Clean Fuels and Petrochemical Synergies

Lecture Advanced Training Course On Clean Fuels Indian Institute of Petroleum, India Dr. A. K. Gupta

 Returns on refining assets fallen to inadequate levels due to

Low growth for major refined products - Poor upgrading margins - Increased competition
-

The drivers to these issues are:

Refinery/ Petrochemical Integration Business diversification challenges (e.g. power generation, retail marketing) Process technology developments Regulatory issues

Growth Rate
Global Petroleum demand is expected to average 2.2% during next 10 years
Global demand for major petrochemical will grow twice as fast.

All the major petrochemical producing regions will be adding petrochemical processing capacity to 2005 Petrochemical Ethylene Benzene Styrene Poly-olefins+ Para-xylene (PX) Terephthalic Acid (PTA) New Investment/addition Million tons/ year 41.3 10.5 11.4 50.1 11.1 15.5

+ Polyolefins includes polypropylene, all grades of polyethylene (including LDPE- 29.2 million tons/year, LLDPE- 20.9 million tons/year and HDPE

WORLD ETHYLENE CAPACITY (MAY 1997)

1997 North America South America West Europe East Europe Africa Middle East Asia Australia 28,732 3365 19,786 7568 1255 4846 17812 505 2000 % increase from 1997 to 2000 31,619 10 3935 8058 1555 6611 22573 505 16.9 6.5 23.9 36.4 26.7 20,046 1.3

TOTAL

83,869

94,902 13.2

Source: Japan Petrochemical Industry Association, Tokyo, May 1997

Propylene demand continues to exceed growth in production from steam crackers

Projects to produce additional propylene from Refinery FCC units are being considered.

ASIAN ETHYLENE PRODUCTION CAPACITY 1991 Japan South Korea China Taiwan East Asia Total Singapore Thailand Malaysia Indonesia Philippines Asean Total India Asia Grand Total 6150 1232 2225 745 10,352 400 230 630 510 11,492 1997 7114 3720 2338 960 14,132 960 1130 530 550 3170 510 17,812 2000* 7478 4380 4205 1390 17,453 1005 1130 1010 715 3860 1260 22,573 2005/10* 8554 4380 6723 2365 22,472 1760 1730 1600 2265 500 7855 3950 34,277

*Few of the above planned projects may not materialize or may be postponed, especially those in China and India.

World-scale steam cracker facilities under construction cannot keep up with demand

ResultRefinery- based petrochemicals can play a significant role in providing a security of supply to petrochemical processors

INDIAN SCENE.
Post Administered Pricing Regime (APR) Allow world market prices for refined products to be applied in India As product prices change, the refineries will be faced with the need to improve allocation of their capital and optimize crude oil selection strategies. The products most in demand will be transportation fuels- diesel and motor, meeting the stringent environmental regulations Capacity increase and meeting specifications of fuels to meet stringent regulations will be involve huge capital investments Refinery profits will squeeze Alternative options to improve profitability need to be looked into

Profitability Cycles
Petrochemicals often exhibit cyclical profitability (6-7 years cycles) Refining industry, cyclically differs in both timing and severity compared to petrochemicals - Integration allows to temper the downturns in petrochemicals by the more stable behavior of refining cycle.

Refinery/ Petrochemical integration also brings other synergistic opportunities

- Energy optimization and cogeneration

- Recycling H2 from integrated petrochemical complexes to refinery for increased demand in hydroprocessing in reformulated products.

Benefits of Integration
Advantage of Counter-seasonal trends in fuel/transport demand vs. Petrochemical feedstock requirements.

Integrated economics often reflect lower refinery values for petrochemical feed-stocks. Many big products from the petrochemical operations can be recycled back to the refinery at higher value. Competitive edge over stand-alone petrochemical complexes Overall economics also improves from shared utilities, transportation, maintenance and administrative functions. Finally, petrochemicals generally offer higher value, better growth opportunities.

Obstacles that can deter investments in extending refinery operations into petrochemical operations include:

High capital costs of new petrochemical units

Product/intermediate transfer costs between refinery and petrochemical divisions Refiners may see a higher rate of return in other business such as retail marketing

In contrast to refiners, many chemical industry players prefer to make smaller acquisitions to fit existing portfolios and minimize risks

The future of petrochemical integration into the refinery cannot be characterized in simple terms. It must first be recognized that petrochemical industry is a large industry with many products and more than 500 processes.

If an existing refining facility does not already produce a sizable quantity of petrochemical products, can it ever hope to achieve an acceptable return on petrochemical projects?

Refiners produce a wide range of chemical feedstocks depending on crude type, refinery complexity, and other operating conditions.

Typically a limited number of refinery processes/ streams provide the primary feedstocks to support competitively sized petrochemical production.

PETROCHEMICALS FROM REFINERY STREAMS

Petrochemical Stream Base Petrochemicals Ethylene Propylene Benzene, toluene, xylenes (BTX) Downstream Derivatives Ethylbenzene Polypropylene Isopropanol Cumene Dilute ethylene (FCC and delayed coker off-gases) Refinery propylene (FCC product) Refinery propylene (FCC product) Refinery propylene (FCC product) Fuel gas Alkylation Alkylation Alkylation
Contd..

Refinery Stream

Alternative Refinery Use Fuel gas Alkylation Gasoline blending

Naphtha and LPG Refinery propylene (FCC product) Reformate

Oligomers

Refinery propylene (FCC and delayed coker)

Alkylation

MEK MTBE
Cyclohexane Ortho-Xylene Para-Xylene Normal paraffins Naphthalene

Butylenes (FCC and delayed coker) Butylenes (FCC and delayed coker)
Reformate Reformate Reformate Kerosene FCC light cycle oil

Alkylation, MTBE Production Alkylation, MTBE Production

Gasoline blending Gasoline blending Gasoline blending Refinery product Diesel blend-stock after hydro-treating

REFINERY-GENERATED FEED-STOCKS AND THEIR COMMON AND POTENTIAL USAGE Feed-Stock LPG (Propane, Butane) Derivatives Feedstock for: Ethylene, Propylene, Butylenes by cracking/dehydrogenation: Aromatics by aromizing Acid, aldehydes & ketones through oxidn. steam

Naphtha

Light and heavy for olefins and aromatics production, depending upon the composition (steam cracking/Reforming) Light naphtha to C5-stream Hydrogenation of benzene rich fraction (69-90C) for cyclohexane/ cyclohexene, which is feed stock for fibre industry. n-paraffins for LAB, LAS etc. specialty chemicals, plasticizers and solvent
Contd.

Kerosene

Gas Oil

Feedstock for steam cracking to produce olefins (commonly used in china). Gas oil from thermal conversion process- alpha olefins for AOS.
Propylene, isopropanol, cumene, oligomers, polypropylene, acrylic acid. Butylenes- MEK, MTBE, oligomers, pure butene-1, alkyl phenols and additives, acrolein, MMA acrylic acid. High octane, benzene free gasoline blending component by alkylating benzene rich naphtha with FCC- off gases and isobutene. Olefins

FCC off gases

DCC

Kerosene from n-paraffins, alpha olefins, thermal process (visbreaking, coking) aromatics naphthalene
Contd.

Reformate

BTX C9+ aromatics from reformate and their conversion, sludge, Power (IGCC), steam, H2, Syn gas-chemicals, High cetane, zero sulfur diesel, specialty linear waxes, olefins, alcohols etc. Use based on acetylene chemistry

Residues coke etc.

Petroleum Coke

Levels of Refining and Petrochemical Integrations

Forward Integration
Utilization of refinery manufactured products as petrochemical feedstock rather than gasoline blending component.

Backward Integration
Disposal of petrochemical by-products to refinery applications, namely gasoline blending.

Site-wide and System-wide Integration

Side-wide integration
Petrochemical and refining operations are integrated on one site.

System-wide integration
Products are traded between several independent refinery and petrochemical sites.

Figure 1: process Flow diagram of an integrated refinery & Petrochemicals plant

Basic Petrochemical Plans

1. 2. Steam cracker or olefins plant. Aromatic Plant

Both units obtain feedstocks from refining section.

LPG, light or full range naphtha and unconverted oil for steam cracker.

Reformate for aromatics.

Alternatively these feedstocks are also available from the market.

Alternatives for light naphtha

1. Feedstock for steam cracker 2. Feed stock for isomerisation unit

Alternatives for Reformate

1. Feedstock for Aromatics

2. Gasoline Blending Component

Auto Oil Programmes will Affect

Recipe for gasoline blending Choice for feedstocks for steam cracking and aromatics unit.

Both steam crackers and aromatics units

Produce by-products in addition to C2H4, C3H6 or aromatics. Some of these by-products return to the refinery as gasoline blend stocks called Chemical Returns.

Changing fuel specifications will have an impact on the interfaces or synergies of refining and petrochemical operations.

 Chemical returns from steam cracker include : pyrolysis gasoline, following benzene extraction
Pygas split Light & heavy

Chemical returns from aromatic unit consists of C9 or C8 (xylenes) aromatics.

The fuel regulations being enacted will change the blending values and opportunities for chemical returns as well as the availability of light naphtha as cracker feed.
This effect will be increased by the fact that gasoline demand is expected to increase at low pace than demand for C2H4 and C3H6.

Gasoline Specification due to AOP

Before AOP AOP 200 AOP 2005
Sulphur Benzene Aromatics Olefins ppm Max. 500 %v/v Max. 5 %v/v %v/v Max. 150 Max. 50 Max. 1 Max. 42 Max. 18 Max. 1 Max. 35 Max. 18

Changing Gasoline Specifications

Sulfur
Benzene Aromatics Olefins

Impact of Changing Gasoline Specifications

The changing Gasoline specifications will influence: Quantity and quality of feed stocks available for petrochemical production. Gasoline blending strategies.

The reduction in aromatics content of gasoline will have major impact on refiningpetrochemical synergies.
All other parameters also needs to be considered; these will limit the blending returns into gasoline pool and restrict the availability of light naphtha as petrochemical feedstock.

There are four general refinery types

Hydroskimmer, refineries consisting only of topping and reforming.
FCC-type, refineries with FCC plant for VGO or rasid cracking without additional hydrogen. Hydrocracker type, refineries including a hydrocracker plant for VGO cracking with hydrogen addition. Complex or FCC/Hydrocracker type, are refineries with both types of cracking units.

Refinery types and aromatics content in gasoline

Hydroskimmer Topping and Reforming units only About 51% aromatics content in gasoline; corresponding to 77% reformate FCC type Hydroskimming and additional FCC for VGO cracking without hydrogen addition less than 35% aromatics content in gasoline; corresponding to about 38% reformate Hydrocracker type Hydroskimming and additional Hydrocracker for VGO cracking with hydrogen addition about 54% aromatics content in gasoline; corresponding to 83% reformate. Complex or FCC/HC type Hydroskimming plus FCC and HC units About 45% aromatics content in gasoline; corresponding to 60% reformate

Qualities of typical gasoline blending components

Blending Component
Reformate FCC gasoline -light cut -heavy cut Isomerisate

Benzene Vol%

Sulphur ppm

Olefins vol%

Aromatics Vol%

RON/MON

1,0-10 0,7-1,0 0,9-1,5 0,1-1,1 0

1 100-2000 15-300 350-3500 0

0 30-40 20-55 2-14 0

60-75 5-45 1-2 40-60 0

99/98 91-96 / 78-84 98-96/80-82 91-96/78-84 87-92/84-90

Alkylate
MTBE Pyrolysis gasoline

0
0 0-6

0
0 0-600

1
1 25-35

0
0 75-88

95/93
111/96 98/84

- light cut
-heavy cut C9-Aromatics

0-6
<1 0

0-50
0-600 0

55
0 0

5
86 100

96/80
99/84 105/93

Blend Stock Qualities

Pyrolysis Gasoline (PG) Pyrolysis Gasoline quality parameters are similar to FCC gasoline. PG has favourable RON and acceptable MON. Sulfur, olefins and aromatics content of PG exceed future gasoline specs. Light PG is low in aromatics but olefins content is extremely high; MON is insufficient. Reverse is true for heavy PG high aromatics low olefins.

C-9 Aromatics
C-9 aromatics are excellent gasoline blend stock
High aromaticity. Negligible olefin content. Octane comparable to reformate

High aromaticity will limit the future usage as blends.

 Reformate has added advantages over C-9 aromatics

Reformate has lower aromatic content. Naphtha reforming generates H2 as by-product. Distillation range of reformate favourable to gasoline blending. C9-aromatics production can be reduced by cutting reformer feed TBP (140C max.) One option to limit aromatics in gasoline is dilution with MTBE, alkylate, isomerisate etc.

Due to high aromatics and olefins content chemical returns used as gasoline blending components is likely to provide less revenues

At 42% aromatics level:

As gasoline blends Hydroskimmer and Hydrocracker refineries are limited by aromatics specifications. Sulfur is constraint for FCC and complex refineries FCC gasoline blending is not limited by aromatics content.

At 35% aromatic limitation:

FCC refineries will not be able to take aromatics surplus-refineries or C9-aromatics from petrochemical operations. Solution lies in dilution - isomerisate - Extraction of aromatics

The reasons for increasing the isomerate capacity may be summarized as follows:

Easy availability of light naphtha, Increasing gasoline demand, Lead phase-out, Regular grade versus Euro Super and Super 98, Benzene limitation, Aromatics limitation, Sulphur limitation, as the octane losses of FCC light gasoline due to deep hydrogenation have to be compensated.

Steam Cracker feed stock

Increasing use of isomerisation will affect steam cracker feed supply and quality.
Unconverted oil (UCO) form hydrocracker produces less ethylene than high quality naphtha.

Ethane and LPG are other alternatives. Condensate may emerge as real alternative.

Naphtha volume and quality will change due to:

Increasing light naphtha/isomerate requirements at refinery site for aromatics dilution. And because of growing olefins demand while fuel requirements are stable or relaxed.

Changing naphtha quality:

will cause lower ethylene and propylene yields at the same throughput, while pygas output will increase. changing naphtha quality will also cause higher aromatics content in pygas and larger heavy pygas volumes. due to more stringent gasoline specifications especially with respect to aromatics. there will be lower blending values of pygas and C9aromatics. and a limiting of light pygas blending into gasoline due to high olefin content.

Synergies between FCC and olefin production

Catalytic Cracking can be a supplementary source for olefins.

OLEFINS FROM FCC

Generally FCC is designed to produce gasoline and diesel. (Large pore zeolites) Medium pore zeolites over crack gasoline to propylene and butylenes - Pentasil family of molecular sieves are used for this application - ZSM-5 structure most successful - Product gases contain 5-7 wt% propylene

DEEP CATALYTIC CRACKING (DCC)

DCC is an extension of FCC process to produce more propylene and butylenes. Propylene yields of 18-20% can be obtained Modes of operation - maximization of propylene - maximization of iso-olefins Overall scheme is very similar to that of a conventional FCC

Typical Operation Conditions

DCC Temperature C 1020-1100 Cat./oil ratio Dispersion steam wt% Pressure, psig 8-15 10-30 15-30 FCC 920-1020 4-10 0-2 15-30 Steam Cracking 1400-1600 -30-80 atm

Petro FCC
Targets producing petrochemical feedstocks rather than fuel

products

Based on new catalyst (Rx-Cat) to improve yield of propylene and aromatics.

- Lower HC partial pressure - Slightly higher reactor outlet temperature - Improved spent catalyst stripping

- Nearly eliminating post-riser, non-selective back-mixed cracking

- High catalyst flux rates

Yield Patterns
Component, wt%
H2S, H2, C1 & C2 Ethylene Propane Propylene Butanes Butylenes Naphtha Distillate Fuel Oil Coke

Traditional FCC
2.0 1.0 1.8 4.7 4.5 6.5 53.5 14.0 7.0 5.0

Petro FCC
3.0 6.0 2.0 22.0 5.0 14.0 28.0 9.5 5.0 5.5

Catalytic Pyrolysis Process (CPP)

It is a hybrid DCC- steam cracking system. Operated under more severe conditions than DCC Combined yield of C2-C4 is very high It is a petrochemical process designed to make a range of olefins and aromatics.

CATALYTIC PYROLYSIS PROCESS- TYPICAL PRODUCT DISTRIBUTION

Product yield, wt%
Ethylene Propylene & butylene C5+ naphtha LCO HCO Coke Conversion, wt% (Feed: atm residue) 22.78 29.62 14.93 3.72 4.56 8.67 91.72

RESID PROCESSING
Currently the primary goal of an Indian refinery is: To upgrade as much crude as possible into saleable fuel products. Maximizing overall profitability.

Current options: Carbon rejection (coking, deasphalting) Hydrogen addition (resid hydroprocessing) (needs additional hydrogen) These options leave behind undesired hydrogen-deficient material rich in carbon, sulfur, metals etc.

OTHER OPTIONS..
The ability to convert this unmarketable material to produce electricity, clean lighter fuels and petrochemicals permits the refinery to increase its profitability

The refiner can choose among three electricpower-generation methods: Circulating-fluidized beds (CFB) Boilers with flue gas desulfurization (FGD) Integrated gasification combined cycle (IGCC)

Primary factors affecting the selection for power generation need balancing - Environmental issues - Efficiency - Economics while preserving strategic options for future investments.

RESIDUE CONVERSION
GASIFICATION
Gasification Power, hydrogen Syn gas petro-chemicals

Offers an alternative to handle high sulfur and metal containing residues in a refinery with value addition
Alternative economically attractive option for many of the problems associated with changing scenario in the petroleum refining industry Great advantage in co-generation and petro-chemicals via syn gas

COMPARISON OF ELECTRICAL GENERATION OPTIONS

CFB Sulfur-removal experience Merchantable sulfur Oxygen/ nitrogen byproduct

Hydrogen byproduct Cost. $/kw

FGD 95%
No

IGCC +98%
Yes

95%
No

No

No

Yes

No 900

No 700

Yes 800-1,000

COMPARISON OF TYPICAL EMISSIONS, LB/MW-HR @ 100% CAPACITY

Natural gas combined cycle Coke gasif. Combined cycle Coke circulating fluid bed Coke boiler FGD & SCR*

SO2

0.0

0.5

3.7

3.6

NOx CO
VOC Particulates CO2 Solid waste

0.3 0.2
0.02 0.05 820 0.00

0.4 0.3
0.07 0.07 1,930 9.1

0.9 1.5
0.08 0.2 2,170 350

1,5 NA
NA 0.2 2,120 190

*Fuel gas desulfurization and selective catalytic reduction. The solid wastes from a
coke gasifier contain only the feed metals plus some carbon.

PETRO-CHEMICALS FROM REFINERY COKE

Valuable material for producing petrochemicals Excellent source for high purity acetylene which is a useful starting material for host of petro-chemicals such as acrylonitrile, vinylchloride, acrylic monomer etc.

PETRO-CHEMICALS FROM REFINERY COKE

REFINERY GASOLINE, DISTILLATE, ETC CRUDE OIL

REFINERY

COKE

CALCIUM CARBIDE PLANT

ACETYLENE OR CARBIDE

PETROCHEMICAL PLANT

ELECTRIC UTILITY

POWER

PETROCHEMICAL PRODUCTS CaCN 2 HCN Mg ACRYLONITRILE VINYL CHLORIDE PLASTICS ACRYLIC MONOMER ACETYLENE BLACK CHLORINATED SOLVENTS ACETALDEHYDE ACETIC ACID ACETIC ANHYDRIDE ACETYLENE CHEMICALS FROM REPPE CHEMISTRY

RES. & COMM. POWER TO COMMUNITY

Figure -12: Fuel power relationship between refinery, utility plant, carbide plant, and petrochemical plant

Impact of Diesel Quality

If only further sulfur reduction is involved, there is likely no impact on petro-chemicals.

Summary:
More stringent gasoline specifications will change refining and petrochemical synergies, as they will have an impact on refinery/ petrochemical interfaces. Future diesel specifications are likely to have very little or no impact on refining and petrochemical integration. Isomerization of light naphtha likely to play an important role. Pyrolysis gasoline upgradation need to be relooked. FCC, DCC and CPP will have major impact on petrochemical refinery integration

THANK YOU