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56 posts
Posted 26 March 2009 - 12:23 AM
Dear All,
I am doing a kind of research on Natural gas steam reforming for syngas production , my basic
objective is to find out methane slip ( Amount of methane i.e. mole percent that can be allowed in the
reformer outlet ) of a reformer with respect to its application like Ammonia production , Methanol
production , hydrogen production , Carbon monoxide production etc . I am trying to understand
whether methane slip depends on factors like
1. Reformer outlet temperature: At high temperatures methane slip will be low (change in
temperature will affect energy optimization and change the steam balance in the reforming section)
If this is the only reason then methane slip is fixed by energy optimization
2. Catalyst: If methane slip depends on the catalyst then catalyst selection is the guiding factor for
fixing the methane slip , I doubt this because equilibrium composition at reformer outlet is limited by
thermodynamics , which may not depend on catalyst .
Actually I am not clear how to approach this
Any experts having worked on reforming can throw some light on this , you can suggest some
papers or books or your views
I appreciate your help
thank you

Regards ,

Satish

#2 astro
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72 posts
Posted 29 March 2009 - 11:50 PM
Satish, reviewing the chemical reactions (the 1st is largely endothermic, the 2nd is slightly
exothermic) involved is useful to support discussion:

CnHm + n H2O n CO + (m/2 + n) H2

CO + H2O CO2 + H2

Given the net endothermic nature of the reactions, you are quite correct in identifying that increasing
temperature will generally drive the reaction forward. However as Chemical Engineers we need to
be aware of issues that extend beyond chemistry and one of those areas is Materials Engineering.
The high alloy steels that are used in steam reformer tubes are susceptible to creep rupture at the
elevated temperatures that drive the reforming reactions forward. So much so, that a small increase
in tube wall temperature can have a marked reduction in the service life of the tube metal.

Reverting to chemistry and applying Le Chatlier's principle of mass action, the reactions imply that
an increase in the proportion of steam will also drive the reaction forward. However this comes at an
energy cost to heat the steam and increases the fluid flow through the system, increasing pressure
drop (and hence energy costs) and increasing the size of the process plant.

Catalyst activity is very important, which is why it is sensible to design for "end of run" catalyst
conditions to give a worst credible case scenario for design and sizing. Catalyst suppliers go to great
pains to show that their catalyst provides the best activity while offering low pressure drop and
robustness (low propensity to breakage and dusting) over time.

It is difficult to be specific because the conditions and constraints around an individual application
will influence the design (which is a balance of compromises). Typically the design process will
involve the catalyst suppliers, as they have substantial experience that is supported with process
guarantees.

To my knowledge, the cornerstone reference for this area of study is the Catalyst Handbook:
Catalyst Handbook
If you can source a copy, you would be well advised to hold on to it and treat it with care.

#3 iplan
Veteran Member

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48 posts
Posted 30 March 2009 - 01:48 PM
Satish,

In the steam methane reforming, following factors can contribute to a reduction in methane slip.

1. Increased reformer outlet temperature .

2. Increased steam / carbon ratio.

There is a term called "Approach to equilibrium" in steam methane reforming reactions( CH4 + H20 -
> CO + 3H2). It is the difference between the actual reformer outlet temperature at which you have a
particular methane slip and the theoretical temperaure at which the same methane slip would have
been obtained had there been a perfect equilibrium. Normally designers design around 20 deg F as
Approach. So if you increase the temperature your methane slip will decrease but you will also move
away from equilibrium.

As Astro points out, the reformer outlet temperature is limited by the mechanical design of the tube
material. They are subjected to creep and are normally designed to have a life of 100000 hours of
operation.

Lastly,by Le Chatlier's principle number of moles increase in the products and therefore decreased
pressure drives the reaction to forward direction and decreases methane slip. But again as Astro
says, if the pressure is reduced, the size of equipment / piping go up which may not be economical.

Thanks
iplan

#4 Srikrishna Chaitanya
Gold Member

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56 posts
Posted 06 April 2009 - 01:21 AM

Dear Astro ,
thank you very much for the reply and sharing your knowledge , this going to help me a lot

#5 Srikrishna Chaitanya
Gold Member

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56 posts
Posted 06 April 2009 - 01:31 AM
Dear Iplan ,

thank you very much for the reply

this approach, has it got some thing to do with Application like Reformer in Ammonia plant ,
Reformer in Hydrogen plant etc. ?? Can you please throw some more light on approach

#6 iplan
Veteran Member

ChE Plus Subscriber

48 posts
Posted 11 April 2009 - 08:54 AM
Satish,

This Approach to equilibrium is applicable for all steam methane reforming processes. Hence it is
applicable in Ammonia plant steam refomers as well as hydrogen plant steam reformers. All
equilibrium driven reactions have this Approach to equilibrium concept. To know more on this , You
can refer to the techology supplier like Haldor Topsoe manuals or ICI katalco manual.

I am not sure what is the objective of your research , but it will be greatly helpful if you refer these
manuals.

Many thanks,
iplan

#7 Srikrishna Chaitanya
Gold Member

Members

56 posts
Posted 12 April 2009 - 11:49 PM
Dear ,
Can you please tell me manual means thats the operating manual given by TOPSOE or broachers
we get in TOPSOE website , how do I get that , I appreciate if you provide me some links

#8 Ahmed Mohamed Khater

Brand New Member

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2 posts
Posted 09 October 2011 - 09:22 PM
The steam reforming of saturated hydrocarbons can be represented by the three reactions: C
n
H
m
+ nH
2
O nCO + (n+m/2) H
CO + 3H
2
CH
4
+H
O CO + H
2
O CO
2
+H
2
2
2
An excess of steam is required to suppress carbon formation and promote the reforming reaction, so
that the steam ratio is normally in the range 2.5 3.5 for ammonia and methanol plants, 2.5-5.0 for
hydrogen plants, and 1.6-2.5 for H
/CO plants. Also despite the thermodynamics of the process, reformers operate at high pressure to
optimize the overall

#9 S.AHMAD
Gold Member

ChE Plus Subscriber

786 posts
Posted 09 October 2011 - 11:06 PM
Attached graphs may be helpful
Attached Files