Creating future fuels

Creating future fuels

Refinery Technologies Meeting

Future Fuel Specifications

Petroleum Refining Industry has been Processing

Crude oil and upgrading quality of Petroleum Products
to meet the Energy Requirement of Mankind

Catalytic Technologies for Petroleum Refining

Transportation Sector Accounts for 40% of Oil Consumption in

USA

Crude Oil reserves could come to an end by middle of 21st Century

Realization that crude oil reserves are limited

Consumption continue to grow (0.2 Btoe/ annum)

Dr G Murali Dhar

Attention focused on raw materials which were considered less

important in the past for converting to transportation fuel
Natural Gas

Indian Institute of Petroleum

Dehradun

Heavy Oil
1

Creating future fuels

Creating future fuels

Last Decade: Natural Gas Reserves Increased considerably

Enormous Methane Reserves
Gas Hydrates Bottom of Ocean
Coal Bed Methane
Gradual Take over to Gas Era from Oil Era by Middle of the 21st
century

Renewable Energy Sources

Solar (Photovoltaic)
Bio Mass : Substitute for Transportation Fuel (Diesel)
Hydrogen: Fuel Cells

Developments in Refining Quality Trends /

Environmental Concern

World Oil Crisis in 1970s

Search for substitute for fossil fuels Alternative fuels

Refining Heavier Fractions Resid Catalytic Cracking

End 1970 Protect Environment from Noxious Emissions Strong Impact on Refining

Gasoline - Lead Phase Out: Complete ban since Jan 2000 in

Europe

Sulfur (<10 ppm), Aromatics (<35%), Benzene (<1%)

Oxygenates (2.7%)

California Still More Stringent Banned MTBE

Sulfur in Diesel (50/10 ppm)

Creating future fuels

Creating future fuels

1990s : Change of Climate by Green House Gases: CO2

- Global Warming

Evolution of Motor Fuel Specifications in Europe

Since 1994
Fuel

1994

1995

2000

2005

2010

<10

Gasoline
Sulfur (ppm) max

Reduction in emission of CO2, i.e., restriction in

combustion of fossil fuel
Capture & Chemical Sequestration of CO2
Fuel efficient / advanced technology zero pollution IC
engine with three way exhaust catalyst for Gasoline
engines
DeNOx catalyst: For Diesel Engine Applications
5

1000

500

150

50/10

Benzene (Vol%) max

--

<1

Aromatics (Vol%)
max

--

--

42

35

< 35

Olefins (Vol%) max

--

--

18

18

< 10

Oxygen (Vol%) max

(Oxygenates)

--

2.7

2.7

2.7

--

RON / MON min

--

--

95/98

95/98

95/98 (?)

RVP kPa max

80

--

60

--

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Creating future fuels

Evolution of Motor Fuel Specifications in Europe

Since 1994
Fuel

1994

1995

2000

2005

Creating future fuels

2010

Emission Limits Europe 2007

Diesel Oil
Density (g/ ml) max

0.845

0.8450.840

0.84-0.82

Cetane number, min

49

51

51-53

> 55

Sulfur (ppm) max

2000

350

50/10

< 10

Distillation, 95% TC
max

370

360

360340

< 340

11

11-3

<2

PolyNuclear Aromatics
PNA (wt%) max

Exhaust Emissions: Gaseous Streams main

concern NOx, SOx, VOC

Pollutant

Power > 500 MW

Power < 300 MW

SO2 mg/ Nm3

400

1700

NOx mg/Nm3

450

450

Particulate mg/ Nm3

50

50

Creating future fuels

4.0

Creating future fuels

3.0

Catalysis play a vital role in petroleum

industry
More than 90% of finished refinery
products come through a catalytic process
Importance of Purely Thermal Processes
declined in past 40 years due to high
performance and cost effectiveness of
catalytic processes.

2.0

1.0

0.0

Gasoline

LPG

Gasoil

Jet/ Kerosene

Liquid Fuels: Main transportation fuel demand increase, 2000 - 2010

Demand Shifting from Gasoline to Middle Distillates: JET/ Kerosene/ Diesel
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Creating future fuels

Petroleum Refining

10

Creating future fuels

Hydrocracking

Hydrocracking : High Pressure: 100 200 bar ,Temp : 300- 450C

Bifunctional Catalyst: Metal Hydrogenation Function
Acid Sites Support - Acid function for cracking
Flexible Products :Gasoline, Diesel -By changing reaction
parameters.
Catalysts:Sulfides NiMo, NiW on SiO2/ Al2O3
NiW > NiMo > Co Mo Hydrogenation Activity
Conventional Amorphous SiO2 / Al2O3 has been replaced by
USY Ultra Stable Zeolite
Pt/Pd also added in some catalyst as Additives
Perfect Balance between hydrogenation / Acid Function
- A weak Acid / Strong hydrogenation combination Suit Middle
Distillates (Diesel)
- A Strong Acid / Weak Hydrogenation Suit Gasoline Production.
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12

Hydrocracking a Two Stage Process

Hydrotreating

Creating future fuels

Creating future fuels

Pretreatment: HDS/ HDN

HDN Hydrodenitrogenation NiMo/ Al2O3 important as nitrogen in the
feed forms NH3 and poison acid sites of the cracking catalyst
AKZO Nobel Developed Improved HDN Catalyst NiMo

Widely used Process in Refinery

Purification of Different Petroleum Fractions
Organo-S-Compound + H2 H2S + Hydrocarbons - HDS (Hydrodesulfurization)
Organo-N-Compound + H2 NH3 + Hydrocarbons - HDN (Hydrodenitrogenation)
Organo-O-Compound + H2 H2O + Hydrocarbons - HDO (Hydrodeoxygenation)

Relative activity

Improve Quality of Products

- Desulfurize Naphtha prior to Reforming
- Reduce S & Aromatics in Kerosene & Diesel
- Improve Color & Stability of waxes & Lube Base Oil
- Lower S & Metal Content in Hydrocracker & FCC Feedstock

Catalysts: CoMo > NiMo > NiW / Al2O3 (HDS)

NiMo > CoMo / Al2O3 .
(HDN)
Active Metal : Mo, W 15 25% MoO3 / WO3
Promoters: Co, Ni 4 8 % CoO, NiO
Used in sulfided form. Very stable: Long Life 5 years

0
1965

1980

1990

2000

2005 Years

Relative volume activities for hydrocrackers pretreater catalysts

13

Creating future fuels

14

Reaction Rates of DBT

Creating future fuels

Relative Rate
R

+ H2

40 f

+ H2S

S
R2
R1

+ H2

+ H2S

10 f

S
R2

R2
R1

+ H2
S

R1

+ H2S

R3

R2

R2
R1

Intermediate

R3

+ H2

R1

+ H2S

f
(slowest)

S
R4

R3

R4

R3

15

Reactor Temperature and Catalysts Effects

Creating future fuels

Creating future fuels

Deep HDS: Costly H2 Consumption

Alternative Routes explored:

Product Sulfur ppm

250

16

Co Mo cat

Bio - Desulphurization: Last decade Much Progress

Technically viable but economic viability to be explored.

Ni Mo cat

200

Smart cat system

150

Oxidative Desulfurization
Sulfur Compounds Sulphones / Extracted with solvent
Oxidizing Agents: H2O2, Organic Peroxides
Hydrocarbon Sulphones Adsorbed on Alumina/
Adsorbents.

100

50

0
Low Temperature

High Temperature
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Creating future fuels

Alkylation

Fluid Catalytic Cracking ( FCC )

Creating future fuels

1930 - First Catalytic cracking - Silica- Alumina

1960 - Y- zeolite Containing Rare Earth (REY) Increased Gasoline Yields
1980 - USY ( Dealuminated Y ) + ZSM-5 Octane Booster
1990 USY -ZSM-5 regulation to Maximize Olefins ( Propylene )
FCC Gasoline - Represents 35% of Gasoline Pool contributes
- 95% of Sulfur in Gasoline
Process Conditions: Temp. -500 -550 C, Press.15-20 psi, Res. Time 1-10s
Regeneration : 650 700C , Res. Time >10s
Feed : VGO, Resid
Moving Bed Operation: Sufficient Attrition Resistance
Catalyst Fines Formed , Make up Fresh Catalyst 0.5 -1 ton /day for plant
1000 #ton catalyst
Catalyst :
Silica-Alumina Matrix with binder primary cracking of
Recipe
heavy molecules
Zeolite Y (USY ) - secondary cracking in pores of zeolite
ZSM -5 Additive ( small % ) - Gasoline, Olefins production
Reactions : Acid catalyzed cracking reaction - Carbenium ion mechanism

MTBE Phase Out -- USA -- California Banned MTBE

Refineries have To Manage : Loss in Octane in gasoline pool
Demand of Gasoline with Lower Aromatics < 35% , Lower Benzene ( <1% )
Importance of Alkylation & Isomerization Greatly Increased
Alkylation: Reaction of
Isobutane + C4= Olefins ( Butene-1/ Butene -2)

2,2,4 Trimethyl Pentane

Iso octane ( ON 100)

Catalysts : Since 1940 - To Date - Liquid Catalysts HF & Conc. Sulfuric Acid
1990 Solid Catalysts : BF3/ Al2O3, BF3/Amberlite,Supported SbF5,
Sulfated Zirconia, Zeolites Shell/Akzo- Not Yet Commercial
World Production Alkylates --- 40% From HF Catalyst
--- 60% From Sulfuric Acid

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20

Isomerization
Creating future fuels

Creating future fuels

Catalytic Reforming

C5 C6 ( 60 80 oC ) Cut -- Good Feed Option for Isomerization

Originally Developed for

Process Conditions : Fixed Bed, Temp. 200 -250oC, Pressure 10 -15 bar

Production of High Octane Motor gasoline from SR Naphtha

Single Cycle isomerization -- 10 15 units Octane Gain

Recycle Isomerized Feed Till Mono alkane Extinction --- 20- 25 Units Octane Gain

Today
Catalytic reforming is aimed to produce:-

Catalyst : Very Strong Acid Catalyst to operate at

Low Temperature Favorable Thermodynamically for Branching

High octane motor spirit

- Broensted Superacid monofunctional HAlCl4 First Used

1960 -70 Bifunctional Catalyst, Pt/Al2O3-Cl & Pt/Mordenite
Hydroisomerization : To Suppress Coke Formation
Hydrocracking Negligible / H2 Consumption Very Low

Aromatics - BTX for Petrochemicals

High Purity Hydrogen
LPG

Pt /Zeolite Superior over Pt/Al2O3 in Better Activity, Regenerability, Longer life, Resistant
to Poisons

Upgrading Paraffin stocks and Olefins

21

Reforming

Reforming

Creating future fuels

22

Creating future fuels

Process Conditions : Temp: 480 510oC / Pressure :

Catalysts :

5-25 bar

Catalytic Reforming has undergone several stages of Improvement

1940 : Chromia & Molybdena/ Al2O3

1949 : Pt/Al2O3-Cl
Monometallic Bifunctional
1969 : Pt-Re/Al2O3-Cl
Bimetallic
,,
Pt-Ir/Al2O3 Cl
,,
,,
1970 Pt-Sn/Al2O3-Cl
,,
,,

Process Technology : Continuous Efforts to Decrease H2 Press.

To Favor Dehydrocyclization ( Aromatization)
Optimum Metal Acid Function Balance
Chlorine - Less - Low Cyclization/ Isomerization ; Low C5+ Yields
Chlorine High - Excessive Hydrocracking - High Gas make ( C3-C4 ),Low C5+

Amer. Oil Co
Fixed Bed / SR UOP
,,
/ SR
Chevron
,,
,,
Moving Bed/CCR UOP

Thermodynamics/ Kinetics:
Reaction
Rate
Site
Thermal Effect Favorable Conditions
Dehydrogenation
Very rapid Metal
Endothermic
Low Press./High Temp
Dehydrocyclization Slow
Metal/Acid Endothermic
,,
Isomerization
Rapid
Acid
Mild Exothermic
Press. No Effect
Hydrocracking

Very Slow

Metal/Acid Exothermic

High Press/High Temp

Trends in operating conditions
Catalytic Reforming
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Gasoline Blend

Creating future fuels

Light Naphtha

Alkylation / Isomerization

Heavy Naphtha

Cat. Reforming

Creating future fuels

Hydrogen Economy -- Enormous Impact on Energy Industry/ Existing Infrastructure

Hydrogen Generation/ Consumption : Technology Emerging
Link between H2 Generation & Distribution No Convincing Technology
H2 Distribution : Storage / Transportation / Release on Demand ----- Barriers
Transportation Gas State Pipelines Risky
Liquefication Cryogenic Technology --- Expensive
Chemical Storage : Metal Hydrides / Carbon Nano tubes
--Small Scale Only
Production of Hydrogen Based on Hydrocarbon Feed Stock ---- CO2 as a Byproduct
Chemical Sequestration of CO2 ------- Additional Technology Required
Two Ways Producing Mechanical Energy From Hydrogen: Direct Use in IC Engine
Through a Fuel Cell
Options: 1. H2 in Fuel Cell in-situ on board car or 2. From Residential units
Sulfur Should be very Low- Poison Every stage of Processing Chain of Fuel Cell

Reformulated
Gasoline (RFG )
Light Olefins

MTBE

FCC Gasoline

DHDS/ Isomerization

Future Catalytic Technologies

Alternative Fuels :
Hydrogen

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26

Alternative Fuels
Creating future fuels

Natural Gas

Creating future fuels

Transformation of Natural Gas ( > 95% Methane) to Syn Gas Followed by

Hydrogen Production :
Catalytic Reforming of Naphtha
Steam Reforming of Light Naphtha
Steam Reforming of Natural Gas
Gasification of Coal / Petroleum residues
Syn Gas / WGS Reaction
Bio- Mass
Electrolysis

Fischer- Tropsch Synthesis ! Hydrocarbons ---- GTL (Gas to Liquid ) Technology

Steam Reforming : CH4 + H2O --( Ni Cat./ 800 oC,20 bar)
Partial Oxidation : 2CH4 + O2

-!

3H2+ CO

( 1200-1500 oC),>140 bar ) ----! 2CO + 4 H2

Potential FT Catalyst : Carbon Rich Source ( Coal) -- Ni /Fe / Alumina or Silica

Hydrogen Rich Source ( Natl. Gas )

Co / Alumina

FT Process Since 1920 : Catalyst & Process Development Still in Progress

Production of Syn Gas itself Accounts for 60% of the Capital Cost
FT Synthesis : Temp. 200 300 oC , Press. 10 40 bar
n CO + ( 2n+1) H2 ----! Cn H2n+2 + n H2O
FT Diesel Quality

(H = - 39.4 Kcal/ mol)

: S < 5ppm, Aromatics < 1%, Cetane >70, Density<0.78g/cc

Reactors: Tubular Fixed bed ,Fluidized Bed, Circulating Fluidized Bed

Slurry Phase Bubble Column Reactor ( CBCR) - - Future Reactors for Qatar (Exxon/Mobil)
& Nigeria (Chevron ) Plants 2005
Commercial Plants ; Sasol South Africa -- Since 1955/1980/1982

Fuel processor for small-scale hydrogen production for fuel cell

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28

20th Century catalytic technologies in refining

Fuels from Syngas

Creating future fuels

Creating future fuels

Year

Steam reforming
Partial oxidation

Deep desulfurization of diesel and gasoline

2000

HDS of FCC gasoline /

Three way Exhaust Catalyst

Syngas (H2, CO, CO2)

Etherification / Catalytic Distillation Column

MeOH

DME
Alcohols

DMC
(Dimethyl
Carbonate
solvent)

DMM
(Dimethoxy
Methane

CCR Reforming

Fischer Tropsch
Olefins

Ethers (MTBE)
(TAME)

Gasoline

Heavy Oil

1950

Paraffins

Hydrotreating
Cat cracking + alkylation + polymerization

UPGRADING
Kerosene

Zeolites in FCC

Platforming

Hydrogenation
Thermal Cracking

Diesel

Speciality
product
29

1900

Continuous distillatioin

30

Creating future fuels

Catalysis in 21st Century Would be Centered around

A Shift from Oil to Gas Era
Environmentally Benign Technologies

Creating future fuels

Sulfur Reduction : Deep HDS : Diesel

FCC Gasoline
Aromatics / Benzene :

Gasoline -- Alkylation / Isomerization

Alternative Fuels :

Natural Gas
GTL Syn Gas -- FT HC ( Diesel/ Gasoline )
DME ( Diesel)
Bio-mass Jatropha Seeds Diesel
Methane Activation
C1 C4 Alkane Oligomerization ( Aromatics)
Hydrogen Fuel Cell

Catalytic Combustion :

DeNOx Catalyst Pollution Abatement -- Diesel Fuel

Petrochemicals

Propylene ---- FCC ( DCC)

BTX

31

Creating future fuels

Thank You

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