Hydrogen Energy: Production, Storage, Transportation and Safety

Prof. Pratibha Sharma

Department of Energy Science and Engineering
Indian Institute of Technology, Bombay

Lecture - 05
Steam Methane Reforming Part - 2

In the last class we have seen the 3 steps involved in the steam reforming process. These were
feedstock pretreatment process, the major steam methane reforming and the third one was
water gas shift also known as carbon monoxide shift reaction.

(Refer Slide Time: 00:44)

Now, today we will see the 4th step in the steam reforming . So, the last step which is the
purification step that determines which water gas shift reaction reactor will be there. If it is
pressure swing adsorption is the purification technique which is being utilized then only high
temperature water gas shift reactor will be there.

However, if there is a change in the purification technique, a low temperature water gas shift
will be followed if the final purification stage is carbon dioxide solvent based purification
technique to get pure hydrogen.
(Refer Slide Time: 02:24)

So, if solvent based carbon dioxide removal method is being used, in that case we know that
from the low temperature water gas shift less than 1 percent of carbon monoxide is left and
that can undergo preferential oxidation to convert into carbon dioxide.

Now, various solvents are being used to remove the carbon dioxide formed and the
preferable ones are mono ethanol amine, this is the most widely being used. Ammonia
solution, methanol, potassium carbonates, there are many solvents which are available, which
absorb carbon dioxide to reduce the carbon dioxide content in the product to about 100 ppm.
Now whatever is the left out carbon monoxide and carbon dioxide remaining in the product
gas that can undergo methanation reaction in the methanator to finally, convert into methane.
So, this is one type of purification.
(Refer Slide Time: 03:46)

If however, pressure swing adsorption is used for purification in that case various adsorbents
can be used. So, different sorbents can be used wherein on the surface of which the impurities
like carbon monoxide, carbon dioxide, methane can get sorbed, so that we can remove all
these impurities and we can get pure hydrogen as the product.

Now, primarily molecular sieves are being used for the separation of carbon dioxide or
carbon based species and get pure hydrogen. Now, in these sorbents adsorption and
desorption of the impurities occurs on the change of pressure that is why the name is pressure
swing adsorption and we can get high purity hydrogen when all these impurities are
selectively adsorbed on to the adsorbent surface.

After hydrogen is being obtained which is of high purity, the remaining off gas or tail gas
itself has a certain amount of hydrogen and it has a calorific value; so that this off gas or tail
gas from the pressure swing adsorption can be used as a fuel in burner in the reformer. So,
this is about the purification step involved as the last step in the steam methane reforming.
So, we have seen all the four steps separately.
(Refer Slide Time: 05:59)

Now, let us see them together, so that we can know about the complete steam methane
reforming process. Now, as we have seen natural gas acts as both fuel and feedstock in the
steam methane reforming process. So, it acts as a feedstock entering into the desulphurisation
unit and it acts as a fuel and supplies the required heat to the burners of the steam methane
reformer.

(Refer Slide Time: 06:27)

In the first step a small split steam of hydrogen from the product side is used for catalytic
hydrogenation of sulphur containing compounds on a sulphur tolerant catalyst, which is
cobalt molybdenum catalyst at a temperature of 290 to 370 degree centigrade and that forms
H2S. This H2S which is formed is scrubbed on a zinc oxide bed to form ZnS and steam.

(Refer Slide Time: 07:13)

Now, once the sulphur containing impurities are removed in the desulphurisation unit, the
treated natural gas goes to the second step which is the steam methane reforming process
wherein methane is pretreated and the sulphur containing impurities are removed.

It is preheated and compressed along with steam at 2.6 MPa with a steam to carbon ratio of
2.5 to 3, an excess of steam to carbon ratio is required so as to reduce coke deposition. These
are fed into the primary reformer or the main reformer unit which is the steam methane
reformer.

Now, preheated natural gas along with steam enters into the reformer tubes, wherein it is a
catalyst bed containing nickel on alumina and the reforming reaction takes place, methane
reacting with steam to give syn gas.
(Refer Slide Time: 08:19)

Now, these are tubular reformers tubular box type of furnace, wherein depending on where
the burner is located these can be either top fired reformer, bottom fired reformer if the
burners are on the bottom side, side fired reformer or terrace fired reformer.

In an industrial scale steam methane reformation plant there are hundreds of such tubes
arranged in a reformer wherein the length of these tubes is somewhere around 9 to 15 meters.
Its inner dia is around 7.5 to 12.5 centimeters with thickness of 1.2 centimeter.

Now, the heat which is required for the endothermic reaction that takes place in these
reformer tubes is supplied by burning of the combustion of the fuel which is again natural gas
along with air which is fed to the burners and on the combustion of it supplies the required
heat.

Now, as we know that it is a very endothermic process, it requires lot of heat reaction takes
place somewhere between 700 to 950 degree centigrade and because the reason for very high
temperature both your feedstock as well as the oxidant are inert. So, a large amount of
energy is required to make them active and react.
(Refer Slide Time: 09:49)

In this process of combustion which is taking place in the burner 50% of the heat which is
being supplied is taken up for the reforming reaction in the tubes; however, the remaining
heat which comes with the combustion gases or the flue gases that can also be utilized. So,
the rest of the heat is recovered in a heat recovery section and that heat which is extracted
from the reformer, from the combustion flue gases coming out from the reformer can be used
either for steam generation or it can also be used for preheating the natural gas before it
enters into the reformer.

(Refer Slide Time: 10:38)

Now, the next step as we have seen is water gas shift reaction, wherein more hydrogen can
be extracted. Carbon monoxide reacts with steam to produce carbon dioxide and one more
mole of hydrogen. This reaction occurs at a temperature of 340 to 360 degree centigrade and
this is slightly exothermic reaction; that means, it will be favored at lower temperature.

However, if we see the syn gas which is obtained from the steam methane reformer the
temperature of it is around 750 to 900 degree centigrade and the required temperature for
water gas shift reaction is approximately 350 degree centigrade. It has to be cool down from
750 to 900 to 350 degree centigrade and again that much of amount of heat is removed and
can be utilized for steam generation.

(Refer Slide Time: 11:34)

In the last step which we have seen today is purification step, finally, the product gas obtained
after water gas shift goes to the pressure swing adsorption unit, wherein there is a batch
process; however, using multiple adsorbent bends beds can made it continuous. And after
PSA we get pure hydrogen with a purity of 99.999 percent pure at a pressure of
approximately 14 bar.

However, there is still sufficient amount of hydrogen and other gases which have a certain
calorific value are there in the tail gas or PSA off gas, that goes to the burner of the catalytic
reformer steam reformer and can be used as a fuel for heating up and for the conduction of
the endothermic steam methane reforming process.
(Refer Slide Time: 12:33)

So, this is all about the reforming process; however, catalyst is an important part of the steam
reforming reaction and we know that catalyst is actually a substance that increases a rate of
the reaction, but it is not consumed in the reaction.

When it comes to steam methane reforming, there are several requirements that the catalyst
need to meet out like, it should be robust under the stringent operating conditions; conditions
like at the inlet of steam reformer temperature is about 450 to 650 degree centigrade. At the
outlet it is 750 to 900 degree centigrade and the catalyst has to sustain under these
temperature gradient temperature conditions.

It should have high catalytic activity. It should be thermally and mechanically stable. It
should show acceptability towards certain change in the feedstock so, a variety of feedstocks.
Definitely long cycle life is important. Cost, it should be less expensive, low in terms of cost.
It should also show stability under transient conditions.

At the time of startup or shutdown, under those transient condition the catalyst should be
stable enough. Pressure drop across the deformer should be lower in the catalyst bed and its
heat transfer characteristic should be good.

So, these are the requirements in terms of the catalyst while selecting a catalyst it ideally
should meet out these requirements.
(Refer Slide Time: 15:41)

We know that when we are talking about a catalytic process, in the catalytic process on the
surface of the catalyst the reactants adsorb, they undergo different reactions, bonds are
formed, bonds are broken and finally, the product is formed and then catalyst returns back to
its original initial state.

So, various steps which are involved in a catalytic process is first is the bulk diffusion
wherein the reactants reach the catalyst surface. Thereafter the catalyst gets sorbed on the
active sites of the reactants and get chemisorbed onto active sites or nearby sites of the
catalyst.

In the third step, bonds break and bonds are formed leading to product formation. Once the
product is formed thereafter the product has to desorbed from catalyst surface. Finally, it has
to undergo the bulk diffusion from surface into the catalyst bed and finally diffuses into the
mainstream: mainstream of the product gas

Now, if we see these processes process 1, process 5, and process 6, these are actually sort of
physical processes wherein these depends upon the physical properties of catalyst, of active
support and the media. However, if we see the process 2, process 3 and process 4 these are
chemically activated process where reactants are consumed, conversion of reactants takes
place, formation of product takes place, formation of various intermediates before the
formation of product occurs.
So, the interaction between the catalyst support and reactants to form product is more
important. Now, in a catalytic process any of these reactions can be the rate limiting step. In
the whole process any of these out of the 6 processes can be the rate limiting step. Now, let us
come back to the steam methane reforming, we know that the catalyst plays a dominant role.
It is not only catalyst alone, but the support in the promoter that also plays a dominating role.

(Refer Slide Time: 20:08)

Now, when we talk about industrial scale hydrogen production using the steam methane
reforming, primarily the catalyst which is being used is nickel. So, there are several
advantages of having nickel catalyst that it is showing activity which is good, it is stable
under the operating conditions and it is low cost. However, at the same time there are certain
disadvantages or issues associated with the nickel catalyst that it is more prone to
deactivation and sintering.

So, in that case there are several other catalyst which has also been looked at by the
researchers including the noble metal catalyst, ruthenium, rhodium, iridium, platinum
palladium. So, these are the catalysts which have also been looked at for the reforming
reaction, but the major issue that comes in while using on an industrial scale is the high cost
of the catalyst. Now, there are several factors which also affect are the heat transfer, the
pressure drop, the conditions inside the catalyst bed.

And primarily if we look at the catalyst design we have to consider the factors like what is the
shape of the catalyst, what is the size of the catalyst, surface area associated, the methods by
which these are synthesized that also affect the catalytic process. All these factors can affect
the pressure drop, the heat transfer characteristic from the reactor walls to and from the
reformer tube walls to the reactant.

(Refer Slide Time: 22:16)

Like for if we see the pressure drop, size has a very important effect in the pressure drop. So,
what we want is the pressure drop in the catalyst bed should be low. Now, this pressure drop
depends upon the void fraction inside the catalyst bed. And if we say that the particle size of
the catalyst is lower then we can see that the pressure drop inside the bed will be higher.

So, there should be an optimum because, we want better heat transfer at the same time we
want a lower pressure drop. So, the void fraction should be higher in order to keep that. We
need to optimize the conditions inside the catalytic bed. The shape of the catalyst also affects
the reforming reaction.

Herein there are several shapes which has been looked at like rings, cylinders, cylindrical
shape with holes, then there are gear wheel type of catalyst, spoked wheel type of catalyst,
multi channel catalyst have been used they all having holes, so as to have the required flow of
the gases inside.

Most widely used one are the multi channel catalyst having several holes. Size again is
important here. The size determines the pressure drop at the same time: it will also determine
the heat transfer across the bed. Now, for example, if size is lower i.e., for small size of the
catalyst heat transfer will be better, but at the same time pressure drop will be higher.

So, there should be an optimum size of the catalyst to be decided so as to have a lower
pressure drop at the same time having a higher heat transfer characteristics. Usually the
catalyst are supposed to operate stably for long hours typically about 5 years of continuous
operation is required without any loss of the activity.

(Refer Slide Time: 25:09)

Now, other than the catalyst, support again is very important and that plays a dominating role.
There are several requirements for the support when it is to be used along with the catalyst.
We know that support should have a very good dispersion. It should stabilize the catalyst. It
should ensure high surface to volume ratio. It should withstand the conditions of operation
inside the reformer. It should provide good interaction between the reactants and the catalyst
and that will reduce the catalyst deactivation and sintering.
(Refer Slide Time: 27:27)

So, these are ideally the requirements when a catalyst support is being looked at. For
industrial scale hydrogen production mostly nickel on alumina support is being used as a
catalyst in the reformer tubes. Other than alumina there are several other catalyst support
which are being studied like magnesium oxide, magnesium aluminium oxide, zirconia,
titania, ceria these are the other support which are being studied and reported in the literature.

Now, each of these have their own characteristics like alumina it has slightly acidic character
that promotes reforming reaction. However, if we look at magnesium oxide then this reduces
coke formation or it promotes the carbon gasification reaction. Zirconium oxide has good
performance. So, all of these supports have their own characteristic. Cerium oxide is less
prone to coking. So, these are the characteristic of these support materials which have been
studied in literature.
(Refer Slide Time: 29:18)

Now, other than the catalyst and support, a small quantity of promoters are added and this
addition of promoters suppresses coke deposition onto the catalyst surface. The catalyst
promoters are used includes alkali metal elements like potassium, alkaline magnesium and
calcium. Transition metal based including molybdenum and tungsten from the lanthanide
series, lanthanum and cerium.

So, when a small quantity of these promoters is being added this is beneficial and reduces the
carbon formation on the surface of the catalyst.

(Refer Slide Time: 30:25)

Now, if we look at the catalyst the major challenges which are associated with the catalyst
bed, then there are lot many factors that needs to be taken care of which are the primary
constraint for the catalyst poisoning or deactivation which is basically caused because of the
presence of impurities, because of the carbon deposition.

Now, this carbon deposition has a substantial effect onto the catalyst deactivation. Now what
that leads to is either it can cause partial or complete blockage of the reformer tubes and
when it causes blockage of the tubes there will be a pressure drop, uneven flows and that
uneven gas flows can result into formation of hot spots that can increase tube wall
temperature which is highly undesirable, uneven fluxes and that can even lead to a times tube
failure. So, this catalyst deactivation is a highly undesirable when it is into the reforming
reaction.

(Refer Slide Time: 32:00)

However, for carbon formation it has been known from the thermodynamics that it takes
place at a lower temperature below 500 degree centigrade. There can also be problems
associated with the catalyst breakage and that catalyst can break under transient conditions.
The breakage is mainly observed when it is either starting up or shutting down of the reactor.
The catalyst can lose its mechanical strength during that or it can be because of the pressure
which is exerted inside the reformer tube.

There can be certain thermal stresses if there is a cooling that can lead to catalyst breakage
and this is always undesirable in the reforming process. What is actually required is a uniform
catalyst loading and that can lead to stable operation over longer duration for prolonged
operation. If however, there is a non uniform catalyst loading then that non uniform catalyst
loading can again give rise to several issues.

There will be uneven flows, there will be temperature gradients that will be there, there will
be uneven pressure drop inside the column, hot spots will be created and that can lead to tube
damage and reduced tube life. So, that is highly undesirable. Besides these there could be a
problem which is associated with the catalyst settling and that can also create problems.

(Refer Slide Time: 34:42)

Now, what are the ways to address these? The ways to address these problems is first we have
to select the appropriate combination of catalyst support and promoter. Other than that the
design of the reactor, of both reformer and tubes is very important.

Now, we talk about the catalyst deactivation: deactivation can be reduced or the carbon
formation can be reduced by high steam to carbon ratio and ideally it should be somewhere
between 2.5 to 3. At the same time with the proper choice of promoters carbon formation can
be reduced. If there are higher hydrocarbons present then a pre reforming unit is essential.
And the use of noble metals or bimetallic, although these are expensive, but could be
beneficial against the carbon deposition.
(Refer Slide Time: 36:51)

Now, we have seen that there are challenges associated with the reformer and the major
limitation in the reformer seems that the catalytic activity could be the major challenge, but it
has been observed that the catalytic activity definitely could be the rate limiting step but at
the same time the heat transfer characteristics, the heat transfer is prominently or the major
limiting factor when it comes to the operation of a steam methane reformer.

Now, although the catalytic activity decides the rate of the reaction, but the heat transfer is
found to be the major rate limiting step. So, when it is up to designing the reformer a proper
heat transfer or thermal management is very important. At the same time the thermal
conductivity of the support is also important. Now, when it comes to designing the reformer
there are several heat transfer considerations that need to be taken care of.
(Refer Slide Time: 38:18)

And these design concentrations that need to be taken care of includes the temperature, the
pressure that will be there in the reformer, the material with which the reformer tubes are
being made and their rupture strength. So, the materials which are highly temperature
resistant could be used for making the reformer tubes that can sustain such high temperatures
and pressure. Now, when heat transfer calculations are being done, then we have to see the
heat transfer not only from the burners, but till the point where heat of reaction goes to the
reactants.

So, all the heat transfer aspects needs to be considered - radiation which is taking place from
the walls of the tube and the reformer. Then comes the convection from the gas; the
combustion gases, the flue gases to the tube walls, conduction across the tube walls,
convection from tube walls across the catalyst bed to the catalyst and to the reactants.

So, all these aspects need to be taken care of while designing the reformer and reformer
tubes. Now, besides these major heat transfer considerations, also how the kinetics of the
reaction inside the tubes is, what is the interaction of the catalyst with the different reactants,
what is the heat and mass transfer limitations within the tubes that are also need to be taken
care of. However, in a well-designed reformer it is observed that under stable operations
these are not much of a problem; however, the major problem arises under the transient
conditions of starting up as well as shutting down. So, this is all about the steam methane
reforming.
So, in the today’s lecture we have seen the entire steam methane reforming process
considering all the 4 steps. Thereafter we have seen what are the different catalyst support,
promoters which can be used, we have seen what are the requirements in terms of the catalyst
as well as support, what are the different design considerations that needs to be taken care of
while selecting a catalyst, selecting a support, also the heat transfer characteristics of the
reformer, what are the various parameters that needs to be taken care of while designing the
reformer and reformer tubes.

Thank you.