CN106946254A - A kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation - Google Patents
A kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation Download PDFInfo
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- CN106946254A CN106946254A CN201710159671.6A CN201710159671A CN106946254A CN 106946254 A CN106946254 A CN 106946254A CN 201710159671 A CN201710159671 A CN 201710159671A CN 106946254 A CN106946254 A CN 106946254A
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- hydrogen
- methanation
- gas
- carbon monoxide
- methane
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Abstract
The present invention relates to a kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation, carbon monoxide gas concentration >=98.5%, density of hydrogen≤1.5%, hydrogen is removed using methanation process, make density of hydrogen≤1ppm, using the hydrogen methanation catalyst of activated centre Preferential adsorption hydrogen, methanation operation temperature is controlled below 400 DEG C；Dimethyl oxalate process is sent after the cooling of methanation gas, when carbon monoxide cycle gas methane concentration is close to or up 3%, part circulating air is drawn, methane is removed using absorption method or membrane separating, dimethyl oxalate production system is sent in circulating air boosting back to.
Description
Technical field
It is a kind of effective method for reducing ethylene glycol production process energy consumption the present invention relates to chemical industry, energy-saving and environmental protection field.
Background technology
In coal-ethylene glycol production process, separated according to absorption method, easily make to be mixed with 0.2 in CO gas ~
1.5% hydrogen.
The minimizing technology of hydrogen is typically to use oxygenation catalytic oxidative desulfurization method and adsorption method of separation in CO gas.
Oxygen is added in CO gas, catalysis oxidation wherein hydrogen needs to use noble metal catalyst, and catalyst is held high
Expensive, service life is short.And during catalysis oxidation hydrogen, part Oxidation of Carbon Monoxide can be made into carbon dioxide, an oxygen is caused
Change carbon yield less than normal.After oxic gas cooled dehydrated, carbon dioxide removal, dimethyl oxalate production process is sent, process investment is big,
Complex operation.
Hydrogen in carbon monoxide uses special hydrogen-absorbing material, sets up more than two adsorption towers, can be by density of hydrogen
≤ 1ppm is dropped to, hydrogen-absorbing material is reached after certain saturation degree, switch adsorption tower, the absorption after hydrogen is inhaled using oxygen high temperature regeneration
Agent, is thus back and forth used, and has a certain degree of inactivation, adsorbent after reaching the purpose of separation hydrogen, the process adsorbent reactivation
Activation process operation difficulty is big, careless slightly directly to damage adsorbent activity surface.After adsorbent is damaged, absorption is changed
Agent is bothered.Adsorbent is expensive, and investment is big.
Methanation is the conventional method of carbon monoxide in decontaminating syngas in production of synthetic ammonia, and the methanation exists
In the presence of a large amount of hydrogen, carbon monoxide, carbon dioxide and hydrogen catalytic react, and generate methane.Thus carbon monoxide,
Gas concentration lwevel each drops to≤5ppm.Carbon monoxide and carbon dioxide are preferentially adsorbed on catalytic active center, hydrogen again with
The carbon monoxide in activated centre, carbon dioxide reaction, generate methane, thus reach the purpose of purification carbon monoxide.If hydrogen is excellent
First adsorb in catalytic active center, then carbon monoxide, purifying carbon dioxide difficulty are just very big, it is difficult to all drop to concentration≤
5ppm.Therefore, the inevitable method that Preferential adsorption carbon monoxide, the activated centre of carbon dioxide are the processes is selected.We are this
Plant methanation and be referred to as carbonoxide methanation.
The content of the invention
During the present invention is a kind of ethylene glycol production process, the improved method of CO gas catalytic dehydrogenation, carbon monoxide
Gas concentration >=98.5%, density of hydrogen≤1.5% removes hydrogen using methanation process.Methanation mild condition, operation temperature
≤ 400 DEG C are can be controlled in, using the catalyst of catalytic active center Preferential adsorption hydrogen, this methanation is referred to as hydrogen methane
Change.Density of hydrogen in carbon monoxide is reduced by hydrogen methanation, the purpose of removing hydrogen is realized, density of hydrogen can be dropped to
≤1ppm.Methanation outlet temperature is higher than dimethyl oxalate production system temperature, cooling feeding dimethyl oxalate production system.
The methane of hydrogen methanation generation is mixed into carbon monoxide and send dimethyl oxalate production system, and methane is not involved in instead
Should, as inert gas.When methane concentration >=3% can hinder carbon monoxide conversion, it is necessary to extension circulating air.Using absorption
Method or membrane separating remove methane, and dimethyl oxalate production system is sent back to after the boosting of demethanation circulating air.
Embodiment 1
Ethylene glycol production system, carbon monoxide is obtained in carbon monoxide, CO gas using pressure swing adsorption method contains 0.2%
Hydrogen, temperature 60 C, heat gas temperatures reach 200 ~ 300 DEG C, and hydrogen is adsorbed in methanation catalyst activated centre, one first
Carbon oxide gas enter methanation catalyst activated centre and reacted with hydrogen, generate methane, density of hydrogen drops to≤1ppm, methane
Concentration reaches 0.067%.Gas containing methane is sent to after dimethyl oxalate process, Partial Conversion carbon monoxide, methane is dense
Contracting, methane concentration reaches or during close to 3% that extension recyclegas uses UF membrane or pressure-variable adsorption to remove in recyclegas
Methane concentration is less than 0.067% in methane, carbon monoxide, sends into circulating air.
Embodiment 2
Ethylene glycol production system, carbon monoxide is obtained in carbon monoxide, CO gas using pressure swing adsorption method contains 0.6%
Hydrogen, temperature 60 C, heat gas temperatures reach 200 ~ 300 DEG C, and hydrogen is adsorbed in methanation catalyst activated centre, one first
Carbon oxide gas enter methanation catalyst activated centre and reacted with hydrogen, generate methane, density of hydrogen drops to≤1ppm, methane
Concentration reaches 0.2%.Gas containing methane is sent to after dimethyl oxalate process, Partial Conversion carbon monoxide, methane is concentrated,
Methane concentration reaches or during close to 3% in recyclegas, extension recyclegas, uses UF membrane or pressure-variable adsorption removing first
Methane concentration is less than 0.2% in alkane, carbon monoxide, sends into circulating air.
Embodiment 3
Ethylene glycol production system, carbon monoxide is obtained in carbon monoxide, CO gas using pressure swing adsorption method contains 1.5%
Hydrogen, temperature 60 C, heat gas temperatures reach 200 ~ 300 DEG C, and hydrogen is adsorbed in methanation catalyst activated centre, one first
Carbon oxide gas enter methanation catalyst activated centre and reacted with hydrogen, generate methane, density of hydrogen drops to≤1ppm, methane
Concentration reaches 0.5%.Gas containing methane is sent to after dimethyl oxalate process, Partial Conversion carbon monoxide, methane is concentrated,
Methane concentration reaches or during close to 3% in recyclegas, extension recyclegas, uses UF membrane or pressure-variable adsorption removing first
Methane concentration is less than 0.5% in alkane, carbon monoxide, sends into circulating air.
The loss maximum only 0.5% of carbon monoxide during method removing hydrogen.With the concentration phase of hydrogen in carbon monoxide
Close.
Claims (1)
1. a kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation, it is characterised in that：Carbon monoxide gas
Bulk concentration >=98.5%, density of hydrogen≤1.5% removes hydrogen using methanation process, makes density of hydrogen≤1ppm, using activity
The hydrogen methanation catalyst of center Preferential adsorption hydrogen, methanation operation temperature is controlled below 400 DEG C；After the cooling of methanation gas
Dimethyl oxalate process is sent, when carbon monoxide cycle gas methane concentration is close to or up 3%, part circulating air is drawn, using suction
Attached method or membrane separating remove methane, and dimethyl oxalate production system is sent in circulating air boosting back to.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710159671.6A CN106946254A (en) | 2017-03-17 | 2017-03-17 | A kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710159671.6A CN106946254A (en) | 2017-03-17 | 2017-03-17 | A kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation |
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| CN106946254A true CN106946254A (en) | 2017-07-14 |
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| CN201710159671.6A Pending CN106946254A (en) | 2017-03-17 | 2017-03-17 | A kind of improved method of ethylene glycol production process CO gas catalytic dehydrogenation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114394594A (en) * | 2022-01-16 | 2022-04-26 | 四川天人化学工程有限公司 | Improved process for purifying low-hydrogen high-concentration carbon monoxide |
| CN114452771A (en) * | 2022-01-16 | 2022-05-10 | 四川天人化学工程有限公司 | Improved process for purifying low-hydrogen high-concentration carbon monoxide |
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| CN102247851A (en) * | 2010-05-12 | 2011-11-23 | 中国科学院福建物质结构研究所 | Methanation process for removing a small amount of H2 from industrial CO gas and preparation method of catalyst |
| CN102838116A (en) * | 2012-09-10 | 2012-12-26 | 太原理工大学 | Method for preparing carbon monoxide from coke oven gas and carbon dioxide |
| CN103890147A (en) * | 2011-08-17 | 2014-06-25 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock |
| CN104418321A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | Method of removing H2 in CO raw material |
| CN106268858A (en) * | 2016-07-16 | 2017-01-04 | 中国科学院山西煤炭化学研究所 | The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation and preparation method and application |
| JP2019044238A (en) * | 2017-09-05 | 2019-03-22 | 千代田化工建設株式会社 | Synthesis gas generation system |
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2017
- 2017-03-17 CN CN201710159671.6A patent/CN106946254A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247851A (en) * | 2010-05-12 | 2011-11-23 | 中国科学院福建物质结构研究所 | Methanation process for removing a small amount of H2 from industrial CO gas and preparation method of catalyst |
| CN103890147A (en) * | 2011-08-17 | 2014-06-25 | 格雷特波因特能源公司 | Hydromethanation of a carbonaceous feedstock |
| CN102838116A (en) * | 2012-09-10 | 2012-12-26 | 太原理工大学 | Method for preparing carbon monoxide from coke oven gas and carbon dioxide |
| CN104418321A (en) * | 2013-09-04 | 2015-03-18 | 中国石油化工股份有限公司 | Method of removing H2 in CO raw material |
| CN106268858A (en) * | 2016-07-16 | 2017-01-04 | 中国科学院山西煤炭化学研究所 | The catalyst of a kind of high-performance hydrogenation of carbon dioxide methanation and preparation method and application |
| JP2019044238A (en) * | 2017-09-05 | 2019-03-22 | 千代田化工建設株式会社 | Synthesis gas generation system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114394594A (en) * | 2022-01-16 | 2022-04-26 | 四川天人化学工程有限公司 | Improved process for purifying low-hydrogen high-concentration carbon monoxide |
| CN114452771A (en) * | 2022-01-16 | 2022-05-10 | 四川天人化学工程有限公司 | Improved process for purifying low-hydrogen high-concentration carbon monoxide |
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Application publication date: 20170714 |
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