1.

CHAPTER-1 INTRODUCTION

1.1

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

1.2

INTRODUCTION OF THE UNIT To meet the regulatory norms, Diesel Hydro Desulfurization (DHDS) unit at Gujarat Refinery was installed and commissioned in the year 1999 with a aim to produce low sulfur diesel of 500 PPMW from a blend consisting of SR LGO, SR HGO, SR GO and LCO having S level of 1.46% w/w. Other features of the unit are as under:* * * * * * * * * UNIT COMMISSIONING DATE PURPOSE OF THE UNIT PROCESS LICENSOR PROJECT CONSULTANT PLANT CAPACITY UNIT TURN DOWN RATIO FEED RATE (BASED ON 100% CAP.) ON STREAM FACTOR FEED TANK 12.06.1999 To produce Low Sulfur Diesel of < 500ppmw M/s UOP, USA M/s DELIM 1.44 MMTPA 50% of the design capacity 208 M3/HR 8000 HRS/YEAR 1. TK-823 2. TK-824 Both Feed Tanks are located at FCC Offsites. 1. SRLGO 3. LCO 2. SRHGO 4. SRGO

FEED STREAMS TO FEED TANK

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

When DHDS unit was run at 245 M3/Hr, heavy vibrations were observed in feed inlet to reactor lines and reactor effluent lines. These Vibrations in were studied by Inspection / E/S department together with UOP personnels. As per the joint guidelines of UOP personnels/Inspection and E/S department U-tube bundle of 1010E-02A/B/C/D and 1010E04A/B/C/D/E/F were changed in JAN-2005 shut down with new ones having new baffle arrangements to reduce the vibrations in both CFE trains I/L and O/L lines. Again vibration survey were carried out in the H.P. section by Inspection / E/S department together with UOP personnels. New baffle arrangement has reduced the vibrations to quite some extent but could not eliminate the vibrations. As per their joint recommendations, additional structural support has provided in the tube side O/L line of 1010E-02A/B/C/D and tube side inlet line of 1010EA-01AH in JULY-2005 shut down. After that vibrations in feed inlet to reactor lines and reactor effluent lines reduces to minimum.
In AUG-2008 Catalyst turnaround, Both DHDS Reactors existing catalyst from Criterion Catalyst was replaced with ART catalyst for the First cycle length. Catalyst selected is capable of producing 150 PPMW product sulfur from feed diesel having 1.8% w/w S and achieve First cycle length of THREE years. Also It was decided after AUG-2008 shut down to run the unit with higher capacity of 1.78 MMTPA (corresponding Feed Rate 260 m3/HR) with the target product S < 150 PPMW.

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CHAPTER-2 BASIC REACTION CHEMISTRY OF HYDROTREATING

2.1 Basics of Hydrotreating Hydrotreating of diesel stream from various units is mainly done to meet the stringent diesel fuel specification in force from time to time. The hydrotreating of any hydrocarbon stream is done to achieve following objectives * * * * * * * Sulfur removal Nitrogen removal Aromatic saturation Olefin saturation Metals removal CCR/RCR removal Cracking

The diesel boiling range hydrotreatment is mainly done to achieve the sulfur and aromatic specification. For VGO and heavier fraction hydrotreatment in addition to S, N and aromatic saturation, metals removal , CCR reduction becomes important. Some cracking is also achieved (though not desirable some times due to product yield loss) due to operating severity and feed quality. We will briefly describe some of the basic reactions for some of the above reactions. 2.2 Sulfur Removal Sulfur is found in various molecular forms in hydrocarbon stream. H2S is the main by product due to desulfurization of the hydrocarbon stream. HDS reaction produces moderate heat release and consumes approximately (20 Nm3/m3of feed ) of hydrogen for 1 % wt sulfur removal from feed. Some of the basic sulfur compound reactions are described below Mercaptan : RSH + H2 --------> H + H2S Sulfides: RSR' + H2 --------> RSH + R'H RSR' + 2H2 --------> RH + R'H + H2S Thiophene:

OR

4C4H4S + 12 H2 ------> C4H9SH + C4H6 + C4H8 + C4H10 + 3H2S C4H9SH + C4H6 + C4H8 + C4H10 + 3H2S + 4H2 ------> 4C4H10 + 4H2S C4H4S + 2H2------> C4H8S + H2 -----> C4H9SH + H2 ------> C4H10 + H2S

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2.3

Nitrogen Removal Nitrogen is found in many forms in hydrocarbon molecules. Nitrogen is generally present in unsaturated molecules. Cracked streams contain more unsaturated molecules and hence contain higher nitrogen compounds. Coker and FCC diesel fractions have higher level of nitrogen than SR diesel fraction. HDN reaction is irreversible reaction and by product NH3. HDN produces moderate heat release like the HDS reactions. Typical hydrogen consumption for HDN reaction is approximately 0.7 Nm3/m3 of feed per 100 PPM nitrogen removed. Some of the HDN reactions are Cyanides Amines Pyrrole HCN + 3H2 RNH2 + H2 C4HSN + 2 H2 C4H9N + H2 C4H9NH2 + H2 CH4 + NH3 RH + NH3 C4H9N C4H9NH2 C4H10 + NH3

2.4

Olefin saturation Olefins saturate rapidly and completely. Only traces of olefins are usually present in straight run fractions. Cracked streams from coker and FCC units contains higher levels of olefins. Olefin saturation is highly exothermic reaction. Biggest contributor to heat release. Higher hydrogen partial pressure and lower temperature favour formation of saturate compounds. No by-product generation due to olefin saturation. Typical hydrogen consumption for olefin saturation reaction is 1.5 Nm3/m3 of feed per 1 wt % olefins. Some of the olefin saturation reaction is given below RCH=CH2 + H2 RCH=CHCH=CH2 + H2 Cycloolefins + H2 RCH2CH3 R(CH2)3CH3 Cycloparaffins

2.5

Aromatic Saturation Aromatic saturation contributes significantly to hydrogen consumption and heat release. Aromatic saturation depends on many factors like the type of aromatic in feed, operating pressure, LHSV and temperature. Aromatic saturation is limited by equilibrium. Cracked streams from FCC and Coker units has more potential for aromatic saturation than straight run diesel fraction. LCO and other cracked streams contain more of the poly aromatic which is easier to saturate under normal hydrotreating conditions. It will be difficult to saturate the mono aromatics in the feed.

2.3
Aromatic saturation is favored by high hydrogen partial pressure and lower operating temperature. Aromatic saturation helps in lowering the product density and improving the Cetane number of the product. Typical hydrogen consumption for aromatic saturation is 27 Nm3/m3 of feed per each one percent reduction in aromatic content. No by-products generated due to these reaction. The CCR removal and cracking are not major reactions associated with diesel fraction hydrotreatment at moderate pressure. These reactions will be critical for high severity operation while treating VGO and heavier fraction.

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CHAPTER-3 BRIEF PROCESS DESCRIPTION

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

3.1

FEED SECTION
In this section, Sour Diesel is received from storage tank in to a surge vessel V-01, after passing through feed filter G-01A/B. The purpose of both equipments are as under:1010G-01A/B:- It removes the foreign particles that comes along with

feed. 1010 V-01:01A/B. (b) It provides sufficient NPSH to the feed pump. (c) It removes water coming with feed. The water gets collected in the boot. (a) It provides sufficient surge volume to the feed pump P-

3.2

REACTOR SECTION
Feed from feed pump P-01A/B splits in to two identical exchanger trains and combined with Recycle gas (from discharge of RGC 1010K-01A/B). Combined feed gets preheated in the shell side of CFE trains (Train 1st contains 1010E-04A/B/C and 1010E-02A/B and Train 2nd contains 1010E04D/E/F and 1010E-02A/B) and F-01 coils up to the required reaction temp. and then entered in to two identical reactors R-01 and R-02, installed in series. Desulphurisation reaction takes place as the stream passes through across the reactors catalyst bed. As the desulphurisation reaction is an exothermic reaction in nature, so an increase in temp. profile down through the reactor bed shows that the desulphurisation reaction is going on. Provision of Quench with Recycle gas is given in the 2nd bed I/L of R-01 and 1st bed of R-02 for controlling the reactor bed I/L temps.

2.5

The recycle gas compressor discharge line was modified and a spill back control valve was given from discharge of RGC to 1010EA-01 A---H I/L, in order to control the recycle & quench flow and recycle compressor discharge pressure. The modification scheme of RGC spill Back control system was commissioned on 27.10.2007, & immediately after commissioning this scheme DHDS T,put was increased from 245 M3/Hr to 255 M3/Hr, on 29.10.2007. Reactor effluent is cooled in the tube side of 1010E-02A/B/C/D, 1010E-05, 1010E-04 A---F, 1010EA-01A---H and then gets collected in HP Separator Vessel 1010V02. Wash water is injected to dissolve the H2S formed during the reaction and to prevent the precipitation of salts inside the tubes of 1010EA-01AH and 1010E-04A--F, which is formed during the reactions. These salts gets dissolved in wash water, which is collected in to 1010V-02 boot as sour water, and then sent to SRU for stripping.

3.3

SEPARATOR /COMPRESSOR SECTION

The Recycle gas (containing unutilized H2 gas and H2S formed during reaction) gets separated in 1010V-02 and cooled in recycle gas water cooler 1010E-07. The purpose of the recycle gas cooler is to decrease the dew point of the recycles gas and condense any H.C. which may cause foaming of amine, during amine treatment of recycle gas, resulting loss of operation of Recycle gas scrubber 1010C-01. H2S from Recycle gas gets absorb in Lean Amine (received from SRU & fed to C-01 via P07A/B). This H2S rich amine (called Rich Amine) routed to SRU from bottom of the column. 20% level of D.M. water is maintained and start circulation of water in the chimney tray of C-01 by running 1010PA02A/B, to remove the traces of amine that may have entrained in the RG leaving the amine column. This rich amine containing water is drained in to ABD through the new drain line of 1010PA-02A/B to ABD, when the chimney tray level increases up to 80%, and then again take fresh water in chimney tray up to 20% for circulation. H2S free, Recycle gas from the top of the column goes to the suction of the Recycle gas compressor after combining with make up gas (i.e pure H2 gas from H2UII/H2U-I) from Make Up gas compressor 1010K-02A/B, via RGC suction KOD. The purpose of make up gas compressor, is to supply H2 which is required for the reaction, to the suction of RGC.

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3.4

STRIPPER SECTION
The purpose of this section is to remove the dissolved H2S from the Diesel along with removal of low boiling H.C. in the form of Wild Naphtha and volatile H.C. in the form of FG. Liquid H.C. from HP separator and Slop oil after getting heated in 1010E-602 mixes in the downstream of 1010LC-3501 and , gets heated in the shell side of 1010E-03A/B and 1010E-05A/B up to 215240 degree centigrade and entered in to the stripper column 1010C02. MP steam is used as stripping steam. By adjusting the operating parameters of column, required flash point of Diesel can be achieved.

By increasing column I/L temperature, reducing column top pressure and increasing the flow of stripping steam, FLASH POINT CAN BE INCREASED, but WILD NAPHTHA generation will also be increased. By reducing the column top temperature, Wild Naphtha generation can be decreased.

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

(B) STRIPPER COLUMN BOTTOM SECTION

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

In winter seasion (Nov-Feb), in order to maintain sweet diesel pour point between 0-3 deg.C, PPD solution doping should be started by lining up & starting the 1010P-11C/D. The doping rate should be adjusted on the basis of guidelines provided by the T/S department from time to time. The PPD doping facility was successfully commissioned in August2004.