CN1149175C - Process for purifying gas - Google Patents
Process for purifying gas Download PDFInfo
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- CN1149175C CN1149175C CNB011272201A CN01127220A CN1149175C CN 1149175 C CN1149175 C CN 1149175C CN B011272201 A CNB011272201 A CN B011272201A CN 01127220 A CN01127220 A CN 01127220A CN 1149175 C CN1149175 C CN 1149175C
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- oxygen
- purifying
- dehydrogenation
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Abstract
The present invention relates to technology for purifying gas, which is used for removing impurities such as hydrogen, oxygen, moisture content, etc. in gas to obtain gas with high purity. In the present invention, little hydrogen is mixed in raw gas, and the amount of the hydrogen is changed by periods from excess to insufficiency. The mixed gas generates a deoxidation reaction under the action of hydrogenation and deoxidation catalysts. After reaction, residual hydrogen and oxygen impurities in the gas are removed under the action of oxygen absorption and dehydrogenation agents. Then, purified gas can be obtained by gas cooling and drying. In the present invention, the oxygen absorption and dehydrogenation agents carry out dehydrogenation during the excess of the hydrogen and simultaneously regenerate oxygen absorption capability and simultaneously regenerate hydrogen absorption capability during the excess of the oxygen. During a reaction process, the problem that a large quantity of semi-finished goods or finished product gas as regenerated gas are discharged in the existing art are avoided. The present invention has no gas waste consumption, simultaneously does not need to prepare duplicate dehydrogenation agents and dehydrogenation equipment, reduces the investment of equipment materials, reduces cost but improves purification efficiency and gaseous mass.
Description
Technical field: the present invention relates to a kind of purification for gas treatment process, particularly in gas, remove the purifying process of hydrogen, oxygen impurities.
Background technology: general industrial gasses to be removed the technology that impurity such as oxygen, hydrogen carry out purifying all be to be mixed into excess hydrogen in unstripped gas, hydrogen elder generation and oxygen reaction are removed oxygen under the hydrogenation deoxidation catalyst effect, remove hydrogen with dehydrogenating agent reaction again, and then cooling, drying are removed moisture and are obtained purified gases.Because it is active that dehydrogenating agent can lose after long-time the use, must feed oxygen containing half purified feed stock gas and make its regeneration as resurgent gases, and the sorbent material in the calcium chloride jar also needs to feed the regeneration of resurgent gases absorption moisture, resurgent gases can account for 20% of total finished product purified gas, consume very greatly, significantly increased cost.French Patent FR2640159A provides a kind of purifying process, the amounts of hydrogen that is mixed in unstripped gas changes to the cycle deficiency from excessive, regeneration ability to take oxygen in like this can dehydrogenation when hydrogen is excessive, the oxygen uptake dehydrogenation ability of regenerating simultaneously then when oxygen is excessive need not resurgent gases consumption in purge process.And, the drying of purified gas has adopted the alternate operation form of a double tower regeneration, a job, but the gas that comes out in the regenerated tower is sent back in the unstripped gas, though there is not resurgent gases emptying, but gas purifying once more needs supercharging to consume energy in a large number, production efficiency is influenced, if the non-rare gas of purifying, more than the cost of recovery gas ratio emptying increases.
Summary of the invention: the present invention solves to need consumption in the existing process for purifying gas or repeat the purifying regeneration gas, makes the problem of the cost increase of purifying, provides the dry whole process of a kind of purifying not have the process for purifying gas of resurgent gases discharging or repetition purifying.
Process for purifying gas of the present invention comprises and will be mixed into small quantity of hydrogen in the unstripped gas, deoxygenation is removed the oxygen impurities that unstripped gas contains under the hydrogenation deoxidation catalyst effect, the amounts of hydrogen that is mixed into changes to the cycle deficiency from excessive, will make the gas of unstripped gas behind deoxygenation cross the hydrogen amount when excessive is 150-3000ppm, to make when not enough that gas peroxide amount is 75-1500ppm behind the deoxygenation, gas behind the deoxygenation is again under the effect of oxygen uptake dehydrogenating agent, according to reacted gas was hydrogen or peroxide, the corresponding reaction removed excess hydrogen or oxygen impurities, and then with gas cooling, drying is removed moisture, the drying of gas adopts the dry route of two drying tower associatings, gas after the oxygen uptake dehydrogenation falls most of moisture through refrigerated separation, take away moisture through a drying tower to adsorbent reactivation, and then after cooling, enter another drying tower and be dried and remove moisture and obtain purified gases, two drying tower cycles are switched alternations, regeneration.
The hydrogen that is mixed into unstripped gas among the present invention changes to the cycle between deficiency excessive, regeneration ability to take oxygen in like this can dehydrogenation when hydrogen is excessive, the oxygen uptake dehydrogenation ability of regenerating simultaneously then when oxygen is excessive, need not the resurgent gases discharging in the purge process consumes, and purified gas adopts two drying tower cycles to switch alternation, regeneration, directly can get finished product after the purified gases drying, need not recovery part gas and repeat purifying, drying tower is alternation continuously then, can make the dry full technological process of purification for gas not have gas emptying waste or repeat the purifying power consumption like this, significantly reduce cost, make purifying process more efficient, and improved the purifying quality.
If whole process does not have gaseous emission, may make some very micro-impurity accumulation increased concentrations for a long time, can carry out emptying method solution once every several months or gap.
Wide adaptability of the present invention all is suitable for the industrial gasses of main hydrogen, oxygen impurities, as rare gas elementes such as nitrogen, carbon monoxide, methane, ethane etc. and argon gas, helium.According to differences such as the unstripped gas of need purifying, flow, pressure, the amounts of hydrogen period of change from excessive to insufficient that is mixed into unstripped gas also has some adjustment, is generally 2-24 hour.
The general available metal type of oxygen uptake dehydrogenating agent oxygen uptake dehydrogenating agent utilizes its oxygen uptake when oxidation, dehydrogenation during reduction, and the temperature of reaction that needs is 100-400 ℃ usually, commonly used is palladium oxygen uptake dehydrogenating agent.
Remove in some fields has requirement to gas purity, and cleanliness factor requires also higher, and gas can smartly again filter after drying is removed the moisture purifying, removes micro-dust.
Further specify the present invention below in conjunction with drawings and Examples.
Description of drawings: accompanying drawing is a process flow sheet of the present invention.
Embodiment 1: unstripped gas is a nitrogen, and oxygen level is 3%.The art breading flow process as shown in drawings, be mixed into hydrogen, period of change is 6 hours, in the hydrogenation deoxidation tower, remove all or part of oxygen then, temperature of reaction can be from room temperature according to catalyst activity, it crossed hydrogen amount 500ppm when reacted gas was crossed hydrogen, its peroxide amount is 250ppm during peroxide, and then in oxygen uptake dehydrogenation tower, remove remaining oxygen or hydrogen, gained gas is separated out most of moisture through heat exchanger 1 cooling again through water-cooled, and then after heat exchanger 2 heat absorptions, enter drying tower A, in the state shown in the lines arrows, drying tower A is regeneration in the accompanying drawings, drying tower B work.Gas comes out after heat exchanger 2 heat radiation again through the refrigerator cooling, and then enters drying tower B and is removed moisture and obtains purified gases behind heat exchanger 1 from drying tower A.It is in order to improve thermo-efficiency that flow process shown in the accompanying drawing has a plurality of heat exchangers, and makes gas heating and cooling progressively.The switching of drying tower A, B is undertaken by the valve opening and closing in the pipeline.Because the drying tower A recovery time is shorter than the working hour of drying tower B, regeneration can open and close valve when finishing makes gas arrive drying tower B again through directly entering refrigerator after the water-cooled, as the accompanying drawing dashed path.
The oxygen level of gained purification nitrogen is 1ppm, and hydrogen content also is 1ppm, and dew points at normal pressure is not higher than-60 ℃.
Embodiment 2: unstripped gas is a carbon monoxide, oxygenous 1%.Process treatment process is with embodiment 1, and wherein the temperature of oxygen uptake dehydrogenation tower is 200 ℃.Gained purifying CO (carbon monoxide converter) gas oxygen level is 0.5ppm, and hydrogen content is 0.9ppm, and dew points at normal pressure is-65 ℃.
Embodiment 3: unstripped gas is a methane, and oxygen level is 1%.Process treatment process is wherein being crossed periodical change between hydrogen amount 500ppm and peroxide amount 250ppm at the gas of hydrogenation deoxidation tower outlet with embodiment 1, and the temperature of oxygen uptake dehydrogenation tower is 180 ℃.Gained purifying methane gas contains oxygen 1ppm, and hydrogeneous 1ppm, dew points at normal pressure are-65 ℃.
Embodiment 4: unstripped gas is an argon gas, contains oxygen 2%.Process treatment process is with embodiment 1, and gained purifying argon gas contains oxygen 0.8ppm, hydrogeneous 0.5ppm, dew points at normal pressure-65 ℃.
Claims (4)
1, a kind of process for purifying gas, comprise and to be mixed into small quantity of hydrogen in the unstripped gas, deoxygenation is removed the oxygen impurities that unstripped gas contains under the hydrogenation deoxidation catalyst effect, the amounts of hydrogen that is mixed into changes to the cycle deficiency from excessive, will make the gas of unstripped gas behind deoxygenation cross the hydrogen amount when excessive is 150-3000ppm, to make when not enough that gas peroxide amount is 75-1500ppm behind the deoxygenation, gas behind the deoxygenation is again under the effect of oxygen uptake dehydrogenating agent, according to reacted gas was hydrogen or peroxide, the corresponding reaction removed excess hydrogen or oxygen impurities, and then with gas cooling, drying is removed moisture, it is characterized by: the drying of gas adopts the dry route of two drying tower associatings, gas after the oxygen uptake dehydrogenation falls most of moisture through refrigerated separation, take away moisture through a drying tower to adsorbent reactivation, and then after cooling, enter another drying tower and be dried and remove moisture and obtain purified gases, two drying tower cycles are switched alternations, regeneration.
2, process for purifying gas according to claim 1 is characterized by: the amounts of hydrogen period of change from excessive to insufficient that is mixed into unstripped gas is 2-24 hour.
3, process for purifying gas according to claim 1 and 2 is characterized by: unstripped gas is a nitrogen.
4, process for purifying gas according to claim 1 and 2 is characterized by: unstripped gas is a rare gas element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011272201A CN1149175C (en) | 2001-09-14 | 2001-09-14 | Process for purifying gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011272201A CN1149175C (en) | 2001-09-14 | 2001-09-14 | Process for purifying gas |
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| CN1346788A CN1346788A (en) | 2002-05-01 |
| CN1149175C true CN1149175C (en) | 2004-05-12 |
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| CNB011272201A Expired - Fee Related CN1149175C (en) | 2001-09-14 | 2001-09-14 | Process for purifying gas |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI476038B (en) * | 2010-02-10 | 2015-03-11 | Sumitomo Seika Chemicals | Purifying method and purifying apparatus for argon gas |
| TWI478761B (en) * | 2010-02-25 | 2015-04-01 | Sumitomo Seika Chemicals | Purifying method and purifying apparatus for argon gas |
| CN102285647A (en) * | 2010-06-18 | 2011-12-21 | 上海瑞气气体设备有限公司 | Energy-saving Purification Method of Nitrogen |
| CN102284226A (en) * | 2010-06-18 | 2011-12-21 | 上海瑞气气体设备有限公司 | Combined Process of Pressure Swing Adsorption and Cryogenic Separation of Methane from Low Concentration Coalbed Gas |
| CN102039083B (en) * | 2010-08-23 | 2012-11-14 | 杭州普菲科空分设备有限公司 | Isotonic purifying and drying system without resurgent gas loss and technological process thereof |
| CN107362683A (en) * | 2017-08-21 | 2017-11-21 | 昆明鹏翼达气体产品有限公司 | A kind of ultra-pure gases purification devices and purification process |
| CN116272331A (en) * | 2023-02-20 | 2023-06-23 | 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) | A processing system for producing hydrogen-containing tail gas in ultrafine metal particles by physical method |
| CN117902554B (en) * | 2024-03-19 | 2024-07-12 | 上海联风气体有限公司 | Inert gas purification treatment system and method |
| CN120964721B (en) * | 2025-10-21 | 2025-12-16 | 安徽万瑞冷电科技有限公司 | A method for deep hydrogen removal and moisture removal |
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| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI RUIQI GAS EQUIPMENT CO., LTD. Free format text: FORMER OWNER: WENZHOU RUIQI AIR SEPARATING EQUIPMENT CO., LTD. Effective date: 20080516 |
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Effective date of registration: 20080516 Address after: Shanghai Jinshan District Shanyang town Ting Wei Road No. 2099 Patentee after: Shanghai Rich Gas Equipment Co., Ltd. Address before: District 33, Wenzhou economic and Technological Development Zone, Zhejiang, China Patentee before: Ruiqi air Separation Equipment Co., Ltd., Wenzhou |
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| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI TONGXUE INDUSTRIAL CO., LTD. Free format text: FORMER OWNER: SHANGHAI RICH GAS EQUIPMENT CO., LTD. Effective date: 20150204 |
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Effective date of registration: 20150204 Address after: Jinshan District Wei Chang Road 201505 Shanghai City No. 293 Building 2 room 6105 Patentee after: SHANGHAI TONGXUE INDUSTRIAL CO., LTD. Address before: 201508 Shanghai Jinshan District Shanyang town Ting Wei Road No. 2099 Patentee before: Shanghai Rich Gas Equipment Co., Ltd. |
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Granted publication date: 20040512 Termination date: 20200914 |
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| CF01 | Termination of patent right due to non-payment of annual fee |