US20080282891A1 - Pressure swing adsorption process for large capacity oxygen production - Google Patents
Pressure swing adsorption process for large capacity oxygen production Download PDFInfo
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- US20080282891A1 US20080282891A1 US12/132,417 US13241708A US2008282891A1 US 20080282891 A1 US20080282891 A1 US 20080282891A1 US 13241708 A US13241708 A US 13241708A US 2008282891 A1 US2008282891 A1 US 2008282891A1
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- 238000000034 method Methods 0.000 title abstract description 81
- 230000008569 process Effects 0.000 title abstract description 81
- 238000004519 manufacturing process Methods 0.000 title description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title description 26
- 239000001301 oxygen Substances 0.000 title description 26
- 229910052760 oxygen Inorganic materials 0.000 title description 26
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
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Images
Classifications
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- 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
-
- 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
-
- 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
- B01D53/0476—Vacuum pressure swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/12—Oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
- B01D2259/40058—Number of sequence steps, including sub-steps, per cycle
- B01D2259/40075—More than ten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/404—Further details for adsorption processes and devices using four beds
-
- 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
- B01D53/0407—Constructional details of adsorbing systems
- B01D53/0446—Means for feeding or distributing gases
Definitions
- the present invention generally relates to large capacity (e.g., greater than 350 tons/day O 2 ) vacuum pressure adsorption (VPSA) systems and processes that employ a single train including four beds, at least one feed compressor feeding two beds simultaneously at any given instant in time, and a single vacuum pump.
- the compressor(s) and the vacuum pump can be utilized 100% of the time.
- Use of product quality gas for purging is avoided, with about 10-20% improvement in O 2 productivity and 5-10% reduction in capital cost expected.
- VPSA vacuum pressure swing adsorption
- PSA pressure swing adsorption
- VPSA or PSA processes In the application of VPSA or PSA processes, the energy input required to achieve the separation of O 2 from the feed mixture (e.g., air) is provided as mechanical work through feed compressor(s) and vacuum pump(s). The cost of this work is a significant component of the total operating cost of the VPSA or PSA process.
- VPSA or PSA technology is currently economically competitive with cryogenic distillation only for small scale applications. In order for PSA or VPSA processes to become cost competitive with cryogenic distillation for large scale applications, improved cycles are required to operate the PSA or VPSA processes.
- FIG. 1 shows the VPSA cycle for the production of oxygen from air disclosed in Smolarek et al., U.S. Pat. No. 6,010,555.
- FIG. 1 shows the VPSA cycle for the production of oxygen from air disclosed in Smolarek et al., U.S. Pat. No. 6,010,555.
- 5,518,526 and 6,010,555 are both for small scale ( ⁇ 200 tons per day, (TPD)) oxygen production.
- Adsorption and desorption pressures in U.S. Pat. Nos. 5,518,526 and 6,010,555 are characterized by a low pressure ratio and relatively high desorption pressure values.
- Significant reduction in equipment and operating costs can be realized using the small scale ( ⁇ 200 TPD O 2 ) VPSA processes of U.S. Pat. Nos. 5,518,526 and 6,010,555.
- a four bed VPSA system operating as two pairs of adsorption beds to produce about 100 tons per day (TPD) oxygen is disclosed in Doong, U.S. Pat. No. 5,997,612 to Doong.
- the VPSA process includes two pairs of beds, an intermediate storage tank (to collect co-current depressurization gas), one gas blower and a pair of vacuum pumps.
- the system disclosed in Doong (U.S. Pat. No. 5,997,612) includes three pumps as compared to the four pumps disclosed in U.S. Pat. No. 5,656,068.
- the system shown in Doong (U.S. Pat. No. 5,997,612) is for small scale oxygen production ( ⁇ 200 tons per day) rather than large scale O 2 production using the dual feed VPSA process of Smolarek et al. (U.S. Pat. No. 5,656,068).
- the present invention generally relates to four bed VPSA systems and processes with dual feed inlet for large scale oxygen production (e.g., >350 tons/day O 2 ).
- the systems of the present invention include the implementation of three pumps (e.g., two compressors and one vacuum pump) rather than four pumps (e.g., two compressors and two vacuum pumps) as disclosed in U.S. Pat. No. 5,656,068.
- the present invention additionally contemplates the use of unique four-bed VPSA cycles that include 100% utilization of the compressors and vacuum pump while at the same time allows two beds to simultaneously receive feed gas. Moreover, at any instant in time during the four bed VPSA cycle, two beds are receiving feed simultaneously while the other two beds are in the regeneration/refluxing mode.
- systems and processes of the present invention can include: (1) continuous feed and product make steps; (2) a minimum of one compressor and one vacuum pump; (3) 100% utilization of the compressors and vacuum pump; (4) smaller product storage/buffer tanks relative to prior art processes due to continuous feed and product make steps; (5) the option of using the same or different compressors (e.g., centrifugal and Roots) for compressing the inlet feed to the VPSA process; (6) the purging gas coming from another bed that is undergoing co-current depressurization step, and this purging gas goes directly to another bed undergoing the purging step without the use of any additional storage tank; (7) the purging step sandwiched between the evacuation steps in the VPSA cycle (i.e., the VPSA cycle has an evacuation step before and after the purging step to allow the use of void space gas for purging of another bed directly (without the need of an additional storage tank) or to avoid using product
- systems of the present invention are thus expected to provide about 10-20% improvement in O 2 productivity/recovery and 5-10% reduction in capital cost as oxygen is produced on a large scale (>350 Tons/day) basis using a single train, one less pump, lower bed size factor, and avoids the use of product quality gas for purging.
- FIG. 1 illustrates the VPSA cycle for the production of oxygen from air disclosed in Smolarek et al., U.S. Pat. No. 6,010,555;
- FIG. 2 illustrates a schematic of a four bed process using two compressors to deliver the total feed to a dual inlet feed VPSA process in accordance with the present invention
- FIG. 3 shows a column cycle for the dual feed inlet four bed VPSA process of FIG. 2 ;
- FIG. 4 illustrates a four bed VPSA process using two compressors to deliver the total feed to a dual inlet feed VPSA process in accordance with an alternative embodiment of the present invention
- FIG. 5 shows a column cycle for the dual feed inlet four bed VPSA process of FIG. 4 ;
- FIG. 6 shows an alternate schematic of a four bed VPSA process using two compressors to deliver the total feed to a dual inlet feed VPSA process in accordance with the present invention
- FIG. 7 shows a column cycle for the dual feed inlet four bed VPSA process of FIG. 6 ;
- FIG. 8 illustrates an alternative column cycle for the dual feed inlet four bed VPSA process of FIG. 6 in which the cycle uses two product pressurization steps and one equalization step;
- FIG. 9 shows another alternative column cycle for the dual feed inlet four bed VPSA process of FIG. 6 in which the cycle uses eight steps instead of twelve steps.
- the present invention relates to vacuum pressure swing adsorption (VPSA) processes and apparatus for large scale (preferably >350 tons/day) oxygen production.
- the present invention includes systems and processes in which twelve-step VPSA cycles are carried out employing four adsorption beds, at least one feed compressor (preferably two, e.g., one centrifugal and one positive displacement such as Roots), and a single vacuum pump. At any instant in time, two of the beds are simultaneously in the feed mode while the other two beds are in the regeneration/refluxing mode. Feed to these two beds can be supplied from separate compressors or from a single compressor. Gas generated during a co-current depressurization step can be sent as purge gas to another bed without the use of any additional storage tank.
- steps of the four bed VPSA process provided in accordance with the present invention are fully integrated so that none of the beds has any idle step(s), i.e. 100% utilization of the compressor(s) and vacuum pump in the VPSA cycle.
- systems of the present invention can include some or all of the following advantageous features.
- the present invention includes the application of a single train four bed VPSA process rather than two trains of two bed VPSA processes for large scale O 2 production.
- lower capital cost and enhanced process performance, e.g., higher O 2 recovery, relative to parallel trains of two bed VPSA processes can be expected.
- systems of the present invention are expected to have less spreading of the impurity (e.g. N 2 ) concentration fronts as a result of the novel four bed VPSA cycles. This is due to the expectation that less purge gas will be required during bed regeneration relative to prior art techniques.
- Continuous product, feed and evacuation steps in the cycle allow for 100% utilization of the compressor(s)/vacuum pumps.
- the present invention further provides for the application of dual feed inlet at any instant during the VPSA cycle.
- the incorporation of a counter-current blow down step in the VPSA cycle can allow a portion of the waste (obtain during bed regeneration) to bypass the vacuum pump instead of having the waste go through the vacuum pump as in U.S. Pat. Nos. 5,656,068 and 6,010,555.
- the present invention additionally includes cleaner gas used for refluxing.
- the lowest O 2 purity gas is used for purging and the highest O 2 purity gas is used for product pressurization, i.e., product gas of increasing purity is being used for purging, equalization rising and product pressurization in the VPSA cycle of the present invention, thereby resulting in sharper O 2 concentration fronts or better bed regeneration prior to bringing the bed online for O 2 production.
- a further advantage of the present invention is expected due to a higher pressure gradient driving force for void gas recovery during bed-to-bed equalization and the unique arrangements of the various steps in the VPSA cycle relative to prior art systems.
- all of the purging gas can come from void space gas recovered from another bed that is undergoing co-current depressurization step.
- this purging gas can be used directly for another bed undergoing the purging step without the use of any additional storage tank (as in for example U.S. Pat. No. 5,997,612).
- the purging step is sandwiched between the evacuation steps in the VPSA cycle. More specifically, the VPSA cycle has evacuation steps before and after the purging step to allow using void space gas for purging of another bed directly or to avoid using product quality gas for purging as in U.S. Pat. No. 5,656,068 and U.S. Pat. No. 6,010,555.
- Systems of the present invention further provide the option of using the same or different compressors (e.g., centrifugal and Roots or positive displacement) for compressing the inlet feed to the VPSA process and 100% utilization, i.e., no compressor unloading throughout the VPSA cycle.
- compressors e.g., centrifugal and Roots or positive displacement
- the four bed VPSA system ( 30 ) shown in FIG. 2 includes four adsorber beds ( 42 , 44 , 46 , 48 ), 24 ON/OFF valves (some or all of which may or may not have flow control), two feed compressors 36 , 38 , one vacuum compressor 52 , feed inlet silencer/filter 34 for feed 32 , feed discharge silencer/aftercooler ( 40 ), vacuum discharge silencer 54 and associated piping and fittings.
- FIGS. 2 and 3 and Table 1 one embodiment of the present invention is illustrated over one complete VPSA cycle.
- “C” represents valves in the closed position while “O” represents valves in the fully opened or partially opened position, depending on whether the valve is an ON/OFF or flow control valve for manipulating the desired flow. It will be appreciated by those skilled in the art that flow control valves will be used during product pressurization (for example, step 3 in FIG. 3 ).
- the pressure in bed 42 (B 1 ) is at the adsorption pressure.
- Valve 1 is open to allow feed gas into the bottom of bed 42 and valve 21 is open to allow product 50 out of the top of bed 42 .
- Feed gas is supplied to Bed 1 from compressor 38 (C 1 ).
- Valve 11 is open to allow evacuation of bed 44 (B 2 ) thru compressor 52 (C 3 ) to vacuum discharge silencer 54 to waste 56 .
- Valve 13 opens to allow bed 46 (B 3 ) to blowdown to the atmosphere.
- Valve 8 is open to allow feed gas into the bottom of bed 48 (B 4 ) and valve 24 is open to allow product 50 out of the top of bed 48 .
- Feed gas is supplied to bed 48 from compressor 36 (C 2 ).
- valve 1 closes and valve 2 opens to allow feed gas from compressor 36 (C 2 ) into the bottom of bed 42 .
- Valve 21 remains open to allow product production to continue from bed 42 .
- Valve 11 closes and valve 3 opens to stop the evacuation of bed 44 and allow feed gas from compressor 38 (C 1 ) to enter the bottom of bed 44 .
- valves 18 and 20 open to allow equalization gas to flow from bed 48 into the top of bed 44 .
- Valve 13 closes and valve 14 opens to start the evacuation of bed 46 (B 3 ).
- valves 2 and 21 remain open to allow product 50 production to continue from bed 42 .
- Valve 3 remains open and allows feed gas from compressor 38 to continue to enter the bottom of bed 44 .
- Valve 22 opens to allow product pressurization gas to enter the top of bed 44 .
- Valve 20 remains open and valve 19 opens to allow purge gas to flow from bed 48 to bed 46 .
- Valve 14 remains open to continue the evacuation of bed 46 .
- Valve 18 closes.
- valves 2 and 21 remain open to allow product production to continue from bed 42 .
- Valves 3 and 22 remain open and product production begins in bed 44 .
- Valve 14 remains open to continue the evacuation of bed 46 .
- Valve 16 opens to allow bed 48 to blowdown to the atmosphere.
- valves 17 and 19 open to allow equalization gas to flow from bed 42 into the top of bed 46 .
- Valve 3 closes and valve 4 opens to allow feed gas from compressor 36 (C 2 ) into the bottom of bed 44 .
- Valve 22 remains open to allow product production to continue from bed 44 .
- Valve 13 closes and valve 5 opens to stop the evacuation of bed 46 and allow feed gas from compressor 38 (C 1 ) to enter the bottom of bed 46 .
- Valve 16 closes and valve 15 opens to start the evacuation of bed 48 .
- valve 17 remains open and valve 20 opens to allow purge gas to flow from bed 42 to bed 48 .
- Valves 4 and 22 remain open to allow product production to continue from bed 44 .
- Valve 5 remains open and allows feed gas from compressor 38 (C 1 ) to continue to enter the bottom of bed 46 .
- Valve 23 opens to allow product pressurization gas to enter the top of bed 46 .
- Valve 15 remains open to continue the evacuation of bed 48 while it receives purge gas.
- Valve 19 closes.
- valve 9 opens to allow bed 42 to blowdown to the atmosphere.
- Valves 4 and 22 remain open to allow product production to continue from bed 44 .
- Valves 5 and 23 remain open and product production begins in bed 46 .
- Valve 15 remains open to continue the evacuation of bed 48 .
- valve 9 closes and valve 10 opens to start the evacuation of bed 42 .
- Valves 18 and 20 open to allow equalization gas to flow from bed 44 into the top of bed 48 .
- Valve 5 closes and valve 6 opens to allow feed gas from compressor 36 (C 2 ) into the bottom of bed 46 .
- Valve 23 remains open to allow product production to continue from bed 46 .
- Valve 15 closes and valve 7 opens to stop the evacuation of bed 48 and allow feed gas from compressor 38 (C 1 ) to enter the bottom of bed 48 .
- valve 10 remains open to continue the evacuation of bed 42 while it receives purge gas.
- Valve 18 remains open and valve 17 opens to allow purge gas to flow from bed 44 to bed 42 .
- Valves 6 and 23 remain open to allow product production to continue from bed 46 .
- Valve 7 remains open and allows feed gas from compressor 38 (C 1 ) to continue to enter the bottom of bed 48 .
- Valve 24 opens to allow product pressurization gas to enter the top of bed 48 .
- Valve 20 closes.
- valve 10 remains open to continue the evacuation of bed 42 .
- Valve 12 opens to allow bed 44 to blowdown to the atmosphere.
- Valves 6 and 23 remain open to allow product production to continue from bed 46 .
- Valves 7 and 24 remain open and product production begins in bed 48 .
- valve 10 closes and valve 1 opens to stop the evacuation of bed 42 and allow feed gas from compressor 38 (C 1 ) to enter the bottom of bed 42 .
- Valve 12 closes and valve 11 opens to start the evacuation of bed 44 .
- Valves 17 and 19 open to allow equalization gas to flow from bed 46 into the top of bed 42 .
- Valve 7 closes and valve 8 opens to allow feed gas from compressor 36 (C 2 ) into the bottom of bed 48 .
- Valve 24 remains open to allow product production to continue from bed 48 .
- valve 1 remains open and allows feed gas from compressor 38 (C 1 ) to continue to enter the bottom of bed 42 .
- Valve 21 opens to allow product pressurization gas to enter the top of bed 42 .
- Valve 11 remains open to continue the evacuation of bed 44 while it receives purge gas.
- Valve 19 remains open and valve 18 opens to allow purge gas to flow from bed 46 to bed 44 .
- Valves 8 and 24 remain open to allow product production to continue from bed 48 .
- Valve 17 closes.
- the embodiment described hereinabove utilizes two compressors to deliver feed gas to the VPSA vessels.
- one Roots compressor 38 (C 1 or compressor 1 ) and one centrifugal compressor 36 (C 2 or compressor 2 ) will deliver the total feed flow to an integrated four bed VPSA process.
- radial beds are used in the VPSA process. Additional details of radial bed adsorbers are given by Ackley et al., U.S. Pat. No. 6,506,234 B1.
- step 1 of the VPSA cycle one portion of the total feed (dual feed VPSA process) is delivered via the Roots compressor to bed 42 (B 1 ) while the centrifugal compressor delivers the other portion of the total feed to bed 48 (B 4 ).
- two beds are receiving feed gas simultaneously and a continuous product make exists throughout the VPSA cycle.
- Table 2 gives an example of the operating conditions and the VPSA process performance using a nitrogen selective adsorbent in the beds.
- the nitrogen equilibrium selective adsorbent in Table 2 is highly exchanged Li—X (>95% Li), as disclosed by Chao et al., U.S. Pat. Nos. 5,413,625 and 4,859,217, both of which are incorporated herein by reference to the extent consistent herewith.
- highly exchanged LiX adsorbent is disclosed in these patents, it is anticipated that layers of adsorbents or mixtures of adsorbents could be used and may preferably be used (e.g., when there is moisture in the air) in each bed of the VPSA process without deviating from the scope of this invention.
- Representative examples of various adsorbents for use in this invention include but not limited to those disclosed in U.S. Pat.
- the adsorbent could be a mixture of adsorbents or a layered adsorbent(s).
- the same adsorbent, whether it is a single adsorbent, mixture of adsorbents or layer of adsorbent(s), is the same in all four beds.
- Adsorbent in each Bed Li-X Feed Composition (N 2 /O 2 /Ar): 78.12%/20.95% O 2 /0.934% High Pressure: 160 kPa Low Pressure: 30 kPa Total Feed: 2.85 ⁇ 10 6 NCFH Amount of O 2 Produced: 3.58 ⁇ 10 5 NCFH (355 TPD O 2 ) Oxygen Purity: 90% Overall oxygen Recovery: 60% Bed Size Factor: 350 lb/TPD O 2 Temperature 300K
- the VPSA process discussed hereinabove is focused on O 2 production from air using a four VPSA bed process and system.
- less than four (e.g., three bed) or more than four beds could be used.
- additional storage tanks may or may not be required in such alternative embodiments to incorporate the features of the invention depending on whether three or >4 beds in the VPSA cycles are employed.
- each bed could alternatively include one or several layers of adsorbents, or a mixture of adsorbents.
- adsorbents could also be used in the VPSA process for O 2 production from air. Details of preferred suitable adsorbents and layering of the adsorbents are disclosed in U.S. Pat. Nos. 5,413,625; 4,859,217; 6,027,548; and 6,790,260 B2.
- other adsorbents could be used in the aforementioned VPSA processes of the present invention.
- 5A, 13X, CaX, and mixed cations zeolites could be used as the N 2 selective adsorbent in the VPSA process.
- a pre-purifier section is positioned at the upstream end of each zeolite bed to remove water and carbon dioxide from the feed air.
- a layer of alumina or silica is preferably positioned upstream of each of the adsorbent beds to remove water and carbon dioxide from the feed air prior to passing to the N 2 selective adsorbent in the VPSA process.
- the adsorber configuration selected e.g., radial, axial, structured, etc.
- choice and arrangement of the adsorbents will be determined based on the size of the feed flow, the type of feed source, and VPSA process operating conditions.
- axial beds can be used in the VPSA process. It is preferred that all the beds have the same configuration.
- one compressor could be used to deliver the total feed to the dual inlet VPSA process (e.g., the VPSA processes illustrated in the Figures).
- the highest adsorption pressure is in the range of 100 kPa to about 2000 kPa, and the lowest desorption pressure is in the range of 20 kPa to about 100 kPa.
- the optimization between achieving high O 2 recovery and low power consumption in the VPSA process will determine optimum adsorption and desorption pressures for a given adsorbent.
- the average purity of the oxygen product is expected to be in the range of 85 percent oxygen to about 95 percent oxygen, corresponding to an expected O 2 recovery of about 55-75%.
- the lowest O 2 recovery is expected to correspond to the highest the O 2 purity, and vice versa.
- FIG. 4 shows an alternate schematic of a four bed system 60 and process using two compressors 36 , 38 to deliver the total feed 32 to the dual inlet feed VPSA process and two compressors 52 , 53 to evacuate the waste 56 from the VPSA process.
- only one vacuum blower 52 preferably, a Roots type blower
- a first vacuum blower 52 is used to evacuate the waste (preferably a Roots type blower) followed by a second vacuum blower 53 (preferably a centrifugal type blower).
- FIG. 5 shows the column cycle for the dual feed inlet four bed VPSA process of FIG. 4 .
- an additional purge gas obtained from another bed in the adsorption step (e.g., bed 42 (B 1 ) undergoing AD 4 in FIG. 5 while simultaneously supplying purge gas to another bed), is utilized in the VPSA process.
- the equalization down step in this alternative mode is overlapped with a countercurrent evacuation to hasten bed depressurization. Also, during the provide purging step (e.g., bed 42 (B 1 ) in step 6 of FIG. 5 ), the bed is simultaneously undergoing countercurrent evacuation.
- AD Adsorption/Product Production
- ED Equalization Down
- PPG Provide Purge Gas
- PPP Provide Product Pressurization Gas
- BD Blowdown
- PG Receive Purge
- EU equalization up (EU is the same as EQUP)
- PP product Pressurization
- FP Feed Pressurization
- RC Roots Compressor
- CC Centrifugal Compressor
- RV Roots Vacuum
- CV Centrifugal Vacuum
- EV Evacuation.
- Suitable adsorbents, mixtures and layering of such adsorbents are discussed hereinabove.
- FIG. 6 shows another alternate schematic of a four bed system 70 and process in accordance with the present invention using two compressors 36 , 38 to deliver the total feed to the dual inlet feed VPSA process.
- FIG. 7 shows a column cycle for the dual feed inlet four bed VPSA process of FIG. 6 .
- eight waste valves are used to allow for a blowdown step (bypassing the vacuum blower) followed by evacuation steps using the vacuum blower.
- FIGS. 6 and 7 only four waste valves are required. As a result, all of the waste gas is evacuated through the vacuum blower.
- FIGS. 2 and 3 eight waste valves are used to allow for a blowdown step (bypassing the vacuum blower) followed by evacuation steps using the vacuum blower.
- equalization is not overlapped with evacuation as in the alternative mode illustrated in FIGS. 6 and 7 .
- purge is provided from co-current depressurization gas in the embodiment shown in FIGS. 2 and 3 while purge is provided from the bed in production in the embodiment shown in FIGS. 6 and 7 .
- FIGS. 8 and 9 Additional alternative column cycles for the dual feed inlet four bed VPSA process of FIG. 6 are shown in FIGS. 8 and 9 .
- the cycle shown in FIG. 8 uses two product pressurization steps and one equalization step and the cycle shown in FIG. 9 uses eight steps instead of twelve steps.
- the illustrated column cycles for the dual feed inlet four bed VPSA processes shown in FIGS. 2 , 4 and 6 and the associated column cycles are arranged in the order from most preferred ( FIG. 2-3 ) to the least preferred ( FIGS. 6 and 9 ).
- the column cycles are arranged in the order of most preferred to least preferred; i.e., the cycle in FIG. 7 is preferred over the cycle shown in FIG.
- the column cycles for the dual feed inlet four bed VPSA process of FIG. 6 illustrated in FIGS. 7-9 are expected to vary in bed size factor and power consumption, with the cycle depicted in FIG. 7 being more efficient than that shown in FIG. 8 and the cycle in FIG. 8 being more efficient than that shown in FIG. 9 . It is thus expected that the BSF and power consumption are highest for FIG. 9 , less for FIG. 8 and even less for FIG. 7 for the schematic in FIG. 6 because the efficiencies for the cycles shown are expected to decrease with increasing figure numbers.
- the systems and processes of the present invention are likewise expected to be useful for feed streams other than air such as rare gas (e.g., He, Ar, Ne, Kr) containing feed streams or H 2 -containing feed streams such as those obtained from steam methane reforming reactions or partial oxidation of hydrocarbons, etc.
- rare gas e.g., He, Ar, Ne, Kr
- H 2 -containing feed streams such as those obtained from steam methane reforming reactions or partial oxidation of hydrocarbons, etc.
- a H 2 containing feed mixture from synthesis gas, generated from steam methane reforming is expected to be suitable for use in accordance with the present invention.
- hydrogen could be recovered. It is anticipated that the process and system could be adapted quite readily for the desired product or co-products production.
- PSA pressure swing adsorption
Abstract
The present invention generally relates to large capacity (e.g., greater than 350 tons/day O2) vacuum pressure adsorption (VPSA) systems and processes that employ a single train including four beds, at least one feed compressor feeding two beds simultaneously at any given instant in time, and a single vacuum pump. The compressor(s) and the vacuum pump can be utilized 100% of the time. Use of product quality gas for purging is avoided, with about 10-20% improvement in O2 productivity and 5-10% reduction in capital cost expected.
Description
- The present invention generally relates to large capacity (e.g., greater than 350 tons/day O2) vacuum pressure adsorption (VPSA) systems and processes that employ a single train including four beds, at least one feed compressor feeding two beds simultaneously at any given instant in time, and a single vacuum pump. The compressor(s) and the vacuum pump can be utilized 100% of the time. Use of product quality gas for purging is avoided, with about 10-20% improvement in O2 productivity and 5-10% reduction in capital cost expected.
- The production of oxygen from air currently uses vacuum pressure swing adsorption (VPSA) or pressure swing adsorption (PSA) systems technology. These systems often have a capacity of <200 tons per day O2. Presently, there is renewed interest in extending the capacity of VPSA or PSA systems from such small scale (<200 tons per day O2) to large scale (about 350 tons per day O2 or higher) oxygen production from air.
- In the application of VPSA or PSA processes, the energy input required to achieve the separation of O2 from the feed mixture (e.g., air) is provided as mechanical work through feed compressor(s) and vacuum pump(s). The cost of this work is a significant component of the total operating cost of the VPSA or PSA process. In addition, VPSA or PSA technology is currently economically competitive with cryogenic distillation only for small scale applications. In order for PSA or VPSA processes to become cost competitive with cryogenic distillation for large scale applications, improved cycles are required to operate the PSA or VPSA processes.
- Two bed vacuum pressure swing adsorption (VPSA) processes for the production of oxygen from air are disclosed U.S. Pat. No. 5,518,526 to Baksh et al. and U.S. Pat. No. 6,010,555 to Smolarek et al. U.S. Pat. Nos. 5,518,526 and 6,010,555 employ VPSA processes with simultaneous equalization and evacuation steps followed by simultaneous feed and product pressurization steps.
FIG. 1 shows the VPSA cycle for the production of oxygen from air disclosed in Smolarek et al., U.S. Pat. No. 6,010,555. U.S. Pat. Nos. 5,518,526 and 6,010,555 are both for small scale (<200 tons per day, (TPD)) oxygen production. Adsorption and desorption pressures in U.S. Pat. Nos. 5,518,526 and 6,010,555 are characterized by a low pressure ratio and relatively high desorption pressure values. Significant reduction in equipment and operating costs can be realized using the small scale (<200 TPD O2) VPSA processes of U.S. Pat. Nos. 5,518,526 and 6,010,555. - In applications where large scale oxygen production (e.g., 350 tons per day O2) is desirable, four bed VPSA processes are used. One such VPSA process is disclosed by Smolarek et al., U.S. Pat. No. 5,656,068. The four bed VPSA process disclosed in U.S. Pat. No. 5,656,068 is operated as two pairs of 2-bed systems, referred to as a 2×2 cycle/system. Each pair of beds is operated 180° out of phase and the two pairs of beds are operated out of phase by one-half of a half-cycle. Two compressors (one Roots or positive displacement and one Centrifugal) and two vacuum pumps (one Roots or positive displacement and one Centrifugal) are disclosed in the VPSA process of U.S. Pat. No. 5,656,068. One of the two compressors is periodically in the idle or vent mode. A four bed VPSA system operating as two pairs of adsorption beds to produce about 100 tons per day (TPD) oxygen is disclosed in Doong, U.S. Pat. No. 5,997,612 to Doong. The VPSA process includes two pairs of beds, an intermediate storage tank (to collect co-current depressurization gas), one gas blower and a pair of vacuum pumps. The system disclosed in Doong (U.S. Pat. No. 5,997,612) includes three pumps as compared to the four pumps disclosed in U.S. Pat. No. 5,656,068. In addition, the system shown in Doong (U.S. Pat. No. 5,997,612) is for small scale oxygen production (<200 tons per day) rather than large scale O2 production using the dual feed VPSA process of Smolarek et al. (U.S. Pat. No. 5,656,068).
- It would thus be desirable to provide cost efficient, highly productive four bed VPSA processes and systems with the capacity for large scale oxygen production (e.g., >350 tons/day O2).
- The present invention generally relates to four bed VPSA systems and processes with dual feed inlet for large scale oxygen production (e.g., >350 tons/day O2). The systems of the present invention include the implementation of three pumps (e.g., two compressors and one vacuum pump) rather than four pumps (e.g., two compressors and two vacuum pumps) as disclosed in U.S. Pat. No. 5,656,068. The present invention additionally contemplates the use of unique four-bed VPSA cycles that include 100% utilization of the compressors and vacuum pump while at the same time allows two beds to simultaneously receive feed gas. Moreover, at any instant in time during the four bed VPSA cycle, two beds are receiving feed simultaneously while the other two beds are in the regeneration/refluxing mode.
- The processes and systems provided in accordance with the present invention include multiple advantages. For example and while not to be construed as limiting, systems and processes of the present invention can include: (1) continuous feed and product make steps; (2) a minimum of one compressor and one vacuum pump; (3) 100% utilization of the compressors and vacuum pump; (4) smaller product storage/buffer tanks relative to prior art processes due to continuous feed and product make steps; (5) the option of using the same or different compressors (e.g., centrifugal and Roots) for compressing the inlet feed to the VPSA process; (6) the purging gas coming from another bed that is undergoing co-current depressurization step, and this purging gas goes directly to another bed undergoing the purging step without the use of any additional storage tank; (7) the purging step sandwiched between the evacuation steps in the VPSA cycle (i.e., the VPSA cycle has an evacuation step before and after the purging step to allow the use of void space gas for purging of another bed directly (without the need of an additional storage tank) or to avoid using product quality gas for purging); (8) use of sorbents with high intrinsic adsorption rates and optimum particle size to increase mass transfer rate, high O2 product recovery, and low bed size factor (BSF) in fast-cycle shallow adsorbers in the VPSA process, and/or (9) all the steps of the four bed VPSA process fully integrated so that none of the beds has any idle step(s).
- Consequently, systems of the present invention are thus expected to provide about 10-20% improvement in O2 productivity/recovery and 5-10% reduction in capital cost as oxygen is produced on a large scale (>350 Tons/day) basis using a single train, one less pump, lower bed size factor, and avoids the use of product quality gas for purging.
- For a more complete understanding of the present invention and the advantages thereof, reference should be made to the following Detailed Description taken in conjunction with the accompanying drawings in which:
-
FIG. 1 illustrates the VPSA cycle for the production of oxygen from air disclosed in Smolarek et al., U.S. Pat. No. 6,010,555; -
FIG. 2 illustrates a schematic of a four bed process using two compressors to deliver the total feed to a dual inlet feed VPSA process in accordance with the present invention; -
FIG. 3 shows a column cycle for the dual feed inlet four bed VPSA process ofFIG. 2 ; -
FIG. 4 illustrates a four bed VPSA process using two compressors to deliver the total feed to a dual inlet feed VPSA process in accordance with an alternative embodiment of the present invention; -
FIG. 5 shows a column cycle for the dual feed inlet four bed VPSA process ofFIG. 4 ; -
FIG. 6 shows an alternate schematic of a four bed VPSA process using two compressors to deliver the total feed to a dual inlet feed VPSA process in accordance with the present invention; -
FIG. 7 shows a column cycle for the dual feed inlet four bed VPSA process ofFIG. 6 ; -
FIG. 8 illustrates an alternative column cycle for the dual feed inlet four bed VPSA process ofFIG. 6 in which the cycle uses two product pressurization steps and one equalization step; and -
FIG. 9 shows another alternative column cycle for the dual feed inlet four bed VPSA process ofFIG. 6 in which the cycle uses eight steps instead of twelve steps. - As discussed hereinabove, the present invention relates to vacuum pressure swing adsorption (VPSA) processes and apparatus for large scale (preferably >350 tons/day) oxygen production. The present invention includes systems and processes in which twelve-step VPSA cycles are carried out employing four adsorption beds, at least one feed compressor (preferably two, e.g., one centrifugal and one positive displacement such as Roots), and a single vacuum pump. At any instant in time, two of the beds are simultaneously in the feed mode while the other two beds are in the regeneration/refluxing mode. Feed to these two beds can be supplied from separate compressors or from a single compressor. Gas generated during a co-current depressurization step can be sent as purge gas to another bed without the use of any additional storage tank. At any given time, only one bed is in the evacuation step, thereby allowing the use of only one vacuum pump which results in capital and operating cost savings. The evacuation step is carried out before and after the purging step. This mode of operation allows flexibility in the VPSA cycle to enable the use of void space gas, obtained during co-current depressurization of another bed, for purging of the bed directly (without using an additional storage tank) or to avoid using product quality gas for purging.
- In addition, the steps of the four bed VPSA process provided in accordance with the present invention are fully integrated so that none of the beds has any idle step(s), i.e. 100% utilization of the compressor(s) and vacuum pump in the VPSA cycle.
- While not to be construed as limiting, systems of the present invention can include some or all of the following advantageous features. For example, the present invention includes the application of a single train four bed VPSA process rather than two trains of two bed VPSA processes for large scale O2 production. As a result, lower capital cost and enhanced process performance, e.g., higher O2 recovery, relative to parallel trains of two bed VPSA processes can be expected. In addition, systems of the present invention are expected to have less spreading of the impurity (e.g. N2) concentration fronts as a result of the novel four bed VPSA cycles. This is due to the expectation that less purge gas will be required during bed regeneration relative to prior art techniques. Continuous product, feed and evacuation steps in the cycle allow for 100% utilization of the compressor(s)/vacuum pumps. The present invention further provides for the application of dual feed inlet at any instant during the VPSA cycle. Moreover, the incorporation of a counter-current blow down step in the VPSA cycle can allow a portion of the waste (obtain during bed regeneration) to bypass the vacuum pump instead of having the waste go through the vacuum pump as in U.S. Pat. Nos. 5,656,068 and 6,010,555.
- The present invention additionally includes cleaner gas used for refluxing. For example, the lowest O2 purity gas is used for purging and the highest O2 purity gas is used for product pressurization, i.e., product gas of increasing purity is being used for purging, equalization rising and product pressurization in the VPSA cycle of the present invention, thereby resulting in sharper O2 concentration fronts or better bed regeneration prior to bringing the bed online for O2 production.
- A further advantage of the present invention is expected due to a higher pressure gradient driving force for void gas recovery during bed-to-bed equalization and the unique arrangements of the various steps in the VPSA cycle relative to prior art systems.
- Furthermore, there can be less feed blow by or during feed pressurization because the equalizing bed starts at the adsorption pressure during the overlapping of the equalization and feed pressurization step of the VPSA cycle.
- In the present invention, all of the purging gas can come from void space gas recovered from another bed that is undergoing co-current depressurization step. In addition, this purging gas can be used directly for another bed undergoing the purging step without the use of any additional storage tank (as in for example U.S. Pat. No. 5,997,612). The purging step is sandwiched between the evacuation steps in the VPSA cycle. More specifically, the VPSA cycle has evacuation steps before and after the purging step to allow using void space gas for purging of another bed directly or to avoid using product quality gas for purging as in U.S. Pat. No. 5,656,068 and U.S. Pat. No. 6,010,555.
- Systems of the present invention further provide the option of using the same or different compressors (e.g., centrifugal and Roots or positive displacement) for compressing the inlet feed to the VPSA process and 100% utilization, i.e., no compressor unloading throughout the VPSA cycle.
- As a result of the present invention, about 10-20% improvement in O2 productivity or recovery and about 5-10% reduction in capital cost is expected due to production of oxygen on a large scale (>350 tons/day) using a single train, one less pump, lower bed size factor (BSF), and avoiding the use of product quality gas for purging.
- The present invention will now be described with reference to the four bed VPSA process shown in
FIG. 2 , the four bed VPSA cycle shown inFIG. 3 , and the valve switching logic as shown in Table 1. - The four bed VPSA system (30) shown in
FIG. 2 includes four adsorber beds (42, 44, 46, 48), 24 ON/OFF valves (some or all of which may or may not have flow control), twofeed compressors vacuum compressor 52, feed inlet silencer/filter 34 forfeed 32, feed discharge silencer/aftercooler (40),vacuum discharge silencer 54 and associated piping and fittings. Referring toFIGS. 2 and 3 and Table 1, one embodiment of the present invention is illustrated over one complete VPSA cycle. In Table 1, it will be appreciated that “C” represents valves in the closed position while “O” represents valves in the fully opened or partially opened position, depending on whether the valve is an ON/OFF or flow control valve for manipulating the desired flow. It will be appreciated by those skilled in the art that flow control valves will be used during product pressurization (for example,step 3 inFIG. 3 ). -
TABLE 1 Valve Firing Sequence for twelve step four bed oxygen VPSA Process. Step 1 2 3 4 5 6 7 8 9 10 11 12 Bed 1 AD1 AD2 AD3/PPP AD4 ED PPG BD EV1 PG/EV2 EV3 EU/FP PP/FP Bed 2 EV3 EU/FP PP/FP AD1 AD2 AD3/PPP AD4 ED PPG BD EV1 PG/EV2 Bed 3 BD EV1 PG/EV2 EV3 EU/FP PP/FP AD1 AD2 AD3/PPP AD4 ED PPG Bed 4 AD4 ED PPG BD EV1 PG/EV2 EV3 EU/FP PP/FP AD1 AD2 AD3/PPP Valve No. 1 O C C C C C C C C C O O 2 C O O O C C C C C C C C 3 C O O O C C C C C C C C 4 C C C C O O O C C C C C 5 C C C C O O O C C C C C 6 C C C C C C C O O O C C 7 C C C C C C C O O O C C 8 O C C C C C C C C C O O 9 C C C C C C O C C C C C 10 C C C C C C C O O O C C 11 O C C C C C C C C C O O 12 C C C C C C C C C O C C 13 O C C C C C C C C C C C 14 C O O O C C C C C C C C 15 C C C C O O O C C C C C 16 C C C O C C C C C C C C 17 C C C C O O C C O C O C 18 C O C C C C C O O C C O 19 C C O C O C C C C C O O 20 C O O C C O C O C C C C 21 O O O O C C C C C C C O 22 C C O O O O O C C C C C 23 C C C C C O O O O O C C 24 O C C C C C C C O O O O AD: Adsorption/Product Production ED: Equalization Down PPG: Provide Purge Gas PPP: Provide Product Pressurization Gas BD: Blowdown EV: Evacuation PG: Receive Purge EU: Equalization Up PP: Product Pressurization FP: Feed Pressurization - At the start of
step 1, the pressure in bed 42 (B1) is at the adsorption pressure.Valve 1 is open to allow feed gas into the bottom ofbed 42 and valve 21 is open to allowproduct 50 out of the top ofbed 42. Feed gas is supplied toBed 1 from compressor 38 (C1).Valve 11 is open to allow evacuation of bed 44 (B2) thru compressor 52 (C3) tovacuum discharge silencer 54 to waste 56.Valve 13 opens to allow bed 46 (B3) to blowdown to the atmosphere.Valve 8 is open to allow feed gas into the bottom of bed 48 (B4) andvalve 24 is open to allowproduct 50 out of the top ofbed 48. Feed gas is supplied tobed 48 from compressor 36 (C2). - At the start of
step 2,valve 1 closes andvalve 2 opens to allow feed gas from compressor 36 (C2) into the bottom ofbed 42. Valve 21 remains open to allow product production to continue frombed 42.Valve 11 closes andvalve 3 opens to stop the evacuation ofbed 44 and allow feed gas from compressor 38 (C1) to enter the bottom ofbed 44. Also,valves bed 48 into the top ofbed 44.Valve 13 closes andvalve 14 opens to start the evacuation of bed 46 (B3). - At the start of
step 3,valves 2 and 21 remain open to allowproduct 50 production to continue frombed 42.Valve 3 remains open and allows feed gas fromcompressor 38 to continue to enter the bottom ofbed 44.Valve 22 opens to allow product pressurization gas to enter the top ofbed 44.Valve 20 remains open andvalve 19 opens to allow purge gas to flow frombed 48 tobed 46.Valve 14 remains open to continue the evacuation ofbed 46.Valve 18 closes. - At the start of
step 4,valves 2 and 21 remain open to allow product production to continue frombed 42.Valves bed 44.Valve 14 remains open to continue the evacuation ofbed 46.Valve 16 opens to allowbed 48 to blowdown to the atmosphere. - At the start of
step 5,valves bed 42 into the top ofbed 46.Valve 3 closes andvalve 4 opens to allow feed gas from compressor 36 (C2) into the bottom ofbed 44.Valve 22 remains open to allow product production to continue frombed 44.Valve 13 closes andvalve 5 opens to stop the evacuation ofbed 46 and allow feed gas from compressor 38 (C1) to enter the bottom ofbed 46.Valve 16 closes andvalve 15 opens to start the evacuation ofbed 48. - At the start of
step 6,valve 17 remains open andvalve 20 opens to allow purge gas to flow frombed 42 tobed 48.Valves bed 44.Valve 5 remains open and allows feed gas from compressor 38 (C1) to continue to enter the bottom ofbed 46.Valve 23 opens to allow product pressurization gas to enter the top ofbed 46.Valve 15 remains open to continue the evacuation ofbed 48 while it receives purge gas.Valve 19 closes. - At the start of
step 7,valve 9 opens to allowbed 42 to blowdown to the atmosphere.Valves bed 44.Valves bed 46.Valve 15 remains open to continue the evacuation ofbed 48. - At the start of
step 8,valve 9 closes andvalve 10 opens to start the evacuation ofbed 42.Valves bed 44 into the top ofbed 48.Valve 5 closes andvalve 6 opens to allow feed gas from compressor 36 (C2) into the bottom ofbed 46.Valve 23 remains open to allow product production to continue frombed 46.Valve 15 closes andvalve 7 opens to stop the evacuation ofbed 48 and allow feed gas from compressor 38 (C1) to enter the bottom ofbed 48. - At the start of
step 9,valve 10 remains open to continue the evacuation ofbed 42 while it receives purge gas.Valve 18 remains open andvalve 17 opens to allow purge gas to flow frombed 44 tobed 42.Valves bed 46.Valve 7 remains open and allows feed gas from compressor 38 (C1) to continue to enter the bottom ofbed 48.Valve 24 opens to allow product pressurization gas to enter the top ofbed 48.Valve 20 closes. - At the start of
step 10,valve 10 remains open to continue the evacuation ofbed 42.Valve 12 opens to allowbed 44 to blowdown to the atmosphere.Valves bed 46.Valves bed 48. - At the start of
step 11,valve 10 closes andvalve 1 opens to stop the evacuation ofbed 42 and allow feed gas from compressor 38 (C1) to enter the bottom ofbed 42.Valve 12 closes andvalve 11 opens to start the evacuation ofbed 44.Valves bed 46 into the top ofbed 42.Valve 7 closes andvalve 8 opens to allow feed gas from compressor 36 (C2) into the bottom ofbed 48.Valve 24 remains open to allow product production to continue frombed 48. - At the start of
step 12,valve 1 remains open and allows feed gas from compressor 38 (C1) to continue to enter the bottom ofbed 42. Valve 21 opens to allow product pressurization gas to enter the top ofbed 42.Valve 11 remains open to continue the evacuation ofbed 44 while it receives purge gas.Valve 19 remains open andvalve 18 opens to allow purge gas to flow frombed 46 tobed 44.Valves bed 48.Valve 17 closes. - The embodiment described hereinabove utilizes two compressors to deliver feed gas to the VPSA vessels. In a preferred embodiment, one Roots compressor 38 (C1 or compressor 1) and one centrifugal compressor 36 (C2 or compressor 2) will deliver the total feed flow to an integrated four bed VPSA process. In addition, in the preferred mode of operation for large scale O2 production, radial beds are used in the VPSA process. Additional details of radial bed adsorbers are given by Ackley et al., U.S. Pat. No. 6,506,234 B1.
- Referring to the bed 42 (B1) steps in
FIG. 3 , if two different compressors (e.g., Roots and centrifugal) are used, then in the preferred mode of operation, the Roots compressor is used insteps steps FIGS. 2 and 3 , duringstep 1 of the VPSA cycle, one portion of the total feed (dual feed VPSA process) is delivered via the Roots compressor to bed 42 (B1) while the centrifugal compressor delivers the other portion of the total feed to bed 48 (B4). It is also noted that at any instant, two beds are receiving feed gas simultaneously and a continuous product make exists throughout the VPSA cycle. - Table 2 gives an example of the operating conditions and the VPSA process performance using a nitrogen selective adsorbent in the beds. In the Table, the symbols have the following meaning: TPD=ton (2000 lb) per day of oxygen, kPa=1000 Pa=S.I. unit for pressure (1.0 atm.=101.323 kPa), s=time unit in seconds.
- In addition, the nitrogen equilibrium selective adsorbent in Table 2 is highly exchanged Li—X (>95% Li), as disclosed by Chao et al., U.S. Pat. Nos. 5,413,625 and 4,859,217, both of which are incorporated herein by reference to the extent consistent herewith. Although highly exchanged LiX adsorbent is disclosed in these patents, it is anticipated that layers of adsorbents or mixtures of adsorbents could be used and may preferably be used (e.g., when there is moisture in the air) in each bed of the VPSA process without deviating from the scope of this invention. Representative examples of various adsorbents for use in this invention include but not limited to those disclosed in U.S. Pat. Nos. 6,027,548 and 6,790,260 B2, both of which are incorporated herein by reference to the extent consistent herewith. See also, U.S. Pat. Nos. 6,743,745 B2; 6,506,234 B1; 6,500,234; 6,471,748 B1; and 6,780,806. The adsorbent could be a mixture of adsorbents or a layered adsorbent(s). Preferably, the same adsorbent, whether it is a single adsorbent, mixture of adsorbents or layer of adsorbent(s), is the same in all four beds.
-
TABLE 2 Large scale (>350 TPD) O2 production example (Figures 2-3, operating conditions and performance). Each of the four beds contains Li-X zeolite for N2 removal. The results shown below were obtained from VPSA simulation and pilot plant experiments using dry air containing 0.934% Ar, 78.12% N2 and 20.95% O2. Adsorbent in each Bed: Li-X Feed Composition (N2/O2/Ar): 78.12%/20.95% O2/0.934% High Pressure: 160 kPa Low Pressure: 30 kPa Total Feed: 2.85 × 106 NCFH Amount of O2 Produced: 3.58 × 105 NCFH (355 TPD O2) Oxygen Purity: 90% Overall oxygen Recovery: 60% Bed Size Factor: 350 lb/TPD O2 Temperature 300K - The VPSA process discussed hereinabove is focused on O2 production from air using a four VPSA bed process and system. In alternative embodiments of the present invention, less than four (e.g., three bed) or more than four beds could be used. In such embodiments, one would need to develop the appropriate three bed VPSA cycles or >4 bed VPSA cycles to incorporate the aforementioned features of the present invention. In addition, additional storage tanks may or may not be required in such alternative embodiments to incorporate the features of the invention depending on whether three or >4 beds in the VPSA cycles are employed.
- Moreover, each bed could alternatively include one or several layers of adsorbents, or a mixture of adsorbents. Various kinds of adsorbents could also be used in the VPSA process for O2 production from air. Details of preferred suitable adsorbents and layering of the adsorbents are disclosed in U.S. Pat. Nos. 5,413,625; 4,859,217; 6,027,548; and 6,790,260 B2. In other modes of operation, other adsorbents could be used in the aforementioned VPSA processes of the present invention. For example, 5A, 13X, CaX, and mixed cations zeolites could be used as the N2 selective adsorbent in the VPSA process.
- In the preferred and alternative modes of operation, a pre-purifier section is positioned at the upstream end of each zeolite bed to remove water and carbon dioxide from the feed air. For example and while not to be construed as limiting, a layer of alumina or silica is preferably positioned upstream of each of the adsorbent beds to remove water and carbon dioxide from the feed air prior to passing to the N2 selective adsorbent in the VPSA process.
- The adsorber configuration selected (e.g., radial, axial, structured, etc.) and choice and arrangement of the adsorbents will be determined based on the size of the feed flow, the type of feed source, and VPSA process operating conditions. In an alternative mode of operation for example, axial beds can be used in the VPSA process. It is preferred that all the beds have the same configuration.
- In yet other alternative modes of operation, one compressor (rather than two compressors) could be used to deliver the total feed to the dual inlet VPSA process (e.g., the VPSA processes illustrated in the Figures).
- In some modes of operation, the highest adsorption pressure is in the range of 100 kPa to about 2000 kPa, and the lowest desorption pressure is in the range of 20 kPa to about 100 kPa. In addition, the optimization between achieving high O2 recovery and low power consumption in the VPSA process will determine optimum adsorption and desorption pressures for a given adsorbent. The average purity of the oxygen product is expected to be in the range of 85 percent oxygen to about 95 percent oxygen, corresponding to an expected O2 recovery of about 55-75%. The lowest O2 recovery is expected to correspond to the highest the O2 purity, and vice versa.
- In alternative modes of operation, other processes and cycles could be used. For example,
FIG. 4 shows an alternate schematic of a fourbed system 60 and process using twocompressors total feed 32 to the dual inlet feed VPSA process and twocompressors waste 56 from the VPSA process. In the preferred mode of operation only one vacuum blower 52 (preferably, a Roots type blower) is used to evacuate the waste. In this alternative mode, afirst vacuum blower 52 is used to evacuate the waste (preferably a Roots type blower) followed by a second vacuum blower 53 (preferably a centrifugal type blower).FIG. 5 shows the column cycle for the dual feed inlet four bed VPSA process ofFIG. 4 . In this alternative mode, an additional purge gas, obtained from another bed in the adsorption step (e.g., bed 42 (B1) undergoing AD4 inFIG. 5 while simultaneously supplying purge gas to another bed), is utilized in the VPSA process. In addition, the equalization down step in this alternative mode is overlapped with a countercurrent evacuation to hasten bed depressurization. Also, during the provide purging step (e.g., bed 42 (B1) instep 6 ofFIG. 5 ), the bed is simultaneously undergoing countercurrent evacuation. - Referring to
FIGS. 4 and 5 and Table 3, an alternative embodiment of the present invention is illustrated over one complete VPSA cycle. In Table 3, AD represents Adsorption/Product Production, ED: Equalization Down, PPG: Provide Purge Gas, PPP: Provide Product Pressurization Gas, BD: Blowdown, PG: Receive Purge, EU: equalization up (EU is the same as EQUP), PP: product Pressurization, FP: Feed Pressurization, RC: Roots Compressor, CC: Centrifugal Compressor, RV: Roots Vacuum, CV: Centrifugal Vacuum, EV: Evacuation. As discussed above with reference to Table 1, it will be appreciated that in Table 3, “C” represents valves in the closed position while “O” represents valves in the opened or partially opened position, depending on whether the valve is an ON/OFF or flow control valve for manipulating the desired flow. It will also be appreciated by those skilled in the art that flow control valves will be used during product pressurization (for example,step 3 inFIG. 5 ). -
TABLE 3 Valve Firing Sequence for twelve step four bed oxygen VPSA Process. Step 1 2 3 4 5 6 7 8 9 10 11 12 Bed 1 AD1 AD2 AD3 AD4 ED/ PPG/EV2 EV3 EV4 PG1/EV5 PG2/EV6 EU/FP PP/FP (RC) (CC) (CC)/PPP (CC)/PPG EV1(RV) (RV) (RV) (CV) (CV) (CV) (RC) (RC) Bed 2 PG2/EV6 EU/FP PP/FP AD1 AD2 AD3 AD4 ED/EV1 PPG/EV2 EV3 EV4 PG1/EV5 (CV) (RC) (RC) (RC) (CC) (CC)/PPP (CC)/PPG (RV) (RV) (RV) (CV) (CV) Bed 3 EV3 EV4 PG1/EV5 PG2/EV6 EU/FP PP/FP AD1 AD2 AD3 AD4 ED/EV1 PPG/EV2 (RV) (CV) (CV) (CV) (RC) (RC) (RC) (CC) (CC)/PPP (CC)/PPG (RV) (RV) Bed 4 AD4 ED/EV1 PPG/EV2 EV3 EV4 PG1/EV5 PG2/EV6 EU/FP PP/FP AD1 AD2 AD3 (CC)/PPG (RV) (RV) (RV) (CV) (CV) (CV) (RC) (RC) (RC) (CC) (CC)/PPP Valve 1 2 3 4 5 6 7 8 9 10 11 12 No. 1 O C C C C C C C C C O O 2 C O O O C C C C C C C C 3 C O O O C C C C C C C C 4 C C C C O O O C C C C C 5 C C C C O O O C C C C C 6 C C C C C C C O O O C C 7 C C C C C C C O O O C C 8 O C C C C C C C C C O O 9 C C C C O O O C C C C C 10 C C C C C C C O O O C C 11 O C C C C C C C C C O O 12 C C C C C C C O O O C C 13 O C C C C C C C C C O O 14 C O O O C C C C C C C C 15 C C C C O O O C C C C C 16 C O O O C C C C C C C C 17 C C C O O O C C O O O C 18 O O C C C C O O O C C O 19 C C O O O C C C C O O O 20 O O O C C O O O C C C C 21 O O O O C C C C C C C O 22 C C O O O O O C C C C C 23 C C C C C O O O O O C C 24 O C C C C C C C O O O O - Suitable adsorbents, mixtures and layering of such adsorbents are discussed hereinabove.
-
FIG. 6 shows another alternate schematic of a fourbed system 70 and process in accordance with the present invention using twocompressors FIG. 7 shows a column cycle for the dual feed inlet four bed VPSA process ofFIG. 6 . In the preferred mode of operation (FIGS. 2 and 3 ) described hereinabove, eight waste valves are used to allow for a blowdown step (bypassing the vacuum blower) followed by evacuation steps using the vacuum blower. In the alternative mode of operation shown inFIGS. 6 and 7 , only four waste valves are required. As a result, all of the waste gas is evacuated through the vacuum blower. In the preferred mode shown inFIGS. 2 and 3 , equalization is not overlapped with evacuation as in the alternative mode illustrated inFIGS. 6 and 7 . In addition, purge is provided from co-current depressurization gas in the embodiment shown inFIGS. 2 and 3 while purge is provided from the bed in production in the embodiment shown inFIGS. 6 and 7 . Further, there is an evacuation step after the purge step in the preferred embodiment shown inFIGS. 2 and 3 while there is no evacuation step following the purge in the alternative embodiment disclosed inFIGS. 6 and 7 . - Additional alternative column cycles for the dual feed inlet four bed VPSA process of
FIG. 6 are shown inFIGS. 8 and 9 . In particular, the cycle shown inFIG. 8 uses two product pressurization steps and one equalization step and the cycle shown inFIG. 9 uses eight steps instead of twelve steps. The illustrated column cycles for the dual feed inlet four bed VPSA processes shown inFIGS. 2 , 4 and 6 and the associated column cycles are arranged in the order from most preferred (FIG. 2-3 ) to the least preferred (FIGS. 6 and 9 ). In addition, for the VPSA process ofFIG. 6 and the associated column cycles (FIGS. 7-9 ), the column cycles are arranged in the order of most preferred to least preferred; i.e., the cycle inFIG. 7 is preferred over the cycle shown inFIG. 8 , and the cycle shown inFIG. 8 is preferred over the cycle shown inFIG. 9 . This is because VPSA O2 recovery and O2 productivity are expected to be less using the cycle shown inFIG. 8 than using the cycle illustrated inFIG. 7 and the O2 recovery is expected to be less using the cycle depicted inFIG. 9 relative to using the cycle shown inFIG. 8 . - The column cycles for the dual feed inlet four bed VPSA process of
FIG. 6 illustrated inFIGS. 7-9 are expected to vary in bed size factor and power consumption, with the cycle depicted inFIG. 7 being more efficient than that shown inFIG. 8 and the cycle inFIG. 8 being more efficient than that shown inFIG. 9 . It is thus expected that the BSF and power consumption are highest forFIG. 9 , less forFIG. 8 and even less forFIG. 7 for the schematic inFIG. 6 because the efficiencies for the cycles shown are expected to decrease with increasing figure numbers. - In the VPSA processes and systems discussed hereinabove, it is contemplated to use air as the feed gas to recover oxygen on a large scale basis. Because oxygen can be produced on a large scale (>350 Tons/day) using a single train, one less pump (i.e., one less than using 2 feed and 2 vacuum pumps), lower bed size factor, and avoiding the use of product quality gas for purging, it is expected that there will be about 10-20% improvement in O2 productivity/recovery and 5-10% reduction in capital cost.
- The systems and processes of the present invention are likewise expected to be useful for feed streams other than air such as rare gas (e.g., He, Ar, Ne, Kr) containing feed streams or H2-containing feed streams such as those obtained from steam methane reforming reactions or partial oxidation of hydrocarbons, etc. For example and while not be construed as limiting, a H2 containing feed mixture from synthesis gas, generated from steam methane reforming, is expected to be suitable for use in accordance with the present invention. In such an embodiment, hydrogen could be recovered. It is anticipated that the process and system could be adapted quite readily for the desired product or co-products production. For example, co-production of O2 and N2 or H2 and CO could be readily achieved from air feed and H2 containing feed, respectively. Those skilled in the art will recognize that appropriate modifications to the adsorbent, pre-purifier and process operating conditions will be selected based on the intended application.
- The systems and processes discussed hereinabove have contemplated the use of VPSA processes to produce oxygen from air. In alternative embodiments of the invention, pressure swing adsorption (PSA) could be utilized, wherein, the operating pressures are above ambient pressure, thus a vacuum pump may not be necessary. In still other embodiments, more than one vacuum pump may be desirable.
- It should be appreciated by those skilled in the art that the specific embodiments disclosed above may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
Claims (10)
1-40. (canceled)
41. A vacuum pressure swing adsorption (VPSA) system for separating a feed supply gas containing at least one more strongly adsorbable component and at least one less strongly adsorbable product gas component, the system comprising:
four adsorption beds in a single train configured such that a feed supply gas can be continuously fed into feed input ends of two of the adsorbtion beds;
at least one feed compressor configured to supply the feed supply gas to the adsorption beds; and
a vacuum pump.
42. The vacuum pressure swing adsorption system of claim 41 , wherein the at least one feed compressor comprises two feed compressors.
43. The vacuum pressure swing adsorption system of claim 42 , wherein one feed compressor is a Roots compressor and one feed compressor is a centrifugal compressor.
44. The vacuum pressure swing adsorption system of claim 41 , wherein the vacuum pump is a Roots type blower.
45. The vacuum pressure swing adsorption system of claim 41 , wherein the at least one feed compressor and the vacuum pump can be utilized 100% of the time of operation of the system.
46. The vacuum pressure swing adsorption system of claim 41 , wherein the system is configured to produce at least 350 tons/day O2.
47. The vacuum pressure swing adsorption system of claim 41 , wherein each adsorption bed contains an N2 selective adsorbent.
48. The vacuum pressure swing adsorption system of claim 47 , wherein the adsorbent comprises at least one of: Li—X zeolite, 5A, 13X, CaX, and mixed cations zeolites.
49. The vacuum pressures swing adsorption system of claim 48 , wherein the adsorbent comprises a LiX adsorbent.
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US11/264,278 US7396387B2 (en) | 2005-11-01 | 2005-11-01 | Pressure swing adsorption process for large capacity oxygen production |
US12/132,417 US20080282891A1 (en) | 2005-11-01 | 2008-06-03 | Pressure swing adsorption process for large capacity oxygen production |
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CN (1) | CN101340969B (en) |
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CN110494204A (en) * | 2017-04-11 | 2019-11-22 | 普莱克斯技术有限公司 | Pass through the middle range purity oxygen of production by pressure swing adsorption |
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CA2627888C (en) | 2011-08-16 |
EP1948348A1 (en) | 2008-07-30 |
JP2009513346A (en) | 2009-04-02 |
WO2007053494A1 (en) | 2007-05-10 |
CN101340969B (en) | 2011-09-14 |
CA2627888A1 (en) | 2007-05-10 |
CN101340969A (en) | 2009-01-07 |
BRPI0618155A2 (en) | 2011-08-16 |
US7396387B2 (en) | 2008-07-08 |
US20070095208A1 (en) | 2007-05-03 |
KR20080066973A (en) | 2008-07-17 |
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