INSTITUT TEKNOLOGI PETROLEUM PETRONAS

(INSTEP)

PTP-2 SEMESTER 3

(JULY 2009)

PROCESS 1

PLANT PROCESS OPERATION PPP 3277

TITLE : CATALYTIC REFORMING UNIT (DEHYDROCYCLISATION).

NAMA: ANTHONY BALAN JOHNNY (292297)

RUSDIN BIN LAKUASA (292265)

CALREN GAVIN ANAK GENDANG (292301)

ABDUL NAZREEN BIN MOHD FIRDAUS (292267)

MOHAMAD NOR JANNAH B MOHD KHALIS (292146)

LEARNING FACILITATOR : ROSLI B RAMLY

Dehydrocyclisation

Catalytic reforming is a process in which hydrocarbon molecules are rearranged, or

reformed in the presence of a catalyst. The molecular rearrangement results in an
increase in the octane rating of the feedstock. Thus, during reforming low octane
hydrocarbons in the gasoline boiling range are converted into high octane components
by dehydrogenation of naphthenes and isomerization, dehydrocyclization and
hydrocracking of paraffins.

Dehydrocyclisable hydrocarbons are converted to aromatics by contacting them

at dehydrocyclisation conditions with an acidic multimetallic catalytic composite
comprising a combination of catalytically effective amounts of a platinum group
component, a cobalt component, a cadmium component, and a halogen component with
a porous carrier material. The platinum group, cobalt,, cadmium and halogen
components are present in the multimetallic catalyst in amounts respectively, calculated
on an elemental basis, corresponding to about 0.01 to about 2 wt % platinum group
metal, about 0.05 to about 5 wt % cobalt, about 0.01 to about 5 wt % cadmium, and
about 0.1 to about 3.5 wt % halogen.
Moreover, the catalytically active sites induced by these metallic components are
uniformly dispersed throughout the porous carrier material and these metallic
components are present in the catalyst in carefully controlled oxidation states such that
substantially all of the platinum group component is in the elemental metallic state,
substantially all of the cadmium component is in an oxidation state above that of the
elemental metal, and substantially all of the catalytically available cobalt component is
present in the elemental metallic state or in a state which is reducible to the elemental
metallic state underdehydrocyclisation conditions, or in a mixture of these states. A
specific example of dehydrocyclisation method disclosed herein is a method for
converting a feed mixture of n-hexane and n-heptane to a product mixture of benzene
and toluene which involves contacting the feed mixture and a hydrogen stream with the
acidic multimetallic catalyst disclosed herein at dehydrocyclisation conditions.
 A dehydrocyclisation process is described comprising:
(a) contacting a naphtha feed in a reaction vessel with
a dehydrocyclisation catalyst at process conditions which favor dehydrocyclisation to
produce an aromatics product and a gaseous stream. The dehydrocyclisation catalyst is
a monofunctional catalyst comprising a large-pore zeolite containing at least one Group
VIII metal;
(b) separating the aromatics product from the gaseous stream;
(c) passing the aromatics product through a molecular sieve which adsorbs normal
paraffins and a substantial portion of the single-branched isoparaffins present in the
aromatics products;
(d) using the gaseous stream to strip the normal paraffins and single-branched
isoparaffins from the molecular sieve and
(e) recycling the gaseous stream and the normal paraffins and single-branched
isoparaffins to the reaction vessel.

Dehydrocyclization of aliphatic C 6 + compounds produces known aromatic

compounds. For example, benzene and toluene are the products of n-hexane and n-
heptane dehydrocyclization reactions.

The temperature at which the C 6 -C 12 paraffin feed (or C 6 -C 12 paraffin containing

naphtha feed) is converted in accordance with the invention can range from 750° F.
(400° C.) to 1100° F. and 1200° F., generally being greater than about 900° F.
Preferably, the temperature of the process ranges from about 900° F. (482° C.) to about
1050° F. The pressure can be subatmospheric, atmospheric to greater than atmospheric
and practically will be up to 500 psig; and it is noted that the non-acidic catalyst used in
accordance with the invention can operate effectively even at low total pressures of 0 to
100 psig.

In addition, hydrogen must be purposefully added during the dehydrocyclization of

the invention. The partial pressure hydrogen created by hydrogen production during the
dehydrocyclization will not allow the process of the invention to sustain long periods of
time. Hydrogen addition is undertaken so that the H 2 / hydrocarbon feed mole ratio
ranges from 1 to 20. The liquid hourly space velocity [LHSV] can range from 0.1 to 20.

In accordance with the invention, catalytic dehydrogenation of C 2 -C 5 paraffins

includes pressures varying from subatmospheric, to atmospheric to greater than
atmospheric. Preferred pressures range from 0.1 atmospheres to 30 psig. However,
pressures up to 500 psig can be employed. The dehydrogenation is conducted at
elevated temperatures ranging from 300° C. to 700° C.; preferably, the temperatures
range from 300° C. (572° F.) to 600° C. and most preferably from 400° C. to 600° C.
Reactor inlet H 2 / feed ratios are 5 or less; even at reactor inlet ratios of zero (0), there
will be a hydrogen partial pressure in the reactor because hydrogen is a bi-product of
dehydrogenation. The liquid hourly space velocity is 0.1 to 50 preferably 0.5 to 10.