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Chemical & BioChemical

PROCESSES

The Haber-Bosch Process


The Haber-Bosh Process, for the fixation of atmospheric nitrogen, and
specifically for the production of Ammonia (NH3), using the atmospheric
nitrogen and hydrogen obtained from hydrocarbons was developed by
Fritz Haber (at the time at Erlangen University of Germany) and Carl
(Karl?)Bosch of BASF (Germany). Both Haber and Bosch won the Nobel
Prize for the invention of this process.
Even though it is over 100 years old, it is a process benefiting ingeniously
from the basic scientific principles as well as using wonderful engineering
insights. The Haber-Bosh Process may be considred in two major parts,
i.e. obtaining the hydrogen and nitrogen gases necessary as raw
materials for the process and the catalytic sysnthesis of ammonia (NH3).

A Summary Qualitative Flow Sheet


of the Haber-Bosch Process.
Below given is a summary flow-sheet of the Haber-Bosch and related
processes. Related Processes means that in time various
modifications of the original Haber-Bosch process was developed, as it
is also shown below, i.e. The Kellog Process.
As is noted in Fig. 1 below the source of H2 for the process is a
hydrocarbon. Presently methane, i.e. CH4, is used as the hydrocarbon
raw material since it is cheap, rich in hydrogen and clean and easy to
handle. However the hydrocarbon used in the original process was
coke, i.e. coal.
The hydrogen producing reaction, i.e. the shift reaction, produces Hr
and CO2. The CO2 is removed from the system via absorption in an
alkaline solution in an aborprion tower. So, we have H2, pure enough
to be used in Ammonia Synthesis.

The other important step is to obtain nitrogen (N2) from air. As it is shown in
the figure below this is done by reacting the oxygen in air with part of the
hydrogen produced in the reaction noted above.
Now we have both of the necessary raw materials, i.e. N2 and H2, and
ammonia is to be synthesized over iron (Fe3O4) catalyst.
As noted on the PFD, the ammonia synthesis is an exothermic reaction which
has to be run at around 450 C and at about 200 atm of pressure.These reaction
conditions have been found to be near optimal when the reaction rate (T), the
reaction equilibrium (T & P), catalyst life (T), and catalyst cost (e.g. osmium is a
better catalyst but very expensive) and the reactor design and manufacturing
conditions (T&P) are considered as a whole.
The reaction chemical equilibrium data, originally obtained by Haber and his
co-worker Rosignol, which establish the foundations of the ammonia synthesis
part of the process are given below.
As noted from these graphs high reaction temperatures are not desireable for a
high eqilibrium conversion. Whereas high pressures favor high equilibrium
conversions. On the other hand, relatively high reaction temperatures are
needed to obtain reasonably high reaction rates.

For this reason, i.e. equilibrium, etc., to obtain a very high


conversion in a single pass through the reactor is impossible and
high conversions should be achieved in a stepwise manner.
What is meant by the stepwise manner is that, as the reaction
starts at about 200 atm and 450 C, the reactor heats up, i.e.
exothermic reaction, but the pressure tends to fall, i.e. reduction
in the number of moles, and a conversion of about 20-25% is
achieved at conditions near (not at) equilibrium. However, since
we want a much higher conversion of the original feed (N2 and
H2) to the final product (NH3), the reactor effluents are cooled,
ammonia, i.e. the product, is thus liquefied and is recovered. The
remaining N2 and H2 is recycled to the reactor with some fresh
feed for further reaction. Thus, more conversion to NH3 is
obtained in the recycled feed along with the conversion of the
fresh feed. So, a few such steps, i.e. recycles, will give us near
100% conversion of the original feed to the desired product.

H 2O ( g )

CH 4 ( g )

(steam)

CH 4 ( g ) H 2O ( g ) Ni 3H 2 ( g ) CO ( g )
CO ( g ) H 2O ( g ) Fe CO2 H 2 ( g )
Remove via absorption

H2

Air O2 N 2

Depleting O2 in Air to get N2


2 H 2 ( g ) O2 ( g ) H 2O

H2

N2
450C
200
Atm
(cat)

More generally:

Cn H m ( g ) nH 2O( g ) Ni nCO ( g ) (
CO ( g ) H 2O( g ) Fe CO2 H 2 ( g )

N 2 ( g ) 3H 2 ( g ) 2 NH 3 ( g )
m
n) H 2 ( g )
2

Chemical Reaction Equilibrium governing Ammonia


Synthesis

Now, let us examine a little bit the details of the


ammonia synthesis reactor, and athe flow sheet of the
Kellogg Ammonia Process, which is a modified form of
the Haber-Bosch Process.
As youll notice in the Kellogg Process the ammonia
synthesis reactor has more than one feed points,
whereas the original reactor design has only one feed
point. This improvement permits an improved, i.e.
smoother, temperature profile in the reactor to obtain
higher conversions per pass and thus hopefully reducing
the number of recycles necessary to obtain the desired
high conversion on the original fresh feed.

This is a sketch of the ammonia


synthesis reactor where the
exothermic reaction occurs. The
feed enters the reactor in the
outer perimeter and is heated by
the exiting hot gases before it
enters the catalytic reaction
zone. So the reactor
configuration permits efficient
heat transfer between the raw
materials fed which have to be
heated to react and the exiting
hot product gases.

Qualitative PFD of the Kellogg Ammonia Process

Now that you have fixed the nitrogen you can use
NH3, i.e. ammonia, to make many nitrogenous
compounds.
Let us start with Nitric Acid, NHNO3, as a process for its
manufacture is depicted on the next page. The basis of
the process is the oxidation of ammonia.

DuPont process for the manufacture


of Nitric Acid from Ammonia

Figure below shows some of the other industrial


chemicals which could be made using ammonia, i.e.
NH3, as a building stone:

Before we go further on with the inorganic , i.e. manufacture of ammonia and other
nitrogenous compounds are inorganic chemicals, let us dwell upon some organic
processes with examples from the petrochemicals industries.
Prior to introducing you to some example petrochemical industries, it will be
appropriate to note the similarities between the petroleum refining and the
petrochemical industries.
The basic similarity petroleum refining and petrochemical processes is that in both the
raw materials are petroleum based.
However, where petroleum refining in general uses the crude petroleum as its raw
material, petrochemical industries in use some portions of the crude, but more
frequently use pre-processed portions of the crude. So, frequently petroleum refineries
and petrochemicals complexes may have considerable materials exchange between
them. The amount of this exchange depends on the type of the crude which is used
in the refinery, as well as on the types of products which are produced both in the
refinery and in the petrochemical plants constituting the petrochemical complex.

Similarities and Differences among


Petroleum Refining and the Petrochemical Industries
Petroleum Refining:
Petroleum refineries in general process unprocessed or very slightly processed, i.e.
stabilized, etc, crude petroleum.
Petroleum refineries are quite flexible in their design and operating conditions. This
enables them to process various kinds of crude depending on availability and
economics to produce varying kinds fuels depending upon the market demands.
Refinery products are generally not sold on the basis of their purities and are
evaluated and sold on the basis of their performance qualities, i.e. the octane
rating of gasoline, vapor pressure, etc.. Many different chemical compositions,
within a range of chemicals, may exhibit equal performance ratings.
Refinery products, with the accept those used as petrochemicals feed-stocks, are
used as they are by the final consumers, i.e. end users.

Petrochemical Industries:
In contrast to petroleum refineries, the various plants in the
petrochemicals complexes are designed, built and operated to produce
products of very well defined chemical compositions from quite pure
chemical feeds.
The feeds to the petrochemicals producing plants are either prepared
in the complex in auxiliary plants, i.e. cracking, reforming, etc, or they
are obtained from refineries.
The petrochemicals complexes may also transfer some materials,
which they find uneconomical or unfit to process, back to refineries to
be blended into various fuels or processed further for such purposes.
The products of petrochemicals plants are seldom directed to the end
users, as are the petroleum refinery products. The petrochemicals are
generally used as raw materials or intermediate chemicals in the
manufacture of many many other chemicals.
So, now we will see in summary some PFDs for some petrochemicals
plants. However, prior to that let us see an incomplete range of
petrochemicals.