CN1074448C - Pressure swing adsorption process for concentration and purification of carbon monooxide in blast furnace gas - Google Patents
Pressure swing adsorption process for concentration and purification of carbon monooxide in blast furnace gas Download PDFInfo
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- CN1074448C CN1074448C CN98111619A CN98111619A CN1074448C CN 1074448 C CN1074448 C CN 1074448C CN 98111619 A CN98111619 A CN 98111619A CN 98111619 A CN98111619 A CN 98111619A CN 1074448 C CN1074448 C CN 1074448C
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Abstract
The present invention relates to a technical process for separating, condensing and purifying nitrogen containing carbon monoxide multi-component mixed blast furnace gas and similar mixed gas in the industries of petroleum, chemical engineering, etc. to separate carbon monoxide in the nitrogen containing blast furnace gas from nitrogen gas to respectively obtain carbon monoxide and nitrogen gas, and simultaneously, carbon dioxide is obtained as a byproduct. The present invention is characterized in that blast furnace gas or similar nitrogen containing carbon monoxide mixed gas of which impurities and carbon dioxide are removed is pretreated, and a plurality of fixed bed absorbers filled with catalytic adsorbing agents are adopted to condense and purify carbon monoxide in a pressure swing adsorption mode. The absorbers are used for repeated adsorption in sequence, multi-step pressure reduction, washing, desorption in vacuum, multi-step pressure increase, etc.
Description
What the present invention relates to is that a kind of catalyst-sorbent that adopts will have the technological process that similar mixed gas separates, concentrates and purify in the industry such as nitrogenous carbon monoxide polycomponent mixing installation for blast furnace gas and oil and chemical industry, make wherein carbon monoxide and nitrogen separately, make carbon monoxide and nitrogen respectively, obtain the by-product carbonic acid gas at the same time.
In the blast furnace gas of Steel Plant, mainly contain carbonic acid gas, carbon monoxide and nitrogen, it is (percent by volume) that the typical case of these three kinds of gases forms: carbonic acid gas 10-20%, carbon monoxide 20-30% and nitrogen 50-65% also have a spot of hydrogen, hydrogen sulfide, oxygen, hydrocarbon polymer and saturated moisture content in addition.Its calorific value has only 2527-3790KJ/NM
3, can not effectively utilize, if carbon monoxide is concentrated, then can improve the calorific value of gas greatly.When carbon monoxide is concentrated to 70% (volume), then calorific value is 8845KJ/NM
3On these three kinds of gas industry purposes widely being arranged all, therefore they are separated being used, is to handle the problem that high furnace exhaust gas faced.The key of sort this problem out is to have suitable method to separate carbon monoxide and nitrogen, because separation and Extraction carbonic acid gas from carbon monoxide and nitrogen, existing sophisticated method can be used suitable sorbent material and process, as adopting the pressure-swing adsorption process of gac and carbon molecular sieve.
The present invention seeks at the weak point that the carbon monoxide of handling nitrogenous gas exists provide a kind of concentrate and the purification installation for blast furnace gas in the pressure swing adsorption technique of carbon monoxide, adopt catalyst-sorbent to realize Separation and Recovery pure carbon monoxide and nitrogen from high furnace exhaust gas, comprise that the preposition transformation absorption process of setting removes or reclaim purifying carbon dioxide by the transformation suction type.
Concentrate and the purification blast furnace gas in the pressure swing adsorption technique of carbon monoxide take following scheme to realize: the primary process of pressure swing adsorption technique Separation and Recovery pure carbon monoxide and nitrogen is under an adsorptive pressure and envrionment temperature, utilize catalyst-sorbent that carbon monoxide is had very strong adsorptive power, make carbon monoxide and nitrogen in the high furnace exhaust gas be adsorbed down and reclaim by being filled with catalyst-sorbent bed carbon monoxide, the nitrogen product of removal of carbon monoxide is discharged from the bed outlet.
(number of patent application is the catalyst-sorbent that the present invention adopts: 96117226.6) by the catalyst-sorbent in the applicant 96.12.20 application " containing carbon monoxide cleaning catalyst and process in the nitrogen ".This sorbent material is a raw material by cupric chloride, gac, natural high-quality attapulgite and mixed rare earth chlorides, through dipping or and mix, the granules of catalyst of reprocessing moulding in 0～55 ℃ temperature, is used for purifying the carbon monoxide of nitrogenous gas trace.
Catalyst-sorbent adopts following method preparation (micro CO cleaning catalyst): the aqueous solution or the cupric chloride and the mixed chlorinated rare earth powder of (1) preparation cupric chloride and mixed chlorinated rare earth; (2) powdered carbon is put into above-mentioned aqueous solution dipping or with above-mentioned powder mixes; (3) for the situation that adopts immersion process for preparing, the solid mixture of parting liquid solid mixture, dry gained; (4) solid mixture of gained and high-quality attapulgite mixing aftershaping; (5) forming mixture 1-5 hour of heating, dry gained, suitable temperature was 100 ℃ and 400 ℃; (6) in reducing gas the forming mixture of gained is reduced processing, suitable reducing atmosphere is a hydrogen or/and the gas of carbon monoxide, and temperature is 120～380 ℃, micro CO cleaning catalyst (catalyst-sorbent).
As being applicable to Steel Plant of the present invention blast furnace gas or similar nitrogenous Co mixed gas, generally except carbon monoxide and nitrogen, also contain carbonic acid gas and a spot of hydrogen, sulfide, oxygen, hydrocarbons and saturated moisture content.Therefore before using Separation and Recovery carbon monoxide of the present invention and nitrogen, several preposition operations need be set, remove some impurity component that can influence catalyst-sorbent absorption carbon monoxide, as remove the operation of sulfide and moisture content, but a spot of oxygen can remove.The existence of carbonic acid gas can influence the adsorptive power and the purity of catalyst-sorbent absorption carbon monoxide in the mixed gas.Among the present invention, a preposition pressure-swing adsorption process is used for removing carbonic acid gas, or absorbing carbon dioxide, obtains thus concentrating or pure carbonic acid gas, and this can depend on the needs.As the occasion of need pure carbon dioxide, in pressure-swing adsorption process, there is the carbonic acid gas of a usefulness product to go to replace adsorbent bed step, with raising product concentration of carbon dioxide, and carbonic acid gas obtains by vacuum decompression.In the process of transformation adsorbing and removing or concentrated purifying carbon dioxide, sorbent material carbonaceous molecular sieve and gac can satisfy the requirement of process preferably, and this process is to be concentrated or the inseparable technology of purifying carbon oxide by blast furnace gas or similar gas mixture.
Remove the blast furnace gas or the similar nitrogenous Co mixed gas of impurity, carbonic acid gas through pre-process, adopt several fixed-bed adsorbers that are filled with catalyst-sorbent to concentrate purifying carbon oxide by the transformation suction type, several adsorbers adopt transformation suction types to carry out the following operating procedure that respectively goes on foot in order respectively repeatedly:
1. absorption: unstripped gas enters and the catalyst-sorbent fixed bed is housed carries out carbon monoxide absorption, 0～55 ℃ of adsorption temp, adsorptive pressure is 0.04～0.7MPa (gauge pressure), when the absorption phase concentration forward position of carbon monoxide moves on to a certain position of bed, just stop absorption, and this moment, effluent air was the nitrogen component that does not contain carbon monoxide, and a spot of oxygen;
2. multi-step pressure reducing: after absorption process finishes to finish, what then carry out is multistep step-down operation, at first this adsorber and another through vacuum outgas or be connected through the adsorber of boost (I), under the situation that air flow direction is identical with absorption the time, make the pressure of this adsorber reduce to a certain lower pressure;
Through and the adsorber that flows step-down further reduce pressure to the normal pressure, this portion gas can be used for boosting (I) through the adsorber of vacuum outgas, when adopting lower adsorptive pressure, then through a top step depressurization step, pressure in the adsorber is lower, can not have this second step all to press step;
4. clean: utilize a part of product carbon monoxide gas and stream by reducing to non-pressurized adsorber, remaining impurities gas in the adsorber is cleaned in displacement, further improves the concentration of carbon monoxide in the adsorption bed, obtains spissated carbon monoxide as needs, can not adopt this step, to improve output;
5. vacuum desorption: carry out vacuum decompression to reducing to non-pressurized adsorber, make the carbon monoxide that adsorbs on the sorbent material be able to desorption, reclaim the carbon monoxide of desorption, obtain product;
6. the adsorber behind vacuum desorption is communicated with the adsorber of finishing adsorption step, carries out (I) step of boosting of adsorber;
7. multistep is boosted: to (II) step of boosting of the adsorber through (I) step of boosting, and as adsorptive pressure higher (adsorptive pressure is greater than 0.2MPa), the available gas that is in the adsorber of depressurization step (II) step that realizes boosting; When process is to be used for purifying carbon oxide, this step can be finished with the waste gas of other adsorber when cleaning; When adsorptive pressure lower (adsorptive pressure is not more than 0.1MPa), and process is to be used for concentrating carbon monoxide, then can remove this step;
8. utilize other adsorber discharging gas when absorption to adsorb (III) step of boosting.
Each adsorber can be realized concentrating continuously or purifying carbon oxide by carrying out the operating procedure of above-mentioned steps successively repeatedly like this.
Concentrate and the purification blast furnace gas in the pressure swing adsorption technique of carbon monoxide, employing is to containing the catalyst adsorbent that carbon monoxide in the nitrogen has highly selective, under the pressure of 0～55 ℃ temperature and 0.04～0.7MPa (gauge pressure), Steel Plant's blast furnace gas is through pressure-swing adsorption process, concentrate purifying carbon oxide gas, obtain simultaneously concentrating the nitrogen of purifying, carbon monoxide is concentrated the calorific value that then can improve gas greatly.In technological process of the present invention, adopt pressure swing absorption process to remove carbonic acid gas or concentrated purifying carbon dioxide with one, can obtain three kinds of carbonic acid gas, carbon monoxide, nitrogen like this at the industrial gas that extensive use is all arranged.Catalyst-sorbent that the present invention adopts and technological process be applicable to Steel Plant's blast furnace gas, and have similar mixed gas in the industry such as oil and chemical industry and need separate the occasion of producing carbon monoxide, nitrogen and carbonic acid gas.
Below two examples illustrated that clearly blast furnace gas and similar nitrogenous carbon mono oxide mixture enter the adsorber bed that is filled with catalyst-sorbent, realize to concentrate and the basic step of purifying carbon oxide by the transformation suction type.
Example 1:
The high furnace exhaust gas of Steel Plant, through having removed hydrogen sulfide, mixed gas behind hydrocarbon polymer and the saturated moisture content consists of (percent by volume): carbonic acid gas 15.7%, carbon monoxide 25.3%, nitrogen 56.3% and oxygen 0.7%, this mixed gas is 50 ℃ in temperature, pressure is under the 0.6MPa, by being filled with the adsorber bed of gac, carry out transformation adsorbing and removing carbonic acid gas, and through the gas of decarbonation, continue to flow through the adsorber bed that is filled with catalyst-sorbent, by the transformation suction type, concentrate carbon monoxide, the product gas that obtains consists of (percent by volume): carbon monoxide 75.6%, nitrogen 23.4%, carbonic acid gas 0.4% and oxygen 0.6%, that drops a hint consists of (percent by volume): nitrogen 98.6%, carbonic acid gas 0.4%, carbon monoxide 0.8% and oxygen 0.2%.The pressure-swing adsorption process that removes carbonic acid gas adopts three adsorber parallel connections that gac is housed, the operation steps that each adsorber boosted through absorption two step step-downs, vacuum desorption, three steps; And the pressure-swing adsorption process that concentrates carbon monoxide also adopts three adsorber parallel connections that catalyst-sorbent is housed, the operation steps that each adsorber boosts through absorption, two step step-downs, vacuum desorption, three steps equally.In this example, owing to be to concentrate carbon monoxide, so in the transformation adsorption step of system carbon monoxide, do not adopt above-mentioned the 4th operation steps, be cleaning step, so the carbon monoxide concentration of product and productive rate are not very high, carbon monoxide concentration is 75.6% (volume), the carbon monoxide productive rate is 7.65 liters of per kilogram catalyst-sorbents, and following example is then different.
Example 2:
With the similar nitrogenous Co mixed gas of Steel Plant's blast furnace gas, mixed gas after having removed hydrogen sulfide, hydrocarbon polymer, saturated moisture content and transformation adsorbing and removing carbonic acid gas consists of (percent by volume): carbon monoxide 21.6%, nitrogen 77.6% and oxygen 0.8%, this mixed gas is that 4 ℃, pressure are under the 0.05MPa in temperature, by being filled with the adsorber bed of catalyst-sorbent, through transformation absorption, the carbon monoxide that obtains purifying.The pressure-swing adsorption process of purifying carbon oxide adopts three adsorber parallel connections that catalyst-sorbent is housed in this example, the operation steps that each adsorber boosted through absorption, a step step-down, cleaning, vacuum desorption, two steps.Owing to be purifying carbon oxide, so in transformation adsorption operations step, has the operation steps that carbon monoxide cleans bed, it is cleaning step, so the carbon monoxide concentration and the productive rate of product are higher, carbon monoxide concentration is 98.7% (volume), and the carbon monoxide productive rate is 9.86 liters of per kilogram catalyst-sorbents.
Claims (2)
- One kind concentrate and the purification blast furnace gas in the pressure swing adsorption technique of carbon monoxide, at first remove the impurity component that can influence catalyst-sorbent absorption carbon monoxide, a preposition pressure-swing adsorption process, be used for removing carbonic acid gas and or absorbing carbon dioxide obtain concentrating or pure carbonic acid gas, it is characterized in that to remove the blast furnace gas or the similar nitrogenous Co mixed gas of impurity and carbonic acid gas through pre-process, the fixed-bed adsorber that employing is filled with catalyst-sorbent concentrates purifying carbon oxide, and adsorber adopts the transformation suction type to carry out the following operating procedure that respectively goes on foot in order respectively repeatedly:(1). absorption: unstripped gas enters and the catalyst-sorbent fixed bed is housed carries out carbon monoxide absorption, 0～55 ℃ of adsorption temp, adsorptive pressure is 0.04～0.7MPa (gauge pressure), when the absorption phase concentration forward position of carbon monoxide moves on to a certain position of bed, just stop absorption, and this moment, effluent air was the nitrogen component that does not contain carbon monoxide, and a spot of oxygen(2). multi-step pressure reducing: after absorption process finishes to finish, what then carry out is the multistep desorption step, at first this adsorber and another through vacuum outgas or be connected through the adsorber of boost (I), under the situation that air flow direction is identical with absorption the time, make the pressure of this adsorber reduce to a lower pressure(3). through and the adsorber that flows step-down further and stream reduce pressure to the normal pressure, this portion gas can be used for adsorber through vacuum outgas boost (I), when adopting lower adsorptive pressure, then through a top step depressurization step, pressure in the adsorber is lower, can there be this second step all to press step(4). clean: utilize a part of product carbon monoxide gas and stream by reducing to non-pressurized adsorber, remaining impurities gas in the adsorber is cleaned in displacement, further improves the concentration of carbon monoxide in the adsorption bed, as only obtaining spissated carbon monoxide, can not adopt this step, to improve output(5). vacuum desorption: carry out vacuum decompression to reducing to non-pressurized adsorber, make the carbon monoxide that adsorbs on the sorbent material be able to desorption, reclaim the carbon monoxide of desorption, obtain product,(6). the adsorber behind vacuum desorption is communicated with the adsorber of finishing adsorption step, carries out (I) step of boosting of adsorber,(7). multistep is boosted: to (II) step of boosting of the adsorber through (I) step of boosting, when adsorptive pressure is higher (adsorptive pressure is greater than 0.2MPa), the available gas that is in the adsorber of depressurization step (II) step that realizes boosting; When process is to be used for purifying carbon oxide, this step can be finished with the waste gas of other adsorber when cleaning; When adsorptive pressure lower (adsorptive pressure is not more than 0.1MPa), and process is to be used for concentrating carbon monoxide, then can remove this step,(8). utilize other adsorber discharging gas when absorption to adsorb (III) step of boosting.Each adsorber can be realized concentrating continuously or purifying carbon oxide by carrying out the operating procedure of above-mentioned steps successively repeatedly like this.
- 2. according to claim 1 concentrate and the purification blast furnace gas in the pressure swing adsorption technique of carbon monoxide, it is characterized in that catalyst-sorbent is by cupric chloride, activated carbon, natural high-quality attapulgite with mix that to contain rare earth chloride be raw material, through dipping or/and mix, the granules of catalyst of reprocessing moulding, 0～55 ℃ temperature, be used for purifying the carbon monoxide that contains the nitrogen trace.
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| CN98111619A CN1074448C (en) | 1998-12-18 | 1998-12-18 | Pressure swing adsorption process for concentration and purification of carbon monooxide in blast furnace gas |
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| CN1074448C true CN1074448C (en) | 2001-11-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101978235A (en) * | 2008-03-18 | 2011-02-16 | 杰富意钢铁株式会社 | Method and apparatus for separating blast furnace gas |
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| US8177886B2 (en) * | 2009-05-07 | 2012-05-15 | General Electric Company | Use of oxygen concentrators for separating N2 from blast furnace gas |
| DE102016209027A1 (en) * | 2016-05-24 | 2017-11-30 | Thyssenkrupp Ag | Plant network for the production of mineral building materials and a process for operating the plant network |
| DE102016209026A1 (en) * | 2016-05-24 | 2017-11-30 | Thyssenkrupp Ag | Plant network for the production of mineral building materials and a process for operating the plant network |
| CN112023619B (en) * | 2020-08-28 | 2024-05-24 | 杨皓 | Process for concentrating carbon monoxide by blast furnace gas |
| CN115990437B (en) * | 2021-10-20 | 2024-08-30 | 中国石油化工股份有限公司 | Method, system and application for controlling feeding temperature and temperature rise of catalyst bed layer of each section in reactor |
| 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 |
| 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 |
| CN114405228B (en) * | 2022-02-17 | 2023-04-11 | 四川天人能源科技有限公司 | Improved process for purifying carbon monoxide by pressure swing adsorption |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1185353A (en) * | 1996-12-20 | 1998-06-24 | 南京化工大学 | Catalyst for purifying nitrogen-contained gas to remove carbon monoxide and course thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1185353A (en) * | 1996-12-20 | 1998-06-24 | 南京化工大学 | Catalyst for purifying nitrogen-contained gas to remove carbon monoxide and course thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101978235A (en) * | 2008-03-18 | 2011-02-16 | 杰富意钢铁株式会社 | Method and apparatus for separating blast furnace gas |
| CN101978235B (en) * | 2008-03-18 | 2013-05-29 | 杰富意钢铁株式会社 | Separation method and device for blast furnace gas |
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| CN1224046A (en) | 1999-07-28 |
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