USOO849 1704B2

(12) United States Patent (10) Patent No.: US 8.491,704 B2

Baksh et al. (45) Date of Patent: Jul. 23, 2013

(54) SIX BED PRESSURE SWING ADSORPTION 3.35 A g 3. Elst 1

OShi et al.
PROCESS OPERATING IN NORMAL AND 4,371.380 A 2, 1983 Benkmann
TURNDOWN MODES 4,381,189 A 4, 1983 Fuderer
4,402.7 12 A 9, 1983 Benkmann ........................ 95/98
(75) Inventors: Mohamed S. A. Baksh, Wheatfield, NY 4,468,237 A 8, 1984 Fuderer
4.475,929 A 10, 1984 Fuderer
(US); Marian Simo, Kenmore, NY (US) 4.482,361. A 1 1/1984 Whysall
4,499,208 A 2, 1985. Fuld
(73) Assignee: Praxair Technology, Inc., Danbury, CT 4,512,780 A 4, 1985 E.
(US) 4,553,981. A 1 1/1985 Fuderer
4,640,694. A 2/1987 Leitgeb et al.
(*) Notice: Subject to any disclaimer, the term of this 1959 A
W-1 -
3. 3. R tal ea.

past is: c.listed

.S.C. 154(b) by ayS.
under 35 4,726,816 A
4,732,578 A
2/1988 Fuderer
3/1988 Benkmann
1 4,761,165 A 8, 1988 Stöcker et al.
(21) Appl. No.: 13/004,706 (Continued)
(22) Filed: Jan. 11, 2011 FOREIGN PATENT DOCUMENTS
(65) Prior Publication Data E. see: A. 1949.
US 2012/O174776 A1 Jul. 12, 2012 (Continued)
(51) Int. Cl. OTHER PUBLICATIONS
BOLD 53/047 (2006.01) J. A.C. Silva and A. E. Rodrigues. Analysis of ZLC Technique for
(52) U.S. Cl. Diffusivity Measurements in Bidisperse Porous Adsorbent Pellets.
USPC .............................................................. 95/96 Gas. Sep. Purif., vol. 10, No. 4, pp. 207-224, 1996.
(58) Field of Classification Search ank
USPC .............. 95/96, 117, 130, 127, 139, 140,143 Primary Examiner Frank Lawrence, Jr.
See application file for complete search history. (74) Attorney, Agent, or Firm — Iurie A. Schwartz
(56) References Cited (57) ABSTRACT
The present invention relates to a six bed pressure Swing
U.S. PATENT DOCUMENTS adsorption (PSA) system utilizing new and advanced cycles
3.430,418 A 3/1969 Wagner to obtain enhanced hydrogen recovery from a hydrogen con
3,564,816 A 2, 1971 Batta taining feed gas (i.e., synthesis gas). In one such cycle each of
3,986,849 A
4,077,779 A
10,3, 1976 Fuderer et al.
1978 Sircar et al.
the six beds has four pressure equalization steps, and at least
4,234.322 A * 1 1/1980 De Meyer et al. ................ 95/19 one of the beds is receiving and processing said feed gas to
4,259,091 A 3/1981 Benkmann obtain a hydrogen product gas (i.e., a 6-1-4 cycle).
4,299,595 A 11, 1981 Benkmann et al.
4,299,596 A 11, 1981 Benkmann 12 Claims, 4 Drawing Sheets

Advanced bed configuration/layering

Layer 5 (zeolite)

Layer 4 (zeolite)

Layer 3 (corbon)

Layer 2 (carbon)

Layer 1 (alumina)
 US 8,491.704 B2
Page 2

U.S. PATENT DOCUMENTS 6,849,106 B2 2/2005 Le Bec

4,834,780 A 5/1989 Benkmann SR 28 MBytet al.
4,957.514 A 9/1990 Golden et al. 6,916.358 B2 7/2005 Nakamura et al.
4,964,888 A 10/1990 Miller - kW
6,918,948 B2 7/2005 Jaussaud et al.
5,012,037 A
5,051,115 A
4, 1991 Doshi et al. 1
9, 1991 Leitgeb 6,923,844 B2 8, 2005 Urakami et al.
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J. 7,025,801 B2 4/2006 Monereau
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3.68 A 88: fish 1 7,166,151 B2 1/2007 Baksh et al.
5.726,118 A 3, 1998 paintal 7,169,210 B2 1/2007 Baksh et al.
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35. A 38. E. st al 7.255,840 B2 8/2007 Papavassiliou et al.
5.753010 A 5, 1998 SE 7,276,107 B2 10/2007 Baksh et al.
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892; A 13. E. 7.306,651 B2 12/2007 Cieutat et al.
6.183539 B1 2/2001 Rode etal 7,395,670 B1 7/2008 Drnevich et al.
6.210466 B1 4, 2001 Whysall et al. 7,396,387 B2 7/2008 Bakshet al.
6,221,492 B1 4/2001 Moreau et al. 7,399,341 B2 7/2008 Patel et al.
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6,293,998 B1 9, 2001 Dolan et al. 7.427,368 B2 9, 2008 Drnevich
6,302,943 B1 10/2001 Johnson et al. 7,452,407 B2 11/2008 Golden et al.
6,315,818 B1 1 1/2001 Monereau 7.467,519 B2 12/2008 Raybold et al.
6,340,382 B1 1/2002 Baksh et al. 7,500,999 B2 3/2009 Aaron et al.
6,379,430 B1 4/2002 Monereau 7,517,390 B2 4/2009 Lang
6,379,431 B1 4/2002 Xu et al. 7,537,742 B2 5/2009 Baksh et al.
6,402,813 B2 6/2002 Monereau et al. 7,588,742 B2 9, 2009 Haik-Beraudet al.
6.425,939 B1 7/2002 Moreau et al. 7,594.955 B2 9, 2009 Ishihara
6,454,838 B1 9/2002 Xu et al. 7.628,842 B2 12/2009 Schwartz et al.
6,475,265 B1 1 1/2002 Baksh et al. 7,628,843 B2 12/2009 Monereau et al.
6,483,001 B2 11/2002 Golden et al. 7,632,476 B2 12/2009 Shah et al.
6,500.235 B2 12/2002 Zhong et al. 7,648,562 B2 1/2010 Monereau et al.
6,503,299 B2 1/2003 Baksh et al. 2001/0009125 A1 7/2001 Monereau et al. .............. 95/117
6,514.317 B2 2/2003 H tal.
5 556 E. 2003, OO15091 A1* 1/2003 Xu et al. 95.96
6.530,975 B2 3/2003 Rodee all 2005/0098.034 A1* 5/2005 Gittleman et al. ................ 95/96
6565,627 B1 5/2003 Golden et al. 2009, 0223371 A1 9, 2009 Nakao et al.
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6,733,568 B2 5/2004 De-Souza et al. EP 1486245 A1 12/2004
6,743,745 B2 6/2004 Jaussaud et al. EP 1972367 A1 9, 2008
6,783,750 B2 8/2004 Shah et al. WO WOO2O96539 A1 12/2002
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6,843,831 B2 1/2005 Van de Kleut et al. * cited by examiner
U.S. Patent Jul. 23, 2013 Sheet 1 of 4 US 8.491,704 B2

Advanced bed configuration/layering

Layer 5 (zeolite)

Layer 4 (zeolite)

Layer 3 (carbon)

Layer 2 (carbon)

Layer 1 (alumina)

FIG. 1
U.S. Patent Jul. 23, 2013 Sheet 2 of 4 US 8.491,704 B2

Relative adsorption rates of N2 and CO versus particle diameter

1 OO

O 1 2 3 4. 5 6
particle diameter mm

FG. 2A
U.S. Patent Jul. 23, 2013 Sheet 3 of 4 US 8.491,704 B2

Relative adsorption rates of CO2 and CH4 versus particle diameter

1 OO

1O

O. 1 w
O 1 2 3 4. 5 6
particle diameter mm

FIG. 2B
U.S. Patent US 8.491,704 B2
 US 8,491,704 B2
1. 2
SIX BED PRESSURE SWING ADSORPTION Surized in one or more steps, counter-currently purged in one
PROCESS OPERATING IN NORMAL AND or more steps and counter-currently blown down in one or
TURNDOWN MODES more steps to permit essentially pure hydrogen product to exit
the bed with a high recovery. The sequence of steps is not
FIELD OF THE INVENTION limited to the one stated above and a combination of two or
more steps can be employed as a single step as well.
The present invention relates to a six bed pressure Swing U.S. Pat. No. 4,834,780 is directed to six bed PSA system
adsorption (PSA) system utilizing new and advanced cycles having one bed in operation of the 6-1-3 and 6-1-4 cycles,
to obtain enhanced hydrogen recovery from a hydrogen con
taining feed gas (i.e., synthesis gas). In one such cycle each of 10 wherein the first number in the cycle refers to the total number
the six beds has four pressure equalization steps, and at least of beds, the second number refers to the number of beds on the
one of the beds is receiving and processing said feed gas to feed step at any instant, and the third number refers to the
obtain a hydrogen product gas (i.e., a 6-1-4 cycle). The six bed number of bed to bed equalization steps in the PSA cycle.
PSA system can be operated in a turndown mode where one Thus, 6-1-3 means a six bed PSA cycle having one bed on
or two beds are taken offline. The new five bed cycle includes 15
feed at any instant, and the PSA cycle contains three bed-to
three equalization steps, while at least one bed is in operation
(i.e., a 5-1-3 cycle). The four bed cycle includes two equal bed equalization steps. This cycle is reproduced in Table 1,
ization steps, while at least one bed is in operation. This below.
TABLE 1.
Gl-SPSA cycle chart.
Step:
Bedi 1 2
1 A1, A2FPP
2 E1' PP
3 E3, E2
4 BD PG
5 E3 PPG
6 E1 E2

turndown mode, achieves a reduction of less than four per In accordance with the teachings of the 6-1-3 cycle, the
cent, and eight percent reduction, respectively, in hydrogen 35
PSA system delivers a continuous flow of PSA tail gas to a
throughput. In addition, the invention relates to a novel adsor Surge drum that removes fluctuations in the pressure, flow
bent layering employed in the beds of the PSA. rates and compositions, prior to sending it to an upstream unit
(e.g., SMR) for use (e.g., SMR burner fuel). However, the
BACKGROUND OF THE INVENTION 6-1-4 cycle of the patent features a discontinuous PSA tail gas
40 flow routed upstream via the Surge drum. The discontinuous
The need for high purity gasses, such as hydrogen, pro PSA tail gas flow can create fluctuations in the hydrogen
cessed from effluents in the chemical process industries plants.
remain. These effluents are hydrogen containing feed mix U.S. Pat. No. 6,454,838, is directed to a modified 6-1-4
tures gases (i.e., synthesis gases), from the likes of steam cycle to remove the undesired discontinuous PSA tail gas
methane reforming of natural gas or naptha, catalytic reform 45 Supply to the Surge drum. However, the solution provided in
ing of hydrocarbons, isomerization processes, etc., which are this patent results in a PSA cycle having several idle steps.
routed to a PSA for further processing. This growing demand Specifically, a twenty four step cycle is described with four
requires the need to develop highly efficient separation pro idle steps and overlapping fourth equalization and blowdown
cesses (e.g., PSA) for hydrogen (H) production from various steps. Those skilled in the art would recognize that idle steps
feed mixtures. In order to obtain highly efficient PSA sepa 50 in the PSA cycle invariably result in degradation in PSA
ration processes, both the capital and operating costs of the process performance (e.g., lower hydrogen recovery). In an
PSA system must be reduced. Some ways of reducing PSA alternative embodiment, U.S. Pat. No. 6,454,838 discloses a
system cost include a decrease in the adsorbent inventory, 6-1-4 PSA cycle wherein the PSA cycle consists of twenty
reduction in the number of PSA beds, and using advanced four steps in the cycle (See Table 3) featuring the following:
cycles in the PSA processes. The aforementioned ways of 55 (1) overlapping provide purge and the fourth equalization
reducing the PSA system cost constitute the elements of the step; (2) additional tank for the temporal storage of gas from
present invention. the second equalization step; (3) no idle steps and (4) con
Conventional PSA systems are well known for separating tinuous off-gas flow. However, in this embodiment a storage
feed mixture gases which contain components with different tank is utilized in order to eliminate the four idle steps. Fur
adsorption characteristics. For example, in a typical PSA 60 thermore, the PSA process recovery drops by 1-1.5% for
system, a multicomponent gas mixture is passed to at least cycles utilizing a fourth equalization compared to the prior art
one of multiple adsorption beds at an elevated pressure to 6-1-3 cycle. See Table 4.
adsorb at least one strongly sorbed component while at least U.S. Pat. No. 6,007,606, co-owned by the assignor of the
one component passes through. In the case of hydrogen PSA, present invention, discloses a PSA process involving the Stor
hydrogen is the most weakly adsorbed component which 65 age of products having various purities in segregated Storage
passes through the bed. At a defined time, the feed step is tanks for Subsequent usage. Products of increasing purities,
discontinued and the adsorption bed is co-currently depres admitted at the product end of the bed are used during purging
 US 8,491,704 B2
3 4
and re-pressurization steps. In addition, different composi on particle size and enables additional improvement in hydro
tion streams collected at the feed end of the bed during the gen recovery. Therefore, an efficient PSA separation process
countercurrent depressurization step are admitted at the feed has been found with high hydrogen recovery, lower adsorbent
end of the bed, in the order of increasing product component requirements, (i.e., lower bed size factor (BSF)), and lower
content during the rising pressure step(s). capital and operating costs. Additionally, the process should
In addition to the cycles, the related art discusses conven operate efficiently when one or more beds are taken offline for
tional adsorbent materials utilized in the beds as a means for operational reasons such as valve failure (referred herein, as
improving the product recovery in hydrogen PSA Systems. “turndown” or “turndown mode').
For example, U.S. Pat. No. 6,814,787 is directed to PSA BACKGROUND OF THE INVENTION
apparatus and process for the production of purified hydrogen 10
from a feed gas stream containing heavy hydrocarbons (i.e., The invention provides a pressure Swing adsorption pro
hydrocarbons having at least six carbon atoms). The appara cess for the separation of a pressurized feed gas Supply con
tus includes at least one bed containing at least three layers. taining one or more strongly adsorbable components and at
The layered adsorption Zone contains a feed end with a low least one less strongly adsorbable product gas in a multiple
surface area adsorbent (20 to 400 m/g) which comprises 2 to 15 bed system. The feed gas is Supplied to a feed end of an
20% of the total bed length followed by a layer of an inter adsorbent bed containing Solid adsorbent material(s), which
mediate surface area adsorbent (425 to 800 m/g) which preferentially adsorbs the more strongly adsorbable compo
comprises 25 to 40% of the total bed length and a final layer nent(s) and withdrawing the least strongly adsorbable prod
of high surface area adsorbent (825 to 2000 m/g) which uct component from an exit end of the adsorber bed, produc
comprises 40 to 78% of the total bed length. ing in cycle including steps in which the continuous feed gas
U.S. Pat. No. 6,340,382, is directed to a PSA process that sequentially co-currently flows through each of the adsorber
purifies hydrogen from a mixture that passes through an alu beds to produce gas product using continuous feed gas, pres
minum oxide (AlO) layer for moisture removal, then Surization steps, pressure equalization steps, blowdown
through activated carbon layer for carbon dioxide (CO), Step(s), and purge step(s).
carbon monoxide (CO), and methane (CH) removal, and 25 The product gas of the process is preferably hydrogen
finally through CaXZeolite layer for nitrogen (N) removal to although the process can be extended to other separation
produce high purity H (>99.99%). CaX is at least 90% Ca processes such as helium purification, natural gas upgrading,
exchanged with SiO/Al2O=2.0. CO production from Synthesis gas or other source containing
U.S. Pat. No. 7,537,742 B2 relates to an optimum set of CO, in the supply feed or in other PSA processes for copro
adsorbents for use in hydrogen PSA systems. Each adsorbent 30
duction of H and CO. One of the novel features of the
bed is divided into four regions. The first region contains present invention is the introduction of a new and advanced
adsorbent for removing water. The second region contains a cycle to a six bed PSA system having four equalization steps
mixture of strong and weak adsorbents to remove bulk impu to achieve enhanced H recovery. This cycle can be further
rities like CO. The third region contains a high bulk density modified and utilized to operate the PSA system in a turn
(>38 lbm/ft) adsorbent to remove remaining CO and most 35 down mode with a relatively small reduction in throughput,
of CH and CO present in the hydrogen containing feed mix thereby allowing the PSA system to operate with as few as
tures. The fourth region contains adsorbent having high Hen four beds, yet maintaining a throughput of hydrogen above
ry's law constants for the final cleanup of N and residual 90%. Another novel feature of the invention is the layered
impurities to produce hydrogen at the desired high purity. adsorbent, which can be utilized in the beds. These layered
U.S. Pat. No. 6,402,813 B2 describes the purification of a 40 configurations of carbon and/or Zeolite components differ
gas mixture by adsorption of the impurities on carbon adsor from another layer of similar adsorbent material in particle
bent formed by a combination of several different active size. These layered configurations of the bed materials com
carbons. In particular, a PSA process is described for purify bined and the PSA cycles provide a synergistic effect with an
ing a gas, Such as hydrogen, nitrogen, oxygen, carbon mon overall improvement in hydrogen recovery and throughput of
oxide, argon, methane orgas mixtures containing these com 45 1-2% over conventional PSA cycles.
ponents. The gas stream to be purified is passed through
layers of carbons, wherein the ordering of the carbon layers BRIEF DESCRIPTION OF THE FIGURES
are such that at least one of the following conditions exist: (1)
the density (D) is such that D1-D2; (2) the specific surface The objects and advantages of the invention will be better
area (SSA) is such that SSA1>SSA2; 3) the mean pore size 50 understood from the following detailed description of the
(MPS) is such that MPS1>MPS2, and (4) the pore volume is preferred embodiments thereof in connection with the
such that PV1>PV2. More specifically, this patent relates to a accompanying figures wherein:
process in which at least two layers of activated carbons are FIG. 1 illustrates an advanced bed configuration/layering
used in which the first layer carbon has lesser density than the in accordance with one aspect of the invention;
second, the first carbon has more specific Surface area, and 55 FIG. 2A is a plot of the relative adsorption rates of N and
also more mean pore size than the second carbon. CO versus particle diameter for the Zeolite layers shown in
To overcome the disadvantages of the related art six bed FIG. 1:
PSA systems, it is an object of the present invention to intro FIG. 2B is a plot of the relative adsorption rates of CO and
duce new and advanced PSA cycles with turndown modes, CH versus particle diameter for the carbon layers shown in
which include all of the following features (1) continuous 60 FIG. 1; and
PSA tail gas (offgas) flow; (2) no need for additional storage FIG.3 is an illustrative six bed HPSA system/skid utilized
tank; (3) no idle steps (4) higher recovery than the related art with the cycles of the present invention.
cycles.
It is another object of the invention to modify the adsorbent DETAILED DESCRIPTION OF THE INVENTION
system in each bed to contain at least three layers of adsor 65
bents (e.g., alumina, activated carbon and Zeolite), wherein The invention discloses high efficiency PSA processes/
the active carbon and Zeolite components are layered based cycles employed in a six bed PSA system to attain 20-50
 US 8,491,704 B2
5 6
million standard cubic feet per day (MMSCFSD) of hydrogen dependence of relative adsorption rates on particle diameter
production. The cycles achieve enhanced recovery of hydro for both nitrogen and carbon monoxide is shown. The Zero
gen from a hydrogen containing gas. The invention provides Length Column (ZLC) technique is employed to obtain the
the following features: data plotted in FIG. 2A. See, J. A. C. Silva & A. E. Rodrigues,
Novel and advanced PSA cycles for six bed PSA systems Gas. Sep. Purif., Vol. 10, No. 4, pp. 207-224, 1996.
which can be operated in turndown mode, and provide high The value of the relative adsorption rate is the ratio of true
hydrogen recovery. adsorption rate and the standard rate value. The standard rate
The novel six bed PSA cycle has at least four bed-to-bed value corresponds to a required minimum rate needed to yield
equalization steps; the enhanced PSA process performance. If the same particle
Continuous tail gas flow: 10 size (e.g., 2.5 mm) is used for both layers in the process the
The elimination of idle steps in the cycles and no need for requirement for nitrogen rate is satisfied. However, as can be
segregated storage tanks. determined from FIG. 2A, the CO relative adsorption rate is
only 40% of the required minimum. Therefore, it is desirable
Another aspect of the invention concerns the adsorbents to decrease the Zeolite particle size in layer four in order to
loaded into the beds of the hydrogen PSA to enhance the increase the rate of carbon monoxide adsorption. A value of
recovery of hydrogen. It has been found that the three layers 15
1.5 mm meets the design specification for the rate of carbon
of adsorbents where in each layer is subdivided into two monoxide in this particular exemplary embodiment. It is
layers containing the same adsorbent, yet with different par obvious that one could increase the nitrogen rate as well by
ticle size, optimal adsorption and desorption kinetics for spe decreasing the particle size in layer five. As a result, only
cific impurities present in the hydrogen containing feed gas is negligible process improvement will be realized since the
attained. This advanced adsorbent layering configuration nitrogen adsorption rate is already above the required mini
thereby results in an improvement in hydrogen recovery. mum value. On the other hand; the process performance can
Typical hydrogen PSA process utilizes three different suffer from the increased pressure drop in the bed. The pre
adsorbents loaded in the vessel from the bottom to the top in ferred layering for this particular example will be particle
the order Such as (1) alumina; (2) activated carbon and (3) sizes larger than 2 mm and Smaller than 3 mm for layer five
Zeolite. There are five major impurities to be removed by 25 and particle sizes larger than 0.5 mm and Smaller than 2 mm
adsorption process. Alumina adsorbs the moisture contained for layer four.
in the feed gas. Activated carbon layer is usually designed to Carbon layers two and three will be occupied with the
take care of carbon dioxide and hydrocarbons such as meth carbon particles of different size as well. The ZLC technique
ane, ethane, and propane. The Zeolite function is to remove is employed once again to measure the adsorption rates for
carbon monoxide, nitrogen, argon and residual methane not 30 carbon dioxide and methane on the carbon material. The rate
taken out by activated carbon placed upstream of the Zeolite. data normalized by the standard rate is summarized in FIG.
Additional details of the layers of adsorbents in each PSAbed 2B. The rate for methane is satisfactory at particle sizes less
are discussed in Baksh et al (U.S. Pat. No. 7,537,742 B2), than 2.25 mm. However, the smaller particles are needed to
which is co-owned by the assignee of the present invention, obtain reasonable rates for carbon dioxide. By inspection of
and is incorporated by reference herein, in its entirety. 35 the data in FIG. 2B, the preferred carbon particle size for
FIG. 1 is illustrative of the adsorbents layers in each of the carbon dioxide take out is less than 1.5 mm and for methane
PSA beds of the invention. The adsorption properties in layers less than 2 mm. Thus the layering for this particular example
two, three, four and five are fine tuned by optimizing the will be particle sizes larger than 1.0 mm and smaller than 2.0
particle size of the adsorbent used to achieve optimal PSA mm for layer three and particle sizes larger than 0.5 mm and
process performance. As an example, layers two and three are 40 smaller than 1.5 mm for layer two.
identical (e.g., both are the same carbon material) except for The novel PSA cycles of the present invention will now be
the difference in particle sizes. Likewise, layers four and five described with reference to various exemplary embodiments.
are identical (i.e., both are the same Zeolite material), but their In one embodiment of the invention, the novel PSA system
particle size is different. The adsorber vessel design and con employs an eighteen-step, six adsorbent bed PSA cycle hav
figuration is such that it will be capable to adsorb five different 45 ing four equalization steps, in addition to purging, blowdown
components. Ideally, layer 1 adsorbs moisture, layer 2 and product pressurization steps (referred hereinas “the 6-1-4
adsorbs carbon dioxide, layer 3 adsorbs methane, layer 4 PSA cycle'). The PSA system includes a continuous supply
adsorbs carbon monoxide and layer 5 adsorbs nitrogen. Those offeed gas to at least one bed which in adsorption. This bed
skilled in the art will recognize that the process recovery will separates the pressurized Supply feed gas containing one or
be maximized when adsorbents are fully utilized. Using a 50 more strongly adsorbable component and allowing the less
three layer design, the skilled artisan has only three degrees of strongly adsorbable hydrogen product gas to exit the bed.
freedom to size the adsorber for removal of five components. In another embodiment of the invention, the PSA system
The inventive approach adds two more degrees of freedom can be utilized in turndown mode with five beds. The PSA
thus making it possible to achieve higher hydrogen recovery cycle for the five beds would include fifteen steps, where one
in combination with the new 6-1-4 cycle of this invention. 55 bed is in adsorption and has three equalization steps in addi
The adjustment of the adsorbent particle size affects the tion to the purging and product pressurization steps (referred
rate of adsorption and desorption process—the adsorption herein as “the 5-1-3 PSA cycle').
capacity is independent of particle size. The diffusion resis In an alternative embodiment of the invention, the PSA
tance in an adsorption process is the sum of all diffusion system having six beds employs an eighteen steps cycle
resistances within the particle of the adsorbent material. The 60 where two of the beds are simultaneously in the adsorption
change in the particle size may or may not affect the overall phase, and each bed has at least three equalization steps in
diffusion resistance depending on the level of contribution of addition to purging and product pressurization steps referred
the diffusion phenomena affected by the particle size. herein as “the 6-2-3 PSA cycle').
In one embodiment, CaX(2.3) Zeolite is used in the fourth With reference to FIG. 3 and Tables 2 and 3, the mode of
and fifth layers of FIG.1. The layers are sized such that layer 65 operation for the 6-1-4 PSA cycle is illustrated. Specifically,
four preferably adsorbs carbon monoxide and layer five pref the sequence of steps for the 6-1-4 PSA cycle is performed in
erably adsorbs nitrogen. With reference to FIG. 2A, the the order recited in each of the adsorption vessels in turn.
 US 8,491,704 B2
TABLE 2
6-1-4 PSA cycle chart
Step:

It will be understood that the nomenclature provided for E3/BD1=Third Equalization Down/First Blowdown Step
this 6-1-4 PSA cycle is the same for all the cycles discussed In Table 2, the rows correspond to a particular bed in the
herein, where: PSA process while the columns represent the step number.
A1=First Adsorption Step The duration of one cycle sequence (one row) is referred to as
A2/PP1=Second Adsorption Step/First Product Pressuriza the total cycle time or cycle time (CT). The cycle time is
tion 25 constant for each bed. The relative shift in the cycle steps
A3/PP2=Third Adsorption Step/Second Product Pressuriza among the beds can be inferred from Table 2 as well. This
tion shift is equal to "/6" of the CT since there are six beds in this
E1 =First Equalization Down particular cycle. In order for the 6-1-4 PSA cycle to be fully
E2=Second Equalization Down 30 defined the step times for step 1, 2 and 3 must be assigned—
E3–Third Equalization Down such as t t and t. The duration of basic block is then defined
PPG=Provide Purge Gas as t+t+ts. Employing the cycle periodicity described above,
E4/BD1=Fourth Equalization Down/First Blowdown the CT=6*(t+t+t) and it follows that the duration of steps 1,
BD2=Second Blowdown 35 4, 7, 10, 13 & 16 are equal in time (i.e., t); steps 2, 5, 8, 11,
PG=Purge 14 & 17 (i.e., t) and steps 3, 6, 9, 12, 15 & 18 (i.e., t). Hence,
E4'-Equalization Up (using gas from E4 step) there are eighteen steps in the cycle, the mode of operation for
E3'-Equalization Up (using gas from E3 step) each bed is offset by three steps.
E2-Equalization Up (using gas from E2 step) 40 The 6-1-4 PSA cycle sequence is now described with
respect to one bed which undergoes the entire PSA cycle. A
E1'=Equalization Up (using gas from E1 step) representative PSA train/skid system having six beds in par
PP1 =First Product Pressurization allel is depicted in FIG.3, and is employed hereinto illustrate
PP2=Second Product Pressurization this embodiment. The system includes 30 on/off valves, and
45 14 control valves, 6 manifolds (although the sixth manifold is
In some of the cycles, as the cycle may require, the follow labeled “7” in FIG. 3 in order to designate the PSA skid
ing additional nomenclature shall be employed: components with consistent nomenclature, as set forth below)
A2=Second Adsorption Step and associate pipings and fitting. The control valves are uti
A3–Third Adsorption Step lized to control the flow rate or pressure during certain pro
50 cess steps while the on/off valves allow communication
A4=Fourth Adsorption Step between the various beds in the PSA system. The valve
A5=Fifth Adsorption Step sequencing representing the steps in the 6-1-4 PSA cycle of
PP=Product Pressurization FIG. 3 is illustrated in Table 3, below, where the valve chart
defines the position or action for each valve (i.e., open-O,
A3/PP1 =Third Adsorption Step/First Product Pressurization 55 closed-C, and CV-control valve) in a particular step of the
Step PSA cycle.
TABLE 3
6-1-4 PSA cycle valve chart
Step it
1 2 3 4 S 6 7 8 9 10 11 12 13 14 15 16 17 18

XV-007 C CV CV C CV CV C CV CV C CV CV C CV CV C CV CV
XV-002 CV CV CV CV CV CV CV CV CV CV CV CV CV CV CV CV CV CV
XV-O11 O O O C C C C C C C C C C C C C C C
 US 8,491,704 B2
9 10
TABLE 3-continued
6-1-4 PSA cycle Valve chart
Step it
1 2 3 4 5 6 7 8 9 1O 11 12 13 14 15 16 17 18

XV-O12
XV-013
XV-014 V V V
XV-O15
XV-017
XV-018 V V V V V
XV-021
XV-022
XV-O23
XV-O24 V V V
XV-O25
XV-O27
XV-O28 V V V V
XV-O31
XV-O32
XV-033
XV-O34 V V V
XV-035
XV-037
XV-038 V V V
XV-041
XV-042
XVO43
XV-044 V V V
XV-045
XV-047
XV-048 V V V V V V
XV-OS1
XV-052
XV-053
XV-OS4 V V V
XV-055
XV-057
XV-OS8 V V V V V V
XV-061
XV-062
XV-063
XV-064 V V V
XV-06S
XV-067
XV-068 V V V V V V

Step No. 1 (A1): The feed gas mixture is introduced to the rates are regulated by valve 007 to be as low as possible in
bottom of Bed 1 from the feed manifold at high pressure. Both order to prevent the fluidization and to keep the pressure in
valves 011 (i.e., XV-011) and 012 (i.e., XV-012) are open 45 Bed 1 as high as possible.
while all other Bed 1 valves (XV-01x) are closed. Hereinafter Step No. 4 (E1): Bed 1 undergoes the first bed-to-bed
valve tag numbers will be referred to without using the prefix equalization step while Bed 3 is counter currently receiving
XV. The feed mixture flows from the bottom to the top of the the equalization gas—Step (E1'). The (E1) step is sometimes
bed. This upward flow direction in the vessel is referred to as referred to as co-current depressurization step. Bed 1 valves
co-current flow with respect to feed. During this adsorption 50 017, 018 and Bed 3 valves 037 and 038 are open while all
step the impurities are adsorbed and high purity hydrogen is other Bed 1 and Bed 3 valves (i.e., 01x and 03x) are closed.
collected and routed through product manifold number 2. The rate of (E1)-(E1') steps is controlled by control valve 018.
Control valve 002 is used to control the pressure in the bed in Steps No. 5 and 6 (E2): Bed 1 undergoes the second equal
(A1), (A2) or (A3) steps (i.e. the feed/production steps). ization (E2) for the duration of these two steps. Specifically,
55 the pressure in Bed 1 drops due to co-current gas flow from
Steps No. 2 and 3 (A2/PP1 and A3/PP2): These steps are Bed 1 to Bed 4 undergoing step (E2) during these steps. The
identical except for their respective duration t and ts. Valves pressures in both beds are equal at the end of step No. 6.
011 and 012 remain open, and Bed 1 continues in the feed/ Valves 015, 045 and 048 are fully open while valve 018
production step. In addition, control valve 007 is used to controls the rate of (E2)-(E2) steps.
control the rate of product pressurization steps (PP1) and 60 Step No. 7 (E3): Bed 1 executes the third equalization step
(PP2). As shown in Table 2, above, it is the Bed 2 that is (E3). This step uses the same equalization manifold as the
receiving the product pressurization gas from Bed 1 in Steps previous step (E2). Valves 015, 055 and 058 are fully open
No. 2 and 3 through valves 007,027 and 028. All other valves while valve 018 controls the rate of (E3)-(E3) steps. It is clear
associated with Bed 2 are closed. It is important that the from the valve nomenclature that Bed 5 is in communication
pressures in Bed 1 and Bed 2 are equal at the end of (A3/PP2) 65 with Bed 1 using manifold number 5.
step so that the Bed 2 can enter the feed/production step (A1) Step No. 8 (PPG): Bed 1 co-currently provides purge gas to
in Step 4. It is also desirable that the (PP1) and (PP2) step flow Bed 6, which is being purged. To this end valve 013 is open
 US 8,491,704 B2
11 12
and control valve 018 is used to control the rate of the (PPG) Steps No. 14 and 15 (E2). Bed 1 is receiving gas from Bed
step. The purge gas flows to the purge manifold number 3 to 4. Valves 015, 045 and 018 are fully open and the action of
Bed 6 while valves 063 and 068 are fully open. Counter control valve 048 provides means to control the rate.
current purge step uses hydrogen rich stream to aid the regen Step No. 16 (E1'): The last equalization step where Bed 1
eration of adsorbents in the vessels. Desorbed impurities receives the gas from Bed5. Valves 017,057 and 018 arefully
leave the Bed 6 through the control valve 064 and eventually open and the action of control valve 058 provides means to
are collected in a Surge drum (not shown). From the opera control the rate.
tional standpoint, the longer the purge step the better the Steps No. 17 and 18 (PP1 and PP2): The last two steps in
adsorbent regeneration and thus better process working the cycle description with regards to Bed 1 are the (PP1) and
capacity. This means that the purge step time (t) should be 10 (PP2) steps already described above.
long and as mentioned above the product pressurization step Basic functionality of the cycle can be described in the
time (t+ts) should be long as well, if permitted by process. same fashion for any bed. However, once the step sequence
This condition is easily satisfied for 6-1-4 cycle shown in for one bed is defined the step sequences for other beds will
Table 2 since the (PG) and (PP1) steps overlap; their step time follow in the same order and the relative time shift will be /6"
is t2. 15 of the cycle time (CT), (e.g., Bed 2 starts the adsorption (A1)
Step No. 9 (E4/BD1): This step is the fourth equalization in step number 4, compared to Bed No. 1 that goes through
step (E4) coupled with a blowdown step (BD1). Both ends of (A1) in step number 1).
Bed 1 are open. Valve 014 is opened to enable the blowdown During the operation of a plant employing a six bed PSA
step where a portion of the gas in Bed 1 is directed to the Surge process it may be desirable to operate the plant in the turn
drum (not shown). The (BD1) flow rate is controlled by valve down mode for a limited period of time. In the case of a six
014. In the meantime, valves 013,063 and 068 are open and bed/vessel PSA system, this mode enables the continuous
valve 018 is used to control the rate of fourth equalization production with only five vessels online while one of the beds
step. Proper management of adsorption/desorption processes or valves associated with a given bed failed and need to be
taking place in this step is essential for the Superior 6-1-4 serviced. It is often seen in the industry that the plant perfor
cycle performance. The gas used for the co-current depres 25 mance significantly deteriorates when operating in excep
Surization step (E4) must be rich in hydrogen. This is tional mode. With reference to Table 4, below, the mode of
achieved by advanced layering technology (i.e. the use of operation of the new 5-1-3 PSA cycle is described.
TABLE 4
5-1-3 PSA cycle chart
Bed Step:
7

40

CaX type Zeolite adsorbent while larger particles located at In order for the 5-1-3 PSA cycle to be fully defined the step
the top of the vessel and smaller particles below), discussed in times for step 1, 2 and 3 must be assigned—such as t t and
detail above. The flows in this step must be adjusted such that ts. The duration of basic block is then defined as t+to+ts. By
the impurities leave the vessel through valve 014 and hydro 45 using the cycle periodicity the total CT=5*(t+t+t) and it
gen rich gas through valve 018. follows that the duration of steps 1,4,7,10 & 13 equal to t.
Step No. 10 (BD2): This step in Bed 1 is carried out to rid steps 2, 5, 8, 11 & 14 equal to t and steps 3, 6, 9, 12 & 15 equal
the vessel of the impurities adsorbed during co-current steps to t. The cycle sequence will be described bellow in detail
(AD, EQ, PPG) through the bottom of the vessel. At this point with respect to Bed 1 for illustration purposes assuming that
in the cycle, the pressure in the vessel is too low to hold on to 50 Bed 6 is offline and completely isolated from the rest of the
the impurities. As a result, they are desorbed and counter process. Functionality of the cycle is explained using hydro
currently directed to the surge drum through valve 014. All gen the PSA process valve skid shown FIG.3. The 5-1-3 PSA
other valves associated with Bed 1 are closed during this step. cycle sequence is now described with respect to one bed
Step No. 11 (PG): Bed 1 is receiving the purge gas from which undergoes the entire PSA cycle (i.e., CT).
Bed 2. Valves 018,013,023 are fully open; the rate of (PPG) 55 Steps 1 and 2 (A1 and A2): Bed 1 begins the process cycle
step and the pressure in Bed 1 is controlled via valves 028 and in the adsorption steps (A1) and (A2). Both valves 011 and
014, respectively. 012 are open while all other Bed 1 valves (01x) are closed; the
Step No. 12 (E4): The first step designated as equalization high purity hydrogen is collected and sent through the prod
up to reference the bed receiving the gas. The beds in (E4/ uct manifold number 2. Control valve 002 is used to control
BD1) and (E4) steps are interacting such that the content of 60 the pressure in the bed in (A1), (A2) or (A3) steps (i.e. all
Bed 2 is transferred to Bed 1 until the pressures in both beds feed/production steps).
is equalized. Valves 023,013 and 018 are fully open and the Step 3 (A3/PP1): Valves 011 and 012 remain open, Bed 1
action of control valve 028 provides means to control the rate continues in the feed/production step. In addition, the control
of this step. valve 007 is used to control the rate of product pressurization
Step No. 13 (E3): Bed 1 is receiving gas from Bed3.Valves 65 step (PP1). Therefore, Bed 2 is receiving the product pressur
015,035 and 018 are fully open and the action of control valve ization gas from Bed 1 through valves 007,027 and 028. All
038 provides means to control the rate. other valves associated with Bed 2 are closed.
 US 8,491,704 B2
13 14
Steps 4 and 5 (E1): Bed 1 undergoes the first bed-to-bed TABLE 5
equalization step (E1) while Bed 3 is counter-currently
receiving the equalization gas—step (E1'). Bed 1 valves 017, H2 PSA cycles and corresponding process performance
018 and Bed 3 valves 037 and 038 are open while all other
5
Bed 1 and Bed 3 valves (01x) and (03x) are closed. The rate PSA cycle
of (E1)-(E1') steps is controlled by control valve 018.
4-1-2
Step 6 (E2): The pressure in Bed 1 drops due to gas flow 6-1-4 5-1-3 (Related Art)
from Bed 1 to Bed 4 undergoing step (E2). The pressures in
both beds are equal at the end of step 6. Valves 015, 045 and 10 Cycle Time min 10.6 9.17 9.O
048 are fully open while valve 018 controls the rate of (E2)- t1, t2, t3. Sec 25, 65, 15 55, 15, 40) 35, 65,35
(E2) steps. High Pressure Psig 360 360 360
Step 7 (PPG): Bed 1 sends purge gas to Bed 5 in the purge Low Pressure Psig S.O S.O S.O
step (PG). Valve 013 is open and control valve 018 is used to 15
Temperature K 310 310 310
control the rate of (PPG) step. The purge gas flows through the Bed ID ft) 12.5 12.5 12.5
Feed Rate MMSCFD 62 62 62
purge manifold number 3 to the Bed 5 while valves 053 and H. Product Rate MMSCFD 40.3 39.15 37.1
058 are fully open. Desorbed impurities leave the Bed 5 Total BSF Ibs/TPDH, 5,618 4,820 4,069
through the control valve 054 and eventually are collected in H. Purity (9%) 99.999 99.999 99.999
the Surge drum (not shown). H. Recovery 9% 88.0 85.5 81.0
Step 8 (E3/BD1): In Bed 1, the (E3) step coupled with a Note 1: MMSCFD represents million standard cubic feet per day of gas where assumed
blowdown step (BD1). Both ends of Bed 1 are open. Valve standard conditions are 1 atmosphere pressure and temperature 70°F;
014 is opened to enable the blowdown step where a portion of Note 2:1 Psigis a unit of pressure corresponding to 6894,757 Pascal; 1 lbs is a mass unit
25 corresponding to 0.4535924 kg; K correspond to SI units for temperature of 1 Kelvin; ft
the gas in Bed 1 is directed to the Surge drum. In the mean represents distance 1 feet equal to 0.3048 meters;
time, valves 015, 055 and 058 are open and valve 018 is used Note 3: TPDH represents tons (2000 lbs) of hydrogen per day;
to control the rate of third equalization step. Note 4: BSF (bed size factor) is the ratio of total mass of adsorbents in all beds and daily
production of hydrogen intons per days (see Note 3);
Step 9 (BD2): The purpose of this step is to rid the vessel of Note 5: The 4-1-2PSA cycle has been modified for the purposes of the simulation to include
the adsorbent layering of the present invention. This provides a one-to-one comparison of the
the impurities adsorbed during co-current steps (AD, EQ. 30 cycles,
PPG) through the bottom of the vessel via valve 014. All other
valves associated with Bed 1 are closed during this step. As shown in the Table 5, the new cycles having an addi
Step 10 (PG): Is a purge step where Bed 1 is receiving the tional equalization step, without the need for idle steps or
purge gas from Bed 2. Valves 018,013, 023 are fully open. otherwise offline storage tanks provides for a recovery of
The rate of (PPG) step and the pressure in Bed 1 is controlled 35 hydrogen as high as 88.0%. On the other hand, in the turn
via valves 028 and 014 respectively. down mode with five and four beds online, the hydrogen
recovery drops to 85.5% and 81.0%, respectively.
Step 11 (E3): This first equalization up step designates that
the bed is receiving the gas. The beds in (E3) and (E3') steps An alternative embodiment of the present invention is a six
are interacting such that the content of Bed 2 is transferred to 40
bed PSA system having dual feed. One of the benefits of using
Bed 1 until the pressures in both beds are equalized. Valves a dual feed cycle is higher throughput and lower bed size
025,015 and 018 are fully open and the action of control valve factor (BSF). As discussed with respect to the cycles above,
028 provides means to control the rate. BSF is a measure of process productivity perton of hydrogen
produced per day. This alternative PSA cycle has eighteen
Step 12 (E2): Bed 1 is receiving gas from Bed 3. Valves 45 steps, two beds are simultaneously on the feed/process stage
015,035 and 018 are fully open and the action of control valve and three steps in the cycle are dedicated to bed-to-bed equal
038 provides means to control the rate. ization. This 6-2-3 PSA cycle has an increased throughput
Step 13 and 14 (E1"): Bed 1 receives gas from Bed 4.Valves capability of producing 40-70 MMSCFD of hydrogen versus
017,047 and 018 are fully open and the action of control valve 20-50 MMSCFD for 6-1-4 PSA cycle. The remainder of the
048 provides means to control the equalization step rate in 50 innovative characteristics of the 6-2-3 PSA cycle are the same
steps 13 and 14. as the ones discussed with respect to the newly designed 6-1-4
Step 15 (PP1): The last step in the cycle description with and 5-1-3 PSA cycles.
regards to Bed 1 where the product pressurization occurs, as The 6-2-3 PSA cycle has eighteen steps with two parallel
described above.
55
feeds and three bed to bed equalization steps. Since six beds
The five bed PSA system, it may be desirable to further are used with an eighteen step cycle (18+6), three cycle steps
operate the plant in a turndown mode with only four beds/ and their times (t, t, t) must be described for full cycle
vessels online. In such a case, the 4-1-2 PSA cycle of Baksh definition. An alternative way for describing a cycle chart is to
et al. (U.S. Pat. No. 6,340,382) is utilized and incorporated by provide information on all of the beds for the duration of the
reference in its entirely. 60 unit block rather than describing the whole sequence for a
An example, a PSA process with the cycles described single bed. For example, by defining all cycle steps in steps 1,
herein were simulated under the process conditions listed in 2 and 3 for 6-2-3 PSA cycle in Table 6, one has qualitatively
Table 5, below. The model assumes the following feed gas defined all possible interactions among beds, valves and
composition for all cycles: 73.87% hydrogen, 0.23% nitro manifolds. The same sequence will be periodically repeating
gen, 3.31% carbon monoxide, 16.37% carbon dioxide, 5.94% 65 with period equal to t+t+ts. This new method will be used to
methane and 0.3% water. The feed gas temperature was 100° explain the functionality of 6-2-3 PSA cycle with reference to
F. and feed gas pressure was 360 Psig. Table 6, below, in conjunction with FIG. 3.
 US 8,491,704 B2
15 16
TABLE 6
6-2-3 PSA cycle chart
Bed Step:
# 1 2 3 4 5 6 7 8 9 1O 11 12 13 14 15 16 17 18

1 A1 A2 A3 A4 AS A6, E1 E1 E2 PPG E3, BD2 PG E3' E2" E1 E1' PP

PP BD1
2 E1' E1' PP A1 A2 A3 A4 AS A6 PP
3 PG E3' E2" E1' E1' PP A1 A2 A3
4 PPG E3, BD2 PG E3' E2' E1' E1' PP A1 A2 A3 A4 AS A6 E1 E1 E2
BD1 PP
5 E1 E1 E2 PPG E3, BD2 PG E3' E2' E1' E1' PP A1 A2 A3 A4 AS A6,
BD1 PP
6 A4 AS A6, E1 E1 E2 PPG E3, BD2
PP BD1

Step No. 1: Two beds are processing feed (adsorption step), TABLE 7-continued
namely Bed 1 and Bed 6. It follows that the valves 011, 012,
061 and 062 will be open. Bed 5 and Bed 2 are in communi Dual feed six bed H2 PSA cycles and corresponding process
performance
cation executing (E1)-(E1') steps, where valves 057,027,028
are open and valve 058 is used to control the rate. Bed 4 is 6-2-2 6-2-3
providing the purge gas (PG) for Bed 3. The rate of the (PPG) High Pressure Psig 360 360
step is controlled by valve 048, while valves 043,033,038 are 25
Low Pressure Psig S.O S.O
fully open and valve 034 is used to control the pressure in Bed Temperature K 310 310
3. Bed ID ft) 12.5 12.5
Feed Rate MMSCFD 77.3 77.3
Step No. 2: Two beds are processing feed (adsorption step), H. Product Rate MMSCFD 48.8 49.4
namely Bed 1 and Bed 6. Thus, it follows that valves 011, 012, Total BSF Ibs/TPD H. 4,639 4,583
061 and 062 are open. Bed 5 and Bed 2 are continuing in H. Purity (%) 99.999 99.999
30 H. Recovery 9% 8S.O 86.O
equalization steps (E1)-(E1'), valves 057,027,028 are open
and valve 058 is used to control the rate. Bed 4 and Bed 3 are Note 1: MMSCFD represents million standard cubic feet per day of gas where assumed
standard conditions are 1 atmosphere pressure and temperature 70°F.
undergoing (E3/BD1)-(E3') steps (i.e., overlapping low pres Note 2:1 Psigis a unit of pressure corresponding to 6894,757 Pascal; 1 lbs is a mass unit
sure equalization step and blowdown—(BD1). Valves 045, corresponding to 0.4535924 kg; K correspond to SI units for temperature of 1 Kelvin; ft
represents distance 1 feet equal to 0.3048 meters.
035, 038 are open and valve 048 is used to control the flow 35 Note 3: TPDH2 represents tons (2000 lbs) of hydrogen per day
rate of gas to Bed 3. At the same time, Bed 4 is blown down Note 4: BSF (bed size factor) is the ratio of total mass of adsorbents in all beds and daily
production of hydrogen intons per days (see Note 3)
through valve 044 and (BD1) step gas is directed towards the Note 5: The 6-2-2PSA cycle has been modified for the purposes of the simulation to include
the adsorbentlayering of the present invention. This provides a one-to-one comparison of the
Surge drum via manifold number 4. cycles,
Step No. 3: Two beds are processing feed (adsorption step), The simulation results show that the benefit from new
namely Bed 1 and Bed 6. Thus, it follows valves 011, 012,061 40 6-2-3 PSA cycle is one additional point in hydrogen recovery.
and 062 will be open. Bed 2 is in the product pressurization Thus, in both cycles reported in Table 7, the adsorbent layer
step (PP). Valves 027 and 028 are open while valve 007 ing of the present invention has been incorporated into the
controls the rate of this step. Bed 5 and Bed 3 are in commu cycles. Accordingly, the performance of 6-2-2 cycle in Table
nication executing (E2)-(E2) steps, valves 055, 035, 038 are 7 does not correspond to prior art performance. The recovery
open and valve 058 is used to control the rate. Bed 4 is in the 45 of prior art H. PSA process using 6-2-2 cycle without the
blowdown step, when the bed is counter-currently depressur advanced layering of the adsorbents is the range of 82 to 83%.
ized and its content is released to the Surge drum through The major advantage of 6-2-3 cycle Versus 6-1-4 cycle is
valve 044 and manifold number 4. the lower bed size factor (BSF). The BSF is 5618 lbs/TPDH
The performance for the 6-2-3 PSA cycle was obtained via for the 6-1-4 PSA cycle (Table 5) and 45831bs/TPDH2 for the
mathematical modeling of hydrogen PSA processes. The 50 6-2-3 PSA cycle (Table 7), respectively. As a result, the 6-2-3
results are summarized in Table 7. The model assumed fol PSA cycle can produce a greater quantity of hydrogen using
lowing feed gas composition for all cycles: 73.87% hydrogen, Smaller amount of adsorbents.
0.23% nitrogen, 3.31% carbon monoxide, 16.37% carbon While the invention has been described in detail with ref
dioxide, 5.94% methane and 0.3% water. The feed gas tem erence to specific embodiment thereof, it will become appar
perature was 100°F. and feed gas pressure was 360 Psig. The 55
ent to one skilled in the art that various changes and modifi
configuration of vessels and adsorbents used were exactly cations can be made, and equivalents employed, without
same as those considered for single feed cycles (i.e., See departing from the scope of the appended claims.
What is claimed is:
Table 5). 1. A pressure Swing adsorption process for separating a
TABLE 7 pressurized supply feed gas containing one or more strongly
60 adsorbable component from at least one less strongly adsorb
Dual feed six bed H2 PSA cycles and corresponding process able product gas component in a six bed adsorbent system to
performance produce a continuous stream of product gas enriched in the
6-2-2 6-2-3
less strongly adsorbable component and a continuous stream
of offgas that is enriched in the strongly adsorbable compo
Cycle Time min 10.1 9.8 65 nents; wherein, the process cycle has eighteen steps including
t1, t2, t3 sec 56, 45, O 50, 15, 33) four bed-to-bed equalization steps, in accordance to follow
ing cycle chart:
 US 8,491,704 B2
17 18

Step:
Bed # 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

1 A1 A2. A3, E1 E2 E2 E3 PPG E4. BD2 PG E4' E3' E2' E2" E1' PP1 PP2
PP1 PP2 BD1
2 E1' PP1 PP2 A1 A2 A3. E1 E2 E2 E3 PPG E4 BD1 BD2 PG E4' E3' E2' E2'
PP1 PP2
3 E3' E2' E2" E1' PP1 PP2 A1 A2 A3. E1 E2 E2 E3 PPG E4. BD2 PG E4'
PP1 PP2 BD1
4 BD2 PG E4' E3' E2' E2" E1' PP1 PP2 A1 A2, PP1 A3 PP2 E1 E2 E2 E3 PPG E4fBD1
5 E3 PPG E4f BD2 PG E4' E3' E2' E2' E1' PP1 PP2 A1 A2 A3. E1 E2 E2
BD1 PP1 PP2
6 E1 E2 E2 E3 PPG E4. BD2 PG E4' E3' E2' E2" E1' PP1 PP2 A1 A2; A3 PP2
BD1 PP1

wherein:
A1 = First Adsorption Step
A2/PP1 = Second Adsorption Step First Product Pressurization
A3/PP2 = Third Adsorption StepSecond Product Pressurization
E1 = First Equalization Down
E2 = Second Equalization Down
E3 = Third Equalization Down
PPG = Provide Purge Gas
E4/BD1 = Fourth Equalization Down. First Blowdown
BD2 = Second Blowdown
PG = Purge
E4' = Equalization Up (using gas from E4 step)
E3 = Equalization Up (using gas from E3 step)
E2 = Equalization Up (using gas from E2 step)
E1 = Equalization Up (using gas from E1 step)
PP1 = First ProductPressurization
PP2 = Second Product Pressurization

30
2. The pressure Swing adsorption process of claim 1, 8. The pressure Swing adsorption process of claim 6, where
wherein the six bed system is in turndown mode with five the second of the subdivided carbon layers encountered by the
beds online, where the process cycle has fifteen steps includ Supply feed gas has a particle size of about 2.0 to 3.0 mm and
ing three bed-to-bed equalizations steps, while one of the an affinity for the methane impurities.
beds is in production. 35 9. The pressure Swing adsorption process of claim 6, where
3. The pressure Swing adsorption process of claim 1, the first of the subdivided Zeolite layers encountered by the
wherein said less strongly adsorbable product gas is hydro Supply feed gas has a particle size of about 0.5 to 2.0 mm and
an affinity for the carbon monoxide impurity.
gen. 10. The pressure Swing adsorption process of claim 6.
4. The pressure Swing adsorption process of claim 1, 40 where the second of the subdivided Zeolite layers encountered
wherein the Supply feed gas contains one or more strongly by the supply feed gas has a particle size of about 2.0 to 3.0
adsorbable component selected from the group consisting of mm and an affinity for the nitrogen impurity.
hydrocarbons, carbon dioxide, carbon monoxide, argon, 11. A pressure Swing adsorption process for separating a
nitrogen and water vapor. pressurized supply feed gas containing one or more strongly
5. The pressure Swing adsorption process of claim 1,
wherein each adsorbent bed contains alumina, carbon and
45 adsorbable component from at least one less strongly adsorb
Zeolite material configured in layers in this particular order. able product gas component in a five bed adsorbent system to
6. The pressure Swing adsorption process of claim 5, where produce a continuous stream of product gas enriched in the
the carbon and Zeolite layers are each subdivided into two less strongly adsorbable component and a continuous stream
layers with different particle size. 50 of offgas that is enriched in the strongly adsorbable compo
7. The pressure Swing adsorption process of claim 6, where
the first of the subdivided carbon layers encountered by the nents; wherein, the process cycle has fifteen steps including
Supply feed gas has a particle size of about 0.5 to 1.5 mm and three bed-to-bed equalization steps, in accordance with the
an affinity for the carbon dioxide impurity. following cycle chart:

Step:

Bedi 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

1 A1 A2 A3 PP E1 E1 E2 PPG E3 BD1 BD2 PG E3 E2" E1' E1 PP

2 E1 E1' PP A1 A2 A3 PP1 E1 E1 E2 PPG E3 BD1 BD2 PG E3 E2"

3 PG E3' E2' E1' E1' PP1 A1 A2 A3 PP E1 E1 E2 PPG E3, BD1 BD2

 US 8,491,704 B2
19 20
-continued
Step:
Bed #1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

4 PPG E3 BD1 BD2 PG E3' E2" E1' E1' PP A1 A2 A3/PP E1 E1 E2

5 E1 E1 E2 PPG E3 BD1 BD2 PG E3' E2 E1' E1' PP A1 A2 A3, PP

where:
A1 = First Adsorption Step
A2 = Second Adsorption Step
A3/PP1 = Third Adsorption Step. First Product Pressurization
E1 = First Equalization Down
E2 = Second Equalization Down
PPG = Provide Purge Gas
E3:BD1 = Third Equalization Down. First Blowdown
BD2 = Second Blowdown
PG = Purge
E3 = Equalization Up (using gas from E3 step)
E2 = Equalization Up (using gas from E2 step)
E1 = Equalization Up (using gas from E1 step)
PP1 = First ProductPressurization

12. A pressure Swing adsorption process for separating a

pressurized supply feed gas containing one or more strongly
adsorbable component from at least one less strongly adsorb
able product gas in a six bed adsorbent system where the
process cycle has eighteen steps including three bed-to-bed 25
equalizations steps, while two of the beds are in production, in
accordance to following cycle chart:

Bed Step:
H 1 2 3 4. 5 6 7 8 9 1O 11 12 13 14 15 16 17 18
1 A1 A2 A3 A4 AS A6, E1 E1 E2 PPG E3. BD2 PG E3' E2" E1' E1' PP
PP BD1

5 E1 E1 E2 PPG E3, BD2 PG E3' E2' E1 E1' PP A1 A2 A3 A4 AS A6,

BD1 PP
6 A4 AS A6, E1 E1 E2 PPG E3. BD2 PG E3' E2' E1' E1' PP A1 A2 A3
PP BD1

wherein:
A1 = First Adsorption Step
A2 = Second Adsorption Step
A3 = Third Adsorption Step
A4 = Fourth Adsorption Step
A5 = Fifth Adsorption Step
A6/PP = Sixth Adsorption Step Product Pressurization
E1 = First Equalization Down
E2 = Second Equalization Down
PPG = Provide Purge Gas
E3:BD1 = Third Equalization Down. First Blowdown
BD2 = Second Blowdown
PG = Purge
E3 = Equalization Up (using gas from E3 step)
E2 = Equalization Up (using gas from E2 step)
E1 = Equalization Up (using gas from E1 step)
PP = ProductPressurization