CHAPTER 5

DIESEL HYDROTREATING UNIT (DHDT)

5.1 Introduction The objective of the diesel hydro-treating (DHDT) unit is to treat and upgrade the existing quality of HSD to meet the EURO III & EURO IV equivalent specification and also to produce SKO/ATF in a blocked out operation. DHDT has been designed to operate Diesel mode and Kero mode to produce diesel with Cetane No. 52 and to improve smoke point of kerosene (ATF) to 21 mm. Diesel Hydrotreating is a catalytic refining process employing a selected catalyst and a Hydrogen rich gas to decompose organic sulphur, oxygen and nitrogen compound contained in hydrocarbon fractions. In addition, hydro-treating removes organo-metallic compounds and saturates olefinic and aromatic compounds. The catalyst employed has alumina base impregnated with cobalt or nickel and molybdenum. Volumetric recoveries of products depend on the sulphur and olefinic contents. The products from this unit are Hydro-treated diesel with sulphur content matching with the Euro IV norms, Hydro-treated ATF and stabilized Naphtha which is the feed for the Hydrogen Generation Unit (HGU). 5.2 FEED SPECIFICATION: (FROM ASSAM CRUDE) Basically, two cases of feed are taken in this unit; one from ASSAM CRUDE and the other from the mixture of ASSAM CRUDE and BONNY LIGHT CRUDE. Here the specifications of the feed from ASSAM CRUDE are only tabulated: SR NO TESTS SR KERO-I SR KERO-II SR GAS OIL 1 Total Sulphur(Wt%) 2 Total nitrogen (Wt%) 3 Polyaromatics 61.6 59.4 57.9 76.6 4 15 163 128 0.05 0.10 0.24 COKER KERO 0.16

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(Wt%) 4 5 6 7 8 Monoaromatics Diaromatics PAH Cetane No. Density @ 15C 9 10 11 Flash Pt (C) Pour Pt (C) Distillation ASTM D 86C IBP FBP 168 256 196 290 224 387 128 269 50.8 <0 64.0 <0 79 15 27.3 <0 25.4 12.9 0.1 37.0 0.8454 22 18.3 0.3 38.0 0.8697 20.2 18.3 3.6 41 0.8888 18 4.6 0.8 37 0.8054

5.3 PRODUCT SPECIFICATIONS HYDROTREATED DIESEL : SERIAL NO 1 2 3 4 5 6 7 Parameters Density @15C Cetane No. (CN) Cetane Index (CR) Water Content (ppmw) max Total S content (ppmw) max Colour D-86 Distillation (C) IBP FBP 142 365.7 HSD-SOR 834.3 52 48.3 200 40 Not worse than feed

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STABILIZED NAPHTHA: SERIAL NO 1 2 3 4 5 Parameters Density @15C (Kg/m3) Total S content (ppmw) max C:H ratio (w/w) max Olefins (vol%) max D-86 Distillation IBP (C) FBP (C) 6 RVP @37.8C Kg/cm, max 47 176.1 0.15 Start of Run 744.3 5 5.5 0.5

5.4 EQUIPMENTS MENTIONED IN THE PROCESS DESCRIPTION A) Reactors Design pressure 1) 1st Reactor 2) 2nd Reactor B) Columns 1) 2) 3) Stripper Column Naphtha Stabilizer Column Sour FG Absorber Column 145 Kg/cm2 139 Kg/cm2 design temperature 425C 450C

C) Vessels 1) 2) 3) 4) 5) 6) 7) 8) Feed Surge Drum Wash Water Drum High Pressure Separator Flash Drum (LP Separator) Recycle Gas Suction KOD Stabilizer Reflux Drum Stripper Reflux Drum Sour FG KOD

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D) Compressors 1) Recycle Gas Compressor Type: Centrifugal, Single Stage and Steam Turbine Driven Suction pressure: 105.5 Kg/cm2 2) Make-up Gas Compressor Type: Reciprocating, Three Stage and Motor Driven Suction pressure: 21.2 Kg/cm2 E) Safety valves and control valves F) Feed pump G) Heat exchangers Sl no. 1 2 3 4 5 6 7 8 9 10 11 12 Shell feed H/C Feed Recycle gas Recycle gas H/C Feed H/C Feed Stripper feed Stripper feed Hydro-treated Diesel Stripper O/H Stabilizer feed Stabilized Naphtha Stabilizer O/H Tube feed 2nd Reactor effluent 2nd Reactor effluent 2nd Reactor effluent 2nd Reactor effluent 2nd Reactor effluent Stripper bottom 2nd reactor effluent Cooling water Cooling water Stabilizer bottom Cooling water Cooling water Discharge pressure: 132 Kg/cm2 Discharge pressure: 132 Kg/cm2

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5.5 PROCESS DESCRIPTION The following process is described for the Diesel operating mode as the Kero mode was not implemented presently. 5.5.1 Feed section: Cold blend of straight run feed streams (SRGO + KERO-I + KERO-II) from the CDU and CK from DCU in the ratio 81:19 are taken through the battery limit as feed for this unit. The combined feed is routed to the feed surge drum through an Auto Backwash Filter to remove any over rust and polymeric components of size more than 25m followed by a feed water coalescer for water removal. The pressure in the feed surge drum is maintained by nitrogen blanketing. After proper mixing in the feed surge drum, it is pumped by the centrifugal feed pump to the feed preheat train. 5.5.2 Preheat train and the furnace: The feed is preheated in the shell side of three feed/reactor effluent heat exchangers, reactor effluents being on the tube side. The feed temperature changes from 40C in the surge drum to 340C after preheating. The feed at this point is mixed with recycle gas (discussed later) including the make-up H2 (99.9% pure obtained from HGU) coming from the recycle gas compressor and make-up H2 compressor respectively. Before mixing with the feed, the gases themselves are preheated through the shell side of two recycle gas/ reactor effluent heat exchangers, reactor effluent being on the tube side. The combined preheated feed would now enter the furnace. In the furnace, this is brought to the temperature suitable for the hydrotreating reactions to occur in the reactor, in two pass feed heaters. The furnace is a forced draft type; bottom fired and has 6 Fuel Gas burners. The outlet temperature of the feed from the outlet of the furnace is about 380C. The feed is now ready to enter the reactors. 5.5.3 Reactor section: The reactor section is the most important section of this unit. The feed enters the top of the first reactor at a temperature of 380C. There are two reactors in the unit, the first having three catalyst beds and the second having two. The first bed of the first reactor has five different catalytic regions; this bed is known as the catalyst Guard Bed. The second

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and third beds in the first reactor and the two beds in the second reactor are of same type catalyst. Basically, five types of catalysts are used in these reactors. They are: 1) IE-1: it is a large void inert top bed material commonly used in the Guarded reactor bed. It provides better flow distribution throughout the reactor and increase void for large particle accumulation. 2) IE-2: Iron Guard Bed and particulate capturing Guard Bed. The higher void fraction of this guard bed provides a large reservoir for iron, coke fines and scale. Te catalytic activity of this catalyst slows the rate of coking and fouling and hence it protects the main catalyst bed and extends overall catalyst life. 3) IE-3: Guard Bed catalyst meant for removal gum and polymeric material when feedstock contains cracked components. 4) IE-4: low active Ni/Mo catalyst having hydrogenation and silica removal function. Silica is generally found in coker streams and is a permanent poison for the catalyst. 5) IE-5: It is the main hydrotreating catalyst. It is a highly active Ni/Mo catalyst best suitable for hydrotreating olefin free feedstock. It primarily handles

Hydrodesulphurisation, Hydrodenitrification and aromatic saturation. Some amount of hydrogenolysis and hydrocracking also occurs during normal reaction.

Fig 5.1: arrangements of the catalyst beds in the two reactors

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Hydrotreating reactions start from the last division of the first bed of the first reactor itself and continue till the last bed of the second reactor in stages. All the unwanted impurities gets separated in the first four divisions of the first bed of the first reactor. Cold quenches of H2 are being injected in the inter-bed sections of the reactors as shown in the figure to limit the temperature increases in the reactor. The four main Hydrotreating reactions taking place in the reactor catalyst beds are: 1) Olefin saturation 2) Hydrodesulphurisation 3) Hydrodenitrogenation 4) Aromatics saturation The reactor effluent outlet temperature is around 397C. It is then cooled in the tube side of a series of heat exchanger train of 6 exchangers; 3 being feed/reactor effluent exchangers, 2 being recycle gas/reactor effluent exchangers and 1 being stripper feed/reactor effluent exchanger. Until this point, the temperature drops to around 170C. It is now further cooled in the Reactor Effluent Air Condenser before being finally routed to the High Pressure Separator vessel. To avoid ammonium salt deposits and the risk of corrosion, wash water from the Wash Water Drum is injected at the inlet of the reactor effluent condenser. The wash water is a mixture of recycled non- phenolic water from the sour water stripper and make-up chemically free BFW. 5.5.4 HP Separator and Flash Drum section: The effluent enters the HP Separator at a temperature of 45C and 106 Kg/cm 2 pressure. The separator is designed for a 3-phase separation of gas, hydrocarbon liquid and free water. Water separation takes place in the boot leg of the HP vessel. The overhead gases are sent to the recycle gas suction KOD (knock out drum) to separate out the entrained liquid particles from the gas. The overhead gas from the KOD is the recycle gas which is compressed in the recycle gas compressor and is further mixed with make-up H2 coming from the make-up H2 compressor. This resultant gas is partly used for quenching in the reactor inter-bed section (discussed earlier) and partly mixed with the initial feed before the feed mixture enters the furnace (discussed earlier). As the feed sulphur is low the H2S in this recycle gas is less than 1 mol% and does not require an Amine Absorber for H2S removal for reaching the final product specifications. The hydrocarbon effluent from below the HP Separator is flashed in the flash-drum (also called the LP Separator) under a reduced pressure

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of 20 Kg/cm2. This vast difference in pressure from the HP Separator to the LP Separator is utilised to drive the main feed pump (mentioned earlier). In the Flash Drum there is further 3phase separation of gas, hydrocarbon liquid and free water. The overhead vapours are routed to the stripper overhead. The water is separated in the boot and the hydrocarbon effluent after passing through the shell side of two heat exchangers and gaining heat enter the stripper at 290C. The two exchangers being stripper feed/bottom exchanger and stripper feed/reactor effluent exchanger. 5.5.5 Stripper section: The hydrocarbon effluent enters the stripper at 290C. In the stripper hydrogen sulphide is being stripped off from the reactor products using Medium Pressure Steam. The stripper overhead products are condensed in the stripper overhead condenser followed by the stripper overhead trim condenser. The overhead condenser minimizes the losses of C3, C4 and C5 products to the fuel gas system. The trim condenser outlet is routed to strip reflux drum. The off gas from the reflux drum is routed to the Sour Fuel Gas Amine Absorber along with the stabilizer off gas (discussed later) and the flash drum off gas. The condensed overhead liquid is partly refluxed back to the stripper and the balance routed to the Naphtha Stabilizer for stabilization on flow control cascaded with level in the stripper reflux drum. The bottom product from the stripper comes out at a temperature of 247C is pumped to the tube side of stripper feed/bottom heat exchanger followed product air-cooler and then finally cooled in product cooler using cooling water before being routed to storage. The temperature now is reduced to 40C. this product is Hydro-treated Diesel or Hydro-treated Kero based on the operating mode. The Hydro-treated Diesel is routed to storage through a coalescer. 5.5.6 Naphtha stabilizer section: The unstabilised naphtha from the stripper reflux drum is routed through shell side of a stabilizer feed/bottom exchanger to the Stabilizer for stabilization. The stabilizer overheads are condensed in the stabilized overhead condenser and routed to the stabilizer reflux drum. Corrosion inhibitor diluted in stabilized naphtha is injected into the overheads to prevent corrosion in the overhead system. The condensed liquid hydrocarbon, water and gas are separated in the reflux drum. Water is removed from the boot and is sent to the Sour Water Stripping unit to make it free from sulphur. The stabilizer gas is routed along with the Stripper and Flash Drum off gas to the Sour Gas Amine Absorption Unit (AAU). The bottom product from the Stabilizer is pumped to the tube side of Stabilizer feed/bottom exchanger

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and then cooled in the cooling water exchanger before being routed to the Naphtha storage or as the feed for the HGU. 5.5.7 Sour Gas Amine Absorption section: The sour gases generated in the unit to an Amine Absorber column where the H2S, COS, CO2 and mercaptans are absorbed in lean MDEA (Methyldiethanolamine). The rich MDEA (amine + H2S) is now routed to the Amine Regeneration Unit (ARU) for the recovery of the lean amine. This lean Amine is circulated again to the AAU. Sweet Fuel Gas (sulphur free) is routed to the DHDT fuel gas system for distribution through a sweet Fuel Gas filter separator to knock out carry over amine.

Sour gas from the unit Fresh Amine (MDEA)

to DHDT FG system

AAU ARU

Sweet fuel gas

Rich amine (Amine + H2S)

KOD

Fig.5.2: block diagram of Amine Absorption and Amine Regeneration Units.