ASSIGNMENT 1

AHMAD AT-TARMIDZIE BIN

AHMAD ZAIDI
2016537511
EH2205C
Question 1

a) Chemical degradation or coking is a result from a carbonaceous (coke) material from

fluid phase being deposited on the surface of a catalyst, causing activity loss due to
blocking of sites or pores. To prevent coking the catalyst support technology can be
improved by tailoring the pore size distribution to give greater tolerance to the
contaminants before deactivation is evident. Using noble metal catalyst can also
reduce the likelihood of coking because they do not dissolve carbon compared to
Nickle-based catalyst. Decoking also can be done by combustion or steaming as
coking is a reversible catalyst poisoning.

Mechanical degradation or sintering is the loss of catalytic activity due to a loss of

active surface area which are due to prolonged exposure to high gas-phase
temperatures. The active surface area may be lost by crystal agglomeration and
growth of the metals deposited on the support. The active surface can also be lost by
narrowing or closing of the pores inside the catalyst pellet To prevent sintering,
catalysts may be doped with stabilizers (high melting temperature and preventing
agglomeration of small crystals) such as chromia, alumina, and magnesia. For
platinum catalysts, add a trace amount of chlorinated compounds in the process
stream. Chlorine increases the activation energy for the sintering process of Pt and
thus reduces the sintering rate for platinum catalysts.

Deactivation of catalyst by poisoning is an irreversibly chemisorbed to the active

sites. This reduces the number of sites available for the main reaction. The best
method to reduce poisoning is to decrease to acceptable levels the poison content of
the feed. This is generally achieved by appropriate treatments of the feed. Another
approach that can be taken to prevent poisoning is to choose proper catalyst
formulations and design.
b) Catalyst life may be as short as a few seconds, as in fluid catalytic cracking (FCC), or
if several years for ammonia synthesis but, inevitably, the catalyst will need
regeneration or replacement. However, deactivation of a cracking catalyst will almost
certainly reduce the activity. The three main types of catalyst deactivation are
poisoning, fouling, or thermal degradation (sintering).

The thermal deactivation of a catalyst is a permanent deactivation that occurs at very

high temperatures. Activity loss from thermal effects is caused by the reorganization
of the catalyst structure at these high temperatures. For instant, hydrothermal
deactivation, also a permanent loss of catalyst activity, is the more prevalent
mechanism for activity loss during the regeneration cycle. Hydrothermal deactivation
results from zeolite dealumination and subsequent crystallinity loss, as well as pore
size shifts and surface area loss in the matrix.

For deactivation of catalyst through poisoning, the poisoning is due to irreversible

adsorption of catalysts poisons on the active sites. The poisoning molecule may be a
reactant or a product in the main reaction, but normally is the impurities in the feed
stream. For example, petroleum feed stocks contain trace impurities such as sulfur,
lead, and other components which are too costly to remove. This reduces the number
of sites available for the main reaction. For active site poisoning, there are three
limiting models, uniform site poisoning, selective site poisoning and pore mouth
poisoning. In the uniform site poisoning model, deactivation is assumed to occur
uniformly throughout the catalyst particle and the poison deactivates all sites
identically. Selective site-poisoning applies if the active sites are inhomogeneous. For
In pore mouth poisoning, all acid sites are assumed to be uniformly distributed, but
the rate of reaction is much more rapid than the rate of diffusion. Thus, the area
around the pore mouth quickly becomes deactivated by direct poisoning, further
reducing diffusion into the pore.

Chemical degradation or coking is a result from a carbonaceous (coke) material from

fluid phase being deposited on the surface of a catalyst, causing activity loss due to
blocking of sites or pores. For example, zeolite pores are only slightly larger than the
reactant molecules, and only a few atoms of carbon or other foulant may be required
to effectively block pores. One type of pore blockage is pore mouth plugging.
Essentially all foulant is deposited near the pore mouths and very few of the active
sites are covered by the foulant. The activity declines more rapidly than the number of
deactivated sites and the diffusion rate decreases as the pores become increasingly
blocked. In addition to pore mouth plugging, pore blockage could also occur further
inside the crystal, or the coke could block channels or intersections deeper inside the
crystal. For a zeolite with a three-dimensional channel network, like H-USY, the
effect of a blocked pore would be to poison only those sites within the immediate
super cage. As a result, the activity would be proportional to the number of remaining
and accessible active sites.