LOCATION:

IOCL MATHURA is located on NH-2 , between the historic cities of Delhi and Agra,in Mathura, Uttar pradesh. Commissioned in January, 1982
CAPACITY: 8 MMTPA A Fortune 500 company. Placed at 125 Current turnover of Rs. 271,074 crore and profits of Rs. 10,221 crore for the year 2009-10.

Receives crude oil through the 1870 km long Salaya Mathura Pipeline (SMPL). Processes low sulphur crude from Bombay High, imported low sulphur crude from Nigeria, and high sulphur crude from the Middle East. Mainly produces middle distillates for Northern India supplied though a 760km long product pipeline to Jalandhar in Punjab via Delhi (MJPL) and 100km long Mathura Tundla Pipeline (MTPL). Mathura refinery received Gold Award in petroleum Refinery sector from Greentech Foundation, New Delhi, for outstanding achievement in Safety Management in 2009 .

Downstream Operations

Recent entry into Petrochemicals, E&P and GAS Business

Atmospheric & Vacuum Distillation Unit(AVU ) Visbreaker Unit (VBU) Fluidized Catalytic Cracking Unit (FCCU) Continuous Catalytic Reforming Unit (CCRU) Propylene Recovery Unit (PRU) Hydrogen Generation Unit ( HGU ) Once Through Hydrocracker Unit (OHCU) Sulphur Recovery Unit (SRU) Bitumen Blowing Unit (BBU) Diesel Hydro Desulphurization Unit (DHDS) Merox (Mercaptan Oxidation) Diesel Hydrotreater (DHDT)

1. Liquid Petroleum Gas (LPG) 2. Fuel Oil Products:

Motor Spirit (MS) Superior Kerosene (SK) Aviation Turbine Fuel (ATF) High Speed Diesel (HSD) Furnace Oil (FO) Naptha Gasoline

3. Lube Oil Products 4. Other Products:

Slack Wax Carbon Black Feed Stock Bitumen Sulphur Propylene

New Unit block of Mathura refinery comprises of 4 units namely

HGU (Hydrogen Generation Unit ) OHCU (Once Through Hydrocracker Unit) DHDS (Diesel Hydro Desulfurization Unit ) DHDT (Diesel Hydrotreater Unit)

Purpose of the Unit : To generate High purity Hydrogen for

supply to DHDS unit and Hydrocraker Unit.

Project Details:
Capacity of the Unit (MTPA) Licensor : : 34000 Haldor Topsoe,Denmark.

Project Cost
PMC Consultant

:
:

160 Crores
EIL, Delhi.

FEED: Naptha(from Arab mixed crude oil) Or Natural Gas

PRODUCT QUALITY (DESIRED) H2- 99.99 volume % (minimum) CO,CH4,CO2 15ppm (maximum) CATALYSTS 1) TK 550 2) HTZ-3 3 RKNGR 4) R-67-7H 5) LK-811 - Hydrogenation catalyst - S-adsorption catalyst - Adiabatic pre reforming Catalyst - Reforming catalyst - MT shift catalyst

RECYCLE H2

PRETREATMENT

PREREFORMING

REFORMING

SHIFT SECTION

PSA

OFF GAS FUEL

H2

STEAM

FUEL

DESULFURIZATION
HYDROGENATION ( Hydrogenation of Sulfur contained in the feed ) ABSORPTION OF SULFUR (Removal of Sulfur from the feed )

REFORMING SECTION
FEED MIXING (Mixing of steam and feed after desulfurization) ADIABATIC PRE-REFORMING ( hydrocarbons are decomposed into H2, CO2, CH4 ) TUBULAR REFORMING (Reforming at higher temperatures possible )

CO-CONVERSION SECTION
GAS PURIFICATION SECTION ( SHIFT REACTION ) CO + H2O CO2 + H2 + heat

PSA UNITS:
Purification of gas from reformer to get High purity H2 and offgas containing impurities. H2 from PSA-I and PSA-II are combined and sent to OHCU/DHDS.

FEED HYDROGEN

Chemical Reactions : Desulphurisation section:

RSH+H2 -> RH + H2S R1S-SR2+3H2 -> R1H+R2H+ 2H2S R1SR2+2H2 -> R1H+R2H+H2S COS+H2 -> CO + H2S Catalyst : Co Mo . (TK 550) Normal life : 5years. H2 mixed with feed and passed over catalyst at 380-390 deg C. H2 rate : 0.13 m3/kg of feed. Feed S <200 ppm. Product S < 50 ppb.
R-01

DESIGN PRESS. : 42 Kg/cm2 DESIGN TEMP : 430C

HDS section : Too low a (<350 degree Celcius) temp will lead to gum formation on catalyst Temp > 400 deg C will lead to polymerisation of products leading to coke laydown. So ideally we keep the temprature at about 380390 degree celcius. Absorption of H2S: H2S+ZnO ZnS+ H2O Two absorbers in series with 2 beds each Chloride guard placed on top of ZnO catalyst (HTZ-3) to retain any entry of chloride along with feed to protect MT shift catalyst (LK-811). Normal life of ZnO catalyst and chloride guard is 6 months.

GUARD REACTOR
HTZ-3 : ZnO Catalyst HTG-1 : Chloride Guard HTG-1 HTZ-3
R-02A R-02B

H2S+ZnO

ZnS+H2O

Design Pressure : 34 Kg/cm2 Design Temp. : 430 C.

16

PRE-REFORMING :
CnHm+nH2O CH4+H2O CO+H2O

(Steam)

nCO + ( n+m/2) H2 - heat CO+ 3H2 - heat CO2+H2 + heat

Desulphurised feed along with surplus H2 is mixed with HP saturated steam and passed over pre-reformer and reformer in series. Design Steam/Carbon ratio : 2.5 Normal operating Steam/Carbon ratio : 2.8 If S/C < 1.5, Carbon laydown will be there on prereformer catalyst If feed Temp > 520 deg C, Carbon laydown will happen Normal inlet temp : 490 deg C. Normal range : 470-505 deg C. If feed temp < 445 deg C, gum formation will take place.

490

Optimum Inlet Temperature. : 490 C Temp Range at Inlet : 470-505 C. Temp. > 505 C : Carbon Formation . Temp. < 470 C : Gum Formation Steam /Carbon Ratio : 2.5 Ratio < 1.5 : Risk of Carbon Laydown. Very High : Risk of Oxidation H2 in Process Gas : 0.13 m3/kg of Steam

RKNGR (Ni Cat)

R-03

Fixed Bed , Adiabatic Reactor. Energy Savings. Low Steam / Carbon Ratio. Conversion of Heavy H.Cs to CH4. Reduced Possibility Of Carbon Formation. Preheating Reformer Feed to 650 degree C.

Why pre-reforming and not reforming directly?

Basically there are three reasons for performing pre reforming:

1) By incorporation of the pre-reformer, considerable energy savings are obtained because heat from the waste heat section of the tubular reformer can be utilized for additional preheating of feed to the tubular reformer.
2) Incorporation of the prereformer allows operation at a low steam/carbon ratio whereby the mass flow through the plant is reduced. 3) Furthermore the pre-reformer is reducing the possibility of carbon formation in the tubular reformer.

REFORMING :
CH4+H2O CO+ 3H2 - Heat Gases from prereformer are further heated to 650 deg C and passed over Reformer tubes containing Reforming catalyst (TOPSOE R67-7H)
Since there are no heavier Hydrocarbons at the outlet of Pre-reformer, the coking in Reformer is avoided. However when catalyst is poisoned by S, activity is lost and coke laydown occurs. 126 No. of Tubes in furnace design. Tubes of high alloy metallurgy (CrNiNbTi) 216 No of Burners in 6 rows of 9 burners each on 4 furnace walls. Furnace designed for high heat flux rate. Tube skin temp 990 .

MT SHIFT CONVERTER:
CO+H2O CO2+H2 + heat Catalyst Cu2O reduced to Cu (LK 811 i.e. Oxides of Cu, Zn & Cr.)

REFORMER

205 0C

Inlet Temp : 205 deg C, Outlet Temp. 337 0C Operating range 200-340

R-04

POISONS :

Sulfur : mostly retained by prereformer/reformer catalysts Chloride : HDS outlet monitored to have chloride < 50 ppb using chloride guards

Selective Adsorption of Impurities at High Pressure on Adsorbent. Regeneration of Adsorbent at Low Pressure. Cyclic Pressure Variation Process

OBJECTIVE : To process 1.2 MMT/yr of VGO to convert 65% into products boiling below 370 0C i.e. Diesel, lighter fractions and 35% as unconverted oil i.e. FCC feed.

FEED : Feed to the unit consists of Vacuum gas oil (VGO) 70 % High sulfur & 30 % low sulfur.
PRODUCTS: The primary products from OHCU are L.P.G Stabilized Light Naphtha Heavy Naphtha Aviation Turbine Fuel (ATF)/ Superior Kerosene (SK) High Speed Diesel (HSD) FCC feed

ADVANTAGES OVER OTHER HYDRO-CRACKING PROCESSES:

Yield of middle distillates is very high. Does not yield coke or pitches as by product. No post-treatment is required for Hydrocracker products.

THE HYDROCRACKER IS MADE-UP OF FOUR PRINCIPLE SECTIONS:

Make-up Hydrogen compression section
The compressed make up hydrogen is combined with hydrogen recycle gas in the reaction to from reactor feed gas.

Reactor section
In the reactor section, the feedstock is combined with Hydrogen at high temperatures & pressures and is catalytically converted to lighter transportation fuels. The hydrotreating and hydrocracking takes place in the reaction stage. A high Hydrogen partial pressure is needed to promote hydrocracking reactions and to prevent coking of the catalyst. So excess of Hydrogen is circulated to maintain a high partial pressure.

 The Fractionation section

To separate reaction section products into off gas, light naphtha, heavy naphtha, kerosene, diesel and FCC feed.

Light end recovery section

Remove Light ends and waters from light naphtha ,C-2, H2S Separate LPG from light naphtha and treat LPG to meet the desired specification.

H2 recycle

(Flasher)

Power recovery turbine

(FCC feed)

OBJECTIVE:
Pollution control Producing low sulfur diesel (0.25 w/w%) (as per govt. directive w.e.f. Oct. 1999.)

FEED:

Proportion of straight run LGO, HGO, LVGO. 74% LGO, 21% HGO, 5% LVGO

The feed is a mixture of products containing Unsaturated components (diolefins, olefins), Aromatics, Sulfur compounds and Nitrogen compounds.

What we basically do in DHDS?

The Hydrodesulfurisation reaction releases H2S in gaseous hydrocarbon effluents. This H2S removal is achieved by means of a continuous absorption process using a 25% wt. DEA solution. In addition to the desulfurisation, the diolefins and olefins will be saturated Denitrification will occur. Denitrification improves the product stability. The hydrogen is supplied from the hydrogen unit. The HR-348 and HR-448 are desulfurisation catalysts, it consists of cobalt and molybdenum oxides dispersed on an active alumina. Its fine granulometry and large surface area allow a deep desulfurisation rate.

Lean Amine for absorption operation is available from Amine Regeneration Unit (ARU).

o Feed received from different feed sources namely Diesel Storage tanks and FCC unit. o o o o o Hydrogen recycle join the feed before heat exchangers. Feed then enters heater in four passes and then to reactor. Vapour phase is sent to high-pressure amine absorber. The liquid hydrocarbon under level control is sent as feed to stripper. Sweet diesel from bottom of stripper is pumped to storage tank.

REACTIONS INVOLVED IN THE REACTOR

1.Desulfurization Reaction:

R - S - H H2 2 R - H H2S
2. Denitrification Reaction:

R NH 2 H 2 R H NH 3
3. Deoxygenation (Hydrogenation of C=O bond)

R CH O H 2 R H H 2O
4. Hydrogenation of Olefins & Aromatics

R CH CH 2 H 2 R CH 2 CH 3

CATALYSTS USED :
Catalysts consists of NiMo oxides with alumina support;
For R-01: HR-945 HR-348 For R-02: HR-448 Alumina Balls

For Hydrogenation of Olefins and Aromatics. For Desulfurization, Denitrification, and Saturation of Olefins and Aromatics. For Desulfurization, Denitrification, and Saturation of Olefins and Aromatics. and dia. . arranged around the 3 catalyst beds to safegaurd catalysts.

126 C 50 kg/cm2

374 C

280 C

383 C

60 C 34 kg/cm2

S T R I P P E R

OBJECTIVE :

o To produce a low sulfur diesel product, with substantial cetane number improvement.

FEED:

o Several straight run distillate streams. o Cracked feed from FCC. o A heavy naphtha stream from the Visbreaker unit(VBU).

PRODUCT:

o Desulfurized Diesel with reducad sulphur content and improved ceatne number. o Stabilized Naphtha.

Two main types of chemical reactions, namely :

-Refining -Hydrogenation reaction
-

1.Refining Reaction : involve the removal of heteroatoms, namely, sulfur, nitrogen and oxygen. It also includes the saturation reactions of olefins and diolefins. A)Desulfurization Reaction -Mercaptans, sulfides and disulfides react easily leading to the corresponding saturated or aromatic compounds. Mercaptans : R SH + H2 R H + H2S Sulphides : R-S-R + 2H2 2R H + H2S

B) Denitrogenation Reaction
oNH3 is released following a series of reactions : saturation of the ring to which nitrogen is attached and carbon-nitrogen bond scission.
The rate is lower than for the desulfurization reaction These reaction lead to ammonia formation These reactions are also exothermic.

2.Hydrogenation Reaction :
oSaturation of aromatic compounds and denitrification of heterocyclic compounds having an aromatic structure. oThe polynuclear aromatics are first converted to mononuclear aromatics, which are then converted to naphthene. Aromatics Saturation

+ 3 H2 C6H12