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Monitoring and modelling of variables affecting isomerate octane number

produced from an industrial isomerization process

Article  in  Egyptian Journal of Petroleum · March 2018

DOI: 10.1016/j.ejpe.2018.02.006

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 Egyptian Journal of Petroleum 27 (2018) 945–953

Contents lists available at ScienceDirect

Egyptian Journal of Petroleum

journal homepage: www.sciencedirect.com

Full Length Article

Monitoring and modelling of variables affecting isomerate octane

number produced from an industrial isomerization process
Walaa Mahmoud Shehata a,⇑, Mohamed Fathy Mohamed b, Fatma Khalifa Gad a
a
Suez University, Faculty of Petroleum & Mining Engineering, Chemical & Petroleum Refining Engineering Department, Suez, Egypt
b
Eprom-MIDOR Refinery Company, LPG, Naphtha and Jet Processing Department, Alexandria, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Petroleum refineries are now facing much tighter and stricter transportation and fuel specification stan-
Received 10 September 2017 dards, as well as environmental regulations, than in previous years. Therefore, tough rules have been
Revised 7 February 2018 applied on gasoline specifications. Octane number is a key variable of gasoline quality. Isomerization is
Accepted 15 February 2018
one of many processes that generate profit by increasing low gasoline octane numbers, with better envi-
Available online 2 March 2018
ronmental impacts compared to other processes. Here we analyzed and optimized the various variables
affecting the isomerate octane numbers produced by isomerization. Feed composition (naphthenes and
Keywords:
benzene content in the feed) and operating conditions (temperature, hydrogen consumption and liquid
Isomerization process
Operating variables
hourly space velocity) data were collected from the Midor isomerization plant (Egypt) over a 4-year per-
Octane number iod based on the catalyst lifetime. These data were then used to predict the influence of feed composition
Gasoline and operating conditions on isomerate research octane number using a Response Surface Methodology
(RSM) approach (Design Expert software). Thus, we were able to predict isomerate research octane num-
ber under various operating conditions. All of the studied variables were found to influence octane
number.
Ó 2018 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction octane. These can be converted to high-octane, branched-chain iso-

In the last two decades, gasoline has come under tough environ-
mental regulation [1,2]. Therefore many conversion processes have
been used to produce high quality fuels. There are two approaches
for upgrading fuels. The first reforms the molecular structure of a
feedstock and produces a new molecule with different characteris-
tics, but the same number of carbon atoms. Catalytic reforming
and isomerization processes fall into this category. However, both
catalytic reforming and isomerization are basically upgrading pro-
cesses for refinery naphtha streams to improve the octane number
of the naphtha. These processes have many differences between
them—especially with respect to feedstock, operating parameters,
and product quality. Catalytic reforming upgrades heavy naphtha
stream (C+7) while isomerization upgrades light naphtha streams
(C5/C6). Reforming mainly produces high-octane aromatics from
low octane paraffins and naphthene while isomerization converts
normal paraffins into their respective iso-paraffins, which are the
desired hydrocarbons in gasoline. Some of the normal straight-
chain paraffin components of light straight-run naphtha are low in
Peer review under responsibility of Egyptian Petroleum Research Institute.
⇑ Corresponding author.
E-mail addresses: walaa.sliman@suezuniv.edu.eg, walaashahata78@yahoo.com
(W.M. Shehata).
mers by rearranging the bonds between atoms without changing
the number or kinds of atoms [3,4].
The second approach for upgrading fuels involves breaking
large and heavy hydrocarbon molecules into smaller ones with a
higher octane number. Cracking can use either heat (delayed cok-
ing) or by catalyst (fluid catalytic cracking) [4].
The octane number is related the gasoline knocking (self-
igniting) property in the internal combustion engines. A low knock-
ing intensity is related to high engine performance. Gasoline with
high octane number is required for the engine to give high perfor-
mance especially at high speeds [5,6]. In general, isomerization pro-
cesses with a straight chain of hydrocarbon molecules rearrange to
form branched hydrocarbons and are one of the best processes for
producing isomerate with a high octane number [6,7].
For instance, linear heptanes has an octane number zero, while
2, 3 dimethyl butane as an isomer of n-hexane has an octane num-
ber above hundred octane [5,6,8]. The light naphtha octane num-
ber is around 70, and via isomerization can gain a 14 octane
number increase [9].
Many studies have proposed some modifications to the isomer-
ization process technology by applying experimentally zeolite
membrane reactor concept for the hydro-isomerization of n-
hexane [10]. Watanabe et al. [11] proposed a new isomerization

https://doi.org/10.1016/j.ejpe.2018.02.006
1110-0621/Ó 2018 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
946 W.M. Shehata et al. / Egyptian Journal of Petroleum 27 (2018) 945–953
process with Pt/SO2
4 /Zr O2 catalyst. Graeme and Ross [8] and Yasa-
kova and Sitdikova [12] reviewed existing technologies in isomer-
ization. Chlorinated aluminium oxide and platinum (Pt/Al2O3-
CCl4), zeolite catalyst (Pt/zeolite), and sulfated zirconia (Pt/SO4-
ZrO2) are used as catalysts in isomerization processes [5,8,12].
The Pt/Al2O3-CCl4 catalyst is highly effective at low temperatures
and offers the highest product yield and product octane numbers.
This catalyst demonstrates good selectivity but it is sensitive to
water and sulphur in the feedstock. Pt/zeolite catalyst is the least
common. It requires a high hydrogen/feed ratio because this cata-
lyst operates at higher temperature, which may decrease the selec-
tivity and cause coking. The Pt/SO4-ZrO2 catalyst is active at low
and higher temperatures. It is resistant to poisonous impurities
and can be regenerated [5].
The mechanism of alkane isomerization has been studied inten-
sively [13,14]. However complete mechanism of paraffin isomer-
ization and side reactions occur are difficult to predict despite
models that solve the problem partially—either for the isomeriza-
tion of a single linear paraffin [6,15–17], or for the isomerization
of a mixture of linear paraffin [18–20].
The quality of isomerate from light naphtha isomerization
depends on many variables including the following:
(1) The reactor temperature is the basic process control vari-
able—higher temperatures increase processing severity
because the temperature affects the equilibrium between
normal and isoparaffins. The increase in temperature will
increase dehydrogenation, which initiates the isomerization
reactions. At a certain level, the thermodynamic limitations
intervene and consequently the temperature is optimal for
conversion to iso structures. Hydrocracking is strongly
favoured by increasing temperature. This emphasizes the
initiation reactions for the formation of alkenes that gener-
ate carbonium ions on the acid sites of the catalyst and
increase the rates of cracking reactions taking place on these
sites [3,7,9]. Conversion of n-paraffins to iso-paraffins is an
equilibrium-limited reaction. Paraffin-isomerization cata-
lysts fall into three categories—high-temperature isomeriza-
tion process (250–300 °C) on zeolite catalysts [3], low-
temperature isomerization process on chlorinated-alumina
catalysts (130–170 °C), and lower-temperature isomeriza-
tion process (<130 °C) on sulphated metal oxides [3,9].
(2) Naphthenes can be in the feedstock. As their content
increases in the feed, a large amount of hydrogen is required
to open the naphthene rings and form paraffins for isomer-
ization [9]. This means that naphthene have two stages in
isomerization. The first stage is ring opening reaction and
the second is the isomerization reaction [3,9,21]. The quan-
tity of naphthenic compound methyl-cyclopentane (MCP)
over the equilibrium concentration is ineffective because it
isomerizes in equilibrium reactions to cyclohexane (CH)
and then decylizes to lower octane number hexane isomers
in the form of methyl-pentanes and n-hexane. High content
of cycloparaffin reduces the isomerization reaction because
they sorbe to the active site of the catalyst and inhibit the
formation of multi-branched paraffins. The adsorption
energy of aromatic and naphthenic compounds is higher
than that of paraffins compounds [21]. This means that
higher naphthene content in the isomerization feed will
reduce reactor performance and the isomer ratio—this will
reduce the product octane number [9,21].
(3) The benzene ring is the most common C6 aromatic com-
pound. Burning benzene in the car engine gives very high
amounts of CO2. Modern gasoline specs require very low
benzene contents due to environment regulation [8,9]. Con-
verting benzene rings to iso-hexane requires three steps.
First, the benzene ring is saturated to cyclo-hexane. Second,
the ring is cracked to normal hexane, which is finally iso-
merized to hexane isomers. This reaction proceeds very
quickly and is achieved at very low temperatures
[1,8,9,21]. The presence of benzene decreases the product
octane number as a result of two reasons. First benzene rings
inhibit the isomerization reactions because they are
adsorbed on platinum and partially cover the acidic sites
of the catalyst. The second reason is the formation of cyclo-
hexane from benzene that isomerized to methyl-
cyclopentane. The high content of benzene from 0 to 4.2%
decreases the research octane number in isomerate [21].
(4) Liquid hourly space velocity (LHSV) plays a great roll on pro-
duct quality. The LHSV is the ratio of the volumetric flow rate
(hourly) of the liquid feedstock to the volume of the catalyst
[9]. The LHSV is the inverse of the residence time. Decreasing
LHSV usually improves isomerization. However, an extreme
reduction in LHSV may make the unit operation difficult
[22]. A severe reduction in LHSV may cause channelling that
leads to poor liquid distribution and under-utilization of the
catalyst. On the other hand, increasing the unit capacity for
a fixed amount of catalyst (higher LHSV) will reduce contact
time between reactants and catalyst surface. Consequently,
the mass transfer between catalyst and reactants will be not
enough to complete the reaction; the isomer ratios of the pro-
duct will decrease [9,22].
(5) The hydrogen consumption fed into the isomerization pro-
cess is affected by the amount of naphthene and benzene
present in the feedstock. As the benzene and naphthene con-
tent increase in the naphtha feed stock, hydrogen consump-
tion increases [3,9]. In addition, hydrogen consumption
increases to avoid carbon deposits on the catalyst [6]. An
insufficient hydrogen flowrate leads to incomplete naph-
thene ring opening, incomplete benzene saturation and a
low isomerization ratio [9].
However, previous studies have not considered the modelling of
isomerization processes with light naphtha as a function of feed
composition (naphthene and benzene content). Nor have they con-
sidered operating variables (reactor temperature, LHSV, and hydro-
gen consumption).
This work introduces an approach to model the isomerate
research octane number produced from an existing Penex isomer-
ization plant with the previous variables. The Response Surface
Methodology (RSM) is used to figure out the influence of the stud-
ied variables on the isomerization RON. The program used is the
Design Experts software version 10.0.01, state ease.
The RSM procedure is used for its flexibility. It combines the
concept of experimental design and optimization theory. Conse-
quently, it can be used to determine the optimal operating condi-
tions by modelling the relationship between the independent
variables and the response [23,24]. An important advantage of
RSM is the reduced number of experimental trails needed to eval-
uate multiple parameters and their interactions [24–27]. This work
can be used to provide guidance for the isomerate research octane
number produced from the isomerization process.
2. Case under study
The case study described here is for the Midor isomerization
plant in Alexandria, Egypt. This plant is a Penex Process type with
chlorinated-alumina based catalyst. This process is a recycle iso-
merization process. The recycle isomerization process achieves
higher octane number in isomerates due to the recycling of low-
octane unconverted n-paraffins (n-hexane) into the reactor after
 W.M. Shehata et al. / Egyptian Journal of Petroleum 27 (2018) 945–953 947

Fig. 1. Penex isomerization process with de-hexanizer recycling tower.

separation from the reactor product. De-hexanizer (DH) is used to light naphtha. Detailed light naphtha composition and specifica-
recycle the unconverted n-C6 and the lower octane methyl- tions for isomerization feed are listed in Tables 1 and 2. Make-up
pentanes to the isomerization reactor. To attain higher octane hydrogen is produced at platforming unit that increases heavy
numbers, complete recycling of all normal paraffins to the reactor naphtha octane number by converting the naphthenes to aromat-
is required rather than adopting once-through or partial recycle ics. The composition of the make-up gas supplying hydrogen is
options [3,28]. Separation of the unconverted normal paraffins shown in Table 3.
from the product in the isomerization process plays a major role Note that the data illustrated in Tables 1–3 were taken in the
in the octane isomer quality. original design of the studied isomerization unit (during the early
The plant used light naphtha as feed. Naphtha is separated from stages of designing the unit). The actual various operating feed
crude oil by atmospheric distillation and is produced by the hydro- compositions and feed conditions that affect the isomerization
cracker and the coker unit. The naphtha contaminants include products’ quality are collected during four years based on the cat-
hydrogen sulfide, mercaptan, and sulphur compounds. These are alyst life time. The collected data depends on recording the field
removed by hydrotreating. A flow diagram for the isomerization data and operating conditions in distributed control system
process is shown in Fig. 1. Hence, the light naphtha feed is mixed (DCS), and laboratory for all different feed types of isomerization
with hydrogen to reduce coke formation on the catalyst. The feed unit for the same catalyst type. The isomerization unit under study
is then exchanged with the reactor effluent stream. The reaction was constructed for 13 years. During this period, the catalyst is
temperature is controlled by a steam re-boiler. Hot feed enters changed 3 times (after each four years, exhausted chlorinated-
the reactor through a top distributer, and the reactor effluent con- alumina catalyst is replaced by another new one). We collected
sists of branched hydrocarbons (isomer), cracked gas and the data during one period of the last three periods. The data for
hydrochloric acid. The gases are separated at the sieve tray stripper the other periods are approximately the same and repeated.
(stabilizer) and then washed with 10 wt% caustic solution to The naphtha feed to this isomerization unit is changed 26 times
remove HCl. Hexanes unconverted to isomers are separated from during use of the same catalyst, as described in Table 4. The same
the product using sieve tray fractionators called de-hexanizer feed can be used for a month or above according to the receiving
(DH) as shown in Fig. 1. naphtha feed from the refinery. The feed type is chosen according
The unconverted hexanes are recycled and mixed with feed to the cycloparaffins content (naphthenes). Where the summation
streams to the reactor. This step improves the product octane
number because normal hexane has a low octane number of 25
[5,6,8,14]. Chlorinated alumina is impregnated with 0.25 wt% plat- Table 1
inum and converts normal paraffins, naphthene, benzene and low Design light naphtha feed composition.
octane paraffins to high octane iso-paraffins. The catalyst is loaded
Component Composition (mole%)
in fixed bed reactors in which no oxygen is allowed to contact the
Butane 0.11
catalyst during loading. Hence, the chloride alumina bond is very
iso-Pentane 11.69
sensitive to oxygen. Therefore, the oxygen compounds are N-Pentane 13.3
removed from the feed before the reaction using a molecular sieve. Cyclo-Pentane (CP) 1.95
The catalyst shape is extended and densely loaded to increase the 2,2-Di-Methyl-Butane (2,2 DMB) 0.49
amount of catalyst inside the reactor. To maintain the high acidity 2,3-Di-Methyl-Butane (2,3 DMB) 1.66
2-Methyl-Pentane (2 MP) 10.4
of the catalyst, a few ppm of pre-chloroethylene (chloriding agent)
3-Methyl-Pentane (3 MP) 9.37
is continuously injected to the reactor to maintain the same con- N-Hexane 30.72
centration of chlorides required for catalyst activity. At the inlet Methyl-Cyclo-Pentane (MCP) 8.69
of the reactor, the agent will react with hydrogen to form HCl Cyclo-Hexane (CH) 5.84
Benzene 3.18
and inhibit the loss of chloride from the catalyst [9,29]. The feed
Heptanes 2.6
flow rate to the isomerization unit is 70.7 m3/h of hydro-treated
948 W.M. Shehata et al. / Egyptian Journal of Petroleum 27 (2018) 945–953

Table 2 consumption and research octane number) illustrated in Table 4

Design light naphtha feed specifications. are taken as an average value for many readings at the same type
Specification Value of feed. These data can be used to improve the performance of the
3
Naphtha feed rate (m /h) 70.7 Penex isomerization process.
Density (kg/m3) 671.4 All isomerization unit-operating variables were monitored in
Molecular weight (kg/kg mole) 81.88 the collected data. The relationship between isomerate product
Bromine number (mg Br2/100 g) 4 quality and the following variables were evaluated: naphthene
Copper (PPb)* 20
Lead (PPb) 10
content, benzene content, reactor temperature, LHSV, and hydro-
Arsenic (PPb) 1 gen consumption. Product quality is expressed as product research
Fluorides (PPb) 0.1 octane number (RON) and/or product isomer ratio. Isomerate ratio
Mercury (PPb) <1 was defined in this work as the weight of isomerate to the total
HCl (PPm)** 0.5
weight of reactor effluent [30].
Sulphur (PPm) 0.5
Nitrogen (PPm) 0.5
*
2.1. Effect of naphthene content on product quality
Part per billion.
**
Part per million.
Naphthenes included in Penex feeds include cyclopentane (CP),
methyl-cyclopentane (MCP), and cyclohexane (CH). These naph-
thenic rings are cracked into paraffins before isomerization
Table 3 [21,29]. The naphthene content changed in the range of 5–34 wt
Design make up hydrogen analysis.
%. The data show that higher naphthene content in the isomeriza-
Component Composition (mole%) tion feed will reduce the reactor performance and reduce the pro-
Hydrogen 90.09 duct isomer ratio as presented in Fig. 2. Vuković [31] studied the
Methane 3.18 same effect of naphthene content on product quality and found a
Ethane 2.82 negative effect for cyclo-compounds on product quality. Szoboszlai
Propane 2.33
and Hancsok [21] found that increasing naphthene content in feed
Iso-Butane 0.55
N-Pentane 0.63 decreased product octane number.
Iso-Pentane 0.13
N-Pentene 0.06 2.2. Effect of benzene content on product quality
2,2-Di-Methyl-Butane 0.01
2,3-Di-Methyl-Butane 0.02
2-Methyl-Pentane 0.04 The data show that increasing benzene content reduces RON if
3-Methyl-Pentane 0.01 the other parameters are constants (Fig. 3). Benzene changes in the
N-Hexane 0.01 range of 0.31–3.03 wt%. Hancsók et al. [1] found that the benzene
Water 0.12
content is reversely proportional to the octane number. The
decrease in isomerate octane number is due to strong multi-site
adsorption of benzene on the catalyst surface. This reduces free
of cyclopentane (CP), methyl-cyclopentane (MCP), and cyclohex- active sites in proportion to benzene content [21].
ane (CH) are expressed as naphthenes content. The other parame- In addition, increasing benzene content in the feed will increase
ters (benzene content, reactor temperature, LHSV, hydrogen reactor effluent temperature due to exothermic heat of saturation

Table 4
Data from existing Penex isomerization process.

Naphthenes @ feed, wt% Benzene @ feed, wt% Reactor Temp, °C LHSV H2 Consumption, kmol/h Product research octane number, (RON)
(Factor A) (Factor B) (Factor C) (h
1) (Factor E) (Response)
(Factor D)
10.00 0.31 168.81 0.87 102.6 88.47
6.00 0.64 167.65 1.30 102.8 88.18
12.00 0.76 163.00 0.93 103.0 88.07
5.00 0.75 170.00 0.82 103.0 88.00
15.00 0.86 170.00 0.92 103.9 87.99
9.00 0.87 170.00 0.93 102.6 87.97
13.00 0.99 166.44 1.45 103.2 87.87
11.00 1.20 165.00 1.00 102.8 87.67
17.00 1.40 165.00 1.69 104.9 87.50
14.00 1.80 166.00 1.69 103.5 87.44
19.00 1.80 164.48 1.79 106.1 87.36
16.00 1.85 167.00 1.19 104.4 87.33
20.00 1.85 164.31 1.79 106.9 87.32
18.00 1.85 164.02 2.02 105.5 87.24
21.00 1.80 163.44 1.71 107.7 87.10
22.00 1.80 159.00 1.66 108.5 87.05
23.00 1.15 162.57 2.03 109.4 86.87
24.00 2.20 162.06 2.24 110.4 86.74
31.00 2.60 164.00 1.48 119.2 86.56
28.00 2.60 164.00 1.50 115.0 86.55
32.00 2.70 160.73 2.26 120.7 86.40
29.00 2.76 160.27 2.14 116.4 86.28
25.00 2.94 159.63 2.26 111.5 86.12
27.00 3.00 159.40 2.29 113.8 86.06
30.00 3.00 159.40 2.29 117.8 86.06
34.00 3.03 156.00 2.81 124.0 86.00
 W.M. Shehata et al. / Egyptian Journal of Petroleum 27 (2018) 945–953 949

74.4 89
74.2
Product isomers ratio , %

88.5

Product Research Octane No.

74.0
73.8 88
73.6
73.4 87.5
73.2
87
73.0
72.8 86.5
72.6
72.4 86
0 10 20 30 40
Feed naphthenes content, wt % 85.5
155 160 165 170 175
Fig. 2. Effect of feed naphthene content on product isomers ratio. Reactor inlet temperatur 0C

Fig. 4. Effect of reactor inlet temperature of each feed on the product research
89 octane number.
Product Research Octane ON.

88.5
actually decrease because of the downward shift in equilibrium
88
curve even though the temperature gives a higher reaction rate.
87.5 Such an effect is due to a crack in hydrocarbons to light gases as
a side reaction—this reduces yield [9,29,32].
87

86.5 2.4. Effect of LHSV on product quality

86
85.5
0 0.5 1 1.5 2 2.5
Feed benzene content, wt. %
Fig. 3. Effect of benzene content of each feed on the product research octane
number.
reactions, so that reactor inlet temperature should be decreased
before reaching the design temperature of the catalyst and reactor
vessel [9,32]. The reactor temperature data indicates that the tem-
perature difference across the reactors increases with benzene
content at isomerization feed. Higher temperature differences are
due to many actions such as hydrogenation, naphthene ring crack-
ing and saturated benzene rings that are cracked to paraffin. All of
these reactions are exothermic, which increases the reactor tem-
perature. This effect has been investigated previously [9,29]. It is
noticed from Table 4 that at the lowest benzene content (0.31 wt
%), the naphthenes content is also low (10 wt%) and the research
octane number is the maximum. Hence, the impact on RON could
be attributed to low naphthenes content and low benzene content
as well.
The LHSV changes from 0.82 to 2.81 h
1 The data illustrate that
an increase in LHSV decreases the iso-paraffins in the product
3 3.5 (Fig. 5). Similar results were reported by Vuković [31] who found
that the product isomerate ratio for light naphtha decreases with
higher space velocity. Also, Sinha and Sivasanker [34] found that
conversion of normal paraffin to iso-paraffin decreases with higher
space velocity. Decreasing LHSV will increase the contact time
between the reactants and the catalyst in the reactor and this leads
to a high product isomerate ratio and octane number [9,29].
2.5. Effect of hydrogen consumption on product quality
The hydrogen consumption increases according to the naph-
thene and benzene contents in the feed as shown in Figs. 6 and
7. However, an increase in feed to the Penex isomerization unit
requires more hydrogen. Hydrogen addition is required for two
important reactions—opening of the naphthene rings to form
paraffins and saturation of benzene to cyclo-hexane. Both reactions
consume hydrogen, and it is critical that sufficient hydrogen is pre-
sent to meet the chemical demand of these reactions [35]. For the
previous range of naphthene and benzene, the hydrogen consump-
tion changes from 102.6 to 124 kmol/h. The hydrogen consump-

77
2.3. Effect of temperature on product quality
76
Product isomers rao , %

The reaction is controlled by a thermodynamic equilibrium that 75

is more favourable at low temperatures (<200 °C) [3,9,29]. Equilib-
rium limits the maximum conversion possible at any given set of 74
conditions. This maximum is a strong function of the temperature
73
at which the conversion occurs. A more favourable equilibrium
exists at lower temperatures [9,29]. Fig. 4 shows the data from 72
156 to 170 °C. Higher temperatures increase the catalyst activity
and the resulting research octane number. 71

Similar results were reported by Vuković [31] and Ali et al. [33] 70
who found that increasing temperature will increase conversion. 0.50 1.00 1.50 2.00 2.50 3.00
Despite the good effect of high temperature on product quality, Liquid hourly space velocity (LHSV), hr-1
it may have a bad influence on product yield. At excessively high
temperatures, the concentration of iso-paraffins in the product will Fig. 5. Effect of LHSV of each feed on product isomers ratio.
950 W.M. Shehata et al. / Egyptian Journal of Petroleum 27 (2018) 945–953

130 of Penex isomerization unit. The correlation can guide operating

Hydrogen consumpon, Kmole/hr

125 and designing engineers. It can improve the Penex isomerization

process to produce isomerate with higher octane number. The
120
RSM can generate a relation between these variables and isomer-
115 ate RON.
110 The RON of isomerate produced from Penex isomerization unit
fluctuated between 86.0 and 88.47 (Table 4). It changed as a func-
105
tion of the studied variables. Regression analysis using quadratic
100 polynomial type in Design Expert software version 10.0.01 corre-
95 lates the isomerate RON with the variables as shown in the follow-
ing generalized regression Eq. (1):
90
85 Isomerization RON
80 ¼
78:81947
ð5:7610  naphÞ þ ð19:16095  BZÞ
0 10 20 30 40
ð1:7566  TempÞ
ð11:92181  LHSVÞ þ ð6:82721  HCÞ
Feed naphthenes content, wt % þ ð0:21942  naph  BZÞ þ ð0:032018  naph  TempÞ
Fig. 6. Effect of naphthene content on hydrogen consumption. þ ð0:19833  naph  LHSVÞ
ð0:21345  BZ  HCÞ
þ ð0:21577  Temp  LHSVÞ
ð0:050521  Temp  HCÞ
130
ð0:25395  LHSV  HCÞ
ð0:25974  BZ2 Þ
Hydrogen consumpon, Kmole/hr

þ ð0:019167  Temp2 Þ þ ð0:009074  HC2 Þ ð1Þ

125
120
115
110
105
100
0 0.5 1 1.5 2 2.5
Feed benzene content, wt %
Fig. 7. Effect of benzene content on hydrogen consumption.
tion increases with increasing naphthene and benzene contents.
Similar results were observed by Szoboszlai and Hancsók [21]
and Vuković [31] who stated that increasing cyclo compounds in
the feed would increase the hydrogen-to-hydrocarbon ratio.
The relationship between isomerate product research octane
number and naphthene and benzene content in the feed, reactor
temperature, LHSV, and hydrogen consumption are shown in
Table 4.
Note that each point in the table represents the average
research octane number and operating conditions for each pro-
cessed feed. Where each point reflects the average of about 50 indi-
vidual data.
The data of feed composition and the operating conditions that
collected the case under study were statistically designed using a
Here, naph is the feed naphthene content in wt%; BZ is feed ben-
zene content, wt%; Temp is reactor inlet temperature, °C; LHSV is
liquid hourly space velocity, h
1; and HC is the hydrogen consump-
tion, kmol/h. Eq. (1) is valid when naphthene and benzene in light
naphtha feed are 5.0–34 wt% and 0.31–3.03 wt%, respectively,
reactor temperature range is 156–170 °C, LHSV range is 0.82–
2.81 h
1, and hydrogen consumption range is 102.6–124 kmol/h.
Note that this equation can be used to make predictions about
the response for given levels of each factor. Here, the levels should
be specified in the original units for each factor. This equation
3 3.5 should not be used to determine the relative impact of each factor
because the coefficients are scaled to accommodate the units of
each factor and the intercept is not at the centre of the design
space.
F test was used to show the significance and the interaction of
each factor with octane number. There is a significant effect
between all studied factors and research octane number (p <
0.05; Table 5).
The interaction between these factors AB, AC, AD, BE, CD, CE,
and DE are significant. Where A represents naphthene wt%, B for
benzene wt%, C for temperature, D for LHSV, and E for hydrogen
content. Additionally, the quadratic terms B2, C2 and E2 are signif-
icantly effective in the model.
The R2 test can examine the predictive power of the model. The
value of R2 is close to 1 implying that the model fits the data. The
Table 5
P-value for response surface reduced quadratic model.

standard RSM design of Design Expert software. Source P-value

Two statistical tests (test of the significance of factors and R Model <0.0001
square test) evaluated how well the operating data represented A-napth <0.0001
the model. The significance of these factors or their interactions B-BZ <0.0001
is evaluated using the probability value (p value) with p < 0.05 C-TEMP 0.0050
D-LHSV 0.0017
indicating significance [36].
E-HC <0.0001
AB (napth: BZ) <0.0001
AC (napth: TEMP) 0.0015
3. Results and discussion AD (napth: LHSV) 0.0021
BE (BZ: HC) 0.0001
CD (TEMP: LHSV) 0.0010
Our goal is to predict the relationship between isomerate CE (TEMP: HC) 0.0016
research octane number produced from Penex isomerization pro- DE (LHSV: HC) 0.0024
cess and feed composition (naphthene and benzene content) and B2 0.0024
C2 0.0023
operating variables (reactor temperature, LHSV, and hydrogen con-
E2 <0.0001
sumption) to clarify the effect of these factors on the performance
 W.M. Shehata et al. / Egyptian Journal of Petroleum 27 (2018) 945–953 951

89 adjusted R2 is 0.9962 meaning that the factors and their interac-

tions are significant [24].
Another quantity is obtained, Predicted R2 which has a value
88.5
0.9699 and indicates that the model predicts responses for new
observations well.
Predicted RON from the correlaon

88 The results show that the predictive model fits the data with
Predicted regression coefficients very close to one. The standard error
RON from
the between the isomerate RON from actual isomerization plant and
87.5
correlaon the predicted from the proposed model are in good agreement
Actual
Research
and with average error <1% for each factor as demonstrated in
87 ON Fig. 8.
The generalized equation does not show the dependence of the
product RON on the studied factors. Therefore, for clearing such a
86.5
relationship, the 3-D surface response plots were developed as pre-
sented in Fig. 9. All Fig. 9a–d show that the product octane number
86 increases with decreasing naphthene, benzene, LHSV, and hydro-
gen consumption and increases with increasing temperature.
For clear understanding the dependence studied factors with
85.5
85.5 86 86.5 87 87.5 88 88.5 89 research octane number, a perturbation plot for isomerization fac-
tors is presented in Fig. 10. A perturbation plot shows the effect of
Actual Research ON
each individual factor as the others are kept constant. However it is
Fig. 8. Predicted research octane number from correlation vs actual research octane preferable for interpreting a perturbation plot to be conjunction
number. with the 3-D surface responses [37,38]. It is noticed from the figure

95 95

90 90

85 85
ON
ON

80 80

75 75

102.6 34
0.82 28.2
107.95 1.218 0.31
22.4 0.99
113.3 1.616
2.014 16.6 1.67
118.65
E: HC (KMOL/H) 2.412 A: napth (WT %) 10.8 2.35
124 2.81 D: LHSV (HR-1) 5 3.03
B: BZ (WT %)

(a) (b)

95 95

90 90

85 85
ON
ON

80 80

75 75

0.82 34
156
1.218 158 28.2 156
160 22.4 158
1.616 162 160
2.014 164 16.6 162
164
166 166
D: LHSV (HR-1) 2.412 168 A: napth (WT %) 10.8
168
2.81 170 C: TEMP (C) 5 170
C: TEMP (C)

(c) (d)
Fig. 9. Surface response of the effects of naphthenes (wt%), benzene (wt%), LHSV (h
1), temperature (°C), and Hydrogen consumption (kmole/h) on the isomerization process
octane number.
952 W.M. Shehata et al. / Egyptian Journal of Petroleum 27 (2018) 945–953
Perturbation
95
90
E A
B CD
EC
85
A B
ON
80
75
70
-1.000 -0.500 0.000 0.500
Deviation from Reference Point (Coded Units)
Fig. 10. Perturbation plot for the predicted isomerization octane number (A is
naphthene (wt%), B is Benzene (wt%), C is temperature (°C), D is LHSV (h
1), and E is
hydrogen consumption (kmole/h).
that, all the factors under study are significant. Hence, the effect of
benzene (wt%), temperature (°C), LHSV (h
1), and hydrogen con-
sumption ( kmol/h) on the product research octane number are
considerably close, while the effect of naphthene (wt%) is slightly
greater than the other variables.
4. Conclusion
The first objective of this work is to monitor the effect of feed
composition and operating variables on the performance of an
existing Penex isomerization unit. The feed composition is indi-
cated by naphthene and benzene wt%. The operating variables
are indicated by temperature, LHSV, and hydrogen consumption.
Studying the feed composition and the operating variables are
important to improve product quality, product yield, catalyst activ-
ity, and reduce utilities consumption. The catalyst activity and pro-
duct quality are improved by increasing temperature and reducing
unit capacity (LHSV) because more contact time is obtained. On the
other hand, high temperature reduce product yield due to hydro-
carbons cracking to light gases. These are lost at fired heaters
and flare. Naphthenes (cyclic compounds) reduce product quality
due to extra reactions required for its conversion to iso-paraffins
and consume more hydrogen for ring cracking. The high benzene
content in the feed decreases product quality due to extra reactions
required for its saturation to iso-hexane. In addition, increasing
benzene content in feed increases reactor effluent temperature
due to exothermic heat of saturation reactions. The experimental
data used here are industrial data collected from the Midor isomer-
ization process located at Alexandria- Egypt. The naphthene con-
tent ranges from 5 to 34 wt%, the benzene range is 0.31–3.03 wt
%, the temperature range is 156–170 °C, the LHSV range is 0.82–
2.81 h
1, and the hydrogen consumption range is 102.6–124
kmol/h.
The second objective of our work is the application of RSM in
Design Expert software to obtain a correlated model that can be
used to predict the relation between Penex isomerization product
research octane number and naphthene content, benzene content,
reactor temperature, LHSV, and hydrogen consumption. The results
showed good agreement between the industrial actual data of pro-
duct octane number and the predicted product octane number
from the model. We suggest to use the model for obtaining isomer-
ization product octane number within the range of the dependent
factors presented here.
Finally, the obtained model can predict the isomerization per-
formance at various operating variables. It can improve the Penex
isomerization process to produce isomerate with higher RON
needed to motor engines.
D
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