CN114229844B - Improved process for preparing carbon monoxide by pressure swing adsorption - Google Patents
Improved process for preparing carbon monoxide by pressure swing adsorption Download PDFInfo
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- CN114229844B CN114229844B CN202111459339.4A CN202111459339A CN114229844B CN 114229844 B CN114229844 B CN 114229844B CN 202111459339 A CN202111459339 A CN 202111459339A CN 114229844 B CN114229844 B CN 114229844B
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- carbon monoxide
- carbon dioxide
- crude product
- adsorption tower
- copper
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 60
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 54
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003463 adsorbent Substances 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 27
- 239000012043 crude product Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000741 silica gel Substances 0.000 claims abstract description 18
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000011010 flushing procedure Methods 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 8
- 238000011069 regeneration method Methods 0.000 claims abstract description 8
- 230000006835 compression Effects 0.000 claims abstract description 6
- 238000007906 compression Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 10
- 238000010926 purge Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention relates to an improved method for separating and purifying carbon monoxide by pressure swing adsorption, which comprises the steps of placing a copper-loaded adsorbent at the inlet end of a first-stage adsorption tower and silica gel at the outlet end of the adsorption tower, wherein 10% -60% of carbon monoxide, 10% -60% of carbon dioxide and the balance of mixed gas of nitrogen and hydrogen, and the adsorption pressure is 0.05-1.0 MPa, and the copper-loaded adsorbent adsorbs carbon monoxide and carbon dioxide and the silica gel adsorbs carbon dioxide; after the pressure equalizing and reducing and the forward discharging processes, the crude product is adopted to replace an adsorption tower, and the replaced effluent is sent to compression or other towers for pressure increasing; the total concentration of carbon monoxide and carbon dioxide desorbed in the reverse discharge and evacuation process reaches more than 99 percent and is called as a crude product, and the carbon dioxide desorbed by silica gel is used as a flushing gas for the carbon monoxide adsorbed by the copper-carrying adsorbent in the reverse discharge and evacuation regeneration process, so that the carbon monoxide is completely desorbed; pressurizing the crude product to 0.05-4.0 MPa, and sending the crude product into a second-stage adsorption tower to separate carbon dioxide, wherein carbon monoxide with the concentration of more than 98.5% is obtained from a non-adsorption phase and is called product gas.
Description
Technical Field
The invention relates to the fields of chemical industry, energy conservation and environmental protection, in particular to a method for effectively reducing catalyst consumption, improving catalyst utilization efficiency and saving energy.
Background
Carbon monoxide is purified from carbon monoxide-containing gases, typically by pressure swing adsorption process separation techniques.
In the 80 s of 20 th century, germany, a two-stage pressure swing adsorption CO separation process based on a 5A molecular sieve adsorbent is developed, wherein one-stage pretreatment process is used for removing CO which is difficult to desorb on the 5A molecular sieve, and the two-stage process is used for purifying CO.
Copper-based molecular sieves developed by university of Beijing Xie You teach CN86102838B to directly separate carbon monoxide, and the adsorbent simultaneously adsorbs a small amount of carbon dioxide, and to improve purity, pure carbon monoxide is used to replace co-adsorbed gas with non-adsorbed phase gas in the adsorption column. Either pre-purge or post-purge of carbon dioxide may be employed.
The copper-based activated carbon developed by university of south Beijing industry, ma Zhengfei, teaches that CN1185353a directly separates carbon monoxide, and the adsorbent simultaneously adsorbs a large amount of carbon dioxide, and more pure carbon monoxide is used to replace co-adsorbed gas with non-adsorbed phase gas in the adsorption column for purity. Either pre-purge or post-purge of carbon dioxide may be employed.
All three processes are successfully industrialized. Wherein the copper-carrying adsorbent is carbon monoxide and carbon dioxide which are subjected to competitive adsorption, the carbon monoxide adsorption capacity is higher than that of carbon dioxide, and the carbon dioxide can be adsorbed out by carbon monoxide displacement after being adsorbed. It has been found experimentally that regeneration processes, such as flushing the carbon monoxide adsorbent with carbon dioxide, can easily collide with the carbon monoxide.
The use of carbon monoxide for displacing the non-adsorbed phase gas, displacing the adsorbed phase co-adsorbed gas, is a necessary means. The carbon monoxide is obtained from the evacuation stage and the reverse discharge stage, and the pressure of the carbon monoxide used in the subsequent oxo synthesis is generally higher than 0.1MPa.
Disclosure of Invention
An improved method for separating and purifying carbon monoxide by pressure swing adsorption is characterized in that mixed gas containing 10% -60% of carbon monoxide, 10% -60% of carbon dioxide and the balance of nitrogen and hydrogen is adsorbed at the pressure of 0.05-1.0 MPa, a copper-loaded adsorbent is placed at the inlet end of a first-stage adsorption tower, silica gel is placed at the outlet end of the adsorption tower, the copper-loaded adsorbent adsorbs carbon monoxide and carbon dioxide, and the silica gel adsorbs carbon dioxide; after the pressure equalizing and reducing and the forward discharging processes, the crude product is adopted to replace an adsorption tower, and the replaced effluent is sent to compression or other towers for pressure increasing; the total concentration of carbon monoxide and carbon dioxide desorbed in the reverse discharge and evacuation process reaches more than 99 percent and is called as a crude product, and the carbon dioxide desorbed by silica gel is used as a flushing gas for the carbon monoxide adsorbed by the copper-carrying adsorbent in the reverse discharge and evacuation regeneration process, so that the carbon monoxide is completely desorbed; pressurizing the crude product to 0.05-4.0 MPa, and sending the crude product into a second-stage adsorption tower to separate carbon dioxide, wherein carbon monoxide with the concentration of more than 98.5% is obtained from a non-adsorption phase and is called product gas.
Compared with the methods of other patent publications, the invention has the following advantages: (1) The carbon dioxide desorbed by the carbon dioxide adsorbent at the outlet end of the reverse discharge process has a prominent flushing effect on the carbon monoxide adsorbed by the adsorbent at the inlet end, and is favorable for the regeneration of the carbon monoxide from the adsorbent. (2) The carbon dioxide desorbed by the carbon dioxide adsorbent at the outlet end of the evacuation process has a prominent flushing effect on the carbon monoxide adsorbed by the adsorbent at the inlet end, and is favorable for thoroughly regenerating the carbon monoxide from the adsorbent. Thereby reducing cycle time and improving adsorbent utilization efficiency. Saving expensive copper adsorbent. (3) Carbon dioxide belongs to the easily desorbed gas on both adsorbents, and the power consumption for evacuating is greatly reduced compared with that of the carbon dioxide without flushing. (4) The carbon dioxide separation at the rear stage saves more energy consumption than the common process. (5) The carbon dioxide concentration in the carbon monoxide can be controlled by utilizing the mixed gas at the rear stage to separate the carbon dioxide, and the method is extremely convenient for certain carbon-based synthesis processes needing to add the carbon dioxide.
Detailed Description
Example 1: a mixed gas containing 50% of carbon monoxide, 20% of carbon dioxide and the balance of nitrogen and hydrogen, wherein the adsorption pressure is 0.10MPa, a copper-loaded adsorbent is placed at the inlet end of a first-stage adsorption tower, silica gel is placed at the outlet end of the adsorption tower, the copper-loaded adsorbent adsorbs carbon monoxide and carbon dioxide, and the silica gel adsorbs carbon dioxide; after the pressure equalizing and reducing and the forward discharging processes, the crude product is adopted to replace an adsorption tower, and the replaced effluent is sent to compression or other towers for pressure increasing; the total concentration of carbon monoxide and carbon dioxide desorbed in the reverse discharge and evacuation process reaches more than 99 percent and is called as a crude product, and the carbon dioxide desorbed by silica gel is used as a flushing gas for the carbon monoxide adsorbed by the copper-carrying adsorbent in the reverse discharge and evacuation regeneration process, so that the carbon monoxide is completely desorbed; the crude product is pressurized to 3.0MPa and is sent to a second-stage adsorption tower to separate carbon dioxide, and carbon monoxide with the concentration of more than 98.5% is obtained from a non-adsorption phase and is called product gas.
Example 2: a mixed gas containing 45% of carbon monoxide, 25% of carbon dioxide and the balance of nitrogen and hydrogen, wherein the adsorption pressure is 0.09MPa, a copper-loaded adsorbent is placed at the inlet end of a first-stage adsorption tower, silica gel is placed at the outlet end of the adsorption tower, the copper-loaded adsorbent adsorbs carbon monoxide and carbon dioxide, and the silica gel adsorbs carbon dioxide; after the pressure equalizing and reducing and the forward discharging processes, the crude product is adopted to replace an adsorption tower, and the replaced effluent is sent to compression or other towers for pressure increasing; the total concentration of carbon monoxide and carbon dioxide desorbed in the reverse discharge and evacuation process reaches more than 99 percent and is called as a crude product, and the carbon dioxide desorbed by silica gel is used as a flushing gas for the carbon monoxide adsorbed by the copper-carrying adsorbent in the reverse discharge and evacuation regeneration process, so that the carbon monoxide is completely desorbed; the crude product is pressurized to 3.5MPa and is sent to a second-stage adsorption tower to separate carbon dioxide, and carbon monoxide with the concentration of more than 98.0% is obtained from a non-adsorption phase and is called product gas.
Example 3: a mixed gas containing 60% of carbon monoxide, 30% of carbon dioxide and the balance of nitrogen and hydrogen, wherein the adsorption pressure is 0.12MPa, a copper-loaded adsorbent is placed at the inlet end of a first-stage adsorption tower, silica gel is placed at the outlet end of the adsorption tower, the copper-loaded adsorbent adsorbs carbon monoxide and carbon dioxide, and the silica gel adsorbs carbon dioxide; after the pressure equalizing and reducing and the forward discharging processes, the crude product is adopted to replace an adsorption tower, and the replaced effluent is sent to compression or other towers for pressure increasing; the total concentration of carbon monoxide and carbon dioxide desorbed in the reverse discharge and evacuation process reaches more than 99 percent and is called as a crude product, and the carbon dioxide desorbed by silica gel is used as a flushing gas for the carbon monoxide adsorbed by the copper-carrying adsorbent in the reverse discharge and evacuation regeneration process, so that the carbon monoxide is completely desorbed; the crude product is pressurized to 4.0MPa and is sent to a second-stage adsorption tower to separate carbon dioxide, and carbon monoxide with the concentration of more than 99.0% is obtained from a non-adsorption phase and is called product gas.
Claims (1)
1. An improved method for separating and purifying carbon monoxide by pressure swing adsorption is characterized in that mixed gas containing 10% -60% of carbon monoxide, 10% -60% of carbon dioxide and the balance of nitrogen and hydrogen is adsorbed at the pressure of 0.05-1.0 MPa, a copper-loaded adsorbent is placed at the inlet end of a first-stage adsorption tower, silica gel is placed at the outlet end of the adsorption tower, the copper-loaded adsorbent adsorbs carbon monoxide and carbon dioxide, and the silica gel adsorbs carbon dioxide; after the pressure equalizing and reducing and the forward discharging processes, the crude product is adopted to replace an adsorption tower, and the replaced effluent is sent to compression or other towers for pressure increasing; the total concentration of carbon monoxide and carbon dioxide desorbed in the reverse discharge and evacuation process reaches more than 99 percent and is called as a crude product, and the carbon dioxide desorbed by silica gel is used as a flushing gas for the carbon monoxide adsorbed by the copper-carrying adsorbent in the reverse discharge and evacuation regeneration process, so that the carbon monoxide is completely desorbed; pressurizing the crude product to 0.05-4.0 MPa, and sending the crude product into a second-stage adsorption tower to separate carbon dioxide, wherein carbon monoxide with the concentration of more than 98.5% is obtained from a non-adsorption phase and is called product gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111459339.4A CN114229844B (en) | 2021-12-02 | 2021-12-02 | Improved process for preparing carbon monoxide by pressure swing adsorption |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111459339.4A CN114229844B (en) | 2021-12-02 | 2021-12-02 | Improved process for preparing carbon monoxide by pressure swing adsorption |
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| CN114229844A CN114229844A (en) | 2022-03-25 |
| CN114229844B true CN114229844B (en) | 2024-03-22 |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4019879A (en) * | 1975-09-26 | 1977-04-26 | Union Carbide Corporation | Selective adsorption of carbon monoxide from gas streams |
| GB8621999D0 (en) * | 1985-09-17 | 1986-10-22 | Kansai Coke & Chemicals | Adsorbent for separation-recovery of co |
| US5993517A (en) * | 1998-03-17 | 1999-11-30 | The Boc Group, Inc. | Two stage pressure swing adsorption process |
| CN101596396A (en) * | 2009-06-23 | 2009-12-09 | 杨皓 | A kind of method of deeply drying gas |
| CN102755810A (en) * | 2012-08-02 | 2012-10-31 | 南京圣火水泥新技术工程有限公司 | Rotor type pressure swing adsorption gas separation device |
| CN102899096A (en) * | 2012-09-28 | 2013-01-30 | 四川天一科技股份有限公司 | Method for decarburizing coke oven gas |
| CN104059695A (en) * | 2014-06-19 | 2014-09-24 | 衡阳华菱钢管有限公司 | Device and method for purifying blast furnace gas by pressure swing adsorption |
| CN110180322A (en) * | 2019-06-05 | 2019-08-30 | 杨皓 | A kind of technique obtaining highly concentrated unsaturated component mixed gas from off-gas |
-
2021
- 2021-12-02 CN CN202111459339.4A patent/CN114229844B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4019879A (en) * | 1975-09-26 | 1977-04-26 | Union Carbide Corporation | Selective adsorption of carbon monoxide from gas streams |
| GB8621999D0 (en) * | 1985-09-17 | 1986-10-22 | Kansai Coke & Chemicals | Adsorbent for separation-recovery of co |
| US5993517A (en) * | 1998-03-17 | 1999-11-30 | The Boc Group, Inc. | Two stage pressure swing adsorption process |
| CN101596396A (en) * | 2009-06-23 | 2009-12-09 | 杨皓 | A kind of method of deeply drying gas |
| CN102755810A (en) * | 2012-08-02 | 2012-10-31 | 南京圣火水泥新技术工程有限公司 | Rotor type pressure swing adsorption gas separation device |
| CN102899096A (en) * | 2012-09-28 | 2013-01-30 | 四川天一科技股份有限公司 | Method for decarburizing coke oven gas |
| CN104059695A (en) * | 2014-06-19 | 2014-09-24 | 衡阳华菱钢管有限公司 | Device and method for purifying blast furnace gas by pressure swing adsorption |
| CN110180322A (en) * | 2019-06-05 | 2019-08-30 | 杨皓 | A kind of technique obtaining highly concentrated unsaturated component mixed gas from off-gas |
Non-Patent Citations (1)
| Title |
|---|
| "变压吸附制氢装置吸附剂粉化原因分析及解决方案";何银宝 等;《内蒙古石油化工》;20140215;第40卷(第03期);第42-43页 * |
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