1.

CHAPTER-1

INTRODUCTION

1.1 NEED FOR DHDS UNIT

We are all aware of the fact that to protect the environment from toxic emissions
of SO2 from diesel engines, the demand of cleaner fuel (in terms of “S” content)
in all over the world is increasing day by day. According to the Environment
Policy of Gujarat Refinery, Refinery has committed to produce HSD as per the
stringent regulatory norms.

1.2 INTRODUCTION OF THE UNIT

To meet the regulatory norms, Diesel Hydro Desulfurization (DHDS) unit at

Gujarat Refinery was installed and commissioned in the year 1999 with a aim
to produce low sulfur diesel of 500 PPMW from a blend consisting of SR LGO,
SR HGO, SR GO and LCO having ‘S’ level of 1.46% w/w. Other features of the
unit are as under:-

* UNIT COMMISSIONING DATE 12.06.1999

* PURPOSE OF THE UNIT To produce Low Sulfur

Diesel of < 500ppmw

* PROCESS LICENSOR M/s UOP, USA

* PROJECT CONSULTANT M/s DELIM

* PLANT CAPACITY 1.44 MMTPA

* UNIT TURN DOWN RATIO 50% of the design capacity

* FEED RATE (BASED ON 100% CAP.) 208 M3/HR

* ON STREAM FACTOR 8000 HRS/YEAR

* FEED TANK 1. TK-823 2. TK-824

Both Feed Tanks are located
at FCC Offsites.

* FEED STREAMS TO FEED TANK 1. SRLGO 2. SRHGO

3. LCO 4. SRGO
 1.2

In JAN-2005 Catalyst turnaround, Both DHDS Reactors existing catalyst from

UOP was replaced with Criterion catalyst. For the next cycle of the DHDS unit,
catalyst selected is capable of producing 200 PPMW product sulfur from feed
diesel having 1.77% w/w ‘S’ and achieve cycle life of three years. Also It was
decided after JAN-2005 shut down to run the unit with higher capacity of 1.7
MMTPA (corresponding Feed Rate 245 m3/HR) with the target product ‘S’ <
200 PPMW.

When DHDS unit was run at 245 M3/Hr, heavy vibrations were observed in
feed inlet to reactor lines and reactor effluent lines. These Vibrations
in were studied by Inspection / E/S department together with UOP
personnels. As per the joint guidelines of UOP personnels/Inspection and
E/S department U-tube bundle of 1010E-02A/B/C/D and 1010E-
04A/B/C/D/E/F were changed in JAN-2005 shut down with new ones having
new baffle arrangements to reduce the vibrations in both CFE trains I/L and
O/L lines. Again vibration survey were carried out in the H.P. section by
Inspection / E/S department together with UOP personnels. New baffle
arrangement has reduced the vibrations to quite some extent but could not
eliminate the vibrations.

As per their joint recommendations, additional structural support has

provided in the tube side O/L line of 1010E-02A/B/C/D and tube side inlet
line of 1010EA-01A—H in JULY-2005 shut down. After that vibrations in
feed inlet to reactor lines and reactor effluent lines reduces to
minimum.

In AUG-2008 Catalyst turnaround, Both DHDS Reactors existing catalyst from

Criterion Catalyst was replaced with ART catalyst for the First cycle length.
Catalyst selected is capable of producing 150 PPMW product sulfur from feed
diesel having 1.8% w/w ‘S’ and achieve First cycle length of THREE years. Also
It was decided after AUG-2008 shut down to run the unit with higher capacity of
1.78 MMTPA (corresponding Feed Rate 260 m3/HR) with the target product ‘S’
< 150 PPMW.
 2.1

CHAPTER-2

BASIC REACTION CHEMISTRY OF HYDROTREATING

2.1 Basics of Hydrotreating

Hydrotreating of diesel stream from various units is mainly done to meet the
stringent diesel fuel specification in force from time to time.

The hydrotreating of any hydrocarbon stream is done to achieve following

objectives

* Sulfur removal
* Nitrogen removal
* Aromatic saturation
* Olefin saturation
* Metals removal
* CCR/RCR removal
* Cracking

The diesel boiling range hydrotreatment is mainly done to achieve the sulfur and
aromatic specification. For VGO and heavier fraction hydrotreatment in addition
to S, N and aromatic saturation, metals removal , CCR reduction becomes
important. Some cracking is also achieved (though not desirable some times
due to product yield loss) due to operating severity and feed quality.

We will briefly describe some of the basic reactions for some of the above
reactions.

2.2 Sulfur Removal

Sulfur is found in various molecular forms in hydrocarbon stream. H2S is the

main by product due to desulfurization of the hydrocarbon stream. HDS reaction
produces moderate heat release and consumes approximately (20 Nm3/m3of
feed ) of hydrogen for 1 % wt sulfur removal from feed. Some of the basic sulfur
compound reactions are described below

 Mercaptan : RSH + H2 --------> H + H2S

 Sulfides: RSR' + H2 --------> RSH + R'H OR
RSR' + 2H2 --------> RH + R'H + H2S
 Thiophene:

4C4H4S + 12 H2 ------> C4H9SH + C4H6 + C4H8 + C4H10 + 3H2S

C4H9SH + C4H6 + C4H8 + C4H10 + 3H2S + 4H2 ------> 4C4H10 + 4H2S

C4H4S + 2H2------> C4H8S + H2 -----> C4H9SH + H2 ------> C4H10 + H2S

 2.2

2.3 Nitrogen Removal

Nitrogen is found in many forms in hydrocarbon molecules. Nitrogen is
generally present in unsaturated molecules. Cracked streams contain more
unsaturated molecules and hence contain higher nitrogen compounds. Coker
and FCC diesel fractions have higher level of nitrogen than SR diesel fraction.

HDN reaction is irreversible reaction and by product NH3. HDN produces

moderate heat release like the HDS reactions. Typical hydrogen consumption
for HDN reaction is approximately 0.7 Nm3/m3 of feed per 100 PPM nitrogen
removed. Some of the HDN reactions are

Cyanides HCN + 3H2 CH4 + NH3

Amines RNH2 + H2 RH + NH3
Pyrrole C4HSN + 2 H2 C4H9N
C4H9N + H2 C4H9NH2
C4H9NH2 + H2 C4H10 + NH3

2.4 Olefin saturation

Olefins saturate rapidly and completely. Only traces of olefins are usually
present in straight run fractions. Cracked streams from coker and FCC units
contains higher levels of olefins.

Olefin saturation is highly exothermic reaction. Biggest contributor to heat

release. Higher hydrogen partial pressure and lower temperature favour
formation of saturate compounds. No by-product generation due to olefin
saturation. Typical hydrogen consumption for olefin saturation reaction is

1.5 Nm3/m3 of feed per 1 wt % olefins. Some of the olefin saturation reaction
is given below

RCH=CH2 + H2 RCH2CH3
RCH=CHCH=CH2 + H2 R(CH2)3CH3
Cycloolefins + H2 Cycloparaffins

2.5 Aromatic Saturation

Aromatic saturation contributes significantly to hydrogen consumption and

heat release. Aromatic saturation depends on many factors like the type of
aromatic in feed, operating pressure, LHSV and temperature.

Aromatic saturation is limited by equilibrium. Cracked streams from FCC and

Coker units has more potential for aromatic saturation than straight run diesel
fraction. LCO and other cracked streams contain more of the poly aromatic
which is easier to saturate under normal hydrotreating conditions. It will be
difficult to saturate the mono aromatics in the feed.
 2.3

Aromatic saturation is favored by high hydrogen partial pressure and lower

operating temperature. Aromatic saturation helps in lowering the product density
and improving the Cetane number of the product.

Typical hydrogen consumption for aromatic saturation is 27 Nm3/m3 of feed per

each one percent reduction in aromatic content. No by-products generated due to
these reaction.

The CCR removal and cracking are not major reactions associated with diesel
fraction hydrotreatment at moderate pressure. These reactions will be critical for
high severity operation while treating VGO and heavier fraction.
 2.4

CHAPTER-3

BRIEF PROCESS DESCRIPTION

The Unit comprises of mainly Four sections viz. Feed Section, Reactor Section,
Separator/Compressor Section and Fractionation Section. The purpose and brief
description of each section is as under:-

3.1 FEED SECTION

In this section, Sour Diesel is received from storage tank in to a surge
vessel V-01, after passing through feed filter G-01A/B. The purpose of
both equipments are as under:-

1010G-01A/B:- It removes the foreign particles that comes along with

feed.

1010 V-01:- (a) It provides sufficient surge volume to the feed pump P-
01A/B.
(b) It provides sufficient NPSH to the feed pump.

(c) It removes water coming with feed. The water gets

collected in
the boot.

3.2 REACTOR SECTION

Feed from feed pump P-01A/B splits in to two identical exchanger trains and
combined with Recycle gas (from discharge of RGC 1010K-01A/B).
Combined feed gets preheated in the shell side of CFE trains (Train 1st
contains 1010E-04A/B/C and 1010E-02A/B and Train 2nd contains 1010E-
04D/E/F and 1010E-02A/B) and F-01 coils up to the required reaction temp.
and then entered in to two identical reactors R-01 and R-02, installed in
series. Desulphurisation reaction takes place as the stream passes through
across the reactor’s catalyst bed. As the desulphurisation reaction is an
exothermic reaction in nature, so an increase in temp. profile down through
the reactor bed shows that the desulphurisation reaction is going on.

Provision of Quench with Recycle gas is given in the 2nd bed I/L of R-01
and 1st bed of R-02 for controlling the reactor bed I/L temps.
 2.5

The recycle gas compressor discharge line was modified and a spill back
control valve was given from discharge of RGC to 1010EA-01 A---H I/L,
in order to control the recycle & quench flow and recycle compressor
discharge pressure. The modification scheme of RGC spill Back control
system was commissioned on 27.10.2007, & immediately after
commissioning this scheme DHDS T,put was increased from 245 M3/Hr
to 255 M3/Hr, on 29.10.2007.

Reactor effluent is cooled in the tube side of 1010E-02A/B/C/D, 1010E-05,

1010E-04
A---F, 1010EA-01A---H and then gets collected in HP Separator Vessel 1010V-
02.

Wash water is injected to dissolve the H2S formed during the reaction and to
prevent the precipitation of salts inside the tubes of 1010EA-01A—H
and
1010E-04A--F, which is formed during the reactions. These salts gets
dissolved in wash water, which is collected in to 1010V-02 boot as sour
water, and then sent to SRU for stripping.

3.3 SEPARATOR /COMPRESSOR SECTION

The Recycle gas (containing unutilized H2 gas and H2S formed during
reaction) gets separated in 1010V-02 and cooled in recycle gas water
cooler 1010E-07. The purpose of the recycle gas cooler is to decrease
the dew point of the recycles gas and condense any H.C. which may
cause foaming of amine, during amine treatment of recycle gas, resulting
loss of operation of Recycle gas scrubber 1010C-01. H2S from Recycle
gas gets absorb in Lean Amine (received from SRU & fed to C-01 via P-
07A/B). This H2S rich amine (called Rich Amine) routed to SRU from
bottom of the column. 20% level of D.M. water is maintained and start
circulation of water in the chimney tray of C-01 by running 1010PA-
02A/B, to remove the traces of amine that may have entrained in the RG
leaving the amine column. This rich amine containing water is drained
in to ABD through the new drain line of 1010PA-02A/B to ABD, when
the chimney tray level increases up to 80%, and then again take fresh
water in chimney tray up to 20% for circulation. H2S free, Recycle gas
from the top of the column goes to the suction of the Recycle gas
compressor after combining with make up gas (i.e pure H2 gas from H2U-
II/H2U-I) from Make Up gas compressor 1010K-02A/B, via RGC suction
KOD. The purpose of make up gas compressor, is to supply H2 which is
required for the reaction, to the suction of RGC.
 2.6

3.4 STRIPPER SECTION

The purpose of this section is to remove the dissolved H2S from the
Diesel along with removal of low boiling H.C. in the form of Wild Naphtha
and volatile H.C. in the form of FG.

Liquid H.C. from HP separator and Slop oil after getting heated in
1010E-602 mixes in the downstream of 1010LC-3501 and , gets
heated in the shell side of 1010E-03A/B and 1010E-05A/B up to 215-
240 degree centigrade and entered in to the stripper column 1010C-
02. MP steam is used as stripping steam. By adjusting the operating
parameters of column, required flash point of Diesel can be
achieved.

By increasing column I/L temperature, reducing column top pressure and

increasing the flow of stripping steam, FLASH POINT CAN BE
INCREASED, but WILD NAPHTHA generation will also be increased.

By reducing the column top temperature, Wild Naphtha generation can

be decreased.

STRIPPER COLUMN OVERHEAD SECTION

Vapours from the top of the column gets condensed in the overhead Fin
cooler 1010EA-02 and water cooler 1010E-09 collected in the overhead
receiver1010V-06. Sour water from boot of the receiver, transferred to
SRU through P-13A/B. Uncondensed gases containing H2S and volatile
H.C. gases goes to Amine treater column 1010C-03 via KOD 1010V-07
where any entrained liquid H.C. gets removed from the gas stream.
Gases from V-07 enters in to 1010C-03. Here H2S gets absorbed in
Lean Amine and H2S rich amine (called Rich Amine) transferred to SRU
by the column bottom pump 1010P-14A/B. Overhead H2S free H.C.
gases passes through another KOD 1010V-08 to remove any entrained
amine and then goes to FG/ flare header via 1010PC4501, which
controls the pressure of the system.

(B) STRIPPER COLUMN BOTTOM SECTION

 2.7

Diesel from the bottom of the column C-02 is transferred to OM&S tanks
by the pump 1010P-04A/B, after cooling up to 40 deg.C in (a) Tube side
of 1010E-03A/B (b) Tube side of 1010E-01(c) Tube side of Air Fin cooler
1010EA-03A/B and (d) Shell side of water cooler 1010E-11 A/B and
1010E-12 , in series and after removing the water from the product diesel
in diesel coalscer 1010 V-109 and Salt Dryer (1010V-111). The sour
water from product diesel coalscer, is routed to SRU through sour water
pump 1010P-13A/B.

In winter seasion (Nov-Feb), in order to maintain sweet diesel pour point

between 0-3 deg.C, PPD solution doping should be started by lining up &
starting the 1010P-11C/D. The doping rate should be adjusted on the
basis of guidelines provided by the T/S department from time to time.
The PPD doping facility was successfully commissioned in August-
2004.