Module 10

THE REFINERY-
PETROCHEMICAL
LINKAGES

Petroleum Ref./Upes/GCT/July-05/ Mod-10/01

 THE REFINERY PETROCHEMICALS
LINKAGES

 Refineries have been built in the past primarily to cater to

the growing demand of fuels. In the initial stages of
development of petrochemical industry in India it was totally
based on these natural gas components. Apart from
refinery naphtha, other refinery streams have been already
used in the country to produce a host of petrochemicals
products.

Petroleum Ref./Upes/GCT/July-05/ Mod-10/02

 Major petrochemicals feedstocks originating from refineries
Refinery Stream Petrochemicals
Naphtha Olefins (steam cracking) aromatics (reforming,
isomerisation)
Kerosene LAB
FCC LPG C3 petrochemicals
C4 petrochemicals
FCC offgases Olefins
Heavier fractions Olefins (steam cracking)
NAPHTHA
Basic building blocks of petrochemicals viz. Ethylene, propylene
and butadiene are produced by steam cracking of light naphtha
(C5-1000C). Aromatics viz benzene, toulene and xylenes are
produced by reforming heavy naphtha. Benzene is a versatile
feedstock from which a number of petrochemicals such as
styrene, phenol etc. are produced. P-xylene is the feedstock for
terephthalic acid and DMT which in turn are the raw materials
for the polyester industry
Petroleum Ref./Upes/GCT/July-05/ Mod-10/03
  Propylene & Ethylene:
For steam cracking or ethane / propane from natural gas are
major feedstocks. While naphtha cracking gives ethylene
and propylene in the ratio of 2:1, gas cracking gives a ratio
of approximately 10:1 thus hardly any propylene is produced
in gas cracking. Since propylene is a very important building
block particularly in view of the high growth rate seen for
polypropylene among the commodity polymers, a proper
balance has to be struck between naphtha and ethane /
propane feedstocks for steam cracking. Alternatively,
independent sources of propylene have to explored. A
source for propylene is refinery FCC: LPG. Typically, in
Indian refineries, where maximization of middle distillates is
the objectives, a 1 MMTPA FCC unit gives about 30,000
TPA propylene. However, if the FCC unit is operated to
maximize gasoline and if its size is larger, propylene
potential in LPG as well as ethylene potential in offgases
could be higher.
Petroleum Ref./Upes/GCT/July-05/ Mod-10/04
  Aromatics:

Naphtha cut of 900-1500C is reformed and the reformate

is further processed to obtain benzene, toulene and
xylenes. Alternatively, this reformats is used in the
gasoline pool. As we move towards more cleaner
automotive fuels, demand for this reformat within the
refinery operations may increase. A reformer can be
designed either to produce reformate for gasoline
blending or to maximize xylenes (suitablefor a
downstreams aromatics complex) or to produce both
.in suitable proportions

Petroleum Ref./Upes/GCT/July-05/ Mod-10/05

  Kerosene

Linear Alkyl Benzene (LAB), an important detergent base

material is produced by alkylation of benzene by n-
paraffins. N-paraffins are extracted from kerosene.
Kerosene fraction containing about 15% n-paraffins and
low in aromatics content would be an ideal LAB feedstock.
However about 85-90% of the kerosene drawn by LAB
plant is returned back to the refinery after n-paraffin
extraction. Impact of its blending in the kerosene pool in
terms of smoke point and freezing point however, needs
careful checking before action can be taken on blending of
returned fraction in kerosene.

Petroleum Ref./Upes/GCT/July-05/ Mod-10/06

 FCC LPG

 C3 CUT
C3 cut from FCC unit contain 40-50% propylene. Normally a
propylene fractionators with feed preparation unit is required to
recover this propylene from C3 cut stream. The propylene so
recovered from a large refinery (cap> 20 MTPA) is considerable
and matches that required for an economics size PP plant
(100,000 TPA) or CAN plant (70, 000 TPA). From small
Refineries, propylene from 2 or 3 refineries can be clubbed
together at one location to consider an economics size PP or
ACN plant.

Petroleum Ref./Upes/GCT/July-05/ Mod-10/07

 Propylene requirement for various plants is given below:

PLANT CAPACITY TPA PROPYLENE

REQIRED TPA

Phenol 60,000 31,000

PP 100,000 100,000

2-Ethylene hexanol 30,000 33,000

ACN 70,000 77,000

Epichlorohydrine 10,000 6,900

Acrylic Acid 45,000 33,000

Petroleum Ref./Upes/GCT/July-05/ Mod-10/08

C4 CUT
The typical composition FCC C4 from refinery is given
below:
Wt%

i-butane 32.1
N-butane 10.5
i-Butylene 15.0
Butene-1 11.9
i-Butene-2 17.8
C-Butene-2 10.3
Pentane / pentene 2.4

Total C4 production from 1.0 MMTPA FCC is about 75,000 TPA

Petroleum Ref./Upes/GCT/July-05/ Mod-10/09

 Petrochemicals Based On Refinery Streams In India
IOCL Guwahati Naphtha Aromatics
BRPL Bongaigaaon Naphtha Aromatics
IOCL Koyali Naphtha Aromatics Olefins
FCC gases Polypropylene
Kerosene LAB
IOCL Haldia Lub extract Carbon Block
(CBFS)
BPCL Bombay Naphtha Aromatics
FCC C3 Stream Polypropylene
FCC C4 Stream MTBE
HPCL Bombay Naphtha Olefins
Lube Extract Carbon Block
(CBFS)
HPCL Vizag FCC C3 Stream Oxoalcohols
CRL Cochin FCC C# Stream Phenol
FCC C# Stream) + Polyisobutenes
Benzene
FCC C$ Stream
Petroleum Ref./Upes/GCT/July-05/ Mod-10/10
 CPCL Madras FCC C3 Stream Po/PG/Polyols
FCC C3 Stream MEK
Kerosene LAB
Lube extract (CBFS) Carbon black
RIL Jamnaga Naphtha Olefins (At
r Naphtha Reforming Hazira)
FCC: C# Stream Aromatics
Polypropylene
IOCL Panipat Kerosene LAB
Aromatics

Petroleum Ref./Upes/GCT/July-05/ Mod-10/11

 HEAVY REFINERY FRACTIONS
Consequent to the energy crunch in the seventies, steam cracking process
has been developed to take heavier refinery fractions as feedstock. Heavier
fractions which are traditionally sent for catalytic or hydrocraking can now be
sent for olefins production. For the same ethylene capacity, investment and
feedstock requirements are higher when compared to naphtha cracking.

Feedstock Naphtha Light Atm. Gas Vac. Gas

Oil (desulphurised)
Product:
Ethylene 1.00 1.00 1.00
Propynene 0.42 0.47 0.63
C4S 0.25 0.30 0.55
Gasoline 0.74 0.71 0.73
F.O. 0.2 0.69 1.45
Feedstock (in) 3.13 3.65 4.79
INVESTMENT 1.00 1.10 1.25
(Relative)
Petroleum Ref./Upes/GCT/July-05/ Mod-10/12
 PETROLEUM REFINERY / PETROCHEMICALS INTEGRATION

Naphtha
Kerosene

Gasoline

Diesel
crude LPG
Crude CDU/
Tanks VDU

FCC Aro Paraxylene

Propylene
PP
Coker Polypropelene

Sulfur MPP Power

INTEGRATED REFINERY AND PETROCHEMICAL BLOCK DIAGRAM

Petroleum Ref./Upes/GCT/July-05/ Mod-10/13
 C5-
C6-C7 Raffinate
Benzene
Toulene
Light Ends column
C4 / C5 Benzene
column
C6 /C7
Aromatics

Naphtha Catalytic
(C4-C9) Reforming Aromatics
extraction
Xylene
Isomerization Paraxylene
Orthoxylene
Reformate
splitter O/m xylene

OX
Xylene tower
splitter
C9+ C7+

Reforming and BTX Production Process

Petroleum Ref./Upes/GCT/July-05/ Mod-10/14
 Naphtha To Petrochemicals
ETHYLENE POLYTHENE, PVC EP
PROCESSING

PROPYLENE POLYPROPYLENE, ACETONE

PROCESSING

BUTULENE MEK
PROCESSING

NAPHTHA NAPHTHA ISOBUTYLENE

CRACKER PROCESSING MTBE, POLYBUTENES , BUTANOL MEK
BUTADIENE

BENZENE PROCESSING CAPROLACTUM, NYLON

XYLENE
REFORMING AROMATICS
SEPARATION PROCESSING POLYESTER

POLYESTER
ETHYLBENZENE
PROCESSING

Petroleum Ref./Upes/GCT/July-05/ Mod-10/15