Homogeneous Catalysis

The processes we covered so far used heterogeneous catalysis where the catalyst is a solid
and reactants are gases [they could be liquids also]. The reactants adsorb on catalyst surface
from the gas phase, adsorbed molecules react to form products that desorb from the surface
into the gas phase.

In homogeneous catalysis, the catalyst is dissolved in solution. The reactants, if they are
gases dissolve in the solution and react. Dissolved catalysts promote these reactions. Acetic
acid, n- and iso-butyraldehydes, terephthalic acid are some of the bulk chemicals made by
homogeneous catalysis route. The processes for these chemicals will be discussed in
homogeneous catalysis.

A quick recall of some of the heterogeneous processes reveals that the operating temperatures
are very high. For example, styrene production occurs at 600-620 oC, steam reforming of
natural gas happens at ~800 oC.

What is the implication of intense conditions on formation of side products?

In addition to this drawback of heterogeneous catalysis, there are other shortcomings too.
These and some advantages of homogeneous catalysis are captured in Table below.

Homogeneous means the reaction mixture contains catalyst dissolved in solution.

Heterogeneous Homogeneous
Catalyst Form Solid Metal Complex
Activity Low High
Selectivity Low (usually) High
Stability More stable Less stable
Reaction Conditions Harsh/ intense Mild
Sensitivity to poisons High Low
Diffusion limitations High Do not exist
Solvent Not needed Needed
Catalyst separation and Not required Difficult
recycle

Catalyst separation, waste generation, pollution, solvent recovery and separation off-set many
advantages offered by homogeneous catalysis. For these reasons many homogeneous

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processes have been superseded by heterogeneous catalysis. The details of catalyst recovery,
recycle are usually proprietary and not discussed in detail.

Tables below, reproduced from the text book, show the operating conditions and capacities of
homogeneously and heterogeneously catalyzed processes.

Homogeneous catalysis

Processes World capacity Catalyst metal Temperature (K) Pressure

Million ton/year (bar)
Acetic acid 16 Rh or Ir 425-475 20-60
Oxo-alcohols 9 Rh 370-390 20-50
1-Alkenes 7 Ni 350-390 70-140
Dimehtyl 2 Co 415-445 4-8
Terephthalate
Terephthalic 50 Co 450-505 15-30
aicd

Heterogeneous catalysis

Processes World capacity Catalyst metal Temperature (K) Pressure

Million ton/year (bar)
Methanol 70 Cu 530 50-100
Ammonia 205 Fe 675 100-200
H2SO4 240 V 700 1
FCC >650 Zeolite-Y 775 1
Ethene oxide 24 Ag 550 20

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 Acetic acid production
Acetic acid is used in the production of vinyl acetate, acetic anhydride, terephthalic acid and
foods such as vinegar.

In 1968, Monsanto introduced a novel, highly active and selective rhodium-based catalytic
process for the production of acetic acid by carbonylation [addition of CO] of methanol.

The carbonylation reactions are summarized as:

Reaction of HI with MeoH: CH3OH + HI CH3I + H2O = 53.1

Carbonylation of methyl iodide with CO: CH3I + CO CH3COI = 66.9

Hydration of CH3COI: CH3COI + H2O CH3COOH + HI = 15.6

These reactions are a part of catalytic cycle for carbonylation shown in next page. Go
through the cycle to understand how catalyst participates in the reaction. Generation of this
cycle falls under chemists scope. You need not remember this cycle.

Catalytic cycle for the Monsanto process

The reaction between CH3I and [Rh (CO)2I2]- is found to be rate determining step, when
water content is > 8%

3 = 3

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At lower water contents (< 8 wt%), reductive elimination of the catalyst complex,
[RhI3(CO)2(CH3CO)]- is the slowest step.

This complex reacts with HI to produce acetaldehyde and other Rh-complexes, which are
inactive. This inactivity means loss of catalyst and also slower rates of reaction. Rhodium is
an expensive catalyst.

Reactor and its operating conditions:

Overall reaction: 3 + 3 , = 138/

Carbonylation of methanol is an exothermic reaction. For homogeneous catalytic process,

the catalyst should dissolve in solution. Some of the side reactions produce CO2 and H2,
(What is this reaction called? ), propionic acid, dimethyl ether,
methyl acetate.

Side Reactions:

3 + 3 3 3 + 2

Methyl acetate

23 3 3 + 2

dimethyl ether

Methyl iodide, methyl acetate and dimethyl ether are light side products meaning they are
more volatile. Normal boiling points of acetic acid and propionic aicd are 118 oC and 141 oC,
respectively. Because the catalyst is highly selective, the side products are formed in small
quantities.

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The reaction is almost complete even at 1 bar at temp 400-500 oC. At these temperatures all
of the reactor contents are in vapor form.

Actual operating pressure is ~ 30 bar. Why this pressure?

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The following reactors are used for homogeneous systems.

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Table below shows mass transfer parameters for the reactors shown in previous page

Reactor type Liquid holdup (%) Gas holdup (%) kl al (s-1) (m3 liq/m3 film)
Stirred tank >70 2-30 0.15-0.5 103-104
Bubble column >70 2-30 0.06-0.3 103-104
Spray column <30 >70 0.05-0.1 10-40
Packed column 5-15 50-80 0.05-0.1 10-40

signifies ratio of volume of liquid to volume of diffusion layer surrounding the gas bubbles.
The gas components diffuse through this layer into bulk liquid and react there.

Rates of some chemical reactions are fast and some are slow compared to rates of mass
transfer. Which reactors do you recommend for fast and slow reactions?

Fast:

Slow:

Carbonylation of methanol is controlled by chemical reaction at 180 oC and 30 bar, the

operating temperature and pressure of the reactor. That is, the solution in the reactor is more
or less saturated with CO. Which reactor type do you recommend for carbonylation? How is
heat of the reaction removed?

What are the components of reactor outlet stream? List them here. They exit the reactor at
reactor conditions, ~450 K (~180 oC) and 30 bar.

What should the process downstream of reactor achieve? How?

Draw a block diagram for carbonylation of methanol to produce acetic acid.

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Vapour-liquid equilibrium diagram for acetic acid-water system at 1 atm is shown below.
What are the issues in producing glacial acetic acid with 99.8% purity?

100
mole fractio of water in vapour

90
80
70
60
phase, y

50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100

mole fraction of water in liquid phase, x

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 Off-gas to
scrubber
450 k REACTOR
30 bar

Acetic acid

Methanol

CO

FLASH
VESSEL Propionic acid

DRYING PRODUCT
Catalyst rich stream COLUMN COLUMN

Simplified flow scheme of the Monsanto process for acetic acid production
production

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Research efforts were directed to reduce operating costs/investment costs by lowering water
content in the carbonylation process. Cativa process was developed with iridium, Ir,
catalyst that works effectively at lower water contents than Rh. The oxidative addition of
methyl iodide addition to the iridium complex is 150 times faster than similar addition in Rh
process. Recall that this addition was the rate limiting step in Rh process. In the Ir process,
because of enhancement of oxidative addition rates, the rate limiting step is the reaction of
CO and the Ir complex, shown in Figure below.

The Cativa process is found to work at low concentrations of water unlike Monsanto process.
Less propionic acid is generated in the Cativa process.

The reaction rate law for Ir process was found to be

3 =
[ ]

Catalytic cycle of Cativa Process [You need not remember this cycle]

Promoters are used to reduce [I-], thus enhance reaction rates.

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Rates of carbonylation for Cativa process are higher the Monsanto process. What reactor
configuration do you recommend for Cativa process? Draw the configuration. What are its
advantages over the configuration used for Monsanto process?

Methanol

CO
Off-gas to
scrubber

450 k
30 bar
Acetic acid

SECONDARY
Propionic acid
REACTOR

REACTOR Catalyst rich stream FLASH

DRYING PRODUCT
VESSEL
COLUMN COLUMN
Simplified flow scheme of the Cativa process for acetic acid production
production

Why is a secondary reactor needed in Cativa process?

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Why are investment and operating costs lower for Cativa process than Monsanto process?

Material of construction is crucial because of corrosive nature of reaction mixture [especially

HI]. Titanium is most often used.

Hydroformylation

It is often referred to as oxosynthesis. It is addition of a formyl group [CHO] and a hydrogen

atom to double bond.

Hydroformylation of propene is most significant of these processes with a large share (~75%)

The aldehydes are intermediates in the production of several types of alcohols, usually called
oxo-alcohols. For example, n-butanol is made by direct hydrogenation of n-butyraldehyde. 2-
ethylhexanol, a widely used plasticizer alcohol can also be made from n-butyraldehyde.

Figures below show thermodynamics of reactions and yields.

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Clearly, high pressures and low temperatures favour high conversion of propylene. A
catalyst is needed to achieve high selectivity toward n-isomer because iso-compound more
favoured.

The catalytic cycle for hydroformylation of propene is shown below.

Rhodium with triphenylphosphine ligands is used as catalyst.

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Hydrogenation of propylene to propane is a side reactions that could occur. Normal boiling
points of n-butyraldehyde and iso-butyraldehyde 75 oC and 63 oC, respectively.

Draw a block diagram for hydroformylation of propene.

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The alkene and synthesis gas have to be purified thoroughly because the catalyst is sensitive
to poisons. H2S and carbonyl sulphide are impurities present in commercial synthesis gas and
propylene. The latter may also contains organic chlorides.

How could we remove the impurities to vanishing levels? They are present in minute
quantities in syn gas and propylene.

A nice feature of this process is that the catalyst dissolves in reaction mixture and no solvent
is needed. What is the implication of no-solvent on separation costs?

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What is the function of demister? What happens if there were no demister?

Propylene is usually supplied in excess. It is recovered in the gas/liq separator and in the
stabilizer where it is stripped from the liquid emerging from the separator.

Why there is a necessity of stabilizer after propene is recovered in the separator?

Why is purge needed?

Should we operate the stabilizer at 20 bar or 1 bar? The lower the pressure, the more is the
recovery of propene.

Normal boiling points

n-butyraldehyde : 75 oC

iso-butyraldehyde : 63 oC

Should we depressurize the liquid stream from the stabilizer before feeding the distillation
column? Why?

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 Terephthalic acid production

Terephthalic acid (TPA) is a monomer for the production of polyethylene terephthalate (PET)
by poly condensation with ethylene glycol. Where is PET used?

Oxidation of p-xylene to TPA:

Catalyst: Cobalt acetate, promoted by bromine; solvent is acetic acid.

Terephthalic acid has a very low solubility in acetic acid. Hence, TPA crystallizes as it
forms.

Due to the presence of acetic acid and bromine, the reaction mixture is highly corrosive;
special material such as Hast alloy C or titanium is needed to prevent corrosion.

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 Simplified flow scheme for the production of pure terephthalic acid (Amoco process)

Why is acetic acid needed?

How is the heat generated during oxidation removed? There is no cooling jacket around the
reactor.

What is the function of scrubber?

What does off-gas contain?

What does filter separate?

The slurry into moist TPA and filtrate (acetic acid, water, less TPA, little catalyst)

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Which two separations in the flow sheet can be improved to conserve energy?

The crude TPA is 99% pure but contains 4-formylbenzoic acid, commonly known as 4-
carboxybenzaldehyde (CBA). This compound co-crystallizes with TPA in the reactor and is
carried with TPA through all separation units. CBA terminates polymerization reaction in the
production of PET. Hence CBA needs to be removed below specified limits. This removal is
done by converting CBA into p-toluic acid in a fixed bed reactor over palladium catalyst at
~250 oC.

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