CN104709907A - Process and system for selectively removing small amount of H2 from high-concentrations CO gas - Google Patents
Process and system for selectively removing small amount of H2 from high-concentrations CO gas Download PDFInfo
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- CN104709907A CN104709907A CN201510129883.0A CN201510129883A CN104709907A CN 104709907 A CN104709907 A CN 104709907A CN 201510129883 A CN201510129883 A CN 201510129883A CN 104709907 A CN104709907 A CN 104709907A
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- oxidation reactor
- small amount
- selectively removing
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Abstract
The invention relates to a process and a system for selectively removing a small amount of H2 from high-concentrations CO gas, which solve the problem that a small amount of H2 in existing high-concentrations CO gas is difficult to remove. The method comprises the following steps: after CO virgin gas and oxygen are mixed in a mixer, feeding the obtained mixed gas into an oxidation reactor to carry out an oxidation reaction so as to remove hydrogen in the virgin gas, wherein the volume rate of the oxygen and H2 in the CO virgin gas is controlled at 0.6-0.9; and then feeding the reaction gas into an alkaline washing tower to wash by using alkaline liquor so as to absorb CO2 in the reaction gas, and carrying out further dehydrogenation by using a molecular sieve adsorber, so that high-purity CO gas with a hydrogen content of less than 100 ppm is obtained. The process disclosed by the invention is simple in method and low in equipment investment and operation cost, and can control the hydrogen content of the CO virgin gas below 100 ppm so as to meet the demands of downstream working procedures.
Description
Technical field
The present invention relates to a kind of ethylene glycol production technique and system, specifically in ethylene glycol production process, a small amount of H of selectively removing in high concentration CO gas
2technique and system.
Background technology
At present, China's ethylene glycol is produced and is mainly adopted petroleum path, i.e. ethylene oxide hydration technology, its advantage such as maturation, wide application that possess skills, but this route relies on petroleum resources, and process water consumption, energy consumption are large, cost is higher.Coal-ethylene glycol technology in Non oil-based route, namely makes synthetic gas with coal, then prepares ethylene glycol with CO and H2 in synthetic gas for raw material, has that cost is low, energy consumption is low, water consumption is low, discharge the advantages such as low.For the present situation of China's oil starvation, weak breath, coal resources relative abundance, Development of Coal preparing ethylene glycol technology has great importance.
In coal-ethylene glycol technology, CO oxidative coupling method processing requirement is not high, and reaction conditions is gentleer, be research both at home and abroad the most extensive, be also the synthetic gas synthesizing glycol route being hopeful large-scale industrial production at present most.The principal reaction of CO oxidative coupling method preparing ethylene glycol comprises the oxonation of carbon monoxide and methyl nitrite (MN) oxalic dimethyl ester (DMO), the reaction of Hydrogenation of Dimethyl Oxalate generating glycol (EG), nitrogen protoxide, oxygen and methyl alcohol generate the esterification regenerative response of methyl nitrite, and principal reaction is as follows:
Barkite synthesizes
The regeneration of reaction end gas
2NO+1/2O
2+2CH
3OH→2CH
3ONO+H
2O
Hydrogenation of oxalate for preparing ethylene glycol
From the hydrogen of CO unstripped gas generally containing 0.3% ~ 1.6% (v) of upstream process, the existence of a small amount of hydrogen has a great impact for the synthesis of subsequent handling dimethyl oxalate in preparation, hydrogen both can produce with methyl nitrite the product yield that side reaction affects dimethyl oxalate, the existence of protium is simultaneously unfavorable for the activation of dimethyl oxalate catalyzer and may causes dimethyl oxalate catalyst deactivation, these have all had a strong impact on the synthesis of dimethyl oxalate, therefore the hydrogen content in CO unstripped gas must be controlled to below 100ppm to meet the demand of dimethyl oxalate synthesis procedure.Because the hydrogen content in unstripped gas is natively low, be difficult to hydrogen content to control to below 100ppm with current various methods.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, there is provided that a kind of processing method is simple, facility investment and running cost is low, hydrogen content in CO unstripped gas can be controlled to below 100ppm, meet a small amount of H of selectively removing in the high concentration CO gas of lower procedure demand
2technique.
The present invention also provides a kind of system for above-mentioned technique.
Present invention process is: send in oxidation reactor and carry out oxidizing reaction to remove the hydrogen in unstripped gas after CO unstripped gas and oxygen being mixed in mixing tank, the H in described oxygen and CO unstripped gas
2volume ratio control 0.6 ~ 0.9; Then reactant gases is sent in soda-wash tower with the CO carried out in alkali liquid washing absorption reaction gas
2, then obtain the high-purity CO gas of hydrogen content lower than 100ppm through the further dehydrogenation of molecular sieve adsorber.
Described oxidation reactor is calandria type fixed bed reactor, comprise epimere and hypomere, the epimere that mixed gas mixture is introduced into oxidation reactor carries out main reaction, controlling epimere temperature of reaction is 170 ~ 190 DEG C, and then the hypomere entering oxidation reactor carries out side reaction, control hypomere temperature of reaction at 200 ~ 240 DEG C, send into again in soda-wash tower after reacted reactant gases heat exchange is cooled to 40 ~ 60 DEG C; The reaction formula of described oxidation reactor epimere main reaction is: H
2+ 1/2O
2→ H
2o; The reaction formula of hypomere side reaction is CO+1/2O
2→ CO
2.
Use high alkali liquid to wash in described soda-wash tower, its mass concentration is 20% ~ 50%.Described CO unstripped gas is through preheater heat exchange to 150-170 DEG C, and with oxygen mix in rear feeding mixing tank, the mixture temperature controlling to enter oxidation reactor is temperature 148 ~ 168 DEG C; The reactant gases going out oxidation reactor first sends into soda-wash tower again after feed gas heater and the heat exchange of CO unstripped gas are cooled to 180-190 DEG C after interchanger heat exchange cools to 40 ~ 60 DEG C further.
The tube length of reaction tube of described oxidation reactor epimere: the tube length of reaction tube of hypomere is (5:1)-(5:4).
The a small amount of H of selectively removing in high concentration CO gas of the present invention
2system, comprise the mixing tank, oxidation reactor, soda-wash tower and the molecular sieve adsorber that connect successively.
Described oxidation reactor is calandria type fixed bed reactor, comprises epimere and hypomere.
The tube length of reaction tube of described oxidation reactor epimere: the tube length of reaction tube of hypomere is (5:1)-(5:4).
The outlet of described oxidation reactor is connected with soda-wash tower through feed gas heater, interchanger, and the raw material gas inlet of described mixing tank is connected with feed gas heater.
Oxygen mixes with CO unstripped gas by contriver, utilizes the hydrogen reaction in oxygen and CO unstripped gas to remove the hydrogen in CO unstripped gas, then passes through the method for alkali cleaning, molecular sieve adsorption, makes the content of hydrogen in unstripped gas be down to below 100ppm.But, in oxidation reaction process, when hydrogen content continuous decrease in CO unstripped gas, when being down to below 300ppm, efficiency can sharply decline, in order to ensure oxidizing reaction normally carry out make the content of hydrogen in unstripped gas be down to 100ppm (volume percent) below, make oxygen excessive, the H namely in oxygen and CO unstripped gas
2volume ratio control 0.6 ~ 0.9, to ensure that in CO unstripped gas, hydrogen as much as possible all participates in oxidizing reaction.
Simultaneously, this also brings another one problem, even if the excessive rear oxygen of oxygen fully participates in oxidizing reaction, make the content of hydrogen in CO unstripped gas be down to below 100ppm, but contain again unreacted oxygen in reacted gas, oxygen molecule enlivens, be unfavorable for the carrying out of lower procedure in CO unstripped gas containing oxygen, therefore consider to make excessive oxygen and CO reaction by side reaction, generate rare gas element carbonic acid gas, to remove the oxygen in reactant gases, ensure normally carrying out of subsequent technique.Therefore, oxidation reactor is divided into epimere and hypomere, controls the temperature of reaction of two sections respectively, impel main reaction (oxidizing reaction) to concentrate on epimere and carry out, side reaction is carried out at hypomere, to make in reacted gas hydrogen richness lower than 100ppm and oxygen level lower than 200ppm.Meet the needs of lower procedure.
Further, preferred described oxidation reactor is calandria type fixed bed reactor, fills conventional dehydrogenation catalyst, as Pd/ gac, Pd/Al in fixed bed
2o
3system Catalyst etc., the tube length of reaction tube of described epimere: the tube length of reaction tube of hypomere is 5:1-4, to coordinate the proportional quantity of hydrogen and oxygen reaction in CO unstripped gas, ensures efficiently carrying out of main reaction and side reaction.
Further, because reacted reactant gases temperature is high, reach 200 ~ 240 DEG C, thus can utilize this part heat energy preheating CO unstripped gas, to reach the object reclaiming heat energy.
Beneficial effect:
1. utilize simple oxidizing reaction to remove hydrogen in CO unstripped gas, technique be simple, raw material and production cost low.
2. adopt excess of oxygen with addition of method, ensure fully removing of the hydrogen in CO unstripped gas, and by controlling side reaction, excessive oxygen being reacted with CO further and generates CO
2to remove excessive oxygen, meet the air inlet requirement of lower procedure.
3, completed in an oxidation reactor by Discrete control main reaction and side reaction, controlled the generation of main side effect by control temperature, sufficient reacting is reliable, need not special de-aerator plant be set again, thus decreases e-quipment and pipe quantity, greatly reduce facility investment and maintenance cost.
4. utilize oxidation reactor to remove hydrogen and the oxygen of the overwhelming majority in CO unstripped gas, then absorbing carbon dioxide in soda-wash tower, dewater in molecular sieve adsorber, hydrogen richness in the high-purity CO gas obtained is at below 100ppm, oxygen level, at below 200ppm, solves a small amount of H of selectively removing in prior art middle and high concentration CO gas
2technical barrier.
Accompanying drawing explanation
Fig. 1 is present invention process schema and system diagram.
Wherein, 1-mixing tank, 2-oxidation reactor, 2.1-epimere, 2.2-hypomere, 3-feed gas heater, 4-heat exchanger, 5-soda-wash tower, 6-molecular sieve adsorber.
Specific implementation method
System embodiment:
In the present invention, the tube side of mixing tank 1, oxidation reactor 2, feed gas heater 3 or shell side, interchanger 4, soda-wash tower 5 are connected successively with molecular sieve adsorber 5.The raw material gas inlet of described mixing tank 1 is also connected with the shell side of feed gas heater 3 or tube side.Described oxidation reactor 2 is calandria type fixed bed reactor, comprises epimere 2.1 and hypomere 2.2, the tube length of reaction tube of described oxidation reactor epimere 2.1: the tube length of reaction tube of hypomere 2.2 is (5:1)-(5:4).
Process example
Unstripped gas charge flow rate 20000Nm
3/ h, gas composition is CO 98.5%, H
21%, N
20.4%, CO
20.1%, pressure is 0.4 ~ 0.6MPa (G), temperature 110 DEG C, and the shell side through feed preheater 3 is preheating to 150 ~ 170 DEG C, pressure 0.39 ~ 0.59MPa (G), after preheating in mixing tank 1 with the O of pressure 0.5 ~ 0.7MPa (G), temperature 25 DEG C
2(containing N
20.4%) according to H
2and O
2the ratio of volume ratio 0.6 ~ 0.9 fully mixes (temperature 148 ~ 168 DEG C, pressure 0.44 ~ 0.64MPa (G)) form gas mixture, then pass in oxidation reactor 2, this reactor is the calandria type fixed bed reactor being removed heat by heat-eliminating medium, the catalyzer that fixed bed is filled adopts high selectivity dehydrogenation catalyzer, as Pd/ gac, Pd/Al
2o
3system Catalyst.Described oxidation reactor 2 is divided into epimere 2.1, equal with the reaction tubes caliber of hypomere 2.2, two sections, and the reaction tubes of epimere 2.1 controls at 5:1-4 with the length ratio of hypomere 2.2 reaction tubes, and the internal diameter of reaction tubes is 24 ~ 45mm, and heat-eliminating medium walks shell side.Gas mixture is first through carrying out main reaction (oxidizing reaction: H by the reaction tubes of epimere 2.1
2+ 1/2O
2→ H
2o) reaction tubes entering hypomere 2.2 after again carries out side reaction (deoxygenation: CO+1/2O
2→ CO
2), control epimere temperature of reaction within the scope of 170 ~ 190 DEG C, control hypomere temperature of reaction within the scope of 200 ~ 240 DEG C, reacted reactant gases consists of CO 97.6 ~ 98.2%, H
2o 1%, N
20.4%, CO
20.3 ~ 0.9%, H
250ppm, O
2100ppm, reactant gases temperature after feed gas heater 3 preheating material gas reduces to 180-190 DEG C, then enters interchanger 4 and continues cooling temperature and reduce to 40 ~ 60 DEG C, reaction gas pressure is 0.37 ~ 0.57MPa (G), enter soda-wash tower 5 afterwards, adopt column plate form, stage number 5 ~ 15, alkali lye mass concentration is 60 ~ 80%, temperature 25 DEG C, outlet gas pressure 0.32 ~ 0.52MPa (G), temperature 32 ~ 42 DEG C, consist of CO 97.1%, H
2o 2.5%, N
20.3%, H
240ppm, CO
210ppm, O
290ppm, then enters molecular sieve adsorber 6 and carries out processed, service temperature 30 ~ 50 DEG C, and go out the gas temperature 30 ~ 50 DEG C of molecular sieve, pressure 0.31 ~ 0.51MPa (G), consists of CO99.6%, N
20.38%, H
250ppm, CO
215ppm, O
2100ppm, i.e. high-purity CO gas, its foreign matter content has met the needs of lower procedure.
Claims (9)
1. a small amount of H of selectively removing in a high concentration CO gas
2method, it is characterized in that, send in oxidation reactor and carry out oxidizing reaction to remove the hydrogen in unstripped gas after CO unstripped gas and oxygen are mixed in mixing tank, the H in described oxygen and CO unstripped gas
2volume ratio control 0.6 ~ 0.9; Then reactant gases is sent in soda-wash tower with the CO carried out in alkali liquid washing absorption reaction gas
2, then obtain the high-purity CO gas of hydrogen content lower than 100ppm through the further dehydrogenation of molecular sieve adsorber.
2. a small amount of H of selectively removing in high concentration CO gas as claimed in claim 1
2method, it is characterized in that, described oxidation reactor is calandria type fixed bed reactor, comprise epimere and hypomere, the epimere that mixed gas mixture is introduced into oxidation reactor carries out main reaction, and controlling epimere temperature of reaction is 170 ~ 190 DEG C, and then the hypomere entering oxidation reactor carries out side reaction, control hypomere temperature of reaction at 200 ~ 240 DEG C, send into again in soda-wash tower after reacted reactant gases heat exchange is cooled to 40 ~ 60 DEG C; The reaction formula of described oxidation reactor epimere main reaction is: H
2+ 1/2O
2→ H
2o; The reaction formula of hypomere side reaction is CO+1/2O
2→ CO
2.
3. a small amount of H of selectively removing in high concentration CO gas as claimed in claim 1 or 2
2method, it is characterized in that, use high alkali liquid to wash in described soda-wash tower, its mass concentration is 20% ~ 50%.
4. a small amount of H of selectively removing in high concentration CO gas as claimed in claim 2
2method, it is characterized in that, described CO unstripped gas send into after preheater heat exchange is to 150-170 DEG C in mixing tank with oxygen mix, the mixture temperature controlling to enter oxidation reactor is temperature 148 ~ 168 DEG C; The reactant gases going out oxidation reactor first sends into soda-wash tower again after feed gas heater and the heat exchange of CO unstripped gas are cooled to 180-190 DEG C after interchanger heat exchange cools to 40 ~ 60 DEG C further.
5. a small amount of H of selectively removing in high concentration CO gas as claimed in claim 2
2method, it is characterized in that, the tube length of reaction tube of described oxidation reactor epimere: the tube length of reaction tube of hypomere is (5:1)-(5:4).
6. a small amount of H of selectively removing in a high concentration CO gas
2system, it is characterized in that, comprise the mixing tank, oxidation reactor, soda-wash tower and the molecular sieve adsorber that connect successively.
7. a small amount of H of selectively removing in high concentration CO gas as claimed in claim 6
2system, it is characterized in that, described oxidation reactor is calandria type fixed bed reactor, comprises epimere and hypomere.
8. a small amount of H of selectively removing in high concentration CO gas as claimed in claim 7
2system, it is characterized in that, the tube length of reaction tube of described oxidation reactor epimere: the tube length of reaction tube of hypomere is (5:1)-(5:4).
9. a small amount of H of selectively removing in high concentration CO gas as claimed in claim 7
2system, it is characterized in that, the outlet of described oxidation reactor is connected with soda-wash tower through feed gas heater, interchanger, and the raw material gas inlet of described mixing tank is connected with feed gas heater.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510129883.0A CN104709907A (en) | 2015-03-24 | 2015-03-24 | Process and system for selectively removing small amount of H2 from high-concentrations CO gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510129883.0A CN104709907A (en) | 2015-03-24 | 2015-03-24 | Process and system for selectively removing small amount of H2 from high-concentrations CO gas |
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|---|---|
| CN104709907A true CN104709907A (en) | 2015-06-17 |
Family
ID=53409713
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510129883.0A Pending CN104709907A (en) | 2015-03-24 | 2015-03-24 | Process and system for selectively removing small amount of H2 from high-concentrations CO gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111672427A (en) * | 2020-05-15 | 2020-09-18 | 中国科学院福建物质结构研究所 | CO dehydrogenation circulation reaction device capable of controlling reactant ratio in real time |
| CN112657431A (en) * | 2020-12-01 | 2021-04-16 | 安徽成泰医药科技有限公司 | Evacuating device for hydrogen production by methanol cracking |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583374A (en) * | 2012-02-09 | 2012-07-18 | 中国科学院福建物质结构研究所 | Purification process of industrial CO gas for preparing oxalate or carbonic ester |
| CN102627280A (en) * | 2011-07-14 | 2012-08-08 | 西南化工研究设计院 | Method for purifying and concentrating CO from calcium carbide furnace gas |
| CN103523781A (en) * | 2013-10-22 | 2014-01-22 | 沙隆达集团公司 | High-purity CO preparation method |
-
2015
- 2015-03-24 CN CN201510129883.0A patent/CN104709907A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627280A (en) * | 2011-07-14 | 2012-08-08 | 西南化工研究设计院 | Method for purifying and concentrating CO from calcium carbide furnace gas |
| CN102583374A (en) * | 2012-02-09 | 2012-07-18 | 中国科学院福建物质结构研究所 | Purification process of industrial CO gas for preparing oxalate or carbonic ester |
| CN103523781A (en) * | 2013-10-22 | 2014-01-22 | 沙隆达集团公司 | High-purity CO preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111672427A (en) * | 2020-05-15 | 2020-09-18 | 中国科学院福建物质结构研究所 | CO dehydrogenation circulation reaction device capable of controlling reactant ratio in real time |
| CN112657431A (en) * | 2020-12-01 | 2021-04-16 | 安徽成泰医药科技有限公司 | Evacuating device for hydrogen production by methanol cracking |
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Application publication date: 20150617 |
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