Europäisches Patentamt

(19) European Patent Office

Office européen des brevets (11) EP 1 097 902 A1

(12) EUROPEAN PATENT APPLICATION
(43) Date of publication: (51) Int. Cl.7: C01B 3/56
09.05.2001 Bulletin 2001/19

(21) Application number: 00123877.3

(22) Date of filing: 02.11.2000

(84) Designated Contracting States: (72) Inventors:

AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU • Baksh, Mohamed Safdar Allie
MC NL PT SE TR Anherst, New York 14228 (US)
Designated Extension States: • Terbot, Charles Edward
AL LT LV MK RO SI Tonawanda, New York 14150 (US)

(30) Priority: 03.11.1999 US 432215 (74) Representative:

Schorer, Reinhard, Dipl.-Phys. et al
(71) Applicant: Schwan Schwan Schorer
PRAXAIR TECHNOLOGY, INC. Patentanwälte,
Danbury, CT 06810-5113 (US) Elfenstrasse 32
81739 München (DE)

(54) Pressure swing adsorption process for the production of hydrogen

(57) This invention provides a two bed pressure

swing adsorption process for recovering a primary gas-
eous component at a purity of over 99% from a feed gas
comprising the primary component and one or more
impurities. One such process includes: (a) passing the
feed gas through a first adsorption bed to remove one or
more impurities; (b) conducting a pressure swing
adsorption cycle in the first bed; (c) separately passing
effluent gases from the first bed into at least two sepa-
rate tanks for subsequent purging and pressurization of
the beds; (d) storing a gas mixture in the first of the
tanks containing the primary component in a concentra-
tion higher than the concentration of the primary com-
ponent in the gas mixture in the second of the tanks; (e)
refluxing the mixture of the primary component from the
second tank in the first adsorption bed during the regen-
eration steps therein; (f) refluxing the mixture of the pri-
mary component from the first tank in the first
adsorption bed during the regeneration steps therein;
(g) simultaneously and non-concurrently performing
steps (a) to (f) in a second bed; and (h) recovering the
product gas stream.
EP 1 097 902 A1

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 EP 1 097 902 A1

Description

FIELD OF THE INVENTION

5 [0001] This invention relates to a two-bed pressure swing adsorption (PSA) process for purifying impure gas
streams containing more than 50 mole % hydrogen, and more particularly to such a process for the production of high
purity hydrogen from various hydrogen-containing feed mixtures such as synthesis gas. The process provides higher
hydrogen recoveries and requires fewer adsorption beds than previously known PSA processes for hydrogen produc-
tion.
10
BACKGROUND OF THE INVENTION

[0002] The need for high purity (>99.9%) hydrogen is growing in the chemical process industries, e.g., in steel
annealing, silicon manufacturing, hydrogenation of fats and oils, glass making, hydrocracking, methanol production, the
15 production of oxo alcohols, and isomerization processes. This growing demand requires the development of highly effi-
cient separation processes for H2 production from various feed mixtures. In order to obtain highly efficient PSA separa-
tion processes, both the capital and operating costs of the PSA system must be reduced.
[0003] One way of reducing PSA system cost is to decrease the adsorbent inventory and number of beds in the
PSA process. In addition, further improvements may be possible using advanced cycles and adsorbents in the PSA
20 process. However, H2 feed gas contains several contaminants, e.g. a feed stream may contain CO2 (20% to 25%) and
minor amounts of H2O (<0.5%), CH4(<3%), CO(<1%) and N2 (<1%). Such a combination of adsorbates at such widely
varying compositions presents a significant challenge to efficient adsorbent selection, adsorbent configuration in the
adsorber, and the choices of individual adsorbent layers and multiple adsorbed bed systems to obtain an efficient H2-
PSA process.
25 [0004] There are a variety of known processes for producing hydrogen. For example, Figure 1 of the accompanying
drawing shows the steam reforming of natural gas or naptha wherein a feedstock, e.g., a natural gas stream 11, is com-
pressed and fed to a purification unit 12 to remove sulfur compounds. The desulfurized feed is then mixed with super-
heated steam and fed to a reformer 13 to produce primarily H2 and CO. The effluent stream from the reformer is sent
to a heat recovery unit 14, then to a shift converter 15 to obtain additional H2. The effluent from the shift converter goes
30 through a process cooling and recovery unit 16 prior to sending the effluent (e.g., a synthesis gas stream 17 having on
a dry basis a composition of about 74.03% H2, 22.54% CO2, 0.36% CO, 2.16% CH4, and 0.91% N2) to a PSA purifica-
tion system 18 to produce a high purity hydrogen product stream 19.
[0005] Representative prior art PSA processes for hydrogen purification include the following: (1) Wagner, U.S. Pat.
No. 3,430,418, (2) Batta, U.S. Pat. No. 3,564,816, (3) Sircar et al., U.S. Pat. No. 4,077,779, (4) Fuderer et al., U.S. Pat.
35 No., 4,553,981, (5) Fong et al, U.S. Pat. No. 5,152,975, (6) Kapoor et al., U.S. Pat. No. 5,538,706, (7) Baksh et al., U.S.
Pat. No. 5,565,018, and (8) Sircar et al., U.S. Pat. No. 5,753,010.
[0006] Wagner, U.S. Pat. No. 3,430,418 describes an eight-step PSA cycle for hydrogen purification. At least four
beds are used in the process; following the bed-to-bed equalization step each bed undergoes a co-current depressuri-
zation step prior to countercurrent blowdown to recover void space gas for purging of another bed.
40 [0007] Batta, U.S. Pat. No. 3,564,816 describes a twelve-step PSA cycle using at least four adsorbent beds and two
pressure equalization stages for separating hydrogen-containing gas mixtures contaminated with H2O, CO2, CH4 and
CO produced in steam reforming of natural gas. In the Batta process, after the first bed-to-bed equalization step, a co-
current depressurization step is used to recover void space gas for purging of another bed, then a second bed-to-bed
equalization step is used prior to the countercurrent blowdown step in the PSA cycle.
45 [0008] Scharpf et al., U.S. Pat. No. 5,294,247 discloses a vacuum PSA process for recovering hydrogen from dilute
refinery off gases, preferably containing less than 60% hydrogen. The patent discloses the use of six adsorbent beds.
[0009] Baksh et al., U.S. Pat. No. 5,565,018 discloses a 12 bed PSA process using external gas storage tanks to
allow gases of increasing purity to used during repressurization.
[0010] Sircar et al., U.S. Pat. No. 5,753,010 discloses a PSA hydrogen recovery system where a portion of the
50 hydrogen is recovered from the PSA depressurization and recycled to the PSA system.
[0011] Baksh, EP Application No. 00 117 437.4 (IG-20731-EP),for Pressure Swing Adsorption Process for the Pro-
duction of Hydrogen, filed August 11,2000 discloses a pressure swing adsorption process for purifying an impure gas
stream by passing it through an adsorbent bed containing an alumina layer for adsorption of H2O, an activated carbon
layer for adsorption of CH4, CO2, and CO, and a layer containing the zeolite for adsorption of nitrogen from the gas
55 stream. The pressure swing adsorption process provided in the Baksh application is a 4 bed system employing a 12
step process (see inter alia pages 13-16). The invention described in the present application differs in several important
respects from the process disclosed in the Baksh application. These differences include, but are not limited to, the fact
that the present invention uses a 2 bed system which allows for a reduction in the bed size factor; and in several embod-

2
 EP 1 097 902 A1

iments, the present invention uses storage tanks (separate from the adsorption beds) which allow for the use of gas of
increasing H2 purity during refluxing.
[0012] It is among the objects of the present invention to provide an improved PSA process for the production of
hydrogen from an impure gas stream containing more than 50 mole % hydrogen, which provides increased hydrogen
5 recovery and reduced PSA adsorbent requirements with consequent lower capital and operating costs. Other objects
and advantages of the invention will be apparent from the following description taken in connection with the accompa-
nying drawing.

SUMMARY OF THE INVENTION

10
[0013] This invention provides a two bed pressure swing adsorption process (as distinguished from the four or more
bed processes utilized in prior art designs) for recovering a primary component (e.g. hydrogen) at a purity of over 99%
from a feed gas, e.g., synthesis gas, comprising the primary component and one or more impurities. The process is
capable of producing high purity (>99.99%) hydrogen at high recoveries with a significant reduction in the total cycle
15 time versus prior art PSA processes used in H2 production.
[0014] This invention includes a two bed pressure swing adsorption process for recovering a primary component at
a purity of over 99% from a feed gas comprising the primary component and one or more impurities, wherein the proc-
ess comprises: (a) passing the feed gas through a first adsorption bed to remove one or more impurities; (b) conducting
a pressure swing adsorption cycle in the first bed; (c) separately passing effluent gases from the first bed into at least
20 two separate tanks for subsequent purging and pressurization of the beds; (d) storing a gas mixture in the first of the
tanks containing the primary component in a concentration higher than the concentration of the primary component in
the gas mixture in the second of the tanks; (e) refluxing the mixture of the primary component from the second tank in
the first adsorption bed during the regeneration steps therein; (f) refluxing the mixture of the primary component from
the first tank in the first adsorption bed during the regeneration steps therein; (g) simultaneously and non-concurrently
25 performing steps (a) to (f) in a second bed; and (h) recovering the product gas stream.
[0015] In accordance therewith, decreased adsorbed inventories are required (without decreasing the H2 product
purities and recoveries), greater flexibility in controlling the duration and the pressures and end points of each step are
achieved, and significant reductions (>45%) in the amount of the adsorbent (e.g. zeolite) in the purification zone of each
adsorbent bed are obtained.
30 [0016] The process of the present invention can handle a continuous feed and utilize several overlapping steps in
the PSA cycle. Generally the feed gas will contain H2, CO, CO2, CH4, N2, and H2O, and H2 as the primary component.
[0017] Preferably, these processes utilize storage tanks to collect gas from certain steps in the PSA cycle, and then
utilize the gas at a later time for purging and pressurization. The gases collected in the storage tanks are used in the
order of increasing H2 purity for refluxing of a bed that is undergoing regeneration.
35 [0018] In one variation, the first and second beds each comprise an alumina layer at the feed end of the bed, a zeo-
lite layer at the product end of the bed, and a carbon layer between the alumina layer and the zeolite layer. Suitable zeo-
lites include, but are not limited to, CaX zeolite and VSA6 zeolite.
[0019] Suitable zeolites include, but are not limited to, CaX, VSA6, 5A, Li-X, 13X, and LiA. CaX zeolites, most desir-
ably CaX (2.0), are particularly preferred. CaX (2.0) is a zeolite of the faujasite type exchanged at least 90% with cal-
40 cium and having a SiO2/Al2O3 molar ratio of 2.0. CaX (2.0) processes more feed gas per unit weight of adsorbent at a
given P/F (purge to feed) ratio than other N2-selective adsorbents. Other useful Ca-exchanged zeolites may be pre-
pared from naturally occurring crystalline zeolite molecular sieves such as chabazite, erionite and faujasite. Alterna-
tively, the CaX zeolites useful herein include mixed cation (e.g. Ca2+ and Na+) zeolites such as VSA-6 developed by
UOP of Des Plaines, IL. with 74% Ca2+ and a SiO2/Al2O3 ratio of 2.3. LIA and LIX zeolites having SiO2/Al2O3 ratios
45 within the range of 2.0-2.5 are also useful in the practice of the present invention. Other adsorbents useful herein
include mixed lithium/alkaline earth metal Type A and Type X zeolites having SiO2/Al2O3 molar ratios in the range of
2.0-2.5 such as CaLiX (2.3), having calcium contents of 15-30% (see Chao et al, U.S. Pat. Nos. 5,413,625; 5,174,979;
5,698,013; 5,454,857 and 4,859,217). The zeolite disclosures of the foregoing patents are incorporated by reference
herein.
50
BRIEF DESCRIPTION OF THE DRAWING

[0020] In the accompanying drawing:

55 Figure 1 is a schematic illustration of the prior art technique for the production of hydrogen by the steam reforming
of natural gas.
Figure 2 is a schematic drawing of a PSA adsorption bed utilized in the practice of the present invention.
Figure 3 is a schematic drawing of a two bed PSA system for carrying out the PSA process of the invention.

3
 EP 1 097 902 A1

Figure 4 is a schematic drawing of the 12 step PSA cycle utilizing product pressurization in the 2 bed PSA system
of Figure 3.
Figure 5 is a graphic depiction of the bed pressure profile during one complete cycle in the two-bed PSA system
of Figure 3, utilizing the 12 step cycle illustrated in Figure 4.
5 Figure 6 is a schematic drawing of an alternative two bed PSA system for carrying out the process of the invention.
Figure 7 is a schematic drawing of a 12 step PSA cycle, without product pressurization, in the two bed PSA system
of Figure 6.
Figure 8 is a schematic drawing of a further alternative two bed PSA system, in which the purge tank and equalized
tank are combined in a storage tank (ST) for carrying out the PSA process of the invention.
10 Figure 9 is a schematic drawing of a 10 step PSA cycle utilizing the two bed system of Figure 8, wherein the resid-
ual gas after purging is used for the first equalization.
Figure 10 is a schematic drawing of an 8 step PSA cycle utilizing the two bed system of Figure 8.
Figure 11 is a schematic drawing of a four bed adsorbent bed control system for carrying out a PSA process.
Figure 12 is a schematic drawing of a 12 step PSA cycle utilizing the four bed control PSA system of Figure 11.
15 Figure 13 is a graphic depiction of the bed pressure profile during one complete cycle in the four-bed PSA system
of Figure 11, utilizing the 12 step PSA cycle illustrated in Figure 12.
Figure 14 is a graphic comparison of the hydrogen purities and recoveries obtained with the 8-step 2-bed, 10-step
2-bed, 12-step 2-bed, and 12-step 4-bed PSA processes described.

20 DETAILED DESCRIPTION OF THE INVENTION

[0021] As pointed out above, the present invention includes novel two-bed PSA processes that are capable of han-
dling continuous gas feeds and produce high purity (>99.99%) hydrogen at high recoveries with a significant reduction
in the total cycle time versus prior PSA processes used in H2 production. The two bed PSA cycles of this invention also
25 provide more flexibility in controlling the duration and the pressure end points of the PSA steps versus four bed prior art
processes, and thus require less bed synchronization. Further, the two bed process of the invention uses product gas
of increasing purity for refluxing during bed regeneration, and requires a reduced number of valves and piping, resulting
in a less complex, less costly process with increased portability. In addition, because of the smaller void volume, due to
the reduction in bed size factor, less hydrogen is lost during the regeneration of the bed and higher H2 recoveries result.
30 These processes can handle a continuous feed and utilize several overlapping steps in the PSA cycle. For example, the
two bed PSA cycles may utilize feed overlapping with equalization steps, and feed overlapping with product pressuriza-
tion steps to produce high purity hydrogen from a feed mixture such as synthesis gas. Preferably, these processes uti-
lize storage tanks to collect gas from certain steps in the PSA cycle, and then utilize the gas at a later time for purging
and pressurization. The gases collected in the storage tanks are used in the order of increasing H2 purity for refluxing
35 of a bed that is undergoing regeneration.

A. The Embodiment of Figure 3-5

[0022] This invention will initially be described with reference to the two bed PSA system shown in Figure 3, the 12
40 steps PSA cycle shown in Figure 4, and the bed pressure profile depicted in Figure 5. Referring to those figures, the
following 12 step cycle is illustrated

Step 1 (AD1): Bed 1 (B1) is in the first adsorption step (AD1) at 11.72 bars, while bed 2 (B2) is undergoing coun-
tercurrent blowdown (BD).
45 Step 2 (AD2): Bed 1 is in the second adsorption step (AD2), and at the same time, bed 2 is undergoing the purging
step. The gas used for purging comes from the purge tank (PGT) in Figure 3.
Step 3 (AD3): Bed 1 is in the third adsorption step (AD3), and at the same time, bed 2 is undergoing the first pres-
surization step, i.e., bed-to-tank equalization (TEQ). The gas used for the first pressurization comes from the equal-
ization tank (ET) in Figure 3.
50 Step 4 (EQ1): Bed 1 is undergoing the first equalization falling step (EQ1), while bed 2 receives gas from bed 1 and
is undergoing the second equalization rising step (EQU). In addition, bed 2 is also receiving feed gas during the
second equalization rising step.
Step 5 (EQ2): Bed 1 is undergoing the second equalization falling step (EQ2). The gas recovered in this step is col-
lected in the equalization tank (ET). At the same time, bed 2 is undergoing both feed pressurization (FP) and prod-
55 uct pressurization (PP). The gas for product pressurization comes from the product tank (PT) in Figure 3. The
product pressurization provides additional refluxing gas beyond that produced using the purging and equalization
rising steps. The pressurization also improves mass transfer in the purification zone to provide higher hydrogen
purity.

4
 EP 1 097 902 A1

Step 6 (PPG): Bed 1 is undergoing a cocurrent depressurization step to provide purge gas (PPG). The gas recov-
ered during this step is stored in the purge tank (PGT), and later used in the purging step of the PSA cycle. At the
same time, bed 2 continues to undergo feed pressurization, and starts producing product if the desired adsorption
pressure is achieved prior to initializing the next step.
5 Step 7 (BD): Bed 1 (B1) is undergoing countercurrent blowdown (BD), while bed 2 (B2) is in the first adsorption step
(AD1) at the adsorption pressure (11.72 bars).
Step 8 (PG): Bed 1 is undergoing the purging step, while bed 2 is in the second adsorption step (AD2). The gas
used for purging comes from the purge tank (PGT) in Figure 3.
Step 9 (TEQ): Bed 1 is undergoing the first pressurization step, i.e., bed-to-tank equalization (TEQ), while bed 2 is
10 in the third adsorption step (AD3). The gas used for the first pressurization comes from the equalization tank (ET)
in Figure 3.
Step 10 (EQU & PP): Bed 1 receives gas from bed 2 and is undergoing the second equalization rising step (EQU).
In addition, bed 1 is also undergoing feed pressurization (FP) during the second equalization rising step. Simulta-
neously, bed 2 is undergoing the first equalization falling step (EQ1).
15 Step 11 (PP and FP): Bed 1 (B1) is undergoing feed pressurization (FP) and product pressurization (PP) simulta-
neously. The gas for product pressurization comes from the product tank (PT) in Figure 3. During this interval, bed
2 is undergoing the second equalization falling step (EQ2). The gas recovered during the second equalization fall-
ing step is collected in the equalization tank (ET).
Step 12 (FP and AD): Bed 1 continues to undergo feed pressurization, and starts producing product if the desired
20 adsorption pressure is achieved prior to initializing the next step. During this same time interval, bed 2 is undergo-
ing the cocurrent depressurization step to provide purge gas (PPG). The gas recovered in the cocurrent depressu-
rization step is stored in the purge tank (PGT), and later used in the purging step of the PSA cycle.

[0023] A summary of the preceding twelve steps is given in Tables 1 and 2 below. In particular, Table 1 summarizes
25 the valve sequence over one complete PSA cycle for the two bed system shown in Figure 3, and Table 2 gives the
respective time intervals and the corresponding status of each bed during one complete PSA cycle. Note from Tables
1 and 2 that the two beds operate in parallel, and that the two bed PSA process handles a continuous feed by utilizing
overlapping steps in the PSA cycle.

30
Table 1
Two Bed H2 PSA Valve Switching (O = OPENED, C = CLOSED)
Step 1 2 3 4 5 6 7 8 9 10 11 12
35 Bed 1 AD1 AD2 AD3 EQ1 EQ2 PPG BD PG TEQ EQU & PP & FP FP &
(B1) FP AD
Bed 2 BD PG TEQ EQU & PP & FP & AD1 AD2 AD3 EQ1 EQ2 PPG
(B2) FP FP AD
40 Valve
No.
1 O O O C C C C C C O O O
2 C C C O O O O O O C C C
45
3 C C C C C C O O C C C C
4 O O C C C C C C C C C C
5 O O C C C C O O C C C C

50
6 C C C O O O C O O O C C
7 C O O O C C C C C O O O
8 O O O C C C C C C C C O

55
9 C C C C C O O O O C C C
10 C O C C C O C O C C C O

5
 EP 1 097 902 A1

Table 1 (continued)
Two Bed H2 PSA Valve Switching (O = OPENED, C = CLOSED)
Step 1 2 3 4 5 6 7 8 9 10 11 12
5 Bed 1 AD1 AD2 AD3 EQ1 EQ2 PPG BD PG TEQ EQU & PP & FP FP &
(B1) FP AD
Bed 2 BD PG TEQ EQU & PP & FP & AD1 AD2 AD3 EQ1 EQ2 PPG
(B2) FP FP AD
10 Valve
No.
11 C C O C O C C C O C O C
12 C C C C C C C C C C O C
15
13 C C C C O C C C C C C C

20
Table 2
Two Bed Time Interval and Step Sequence
Step Number Time Interval BED #1 BED #2
25 1 0-40 AD1 BD
2 40-100 AD2 PG
3 100-120 AD3 TEQ
4 120-133 EQ1 EQU & FP
30
5 133-148 EQ2 PP & FP
6 148-168 PPG FP & FP
7 168-208 BD AD1
35 8 208-268 PG AD2
9 268-288 TEQ AD3
10 288-301 EQU & FP EQ1
11 301-316 PP & FP EQ2
40
12 316-336 FE & AD PPG
AD1 = First Adsorption Step
AD2 = Second Adsorption Step
AD3 = Third Adsorption Step
45 EQ1 = First Equalization Down
EQ2 = Second Equalization Down
PPG = Provide Purge Gas Using Purge Tank (PGT)
BD = Blowdown
PG = Purge
50 TEQ = First Equalization Up Using Tank (ET)
EQU = Second Equalization Up
PP = Product Pressurization Using Product Tank (PT)
FP2 = Feed Pressurization
AD = Adsorption
55

[0024] The twelve step PSA cycle described above is illustrative only and is given to demonstrate the superior per-
formance of the two bed PSA process of the present invention. Other PSA cycles may also be used to achieve the supe-

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 EP 1 097 902 A1

rior performance obtained in accordance with the invention without deviating from its scope.

1. Use of VSA 6 Zeolite Adsorbent in the 2 Bed PSA Process of Figures 3-5

5 [0025] Table 3 below discloses the operating conditions and PSA process performance using the VSA 6 zeolite in
the top layer of each of the adsorbent beds B1 to B2 in the system illustrated in Figure 3, and carrying out the process
in the manner set forth in Tables 1 and 2 above and illustrated in Figures 4 and 5. The symbols in Table 3 have the fol-
lowing meanings: TPD = ton (2000 lb) per day of hydrogen, kPa = 1000 Pa = S.I. unit for pressure (1.0 atm. = 1.01325
bars = 101.325 kPa), and s = time in seconds.
10

Table 3
VSA6 Performance in the Process of Figures 3-5*

15
Cycle time(s) 336
Adsorbent in first layer of Bed Alumina
Amount of alumina (lb/TPD H2) 578
Adsorbent in second layer of bed activated carbon
20
Amount of activated carbon (lb/TPD H2) 2862
Adsorbent in third layer of bed VSA6 zeolite
Amount of VSA6 zeolite (lb/TPD H2) 1574

25 High Pressure 1.171 x 103 kPa

Low Pressure 1.327 x 102 kPa
Feed Rate 227.6 SCFH
H2 Purity 99.991%
30
H2 Recovery 77.81%
Total Bed Size Factor (lb/TPD H2) 5014
Feed Temperature 102°F

35 Bed Length 111.25 inches

* The results shown in Table 3 were obtained from pilot plant data
using a feed mixture, on a dry basis, of: 74.45% H2, 22.20% CO2,
0.38% CO, 2.12% CH4 and 0.85% N2.

40
B. The Embodiment of Figures 6-7

[0026] Figure 6 shows an alternative two bed PSA system for use with the PSA cycle depicted in Figure 7. The key
differences between this process and the PSA process described in Figures 3-5 are: (1) the absence of the product
45 pressurization step in the cycle, and (2) the absence of conduits connecting the beds to the product tank (PT). The
process of Figures 6 and 7 gives higher H2 recovery and lower H2 purity.

C. The Embodiments of Figures 8-10

50 [0027] Figure 8 shows a modified two bed PSA system for use with the ten step PSA cycle depicted in Figure 9.
The key differences between this process and the PSA process described in Figures 3-5 are: (1) the absence of the
product pressurization step in the cycle; (2) the absence of conduits connecting the beds to the product tank (PT); and
(3) the presence of a single storage tank (ST) in place of the purge tank (PGT) and equalization tank (ET) shown in Fig-
ure 3. In addition, Figure 10 shows an eight step PSA cycle that could be implemented using the PSA process of Figure
55 8.

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 EP 1 097 902 A1

1. Use of VSA6 Adsorbent in the 10-Step 2-Bed PSA Process of Figures 8-9

[0028] Table 4 below discloses the operating conditions and performance of the two bed PSA process of Figure 8
utilizing a VSA6 zeolite in the third (top) layer of each of the adsorbent beds B1 to B2, following the PSA cycle of Figure
5 9.

Table 4
VSA6 Performance in Process of Figures 8-9*
10
Cycle time(s) 360
Adsorbent in first layer of Bed Alumina
Amount of alumina (lb/TPD H2) 520.2
15 Adsorbent in second layer of bed activated carbon
Amount of activated carbon (lb/TPD H2) 2575.2
Adsorbent in third layer of bed VSA6 zeolite
Amount of VSA6 zeolite (lb/TPD H2) 1416.6
20
High Pressure 1.171 x 103 kPa
Low Pressure 1.327 x 102 kPa
Feed Rate 248.6 SCFH
25 H2 Purity 99.9964%
H2 Recovery 76.3%
Total Bed Size Factor (lb/TPD H2) 4,512.00
Feed Temperature 84°F
30
Bed Length 111.25 inches

* The results shown correspond to pilot plant data using a feed

mixture on a dry basis: 75.02% H2, 21.81% CO2, 0.36% CO,
2.06% CH4 and 0.75% N2.
35

2. Use of VSA6 Adsorbent in the 2 Bed PSA Process of Figures 8 and 10

[0029] Table 5 below discloses the operating conditions and performance of the two bed PSA process of Figure 8
40 utilizing VSA6 zeolite in the third (top) layer of each of the adsorbent beds B1 to B2 and following the PSA cycle of Fig-
ure 10.

45

50

55

8
 EP 1 097 902 A1

Table 5
Cycle time(s) 360
5
Adsorbent in first layer of Bed Alumina
Amount of alumina (lb/TPD H2) 642.5
Adsorbent in second layer of bed activated carbon

10 Amount of activated carbon (lb/TPD H2) 3180.9

Adsorbent in third layer of bed VSA6 zeolite
Amount of VSA6 zeolite (lb/TPD H2) 1749.8
High Pressure 1.171 x 103 kPa
15
Low Pressure 1.327 x 102 kPa
Feed Rate 231.4 SCFH
H2 Purity 99.97%
20 H2 Recovery 66.7%
Total Bed Size Factor (lb/TPD H2) 5,573.2
Feed Temperature 75° F
Bed Length 111.25 inches
25
* The results shown above correspond to pilot plant data using a
feed mixture on a dry basis: 75.02% H2, 21.81% CO2, 0.36% CO,
2.06% CH4 and 0.75% N2.

30 [0030] A summary of the preceding twelve steps is given in Tables 6 and 7 below. In particular, Table 6 summarizes
the valve sequence over one complete cycle for the four bed PSA system shown in Figure 11, and Table 7 gives the
respective time intervals and the corresponding status of each bed during one complete PSA cycle. Note from Tables
6 and 7 that the four beds operate in parallel, and during  of the total cycle time one of the beds is in the adsorption
step, while the other beds are either undergoing pressure equalization, purge, blowdown, or product pressurization.
35

Table 6
Four Bed H2 PSA Valve Switching (O = OPENED, C = CLOSED)

40
Step 1 2 3 4 5 6 7 8 9 10 11 12
Bed 1 AD1 AD2 AD3 EQ1DN PPG EQ2DN BD PG EQ1UP EQ2UP PP1 PP2
(BD1)
Bed 2 BD PG EQ1UP EQ2UP PP1 PP2 AD1 AD2 AD3 EQ1DN PPG EQ2DN
(BD2)
45
Bed 3 EQ1DN PPG EQ2DN BD PG EQ1UP EQ2UP PP1 PP2 AD1 AD2 AD3
(BD3)
Bed 4 EQ2UP PP1 PP2 AD1 AD2 AD3 EQ1DN PPG EQ2DN BD PG EQ1UP
(BD4)
50
Valve
No.
1 O O O C C C C C C C C C

55 2 C C C C C C O O O C C C
3 C C C C C C C C C O O O
4 C C C O O O C C C C C C

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Table 6 (continued)
Four Bed H2 PSA Valve Switching (O = OPENED, C = CLOSED)
Step 1 2 3 4 5 6 7 8 9 10 11 12
5 Bed 1 AD1 AD2 AD3 EQ1DN PPG EQ2DN BD PG EQ1UP EQ2UP PP1 PP2
(BD1)
Bed 2 BD PG EQ1UP EQ2UP PP1 PP2 AD1 AD2 AD3 EQ1DN PPG EQ2DN
(BD2)
10 Bed 3 EQ1DN PPG EQ2DN BD PG EQ1UP EQ2UP PP1 PP2 AD1 AD2 AD3
(BD3)
Bed 4 EQ2UP PP1 PP2 AD1 AD2 AD3 EQ1DN PPG EQ2DN BD PG EQ1UP
(BD4)
15 Valve
No.
5 O O C O O C O O C O O C
6 C C C C C C O O C C C C
20 7 O O C C C C C C C C C C
8 C C C O O C C C C C C C

9 C C C C C C C C C O O C
25
10 C O O C O O C O O C O O
11 O O O C C C C C C C C C
12 C C C C C C O O O C C C
30
13 C C C C C C C C C O O O
14 C C C O O O C C C C C C
15 C C C C O O C O O C C C

35
16 C O O C C C C C C C O O
17 C O O C O O C C C C C C
18 C C C C C C C O O C O O
19 C C C O C C C C C O O O
40
20 C C C O O O C C C O C C
21 O C C C C C O O O C C C
22 O O O C C C O C C C C C

45

Table 7
50 Time Interval and Step Sequence of the PSA Cycle
Step Number Time Interval BED #1 BED #2 BED #3 BED #4
1 0-40 AD1 BD EQ1DN EQ2UP
2 40-125 AD2/PP 1 PG PPG PP1
55
3 125-150 AD3/PP 2 EQ1UP EQ2DN PP2
4 150-190 EQ1DN EQ2UP BD AD1

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Table 7 (continued)
Time Interval and Step Sequence of the PSA Cycle
Step Number Time Interval BED #1 BED #2 BED #3 BED #4
5 5 190-275 PPG PP1 PG AD2/PP1
6 270-300 EQ2DN PP2 EQ1UP AD3/PP2
7 300-340 BD AD1 EQ2UP EQ1DN
8 340-425 PG AD2/PP1 PP1 PPG
10
9 425-450 EQ1UP AD3/PP2 PP2 EQ2DN
10 450-490 EQ2UP EQ1DN AD1 BD
11 490-575 PP1 PPG AD2/PP1 PG
15 12 575-600 PP2 EQ2DN AD3/PP2 EQ1UP
AD1 = First Adsorption Step
AD2/PP1 = Second Adsorption Step/First product pressurization
AD3/PP2 = Third Adsorption Step/Second product pressurization
20 EQ1DN = First Equalization Down
PPG = Provide Purge Gas
EQ2DN = Second Equalization Down
BD = Blowdown
PG = Purge
25 EQ1UP = First Equalization Up
EQ2UP = Second Equalization Up
PP1 = First Product Pressurization
PP2 = Second Product Pressurization

30 D. The Embodiment of Figures 11-13 (Control)

1. Use of VSA6 Adsorbent in the 4 Bed PSA Process of Figures 11-13 (Control)

[0031] Table 8 below discloses the operating conditions and performance of a four bed PSA process of Figures 11-
35 13 using VSA6 zeolite in the third (top) layer of each of the adsorbent bends B1 to B4. The results shown below corre-
spond to pilot plant data using a feed mixture on a dry basis: 75.02% H2, 21.81% CO2, 0.36% CO, 2.06% CH4 and
0.75% N2.

40 Table 8
Cycle time(s) 600
Adsorbent in first layer of Bed Alumina
Amount of alumina (lb/TPD H2) 810.9
45
Adsorbent in second layer of bed activated carbon
Amount of activated carbon (lb/TPD H2) 5733.6
Adsorbent in third layer of bed VSA6 zeolite

50 Amount of VSA6 zeolite (lb/TPD H2) 3842.3

High Pressure 1.171 x 103 kPa
Low Pressure 1.327 x 102 kPa
Feed Rate 227.2 SCFH
55
H2 Purity 99.999905%
H2 Recovery 77.5%

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Table 8 (continued)
Total Bed Size Factor (lb/TPD H2) 10,386.8
Feed Temperature 78° F
5 Bed Length 111.25 inches

[0032] Figure 14 compares the aforementioned two bed PSA processes using the eight steps (Figures 8 and 10),
ten steps (Figures 8 and 9) and twelve steps (Figures 3-5) with the four bed PSA process summarized above. The
10 upper drawing of Figure 14 compares the H2 purity and recovery using VSA6 zeolite; whereas, the lower diagram of
Figure 14 shows the total bed size factor (TBSF, lb/TPDH2) obtained using each of the aforementioned PSA processes.
In addition, Table 9 gives a summary of the novel/differentiating features of PSA processes depicted in Figure 14.
[0033] Table 9 below compares the operating conditions and performance of PSA processes using eight step, ten
step, and twelve step PSA cycles and VSA6 zeolite (PH = 170 psia).
15

Table 9
Process Varia- 8 Step/2 Bed 10 Step/2 Bed 12 Step/2 Bed 12 Step/2 Bed 12 Step/4 Bed
ble Without Prod. With Prod.
20 Press. Press.
H2 Purity 99.97% 99.996% 99.9% 99.991% 99.9999%
H2 Recovery 66.7% 76.3% 80% 77.81% 77.5%
Total Bed Size 5573.2 4512 4876 5014 10,387
25
Factor (lb/TPD
H2)
Number of Beds 2 2 2 2 4
Number of Tanks 2 (ST & PT) 2 (ST & PT) 2 (ET & PGT) 3(ET,PGT&PT) 1 (PT)
30
PSA Process Fig. 8 Fig. 8 Fig. 6 Fig. 3 Fig. 11
PSA Cycle Fig. 10 Fig. 9 Fig. 7 Fig. 4 Fig. 12
Pressure Profile --- --- --- Fig. 5 Fig. 13
35 Table Number 5 4 --- 3 8
Product Press. No No No Yes Yes
Preference Order 5 3 2 1 4
Preference 1 = Most Preferred Process
40
Product Press. = Product Pressurization
ET = Equalization Tank
PGT = Purge Tank
PT = Product Tank
ST = Storage Tank, i.e., PGT & ET combined as a single tank
45

As shown above in Table 9, the 2 bed PSA process of the present invention has the advantage of a lower bed size factor
than 4 bed PSA processes.
[0034] Although the foregoing PSA processes have been discussed in relation to H2 production, the key features of
50 this invention may be extended to other separation processes, e.g., CO2 production from synthesis gas or other sources
containing CO2 in the feed, or in other PSA processes for the co-production of H2 and CO.
[0035] In addition, the zeolite layer/zone of each adsorbent bed may be replaced with multiple layers of different
adsorbents. For example, the homogeneous zeolite layer may be substituted by a composite adsorbent layer containing
different adsorbent materials positioned in separate zones and employing temperature conditions favoring adsorption
55 performance of the particular adsorbent materials under applicable processing conditions in each zone.
[0036] It will be understood that these and other changes may be made in the preferred parameters of the PSA
process hereof without departing from the invention. Accordingly, it is intended that the scope of this invention should
be determined from the claims appended hereto.

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Claims

1. A two bed pressure swing adsorption process for recovering a primary gaseous component at a purity of over 99%
from a feed gas comprising the primary component and one or more impurities, wherein the process comprises:
5
a. passing the feed gas through a first adsorption bed to remove one or more impurities;
b. conducting a pressure swing adsorption cycle in the first bed;
c. separately passing effluent gases from the first bed into at least two separate tanks for subsequent purging
and pressurization of the beds;
10 d. storing a gas mixture in the first of the tanks containing the primary component in a concentration higher
than the concentration of the primary component in the gas mixture in the second of the tanks;
e. refluxing the mixture of the primary component from the second tank in the first adsorption bed during the
regeneration steps therein;
f. refluxing the mixture of the primary component from the first tank in the first adsorption bed during the regen-
15 eration steps therein;
g. simultaneously and non-concurrently performing steps (a) to (f) in a second bed; and
h. recovering the product gas stream.

2. A two bed pressure swing adsorption process for recovering hydrogen at a purity of over 99% from a feed gas com-
20 prising hydrogen and one or more impurities, wherein the process comprises:

a. passing the feed gas through a first adsorption bed to remove one or more impurities;
b. conducting a pressure swing adsorption cycle in the first bed;
c. refluxing a gas mixture containing increasing purities of hydrogen from the second tank in the adsorption
25 beds during the regeneration steps therein;
d. refluxing a gas mixture containing increasing purities of hydrogen from the first tank in the adsorption beds
during the regeneration steps therein;
e. simultaneously and non-concurrently performing steps (a) to (d) in a second adsorption bed; and
f. recovering hydrogen from the first and second beds, having a purity of over 99%.
30
3. The process of claims 1 or 2, wherein the feed gas contains H2, CO, CO2, CH4, N2, and H2O, and wherein H2 is
the primary component.

4. The process of claims 1 or 2, wherein the feed gas is continuously fed into the pressure swing adsorption system.
35
5. The process of claims 1 or 2, wherein the time for one full cycle is between about 100 and about 400 seconds.

6. The process of claims 1 or 2, wherein at least one of the steps in the cycle involves the transfer of gas from the bed
being depressurized to the bed being pressurized.
40
7. The process of claims 1 or 2, wherein the first and second beds each comprises an alumina layer at the feed end
of the bed, a zeolite layer at the product end of the bed, and a carbon layer between the alumina layer and the zeo-
lite layer.

45 8. The process of claim 2, wherein effluent gases from each of the beds are collected in at least 2 different tanks
resulting in at least 1 tank having a hydrogen concentration at least 10% higher than the hydrogen concentration of
at least 1 of the other storage tanks.

9. The process of claim 1 or 2, wherein the first and second beds each comprises an alumina layer at the feed end of
50 the bed, a zeolite layer at the product end of the bed, and a carbon layer between the alumina layer and the zeolite
layer.

10. The process of claims 1 or 2, wherein the zeolite layer comprises a CaX zeolite or a VSA6 zeolite.

55

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