Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
CHAPTER 2
DOCUMENT NO CHAPTER - 2 ISSUE ISSUE DATE REV REV DATE
PROCESS DESCRIPTION NO NO
HR-PN-OM-CRU-22 01 01/07/2014 01 1/07/2014
Naphthenes dehydrogenation - 50 30
Paraffin dehydrocyclization - 60 1 (base)
Isomerization: Paraffins +2 3
Naphthenes +4
HydroCracking + 10 0.5
Cyclohexane Benzene
RON MON
• Cyclohexane = 83 77.2
• Methylcyclohexane = 74.8 71.1
• 1.3 = 71.7 71.0
dimethylcyclohexane
• Benzene = 114.8 > 100
• Toluene = 120 103.5
• m-Xylene = 117.5 115.0
b) Paraffins dehydrocyclization
This is a multiple step process which applies either to the normal paraffins
(linear) or iso-paraffins (branched). It involves a dehydrogenation with a
release of one hydrogen mole followed by a molecular rearrangement to
form a naphthene and the subsequent dehydrogenation of the naphthene.
The molecular rearrangement to build a naphthene is the most difficult
reaction to promote but the subsequent aromatization of the naphthene
yields a noticeable octane increase.
The reaction can be summarized as follows:
CH CH CH CH CH CH
2 2 2 2 2
+H
CH CH CH CH CH CH CH 2
3 2 2 3 3 CH 2 3
C H C H
7 16 7 14
CH CH
2 2
CH CH CH CH
2 2
H C CH
2 3
CH CH CH CH
3 2 3 CH CH
2 2
Methylcyclohexane
CH CH CH CH
2 2
C
H C CH CH
3 HC CH + 3H
2 3 2
CH CH CH CH
2 2
Toluene
CH
7 16 CH
7 16
These reactions are fast, slightly exothermic and do not affect the number of
carbon atoms. The thermodynamic equilibrium of isoparaffins to paraffins
depends mainly on the temperature. The pressure has no effect.
Iso-N paraffin equilibria
Carbon atom C4 C5 C6 C7 C8
%Isoparaffin 500°C 44 58 72 80 88
C2H5
CH3
Alkylcyclopentane Alkylcyclohexane
(Ethylcyclopentane (Methylcyclohexan
) e)
( (
RON MON
C) Adverse reactions
a) Cracking
Cracking reactions include hydrocracking and hydrogenolysis reactions.
Hydrocracking affects either paraffins (normal or iso) or naphthenes. It
involves both the acid and metallic function of the catalyst. It is, to some
extent, a parallel reaction to paraffin dehydrocyclization.
It can be represented schematically by a first step of dehydrogenation which
involves the metallic function of the catalyst, followed by a cleavage of the
resulting olefin and the hydrogenation of the subsequent short chain olefin.
The second reaction is promoted by the acidic function of the catalyst.
(m)
+H
2
CH CH
7 16 7 14
(a)
+
+H
2
C H C H C H
7 14 4 8 3 8
(m)
+H
2
CH CH
4 8 4 10
+H or
2
CH - C H C H
3 5 9 6 14
or
+H or
2
CH - C H C H
3 6 11 7 16
+H CH +
2 2 6
CH CH
7 16 5 12
+H + CH
2 4
Xylene Toluene
+H + CH
4
2
Toluene Benzene
CH
3
+ CH = CH - CH HC
2 3
CH
3
Benzene Propylene Isopropylbenzene
+ +
The effect of the main operating conditions on the rate of the reactions
involved in the reforming process using the selected catalyst is summarized
below.
A) Effect of hydrogen partial pressure
At 10 barg hydrogen partial pressure, the dehydrogenation of naphthene is
about 10 times, faster than isomerization, 30 times faster than
dehydrocyclization and 50-60 times faster than cracking (hydrocracking and
hydrogenolysis).
– Dehydrogenation
– Isomerization
– Cracking
– Dehydrocyclization
• 3rd reactor:
– Cracking
– Dehydrocyclization
Pretreated naphtha from unit-21 is fed to the unit by the pump 22 P01C/D,
and regulated by 22 FC02. Feed naphtha mixed with the recycle gas from 22
K01 A / B is pre-heated in the welded plates exchanger 22-E-101 (Packinox
exchanger). 22 E01 A/B is kept as standby for feed preheating. The mixture is
also preheated in 22-E-02 against the third reactor effluent and then is
further heated to the required first reactor inlet temperature in pre-heater
22-F-01.Completely vaporized feed from the above exchangers enter the
furnace tubes of 22 F01 and is heated up to the reaction temperature before
entering the reactor 22 R02.
therefore, reheated in furnace 22 F201 to make up the loss of heat in the first
Reactor. Reheated effluent is then passed through the 2nd Reactor 22 R03.
Operating conditions:
512 ºC EOR
22R02 :6 22 TI 20/21/22/23/24/25
22R03 :8 22 TI 28/29/30/31/32/33/34/35
Differential pressure gauges 22 PDI 03, 04 and 04201 are provided to indicate
the pressure drop across the Reactors. Required Reactor inlet temperatures
are controlled by 22TC 01, 22 TIC 5101 and 22TC02. These controllers in
turn act on the fuel gas quantity to the furnace burners.
The reactor effluent is split into gaseous and liquid phases in separator
drum.
A low flow alarm (22 FAL 03) along with the low flow alarm cut off (22
FALCO 03) is connected to the discharge line of the compressors 22 K01 and
the furnaces 22 F01, 22 F201 and 22 F02. This facilitates to stop the latter in
case of compressor failure alongwith the tripping of feed pump. The
compressors 22 K01 A/B are stopped automatically in case of very high level
in the separator drum 22 B01. The complicated lube and seal oil system of
22K01A/B shown in the diagram H/CRU/03.
The liquid from the separator drum is fed to the stabilizer. The liquid is
reheated in the shell side of the exchangers 22 E06 A/B with the stabilizer
bottoms product on the tube side and enters the stabilizer. The stabilizer
column comprises of
B02 through 22PV 05B and flow of OFF gases to LPG recovery of ISOM unit
/ Fuel gas header through flow recorder 22FI07.
The stabilizer bottom part is passed through exchangers 22 E06 A/B and
cooler 22 E07 before it is sent to storage and feed to reformate splitter in unit
85. A 2" dia draw-off from top reflux built-in accumulator (above plate 28) of
22 C01 has been provided for tapping of LPG from Reformer gas. This stream
enters a water separating pot prior to entry into Crude Distillation unit
stabilizer 11C04. A rotameter has been provided for measurement of LPG
rich stream from reformer to Column 1 1 C04.