Hydrogen from refinery offgas

Utilisation of refinery offgases for hydrogen production. Three basic schemes of

ROG integration into a steam reformer plant were investigated
Harald Klein Linde Engineering Division

n the past, hydrogen containing refinery offgas plant producing 100,000Nm3/h of pure hydro(ROG) has been routed into the refinery fuel gen was selected. The purge gas from the steam
gas system where only the heating value of the reformer plant PSA system is routed to the
gas has been used. Since the hydrogen demand burner system of the steam reformer firing. It
for refinery operations is growing, these gases was assumed that fuel export to the refinery fuel
become more and more attractive as a source for system was not feasible. ROG containing 80 per
hydrogen production. This requires purification cent and 50 per cent hydrogen were
steps such as pressure swing adsorption (PSA) investigated.
or membrane systems. However, if the ROG
hydrogen content is too low, these options Common PSA system
become less economical and the direct usage of In the process scheme configured with a PSA
ROG as steam reformer feed is an attractive system, the ROG is routed directly to the PSA
alternative. This presentation outlines the key system of the steam reformer plant. Depending
features of the described processes and intro- on the pressure of the ROG, it may be required
duces a guideline for optimised process to compress it to the required PSA pressure.
selection.
However, in the present study it was assumed
The hydrogen content in ROG varies from 5-10 that ROG is available at a pressure high enough
per cent, up to values of90 per cent. Therefore, to meet the required PSA pressure, which is
their utilisation in the hydrogen production usually fixed by the desired hydrogen product
scheme of a refinery must be evaluated on a pressure.
case-by-case basis. Hydrogen recovery from ROG
Due to the additional feed stream to the steam
using PSA, membrane technology or cryogenic reformer plant PSA system, the purge gas steam
processes can be appliedto generate hydrogen from the PSA increases. Since all purge gas must
streams of any required purity. The offgas be utilised in the steam reformer firing system,
streamsfrom these processes
can be routed to the refinery
Hydrogen
24 bar
fuel gas system. Another
Pressure 100,000 Nm3/h
Feed
Free
Steam
Co-shift
swing
option is using the offgas as
pretreatreforming
conversion
NG
adsorption
ment
(supplementary) feedstock to a
40 bar
steam reformer plant, which
Purge
Fuel
also generates hydrogen from
hydrocarbons such as natural
gas, LPG or naphtha. Three
basic schemes of ROG integraImpurities
Pressure swing
tion into a steam reformer
removal
adsorption
ROG
80%, 50% H2
plant were investigated within
25 bar
Linde Engineering. As a basis
for all comparisons, a natural Figure 1 Common PSA system schematic with ROG pressure high enough to
gas-based steam reformer meet required PSA pressure

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Gas 2007 1

ROG contribution must limited

to 8 per cent. The savings of
this process scheme for an
amortisation time of five years
show
approximately
$1.6
million/yr at 80 per cent
hydrogen contribution and
approximately $0.5 million/yr
at 50 per cent hydrogen contribution. It was assumed that
the heat value-based price for
the ROG is the same as the
natural gas price (1 $/
MMBtu).

100

Design capacity

90

80

70
Reformer, 80% H2
PSA, 50% H
PSA, 80% H2

60

50

10

20

30

40
50
60
70
Contribution of ROG, %

80

90

100

Figure 2 Design capacity of the steam reformer can be reduced by increasing

the amount of ROG to the PSA

12.0
80% H2
50% H2

10.0

Total savings, Mio $

8.0
6.0
4.0
2.0
0.0
2.0
4.0

20

40
60
Contribution of ROG, %

80

100

Figure 3 Savings available from common PSA process scheme

the amount of ROG, which can be routed to the

common PSA, is limited. With this type of
scheme, it can be shown how the design capacity
of the steam reformer can be reduced by increasing the amount of ROG routed to the PSA, which
cannot be decreased in size. This process scheme
is a very economical option to utilise ROG in a
steam reformer plant. However, due to the purge
gas increase along with reduced reformer firing,
the amount of ROG must be limited to12 per
cent if the ROG contains 80 per cent of hydrogen. If the hydrogen content is 50 per cent the

2 Gas 2007

Direct feed to reformer

If the hydrogen content of the
refinery fuel gas becomes as
low as 50 per cent, the usage
of ROG as direct reformer feed
is the preferred option. It can
be seen that the reformer size
can be reduced by more than
10 per cent such that the
savings can add up to a significant value of $4 million. If the
hydrogen content of the ROG
is as high as 80 per cent, the
contribution must be limited
to approximately 40 per cent:
too much hydrogen is routed
to the reformer along with the
ROG feed, such that the
required reformer heating
drops below the available heat
supply via purge gas from the
PSA system.

Dedicated PSA system for

ROG

A dedicated PSA system for the refinery offgas

upstream of the steam reformer plant is shown
in Figure 1. No upper limitation concerning the
contribution of ROG must be considered
(Figure 2). However, the option is not economical for refinery offgases showing the lower
hydrogen content of 50 per cent resulting in
negative savings (Figure 3). The re-compression
of the offgas from the ROG PSA requires additional investment as well as a significant
amount of electrical compression power.
Therefore, the implementation of a dedicated

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ROG PSA system pays off only if the

hydrogen content is as high as 80 per
cent and the ROG contribution is above
40 per cent.

Summary

ROG utilisation in steam reformer hydrogen plant

Common PSA
8%
Direct feed to reformer 74%
Dedicated PSA for ROG 100%

Table 1 summarises the described process option of ROG utilisation in a steam

reformer hydrogen plant. The recommen- Table 1
dations are rough guidelines, the actual
process selection must be evaluated caseby-case, depending on the actual economical
figures of the project.
Harald Klein is manager process engineering, hydrogen and
synthesis gas plants, Linde Engineering Division.
Email: harald.klein@lindegas.com

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Max. ROG contribution

50% H2
80% H2

12%
39%
100%

Savings (million $)
50% H2 80% H2
0.6
4.0
-3.3

1.6
4.0
10.4

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