NATIONAL REFINERY LIMITED

ANNUAL REPORT
(Sep-2022 TO Sep-2023)

NRL #: 12594
Name: Muhammad Shakeel Sajid
Designation: Trainee Senior Management
Unit: Sulfur Recovery Unit (312) & Sulfur Solidification Unit (312X)

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 ACKNOWLEDGEMENT

Firstly, I would thank Allah Almighty for giving me the opportunity to work in National Refinery
Limited as a Trainee Senior Management. I will remember this time period for years to come and
most importantly this learning experience will definitely prove to be worthy for my career. During
my training period, I came across a number of people whose contributions in various ways helped
me and they deserve special thanks. I would like to thank the following people who from time to
time assisted me and shared their knowledge whenever required.

 Mr. Sharjeel Zaheer

 Mr. Osama Bin Nadeem
 Mr. Osama Jamal
 Mr. Eimaaz Turk
 Mr. Navaid Arif
 Mr. Mehmood

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 Table of Contents

COMPANY PROFILE.............. ............................................................................................................................6

1. HRDC TRAINING ...........................................................................................................................................7
1.1. H2S SAFETY..........................................................................................................................................…...7
1.2. FIRE SAFETY………………………………………………………………………………………………………………….……..……………… 8
2. PROCESS THEORIES AND INTRODUCTION………………………………………………………………………………………………12
2.1 BACKGROUND OF STUDY .........................................................................................................................12
2.1.1 Properties of H2S............................................................................................................................. .....12
2.1.2 Properties of liquid sulfur................................................................................................................. ....12
2.2 SULPHUR RECOVERY PROCESS ........................................................................................................... .....13
2.2.1 CLAUSE PROCESS......................................................................................... ..................................... ....14
2.2.2 TAIL GAS TREATMENT...................................................................................................................... ....15
2.2.3 DEGASSING OF LIQUID SULPHUR...........................................................................................................15
3. PROCESS DESCRIPTION................................................................................................................ ..............16
3.1 INTRODUCTION ................................................................................................................... ....................16
3.2 DETAILED DESCRIPTION OF PROCESS.......................................................................................................17
3.2.1 Claus section..........................................................................................................................................18
3.2.2 Tail gas treatment unit..........................................................................................................................19
3.2.3 Degassing of liquid Sulphur....................................................................................................................20
4 .1 PROCESS FLOW DIAGRAM.......................................................................................................................21
4.2 STUDY OF PROCESS FLOW DIAGRAM…………………………………………………………………………………………………..22
4.3 EQUIPMENT LIST………………………………………………………………………………………………………………………………….23
4.4 SAMPLE POINT LIST...................................................................................................... ..........................24
5. OVERVIEW OF AREA CHARGE ....................................................................................................................25
5.1 WASTE HEAT BOILER (312-E01) BLOW DOWN ........................................................................................25
5.2 QUENCH COLUMN (312-C01) PLANT WATER CHANGE ...........................................................................25
5.3 QUENCH COLUMN CONDENSATE FLUSHING AND E-09 STEAMING ................................... ....................25
5.4 SULFUR SWEEPING DURING NORMAL OPERATION…………………………………………………………………………… 26
5.5 SAMPLE COLLECTION….............................................................................................................................26
5.5.1 E-01 Blow down ................................................................................................................. ..................27
5.5.2 Boiler Feed water (BFW)...................................................................................................... .................27
5.5.3 Flue Gases............................................................................................................................ .................27
5.6 PUMP CHANGE OVER.............................................................................................................. .................27
6 SULPHUR SOLIDIFICATION UNIT (312-X)................................................................................... ..................28
6.1 Startup of 312-X........................................................................................................................................28
6.2 Shutdown of 312-X ..................................................................................................................................28
6.3 Storage Capacities....................................................................................................................................28
6.4 SSU Operation……………………………………………………………………………………………………………………………………..29

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 ANNUAL REPORT
As a trainee Engineer at sulfur block I have been go through different tasks & activities which is a
part of my two year training. Initially I have attended some introductory sessions about NRL,
Health & safety at HRDC. After that I joined SRU. My first task is to know about hydrogen
sulphide its properties, hazards, limits and precautions. I have been given all the relevant manuals
& SOP’s of Sulfur recovery unit. During this period I have been go through written tests & viva. In
this report I mention all the important task & activities I have done during last year at SRU

1-HRDC Training (11-September 2022 TO 14-September 2022)

I did training at HRDC where I learnt

 Fire Safety
 H2S Safety
 Overview of refinery

2- Unit 312 & 312X Lineup and SOP’s Study (15-September 2022 TO 15-December 2022)

I did the lineup of unit 312 and 312X and studied all the SOP’s including plant’s normal startup,
hot startup, normal shutdown, emergency shutdown and emergencies handling including Power
failure, MPS failure, Instrument Air failure, BFW failure, Cooling water failure, Nitrogen failure.
Also I studied and learnt the process of the plant.

2- Area Operator (16-December 2022 TO 15-January 2023)

I worked with senior operators for a month and learnt the whole working as area operator.

 To determine operational effectiveness of various plant equipment and machinery,

identifying trends.
 To ensure that the parameters are working within the ranges prescribed as per SOPs.
 To Follow up the DIB & check all the job status and working of the plant in a shift change.
 To follow up with all the checklists, routine/ check samples and field jobs.
 To provide immediate first-line response capability in the event of emergencies in order to
eliminate or limit potential loss or damage to Company personnel, assets or the
environment.
 To operate field equipment in accordance with operating and approved safety procedures to
ensure effective process flows and optimum operational status of equipment.
 To Monitor and log all operating parameters ensuring that all irregularities are reported to
immediate supervisor.
 To prepare field equipment in allocated work area for maintenance activities and follow-up
execution, and re commission equipment upon satisfactory completion of work.
 To monitor sulfur solidification unit for sulfur granules production of desired quality.
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3- Operator Training Simulator (OTS) Training (16-January 2023 TO 28-February 2023)

I did the OTS training where I learnt SOP’s of DCS operator to deal with all the emergencies
including plant’s normal startup, hot startup, normal shutdown, emergency shutdown and
emergencies handling including Power failure, MPS failure, Instrument Air failure, BFW failure,
Cooling water failure, Nitrogen failure and DCS failure and performed their response on the OTS.

4- Dependent Charge of DCS (01-March 2023 TO 15-March 2023)

I was given the charge of DCS under the supervision of Independent DCS operator where I learnt
the operating parameters of the plant, controlling of the unit and dealing with emergencies. I learnt
to make production sheet, filling log sheet and writing log book.

4- Independent Charge of DCS (15-March 2023 TO Present)

I took the charge as independent DSC operator and did the controlling of unit and dealing with
emergencies, startup and shutdown of the unit. My job description is as following.

 Operate the DCS (Distributed Control System) for plants startup and shutdown operations
in order to meet Company’s objectives and production targets.
 Monitor and control all process parameter conditions such as flow rates, pressures,
temperatures, levels, etc., through displays, graphics and trend logs.
 Communicate with field operators for parameter adjustments in field.
 Report to Shift Supervisors in case of parameter abnormalities and process deviations
immediately.
 Makes minor plant adjustments when necessary and reports any serious faults to the
Supervisor with appropriate remedial actions, implements immediately the approved
actions, procedures and standard emergency responses.
 Takes immediate corrective actions to limit risk to personnel, plant equipment and
production during emergency situations.
 Monitor & Control the usage of raw materials, chemicals and other plant utilities effectively
to an optimum level in safe manner.
 Prepare & Assist in preparation of necessary plant - operational reports as requested by
Production Supervisor or Team Leader.
 Ensure the safe shutdown, isolation and blow down of relevant Section/ plant during
emergency situations.
 Identify and investigate the faults and inform the concerned departments, for remedial
action.
 Adhere to Company’s HSE policy, standards and approved operating procedures while
performing the duties / tasks.

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 COMPANY PROFILE
National Refinery Limited (NRL) was incorporated on August 19, 1963 as a public limited
company. The Refinery is situated on Korangi industrial area. Government of Pakistan took over
the management of NRL under the Economic Reforms Order, 1972 under the Ministry of
Production. In June 2003 the Government of Pakistan decided to privatize NRL. After competitive
bidding NRL was acquired by Attock Group in July 2005. The Company has been privatized and
the management control handed over to the new owner Attock Group on July 7, 2005. NRL is
engaged in the manufacturing, production and sale of large range of petroleum products. The
refinery complex of the Company comprises of three refineries i.e. two lube refineries and one fuel
refinery having a total crude oil refining capacity of 24,570,000 Bbl per annum which corresponds
to 70,000 Bbls/day. Two Lube refineries process reduced crude to produce LBO, Bitumen, Wax
and other specialty products. NRL maintains a port terminal installation located at Keamari oils
peers about 18 km from the Refinery premises. The Keamari Terminal is connected with the main
Refinery through pipelines. Very large Crude Oil storage tanks at Keamari Terminal receive
imported Crude from the oil tankers, which is then transferred to the Refinery through pipeline.
Huge tankages are available for export of Naphtha, which is also handled at Keamari Terminal.

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 1-HRDC TRAINING
1.1 FIRE SAFETY
1.1.1 Fire and Elements of Fire HRDC TRAINING

Three things must be present at the same time to produce fire:

 Fuel
 Oxygen
 Heat
 Fire Prevention is based on eliminating one of the components of the “Fire Triangle”.

1.1.2 Four stages of fire

 Incipient Stage: No visible smoke, no flame, very little heat, combustion begins to take
place.
 Smoldering Stage: Combustion increases, smoke becomes visible.
 Flashover-Transition to Fully Developed Fire: Point of ignition, flames begins to become
visible. This is the hottest phase of a fire and the most dangerous for anybody.
 Decay Stage: Large amount of heat, flame, smoke and toxic gases produced.

1.1.3 Classification of fire

Fires are classified according to the type of fuel that is burning. It is very important to understand
the different fire classifications because if you use the wrong type of fire extinguisher on the wrong
class of fire, you might make matters worse.

 Class A: A fires are composed of dry combustibles like Wood, paper, cloth, trash, plastics,
solids that are not metals. Extinguishers eliminate the heat element of the fire.
 Class B: Includes flammable liquids and gases like gasoline, oil, grease, and acetone.
Extinguishers eliminate the oxygen element of the fire.
 Class C: Electrical—energized electrical equipment. An extinguisher is rated for class C
fires if it contains an agent that is nonconductive.
 Class D: It involve metals like potassium sodium, aluminum, magnesium. Requires Metal-
X, foam, and other special extinguishing agents.
 Class K: K is for kitchen fire. Involve cooking oil and greases, such as animal and
vegetable fats. 3.1.4 Fire Extinguishers Different types of fire extinguishers are:
 Water (APW) air-pressurized water: Suitable for fire Class A.
 Carbon Dioxide (CO2): Suitable for Fire Class B and C.
 Multipurpose Dry Chemical: Suitable for Fire Class A, B and C.
 Wet Chemical: Suitable for Fire Class K.
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  1.1.4 Fire Extinguishers

Different types of fire extinguishers are:

 Water (APW) air-pressurized water: Suitable for fire Class A.

 Carbon Dioxide (CO2): Suitable for Fire Class B and C.
 Multipurpose Dry Chemical: Suitable for Fire Class A, B and C.
 Wet Chemical: Suitable for Fire Class K

1.1.5 Technique for operating Fire Extinguishers

In order to operate fire extinguishers in emergency conditions, must remember the P.A.S.S
technique. P = Pull the pin, A = Aim the fire, S = Squeeze the handle, S = Swipe from side to side.

1.2 H2S SAFETY

1.2.1 H2S Properties

Hydrogen Sulfide is an extremely toxic gas that is colorless, flammable, heavier than air, soluble in
water, easily dispersed by wind and has the smell of rotten eggs at lower concentrations. H2S auto
ignites at 260 C with blue flame and produce Sulphur dioxide. Hydrogen sulfide is often produced
from the microbial breakdown of organic matter in the absence of oxygen, such as in swamps and
sewers; this process is commonly known as anaerobic digestion.

1.2.2 Exposure Limits

 Permissible Exposure Limit: 10 ppm for an 8-hr period avg.

 Short Term Exposure Limit: 15 ppm for a 15-minute avg.
 Immediately Dangerous to Life or Health: 100 ppm. 3.2.3 Concentration Levels & Effects
 At 100 ppm: Beginning eye irritation.
 At 50-100 ppm: Slight respiratory tract irritation after 1-hour exposure.
 At 100 ppm: Coughing, eye irritation, loss of sense of smell after 2-15 minutes. Altered
respiration, pain in the eyes and drowsiness after 15-30 minutes followed by throat irritation
after 1 hour. Several hours’ exposure results in gradual increase in severity of these
symptoms and death may occur within the next 48 hours.
 At 200-300 ppm: Severe respiratory tract irritation after 1 hour of exposure. Possible
pulmonary edema (fluid in the lungs).
 At 500-700 ppm: Loss of consciousness and possibly death in 30 minutes to 1 hour.
 At 700-1000 ppm: Rapid unconsciousness, loss of respiration, and death after 1-3 minutes.
 At 1000-2000 ppm: Unconsciousness at once, loss of respiration and death in a few
minutes. Death may occur even if individual is removed to fresh air at once.
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1.2.3 Symptoms of Exposure

 Burning Eyes

 Sore Throat

 Respiratory Irritation

 Headache

 Fatigue

 Loss of Sense of Smell

1.2.4 How To Protect Against Hydrogen Sulfide

 Engineering controls such as ventilation systems that remove gas from workspaces. Since
hydrogen sulfide is highly flammable, the ventilation system must be explosive proof. Alarm
system that serves as an early warning sign.

 Administrative controls can come in the form of company rules for entering, exiting and
working in spaces where hydrogen sulfide gas is present. Safety training and gas level testing are
also effective administration controls. Procedures should be developed to prevent a release of
hydrogen sulphide.

 Hydrogen sulphide detectors are required in all areas that use hydrogen sulphide. All
workers performing experiments involving hydrogen sulphide gas must have personal detectors on
them when working with hydrogen sulphide. The detectors must be maintained and calibrated on a
regularly scheduled basis.

 Always pay attention to the flags or windsocks When alarms

sound, retreat cross wind to the safe briefing area.

 personal protective equipment is the last line of protection against the hazards of exposure
to H2S gas. A supplied air breathing apparatus (SABA) is recommended in confined work
environments or when working duration is more than 30 minutes.

 A self-contained breathing apparatus (SCBA) with fully charged air cylinders should be
used in working conditions in which SABA cannot be used (i.e., open wells), as well as for rescue
activities.

 For exposures below 100 ppm, use an air-purifying respirator with specialized
canisters/cartridges for hydrogen sulfide. A full-face respirator will provide eye protection.

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1.2.5 Effects of different concentration of H2S gas are shown below.

Concentration Symptoms/Effects
(ppm)

0.00011- Typical background concentrations

0.00033

0.01-1.5 Odor threshold (when rotten egg smell is first noticeable to some). Odor becomes
more offensive at 3-5 ppm. Above 30 ppm, odor described as sweet or sickeningly
sweet.

2-5 Prolonged exposure may cause nausea, tearing of the eyes, headaches or loss of sleep.
Airway problems (bronchial constriction) in some asthma patients.

20 Possible fatigue, loss of appetite, headache, irritability, poor memory, dizziness.

50-100 Slight conjunctivitis ("gas eye") and respiratory tract irritation after 1 hour. May
cause digestive upset and loss of appetite.

100 Coughing, eye irritation, loss of smell after 2-15 minutes (olfactory fatigue). Altered
breathing, drowsiness after 15-30 minutes. Throat irritation after 1 hour. Gradual
increase in severity of symptoms over several hours. Death may occur after 48 hours.

100-150 Loss of smell (olfactory fatigue or paralysis).

200-300 Marked conjunctivitis and respiratory tract irritation after 1 hour. Pulmonary edema
may occur from prolonged exposure.

500-700 Staggering, collapse in 5 minutes. Serious damage to the eyes in 30 minutes. Death
after 30-60 minutes.

700-1000 Rapid unconsciousness, "knockdown" or immediate collapse within 1 to 2 breaths,

breathing stops, death within minutes.

1000-2000 Nearly instant death

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1.2.6 H2S safety equipment

 ELSA (Emergency life support apparatus): This breathing unit is composed by a

compressed air cylinder with reducer and valve which provides 10 or 15 minutes to
evacuate.
 Gas Mass Filter: For exposures below 100 ppm, use an air-purifying respirator with
specialized canisters/cartridges for hydrogen sulfide.
 SCABA (Self-contained breathing apparatus): Provides 30 minutes with one oxygen
cylinder for doing maintenance job.
 SABA (Supplied Air Breathing Apparatus): Provides 1 hour with two oxygen cylinder for
doing maintenance job

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 2 PROCESS THEORIES AND INTRODUCTION
2.1 BACKGROUND OF STUDY
Sulfur is removed from several refinery off-gas process streams to meet SOx emission standards
under the Clean Air Act. Process off-gas streams, known as sour gas, are derived from the Coker,
catalytic cracking unit, hydro-treating units, and hydro-processing units. These streams contain
high concentrations of lethal hydrogen sulfide mixed with light refinery fuel gases. Air pollution
control regulations existing in most industrialized countries prohibit the discharge of large amounts
of sulfur compounds to the atmosphere; therefore, Claus plants with tail gas treatment units are
often mandatory. Sulfur-bearing compounds are very detrimental to the environment and to
industrial process equipment. The two sulfur compounds, which need special attention, are:
hydrogen sulfide (H2S) and sulfur dioxide (SO2). Importance of Sulfur Recovery

Sulfur is a natural component of crude oil and natural gas. However, it is important to remove or
reduce the amount of sulfur during refining and processing. For crude oil, reducing the sulfur
content in gasoline and diesel improves emission controls. The sulfur recovery process removes
sulfur compounds from the product and thus reduces air pollution created by the fuel combustion
process when the products are used. Sulfur also presents a problem for natural gas. When natural
gas contains significant amounts of hydrogen sulphide, it is called sour gas.

Oil and gas producers must mediate the issues caused by sulfur compounds. This process is known
as sulfur recovery or sweetening. Once hydrogen sulfide (H2S) is converted to elemental sulfur, it
can be used as fertilizer, feedstock or other byproducts. Recovered sulfur most often used to create
sulfuric acid, which is one of the most commonly used chemicals in manufacturing and industrial
applications. Sulfur can also be used in many household applications such as rubber products,
detergents, paints, carpets and pharmaceuticals.

The true driver for sulfur recovery is the need to reduce emissions. Sulfur recovery is a regulatory
requirement for oil and gas producers. Removing sulfur, helps curb air pollution while creating a
useful byproduct and eliminates the need to mine sulfur directly from sulfur rich earthen deposits.
The vast majority of sulfur produced around worldwide is a byproduct sulfur from refineries and
other hydrocarbon processing plants.

2.1.1 Properties of H2S

Hydrogen Sulfide is an extremely toxic gas that is colorless, flammable, heavier than air, soluble in
water, easily dispersed by wind and has the smell of rotten eggs at lower concentrations. H2S auto
ignites at 260 C with blue flame and produce Sulphur dioxide. Hydrogen Sulfide (H2S) exposure
limits are as follows; Permissible Exposure Limit is 10 ppm for an 8-hr period average, Short Term
Exposure Limit is 15 ppm for 15-minute average and Immediate dangerous to Life or Health is 100
ppm.

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2.1.2 Properties of liquid sulfur

A curious property of liquid sulfur is that its viscosity increases near 160°C, from 0.007 kg/s m at
157°C to 93 kg/s m at 188°C. From the melting point at 120°C to this transformation region sulfur
is a yellow liquid with low Viscosity, like water. Above this region it is a brown liquid, stickier
even than syrup. The viscosity then decreases again regularly from 93 kg/s m at 188°C to 0.1 kg/s
m at 444°C, the boiling point.(

2.2 SULPHUR RECOVERY PROCESS

2.2.1 CLAUSE PROCESS

The Claus process is not a gas-purification process in the true sense of the word, as its principal
objective is recovery of sulfur from gaseous hydrogen sulfide or, more commonly, from acid gas
streams containing hydrogen sulfide in high concentrations. The Claus process can receive H2S-
rich gas streams from the amine units and the sour water stripping system. Other components that
enter the sulfur recovery unit include ammonia (NH3), CO2, and to a minor extent, various
hydrocarbons. Sulfur recovery from sour or acid gas typically involves application of the famous
Claus process using the reaction between hydrogen sulfide and sulfur dioxide (produced in the
Claus process furnace from the partial combustion of H2S with air and/or oxygen) yielding
elemental sulfur and water vapor.

In addition to the oxidation of H2S to SO2and the reaction of SO2 with H2S in the reaction
furnace, many other side reactions can and do occur in the furnace. Several of these possible side
reactions are:

Reactions in the Claus catalytic Reactors First Reactor: The hydrolysis reactions are practically
completed at high temperature over Titania catalyst(TiO2) in the first reactor.

Second Reactor: Alumina catalyst (Al2O3) is used in second reactor which is followed by
condensation and separation of the Sulphur produced in the catalytic conversion.

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Thermal reactor is responsible for 65 to 70 percent of conversion of Sulphur and claus catalytic
reactors converts 20 to 25 percent of elemental Sulphur. Remaining Sulphur is recovered in the tail
gas section. Elemental Sulphur vapors can exist as four separate species, namely: S2, S4, S6, S8.
Most of the Sulphur vapors yielded in the furnace exists there as S2 and as the gas passes through
the Waste Heat Boiler and Sulphur Condensers S8 is produced. Other allotropes of sulfur may also
be present in smaller quantities.

2.2.2 TAIL GAS TREATMENT

More than a dozen processes for TGTU have been developed to enhance the recovery of sulfur
compounds from refinery streams. NRL-312-SRU is equipped with Shell Claus Off-gas Treating
(SCOT) which consist of a combination of a catalytic hydrogenation/hydrolysis step and an amine
scrubbing unit. The SCOT reactor contains a bed of cobalt-molybdenum catalyst that allows the
reducing atmosphere to hydrogenate or hydrolyze most of the Sulphur compounds, contained in the
heated tail gas feed to H2S.

The hydrogenated tail gas is cooled in the steam generator, generating low pressure steam, and the
further cooled down in a quench column. The cool gas enters the absorber where it is contacted
with 40- 60 wt% methyldiethanolamine (MDEA) aqueous solution to absorb selectively H2S. The
rich MDEA solution flows down the stripper where the absorbed H2S and CO2 are stripped by
upward rising steam. 4 The gases from the top of the absorber are fed into incinerator where all the
sulphured compounds present into SO2; the flue gas produced in the incineration is discharged to
the atmosphere via a stack. Tail gas ignition temperature is much higher than the actual tail gas
temperature, as all the fuel components in its present are at very low concentrations; therefore, tail
gas combustion has to be supported by fuel gas combustion. Flue gas oxygen excess is a factor of
the utmost importance for tail gas incineration; on the one hand, it favors the oxidation of
sulphured compounds, on the other, however, it does enhance the unwanted SO3 and NOx
production. In order to obtain a good compromise, an oxygen excess of about 2-3% mol. on wet
basis in the flue gas is regarded as adequate in normal operation.

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2.2.3 DEGASSING OF LIQUID SULPHUR

Liquid Sulphur degassing remains an important component of a Claus Sulphur recovery system as
a result of the need to produce high purity liquid and solid Sulphur (< 10 ppm residual H2S).
Liquid sulphur produced by the Claus process contains residual H2S in both chemically combined
and physically dissolved forms. The total residual H2S in the liquid (200 – 400 ppmw) depends on
numerous operational factors but its presence poses a considerable safety risk as degassing to
headspaces in containers and even from solid formed from the liquid can lead to lethal gas phase
concentrations. Without adequate draft in storage systems, concentrations may exceed the lower
explosive limit for H2S in air. Flowing of liquid Sulphur and a sparge gas (bubbling air) through an
alumina catalyst bed, provides basic sites which initiate polysulphide decomposition. The basic
sites on the alumina can catalyze both polysulphide formation as well as decomposition so a sparge
gas is necessary to remove H2S from the system.

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 3-PROCESS DESCRIPTION
3.1 INTRODUCTION
The Sulphur recovery facility utilizes a modified Claus process to refine H2S rich acid gas into
99.96% pure elemental Sulphur. After the Claus process is complete, the waste gas is routed to a
tail gas cleaning unit, where the SOX emission is reduced by as much as 400 mg/Nm3 and the
maximum amount of Sulphur is recovered from the acid gas. In order to get rid of the free and
dissolved H2S in the liquid Sulphur product, a degassing step has been included. The Sulphur
recovery unit has the capacity to generate 38 metric tons per day of elemental Sulphur.

Specification:

The unit capacity is guaranteed as 38t/d sulfur (under 120% working condition)

purity of liquid sulfur should not be lower than 99.8%, and H2S in the liquid sulfur should not be
higher than 10 ppm(wt)

The concentration of SO2 in the discharge tail gas shall be lower than 400mg/Nm3

Height of emission 65m

Lean amine contain 60% water & 40% MDEA

Feed Gas composition:

Feed from 310 contain 90-95mol% H2S and other are water vapours and few ppm of
hydrocarbons. While gases from 311 contain 55-60mol% H2S, 15-20% ammonia and rest is water
vapours

Specification of liquid sulfur

Purity 99.8 wt.% Min

Hydrocarbon 0.05 wt% Max
colour in solid state Bright yellow
Moisture 0.08 wt.% Max
Dissolved H2S in liquid Sulfur ≤10 ppm wt
Organic ≤500 ppm wt
Ash ≤100 ppm wt
Lean Amine:

Different solvents available for the absorption of H2S like MDEA, DEA and MEA among them
MDEA received great attention for selective reaction with H2S in the presence of CO2. This gives
advantage where only H2S need to be removed from gas stream. MDEA has much lower vapor
pressure then other solvent, so amine losses from vaporization also reduced. MDEA is chemically
weaker than MEA or DEA so less stripping steam is required to regenerate MDEA.
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Trisodium phosphate Na3PO4·12H2O:

Phosphate need to be continuously added to SRU waste heat boiler. Trisodium phosphate (TSP) is
the inorganic compound with the chemical formula Na 3PO4. It is a white, granular or crystalline
solid, highly soluble in water, producing an alkaline solution. TSP is used as a cleaning agent,
builder, lubricant, food additive, stain remover, and degreaser.

Trisodium phosphate (Na3PO4), also known as TSP, is a common boiler water conditioning
chemical that establishes moderately alkaline conditions in the boiler to minimize corrosion and
reduce scaling where hardness ingress occurs. Phosphate treatment programs use blends of tri- di-
and monosodium phosphate for pH control as well.

Function of phosphate treatment is to reduce the effect of hardness producing salt and maintaining
them a non-adherent sludge rather than to deposit and then removing the excess sludge by blow
down.

3.2 DETAILED DESCRIPTION OF PROCESS

NRL-312-SRU is equipped with 3 sections:

 Claus section

 Tail gas treatment unit

 Degassing of liquid Sulphur

3.2.1 Claus section

The Amine Treating Unit's (unit 310's) amine acid gas will be fed into a K.O. drum (312-V01).
After being stripped the No-Phenolic Sour Water from Unit (311), the sour acid gas will be sent to
the SWS acid gas K.O, drum (312-V02) where it will be condensed into sour water. The above
gases will be sent to the thermal reactor's burner nozzle (312-F01). The air distribution quantity of
the thermal reactor is crucial therefore, the flow ratio adjustment will be used to precisely regulate
the amount of air entering the furnace in accordance with the oxygen required by the Sulphur
production process. In order to regularly analyze the H2S/SO2 ratio in the tail gas, an online ratio
analyzer is installed on the starting of tail gas section. The correct partial Combustion Air / Acid
Gas ratio, which leads to optimum Sulphur recovery, is the one that results in an H2S/SO2 ratio of
2:1. The total Combustion Air entering the Main Burner is comprised of two terms:

Total combustion Air to main burner = Main Air + Trim Air

The following table clarifies the Air Demand concept:

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To prevent salt formation in low temperature regions like condensers, the temperature of sour acid
gases from 312-V02 being commissioned in 312-F01 must be greater than 1260 C. For this
purpose, temperature must be achieved by increasing split flow through 312-FV008 as much as
required gradually but keeping the H2S/SO2, ratio of 2:1 as well as feed design temperature of
Amine acid gases and Sour acid gases of 49 C and 85 C respectively to avoid moisture
breakthrough. A Sulphur waste heat boiler(312-E01) will receive the high temperature process gas
discharged by a thermal reactor (312-F01). The 13.5 bar medium pressure steam will be produced
in E-01 from the waste heat source and delivered to the steam super-heater (312-E08) in the tail gas
processing section. Once it reaches about 300 degrees Celsius, the de-super-heater (312-ME01)
will bring the temperature down to 240 degrees Celsius so that it can be combined with the
medium-pressure steam system.

When the process gas reaches a temperature of 320 degrees Celsius, it is sent into the 1st Sulphur
condenser (312- E02), where it is cooled to 160 degrees Celsius before being condensed at the end
of a cooling tube. Sulfur seal pot will receive the cooled molten Sulphur that has been separated
from the process gas(312-V04A). The high-temperature mixing valve 312-TV15 will combine the
process gas leaving the first Sulphur condenser tubes at 160 °C with some of the high-temperature
gas flow from thermal reactor. At around 255°C, it will be heated and fed into the 1st Claus reactor
(312- R01). As part of the processing, the gaseous results of the reaction, including H2S and SO2,
will be converted to elemental Sulphur. Reacted gas has a temperature of roughly 309 degrees
Celsius. After that, the process gas will enter in the tube side of condenser 312-E05 which is
connected to another condenser 312-E03, E05 and E03 have same tubes but different shells, so the
process gas from E05 will enter in the tubes of E03 which will produce 3.8 bar of low pressure
steam. Process gas from E03 will travel backs to E05 shell side to exchange heat with the process
gas in the tube side before entering into second clause reactor 312-R03. Liquid Sulphur produced
in the both condensers E05 and E03 will be collected in seal pots i.e. 312-V04B and 312-V04C.
Gas from the reaction process in 312-R03 will be cooled from 242 °C to 160 °C in the condenser
(312-E04).

At the tube pass exit, the process gas will be separated from the liquid Sulphur that has condensed
in the third Sulphur condenser. From the bottom, it will flow into the Sulfur seal pot (312-V04C).
The process gas from E04 which is not condensed will enter tail gas knock out drum 312-V05. The
residual liquid Sulphur which is not condense will condense in 312-V05 and collected in another
seal pot 312-V04E.
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3.2.2 Tail gas treatment unit

Tail gas from the SRU is routed from the knock-out drum outlet (312-V05) into the tail gas heater
(312- E07) on the shell side, where it is heated to around 300 °C by the high temperature flue gas
before being sent into the hydrogenation reactor (312-R03) alongside the addition of hydrogen gas.
Behind the tail gas quench column is an on-line hydrogen analyzer, AT-002, whose output signal
will be used to control the amount of H2 fed into the hydrogenation reactor.

Once the reaction is complete, high-temperature gases around 326 °C will be fed into the LP-steam
generator (312-E06), which will then produce 4 bar of low pressure steam. When the tail gas
reaches a temperature of 170 °C, it is sent to the bottom of the tail gas quench column (312-C01),
where it is cooled further by the quench water circulating counter-current and attains a temperature
of 40 °C. The quench water pump 312-P01A/B will help the quench water to circulate in column
entering from the top. The liquid level regulating valve (312-LV009) at the base of the column will
direct the unbalanced quench water condensing due to the temperature drop to the upstream non-
phenolic sour water stripping unit 7 311. To prevent corrosion of the equipment, the pH of the
quench water must be adjusted to between 6 and 8 using NH3.

Once the quench cooling is complete, the tail gas will go from the top of the tail gas quench
column (312- C01) to the bottom of the tail gas absorber. Lean amine from 310 is fed to the tail gas
absorber's upper side (312-C02). When the lean amine solution comes into touch with the tail gas
counter-current, H2S will be removed from the tail gas. Rich amine pump (312-P02A/B) raises the
pressure of the MDEA solution that has absorbed the H2S before sending it back to the Amine
treatment unit 310. Incinerator (312-F02) will receive purified tail gas from the top of the tail gas
absorber. When subjected to a temperature of 600 °C, the sulphide in the tail gas is converted to
Sulphur dioxide (SO2). Combusting the remaining hydrogen and the hydrocarbon will produce
water and carbon dioxide. After the steam superheater (312-E08) and the tail gas heater (312-E07)
have recovered some of the heat from the burned high temperature flue gas, the flue-gas
temperature will drop to around 300°C before being released into the atmosphere via the stack
(312-SK01)

3.2.3 Degassing of liquid Sulphur

Liquid Sulphur will flow from the seal pots (312-V04) and into the liquid Sulphur vessel (312-
V07) due to gravity. The liquid Sulphur degassing pump (312-P03A/B) will next transfer to the
degassing column (312- C03). With the help of the catalyst bed, the polysulfide form of H2S
within the liquid Sulphur will be broken down into the free H2S in the gas-liquid mixture. Some of
the H2S will be converted to elemental Sulphur by oxidation, while the rest will be driven from the
liquid phase into the gas phase by the compressed air. Sulfurous gas is released from the top of the
column after passing through the catalyst bed to the thermal reactor (312-F01) or incineration (312-
F02). Liquid Sulphur will flow from the bottom to the Sulphur sealing pot (312-V04G) before
returning to the liquid Sulphur storage vessel (312-V07).
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3.2.4 Operating parameters of SRU:

Thermal reactor temperature 1200-1300C

Acid Gas pressure 0.5-1.0 bar

Sulfur waste heat boiler process gas outlet temp 250-300C

Steam temp & Pressure 190-200C/10-13bar

Sulfur condenser outlet temp 145-160C

First claus reactor inlet/outlet 240-260C/300-310C

Second claus reactor inlet/outlet 200- 220C/220-240C

Hydrogenation reactor 250-280C/280-300C

Hydrogen flow 22-50Nm3/hr

Tail gas steam generator outlet temp 150-170C

Tail gas quench column water inlet/outlet 40C/65C

Quench Water flow 15-20m3/hr

Tail gas absorber outlet temp 40C

Lean MDEA flow 15-20m3/hr

Incinerator temp 600-700C

Steam super heater flue gas outlet temp 420-450C

Tail gas heater tube inlet temp 250-300C

Stack flue gas temp 270-300C

20
4- PROCESS FLOW DIAGRAM

21
4.1 STUDY OF PROCESS FLOW DIAGRAM

After getting brief overview of H2S Gas, next step to study process flow diagram and line tracing
of entire SRU that starts from battery limit where feed comes from 310 & 311. It covers all
equipment of claus section, tail gas section and degassing section and process lines connecting
them including control valves with tag number and position.

Study of P&ID:

Detailed study of P&ID that include

 Study and Line tracing of complete unit

 Study pump seal plan
 Study & line tracing of all utilities with all control valves and shutoff valves (XOV’s
XCV’s)
 Commissioning procedure of all utilities
 Study & line tracing of fuel gas and off gasses circuit
 Study & line tracing of flare network of SRU
 Study & line tracing of steam network
 All sample points
 Complete line tracing of sulfur solidification unit
 All pressure relief valves set point with position
 Study of different types of valves & their symbol used in SRU
 Steam trap, steam tracing, hot insulation, cold insulation, jacketed lines non jacketed lines
and lines diameters
 Study of Cause & effect, ESD’s

22
4.2 EQUIPMENT LIST

S.No Tag Num Name

1 312-F01 Thermal Reactor
2 312-F02 Incinerator
3 312-E01 Sulphur Waste Heat Boiler
4 312-E02 First Sulphur condenser
5 312-E03 Second Sulphur condenser
6 312-E04 Third Sulphur condenser
7 312-E05 Process Gas Exchanger
8 312-E06 Steam generator
9 312-E07 Tail Gas Heater
10 312-E08 Steam Super Heater
11 312-E09 Quench water cooler
12 312-E10 LA cooler
13 312-E11 Air preheater
14 312-R01 First claus reactor
15 312-R02 Second claus reactor
16 312-R03 Hydrogenation Reactor
17 312-C01 Tail Gas Quench Column
18 312-C02 Tail gas absorber
19 312-C03 Degassing column
20 312-V01 Acid Gas Knock out drum
21 312-V02 Sour water gas knock out drum
22 312-V04(A-G) Seal pots
23 312-V05 Tail gas Knock out drum
24 312-V06 Tail gas buffer drum
25 312-V07 Liquid Sulphur vessel
26 312-V08 Vent vessel
27 312-V09 Waste acid water vessel
28 312-V10 Waste amine vessel
29 312-V11 Fuel gas knock out drum
30 312-V12 IA knock out drum
31 312-V50 MPC condensate vessel
32 312-V51 LPC condensate vessel
33 312-S01 Liquid Sulphur storage tank
34 312-K01A/B Claus air blower
35 312-K02A/B Tail gas blower
36 312-P01A/B Quench water pump
37 312-P02A/B RA amine pump
38 312-P03A/B Degassing Sulphur pump
39 312-P04A/B Lifting Sulphur pump
40 312-P05 Acid water pump
41 312-P06 Waste amine pump
42 312-P07 Liquid Sulphur loading pump
43 312-P08A/B/C Acid water loading pump

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Muhammad Shakeel Sajid Annual Report 2022-2023 NRL.No.12594

44 312-ME01 Steam desuper heater

45 312-ME02 Quench water filter
46 312-ME03 LA filter
47 312-ME04 Pressure reducing desuper heater
48 312-ME06 Phosphate dosing system
49 312-ME07 NH3 dosing system
50 312-J01A/B Sulphur degassing ejector
51 312-J02 Water ejector
52 312-J03 Water ejector

4.3 SAMPLE POINT LIST

S.No Tag Num Sample name

1 SN-01 Amine acid gases
2 SN-02 Sour acid gases
3 SN-03 E01 out
4 SN-04 E02 out before TV-15
5 SN-05 E02 out after TV-15
6 SN-06 R01 out
7 SN-07 R02 out
8 SN-08 R03 in
9 SN-09 R03 out
10 SN-10 C02 top outlet
11 SN-11 Flue gases
12 SN-12 Sour water
13 SN-13 Lean amine
14 SN-14 Rich Amine
15 SN-15 Fuel gas for F01
16 SN-16 Fuel gas for F02
17 SN-17 MPS from E01
18 SN-18 Boiler feed water
19 SN-19 E01 blowdown
20 SN-20 Solid Sulphur (312-X)

5-OVERVIEW OF AREA CHARGE

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Muhammad Shakeel Sajid Annual Report 2022-2023 NRL.No.12594

5.1 Waste Heat Boiler (312-E01) Blow Down

Boiler blowdown is water intentionally wasted from a boiler to avoid concentration of impurities
during continuing evaporation of steam. The water is blown out of the boiler with some force by
steam pressure within the boiler. What is the reason for boiler blowdown? It’s typically impossible to
obtain completely pure water in a boiler. No matter the quality of your equipment, impurities will
always seep into the water and begin to increase the water conductivity. Conductivity tell you how
much dissolved substances, chemicals, and minerals are present in the water. Higher amounts of
these impurities will lead to a higher conductivity. The impurities that get into your boiler water may
be referred to as suspended matters, dissolved gases, or dissolved solids. Buildup of these of
impurities can cause scaling. Scaling is likely the most common problem that’s caused by the high
conductivity of boiler water. Scaling refers to the buildup of solid materials because of the reaction
from the tube metal and the other impurities in the water. It is a deposit that forms directly on heat
transfer surfaces when constituent solubility limits are exceeded and the resulting compounds
precipitate onto the tube surfaces. Such deposits may contain calcium, magnesium, phosphate, iron,
and silica. A tenacious form of boiler scale results when calcium precipitates in the form of calcium
carbonate. This buildup will lessen heat transfer in the boiler unit, can cause tube failures, which will
worsen boiler efficiency. To avoid scaling in the boiler phosphate dosing is recommended, trisodium
phosphate is used to precipitate calcium and magnesium hardness from boiler feed water. At the
same time excess trisodium phosphate can also make the knotted portion of scale become soft and
fall off as sludge. This sludge is then easily removed from boiler via blowdown.

5.2 Quench Column (312-C01) Plant Water Change

The first and primary purpose of the quench tower is to cool the hot gas from the hydrogenation
reactor to around 100°F (38°C) by direct contact with cooling water. In addition to lowering the
temperature, generally about 85% of the water content is removed as well. This water would
otherwise need to be purged from the amine system downstream to maintain amine strength. A
sometimes poorly appreciated secondary role of the quench tower is to afford some measure of
protection of the TGTU from harmful contaminants that would otherwise enter with the quenched
tail gas. In particular, any small amounts of ammonia and SO2 in the gas can be removed in the
quench tower. Unless the amine is protected, over a period of time, even small levels of SO2
contamination can generate heat stable salts and other more reactive amine degradation products of
the MDEA solvent, harming the selectivity for hydrogen sulphide. Ammonia and Sulphur dioxide,
being alkaline and acidic respectively, react not just with water, but strongly associate with each
other in the water phase. Ammonia is highly soluble in water, whereas Sulphur dioxide is only
sparingly soluble. Any dissolved ammonia will tend to drag an equal amount of SO2 into the water
phase with it through the aqueous acid base. if the SO2 to NH3 ratio in the gas is less than one, the
cooled gas can be expected to be virtually SO2 free. Conversely, if this ratio is greater than about
one, the gas phase should be ammonia free but will contain whatever SO2 cannot dissolve physically
in the quench water. 15 If the gas has more SO2 than ammonia, the water will be acidic but if there is
more ammonia than SO2 it will be alkaline. This expected behavior is why monitoring the pH of
quench tower pump-around water is a good practice. If SO2 does get into the amine system, it will
act as a heat stable salt and increasingly deactivate the amine and increase solution corrosively at
higher concentrations. Over time, degradation of the MDEA into secondary fragments such as DEA

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Muhammad Shakeel Sajid Annual Report 2022-2023 NRL.No.12594

and MMEA will occur causing increased reactivity with CO2 and lowering the selectivity achievable
in the TGTU. Reduced selectivity means more CO2 gets recycled back to the front of the SRU, both
reducing the quality of the feed gas and possibly overloading the TGTU with additional inert gas
(CO2). SO2 can essentially be totally removed from the quench water by maintaining it pH-neutral
or slightly alkaline. Keeping the pH alkaline also ensures that SO2 is converted by H2S to
thiosulphate rather than elemental Sulphur. Elemental Sulphur is formed when H2S hits SO2 laden
quench water, also plugging the internals. It might be better just to add enough ammonia to keep the
quench water neutral. Due to unavailability of NH3 gas, plant water is changed 2 to 3 times per day
to keep the column’s pH in allowable limits (6-8)

5.3 Quench Column Condensate Flushing and E-09 Steaming

Due to plugging of column’ packing and E-09 process line, temp of quenched tail gas increases
beyond limit. Increased temp of tail gas will affect the absorption efficiency in tail gas absorber (C-
02). Hot condensate from V-51 is fed into C-01 around 60-70% and then hold for 2 to 3 hours to
deplug the packing. This process is repeated twice before commissioning the quench column. E-09
steaming is performed by entering steam in process line to clear out unwanted solid Sulphur that is
affecting the heat transfer area. This process also takes 2-3 hours.

5.4 Sulfur sweeping during normal operation

It is recommended to do hot dipping during normal operation because during normal runs, a certain
quantity of sulphur can condense on the catalyst. Most of the sulphur condensed during normal runs
can be removed by increasing, from time to time, the reactors’ inlet temperatures by 10-20°C for 24
hours, Other procedures concerning sulphur burning with oxygen are not recommended and
moreover they represent a risk for the life of catalyst and for the life of equipment (risk of catalyst
temperatures beyond control and/or SO3 formation with equipment corrosion).

5.5 Sample Collection

Four water samples are collected from sample point (SN-) in every shift and after getting results
from lab necessary actions are taken to maintain plant operations. Following samples are:

 E-01 Blow down SN-19

 Boiler feed water (BFW) SN-18
 Medium pressure steam (MPS) SN-17
 Sour water from 312-C01 SN-12

Special samples are taken only once in a week. Special samples include:

 Flue gas SN-11

 Fuel gas SN-15
 Solid Sulphur SN-20

5.5.1 E-01 Blow down

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Muhammad Shakeel Sajid Annual Report 2022-2023 NRL.No.12594

To avoid scaling in waste heat boiler conductivity of blow down in measure regularly

5.5.2 Boiler Feed water (BFW)

To avoid corrosion and scaling in condensers BFW is check regularly.

5.5.3 Flue Gases

In many countries, as part of a national environmental protection program, exhaust gases must
comply with strict governmental regulations regarding the limit values of pollutants such as dust,
sulfur and nitrogen oxides and carbon monoxide.

5.6 PUMP CHANGE OVER

 Make sure the pump is energized.

 Check the buffer vessel level and pressure.
 Check the shaft by hand and make sure it’s not jam.
 Check oil level.
 Close discharge if its centrifugal pump and open suction.
 Turn on the pump and slightly open discharge to maintain pressure and amperes.
 Then close the discharge of the other pump and press the mushroom button.

5.6.1 Pump Seal Plan:

Different pump seal plans are used for cooling and safety of pump seals and according to the
requirement and type of process fluid. In SRU Pump P01, P02, P05/6 & P08 are centrifugal pumps
having fluid that is hazardous and harmful if it leaks to the environment. Plan 53A is using in these
pumps in which an external reservoir to provide barrier fluid for a pressurized dual seal
arrangement. Reservoir pressure is produced by nitrogen, at a pressure greater than the maximum
process pressure being sealed and Circulation of the barrier fluid is maintained by an internal
pumping ring. Cooling system is typically built into the reservoir by cooling water supply.

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Muhammad Shakeel Sajid Annual Report 2022-2023 NRL.No.12594

6-SULPHUR SOLIDIFICATION UNIT (312-X)

6.1 Startup of 312-X

 Open cooling water valve about 16-20m3/hr.

 Start Z-belt.
 Start draft fan.
 Start distributer inverter.
 Start steel belt (normal amp=4.2-4.4, high amp alarm=6, tripping amp=>6.5).
 Open N2 valve in distributor for at least 5mins.
 Check chemical level in chemical tray.
 Make sure the bypass valve of FV-31 is fully open.
 Open discharge and suction of pump 312-P07A/B and start pump.
 Open block valve of feed valve XOV-509 and open feed valve.
 Set PI-509 to 3 bar by pinching bypass valve of FV-31.

6.2 Shutdown of 312-X

 Close feed valve XOV-509 and open N2 purging in distributor for 5 mins.
 Open bypass valve of FV-31 fully.
 Close block valve of XOV-509.
 Turn off pump 312-PO7A/B and close suction valve.
 Stop steel belt.
 Stop distributor inverter.
 Stop draft fan.
 Stop Z-belt.
 Close cooling water valve.

6.3 Storage Capacities

 1m of silo = 60 Mtons
 1% of S01 produces 5.9 Mtons of solid Sulphur
 1 hour running of 312-X produces 5.5 Mtons of solid Sulphur
 Silo height excluding cone part is 8.6

6.4 SSU Operation

 Releasing agent level in chemical tray should be maintain otherwise sulfur is carryover with
steel belt

 Ensure steel belt motor & distributer ampere within normal range

 Check moisture on steel belt before introducing liquid sulfur because due to moisture sulfur
lumps are formed in silo which cause problem in sulfur truck loading

 Maintain pressure around 2-3 bar by pinching S01 circulation valve

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Muhammad Shakeel Sajid Annual Report 2022-2023 NRL.No.12594

 Check the alignment of z-belt time to time

 Distributer should be purge with nitrogen before startup & after shutdown

 Keep area around z belt clean and put sulfur in drums

 When P07 stop make sure its suction valve should be closed

 Clean S01 & V07 vent when they choked with sulfur

Water showering near p07 & z belt should be done in every shift as there is

29