This is a good start.

The detailed mechanism with DBT is nice, and focusing on sulfided

CoMo catalysts is fine. For the final model, you will need to mimic hydrogenation of both a
mix of aromatics and sulfur species. In reality, the numer of sulfur species will be a small
minority. You may be able to estimate the rate of ring hydrogenation of DBT and use these
adsorption and rate constants are similar to those of DBT itself. Try to make a model that
simulates a blend of aromatics, nonaromatics, and sulfur containing species at the same
time. It is OK if you use only a few model compounds to represent the more complex
stream.

REACTOR DESIGN HYDROTREATING UNIT

Catalytic hydroprocessing ranks in importance with other large-scale petroleum refining processes
(cracking and reforming), and its application is growing to meet several needs, including the
processing of heavier feeds, the production of high-performance lubricants, and the introduction
of cleaner burning fuels.

Several classes of reactions occur simultaneously in hydroprocessing:

1. Hydrogenation
2. Hydrodesulphurization (HDS)
3. Hydrodenitrogenation (HDN)
4. Hydrodeoxygenation (HDO)

The reactant compounds I will consider in this project include aromatic, sulfur compounds and

Most of the available information has been obtained with Co-Mo/ Al2 O3

The selected compounds are clasified in three big groups

1. Aromatic Hydrocarbons: I will take Biphenyl as model compound for this group
2. Organosulfur compounds: I will take Benzothiophene and Dibenzothiophene as model
compounds
3. Organonitrogen Compounds
4. Organo-Oxygen Compmounds
AROMATIC CONTAINING SPECIES

Inferring that biphenyl is representative of the least reactive class of aromatic hydrocarbons, Sapre
and Gates (1982) chose biphenyl hydrogenation for measurement of kinetics. They used a flow
reactor operated under differential conversion conditions (biphenyl conversion less than 16%),
without characterizing the reverse reaction quantitatively. Experiments were conducted at 300-
375 °C and at several hydrogen, biphenyl, and hydrogen sulfide concentrations with a
Co-Mo/A1203 catalyst. Taking into account the available information, to represent the group of
aromatics presented below I chose Biphenyl as my model compound.

The network I used to represent the group of aromatics was

BPH +3 H 2 ↔ CHB

The kinetic constants are presented in so I found the kinetic constant and the adsorption
constant from the data they presented. They proposed the following rate law, the paper doesn`t
present enough information regarding the rate law for the formation of hydrocarbons or
byclohexyl, then I just took the formation of cyclohexylbenzene to represent the aromatic
hydrogenation process occurring in my reactor:
NITROGEN CONTAINING SPECIES

Nitrogen in the feedstock is present predominantly in heterocyclic aromatic compounds. Non

heterocyclic organonitrogen compounds such as aliphatic amines and nitriles are also present, but
in considerably smaller amounts, and they are denitrogenated much more rapidly than the
heterocyclic compounds (Katzer and Sivasubramanian, 1979). Consequently, nonheterocyclic
organonitrogen compounds are less important for purposes of elucidating the nitrogen-removal
chemistry occurring in the hydroprocessing of heavy feeds. To represent this stream, I chose
pyridine as model compound.

The parameters of pyridine hydrogenation as a seudo first order reaction are

E (Kcal /mol) K(L^2/mol/g cat/ min )

32,1 2,41*10^7
SET OF REACTIONS MODELED

PRELIMINARY RESULTS

AROMATIC CONTAINING SPECIES

The picture shows the conversion of biphenyl as a function of W/F (Kg cat hr/kmol) calculated at
three different temperatures with 10 bar of Hydrogen partial pressure when no H 2S is feeded. It is
important to note that the cyclohexylbenzene is not only being produced by the following “
aromatic” path BPH +3 H 2 ↔ CHB , it is also being produced by the DBT hydrogenation. In fact,
as can be seen in the rate law presented above for the BPH hydrogenation, the reaction can be
inhibited by the presence of H 2S, that inhibition can be detected by varying the partial pressure of
H2S while keeping the partial pressure of H2 constant. the figure shows the influence of partial
pressure of H2S, it can be seen that the total conversion of BPH decreases when H2S is co-feeded
in the system.
SULFUR CONTAINING SPECIES

The picture shows the total conversion of DBT as a function of W/F (Kg cat hr/kmol) calculated at
three different temperatures with Hydrogen partial pressure of 9,4 bar.

INLET MOLAR FLOW

COMPOUND COMPOSITION (MOL%) REFERENCE F (MOL/ S) C mol/ m3 Pa atm ps i
GASES 1496,2 17104 18,4 35 16,88052 24 8,14 36
HYDROGEN H 0,00618 12,36 900 225 1028857,5 10,15403 14 9,264 3
HYDROGEN SULFIDE H2S 0,0133 26,6 0 0 0 0 0
NITROGEN N2 0 0 0 0 0 0
AMMONIA NH3 0,00219 4 ,38 0 0 0 0 0
METHANE 0,255 510 510 127,5 583019,25 5,753953 84 ,5831
EHTHANE 0,04 31 86,2 86,2 21,55 9854 1,685 0,972531 14 ,2962
0 0 0 0 0 0
0 0 0 0 0 0
SULFUR COMPOUNDS 0,104091 208,182 4 7,182 53937,28285 0,53232 7,825098
BENZOTHIOPHENE BT 0,0722 144 ,4 20 5 22863,5 0,22564 5 3,316984
DIBENZOTHIOPHENE DBT 0,0233 4 6,6 10 2,5 114 31,75 0,112823 1,658492
4 METHYLDIBENZOTHIOPHENE4Me DBT 0,008591 17,182 17,182 4 ,2955 1964 2,03285 0,193852 2,84 9621
NITROGEN COMPONENT 0,0153 30,6 1000 114 3175 11,28226 165,8492
PYRIDINE 0,0153 30,6 1000 250 114 3175 11,28226 165,8492
PARAFFINS 30 60000 0 0 0 0 0
OTHERS 0 0 0 0 0 0
0 0 0 0 0 0
NAPHTHENES 0,3 600 0 0 0 0 0
AROMATICS 0,0235162 4 7,0324 50,6324 12,6581 57881,69387 0,571248 8,397344
ETHYL BENZENE EB 0,000282 0,564 0,564 0,14 1 64 4,7507 0,006363 0,093539
BIPHENYL BPH 0,0232 4 6,4 50 12,5 57158,75 0,564 113 8,2924 61
CICLOHEXYLBENZENE CHB 0,0000342 0,0684 0,0684 0,0171 78,19317 0,000772 0,01134 4
C13H18 A1 0 0 0 0 0 0
C13H12 A2 0 0 0 0 0 0
C13H18 is omer A3 0 0 0 0 0 0
DIOPHENE D 0 0 0
TOTAL 2594 ,014 12,6581 29654 12,412 29,26635 4 30,2153
NITROGEN CONTAINING SPECIES