Process 1:

Pygas > Gasoline hydrogenation unit > Extraction unit > Fractionation unit >
Hydrodealkylation unit > Product uses
Process 2:
Naphtha > pyrolysis furnace > transfer line exchange > cracked gas > separation
section > products
Process 3:
Raw Material Drum > Hydrogenation Process > Preliminary Fractionation Process
>Extraction Process > Separation Process
Processes 1:
Hydrode alkylation unit
Catalytic hydrodealkylation of heavy aromatics to produce benzene (B), toluene (T)
and xylenes (X) which are the three basic aromatic starting reactants is an
important approach to improve the utilization of heavy aromatics. In this thesis,
hydrodealkylation of C9+ heavy aromatics to produce BTX over zeolite-supported
metal oxide and noble metal catalysts was studied. Firstly, the thermodynamics
analysis for the hydrodealkylation system of C9+heavy aromatics was
accomplished. Then the comparation in catalytic performance between HZSM-5supported metal oxide catalysts and-Al2O3-supported metal oxide catalysts
applied to this reaction system was carried out. Based on the preferred support
type, the effect of zeolite support, active component, loading of active component,
recombination of active components and impregnation sequence on physical and
structural properties and catalytic performance of the employed hydrodealkylation
catalysts was systematically investigated by means of XRD, H2-TPR, N2 adsorption
and desorption, NH3-TPD and FTIR spectrum of adsorbed pyridine. And the
NiO/HMCM-56 catalyst was developed and selected with its excellent catalytic
performance. Moreover,1,2,4-trimethylbenzene was employed as the model
reactant and the reaction mechanism of hydrodealkylation of 1,2,4trimethylbenzene over the NiO/HMCM-56 catalyst was further studied.The
thermodynamics analysis indicates that the main reactions of hydrodealkylation are
irreversible reactions and most liable to occur with their equilibrium constants far
greater than those of isomerization, transalkylation and disproportionation among
the hydrodealkylation system of C9+heavy aromatics.For the hydrodealkylation
process of C9+heavy aromatics feedstock employed in this thesis, the catalytic
performance of metal oxide catalysts with HZSM-5 zeolite as support is superior to
that with-Al2O3 as support.The catalytic performance of zeolite-supported nickel
oxide and molybdenum oxide catalysts indicates that the HMCM-56 zeolite is an
excellent support used to hydrodealkylation of C9+heavy aromatics. For zeolitesupported nickel oxide catalysts, the samples with the moderate interaction

between NiO and zeolite exhibit the relatively high selectivity. And for zeolitesupported molybdenum oxide catalysts, the presence of the molybdenum species
located in the channels of zeolite and associated with Br(?)nsted acid site causes
the remarkable reduction of selectivity of BTX. The presence of Br(?)nsted acid
sites, the growth of the strength of Lewis acid sites, the increase of acid amount and
the accretion of specific surface area can all enhance the conversion of
C9+aromatics in hydrodealkylation of heavy aromatics.The experimental results
about investigation of active components indicate that among the HMCM-56supported catalysts with different metal oxides as active components in this thesis,
the NiO/HMCM-56 catalyst shows the greatest overall catalytic performance. The
effect of NiO loading on the catalytic activity of NiO/HMCM-56 is related to the
dehydrogenation-hydrogenation function of NiO, the acidity of catalysts and the
dispersion state of NiO on the surface of HMCM-56. And the suitable NiO loading is
3wt%-6wt%. For the 6wt% NiO/HMCM-56 catalyst, the conversion of C9+aromatics
is 72.75mol%, the selectivity of BTX is 78.51mol% and the yield of BTX is 57.11mol
%. For the binary composite catalyst of Re-NiO/HMCM-56 containing noble metal Re,
the recombination of Re and NiO active components has a great effect on physical
and structural properties and catalytic performance of Re-NiO/HMCM-56, whereas
the impregnation sequence of Re and NiO has little effect.The reaction mechanism
of hydrodealkylation of 1,2,4-trimethylbenzene over the NiO/HMCM-56 catalyst
shows that the main reaction of hydrodealkylation is catalyzed by Lewis acid sites
and accomplished through a radical mechanism. Disproportionation is catalyzed by
Br(?)nsted acid sites and accomplished through a bimolecular carbenium ion chain
mechanism while isomerization is catalyzed by Br(?)nsted acid sites and
accomplished through monomolecular and bimolecular carbenium ion chain
mechanisms. And catalytic hydrocracking requires the hydrogenation of the
aromatic ring over metal sites in a first step to produce naphthenes, which rapidly
undergo cracking on the Bronsted acid sites and Lewis acid sites to produce light
paraffins. - See more at: http://www.research-degree-thesis.com/science-b/organicchemistry/1476435.html#sthash.x4pmGcuS.dpuf

Processes 3:
Hydrogenation Process - chemical reaction between molecular hydrogen and an
element or compound, ordinarily in the presence of a catalyst. The reaction may be
one in which hydrogen simply adds to a double or triple bond connecting two atoms
in the structure of the molecule or one in which the addition of hydrogen results in
dissociation (breaking up) of the molecule (called hydrogenolysis, or destructive
hydrogenation).
Extraction Process
Aromatics Extraction

The commercialization of catalytic

naphtha reforming after WWII resulted

in the creation of a new source of

aromatics (benzene, toluene, and
xylene, or BTX) to compete against
the other major sources of the time,
coal tar and pyrolysis gas. The strong
growth in consumer plastics that is the
primary end use for aromatics led to
the need for efficient ways to separate
them from reformate. Solvent
extraction has proven to be the
preferred separation technique due to
its low energy use relative to
distillation. In the US, the majority of
the commercial aromatic extraction
units employ one of the following
processes:
UDEX, developed by Dow Chemical,
licensed by UOP
Tetra and Carom, developed by Union
Carbide, licensed by Linde
Sulfolane, developed by Royal Dutch
Shell, licensed by UOP
These processes have many features
in common as described below:
EXTRACTION
The basic principle of all of these
processes is the use of one or more
solvents to selectively extract BTX
from reformate. The UDEX process
uses diethylene glycol, the Tetra
process uses tetraethylene glycol, the
Carom process uses a proprietary
glycol/glycol ether mix, and the
Sulfolane process uses
tetrahydrothiophene 1-1 dioxide. In
addition, these processes also use a
controlled amount of water in the
solvent to further improve the
selectivity. The extractor consists of a
vertical column with numerous
contactor plates, often of proprietary
design. Aromatic-rich reformate feed
enters near the middle of the column,
solvent at the top, and a nonaromatic-heavy recycle stream at the
bottom. BTX-rich solvent leaves the
bottom of the extractor on its way to
the Solvent Stripper, while non-

aromatic raffinate leaves the top to be

washed.
SOLVENT STRIPPING
In the UDEX, Carom, and Tetra
systems, the BTX-rich solvent enters
the top of the solvent stripper, while a
condensed stripper overhead stream
containing mainly solvent with trace
hydrocarbons is fed near the
bottom. A BTX product stream is
removed as a side-cut from the
Stripper. A nearly hydrocarbon-free
solvent stream leaves the bottom of
the Stripper, and a mixed
raffinate/aromatic/solvent stream
leaves the top. This latter stream is
condensed, and hydrocarbon phase is
recycled back to the Extractor. In
contrast, the Sulfolane process uses
two columns (Extractive Distillation
and Aromatics Stripper) to accomplish
these separations.
EXTRACT WASHING
The extract from the Solvent Stripper
is washed with water to remove
residual solvent before being sent for
further processing.
RAFFINATE WASHING
Raffinate leaving the Extraction Tower
is washed with water to remove
residual solvent before being sent for
further processing.
SOLVENT CONDITIONING
The solvents in all of these processes
degrade over time due to the
accumulation of various high boiling
and polar contaminants. Unless steps
are taken to maintain the solvent
purity, the solvent loses efficacy and
causes significant corrosion issues. A
small slipstream of solvent is typically
treated to remove contaminants and
returned to the solvent pool. Some
processes use filtration and adsorption
to remove contaminants, while others
use batch distillation, often done

under vacuum to limit thermal

degradation. One C&I client has
developed a very innovative and
successful use of ion exchange
technology to keep the solvent in likenew condition.
BTX CONDITIONING AND
SEPARATION
The level of processing the BTX
product stream undergoes postextraction varies considerably from
unit to unit. At minimum this stream
goes through a clay filtration to
remove unsaturated compounds. Most
units will also have a distillation
column to separate benzene from the
BTX pool, as it is the most valuable of
the aromatics. Toluene and xylene
distillation columns are the next most
common downstream separation
units. If the various isomers of xylene
are to be separated from ethyl
benzene as well as from each other,
super-fractionation columns (360+
total stages) accompanied by
crystallization units are required due
to the very narrow boiling point
ranges.
BENZENE COMPLIANCE
With increasingly stringent regulations
limiting the amount of benzene that is
allowed in gasoline (MSAT I & II), there
is renewed interest in upgrading
aromatic extraction units, primarily in
the areas of efficiency improvement

and capacity debottlenecking. C&I

Engineering has considerable
experience in these areas, along with
the capability to model the highly nonideal system thermodynamics as well
as the implementation of novel solvent
clean-up technology.
OTHER COMMERCIAL PROCESSES
Other commercial BTX extraction
processes are in use but are much less
common. Their flowsheets are all
similar, though minor variations
exist. The Morphylex Process
(Koppers) and the Formex Process
(SNAM Progretti) both use nformylmorpholine, and can operated
using reformate feed with a nonaromatic content up to 30%. The Lurgi
Arosolvan Process uses N-methyl-2pyrrolidinone in conjunction with
glycol and water. This process uses a
proprietary multistage mixer/settler
extractor. The IFP Process involves
dimethyl sulfoxide (DMSO) and butane
in two extractive steps using K?hni
columns. The two solvent system
minimizes the degradation of the
DMSO solvent, since there is no need
to distill it to remove the
aromatics. Other lesser-known
extraction processes include Mofex
(Leuna-Werke Monomehtylformamide), Arex (Leuna
Werke N-Methyl -caprolactam),
Duo-Sol (Milwhite Co Propane/cresol)
and CIS (Propylene carbonate).

Separation Process
BTX extraction process is the process for the separation of the aromatic
hydrocarbons from the refromate which consists of aromatic hydrocarbons and
nonaromatic hydrocabons, using the solvents which has selective solubilities. 11
BTX extraction processes in Korea are using sulfolane as solvent. The relative
volatilities of aromatic hydrocarbons and non- aromatic hydrocarbons are very close
and the boiling points of aromatic hydrocarbons are located in the middle of the
boiling points of nonaromatic hydrocarbons of the same carbon numbers.
Accordingly, many of distillation columns or trays are required when distillation
process is used for the separation of aromatic hydrocarbons and nonaromatic hydrocarbons. The extraction process using the solvents, such as sulfolane, which has an
affinity for the aromatic hydrocarbons and are insoluble in nonaromatic
hydrocarbons simplifies the separation of aromatic hydrocarbons. After the
introduction of reformate(feed), nonaromatic hydrocarbons are obtained at the
overhead of the extraction column and the aromatic hydrocarbons with sulfolane
are obtained at the bottom of the column. The bottom stream containing aromatic
hydro- carbons are introduced to the low-pressure distillation column and aromatic
hydrocarbons are produced at the overhead of the column. Sulfolane of the bottom
stream of the low-pressure distillation column is recycled after the regeneration. For
the simulation of the BTX extraction process, the experimental phase equilibrium
data for aromatic hydro- carbons, nonaromatic hydrocarbons and sulfolane are
essential. Especially, the liquid-liquid equilibrium data for the nonaromatic
hydrocarbons and sulfolane play an important role for the analysis of the extraction
column. In this research, the liquid-liquid equilibria experiment for the two
cycloalkanes+sulfolane systems - cyclopentane + sulfolane and cyclohexane +
sulfolane systems - and three branchedcycloalkanes + sulfolane systems - methylcyclopentane + sulfolane, methylcyclohexane + sulfolane and ethylcyclohexane +
sulfolane systems- are performed. The thermodynamic parameters the five systems
are calculated using NRTL thermodynamic model. In addition, the simulation of BTX
extraction process is performed by applying the parameters derived from the
experimental data to the BTX extraction process model. The extraction process
model is constructed commercial process simulator, HYSYS. The simulation showed
the very close results to the process data of the process.