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PRES 2007, Ischia, Italy

Hydrogen purification by Pressure Swing Adsorption


Dragan Nikolic1, Apostolos Giovanoglou2, Michael C. Georgiadis3, Eustathios S. Kikkinides1
University of Western Macedonia, Department of Engineering and Management of Energy Resources, Kozani, Greece 2 Process Systems Enterprise Ltd, London, UK 3 Imperial College London, Centre for Process Systems Engineering, Department of Chemical Engineering, London, UK
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June 2007

Overview
1. 2. 3. 4. 5. 6. Motivation Modelling framework Process overview New PSA cycles Results Conclusions

1. Motivation
Why H2: Increasing demand for H2, particularly in petroleum refineries and in the petrochemical processes (99.99+%). Why PSA: Since hydrogen is adsorbed much less than almost any other components, PSA has a clear advantage over almost all other possible approaches. Several ways to improve the separation quality and power requirements:
Multibed PSA configurations Multilayered adsorbents Adsorbent mixture Hybrid systems (such as hybrid PSA and membrane units) Specially designed multibed PSA process for the simultaneous production of pure H2 and CO2 from SMROG (Sircar and Golden, 2000; Sircar and Kratz, 1988)

Generic PSA modelling framework is being developed to support all the above features.
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2. Modelling framework
All feasible inter-bed connectivities Hierarchical model decomposition

Flowsheet model Operating procedures of the whole plant are easily generated by an auxiliary program

Main building block


Source StrongPurge(i)

(N-1) connections from the other beds

V(i)-4

Arbitrary number of beds (main building block can V(i)-5 be replicated through an input parameter)
Layer (n)
SourcePurge(i) SinkHeavy(i)

SinkLight(i) Source Feed(i) Adsorber (i) V(i)-1 V(i)-2

Ni qi
r

Layer (1)

V(i)-3

2. Modelling framework (contd)

Model of the main building block All PSA steps are supported
V(i)-5

(N-1) connections from the other beds

V(i)-4

Feed and product streams


Layer (n)

SinkLight(i) Source StrongPurge(i) Source Feed(i) Adsorber (i) V(i)-1 V(i)-2

SourcePurge(i) SinkHeavy(i)

Ni qi
r

Layer (1)
V(i)-3

2. Modelling framework (contd)

Adsorption column model

Boundary conditions (N-1) connections from the other beds for all PSA steps
V(i)-4 V(i)-5

Support for one or more adsorbent layers

SinkLight(i) Source StrongPurge(i) Source Feed(i) Adsorber (i) V(i)-1 V(i)-2

SourcePurge(i) SinkHeavy(i)

Layer (n)

Layer inter-connections

Ni qi
r

Layer (1)
V(i)-3

2. Modelling framework (contd)


( uCi ) Ci 1 bed C Ni = Dz ,i i , z ( 0, L ) , i = 1, , N comp + + z t bed z z

( c p uT ) ( c pT ) 1 bed 3k T q g + h,wall (T Twall ) = z + + , z ( 0, L ) z t bed bed Rbed z z

Adsorbent layer model Mass and heat transfer through the particle surface is the only information exchanged between the interstitial fluid and the adsorbent particles

(N-1) connections from the other beds

V(i)-4

Single adsorbent or adsorbent mixture V(i)-5

SinkLight(i) Source StrongPurge(i)

Single adsorbent or SourcePurge(i) Source adsorbent mixture Feed(i) SinkHeavy(i)


Adsorber (i) V(i)-2 V(i)-3

Layer (n)

Ni qi
r

Layer (1)

V(i)-1

2. Modelling framework (contd)

Adsorbent particle model


(N-1) connections from the other beds

Film around the particle

* Cip C p 1 2 V(i)-4 Q De + (1 p ) p i = p 2 RV(i)-5 ,i i p t t r R p r


SinkLight(i) Source Feed(i) Adsorber (i) V(i)-1 V(i)-2 V(i)-3

r ( 0, R p ) , z [ 0, L ] , i = 1, , N comp
SourcePurge(i) SinkHeavy(i) Source StrongPurge(i)

Mass and heat flux through the particle surface Mass transfer within the particle can be described by any Layer (1) transport mechanism (LEQ, LDF, SD, PD)
Layer (n)

Ni qi
r

2. Modelling framework (contd)


Original algorithm Modified algorithm
A group: Input: Number of beds Input: Sequence of steps in one bed Input: Number of A and B beds Input: Sequence of steps in A and B group of beds
Adsorption Co-current rinse Blowdown Evacuation Pressure equalization Counter-current pressurization

Example:
Co-current pressurization Adsorption Pressure equalization 1 Pressure equalization 2 Blowdown Purge Pressure equalization 2 Pressure equalization 1

B group:
Adsorption Pressure equalization Blowdown Purge Counter-current pressurization

Try to connect the beds

Try to connect the beds

No

Success?
Yes

No

Success?
Yes

Step 1 Step 2 Step 3 Step 4 Step 5 Step 6 Step 7 Step 8 Bed Bed Bed Bed Bed Bed Bed Bed 1 2 3 4 5 6 7 8
CoCP EQR1 EQR2 Purge Blow EQD2 EQD1 Ads Ads CoCP EQR1 EQR2 Purge Blow EQD2 EQD1 EQD1 Ads CoCP EQR1 EQR2 Purge Blow EQD2 EQD2 EQD1 Ads CoCP EQR1 EQR2 Purge Blow Blow EQD2 EQD1 Ads CoCP EQR1 EQR2 Purge Purge Blow EQD2 EQD1 Ads CoCP EQR1 EQR2 EQR2 Purge Blow EQD2 EQD1 Ads CoCP EQR1 EQR1 EQR2 Purge Blow EQD2 EQD1 Ads CoCP

1 Bed-1 Bed-2 Bed-3 Bed-4 Bed-5 Bed-6


A E B B A B

2
A E B B A P

3
R E E B E P

4
R P+ E B B P+

5
B A E B B A

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B B A E A B

10 11 12 13 14 15 16
B E E B B B A R R E ER1 P+ A ED1 B P P P+ E B B A B A E ER1 B E B B A R P P A ED1 P+ E B R P+ B

B B B A R R E ER1 P+ B E E B P P A ED1 B

3. Process overview
Two types of beds (called type A and B) Each type contains different adsorbent and undergoes different cycle steps
A activated carbon B zeolite 5A

The most distinguishing features:


Co-current CO2 rinse at feed pressure in type A Use of different regeneration methods
Type A: (depressurization and evacuation) Type B: (depressurization and purge)

Pressure equalization between A-B and B-B beds to ensure mass conservation of the interstitial fluid.
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3. Process overview (contd)


Series of steps in type A beds(*,**):
High pressure adsorption (to type B bed) Co-current purge (rinse) by CO2 Counter-current blowdown (to atmospheric P) Counter-current evacuation (to sub-atmospheric P) Pressure equalization (repressurization) Counter-current pressurization (by H2)

Series of steps in type B beds(*,**):


High pressure adsorption (from type A bed) Pressure equalization (depressurization; B-A or/and B-B) Counter-current blowdown (to atmospheric P) Counter-current purge (by H2) Counter-current pressurization (by H2)
* Sircar, S., Kratz, W.C., 1988, Simultaneous production of hydrogen and carbon dioxide from steam methane reformer off-gas by pressure swing adsorption, Separation Science and Technology, 23, 2397 ** Sircar, S., Golden, T.C. 2000, Purification of hydrogen by pressure swing adsorption, Separation Science and Technology, 35, 667 11

4. New PSA cycles


Based on the industrial plant (6+3 beds), three new PSA cycle configurations have been developed by using the program for automatic generation
1 2 A B A 3 R E B 4 R E P 5 B P+ P+ 6 B A A 7 B A A 8 E R B 9 E R P 10 P+ B P+

(2+1)
1 B-1 B-2 A E B B A B 2 A E B B A P

B-1 B-2 B-3

A B A

3 R E E B E P

4 R P+ E B B P+

5 B A E B B A

6 B A E B B A

7 B R ER1 E P ED1

8 B R P+ E P B

9 B B A E A B

10 B B A E A P

11 E B R ER1 ED1 P

12 E B R P+ B P+

13 E B B A B A

14 E B B A P A

15 ER1 E B R P ED1

16 P+ E B R P+ B

(4+2)a

B-3 B-4 B-5 B-6

1 B-1 B-2 A E B B A P

2 A E B B A P

3 R P+ E B ER1 ER1

4 R P+ E B B P+

5 B A E B P A

6 B A E B P A

7 B R P+ E ER1 ED1

8 B R P+ E P+ B

9 B B A E A P

10 B B A E A P

11 E B R P+ ED1 ER1

12 E B R P+ B P+

13 E B B A P A

14 E B B A P A

15 P+ E B R ER1 ED1

16 P+ E B R P+ B

(4+2)b

B-3 B-4 B-5 B-6

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5. Results
High H2/CO2 purity & recovery comparable to the original process Good quality tertiary product (suitable for a fuel gas) Lower capital cost
Products N beds (2+1) (4+2)a (4+2)b (6+3)
Purity, % Recovery, % Purity, % Purity, % Recovery, % Purity, % Recovery, % Recovery, %

H2
99.992 82.289 99.997 85.560 99.991 86.038 99.99+ 87.10

CO2
99.948 85.664 99.940 85.731 99.938 86.209 99.40 94.00

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6. Conclusions
A previously developed generic PSA modelling framework for PSA flowsheet generation is successfully employed in the process of simultaneous H2 and CO2 production from SMROG under high product purity and recovery requirements. In order to improve the separation performance, new complex PSA cycle configurations have been designed and simulated. In the proposed configurations two different types of beds have been employed, which contain different adsorbents and undergo different steps during the process cycle. Comparable primary and secondary product purities, recoveries and power requirements with the conventional PSA cycles are obtained. Capital costs are lower due to the lower number of beds. The proposed PSA cycle configurations exhibit comparable separation performance with the conventional cycles at a lower capital cost 14

Acknowledgements
Financial support from PRISM EU RTN (Contract number MRTN-CT-2004-512233)

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