DHDS BLOCK Operations

Soumen Mondal

18th Jan2012
1

In a Complex Refinery with Separation Process and Secondary Conversion Processes..

3/19/2013

2 2

HALDIA REFINERY -PRODUCTS

LPG (Propane/Butane) GASOLINE (hundreds of blends) JET FUELS DIESEL FUELS HEATING OILS LUBRICATING OILS ASPHALTS COKE (not the kind you drink )

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HALDIA REFINERY PRODUCT RANGE

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HALDIA REFINERY PRODUCT YIELDS PATTARNS

NAPHTHA 9% HSD 37%

FO/LSHS 11%

OTHERS 12% MS 9% LPG 4% FUEL & LOSS 7%

ATF / SKO 11%

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HALDIA REFINERY - PRODUCT PRICE Product price, Rs/MT Product price, Rs/MT LPG 29294 FO 20900 SRN 29265 CBFS 19483 MS(BS-II) 33412 Bitumen 16300 ATF 34514 SK 31650 HSD(BS-II) 32353 LOBS(500N) 31551 Crude: 20300 - 27300

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Product Quality
Product LPG Test Weathering Cu Corrosion Naphtha(HPL) Density Distillation Paraffins MS(Euro-III) RON Sulphur Benzene Specification (+) 2 deg C 1a 0.67 0.71 35 160 deg C 75% by Vol. 91.0 Min. 150 ppm. Max. 1% max.

Product Quality
Product MS(Euro-IV) Test RON Sulphur Benzene ATF Freezing Point Smoke Point Aromatics content SKO(PDS) Flash Point Smoke Point Specification 91.0 Min. 50 ppm. Max. 1% max. (-) 47 Deg C 19 mm 22% Max. 35 Deg C 18 mm

Product Quality
Product HSD(Euro-III) Test Cetane No. Pour Point Recovery Sulphur Flash Point HSD(Euro-IV) Cetane No. Pour Point Recovery Sulphur Specification 51 Min. Summer 15 deg C 95% Min. at 360 Deg C 350 ppm Max. 35 Deg C Min 51 Min. Summer 15 degC 95% Min. at 360 Deg C 50 ppm Max.

Product Quality
Product FO Test Flash Point Density Total Sulphur HLD BN Viscosity Index Pour Point H-500 Gr-II LOBS Viscosity Index Pour Point Specification 66 Deg C Min. 0.991 Max. 4% Max. 90 Min. (-) 3 Deg C Max. 105 Min. (-) 15 Max.

HAL DIA REFINERY BLOCK FLOW DIAGRAM Haldia Refinery Block Flow Diagram
Fuel Gas LPG SRN
H2

ATU&ARU
Off Gas NHDT&CRU

SRU

Sweet Fuel Gas Sulphur LPG Naphtha

MS(BS-II, Euro-III ,Export)

H2

MSQ C D U 1 C D U 2
GO SO

Reformate

HGU-I
FCC Gasoline
HCN

HGU-II
H2

Crude

Kero Cut St.Run G.O JBO

KHDS DHDS

H2

MTO RTF/ATF Kerosene

HSD (BS-II, Euro-III ,Export)

LPG LCN

JBO (2 GRADES)
Kero HCN HSD

FCCU
Extract
OHCU Bottoms

OHCU
H2

ATU&SRU

FG
Sulphur

RCO

Extract

V V D D U U 1 2
SR LO

CBFS
100N/150N/500N/850N/ 150BN GR-I LOBS

LO / IO / HO
DAO

DCO

FEU NMP

Raffinate

SDU
Slack Wax Raffinate

DWO

HFU
H2

PDA
Asphalt

CDWU
H2

70N/100N/150N/500N/ 850N/150BN GR-II LOBS

VBU

VB Tar

MCW
Bitumen Emulsion

MCW
FO (2 GRADES) Bitumen(3GRADES) Bitumen Emulsion

BTU

IFO

Haldia Refinery At a glance

DHDS BLOCK: DHDS HGU I RFCCU VDU II MSQU SRU I / II ARU SWS FUEL OIL BLOCK: CDU-1 CDU-II CRU KHDS CPP-I TPS & UTILITIES LUBE OIL BLOCK: VDU-1 PDA FEU SDU LHFU VBU NMPEU WHFU CDWU

CPP-II GT-II/III

ETP

OHCU BLOCK: OHCU HGU- II

12

HALDIA REFINERY OPERATIONAL BLOCKS FUEL OIL BLOCK

DHDS BLOCK
LUBE OIL BLOCK OHCU BLOCK OIL MOVEMENT & STORAGE
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DHDS BLOCK
HYDROGEN GENERATION UNIT( U-24) DIESEL HYDRO DESULPHURISATION UNIT (U-25) RFCCU(U-17,18,19) VACUUM DISTILLATION UNIT(U-82)

MSQ UPGRADATION UNIT (U-85,86 & 87)

SULPHUR RECOVERY UNIT(U-28,83,95) AMINE REGENARATION UNIT(U-26& 93) SOUR WATER STRIPPER UNIT(U-29& 94)

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HYDROGEN GENERATION UNIT DHDS BLOCK - HGU FLOWSHEET

S = 50 ppb

Naphtha

PDS
S = 1000 ppm S = 5 ppm

FDS

Pre Reformer

Steam
Reformer

Pure H2 to DHDS

PSA
H2 = 99.5%

MT Shift

DHDS -HYDROTREATMENT:GENERAL FLOWSHEET

Purge Recycle Gas Reactor feed heater Reactor(s) Amine Wash

Recycle Compressor

Quench Cold separator

Hot separator M/U H2 M/U Compressor Feed

Hydrotreated Product to Distillation

DHDS BLOCK -DHDS UNIT

DHDS-PFD

DHDS BLOCK- DHDS UNIT

DHDS PROCESS DESCRIPTION - Haldia Unit Capacity = 1.2 MMTPA (Haldia) Design Feed S content = 1.79 (Wt %) Design Product S content = 0.05 (Wt %) Reaction Pressure 39.5 Kg/Cm2 (g) Reaction Temperature 363/377 C Feed Rate = 188.7 M3/Hr H2 Makeup rate = 1221/1329 Kg/Hr

DHDS BLOCK- DHDS UNIT

Hydrodesulfurization Remove sulfur compounds Sulphur is present mainly as Thiophenes, Benzothiophenes and Dibenzothiophenes Minimum conversion of feed to lighter products 10% to 20% conversion
Sulfur is converted to hydrogen sulfide (H2S) Added hydrogen breaks carbon-sulfur bonds & saturates remaining hydrocarbon chains Creates some light ends

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DHDS BLOCK DHDS REACTIONS

C-C-C-C-SH + H2
(Mercaptan)

C-C-C-C + H2S

C-C-S-C-C + 2 H2
(Sulphide)

2 C-C + H2S
2 C-C + 2 H2S

C-C-S-S-C-C + 3 H2
(Disulphide)

(Cyclic Sulphide)

(Thiophenic Sulphur)

DHDS BLOCK DHDS REACTIONS

De-nitro genation is generally more difficult than desulphurization. Nitrogen compounds more difficult to hydrogenate than the original reactants.

(Pyridine) Other reactions are: Olefin Saturation Aromatic Saturation Oxygen removal

DHDS BLOCK - AMINE REGENERATION UNIT

PFD OF U26(AMINE REGENERATION UNIT)
4

26AC06
6

26E04 MP STEAM TO FLARE

7

TO SRU
8

TO FLARE 26C01
18

RICH AMINE FROM CDWU,DHDS

LEAN AMINE FROM E01

CONDENSATE 26V02
13 11

26V01
10

26E03

12 9 3 14

CONDENSATE 26P03A/B 26E02

2 15 16

26E01
17 26FS 01/02/ 03

26AC05

LEAN AMINE

26P01A/B

26P02A/B

DHDS BLOCK - SWS UNIT

DHDS BLOCK SRU FLOWSHEET

H2S + O2 SO2 + H2S + H2O
Fuel gas to unit Process gas reheator

H2S + SO2 S2 + H2O

Process gas reheator Process gas reheator

28E10
28F01&F02 MCC

28E11

28E12
28R01, 28R02 & 28R03:

28E01

Claus reactors

28V01

28R03 28R01 28R02

Acid Gas
Drain

28E02
Sulphur condenser Sulphur to pit

28E03
Sulphur condenser Sulphur to pit

28E04
Sulphur condenser

28E05
Sulphur condenser Sulphur Sulphur to pit to pit

Air to super Claus

Static mixer

28E13
Process gas reheator 28F03&04 Incinerator Fuel gas

28R04 Super Claus reactor 28K01 A/B Air blower Air 28E06
Sulphur to pit

28E14 WHB

28E15

28K02 A/B Incinerator air blower 28V04 Process gas coalescer

Sulphur To pit

Air

DHDS BLOCK SRU REACTIONS

Claus Reactions The main reaction (PARTIAL OXIDATION) in the main burner is :

H2S + 3 O2 2

------>

SO2 + H2O + heat

The major part of the residual H2S combines with the SO2 to form sulphur, according to the equilibrium reaction : 3 S2 + 2H2O - heat 2 By this reaction , known as the Claus reaction, sulphur is formed in vapour phase in the main burner and combustion chamber. 2H2S + SO2 < ------->

DHDS BLOCK SRU REACTIONS

In the SUPERCLAUSR stage the remaining H2S is selectively oxidised to sulphur,

It is essential that the combustion in the main burner is such that the downstream of the third reactor stage the amount of H2S is in the range of 0.5 0.7 vol.% and that the SO2 concentration is as low as possible. Before it enters the reactor a controlled amount of air is added. Proper mixing is obtained in a static mixer, in the reactor H2S reacts with oxygen to sulphur according to the reaction:
2H2S + O2 2 S8 + 2H2O + heat 8

DHDS BLOCK -FCCU

Typical FCC/RFCC Unit

DHDS BLOCK - Role of FCC/RFCC

To produce High RON gasoline. To produce LPG. To produce Petro chemical feed stock. Key process dictating refinery product pattern.

DHDS BLOCK RFCCU (INSIDE)

UNIT R.F.C.C.WITH AMINE TREATER CAPACITY 0.700 MMTPA LICENSOR M/S SWEC , USA

LPG TREATER

0.130 MMTPA

M/S MERICHEM USA M/S MERICHEM USA

GASOLINE TREATER

0.200 MMTPA

FLUE GAS SCRUBBER

119.5 MT/Hr

M/S BELCO USA

DHDS BLOCK FCCU SECTIONS

Feed Section Reactor / Regeneration section (R-R) Main Fractionation Section Gas separation section

DHDS BLOCK RFCCU FEED Typical FCC Feed Blend

FEED PROPERTIES TYPE OF FEED / FEED COMPOSITION SO LO IO HO DAO SR SL WAX EXTRACT RCO WT % 2.1 20.0 44.8 2.6 6.2 11.0 6.8 2.1 5.0 KV 2.5 5.5 - 6.5 12.15 22 - 27 40 - 45

AVERAGE FOR THE YEAR 2008 - 2009

DHDS BLOCK RFCCU

DHDS BLOCK RFCCU OPERATING PARAMETERS

ATTRIBUTE 1 2 3 Feed Preheat TempC Riser Outlet TempC Reactor Outlet TempC RFCC 188 510 510 (MAX 552) VGO 338 488 488 (MAX 552) ACTUAL 195-215 510 510

4
5 6 7 8

1st Stage Regenerator TempC

2nd Stage Regenerator TempC Cat/Oil ratio 1st Regen combustion, % CO/CO2 ratio in 1st stage regenerator

659 (Max.746)
730 (Max.802) 6.87 67 0.36

613 (Max.746)
677 (Max.802) 5.48 67 0.49

658
747 6.5 0.52

DHDS BLOCK RFCCU PRODUCT YIELD

DESIGN (RFCC) ACTUAL

FEED RATE,m3/hr PRODUCT,WT% ACID GAS DRY GAS LPG LCN TCO (INCL HCN) DCO COKE

93.2 1.20 3.00 12.50 18.6 46.45 10.82 7.43

105 1.00/0.85 3.1/3.1 14.5/18.7 31.0/34.1 35.0/29.3 10.2/9.5 5.2/ 4.55

DHDS BLOCK RFCCU

DHDS BLOCK RFCCU

SWEC R-R Design

DHDS BLOCK RFCCU

DHDS BLOCK RFCCU

DHDS BLOCK RFCCU

Cyclones

DHDS BLOCK RFCCU

DHDS BLOCK RFCCU

Cracking Reactions

DHDS BLOCK RFCCU

DHDS BLOCK RFCCU CATALYST

FUNCTION OF CATALYST HYDROTHERMAL STABILITY HIGH OCTANE REQUIREMENT METAL RESISTANCE BOTTOM CONVERTION CHARACTERISTICS COKE BURNING ABILITY DESULFURISATION ABILITY FLUIDISATION CHARACTERISTICS HIGHER RESISTANCE

DHDS BLOCK RFCCU

DHDS BLOCK RFCCU

FCC Reactions An overview
Hydrocarbon Types CHAIN STRUCTURES
H R H H H H H H H H H H H H H R R H H H H H H H H

RING STRUCTURES
H H H H H H H H H H

Paraffin
H H R H H H H H H H H H H H R R H H

Naphthene
H H H H H H H H H R

Olefin Crackability (Conversion):

Alkylaromatic Paraffinic > Naphthenic > Aromatic

DHDS BLOCK RFCCU REACTIONS

DHDS BLOCK RFCCU REACTIONS

DHDS BLOCK RFCCU REACTIONS

DHDS BLOCK RFCCU

DHDS BLOCK RFCCU REACTIONS

DHDS BLOCK RFCCU REACTIONS

DHDS BLOCK RFCCU

Belco DHDS BLOCK BELCO

Spray Tower Absorber Section

Stack Emissions:

SOx removal < / = 219 kg/hr (based on 2.5 kg/ton of feed for 0.7 MMTPA) Particulate outlet </= 50 mg/Nm3-dry

DHDS BLOCK -Mericam BELCO DHDS BLOCK Unit

FLUE GAS SCRUBBING UNIT OBJECTIVE : TO REDUCE SO2 EMISSION TO REDUCE PARTICULATE EMISSION CHEMISTRY: SO2+H2O-> H2SO3 H2SO3 + 2NaOH Na2SO3 + 2H2O SO3+H2O-> H2SO4 H2SO4 + 2NaOH Na2SO4 + 2H2O H2SO3 + NaOH NaHSO3 + H2O NaOH + CO2 -> NaHCO3 2NaOH + CO2--- Na2CO3+ H2O

DHDS BLOCK MERICAM/MERICAT

FCC GASOFLINE UNIT OBJECTIVE : IMPURITIES TOTREATING BE REMOVED * MERCAPTAN * H2S CHEMISTRY 2H2S + 4 NaOH -----.> 2Na2S + 4H 2O 2Na2S + 2O2 + H2O+*---Na2S2O3 +2NaOH 2H2S + 2O2 + 2NaOH +*----Na2S2O3 +3H2O 2RSH + 2NaOH ---- 2NaSR + 2H2O 2NaSR + O2 +H2O+*--- RSSR(DSO) + 2NaOH 2RSH + O2+*----- RSSR +H2O ROH +NaOH ---- RONa + H2O CO2 + 2NaOH ----- Na2CO3 + H2O *CAT : Cobalt Phthalocynine ARI 100L or ARI 100EXL

DHDS BLOCK Distillation VDU-II FLOW Vacuum Unit SHEET Flow sheet
Ejectors

Spindle Oil
RCO Feed
Vacuum Distillati on Column

Light Oil Inter Oil

Heavy Oil

Vacuum residue

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DHDS BLOCK-VDU-II OBJECTIVES

Fuel based VDU
Prepares feedstock to FCC, Hydrocracker

Lube based VDU

Prepares feedstock to Lube plant

Products
Spindle oil Light Neutral Intermediate Neutral Heavy Neutral

Products
Diesel Light Vacuum Gas Oil (LVGO) Heavy Vacuum Gas Oil (HVGO) Slop Distillate Vacuum Residue

Slop
Vacuum Residue

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DHDS BLOCK-VDU-II OBJECTIVES

TOP PRESSURE
COT

20 To 60 mmHg
395-405 Deg C

BOTTOM PRESSURE - 30 To 90 mmHg

TOP TEMPERATURE -

55-60 Deg C

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DHDS BLOCK-MSQ UNITS

NHDT unit (385TMT/yr): ISOM unit (122TMT/yr) : Prime G+ (200TMT/yr) Reformate Splitter (184TMT/yr)

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DHDS BLOCK-MSQ UNIT OBJECTIVES

QUALITY
EURO III SULPHUR (ppmw) max RON min BENZENE,(vol.%), max AROMATICS (vol. %) max 150 91 1 42 EURO IV 50 92 1 42 BS-II 500 88 3 NO SPEC

OLEFINS (vol. %) max

21

18

NO SPEC

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DHDS U-85 FLOW DIAGRAM

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DHDS BLOCK- ISOM FLOW SHEET

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DHDS BLOCK-ISOM REACTION STEPS

The reactions are carried out in three steps

1st step : Sulfur removal (HR 448) {in NHDT}

2nd step : Hydrogenation of benzene (LD 412).

3rd step : Isomerization of normal paraffins 614 A).

(IS

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DHDS BLOCK-ISOM REACTIONS

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DHDS BLOCK-ISOM CHEMICAL INJECTION Tetra chloroethylene (C2Cl4) is the chloriding agent for fresh catalyst C2Cl4 is fully converted to HCl at reactor normal operating conditions.
HCl reacts with the -OH groups at the catalyst surface to form -Cl groups and establish the catalyst acidity.
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DHDS BLOCK-PRIMEG FLOW DIAGRAM

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DHDS BLOCK FCC GASOLINE TREATMENT

High sulfur content in LCN can be due to a higher S / mercaptans content in feed

More light RSH in feed contributes more RSH/S in LCN (@ const. conversion)

Measure the S & RSH content in the feed. Conduct S species analysis (if possible)
Reduce LCN cut point (decrease the heavy RSH & thiophene content present in feed)

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DHDS BLOCK FCC GASOLINE PROPERTIES

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DHDS BLOCK FCC GASOLINE TREATMENT SHU Reactor section In the reactor section, main regulations are :
Inlet T of the reactor : this temperature is regulated steam flow rate to feed preheater

Temperature
conversion

Light mercaptan Hydrogenation Hydrogenation selectivity (diolefin / olefin) Polymerization of gum precursors

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DHDS BLOCK FCC GASOLINE TREATMENT

LCN/Feed Draw Rate (at constant Reflux/Feed Ratio)
Change Result Effect

Increase

LCN cut point

LCN sulfur Olefins in untreated HCN

Decrease

LCN cut point

LCN sulfur Olefins in untreated HCN

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Thank you

3/19/2013

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