO/Al
2o
3copper-based catalysts.In actual use, copper-based catalysts generally can use the time of 6 months ~ 1 year.Need in transformationreation process to heat reactant gases, improve reactant energy, to ensure the chemical energy that has needed for reaction; Select single catalyzer in this file, make temperature of reaction higher, improve production cost.
Summary of the invention
The object of this invention is to provide a kind of methanol-fueled CLC periodic off-gases recovery method.
For reaching above-mentioned purpose, a kind of methanol-fueled CLC periodic off-gases recovery method is provided in one embodiment of the present of invention, methanol-fueled CLC periodic off-gases is the periodic off-gases of preparing methanol from coke oven gas system discharge, purify through pressure-swing absorption apparatus after the part process of periodic off-gases, the gas after purifying is as the hydrogen feed of benzene hydrogenation system; By the fuel of pipeline as burning boiler after another part process of periodic off-gases;
Part periodic off-gases treatment step as hydrogen feed comprises:
Periodic off-gases is carried out water vapor transformationreation, is carbonic acid gas and hydrogen by the carbon monodixe conversion in periodic off-gases, and the methanol recapitalization in periodic off-gases is decomposed into carbonic acid gas and hydrogen; And then through pressure-swing absorption apparatus process;
Add copper-based catalysts and catalyst activator in the transformationreation of periodic off-gases water vapour, copper-based catalysts is CuO/ZnO/Al
2o
3copper-based catalysts, the temperature of reaction of transformationreation is 150 DEG C ~ 170 DEG C; Reaction pressure is 1Mpa ~ 6Mpa; Catalyst activator is the mixture of cerous nitrate 20% ~ 40% and lanthanum nitrate 60% ~ 80%.
In prioritization scheme of the present invention, containing methane 2% ~ 4% in periodic off-gases; Hydrogen 70% ~ 80%; Carbon monoxide 4% ~ 6%; Carbonic acid gas 5% ~ 8%; Nitrogen 5% ~ 8%; The calorific value of periodic off-gases is 2500Kcal/Nm
3~ 3500Kcal/Nm
3.
In prioritization scheme of the present invention, the reaction velocity of transformationreation is 3000/h ~ 12000/h.
In prioritization scheme of the present invention, the elemental mole ratios of copper-based catalysts is Cu:Zn:Al=5:2:1.
In prioritization scheme of the present invention, catalyst activator is the mixture of cerous nitrate 25% and lanthanum nitrate 75%.
In prioritization scheme of the present invention, the add-on of catalyst activator is 4% ~ 10% of copper-based catalysts quality.
In sum, the present invention has the following advantages:
The periodic off-gases produced in methanol production process is used for burning by the present invention or purifying obtains hydrogen, then hydrogen is used for the raw material in benzene hydrogenation system, can improves the effective rate of utilization of periodic off-gases, reduces production cost.
Secondly, the catalyzer of the present invention to water vapour transformationreation is optimized, and adds catalytic activity agent in the catalyst, can improve catalyst activity, reduces the chemical energy required for reaction, carries out reducing temperature of reaction.
Embodiment
The invention provides a kind of methanol-fueled CLC periodic off-gases recovery method, methanol-fueled CLC periodic off-gases is the periodic off-gases of preparing methanol from coke oven gas system discharge, purify through pressure-swing absorption apparatus after the part process of periodic off-gases, the gas after purifying is as the hydrogen feed of benzene hydrogenation system; By the fuel of pipeline as burning boiler after another part process of periodic off-gases.
Embodiment 1
Part periodic off-gases treatment step as hydrogen feed is:
(1), by periodic off-gases carrying out water vapor transformationreation, is carbonic acid gas and hydrogen by the carbon monodixe conversion in periodic off-gases.
Containing methane 2.2% in periodic off-gases; Hydrogen 76%; Carbon monoxide 5.2%; Carbonic acid gas 6.3%; Nitrogen 7%; The calorific value of periodic off-gases is 2912Kcal/Nm
3.
Reaction conditions: temperature 168 DEG C, working pressure 4Mpa, reaction velocity 8500/h, excessive water steam; Add copper-based catalysts CuO/ZnO/Al
2o
3with catalyst activator 6%, wherein the elementary composition of copper-based catalysts is Cu:Zn:Al=5:2:1, and catalyst activator is the cerous nitrate of 25% and the lanthanum nitrate of 75%.
(2), the mixed gas containing hydrogen and carbonic acid gas be obtained by reacting in step 1 is carried out methanol recapitalization decomposition technique step.
In mixed gas after treatment, the ratio of methyl alcohol and water vapour is adjusted to 1:6 ~ 10; Methanol recapitalization in periodic off-gases is decomposed into carbonic acid gas and hydrogen; Concrete reaction formula is:
CH
3OH+H
2O＝CO
2+3H
2
After reducing temperature, the methanol recapitalization in periodic off-gases is decomposed into carbonic acid gas and hydrogen, and the content of methyl alcohol reduces, and the content of hydrogen and carbonic acid gas raises slightly; Now contain the extremely low component of promising carbon monoxide 0.2%, carbonic acid gas 2.0%, hydrogen 86.2%, nitrogen 6.5%, methane 0.15%, methyl alcohol 0.02% and gas content in system.
(3), by the gas after reforming carry out pressure-variable adsorption, remove impurity wherein, obtain highly purified hydrogen, the content of hydrogen is 99.8%.
Different catalysts is on the impact of water vapour transformationreation
Embodiment 2
Water vapour transformationreation is also CO shift reaction, and its reaction formula is:
CO+H
2O＝CO
2+H
2
Reaction process:
Pass in reactor by 10mol carbon monoxide and 12mol water vapour, control temperature 180 DEG C, working pressure 5MPa, reaction velocity is 10000/h, adds catalyzer copper-based catalysts CuO/ZnO/Al
2o
3with 1% cerous nitrate accounting for catalyst weight, the lanthanum nitrate of 3%; It is 1.2% that reaction terminates rear detection carbon monoxide content.
Embodiment 3
Pass in reactor by 10mol carbon monoxide and 12mol water vapour, control temperature 180 DEG C, working pressure 5MPa, reaction velocity is 10000/h, adds catalyzer copper-based catalysts CuO and 1% cerous nitrate accounting for catalyst weight, the lanthanum nitrate of 3%; It is 1.5% that reaction terminates rear detection carbon monoxide content.
Embodiment 4
Pass in reactor by 10mol carbon monoxide and 12mol water vapour, control temperature 180 DEG C, working pressure 5MPa, reaction velocity is 10000/h, adds cerous nitrate and lanthanum nitrate; Reaction can not be carried out.
Implement firepower 5
Reaction process:
Pass in reactor by 10mol carbon monoxide and 12mol water vapour, control temperature 180 DEG C, working pressure 5MPa, reaction velocity is 10000/h, adds catalyzer copper-based catalysts CuO/ZnO/Al
2o
3; It is 3.2% that reaction terminates rear detection carbon monoxide content.
Can be learnt by appeal embodiment, methanol purge gas recovery method of the present invention, by being optimized the component of catalyzer, add activator in the prior art, reduce the minimum energy requirement of chemical reaction, make the catalytic effect of catalyzer better, reaction can be made under some circumstances to carry out towards positive dirction, and then making the reaction of carbon monoxide more thorough, reaction effect is good.
The present invention, by periodic off-gases being divided into the supply of combustion gas and hydrogen feed, solves the problem of complex utilization of periodic off-gases in prior art.
Claims (7)
1. a methanol-fueled CLC periodic off-gases recovery method, is characterized in that:
Described methanol-fueled CLC periodic off-gases is the periodic off-gases of preparing methanol from coke oven gas system discharge, and purify through pressure-swing absorption apparatus after the part process of described periodic off-gases, the gas after purifying is as the hydrogen feed of benzene hydrogenation system; By the fuel of pipeline as burning boiler after another part process of described periodic off-gases;
The described part periodic off-gases treatment step as hydrogen feed comprises:
Periodic off-gases is carried out water vapor transformationreation, is carbonic acid gas and hydrogen by the carbon monodixe conversion in periodic off-gases, and the methanol recapitalization in periodic off-gases is decomposed into carbonic acid gas and hydrogen; And then through pressure-swing absorption apparatus process;
Add copper-based catalysts and catalyst activator in the transformationreation of described periodic off-gases water vapour, described copper-based catalysts is CuO/ZnO/Al
2o
3copper-based catalysts, the temperature of reaction of described transformationreation is 150 DEG C ~ 170 DEG C; Reaction pressure is 1Mpa ~ 6Mpa; Described catalyst activator is the mixture of cerous nitrate 20% ~ 40% and lanthanum nitrate 60% ~ 80%.
2. the method for claim 1, is characterized in that: containing methane 2% ~ 4% in described periodic off-gases; Hydrogen 70% ~ 80%; Carbon monoxide 4% ~ 6%; Carbonic acid gas 5% ~ 8%; Nitrogen 5% ~ 8%.
3. the method for claim 1, is characterized in that: the calorific value of described periodic off-gases is 2500Kcal/Nm
3~ 3500Kcal/Nm
3.
4. the method for claim 1, is characterized in that: the reaction velocity of described transformationreation is 3000/h ~ 12000/h.
5. the method for claim 1, is characterized in that: the elemental mole ratios of described copper-based catalysts is Cu:Zn:Al=5:2:1.
6. the method for claim 1, is characterized in that: described catalyst activator is the mixture of cerous nitrate 25% and lanthanum nitrate 75%.
7. the method for claim 1, is characterized in that: the add-on of described catalyst activator is 4% ~ 10% of copper-based catalysts quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510601379.6A CN105197883A (en) | 2015-09-18 | 2015-09-18 | Methanol synthesis purge gas recycling method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510601379.6A CN105197883A (en) | 2015-09-18 | 2015-09-18 | Methanol synthesis purge gas recycling method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105197883A true CN105197883A (en) | 2015-12-30 |
Family
ID=54945921
Family Applications (1)
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|---|---|---|---|
| CN201510601379.6A Pending CN105197883A (en) | 2015-09-18 | 2015-09-18 | Methanol synthesis purge gas recycling method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107930345A (en) * | 2017-11-21 | 2018-04-20 | 七台河宝泰隆圣迈煤化工有限责任公司 | A kind of exhaust treatment system for exchanging altar lamp burning resolution gas and fuel gas |
| CN114906807A (en) * | 2022-06-08 | 2022-08-16 | 佛燃能源集团股份有限公司 | Hydrogen production system and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155511A (en) * | 1996-01-22 | 1997-07-30 | 中国石化齐鲁石油化工公司 | Process and apparatus for converting methanol vapor into hydrogen |
| CN103264989A (en) * | 2013-05-20 | 2013-08-28 | 西南化工研究设计院有限公司 | Technique for recycling purge gas of device used for synthesizing methyl alcohol by utilizing synthesis gas |
| CN104645999A (en) * | 2015-02-12 | 2015-05-27 | 上海摩醇动力技术有限公司 | Preparation process for catalyst for hydrogen production through methanol steam reforming |
-
2015
- 2015-09-18 CN CN201510601379.6A patent/CN105197883A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1155511A (en) * | 1996-01-22 | 1997-07-30 | 中国石化齐鲁石油化工公司 | Process and apparatus for converting methanol vapor into hydrogen |
| CN103264989A (en) * | 2013-05-20 | 2013-08-28 | 西南化工研究设计院有限公司 | Technique for recycling purge gas of device used for synthesizing methyl alcohol by utilizing synthesis gas |
| CN104645999A (en) * | 2015-02-12 | 2015-05-27 | 上海摩醇动力技术有限公司 | Preparation process for catalyst for hydrogen production through methanol steam reforming |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107930345A (en) * | 2017-11-21 | 2018-04-20 | 七台河宝泰隆圣迈煤化工有限责任公司 | A kind of exhaust treatment system for exchanging altar lamp burning resolution gas and fuel gas |
| CN114906807A (en) * | 2022-06-08 | 2022-08-16 | 佛燃能源集团股份有限公司 | Hydrogen production system and method |
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| PB01 | Publication | ||
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Application publication date: 20151230 |