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ATTACHMENT REPORT

TABLE OF CONTENTS Acknowledgement Table of Contents i 1

CHAPTER 1
1.1 INTRODUCTION (HISTORICAL BACKGROUND OF THE REFINERY) 1.2 RESIDUAL FLUID CATALYTIC CRACKING UNIT (RFCC) 3 4

CHAPTER 2-(UNIT 11)


2.1 RFCC Rx-REGN. SECTION 2.1.1 PROCESS FLOW 2.2 FCC CATALYST SECTION REACTOR (11-R-101/102) 2.3 FCC CATALYST SECTION-REGENERATOR (11-R-103/104) 2.4 CATALYST COOLER (11-E-101) -PROCESS CONTROL 2.5 MAIN AIR-BLOWER- FLUE GAS PROCESS CONTROL 2.6 TORCH OIL NOZZLE CONTROL 2.7 DIRECT FIRED AIR HEATER (DFAH)

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5 5 8 11 13 15 16 18

CHAPTER 3- (UNIT 12)


3.1 FRACTIONATION SECTION (MAIN COLUMN) 3.2 MAIN COLUMN BOTTOMS PUMPAROUND CIRCUIT 3.3 HCO PUMPAROUND CIRCUIT 3.4 LCO PUMPAROUND AND PRODUCT CIRCUIT 3.5 NAPHTHA PUMPAROUND AND PRODUCT CIRCUIT 3.6 MAIN COLUMN OVERHEAD SYSTEM

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ATTACHMENT REPORT 3.7 RAW OIL CHARGE SYSTEM 3.8 MAIN COLUMN AND RELATED EQUIPMENT 3.8.1 MAIN COLUMN BOTTOMS 24 25 30

CHAPTER 4- (UNIT 13)


4.1 GAS CONCENTRATION SECTION (GENERAL PROCESS) 4.2 PROCESS FLOW AND CONTROL 4.2.1 RECOVERY SECTION 4.2.1.1 EQUIPMENTS AT RECOVERY SECTION 4.2.2 FRACTIONATION SECTION 4.2.2.1 DEBUTANIZER (13-C-304) 4.3 WASH WATER

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31 32 32 35 38 40 40

CHAPTER 5- (UNIT 14/UNIT 15)

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5.1 LPG MEROX UNIT (UNIT 14) 42 5.2 PROCESS VARIABLES 42 5.3 PROCESS FLOW AND CONTROLLPG MEROX 43 5.4 GASOLINE MEROX UNIT (UNIT 15) -GENERAL PROCESS PRINCIPLES 44 5.4.1 REACTION CHEMISTRY 45 5.4.2 SWEETING MECHANISM 45 5.4.3 MEROX CATALYSTS 46 5.5 PROCESS VARIABLES--GASOLINE MEROX 46 5.6 PROCESS FLOW AND CONTROL-- GASOLINE MEROX 48

CHAPTER 6 -- (UNIT 16)


6.1 AMINE TREATMENT UNIT (PROCESS DESCRIPTION) 6.2 DEA MAKE-UP AND DRAINAGE

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50 53

CHAPTER 7- (UNIT 17)


7.1 SULPHUR RECOVERY UNIT-- PROCESS FLOW DESCRIPTION

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CHAPTER 8- (UNIT 18)


8.1 SOUR WATER TREATMENT UNIT INTRODUCTION 8.1.1 PROCESS DESCRIPTION

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CHAPTER 1
1.1 INTRODUCTION (HISTORICAL BACKGROUND OF THE REFINERY) The Tema Oil Refinery, formerly known as Ghana Italian Petroleum (GHAIP) Company limited, was formed by the Government of Ghana in conjunction with the National Hydrocarbon Trust of Italy (Entre Nationale Idrocarburi-ENI) to construct a refinery for crude Oil processing in the country. In December 1961, the then GHAIP entrusted a consortium of firms, consisting of SNAM progetti, NUOVO PIGNONE and SAIPEM (companies of ENI group) with the construction of a refinery at Tema, capable of processing varied types of crude. The construction of the refinery with a design capacity of 1,250,000 metric tons of crude per year, an equivalent of 28,000 barrels per stream Day (BPSD) was completed by the middle of 1963.The refinery was formally opened by Osagyefo Dr. Kwame Nkrumah, President of the Republic of Ghana on 28th September, 1963. The refinery covering a total area of 440,000 square meters is linked to an Oil jetty at the Tema Harbor by pipelines of various diameters for the transportation of crude Oil, fuel Oil, white products, (Gasoline, kerosene and gas oil) and LPG. On arrival at the harbor, the ships with crude oil of petroleum product are inspected and certified for quality and quantity before it is pumped through the appropriate pipeline into storage tank at the refinery. After processing of the crude, the residual (also known as atmospheric residue) was sold to other countries which had the facility such as Fluid Catalytic Cracking (FCC) to further process into useful products. This facility is now available to the refinery and they have seized the export of residue. The unit is known as Residue Fluid Catalytic Cracking, RFCC. The Unit (RFCC) was commissioned on 13th November 2002 by the president of the Republic of Ghana, John Agyekum Kuffour. The plant processes atmospheric residue (AR) from the Crude Distillation Unit (CDU) into useful products such as Clarified Oil (CLO), Liquefied Petroleum Gas (LPG), Heavy Cycle Oil (HCO), Light Cycle Oil (LCO) and gasoline. The capacity of the plant is 14000 BPSD. The CDU was revamped to increase its capacity from 28000 BPSD to 45000BPSD. LPG, Kerosene, Heavy Gas Oil (HGO), Light 3

ATTACHMENT REPORT Gas Oil (LGO), Light Naphtha, Heavy Naphtha and Atmospheric Residue are products of the unit. Objectives of the Refinery: To ensure a continuous and adequate supply of petroleum products primarily in Ghana, mainly through the refining of crude oil, in a safe, healthy, cost effective, efficient and environmentally friendly manner to increase shareholder value. Vision of the Refinery: To be the premier refinery counted among the very best in Africa. Departments at Tema Oil Refinery Tema Oil Refinery (TOR) has the various departments. 1. Production 2. Maintenance 3. Administration 4. Fire and Safety 5. Inspection and monitoring 6. Procurement 7. Quality control Sections under Production 1. Residue fluid catalytic cracking (RFCC) 2. Crude distillation unit (CDU) 3. Waste water treatment unit (WWT) 4. Movement of product (MOP) 5. Utilities (Power house)

1.2 RESIDUAL FLUID CATALYTIC CRACKING UNIT (RFCC)


The residue fluid catalytic cracking unit was developed based on the basis that the residue produced after crude distillation could further be cracked using a catalyst to obtain more desirable products. One main advantage of Fluid Catalytic Cracking is the ability to regenerate deactivated (spent) catalyst for use again; this therefore makes it better economically to use Fluid Catalytic Cracking. Another merit is the ease with which catalyst flow between the Reactor and the Regenerator when fluidized with an appropriate vapor phase. The operation of RFCC is a continuous process. The products at RFCC are as follows; LPG (liquefied petroleum gas), Gasoline, Light Cycle Oil (LCO), Heavy Cycle Oil (HCO) and Clarified Oil (CLO). AMOUNT PRODUCTS LPG Gasoline LCO HCO CLO B/D 3510 7460 2050 700 1390 Kg/hr 13039 37771 13000 4700 10085 4

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B/D= Barrel per Stream day The RFCC department has eight sub-units under it where different activities are carried out. These units are as follows: 1. Unit 11- RFCC Rx-REGN. SECTION 2. Unit 12- RFCC FRACTION SECTION 3. Unit 13- RFCC GAS CONCENTRATION SECTION 4. Unit 14- RFCC LPG MEROX UNIT 5. Unit 15- RFCC GASLINE MEROX UNIT 6. Unit 16- AMINE TREATING UNIT 7. Unit 17- SULPHUR RECOVERY UNIT 8. Unit 18- SOUR WATER TREATING UNIT

CHAPTER 2-(UNIT 11)


2.1 RFCC Rx-REGN. SECTION The Residue Fluid Catalytic Cracking (RFCC) process converts heavy crude oil fractions into lighter, more valuable hydrocarbon products at high temperature and moderate pressure in the presence of finely divided silica / alumina based catalyst. The catalytic cracking takes place in the Reactor (11-R-101/102). In the course of cracking a nonvolatile carbonaceous material, commonly referred to as coke, is deposited on the catalyst. The coke laid down on the catalyst deactivates the catalytic cracking activity of the catalyst by blocking access to the active catalytic sites. In order to regain the catalytic activity of the catalyst, the coke deposits on the catalyst is burned off with air in the Regenerator vessel (11-R-103/104). There is a vortex separation system (VSS) and a Cyclone in the Reactor (11-R-101/102) which help in disengaging the hydrocarbons from the spent catalyst respectively. Light hydrocarbons are stripped off the spent catalyst at stripping section of the Reactor (11-R-101/102) with steam. The vapor phase on the Reactor side is vaporized hydrocarbon and steam, while on the regenerator side the fluidization media is air and combustion gases. Fluidization permits hot regenerated catalyst to contact fresh feed; the hot catalyst vaporizes the liquid feed and catalytically cracks the vaporized feed to form lighter hydrocarbon products. In the course of burning the coke a large amount of heat is liberated. Most of this heat of combustion is absorbed by the regenerated catalyst which is consequently carried back to the reactor to supply the heat required to drive the reaction side of the process. The ability to 5

ATTACHMENT REPORT continuously circulate fluidized catalyst between the Reactor and the Regenerator allows the RFCC to operate efficiently as a continuous process. 2.1.1 PROCESS FLOW The preheated raw oil and steam are introduced into the reactor riser at a point approximately 20% up from the bottom of the riser. The feed is contacted with a controlled amount of regenerated catalyst, lift steam and lift gas. The hot regenerated catalyst vaporizes the feed and the resultant vapors carry the catalyst upward through the riser with a minimum of back mixing. Cracking occurs as the hydrocarbon vapors and catalyst travel up the riser. The desired cracking reactions is completed at the top of the riser and the catalyst is quickly separated from the hydrocarbon vapors with a Vortex Separating System and a Cyclone to minimize further cracking reactions. During the cracking reaction, the spent catalyst generated as a result of coke deposits on the circulating catalyst drops from the reactor chamber into the stripping section where a countercurrent flow of steam removes both interstitial and some adsorbed hydrocarbon vapors. The stripped catalyst flows from the reactor stripper through the reactor standpipe to the regenerator where the coke is continuously burned off. The catalyst flow through the reactor standpipe is controlled to balance the circulating catalyst flow by maintaining a constant reactor catalyst level. In the regenerator, the heat of combustion raises the catalyst temperature to the 648 oC -746oC range. The regenerator burns the coke from the catalyst particles and transfer heat to the circulating catalyst. The energy carried by the hot regenerated catalyst is used to vaporize and heat up the oil vapor to the desired reaction temperature in the riser. It also provides the heat of reaction necessary to crack the feedstock to the desired conversion level. Hot regenerated catalyst is pre-accelerated with lift steam and lift gas, dry gas from the gas concentration unit absorber section, at the bottom of the reactor riser prior to contacting the hydrocarbon feed stream further up the riser. The regenerator is normally operated at conditions that achieve complete combustion of CO to CO2. The combustion temperature can be varied for partial CO combustion, if processing conditions allow a minimal of heat generation. The regenerator is equipped with a catalyst recirculation standpipe, which supplies hot regenerated catalyst from the upper to the lower regenerator to provide additional heat for combustion. The regenerator is also provided with a Direct Fired Air Heater (11-F-101) that is used on startup to supply heat to the system until the catalyst temperature is raised sufficiently for auto-regeneration. Flue gas exits through cyclone separators to minimize catalyst entrainment prior to discharge from the regenerator. The sensible heat of the hot flue gas is recovered in a Flue Gas Steam Generator (11-H-101). In order to maintain the activity of the working catalyst inventory at the desired level, and to make up for any catalyst lost from the system, fresh catalyst is introduced into the circulating catalyst system from a Fresh Catalyst Storage Hopper (11V-103). An Equilibrium Catalyst Storage Hopper (11-V-104) is provided to hold regenerated catalyst withdrawn from the circulating system a necessary to maintain the desired working activity and to provide catalyst for startup.

ATTACHMENT REPORT

Figure 1 UOP Fluid Catalytic Cracking Unit with Regenerator and Reactor

ATTACHMENT REPORT

2.2 FCC CATALYST SECTION REACTOR (11-R-101/102) The catalyst flow is normally within the range of 30 to 70 tons of catalyst circulated per minute. Control and good management of catalyst flow is critical to better unit operation. Hot regenerated catalyst exits the upper regenerator at a temperature around 700-735 oC. The catalyst flows down through the regenerator standpipe to the Wye section of the riser where it contacts the lift gas and steam; and flow is regulated by the regenerated slide valve SLV 102. The reactor temperature controller controls the opening of the regenerated slide valve through a low signal selector (LSS) to regulate the amount of catalyst entering the reactor, and it is this amount of catalyst required to raise the gas and oil streams to the desired operating temperature. The Reactor temperature is therefore dependent on the amount of catalyst required in the Reactor. A safety feature incorporated into all the catalyst slide valves is the pressure differential override. If the pressure differential across the slide valve drops very low or becomes negative indicating low or reverse flow, the pressure differential controller sends a signal to the LSS to close the valve. This prevents oil from entering the regeneration section, which could result in very high temperatures, possibly damaging equipment. Lean sponge gas from the gas concentration unit is used as lift gas in the riser. Lift steam and gas flow is typically controlled at about 2wt% of the fresh feed. The lift gas transports regenerated catalyst up into the riser to the feed injection point. Lift gas and steam are controlled to maintain a minimum velocity of 3 m/s (10 ft/s) at operating conditions. The initial velocity of catalyst is 4.5 m/s and subjected to variation for optimization purposes; whereas lift gas and lift steam are interchangeably used as the lift media. The combined feed is mixed with atomizing steam at each of the feed distributors and the mixture is then injected into the riser at a point 4-6 meters above the lift gas distributor where it meets the hot regenerated catalyst. The oil is immediately vaporized with the resulting volumetric expansion forcing the catalyst/vapor mixture up the riser to the riser to the reactor vessel. Cracking reactions take place in the 2-3 seconds required for the catalyst and hydrocarbon vapors to reach the top of the riser. Catalyst is quickly separated from hydrocarbon in the reactor VSS enclosure to reduce over cracking. Cyclones further remove entrained catalyst particles from the hydrocarbon vapors. The vapors exit the cyclones and flow to the main column while recovered spent catalyst flows down the VSS enclosure and the cyclone diplegs to the reactor stripper section. The Catalyst flows down over perforated baffle plates and steam flows upward through the perforations in a counter current arrangement. The steam flow is controlled at a rate of 1-2 kg per ton of catalyst circulation to achieve satisfactory stripping. By this process any remaining hydrocarbon vapors in the catalyst is removed. Catalyst flow to the combustor is regulated by the spent catalyst slide valve (SLV 101) that maintains the reactor catalyst bed level. The level controller sends a signal through the low signal 8

ATTACHMENT REPORT selector to the valve actuator regulating the slide valve opening as shown in Figure 12. Reactor catalyst bed level is controlled just above the bottom of the VSS enclosure thus allowing minimum catalyst inventory while fully utilizing the stripping steam. The pressure differential controller sends a signal to the LSS to close the valve in case of low or negative pressure differential, and thus minimizes the possibility of air entering the reactor during upsets. Figure 2 Regenerated Catalyst Slide Valve Control

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Figure 3 Spent Catalyst Slide Valve Control

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2.3 FCC CATALYST SECTION-REGENERATOR (11-R-103/104) The regenerator is divided into two sections; the lower section being the combustor where the spent, re-circulated and cooled catalyst are mixed with air and coke combustion occurs. The combustor operates in the fast fluidized regime of fluidization. The upper regenerator holds the cyclones, provides volume for the regenerated catalyst to disengage from the flue gas and provides the surge capacity for catalyst in the system. By this system the catalyst returns to the combustor riser. A level recorder (LR) is provided to monitor the regenerator catalyst level. The actual regenerator catalyst level changes with catalyst additions, withdrawals and losses from the system. The recirculation of hot regenerated catalyst from the upper regenerator to the combustor is important in controlling the coke combustion rate. By controlling the amount of catalyst recirculated, the following parameters are affected in the combustor: the pre-combustion mixing temperature, the catalyst density, and catalyst flux and catalyst residence time. This, in turn, allows the optimization of coke combustion rate and catalyst regeneration. The recirculating catalyst slide valve is controlled through a low signal selector and a slide valve DPRC, similarly to the other slide valves. The recirculation slide valve position is controlled by a TRC located in the upper section of the combustor or by a density instrument (XIC) mounted on the combustor vessel. The regenerator pressure is indirectly controlled by operating the flue gas slide valves reset by a controller that measures the differential pressure between the reactor and the regenerator. Using PDRC control minimizes the effect of fractionation section pressure bounces on the catalyst circulation. The reactor-regenerator differential pressure is generally chosen to equalize the differential pressure across the catalyst slide valves, though occasional considerations such as minimizing the main air blower horsepower are made.

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ATTACHMENT REPORT

Figure 4 Reactor/ Regenerator Control System

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ATTACHMENT REPORT 2.4 CATALYST COOLER (11-E-101) -PROCESS CONTROL The Catalyst Cooler permits direct control over the regenerated catalyst temperature. The regenerated catalyst temperature is a major variable governing cracking reactions since it both sets the catalyst to oil ratio and determines the temperature of the catalyst surface at its first contact with the oil feed. A high catalytic reaction severity (high cat/oil ratio and catalyst activity) is desirable for the conversion of heavy bottoms material to lighter products. The normal effect of a decrease in feedstock quality is to increase the coke to catalyst weight ratio on spent catalyst, which in turn increases the regenerator temperature and lowers the catalyst to oil ratio. At a higher reaction severity, there may be more coke generated (higher coke yield on feed), but this is offset by the higher conversion of feed to valuable products and improvement in the yield of gasoline. The operating conditions for the catalyst cooler and regenerator is selected partly on the basis of the feedstock, the desired conversion, and the catalyst to oil ratio as determined from a heat balance around the reactor and regenerator. A regenerated catalyst temperature, which is too high, tends to increase the yield of light gas at the expense of gasoline and LPG. If the catalyst temperature is too low the unit may fall behind in burning since proper combustion cannot be maintained in the regenerator. Thus, the ability to vary the regenerator dense phase heat removal by a catalyst cooler is very important in optimizing the regenerator operation, i.e. maximize cat/oil and conversion while continuing to achieve good regeneration. Hot catalyst from the upper regenerator dense phase flows through the cooler shell, around the water tubes of the inserted tube bundle and out of the cooler through a cooled catalyst standpipe and slide valve into the combustor. The fluidization air lance system delivers fluidization air to the cooler shell to maintain catalyst fluidization and mixing in the shell and ensure that catalyst flows smoothly through the cooler and out through the standpipe. The combination of mixing and net catalyst flux through the cooler provide the driving force for heat transfer by maintaining contact of hot catalyst with the tube wall. Heat transfer is varied by varying degree of aeration through and net catalyst flux flowing through the cooler. The cooler shell is equipped with TLs and a differential pressure instrument to allow the temperature and density of the catalyst in the cooler to be monitored. The tubes are protected from thermal damage and oxidation, by insuring the circulation of large excess of water through the tubes to insure that the tube walls remain wetted. The minimum circulating water to steam weight ratio is 20:1. A low flow signal from the flow recorder activates a spare water circulation pump auto-start. A low-low flow signal from the water circulation flow recorder effectively causes the cooler to shutdown by closing the cooled catalyst slide valve and closing the fluidization air control valve. The mixture of steam and water exiting the cooler tube bundle flows to the steam drum where the steam and water are separated. The saturated steam flow from the drum is metered and flows out to the flue gas steam generator, where it is superheated and sent to the refinery steam system. The water returned to the steam drum is recirculated back to the cooler tube bundle. A small continuous blown down flow of water is removed from the drum to control accumulation of impurities in the circulating water. The outputs of the steam product flow meter and the steam drum level indicator are summed and control the flow of boiler feed 13

ATTACHMENT REPORT water (BFW) makeup entering the steam drum. The steam drum also has a low level alarm and a low level switch which shuts down the cooler by closing the slide valve and stopping the fluidization air in the event of a very low liquid level in the steam drum. Fluidization air for the cooler is normally provided from the plant air system or from a dedicated auxiliary air compressor and fluidization air is controlled by a flow controller. The control valve signal is routed through a solenoid valve, which trips to close the air control valve upon receipt of a shutdown signals from either the circulating water flow recorder or the low-low level indicator at the steam drum. The schematic diagram of a flow-through catalyst cooler installed on a high efficiency regenerator with the associated cooler fluidization air, water circulation, steam drum and control instrumentation is shown below. Figure 5 UOP FCC Catalyst Cooler Process Control

2.5 MAIN AIR-BLOWER- FLUE GAS PROCESS CONTROL

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ATTACHMENT REPORT The MAB (11-TC-101) compresses atmospheric air; the compressed air is sent to the DFAH (11-F-101) and the Regenerator as combustion air. The air flow is measured by the venturi in the discharge line, the FRC control the speed of the turbine, which regulates airflow. A vent line (snort) is located on the air blower discharge and is used to prevent air blower surge. The snort valve is controlled by the anti-surge system. The check valve in the air blower discharge line isolates the blower from the regenerator if the blower trips, or if the regenerator over pressures. This closing action is assisted by a spring-loaded air cylinder, which operates when regenerator pressure falls to a certain predetermined pressure differential with the air blower discharge. The flue gas system on the RFCC unit comprises of double disc slide valves (11-SLV105), an Orifice Chamber (11-V-101), a Flue Gas Steam Generator (11-H-101) and an Electrostatic Precipitator (11-ME-105).A DPRC (differential pressure recording controller) holds the proper pressure balance between the reactor and regenerator by controlling the position of the double disc flue gas slide valves. There is no differential pressure instrument across the flue gas slide valve due to the absence of downstream that can cause over pressure and reverse flow. Figure 6 Air Blowers (Turbine Driven)

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ATTACHMENT REPORT Figure 7 FCC Flue Gas Systems

2.6 TORCH OIL NOZZLE CONTROL The torch oil nozzles provide a means of injecting heavy oil, such as raw oil feed, into the regenerator when extra heat is needed, e.g. during startup. The torch oil assembly is also provided with a continuous steam purge to the annular space around the torch oil nozzle to keep it clear of catalyst. This purge steam flow is regulated to less than 25 kg/hr steam with a restriction orifice. In addition, a small flow of steam is often sent through the nozzle when it is not being fired, to help cool the nozzle and keep it from plugging with catalyst. This cooling steam flow is also regulated with a restriction orifice.

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ATTACHMENT REPORT Figure 8 Torch Oil Instrumentation

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2.7 DIRECT FIRED AIR HEATER (DFAH) The air heaters is used for refractory curing and dry-out following repair or renewal of regenerator linings, as well as during normal startup to heat the regenerator catalyst inventory. The DFAH (11-F-101) outlet temperature is controlled by the fuel gas rate. Because air heater mis-operation can cause damage to regenerator internals, a high temperature shutdown is installed. For additional safety, the air heater shuts down on low air flow and loss of flame detection from a flame sensor.

Figure 9 Direct Fired Air Heater

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CHAPTER 3- (UNIT 12)


3.1 FRACTION SECTION (MAIN COLUMN) The principal activity at this section is product separation based mainly on temperature differences in the main column. The operation of the main Column involves controlled heat removal and sufficient liquid-vapor contacting to cause the required degree of fractionation into desired products. The reactor product vapors at about 530oC flow through the reactor vapor line to the main column; these vapors are condensed and fractionated into products such as Main Column Bottoms(MCB), Heavy Cycle Oil (HCO), Light Cycle Oil (LCO), Heavy Cycle Naphtha( HCN), unstabilized gasoline and wet gas. MCB, HCO and HCN are products directly taken from the main column to storage although some amount of each is used for internal circulation within the RFCCU. The unstabilized gasoline and wet gas are subjected to further separation processes in the gas concentration units. The pump-around circuit aids in heat exchange; which is also based on specific requirements and economics of a given installation. 3.2 MAIN COLUMN BOTTOMS PUMPAROUND CIRCUIT The main column bottoms system de-superheats the reactor vapors, condense the bottoms product and scrub entrained catalyst particle fines from the reactor product gases. Main column bottoms (MCB) is removed from the bottom of the main column and sent to circulating bottoms/raw oil exchangers (E-201 A/B, E-202 A/B and E-205 A/B) and two steam generators (E-204 A/B). The vapors are de-superheated by circulating a large stream of cooled column bottoms (Raw oil is also used sometimes) over the disk and donut trays where it de-superheat the reactor vapors as well as flush catalyst fines out of the column. The cooled bottoms circulation rate should be set at not less than 150% of the design feed rate. And bottoms temperature maintained at 350-360oC to minimize coking in the slurry circuit. The pump around rate and heat removal must be high enough to keep the bottoms temperature below the 360oC maximum, as coking rate depends on time and temperature. There is reflux at the main column bottom to maintain temperature when necessary; and this is achieved by returning cooled stream of circulating main column bottoms. Bottoms product is withdrawn to maintain a steady bottoms level in the main column. The product stream is cooled by heat exchange with a charge Raw Oil and Boiler Feed Water. A minimum spillback is provided for minimum slurry circulation during turndown operation. This ensures enough oil is returned to the main column adequately covering the disc and donut trays, thereby cleansing the reactor vapors of catalyst fines and preventing coke formation on the disk and donut trays due to insufficient liquid flow over the trays. Heat input to the steam generators is the only variable available to the operator for adjustment. Bottoms flow to the steam generators can be adjusted to change the amount of heat rising up the column thus increasing or decreasing the column top reflux rate which acts to heat balance the column. The heat input from the circulating main column bottoms to the feed preheat exchangers is set by product and process considerations. Main column 19

ATTACHMENT REPORT bottoms circulation flows through the exchangers on the tube side and the velocity must be kept between 1.14 m/s and 2.13 m/s for straight tubes and between 1.14 m/s and 1.75 m/s for U-tubes. Deviations outside of these ranges will show up as excessive amounts of settled catalyst fines or erosion to the tubes. The rates required to meet these velocities must be calculated for each exchanger before startup. Figure 10 Main Column Bottoms Circulation and Product

3.3 HCO PUMPAROUND CIRCUIT HCO flow is regulated by a flow controller to the Debutanizer Reboiler (13-E-312), and the controller is set by the operator to achieve desired product and process specification (i.e. flow rates, heat requirement etc.). There is also an HCO stripper where lighter ends are stripped off the HCO product. A calculated amount of HCO is also used for reflux, and this provides proper heat balance at the HCO section at the main column. A decrease in heat removal from the HCO circuit will require an increase in heat removal elsewhere in the column. For example, if less heat is required by the debutanizer reboiler, HCO circulation will be decreased. Lower circulation reduces reflux to the HCO section of the main column, increasing the amount of vapor rising up the column. The reflux to the top of the main column increases to remove any excess heat as a result of inefficient heat exchange during pump around. The HCO circuit as well provides flush oil to the Main Column Bottoms Pumps (12-TP-211 A/B). There is spillback of HCO to the main column and this operates off a level controller on the HCO draw off tray; and this aids in internal reflux. Figure 11 Heavy Cycle Oil Circulation 20

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3.4 LCO PUMPAROUND AND PRODUCT CIRCUIT This unit contains an LCO stripper for LCO product flash point adjustment. The light ends in the LCO are removed by steam stripping. The LCO product is cooled in an air-finexchanger, Light Cycle Oil Product Cooler (12-EA-202) and Light Cycle Oil Product Trim Cooler (12-E-207) and sent to storage (82-G-204). Flow to storage is set by a flow controller (12-FIC-226). The cooled LCO product can also be used as cutter stock to the heavy fuel oil static mixer. The amount of LCO produced depends upon operating conditions, feed quality and catalyst type. Stripped LCO is available for use as instrument flush, flushing oil, and pump flush. The heat to Stripper Reboiler (13-E-309) and Debutanizer Feed Exchanger (13-E-311) is provided by the circulating LCO. Flow to the exchanger is regulated by a flow controller that is set according to process requirements. A stream of LCO, after heat exchange at the circulating Stripper Reboiler is sent to the Sponge Absorber (13-C-302) as lean oil to absorb light gasoline range components from the light gas in the gas concentration section. The rich oil from the sponge absorber is returned to the main column with the cooled LCO circulation stream, providing internal reflux for the main column LCO section.

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ATTACHMENT REPORT Figure 12 Light Cycle Oil Circulation and Product

3.5 NAPHTHA PUMPAROUND AND PRODUCT CIRCUIT Naphtha product is pumped and used for heat exchange with the feed coming in from the Raw Oil Feed Surge Drum (12-V-201) on flow control in the heat exchanger (E-201) and returned to the main column as internal reflux for the main column naphtha section. The increase in heavy naphtha circulation will condense more vapors rising up the column. Less heat will reach the top of the column. The top temperature controller will then reduce the reflux flow to maintain the column to temperature, thus heat balancing the column.

Figure 13 Heavy Naphtha Circulations and Product 22

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3.6 MAIN COLUMN OVERHEAD SYSTEM The main column overhead products contain mainly wet gas and gasoline vapors and these products are condensed in the Main Column Condenser (12-EA-203), the Main Column Trim Condenser (12-E-208) and separated in the Main Column Receiver (12-V-202). A quantity of the condensed hydrocarbon liquid (unstabilized gasoline) is pumped to the main column as reflux to control the overhead vapor temperature. This temperature determines the endpoint of the gasoline product. If heat removal from one section is changed the reflux rate will respond in the opposite direction to maintain a constant top temperature. Some of the unstabilized gasoline liquid in the receiver is pumped to Primary Absorber (C-301) in the gas concentration unit mainly for absorption of C3 and C4 on receiver level control. Wet gas flows to the suction drum of the wet gas compressor in the gas concentration unit. The Sour water which collects at the boot section of the receiver (12V-202) is pumped to the sour water storage. Water from the gas concentration section washes the ammonia chloride and some other salts from the condensers (12-EA-203).

Figure 14 Main Columns Overhead System 23

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3.7 RAW OIL CHARGE SYSTEM Raw oil enters the Feed surge drum (12-V-201) directly from storage or CDU: the drum helps dampen process flow variations from the feed sources. Drum level control is maintained by a level controller that signals valves on the feed streams. Drum pressure floats on the main column pressure through a line connected to the tower in the vapor space above the HCO draw tray. The raw Oil is heated by exchange with the circulating Heavy Naphtha, net MCB, and circulating MCB. Usually all streams except the circulating main column bottoms are flow controlled by the operator. The final raw oil temperature is controlled by passing some oil around the circulating main column bottoms exchanger.

Figure 15 Feed Preheat System

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3.8 MAIN COLUMN AND RELATED EQUIPMENT The main column is made of regular or killed carbon steel, with a 1/8 inch (3 mm) thick Type 405 or 410 (12 Cr) cladding from below the naphtha or LCO draw tray to the bottom outlet. Any nozzle or man ways in this clad section is alloy lined. All the trays and caps in the column are Type 410 stainless. The main column may be divided into two sections: the regular fractionators and the lower disc and doughnut trays. The bottom six trays are designed for high vapor and liquid flow rates. The coke trap prevents large pieces of coke or other debris from entering the bottom line. Steam is used to strip the bottoms material of any lighter hydrocarbons. The overhead vent from each stripper returns to the main column in a vapor space. The main column is fitted with 3-sample lines which are used o check the bottoms levels due to the occasional plugging by fines or coke particles of the level glass and indicators. The support for the main column is a table top and as such aids or simplifies maintenance work on the bottom lines. A separate suction line to each pump (TP-211 A/B) allows operation to continue through one line while the other is cleaned.

Figure 16 Main Column (12-C-201) 25

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Figure 18 Typical Disc and Donut Pans 26

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Figure 19 Typical Coke Trap

Figure 20 HCO Stripper (Bottom)/ LCO Stripper (Top) arrangement

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3.8.1 MAIN COLUMN BOTTOMS The main column bottoms pumps as detailed in the figure below, has minimum distances shown which are important to prevent catalyst fines from setting in a line that is not in service, allowing it to plug. The exchanger metallurgy ranges from carbon to 5 Cr, Mo. The slurry service side of the tubes, tube sheets, and heads of the exchangers is clad with a chrome alloy, such as Type 410 to prevent the carbon steel being exposed to hot main column bottoms. After the first Exchanger (12-201) most of the piping is carbon steel. The Main Column Bottoms Circulation pumps (12-TP-211 A/B) are turbine driven with speed limit of 2000 revolution per minute (rpm) to minimize erosion. Both pump A and B run simultaneously with the standby pump B on slow run, by this system if there is any failure of pump A, then B can still pump sufficient product to prevent unnecessary pressure build up in the column. The shaft is tungsten carbide with a LCO flush to the throat bushing and wear rings and HCO to the mechanical seal. The suction and discharge lines of the main column bottoms pumps range from 5 Cr, Mo to 9 Cr, 1 Mo. Figure 21 Main Column Bottoms Pumps Arrangement

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CHAPTER 4- (UNIT 13)


4.1 GAS CONCENTRATION SECTION (GENERAL PROCESS) The Gas Concentration Unit receives gasoline and all lighter products from a Fluid Catalytic Cracking Unit and separates this mixture into stabilized gasoline, liquefied petroleum gas (LPG) stream, and a non-condensable lean gas stream. The LPG stream is sent to an LPG treating unit for further treatment and is further separated into mixed C3 and mixed C4 streams. The components in the charge and products from a Gas Concentration Unit are summarized in the following table: Table 2 Common Products from a Gas Concentration Unit Component Formula Boiling Point at 1atm, oC Gasoline Normal Butane Isobutane Butylenes Propane Propylene Hydrogen Sulfide Ethane Ehtylene C5 + Hydrocarbons n-C4 H10 i-C4 H10 C4 H8 C3 H8 C3 H6 H2S C2 H6 C2 H4 38-221 -0.6 12 -7 to +4 -42 -48 -61 -88 -104

104 C Methane Hydrogen CH4 H2 -162 -253 31


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ATTACHMENT REPORT

Inerts

N2, CO, CO2

-196, -192, -78

Figure 22 Typical Gas Concentration Units

4.2 PROCESS FLOW AND CONTROL The Gas Concentration Unit can be divided into two main areas known as; 1. The recovery section 2. The fractionation section In the Recovery Section, ethane and lighter components and hydrogen sulfide are removed from the feed stream. The equipments used in the recovery section are the Wet Gas Compressor (13-TC-301), High Pressure Receiver (13-V-303), Primary Absorber (13-C301), Sponge Absorber (13-C-302), Fuel Gas Absorber (16-C-601) and the Stripper (13-C32

ATTACHMENT REPORT 303). The Fractionation Section in its most basic form has a Debutanizer (13-C-304) to split the unstable gasoline into liquefied petroleum gases (LPG) and stable gasoline. 4.2.1 RECOVERY SECTION The charge streams from the main column overhead receiver to the recovery section of the Gas Concentration Unit usually consist of the gas and unstabilized gasoline. Vapor from the Main Colum Receiver (12-V-202) is compressed to 16 kg/cm2 using two separate stages by the compressor. The gas is cooled after each stage to remove heat of compression allowing heavier components to condense out of the gas stream. The gas flows from the Main Column Receiver (12-V-202) through a Compressor Suction Drum (13-V-301) to the first stage of compression of a centrifugal gas compressor. The suction drum contains a wire mesh blanket (demister pad) to trap entrained liquid droplets that could damage the compressor. Any liquid that collects in the first stage suction drum is pumped forward to the Main Colum Condenser (12-EA-203). The first stage discharge flows through the Compressor Interstage Cooler (13-EA-301) and Compressor Interstage Trim Cooler (13-EA-301) to the Compressor Interstage Suction Drum (13-V-302). Gas from the first stage discharge may also return to the FCC Main Column Trim Condenser (12-E-208) to prevent compressor surge or to maintain receiver pressure. Wash water is injected to the Compressor Interstage Cooler, 13-EA-301 to prevent the buildup of salts such as ammonium chloride. Typical injection rates are in the range of 6-7 vol% of the FCC charge rate. The Compressor Interstage Suction Drum (13V-302) gas outlet is also covered with a demister pad to trap any entrained liquid. The liquid collecting in the Compressor Interstage Suction Drum (13-V-302) (hydrocarbon and wash water) is pumped on level control to the inlet of the High Pressure Condenser (13EA-302). From the top of the Compressor Interstage Suction Drum (13-V-302), gas flows to the second stage suction of the gas compressor then on through the High Pressure Condenser (13-EA-302) and High Pressure Trim Condense r (13-E-302) to the High Pressure Receiver (13-V-303). The overhead vapor stream from the Stripper (13-C-303) the Interstage condensate and the rich oil from the Primary Absorber (13-C-301) join the second stage discharge gas upstream of the High Pressure Condenser (13-EA-302). Spillback gas from the compressor second stage also joins the first stage discharge upstream of the Compressor Interstage Cooler (13-EA-301) - this protects the second stage of the compressor from surge. Rich Gas flows from the High Pressure Receiver (13-V-303) to the Primary Absorber (13C-301) for C3/C4 recovery as shown in figure 25. The gas flows upward through the Primary Absorber(13-C-301) contacting a down flow of unstabilized gasoline from the FCC Unit Main Column Receiver(12-V-202) that is introduced into the Primary Absorber at Tray 9. A slipstream of stabilized gasoline from the Debutanizer (13-C-304) is admitted to the top tray of the Primary Absorber. The addition of stabilized gasoline to the Primary Absorber significantly increases C3/C4 recovery. Off-gas exits the top of the Primary Absorber and flows to the bottom of the Sponge Absorber (13-C-302) for final recovery of any C5+ material and some C3/C4 components. The gas flows upward through the Sponge Absorber where it is contacted with a down flow of lean sponge oil (LCO) which enters the column on flow control above the packing. The lean gas leaves the top of the Sponge 33

ATTACHMENT REPORT Absorber and enters a Lean Gas Knockout Drum (13-V-304) which removes any entrained liquid. The gas exits the top of the Lean Gas Knockout Drum (13-V-304) and flows to the bottom of the Fuel Gas Absorber (16-C-601). A portion of the sponge gas will be recycled to the FCC Unit as lift media. In the Fuel Gas Absorber (16-C-601) the gas is contacted with a down flow of lean amine for H2S removal. The amine enters the column on flow control. The treated gas exits the top of Fuel Gas Absorber (16-C-601) and enters a Treated Gas Knockout Drum (16-V-607) that removes any entrained amine. The sponge gas leaves the Treated Gas Knockout Drum (16-V-607) on pressure control to the refinery Fuel Gas System. Light cycle oil (LCO) from the FCC supplies lean oil to the Sponge Absorber. A slipstream of LCO is sent to the Sponge Absorber as lean oil. This lean oil is cooled by heat exchange with rich oil from the bottom of the Sponge Absorber and a Sponge Absorber Lean Oil Cooler (13-E-306). The LCO is pumped on flow control into the top of the tower above the packing. The lean sponge oil flows downward through the absorber contacting the upward flow of gas. From the absorber bottom, the rich oil (flowing on level control) is heated by the lean oil before returning to the FCC Main Column (12-C-201) via the LCO pump around. Liquid hydrocarbon from the High Pressure Receiver (13-V-303) is pumped to the Stripper (13-C-303) where hydrogen sulfide (H2S), ethane and lighter components are stripped out. The Stripper flow is shown in Figure 6. Feed to the Stripper is heated using the total Debutanizer (13-C-304) bottoms stream. Stripper charge enters the column above the top tray. Stripping action is provided via a Stripper Reboiler Exchanger (13-E-310) at the bottom of the column through which heat is supplied from the Debutanizer bottoms stream and a Stripper Reboiler (13-E-309). Circulating LCO flows through the tube side of the Stripper Reboiler with its flow regulated by a flow controller (13-FIC-313) that is reset by the stripper overhead vapor rate. The overhead vapor is returned to the High Pressure Condenser (13-EA-302). Bottoms material is pressured to the Debutanizer (13-C-304) on level control.

Figure 23 Arrangements of wet gas compression process

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ATTACHMENT REPORT

Figure 24 Absorbing process arrangements in the Gas Concentration Unit

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ATTACHMENT REPORT

4.2.1.1 EQUIPMENTS AT RECOVERY SECTION Wet Gas Compressor

1. 2. 3. 4. 5.

Compressor Suction Drum and Compressor Interstage Suction Drum High Pressure Receiver Primary Absorber Sponge Absorber Stripper

Wet Gas Compressor (13-TC-301): The Wet Gas Compressor separates the relatively low pressure of the FCC Main Column (12-C-201) from the high pressure gas concentration unit. A centrifugal compressor is used for this service. Centrifugal Wet Gas Compressors are multi-stage machines, contained within two external stages. Each of the two stages is protected by an anti-surge device that will override normal controls to protect the compressor. Gas leakage out of the casing is prevented by suction and discharge end labyrinth seals. These seals are backed by either buffer gas. The seal system must be kept in operation while the casing is under pressure or gas will leak out.

Figure 25 Centrifugal Compressor

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ATTACHMENT REPORT

1. Compressor Suction Drum and Compressor Interstage Suction Drum (13-V-301/302): A sketch of the compressor suction drum is presented below. Both first and Interstage suction drums are made of carbon steel with a stainless steel mesh blanket (demister pad) to remove any entrained droplets. Mesh blankets provide a large surface area for any entrained liquid to coalesce on and be removed from the gas stream.

37

ATTACHMENT REPORT Figure 26 Compressor Suction Drum

High Pressure Receiver (13-V-303): The High Pressure Receiver collects the liquid streams from the Compressor Interstage Suction Drum (13-V-302) and Primary Absorber (13-C-301) bottoms and the gas streams from the second stage compressor discharge and the Stripper (13-C-303) overhead. Water is separated from the hydrocarbon stream and collected in the receiver water boot. The sour water is pressured from the boot to the Main Column overhead on level control. The hydrocarbon liquid stream is pumped to the Stripper (13-C-303) on level control. The separated gas is sent to the Primary Absorber (13-C-301). The Primary Absorber (13-C-301) floats on the High Pressure Receiver (13-V-303) pressure. The vessel is killed carbon steel. The design operating pressure is 16 kg/cm2. A slotted pipe distributor is provided to minimize liquid level disturbances due to the incoming gas/liquid stream.

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ATTACHMENT REPORT Primary Absorber (13-C-301): The function of the Primary Absorber is to absorb most of the propylene, propane, butylene and butane components in the rich gas stream from the High Pressure Receiver (13-V-303). The column is killed carbon steel with 40 carbon steel trays. Valuable light products such as LPG are absorbed from the gas as it reveals from the bottom to the top outlet. The tower design uses two intercoolers to remove the heat of gas absorption from the gasoline as it flows down the tower. The temperature rise is about 14C. These intercoolers are located roughly one-third and two-thirds of the way down the tower. The circulating gasoline is pumped through the water coolers. Debutanizer gasoline is introduced at the top of the column as a final wash of the gas stream. Improved C3/C4 recoveries result from the use of recycle gasoline although if the C3/C4 recovery is adequate it may be more economical not to recycle gasoline. The gasoline from the bottom of the column is pumped to the High Pressure Condenser (13-EA-302) while the gas goes to the Sponge Absorber (13-C-302). Sponge Absorber (13-C-302): Depending on the absorption efficiency in the Primary Absorber, 5-10% of the propane and heavier components can be lost to the fuel gas system if a secondary absorber is not used. The Sponge Absorber is a guard tower that uses light cycle oil to absorb any remaining liquid from the gas. If any significant quantities of C5 or C6 remain in the gas stream, these will cause problems with treating. If the gas is sent directly to the fuel gas system, condensation of heavy material is dangerous. The Sponge Absorber is half as big as the Primary Absorber. It is a killed carbon steel column filled with packing to provide intimate contact between the lean oil and the gas. A type 304 stainless demister pad, at the top of the absorber, traps any entrained liquid. Stripper (13-C-303): The purpose of this column is to strip off the light ends (C 2-) plus the bulk of the hydrogen sulfide that is present in the gas and liquid streams from the FCC Unit. The charge to the column enters through two distributors that discharge onto the top tray. The stripped vapors leave the top of the column. The heat input to the column is controlled by the top vapor rate. The Stripper bottoms liquid is sent to the Debutanizer on reboiler level control. The gasoline stream from the Debutanizer bottoms provides preheat to the gasoline feed stream. The Stripper is made of killed carbon steel with 36 carbon steel trays. Tray fittings are type 410 stainless. This corrosion is not common and can usually be corrected without the additional expense of a chrome alloy reboiler.
4.2.2 FRACTIONATION SECTION

As shown in Figure 26, the feed to the Fractionation Section is the Stripper (13-C-303) bottoms stream that is pressured into the Debutanizer (13-C-304). Heat is supplied via a Debutanizer Reboiler (13-E-312). The heating oil to the reboiler is heavy cycle oil from the FCC Unit. The HCO is regulated by a flow recording controller (13-FIC-316). Overhead vapors (C3s and C4s) are condensed by an air Debutanizer Condenser (13-EA-304) and then collected in the Debutanizer Receiver (13-V-305). Debutanizer feed is preheated by circulating LCO from the FCC. The net production of light FCC gasoline is pressured from

39

ATTACHMENT REPORT the Debutanizer on level control to the LPG Merox Unit. A recycle stream of stabilized gasoline is also sent to the Primary Absorber to increase the absorption efficiency of C3/C4. A portion of the total overhead is pumped back to the column as reflux. The quantity of reflux is regulated by a flow recording controller (13-FIC-317) which is typically reset by the Tray 9 13-TIC-334 in the top of the column. The net overhead liquid product is pumped out on flow control that is reset by the level controller (13-LIC-322) on the Debutanizer Receiver (13-V-305). The Debutanizer column pressure is controlled by a pressure recording controller (13-PIC-333) on the overhead vapor line and by a pressure differential indicator controller (13-PDIC-334) in the vapor bypass line. The 13-PIC-333 controls vapor flow to condenser to control the column pressure. The 13-PDIC-334 keeps the receiver pressure from dropping too low, bypassing some vapor that keeps the 13-PV-333A valve in range. The receiver pressure is not always constant and will change with changes in the weather conditions. A drag line is provided to vent non-condensable from the top of the Debutanizer Receiver (13-V-305). Column pressure control will not work properly if non-condensable are present. If they are present, first the 13-PDV-334 control valve will close, and then the column pressure will exceed the set point. The Debutanizer overhead product is pumped to the LPG Treating Unit (14 Unit) for mercaptan sulfur removal.

Figure 26 Stripper/Debutanizer Flow (process equipment)

Circulating LCO

Circulating LCO

4.2.2.1 DEBUTANIZER (13-C-304) 40

ATTACHMENT REPORT In the Debutanizer, a majority of the C3 and C4 components are taken overhead. This is the LPG product stream that can be sent for further treating. The gasoline from Debutanizer bottoms usually requires treatment for removal of sulfur and the addition of inhibitors to upgrade its storage quality. The Debutanizer is killed carbon steel with 40 carbon steel trays. Tray fittings are type 410 stainless. The overhead system is usually carbon steel, with inhibited Admiralty brass tubes in the water condenser. The shell of the reboiler is carbon steel, the tubes, tube sheet and floating head cover are 5% Cr 1/2% Mo. Carbon steel clad with type 410 stainless may be used instead of 5% Cr. Hot fluid flow is through the tubes. 4.3 WASH WATER The overhead stream from the Main Column (12-C-201) contains ammonia, sulfides, cyanides, chlorides and phenols that can cause corrosion, plugging or fouling. A wash water stream is used to remove these contaminants since most are ionic or polar species, and soluble in water. Typical flow rates run 2 gram per minute water/1000 BPD feed (6.5-7 vol-%), though less may be used if it does the job. Water is injected after the compressor first stage and is pumped out of the Interstage suction drum to the inlet of the High Pressure Condenser. The water is collected in the water boot of the High Pressure Receiver and then pressured back to the FCC Main Column overhead condensing system. There is always water present in the FCC Main Column and gas concentration section from reactor stripping stream and other sources. If the wash water is not used to flush out the sulfides, ammonia, cyanides and other species, the water present can be highly corrosive from absorption of these contaminants. Sulfide levels of greater than 20,000 ppm have been reported in the Main Colum Receiver (12-V-202) water. Hydrogen blistering and general corrosive attack may become quite severe, especially if feed sulfur is greater than 1%, or feed nitrogen is greater than 1000 ppm. Also, while the Main Column Receiver water may be basic, most of the ammonia that is responsible for this will drop out in the Main Column Receiver. The water in the gas concentration section may become acidic from H2S and CN. If there is any oxygen present, elemental sulfur may be formed from oxidation of the sulfides. This will cause problems in meeting gasoline product specifications. Wash water will solve many of these problems by diluting the corrosives and keeping the water pH at 8-9 where sulfide oxidation is greatly reduced.

Figure 27 Water Wash Process

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CHAPTER 5- (UNIT 14/UNIT 15)


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ATTACHMENT REPORT

5.1 LPG MEROX UNIT (UNIT 14) The UOP (universal oil product) Merox Process is an efficient and economical catalytic process developed for the chemical treatment of petroleum distillates for removal of sulfur present as mercaptan (Merox Extraction) or conversion of mercaptan sulfur to another much less objectionable form (Merox Sweetening). The name Merox is derived from MERcaptan OXidation. The process relies on a special catalyst to accelerate the oxidation of mercaptans to disulfides at or near economical product rundown temperature. The main activity here is extraction of LPG. The Merox process is based on the ability of a catalyst or catalysts composed of iron group metal chelates in an alkaline environment to promote the oxidation of mercaptans to disulfides using air as the source of oxygen. The reaction proceeds at an economically practical rate at normal temperatures for refinery rundown streams. For light stocks, operating pressure is controlled slightly above the bubble point to assure liquid phase operation; for heavier stocks, operating pressure is normally set to keep air dissolved in the reaction section. Low molecular weight mercaptans are soluble in caustic soda solution. Therefore, when treating LPG, the Merox process can be used to extract mercaptans, thus reducing the sulfur content of the treated product. In the extraction unit, sulfur reduction is directly related to the extractable mercaptan content of the fresh charge. The LPG Merox process utilizes liquid-liquid contacting to extract the mercaptans from the LPG with a strong aqueous alkali solvent. The mercaptan-rich solvent, which also contains the dispersed Merox catalyst, is sent to a regeneration section where air is injected and mercaptans are oxidized to disulfides. The disulfides are subsequently separated from the solvent by coalescing, gravity settling, and decanting; the regenerated lean solvent is recycled back to Extractor. Thus, the process consists of two steps; mercaptan extraction and solvent regeneration. 5.2 PROCESS VARIABLES The following represent the five primary process variables in this unit. The effect of these process variables in the LPG Merox on performance is also discussed here. 1.Catalyst Concentration 2.Oxygen 3.Alkalinity 4.Contact 5.Heat 1. Catalyst concentration: Catalyst concentration is a direct operating variable in the extraction process. For initial makeup, or whenever fresh caustic is added to replenish the system, a catalyst concentration of approximately 200 ppm in the caustic is recommended. The use of UOP Merox Reagent WS is essential to the extractive Merox process. It is supplied as a dark blue solution packaged in 3.8 liter (1 U.S. gallon) sealed polyethylene bottles. Each bottle contains one kilogram (2.2 pound) of 43

ATTACHMENT REPORT water soluble ingredient. For a catalyst concentration of 200ppm in the caustic an estimated 2 pound of UOP Merox Reagent WS active ingredient per 1000 U.S. gallons of caustic inventory (0.24 kilograms per 1000liters). To maintain the catalyst level for active extraction, regular schedule of catalyst addition is well followed. 2. Oxygen Injection: Oxygen is supplied to the caustic regeneration section of the Merox unit in the form of compressed atmospheric air. About 0.88 m3 of air is needed for each pound of mercaptan sulfur to be oxidized. The amount of excess air injection necessary is dependent on the individual feedstock, although it normally ranges between 1.2 to 2.0 times the theoretical requirements. All other variables being equal, an increase in air injection results in a more rapid and complete caustic regeneration. Thus, the regenerated caustic returns to the Extractor (14-V-408) with lower sodium mercantile content and possess a greater capacity to extract mercaptan. However, increasing air injection decreases residence time in the Oxidizer (14-V-408). While a low mercaptan concentration is desirable, the caustic should never be completely regenerated for the following reasons. 1. Oxygen can dissolve in the caustic and cause sweetening to occur in the Extractor (14-V-404). 2. The spent air will have a higher oxygen concentration leading to increased corrosion and potential hazards. 3. An increased in catalyst consumption can occur due to increased settling of the catalyst at the oil/caustic interface in the Disulfide Separator (14-V-409). Maintaining a small amount of mercaptide in the circulating caustic ensures better catalyst dispensability in the aqueous caustic 3. Alkalinity: Caustic is the solvent provides for mercaptan extraction and also the medium in which catalyst is dispersed. In addition, it provides the alkaline environment necessary for the mercaptan oxidation reaction to proceed in all versions of Merox process. For low molecular weight mercaptan molecules (methyl and ethyl mercaptan) increasing caustic strength increases extraction. As higher molecular weight mercaptan molecules are encountered, increasing caustic strength decrease extraction. Above this strength, competition from the hydroxide ions already in solution hinders any increase in mercaptan solubility. Also, at these strengths emulsification problems begin to occur. 4. Contact: Contact has to do with the duration of mixing time, by volumetric ratio of reactants, or by differential pressure, which implies degree of dispersion. With a fixed flow restriction, the differential pressure is directly related to the linear velocity so that velocity is often taken to be the process variable. The other important contact variable for extraction is the volume of caustic circulated relative to the volume of hydrocarbon throughput. This is referred to as the caustic to hydrocarbon ratio (C/H). As this ratio is increased, contact is increased and the extraction potential is increased.
5. Heat (Temperature): Mercaptan extraction is favored by lower temperature. The

lowest practical LPG feed temperature for extraction is about 20oC. Below this temperature, caustic entrainment, or caustic haze, may become a problem. Above 50oC, mercaptan extraction can be poor. The LPG extraction Merox units are designed for optimum operation at 38oC.The Merox caustic regeneration reaction is favored by 44

ATTACHMENT REPORT higher temperature. Thus, in Merox extraction units a small Caustic Heater (14-E-401) is provided to heat the rich caustic before it enters Oxidizer (14-V-408). 5.3 PROCESS FLOW AND CONTROLLPG MEROX Virtually, all extraction unit feedstreams need pretreatment before entering the Merox unit proper. The purpose of pretreatment is to remove acidic impurities such as H 2S, and/or CO2. The quantity of impurities or contaminants in feedstock will determine which type pretreatment equipment is required. An LPG Amine Absorber is provided on feedstocks containing relatively high concentration of acid gases (H2S and CO2). An aqueous solution of a diethanolamine (DEA), is utilized in a countercurrent contact to extract the acid gas. This equipment is provided upstream of extractive LPG Merox unit. A LPG Amine Absorber will remove acid gases to an equilibrium level dependent on amine regeneration; however, this level is not low enough to send amine treated feed directly to Merox unit. Further treatment in the form of a caustic prewash is required to remove the last trace of acid gases present. In mercaptan extraction unit, fresh feed is charged to an Extractor column, in which mercaptans are counter currently extracted by a caustic stream containing Merox catalyst. The treated material passes overhead to a Caustic Knockout Drum in which any entrained caustic solution is separated and returned to the circulation systems. The product then passes through a sand filter to coalesce any entrained caustic solution before going to storage. The mercaptan-rich caustic solution from the bottom of the Extractor column flows to the regeneration section where air is injected into this stream and the mercaptans are converted to disulfides. The Oxidizer effluent flows into the Disulfide Separator where spent air, disulfide oil and the caustic solution are separated. Spent air is vented to a safe place while disulfide oil is decanted and sent to FCC unit. The regenerated caustic stream is returned to the Extractor column. Merox catalyst is added periodically to maintain required activity. 5.4 GASOLINE MEROX UNIT (UNIT 15) -- GENERAL PROCESS PRINCIPLES Gasoline sweetening is a process of converting mercaptans in the product (gasoline) directly to disulfides. Because the vapor pressures of disulfide are so low relative to those of mercaptans, their presence is much less objectionable and these disulfides remain in the product and there is no reduction in total sulfur content. The conventional Merox fixed bed sweetening make use of the gross intermittent alkali saturation of catalyst bed but the Merox Minalk unit relies on a small, continuous injection of an appropriate strength alkali solution. This continuous, small injection of alkali such as dilute sodium hydroxide solution (2-5wppm) is held to a minimum but enough to provide the needed alkalinity. In this way mercaptans are oxidized to disulfides and they do not enter into a peroxidtion reaction in case of insufficient alkalinity. For a complete removal of H2S from the charge stock (light gasoline) where more than low ppm (parts per million) levels of H2S are present, the charge stock is passed through a guard caustic scrubber. H2S does not poison 45

ATTACHMENT REPORT the catalyst but it competes with mercaptans for the available catalytic sites and available oxygen. 5.4.1 REACTION CHEMISTRY Merox Reactions The Merox process in all of its applications is based on the ability of an organic metallic catalyst to accelerate the oxidation of mercaptans to disulfides at or near ambient temperatures and pressures. Oxygen is supplied from the atmosphere. The reaction only proceeds in an alkaline environment. The overall reaction is as follows: RSH + 1 1 1 O2 RSSR + HO2 4 2 2

The R is a saturated or unsaturated hydrocarbon chain which may be straight, branched, or cyclic. In most petroleum fractions the R might have 1, 2, 3 or more carbon atoms in the chain. Sometimes when this reaction occurs, two different mercaptans may enter the reaction. This is illustrated as R and R in the reaction equation as: 2 RSH + 2 RSH + O2 2 RSSR + 2HO2 This reaction occurs spontaneously, but at a very slow rate. 5.4.2 SWEETENING MECHANISM On the basis of Licensor (UOP) studies, the thiol portion of the mercaptan (-SH) functional group, first transfers to the aqueous alkaline phase and then combines with the catalyst. The presence of oxygen causes this mercaptan catalyst complex to oxidize, yielding a disulfide molecule and water. The system works efficiently for all lower molecular weight mercaptans which are partially soluble in caustic soda solution. It is the function of the catalyst not only to accelerate the oxidation without allowing side reactions to occur. Most of the other mercaptan oxidation processes utilize oxidation reactions which occur in the oil phase. An oil phase reaction is much less desirable because there are many competing oxidation reactions which can occur in the oil phase to leave contaminants in the product. Mercaptide at Interface The purpose of the caustic soda is in two folds: To transfer the thiol portion of the mercaptan to the aqueous phase and To supply the alkaline environment needed for the reaction to proceed in the direction desired. Figure 28 mercaptide at Interface

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ATTACHMENT REPORT 5.4.3 MEROX CATALYSTS The fixed bed Merox process has the Merox catalyst deposited upon the extended hydrophilic surface of specially selected activated charcoal. The function of the activated charcoal is to provide a vast surface area where mercaptans, catalyst, caustic, and oxygen may come into contact for completion of the sweetening reaction. To provide the alkaline medium, the charcoal is kept saturated with caustic solution. The fixed bed process utilizes a type of Merox catalyst that is not dispersible in caustic so as to prevent caustic from removing the catalyst from the charcoal surface. The Minalk version of the fixed bed Merox process utilizes the same catalyst/charcoal reactor bed as other fixed bed Merox processes. A brief description of Merox catalysts and reagents for the Minalk process is given below. MEROX FB (fixed bed) is the catalyst reagent used to impregnate the specially selected activated carbons to form fixed bed Merox catalysts. Merox FB is supplied as dark blue water slurry which is packaged in 9.5 liter (2.5 gallons) sealed polyethylene bottle. Each bottle contains 2.5 kg (5.5 lb) of active ingredient. MEROX FB requires no additional handling or mixing prior to use. It is recommended that the bottle of reagent be well shaken before dispensing to avoid settling and ensure proper addition to the process.

5.5 PROCESS VARIABLES--GASOLINE MEROX


The following represent the five primary process variables: Catalyst Concentration, Oxygen, Alkalinity, Contact and Heat. Each is discussed independent of the other; 1 Catalyst Concentration: At the Minalk Merox unit, catalyst concentration is invariable. The charcoal should be impregnated with 1.4 kg of UOP Merox FB Reagent per cubic foot of charcoal. Over the course or a run, catalyst activity will gradually decline. At a high state of deactivation, a reactivation with additional catalyst is conducted so as to meet product quality specification. 2 Oxygen Injection: The stoichiometric, or theoretical, amount of oxygen necessary is 0.25 pound per pound of mercaptan sulfur. One cubic foot of atmospheric air at standard conditions of temperature and pressure contains about 0.018 pounds of oxygen, implying that 14.2 SCF (standard cubic feet) of air is needed for each pound of mercaptan sulfur to be oxidized (0.84 Nm3 per kilogram). It is necessary to have at least a slight excess of oxygen present but it is always recommended to keep the excess to a minimum within the ranges of 1.2 to 2.0 times the stoichiometric amount needed. It is however better to start initial injection rate at 1.5 times theoretical calculated. For Minalk and other fixed bed units the air injected must be completely dissolved in the hydrocarbon; otherwise a separate air phase will exist within the fixed bed and eventually lead to channeling. Sufficient amount of pressure is needed to dissolve the required air, since the solubility of air is dependent on pressure. 3 Alkalinity: Alkalinity is needed to selectively drive the mercaptan oxidation reaction. The mercaptans encountered in the feed to Minalk units are typically so readily oxidized that very little alkalinity is required. Thus, only sufficient caustic need be injected to maintain the drain effluent from 9-12 pH. About 2-10 wt-ppm of 47

ATTACHMENT REPORT NaOH at caustic concentrations of 3-5 degrees Be (2-3 wt %) is normally sufficient. The present of Thiophenol with Olefins leads to peroxidation to Thioetherhydrope oxide gum, however the presence of caustic helps prevent this peroxidation. Any acids present in the feed lead to caustic neutralization. As caustic is neutralized, it must be replaced in order to maintain acceptable operation.
4 Contact: Contact can be characterized by duration of mixing time, by volumetric

ratio of reactants, or by differential pressure, which implies degree of dispersion. With a fixed bed flow restriction, the differential pressure is directly related to the linear velocity so that velocity is often taken to be the process variable. The primary source of contact is a fixed bed unit is the charcoal bed itself. The porous structure of the charcoal provides vast interfacial surface area necessary for contact between gasoline, caustic, and catalyst. The variable used to characterize contact is residence time in the charcoal bed; and is often expressed in terms of volume of feed per hour, per volume of catalyst bed. The amount of mercaptan is also dependent on the residence time, as shown below Figure 29 Mercaptan Concentrations against Residence Time

5 Heat (Temperature): Minalk fixed bed sweetening is favored by higher

temperature. Increasing the Gasoline feed temperature increases the rate of mercaptan conversion. However, increasing the temperature will also enhance other oxidation reactions, which may be undesirable because of color deterioration, gum precursor formation, and premature catalyst deactivation. Therefore, the feed temperature should be kept as low as possible while still maintaining the desired degree of mercaptan conversion; normally this is in the range of 38o to 50o.

5.6 PROCESS FLOW AND CONTROL-- GASOLINE MEROX


Air and caustic are injected into the hydrocarbon feed stream, which then enters the Minalk reactor down flow. Sweetened product, essentially free of entrained caustic, is withdrawn 48

ATTACHMENT REPORT directly from the side of the fixed bed near the bottom of the Reactor (15-R-501) .The coalesced aqueous phase collects at the bottom of the vessel and is discharged via a small drain pot to sewer or to the spent caustic disposal system. The charcoal bed is an excellent coalesces. A flow diagram of the Minalk unit is shown below (figure 30). The hydrocarbon feed and process air to the Minalk unit enters on flow control and sweetened product leaves on pressure control. This spent caustic leaves the drain pot on level control. Air is injected into the hydrocarbon stream via an Air Mixer (15-MX-501). This ensures a uniform dissolution of air in the hydrocarbon just before entering the Reactor (15-R-501). The air injection line is provided with a cutoff valve which stops the air flow on low hydrocarbon flow rate. An excessive amount of air injection for a given feed rate can cause the formation of separate air phase at the top of Reactor (15-R-501) which will promote channeling in the catalyst bed. A continuous injection of dilute caustic is required to maintain a minimum level of alkalinity in the Reactor (15-R-501). Caustic is injected through an atomizing nozzle to ensure uniform distribution in the feed.

Figure 30 Fixed Bed Minimum Alkali Merox Sweetening Unit

49

ATTACHMENT REPORT

CHAPTER 6 -- (UNIT 16)


6.1 AMINE TREATMENT UNIT (PROCESS DESCRIPTION) The Amine Treating Unit is designed to remove Hydrogen Sulfide (H2S) and Carbon Dioxide (CO2) from the Sour Fuel Gas Feed stream, through absorption with a 20% wt. Diethanolamine (DEA) solution in the Fuel Gas Absorber. The Sour Fuel Gas Feed contains trace quantities of Sulfur Dioxide (SO2) that is also removed. The Amine Treating Unit also includes a DEA solvent regeneration system, which strips the rich DEA solution of the absorbed H2S and CO2 from the LPG Extraction Unit (LPG- EU) and the Fuel Gas Absorber, and returns the lean solution to the same units. The absorption of H2S and CO2, in the Fuel Gas Absorber with DEA solution, is an exothermic process, and the majority of the heat released is maintained in the rich DEA solution. Therefore, the rich DEA solution from the Fuel Gas Absorber will typically have a 11 C to 22 C higher temperature than the lean DEA solution entering the top of the absorber. The Sour Fuel Gas Feed flows through the Lean Gas Knockout Drum (13-V-304), where entrained liquid are removed, and prior to being routed to the Amine Treating Unit. The Sour Fuel Gas Feed enters the unit at a pressure of 11.5 kg/cm2g, and then flows to the Fuel Gas Absorber (16-C-601), where the H2S and CO2 are removed by absorption with a DEA 50

ATTACHMENT REPORT solution. The Fuel Gas Absorber has two packed sections for contacting the Sour Fuel Gas Feed with the DEA solution and operates at 11.0 kg/cm2g at the top and 11.2 kg/cm2g at the bottom of the column. The solution of lean DEA (Aqueous solution of 20% by weight) at 55 is fed to the top of the Fuel Gas Absorber. The Treated Fuel Gas from the Fuel Gas Absorber flows to the Battery Limits through the Treated Gas KO Drum (16-V-607), where the entrained liquid is removed. The solution of rich DEA exiting the bottom of the absorber flows to the Rich Amine Flash Drum (16-V-601), which operates at 1.0 kg/cm2g. At these conditions, the solution of rich DEA is in two phases (vapor and liquid); the vapor phase constituted by light hydrocarbons is scrubbed using lean DEA solution and then sent to the Acid Gas Flare by means of split range control of pressure with Fuel Gas. On the other hand, the liquid phase constituted by two liquid immiscible (heavy hydrocarbon and solution of rich DEA) is separated by means of internal box in this separator. The hydrocarbon overflows to the internal box by the difference of density and then it is drained to the Slop Oil Header. The Aqueous Amine phase in the right section is extracted by means of level controller of Rich Amine Flash Drum and pumped by the Amine Feed Pumps (16-MP-601A/B) to elevate the pressure from 1.0 to 6.5 kg/cm2g. The rich DEA solution from the Rich Amine Flash Drum is preheated in the Lean/Rich Amine Exchanger (16-E-601A/B), flowing on the tube side to minimize the corrosion problem from a temperature of 59 to 100, before entering the Amine Regenerator(16-C-603), below the packed wash section, which operates at about 1.05 kg/cm2g. The CO2 and H2S are stripped from the rich DEA solution by cascading the rich solution, counter-current to steam produced by the reboiler, over the two randomly packed sections. The maximum operating temperature in the bottom of the Amine Regenerator is limited to 125 to avoid problems of corrosion due to the degradation of amine. The Amine Regenerator also operates at 1.05 kg/cm2g at the top and 1.20 kg/cm2g at the bottom. Stripping vapor is formed in the Amine Reboiler (16-E602) and reboiler heat is supplied from the 3.5 kg/cm2g saturated steam. The water content in the DEA Stripper overhead vapor is partially condensed from the CO2 and H2S. The sour water accumulated in the Reflux Drum (16-V-602) is returned to the DEA Regenerator, as reflux, to the packed wash section at the top of the column. The regenerator overhead vapor is cooled and partially condensed in the Amine Overhead Condenser (16-E-603), where the temperature is reduced to 49. To protect against corrosion of the outlying equipment of the regenerator, a corrosion inhibitor is injected in the vapor line of Amine Overhead Condenser. The mixture of H2S, CO2 and the condensed water flow to the Amine Reflux Drum (16-V-602) operated at 0.9kg/cm2g and 49, where they are separated. The vapor phase constituted by the sour gas is sent to the Sulfur Recovery Unit by pressure control for final sulfur recovery. On the other hand, Make-up water is injected to the Amine Reflux Drum to maintain the amine concentration and to compensate the losses occurring in the different phases of the treatment. The total flow at stripped lean DEA is collected on a chimney tray in the bottom of the Amine Regenerator and sent to the Amine Regenerator Reboiler (16-E-602). Lean DEA solution from the bottom of the DEA Regenerator flows through the Lean/Rich Amine Exchanger and is then pumped in the Lean Amine Pumps (16-MP-603A/B) to the 51

ATTACHMENT REPORT Lean Amine Cooler (16-EA-601). The Lean/Rich Amine Exchanger and the Lean Amine Cooler reduce the hot, lean DEA temperature from 123.9 C to 83.8 C, and then to 55 C. Because of the relatively low flow of lean amine, approximately 25% of the cooled lean DEA solution is filtered in the First Amine Filter (16-FL-601), to remove particulate matter. Then the lean DEA solution is further treated in the Amine Carbon Filter (16-FL-602), which removes degradation products from the DEA solution. Finally, the DEA solution is filtered in the Amine Second Filter (16-FL-603) to remove any of carbon particles that may have entered the solution from the Carbon bed. Finally the cooled, lean, and filtered DEA solution is then routed to the users; (1) the Fuel Gas Absorber (16-C-601), (2) the Rich Amine Flash Column (16-C-602), and (3) the LPG Extraction Unit. 1 Fuel Gas Absorber: Sour Fuel Gas enters from outside battery limits at 11.5 kg/cm2g and 41.0 C from the Lean Gas Knockout Drum (13-V-304) located in the RFCC Unit. The sour Fuel Gas is routed to the Fuel Gas Absorber, 16-C-601, with the quantity of gas being controlled by PIC-604 located on the Lean Gas Knockout Drum outlet. The 800 mm diameter absorber contains two packed beds of random tower packing. The height of the two combined packed beds is sufficient to achieve the desired degree of absorption. Soluble hydrocarbon constituents can cause eventual foaming problems in the absorber. When foaming occurs, the pressure drop across the packed beds will rise and indicate a higher reading on PDI-602, the Pressure Differential Indicator. Normal differential pressure reading on PDI-602 is 0.032 kg/cm2 (320 mmH2O). As the sour gas passes up the tower, H2S and CO2 are absorbed by the 20 wt % DEA solution, as it cascades down through the packed beds. Also, a small amount of light hydrocarbons are absorbed in the solution. The reaction between H2S and CO2 and the DEA solution is exothermic, and the DEA solution increases in temperature as it approaches the bottom of the packed sections. The rich DEA solution temperature increases, limiting the quantity of these acid gas constituents that can be absorbed; therefore, to operate this tower efficiently, the lean solution temperature and rate should be adjusted by FIC-601 and TIC-617 on lean DEA line to achieve the desired degree of removal efficiency. Located in the bottom of the tower is a hydrocarbon skimming pot, which allows the operator to periodically collect and remove any hydrocarbons that may collect and build-up on the surface of the rich DEA solution. The level valve, LV-601 controls the liquid level of the rich solution, in the tower sump section. The pressure of the rich solution is reduced from 11.2 kg/cm2g to 1.00 kg/cm2g across this valve as it enters the Rich Amine Flash Drum, 16-V-601. The pressure of treated gas from the Rich Amine Flash Column, 16-C-602, is regulated by split-range controller, PIC-605. The sweetened Fuel Gas leaving the top of the Fuel Gas Absorber, 16-C-601, may contain some entrained DEA solution during normal operations. 2 Rich Amine Flash Drum: The purpose of the Rich Amine Flash Drum is to provide sufficient residence time so that the dissolved light hydrocarbons can gravity separate from the bulk solution. The flashed gases are scrubbed to recover any H2S and CO2, by absorbing the flashed acid gas constituents in the Rich Amine Flash Column, 16-C-602, and then the treated flash gas is routed to Fuel Gas. The Rich Amine Flash Column is 12 inches in diameter and packed with random tower packing to a height of 52

ATTACHMENT REPORT 1500 mm. The Rich Amine Flash Drum, 16-V-601 is equipped with baffles and weirs, designed to periodically skim off the hydrocarbon layer, collect it, and then drain it to the Slop Oil Drum, 12-V-203. The hydrocarbon skimming compartment in the Rich Amine Flash Drum is equipped with high & low liquid level indicator, LI-602. The flashed and decanted rich DEA solution leaves the Rich Amine Flash Drum and is pumped to the Lean/Rich Amine Exchangers, 16-E-603 A/B to a temperature of around 100 C. The flow of rich DEA solution to the DEA Regenerator is controlled by the flow control valve, FV-604, located at the top and close to the DEA Regenerator inlet nozzle, minimizing the quantity of piping exposed to two-phase flow. The control valve and piping downstream of this valve is stainless steel due to the corrosive and erosive nature of the flashing solution. 3 DEA Regenerator: The flashing, rich, DEA solution enters the DEA Regenerator, 16-C-603, and is distributed over the two packed beds. A specially designed flashingfeed distributor is employed to ensure that proper liquid distribution is achieved. The top section of the DEA Regenerator is clad with stainless steel due to the corrosive nature of the wet H2S and CO2 environment. As the rich DEA solution cascades down through the two packed beds of random packing, H2S and CO2 are stripped from the solution, producing a lean DEA solution. The lean DEA solution is collected on a chimney tray that distributes the solution to the DEA Regenerator Reboiler, 16-E-602. As the lean solution passes through the kettle reboiler, stripping steam is generated and flows up the column, while the lean solution is returned to the sump section in the base of the column. This stripping steam provides the heat to release the absorbed H 2S and CO2 from the rich DEA solution, as it rises up through the packed beds, counter-current to the rich DEA solution. The external heat source for the reboiler is supplied by lowpressure, de-superheated steam, with the rate being controlled by flow control valve FV-606. The DEA Regenerator is equipped with a differential pressure indicator, PDI-609, that allows the operator to view the pressure drop across the total of both packed beds. Normal differential pressure reading on PDI-609 is 0.032 kg/cm2 (320 mmH2O). The lean DEA solution then flows to the shell-side of the Lean/Rich Amine Exchangers, 16E-601 A/B, where it is cooled by exchanging heat to the rich DEA solution. The lean solution is cooled further in the Lean Amine Cooler, 16-EA-601, to a temperature of approximately 55 C. 4 Filtration: A slip-stream of DEA solution of approximately 25% of the main solution flow is routed to the DEA Filter, 16-FL-601, the Amine Carbon Filter, 16-FL602, and the DEA Second Filter, 16-FL-603. The DEA Filter is designed to remove particulates from the DEA solution, normally down to 10 microns in size. After filtration, the slip-stream is routed to the Amine Carbon Filter where soluble amine degradation products, more commonly referred to as Heat Stable Salts (HSS), are removed through adsorption into the carbon active sites. Finally, the slip-stream of DEA solution is filtered in the DEA Second Filter to remove any carbon particles that may have entered the solution from the Amine Carbon Filter.

53

ATTACHMENT REPORT 6 Lean DEA Distribution: The lean DEA solution is split into two separate streams. One stream, of approximately 12214 kg/hr, is routed to the Fuel Gas Absorber. The second steam of lean DEA, of approximately 1077 kg/hr, is routed to the LPG Extraction. This second stream feeds the LPG Liquid-Liquid Contactor. 6.2 DEA MAKE-UP, DRAINAGE AND STORAGE The Amine Treating Unit is equipped with a closed drain and storage system that is comprised of a DEA Sump Drum, 16-V-603, a DEA Sump Pump, 16-MP-605, a DEA Sump Filter, 16-FL-604, a Sump Vent Filter, 16-FL-605, and a Lean DEA Storage Tank, 16-V-604. Under normal situations where instrument level bridles may be periodically drained into the closed drain system, the drained amine solution will collect in the DEA Sump Drum and will be periodically returned back to the operating system. Under abnormal conditions, when a large vessel needs to be drained for inspection, the amine solution will be drained to the DEA Sump Drum and then transferred to the Lean DEA Storage Tank. In either case, the recovered amine solution will be filtered in the DEA Sump Filter before it is routed back to the process or the Lean DEA Storage Tank. The Lean DEA Storage Tank is equipped with Nitrogen blanketing to ensure that oxygen or air does not enter the system and cause amine oxidation. For the initial preparation of the make-up of DEA solution, the Lean DEA Storage Tank will be used to dilute the concentrated DEA solution to a 20 wt% solution. Then the diluted solution will be transferred to the DEA Sump Drum is normally emptied and ready for receiving the drains from the DEA system in the event of Emergency or Normal shutdown.

CHAPTER 7- (UNIT 17)


7.1 SULPHUR RECOVERY UNIT- PROCESS FLOW DESCRIPTION

The flow sequence for the SRU is shown on Process Flow Diagram D-7887-10. The flow sequence for the Incinerator and SO2 Scrubber is shown on Process Flow Diagram D-7887-11. The Amine Acid Gas K.O. Drum (17-V-701) and the SWS Gas K.O. Drum (17-V-702) are designed to remove entrained sour water and condensed hydrocarbons from the amine acid gas and the SWS gas feeds upstream of the Thermal Reactor (17-R701). Normally, there is no sour water flow from the Amine Acid Gas K.O. Drum and SWS Gas K.O. Drum. When enough sour water has accumulated in these drums, the sour water is pumped away by one of the K.O. Drum Pumps (17-MP-701A/B). The SWS gas stream at 90C is fed to the Claus Combustor (17-F-701) located at the front of the Thermal Reactor. At the rear chamber of the Thermal Reactor, amine acid gas at 49oC is fed into it. A small portion of the amine acid gas is combined with the SWS gas feed to the Claus Combustor in some operating cases. This is done to maintain the temperature at or above 1400C in the front chamber of the Thermal Reactor for complete combustion of SWS gas. The remainder of the amine acid gas is fed to the rear chamber of the Thermal Reactor. Hydrocarbons in the acid gas stream are oxidized to CO2 and H2O in the Thermal Reactor front chamber, and CO and H2O in

54

ATTACHMENT REPORT the rear chamber. Thermal Reactor front chamber and the Thermal Reactor rear chamber should be approximately 1449oC and 1416C respectively. When the SWS gas is fed to the Claus Combustor, sufficient air is supplied from one of the Combustion Air Blowers (17-FA-701A/B) to the Thermal Reactor to oxidize all of the hydrogen sulfide in this stream to SO2 and H20, NH3 to N2 and H20 and any hydrocarbons to CO2 and H2O. The total air stream from the Combustion air for the amine acid gas which is added to the combustion air for the SWS gas enters the Claus Combustor at 128C. To ensure the desired H2S/SO2 ratio of 2:1, which ensures the maximum sulfur recovery, the ratio of H2S in the amine acid gas feed to the H2S in the SWS gas feed should not fall below 2:1. The Combustion Air Blowers also supply combustion air to the Incinerator (17-IC-701). Approximately 6% of the H2S in the amine acid gas feed to the rear chamber of the Thermal Reactor directly dissociates to sulfur and hydrogen. In the Thermal Reactor about one-third of the total non-dissociated hydrogen sulfide feed is converted to sulfur dioxide. The desired H2S/SO2 mole ratio of 2:1 is maintained by controlling the amount of combustion air fed to the Claus Combustor. When the SWS gas feed is not available, approximately 80% of the amine acid gas is fed to the Claus Combustor, with the remainder fed to the Thermal Reactor rear chamber. Combustion air oxidizes the desired amount of H2S to SO2 and H2O and hydrocarbons to CO2, CO and H2O.The hot combustion gas from the Thermal Reactor rear chamber passes through a transition section and enters the first two passes of the 6pass Boiler/Sulfur Condenser (17-E-701). The combustion gas is cooled to 285C as it passes through the tube side of these two exchanger passes. The boiling water on the shell side generates low pressure steam (LPS). No sulfur is condensed in the first two passes of the Boiler/Sulfur Condenser. The process gas leaving the Boiler/Sulfur Condenser second pass is cooled from 285C to 163C in the Boiler /Sulfur Condenser third pass, generating LPS. Liquid sulfur condensed in this pass is separated from the gas at the end of the condenser (plenum chamber). The condensed sulfur drains to the Sulfur Pit (17-S-701) through a steam jacketed Sulfur Seal Leg (17-ME-701A). The seal leg maintains a liquid sulfur seal to prevent the process gas from escaping though the Sulfur Seal Leg to the Sulfur Pit. If the system is over pressured, the sulfur will be blown out of the seal leg to allow the pressure to be relieved. The cooled gas from the third pass of the Boiler/Sulfur Condenser flows to the tube side of the Reheat Exchanger #1 (17-E-702).High pressure steam is use as the heat exchange medium for the Reheat Exchanger #1.This Exchanger heats the gas from 163C to 241C. The heated gas flows downward through the first bed of the Catalytic Reactor (17-R-702) where the exothermic Claus reaction of H2S and SO2 occurs over a fixed bed of activated alumina catalyst. The reactor outlet gas, containing newly formed elemental sulfur, leaves the reactor at about 280C and enters the fourth pass of the Boiler/Sulfur Condenser. The gas is cooled to 163C, generating low pressure steam. The condensed sulfur drains to the Sulfur Pit through a separate steam jacketed Sulfur Seal Leg (17-ME-701B). 55

ATTACHMENT REPORT The cooled gas from the fourth pass of the Boiler/Sulfur Condenser flows to the tube side of the Reheat Exchanger #2 (17-E-703). The Reheat Exchanger #2 heats the gas from 163C to 204C using high pressure steam as the heat exchange medium. The heated gas flows downward through the second bed of the Catalytic Reactor where it is heated by the exothermic Claus reaction to 220C. The reactor outlet gas, is routed to the fifth pass of the Boiler/Sulfur Condenser. The gas is cooled to 153C, generating low pressure steam. The condensed sulfur drains to the Sulfur Pit through a separate steam jacketed Sulfur Seal Leg (17-ME-701C). The cooled gas from the fifth pass of the Boiler/Sulfur Condenser flows to the tube side of the Reheat Exchanger #3(17-E-704).High pressure steam is use as the heat exchange medium for the Reheat Exchanger #3.This Exchanger heats the gas from 153C to 188C. The heated gas flows downward through the third bed of the Catalytic Reactor where it is heated by the exothermic Claus reaction to 191C. The reactor outlet gas is routed to the final pass of the Boiler/Sulfur Condenser. The gas is cooled to 149C, generating low pressure steam. The condensed sulfur drains to the Sulfur Pit through a separate steam jacketed Sulfur Seal Leg (17-ME-701D).The condensed sulfur flowing to the Sulfur Pit (17-S-701) from the seal legs contains dissolved and polymerized hydrogen sulfide (H2S and H2SX).A Proprietary Degassing Package (17-PK-701) is used to remove the H2S. Part of the degassing process requires circulation of the sulfur in the pit using both of the Sulfur Degassing Pumps (17-MP-702A/B). Degassed sulfur is transfer from the pit to OSBL by the Sulfur Transfer Pump (17-MP-703). Ambient air is pulled into the pit by ejector (17-J-702) to sweep away gases removed from the sulfur. The ejector uses 3.5 kg/cm2g steam as the motive force. The sweep gas, containing air, hydrogen sulfide, and water, is routed to the Incinerator (17-IC-701). The SRU tail gas leaves the final pass of the Boiler/Sulfur Condenser and is routed to a forced draft Incinerator (17-IC-701). Refinery fuel gas with excess air is combusted in the Incinerator Burner (17-F-702). Sufficient refinery fuel gas is supplied to ensure a complete combustion of the SRU tail gas at 816C. The incinerator effluent passes through the Incinerator Waste Heat Boiler (17-E-705) where it is cooled to 312C while generating medium pressure steam. The cooled gas is vented through the SO2 Scrubber/Stack (17-FS-701) before it is released to the atmosphere. In the SO2 Scrubber/Stack the gas is contacted counter-currently with scrubbing solution for removal of SO2. One of the Scrubbing Solution Recirculation Pumps (17-MP-704A/B) is use to circulate the scrubbing solution. Spent scrubbing solution is sent to OSBL for disposal. Makeup solution is added using the Scrubbing Solution Make-Up Tank (17V-704) and the Scrubbing Solution Makeup Pump (17-MP-705). Caustic and condensate are used to make up the solution. Condensate is also used to maintain the solution level in the scrubber.

56

ATTACHMENT REPORT

CHAPTER 8 (UNIT 18)


8.1 SOUR WATER TREATMENT UNIT - INTRODUCTION The purpose of the Sour Water Treatment Unit is to remove Hydrogen Sulfide (H2S) and Ammonia from a combined sour water stream coming from the RFCCU, and the Amine Treating Unit (ATU). Sour water stripping is similar in operation to the stripping methods described in that it can be viewed as an equilibrium stage operation. The rate of mass transfer of a particular species in the water is proportional to the difference between the equilibrium partial pressure of the species and its partial pressure in the bulk gas. For most situations the equilibrium predictions for NH 3 and H2S, although they strongly interact with one another, can be handled according to the methods and data of Van Krevelin et.al. This procedure assumes that the NH3 and H2S are present in the aqueous solution as ammonium hydrosulfide (NH4SH) which is the salt of a weak acid (H2S) and a weak base (NH4SH). This salt hydrolyzes in water form free NH3 and H2S which then exert a partial pressure and can be stripped. The aqueous phase equilibrium can be represented by NH4 + SH H2S + NH3 57

ATTACHMENT REPORT Increasing the temperature shifts the system equilibrium toward the formation of mere free H2S and NH3 and thereby makes it easier to strip out these gases. H2S is much less soluble in water than NH3 and, therefore, is more readily stripped. To efficiently remove about 90% of NH3, temperature of 110oCor higher (at near atmospheric pressure) is required. For the equilibrium represented be the above equation the tray-by-tray calculations are straightforward, and the pH of the stripped water is related to the residual free H2S and NH3 concentrations. However, when acidic components such as CO2 or CN- which have greater ionization constants than H2S are present, the acidic component replaces the SH- in the above equation and thereby fixes the NH3 in solution hydrolysis is small, and only the H2S is released from the solution. Thus, the H2S removal is higher than predicted and the NH3 removal is lower than predicted. The stripped water will have a residual NH3 concentration even with a high stripping gas rate and a large number of stages. The free H2S is much less soluble in water than is NH3 and therefore NH3 is more readily stripped out; The NH3 becomes the controlling design component and if an acceptable degree of NH3 removal is accomplished, a satisfactory removal of H2S must follow.

8.1.1 PROCESS DESCRIPTION The Sour Water Treatment Unit is designed to remove H2S and NH3 from approximately 12.5m3/hr of sour water to levels of 10 ppm H2S and 50 ppm NH3 by weight, respectively, using steam reboiler. The two refinery source is received at the Sour Water Treatment Unit in the Sour Water Flash Drum (18-V-802). The Sour Water Flash Drum is divided into three sections separated by baffles and weirs. Sour water enters the middle section of the drum where any hydrocarbon liquid present in the sour water forms a layer on top of the sour water in the middle section. Pressure in the Sour Water Flash Drum is maintained at 0.5 kg/cm2g, using pressure controller PIC-803. The split range controller manipulates valves PV-803A and PV-803B, controlling the pressure in the drum by either venting vapors to the Flare, or bringing in Fuel Gas to maintain the pressure. Control valve PV803B opens to vent gas from the flash drum to the Acid Gas Flare if the flash drum pressure is above the set-point pressure. Control valve PV-803A opens to bring in Fuel Gas, if the flash drum pressure falls below the set-point pressure. Sour water entering the drums is reduced in pressure to flash off light hydrocarbons, which are sent to flare. The Hydrocarbons that do separate from the sour water as a liquid form a layer and are skimmed over a weir into the hydrocarbon section of the drum. Skimmed hydrocarbon is drained to the Slop Oil Drum (12-V-203) using the pressure in the Sour Water Flash Drum as the motive force. Skimmed hydrocarbon is drained to the Slop Oil Drum (12-V-203) using the pressure in the Sour Water Flash Drum as the motive force. On the opposite end of the drum from 58

ATTACHMENT REPORT the hydrocarbon section, the hydrocarbon free sour water passes under a baffle then over a weir into the sour water collection section. The Sour water, essentially free of oil, is sent to the Sour Water Storage Tank 18-V-805, which can store sour water for 2 days at an ambient temperature and pressure. In this tank any dissolved gases are flashed, and any oil, which was not skimmed in the Sour Water Flash Drum, 18-V-802, and solids, are separated from the water. This cone roof type tank is blanketed using nitrogen to prevent any hydrocarbons from contacting air in order to prevent a possible hazard like auto combustion. Sour water from the Sour Water Storage Tank is pumped through the tube side of Feed/Stripper Bottoms Exchangers (18-E-801 A/B) and into the Sour Water Stripper (18-C-801) using the Sour Water Feed Pumps (18-MP-801 A/B). The feed/bottoms exchangers use stripper bottoms to heat sour water from 28.2oC to 99.7oC before it enters the Sour Water Stripper. The feed rate to the stripper is set based on unit requirements, and is controlled using flow controller FIC-801. Sour water enters the strippers at the top of the packed sections and travels down the strippers through three (3) packed beds to the sump section of the stripper. Heat is supplied to the stripper by low-pressure steam reboiler. The vaporized water rises through the tower, stripping H2S and NH3 from sour water by contacting it in the three packed sections. The H2S/NH3 rich vapor stream leaves the stripping section and is cooled and partially condensed to 90 oC in the Sour Water Stripper Overhead Cooler (18-EA-801) where excess water from the overhead vapor is condensed. The two-phase mixture is then routed to the Sour Water Stripper Reflux Drum (18-V-801) where the ammonia bearing Sour Water Stripper Acid Gas is separated from the condensed sour water reflux. The reflux water is pumped using the Sour Water Stripper Reflux Pumps (18-MP-803 A/B) and routed back to the top of the Sour Water Stripper and mixed with the incoming sour water feed stream. The flow of the Sour Water Stripper Acid Gas leaving the Sour Water Stripper Reflux Drum is controlled by pressure controller PIC-817, which is set to maintain a stripper overhead pressure of 0.90 kg/cm2g. The flare line from the Sour Water Stripper Reflux Drum to the flare tip is maintained above the ammonium hydrosulfide (NH4SH) salt formation temperature. This entire line segment is insulated to maintain a temperature of no less than 85 oC. Failure to do so can cause the line to become blocked with ammonium bearing salts. The flow of stripped water leaving the bottom of the stripper is controlled by level controller LIC-805. Stripped water exits the bottom of the stripper at approximately 130 C and is cooled to approximately 58 C on the shell side of the Feed/Stripper Bottom Exchanger (18-E-801 A/B). The semi-cooled stripper bottoms is then pumped by the Stripped Water Pumps (18-MP-802 A/B) to the Stripped Water Cooler (18-E-802), where it is cooled to a temperature of approximately 38 C before being routed to the Waste Water Treatment Unit. Sour water enters the strippers at the top of the packed sections and travels down the strippers through three (3) packed beds to the sump section of the stripper. Heat is supplied to the stripper by low-pressure steam reboiler. The vaporized water rises through the tower, stripping H2S and NH3 from sour water by contacting it in the three packed sections. The 59

ATTACHMENT REPORT H2S/NH3 rich vapor Stream leaves the stripping section and is cooled and partially condensed to 90 oC in the Sour Water Stripper Overhead Cooler (18-EA-801) where excess water from the overhead vapor is condensed. The two-phase mixture is then routed to the Sour Water Stripper Reflux Drum (18-V-801) where the ammonia bearing Sour Water Stripper Acid Gas is separated from the condensed sour water reflux. The reflux water is pumped using the Sour Water Stripper Reflux Pumps (18-MP-803 A/B) and routed back to the top of the Sour Water Stripper and mixed with the incoming sour water feed stream. The flow of the Sour Water Stripper Acid Gas leaving the Sour Water Stripper Reflux Drum is controlled by pressure controller PIC-817, which is set to maintain a stripper overhead pressure of 0.90 kg/cm2g. PIC-817 is a split-range controller that controls valves PV-817A and PV-817B. During normal operation PV-817A is open and the sour gas is sent to the Sulfur Recovery Unit. However, when the Sulfur Recovery Unit shuts down, or if the downstream pressure begins to rise above the set-point pressure, the pressure controller senses an increase in system pressure and opens PV-817B, directing the sour gas stream to a dedicated Acid Gas Flare to maintain system pressure. The flare line from the Sour Water Stripper Reflux Drum to the flare tip MUST be maintained above the ammonium hydrosulfide (NH4SH) salt formation temperature. This entire line segment is traced and insulated to maintain a temperature of no less than 85oC. If the line is not traced it is probable that the line will become blocked with ammonium bearing salts. The flow of stripped water leaving the bottom of the stripper is controlled by level controller LIC-805. Stripped water exits the bottom of the stripper at approximately 130 C and is cooled to approximately 58 C on the shell side of the Feed/Stripper Bottom Exchanger (18-E-801 A/B). The semi-cooled stripper bottoms is then pumped by the Stripped Water Pumps (18-MP-802 A/B) to the Stripped Water Cooler (18-E-802), where it is cooled to a temperature of approximately 38 C before being routed to the Waste Water Treatment Unit.

Sour water from two

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