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Smart Tailored Biorefinery: An Integrated Approach to
Increasing Economic Value of Downstream Oil and Minimizing
Environmental Aspects
Professor K.K. Pant
(Petrotech Chair Professor)
Email: [email protected]
DEPARTMENT OF CHEMICAL ENGINEERING
INDIAN INSTITUTE OF TECHNOLOGY DELHI
Concept of Green Chemistry
• Efficient use of (preferably renewable) raw
materials,
• Elimination of wasteful byproducts,
• Avoiding use of toxic/hazardous reagents and
solvents,
• Use of safer final (biodegradable) products,
and
• Increasing energy efficiency.
Defined as: (Chemicals in (kg) - Desired product (kg) ) / Total product (kg)
The enormous waste in different segments of industry are:
Industry segment Product, tonnes/annum kg waste/ kg product
Oil refining 106-108 <0.1
Bulk chemicals 104-106 <1-5
Fine chemicals 102-104 5-50
Pharmaceuticals 10 - 103 25-100
E FACTOR
M. Lancaster, “Green Chemistry : An Introductory Text, Roy.Soc.Chem., cambridge, 2002.
Indian Chemical Market
• Global sales of chemicals more than doubles over last decade and reached $ 5.2 trillion in 2013
• India is 13th largest in terms of ethylene capacity (190 mmtpa) with proposed enhancement in refining
capacity up to 300 mmtpa. Moreover, India is third largest consumer of polymers
Ref: A brief repot on chemical and petrochemical industry in India, April 2015, Corporate Catalysts India Pvt. Ltd.
0
50
100
150
200
250
Specialty
Chemicals
Petrochemicals Chemicals
2015
2020
$ B
illi
on
Smart Refinery Concept
• Economized Small to Medium Scale Stand-Alone compact
Refinery
• Significant Saving of Initial Capital expenditure with New Design
Concept
• Shorter EPC Schedule with Concept of Packaged Refinery
• Simplified Integrated Process Flow Scheme =>Reducing Number
of Process Units
• Biorefinery is the sustainable processing of biomass into a
spectrum of marketable products and energy.
Smart Refinery: Advantages
• Simplified Integrated Process Flow Scheme => Reducing
Number of Process Units
• Co-Generation Utility System => Energy Saving
•Advanced Offsite Design => Saving Storage Tanks
• Integrated Plant Layout => Compact Plot Plan
•Standardized Process Design => Shortening Engineering
Schedule
Smart Industrialization Vision (Source: Cisco IBSG, 2010)
Feedstock
Smart Tailored Biorefinery: A sustainable approach
Conversion Process Fuel Components
Current Oil Crops (Soy, Rape, Corn),
Waste Oil, Jatropha, Camelina etc. and
Fats
Future Crops (Oil from Micro Algae)
Woody Energy Crops, Forestry
Residues, Agricultural Residues
Non Biomass Feedstock’s: Coal & Gas
Biodegradable MSW, sewage sludge,
wet wastes, macro-algae, micro-algal
residues
Sugar and Starch Crops
Hydro treating
Gasification and FT
Pyrolysis and Upgrading
Conversion of Sugars, if
needed, then Biological
and Chemical Routes to
Hydro treated
Renewable Jet Fuel
BTL
Jet Range Cyclic
Hydrocarbons
Synthetic Hydrocarbons
Where is the Problem?
• Low Oil Prices: Sudden decline in crude oil
prices.
• Low Value Product: Energy content of bio oil is
very low.
• Single Product Based Units: Only one or two
products are produced.
• Inefficient Processes: Improper utilization of
resources.
$30 per barrel
Gasoline 35.7(GJ/m3)
Bio-oil 10.6(GJ/m3)
e.g. For furfural production only
hemicellulose is utilized. Rest 73
wt% total biomass is either
unutilized or fired in boilers
Interest in Biomass by- 2030/ Bio Refinery
• Numerous visions/initiatives have been proposed and projects that ethanol and advanced biofuels could provide 10% of transportation fuels in 2030.
• About 10% of available residues (75 GT/Yr by 2030) could provide 120-150 billion lge of liquid biofuels (its has the potency to cover 5% of the 2030 biofuels demand).
• Projected Demand
• IEA projected bio-energy demand 65 EJ for biofuels
• 80 EJ for heat and power requirement
• Bioenergy demand by land availability (IEA projection)
• Today 30 Mha to 100-160 Mha by 2050
• Global CO2 emissions are projected to peak in 2020 and decline
quickly thereafter, reaching 26.4 Gt in 2030, or 10% less than 2007
emission levels.
Composition & Categorization of Biomass
ENERGY CROPS AGRICULTURAL WASTE WOODY CROPS
Cellulose (%) 45 43 45
Hemicellulose (%) 30 27 25
Lignin (%) 15 17 22
First generation Second generation Third generation Fourth generation
Bio fuels produced
from food crops
Bio fuels produced
from non-food crops
Genetically modified
carbon neutral crops
Genetically
modified carbon
negative crops
Advantage of Next Generation Biomass • Reduces greenhouse gas emissions by using industrial and agricultural waste, residues
that would otherwise decompose into methane when land-filled.
• High annual energy yields from dedicated energy crops (poplar trees ), can be achieved
as compared to traditional food crops (1st-generation biomass)
Why Bio Lubricants ?
Estimated 30-45% of all lubricants are “lost” through accidental
spillage, leaks & evaporation …
EPA Report: of 1.4 billion gallons waste oil generated annually…
• 775 million gallons commercially recycled, re-refined or burned
• 170 million gallons dumped in the sewer and landfills
• 150 million gallons burned into our atmosphere illegally
• 305 million gallons are unaccounted for.
Which one is Better? (All are important)
Fuel Density (kg/m3) Energy Content
(GJ/m3)
Gasoline 740 35.7
Diesel 850 39.1
Coal 600-900 11-33
Methanol 790 17.6
Ethanol 790 23.5
Bio-oil 1280 10.6
2-MF 913 28.5
DMF 890 29.3
Biodiesel 900 35.6
Raw Material Challenges
Crop Oil Yield gallons/acre
Corn 18
Cotton 35
Soybean 48
Sunflower 102
Rapeseed/Canola 127
Jatropha 202
Algae 1200-10,000 (High yield)
Need of Hour?? : Genetically Modified Crops
Biomass Availability in India
Non-food & Non-fodder/ Surplus
Lignocellulosic Biomass:
- Cotton Stalk
- Wheat Straw
- Rice Straw
- Sugar Cane trash
- Many others !!
• Annual availability > 300 MT/Yr
• Biomass biofuel potential > 100 MT/Yr
Crop residues
Production Million tons
1994 2014
Field based residues
Cotton stalk 19.39 30.79
Rice straw 214.35 284.99
Wheat straw 103.48 159
Maize Stalk 18.98 29.07
Soybeans 12.87 34.87
Jute stalk 4.58 1.21
Sugarcane
tops
68.12 117.97
Ground nut
straw
19 23.16
Processing Based residue
Rice Husk 32.57 43.31
Rice Bran 10.13 13.46
Coconut shell 0.94 1.50
Coconut husks 3.27 5.22
Ground Nut
Husk
3.94 4.80
Sugarcane
bagasse
65 114.04
I I T D
Utilisation of Seed Cake
S No Seed Name Potential (million metric tonnes per year) Oil Content (%)
Seed Oil Cake
1 Pongamia pinnata (karanja) 0.2 0.055 0.145 27-30
2 Jatropha curcas 0.05 0.015 0.035 30-40
3 Azadirechta indiaca (neem) 0.5 0.1 0.4 20
4 Madhuca indica (Mahua) 0.5 0.18 0.32 35
5 Shorea robusta (Sal) 1.5 0.18 1.32 12-13
Potential Availability of some non edible oil seeds in India
Biodiesel and Seed cake required as per Indian standards for diesel blending
Projected
For every 1 kg
production of bio-diesel
using transesterification
process, 3-4 kg of waste
seed cake is generated
Huge waste seed cake can be converted to fuel
BIOMASS COMPOSITION
Hemicellulose
• Polymer of 5- and 6-carbon
sugars, marginal biochemical feed
Lignin
• Complex aromatic structure
• Very high energy content
• Resists biochemical conversion
Cellulose
• Most abundant form of carbon
in biosphere
• Polymer of glucose, good
biochemical feedstock
Routes of Biomass Conversion
Dumesic & Co-workers, Energy Environ. Sci., 2011,4, 83-99
AGRICULTURAL BIOMASS
FT Synthesis
Alcohols
Hydrocarbons
Gasoline, Diesel
Cracking Gasoline, Diesel
Cracking
Bio-Alcohols
Bio-Hydrogen
Chemicals
DME
Syn-Gas
Bio-Oil
Gasification
Bio oil reforming
SCWG
Hydrogen
Pyrolysis / / Hydropyrolysis
Biofuel Options
Chemical Catalysis
I I T D
BIOMASS CRACKING
Biomass
Coke
Heavy Hydrocarbons
+ oxygenates
Light olefins + light paraffin
Gasoline + CO2 + alcohol + CO +
H2O
Olefin + Paraffin (gasoline,
Diesel and Kerosene
Gases (Light olefin, paraffin
CO, CO2, H2O)
Aromatic
Hydrocarbon
Condensation Cracking and
de-oxygenation
Secondary cracking
and deoxygenation
Oligomerization
Aromatization,
Isomerization,
Alkylation
Po
lym
eriza
tio
n
Biomass cracks to smaller hydrocarbons
via various decarboxylation,
deoxygenation, oligomerization,
aromatization reaction with high oxygen
content
Targeted products
C6 to C11+ aromatics
C2 to C4 paraffins and Olefins
==== Important for petrochemical industries
Desired catalyst Characteristics
Support (ordered silicas with very large mesopores)
for cracking of heavy hydrocarbons
Noble Metal (Pd, Ga, Ru, Rh, Pt) for deoxygenation
reactions
Upgradation
Biomass (dry)
Biomass (slurry)
Energy Crop Plantation, Soil Remediation and CO2 Storage.
Anaerobic Digestion for Biogas Production.
Low Temperature Catalytic Pyrolysis.
Utilization of By-products From Renewable Energy Production
High Rate Algal Pond for Fast , Efficient Waste Water Treatment and Algal Biomass Production.
Synthetic Natural Production from Biogas + Pyrolysis Gas+ Gas from Cracking Pyrolysis Liquid.
Biochar
Effluent
Tre
ate
d
wa
ter
Wastewater
Useful
Commodities Solid wastes
Energy
Animal wastes
(semi-solid wastes)
A. Biomass Production-1 (Algae). A1: Pond design, construction, operation and performance evaluation. A-2: Algal biomass harvest (thickening) , biodiesel and pre-treatment for Anaerobic Digestion (AD) A-3: Chemical and energy analysis of Biomass
C. Renewable Energy Production-1 (Anaerobic Digestion (AD)). C-1: Microbial community analysis and optimization. C-2: Pilot scale testing. C-3: AD plant design, construction.
E. Energy Conversion (SNG). E-1: Convert gas mixture to Synthetic Natural Gas (SNG). E-2: Optimizing internal combustion engine to use SNG.
D. Renewable Energy Production-2 (Pyrolysis).
D-1: Catalysis optimization.
D-2: Pyrolysis equipments and Testing.
B. Biomass Production-2 (Energy Crops). B-1: Marginal/wasteland soil remediation with biochar and liquid fertilizer B-2: Biomass harvesting and high value chemical production.
F. By-Products Utilization (Biochar+AD Effluent). F-1: Biochar for wasteland rehabilitation and AD effluent as sanitized liquid fertilizer F-2: Application Biochar for Recovery nutrient (Phosphate) and algal biomass. F-3: AD effluent as nutrient for algae growth.
Biogas
Pyrolysis gas
Res
idu
e
Hea
t
A
F
D B
E
C
+CO2
Conceptual Framework: Different areas of research projects through PI
XTL Methodology and Overall Objectives
Understand and address problems related
to handling of solid fuels, ash, their mixing
and segregation in gasifiers through
experimentation in cold flow mock-up units;
Modeling of gasifiers and gasification –
modeling of hydrodynamics, heat transfer
and heat management, for intensification of
the gasification process;
Investigation of kinetics of Fischer-
Tropsch (FT) reaction with novel catalyst
formulations through bench scale testing
and modeling;
Modeling of kinetics of FT;
Understand and address problems related
to handling of viscous slurries, phase
segregation and its impact on reactor
performance, and develop ways of process
intensification in FT;
Investigation of novel reactor
configuration for process intensification in
the overall CTL/BTL route, with particular
relevance to Indian feedstocks.
COAL PET COKE BIOMASS
SYNTHESIS GAS GENERATION
Steam + Air
CO + H2
FISCHER -TROPSCH SYNTHESIS
Power
Stea
m
Tail G
as
PRODUCT SEPARATION & UPGRADING naphtha
petrol
diesel
wax
Characterization of solid fuels sourced in India – coal and biomass
Gas purification using electrochemical membrane cell
Fine tuning of properties of synthetic liquid fuels via novel blends and formulations;
GAS CLEANUP
• The solar refinery provides a concept for chemical energy storage science and technologies. Several concepts allow the generation of solar hydrogen
Next Level of Challenge
Upgradation of bio oil into regular fuel is required which is typically done by progressive removal of oxygen content from it? If we can do this, then there will be no blending required. 100% of biofuel can be used in existing engines.
Methods of upgradation of Bio-Oil into Fuel & Bio-Lubricants
Selective Oxidation
HYDROTHERMAL PROPERTIES OF WATER
Three basic steps of biomass hydrothermal
disintegration process are
Depolymerization of biomass
Decomposition of biomass monomers by
cleavage, dehydration, decarboxylation and
deammination
Recombination of reactive fragments
In hydrothermal conversion water acts as
reactant and catalyst, and makes process
different than pyrolysis.
Ionic product of water is very high in subcritical range which accelerates acid- or base catalysed reaction e.g. Biomass hydrolysis .
At conditions close to critical point water has a low viscosity and high solubility of organic substance
+ CH4
Flue gas/ Biogas
Synthesis gas (CO + H2)
H2
CH3OH/ DME
Synthetic fuels
Water gas shift reaction
Fischer - Tropsch synthesis
Methanol synthesis
TEM image of
fresh catalyst
TEM image of
spent catalyst
TRM @ 800oC &1 atm
No
sign of
coke
deposition
Reduction of Carbon Footprint via Tri-reforming
Challenges in F-T Process
Selectivity of catalyst
Lower H2/CO ratio (0.5 - 1.2) of biomass derived syngas.
Excess wax formation.
Catalyst deactivation
Coal
Biomass
Syn gas CO+H2
Fischer Tropsch Process
FT Catalyst
Liquid Fuel
C5-C20
( H2/CO - 0.5-1.5)
Syn Gas to Olefins and Paraffin (FT Synthesis)
Bimetallic catalyst
+ +
+ WGS reaction
FTS reaction
+
H2 H2O CO
CO2
CO
C5+
Hydrocarbon
Reaction Conditions:
Temp. 200-300 deg C
Pressure: 15-25 bar
FT Process
Utilization of Gaseous Products
Cellulose
CO + H2 CH3OH CH3OCH3
CH4
Tri--Reforming
Electricity
Methanol DME Syn Gas
Olefins, Paraffin, Aromatics Non-oxidative
Direct Conversion
Fuels
Chemicals Gaseous
Products
CO, CO2 H2,
CH4
Hemicellulose
Lignin
O2
CO2 H2O
Catalytic Decomposition in Fluidized Bed Reactor CNT + H2
Current Focus of Research
Total Production Cost Reduce by 8%
Utilization of Sugars
Cellulose Glucose 5-HMF
Levulinic Acid
-3H2O -HCOOH Dehydration
CO + H2 CH3OH CH3OCH3
CH4
Tri--Reforming
Electricity
Methanol DME Syn Gas
Olefins, Paraffin, Aromatics Non-oxidative
Direct Conversion
Fuels
Chemicals
Gaseous
Products
CO, H2, CH4
Hemicellulose Pentose Furfural Furfural Alcohol
Dehydration -3H2O +H2
Lignin
O2
CO2 H2O
Catalytic Decomposition in Fluidized Bed Reactor CNT + H2
Proposed Technology Inputs for the Project
Oil Cakes
Medicinal Oils Emulsifiers, Paints,
Lubricants
Glycerol Biodiesel
Syngas (FT Products- (Methanol)
Propylene Glycol
Acrolein
Bio-oils (pyrolysis) Aqueous Phase Sugars
(hydrolysis)
High Value Biochemicals
(proteins,lipids)
Platform Molecules (Pyrones, Lactones)
High Value Chemicals and Fuel Additives
Seeds, Flowers, Leaves
Integrated strategy for the production of chemicals from biomass
Bio Refining :Example of forest products and high value products from
these products
Hydrothermal Treatment (150 oC, 60 min)
(50oC, 24h)
Hydrothermal Carbonization
Liquid Hydrolyzate
Carbon rich Microspheres
Solids
Ethanol + stillage
(Glucose, Xylose,
Oligomers)
Enzymatic Hydrolysis
(50oC, 24h)
Microbial Fermentation
(30oC, 72h)
Lignocellulosic Biomass
Hydrothermal liquefaction (350oC, 60 min)
Biooil
Biochar
Gases For heat Recovery
Water soluble organics
Raw water
Catalyst
Organics
Solids
Liquid Hydrolyzate
Product mixture
Separation Aqueous phase
Gas phase
Solid phase
Diethyl Ether Acetone
LBO Soluble Products HBO Biochar
Approach for conversion of Lignocellulosic Biomass
Major Petrochemical Segments
Petrochemicals
Basic Petrochemicals End Product
Petrochemicals
Olefins:
Ethylene, Propylene,
Butadiene
Aromatics: Benzene,
Xylene
Polymers, Medicine,
Drugs, Surfactants
Segment
Classification
Major Products
Polyalphaolefins
(PAO), additives for
lubricants, Amines
and Amine oxides
Oil field chemicals,
LABS and Wax
replacement
Detergent Alcohols, Linear alkyl
benzene (LAB), LABS,
Nonionics and Oil field
chemicals, Drilling Fluid,
Chloroparaffins
Aldehydes,
Plasticizer Alcohols
Polymers,
Polyethylene (HDPE
& LLDPE) co-
monomer,
Mercaptants
C6+
Olefins
High Value Product
Oil Field Chemicals (also
includes some C14 olefins),
Lube oil additives and
Surfactants, Paper Sizing
Chemicals
C10-C12
One Pot process for Production of Reducing Sugars from Bamboo Biomass
Bamboo
Biomass
Alkaline
Solution
[BMIM] Cl
Pretreatment
Cellulose Rich
Dissolution
Hydrolysis
Separation and Post-treatment
Hydrolysate
Characterization
Catalyst
Effect of temperature and hydrolysis time on total reducing sugar (TRS) yield
Utilization of Lignin
Cellulose Glucose 5-HMF
Levulinic Acid
-3H2O -HCOOH Dehydration
CO + H2 CH3OH CH3OCH3
CH4
Tri--Reforming
Electricity
Methanol DME Syn Gas
Olefins, Paraffin, Aromatics Non-oxidative
Direct Conversion
Fuels
Chemicals
Gaseous
Products
CO, H2, CH4
Hemicellulose Pentose Furfural Furfural Alcohol
Dehydration -3H2O +H2
Lignin
O2
CO2 H2O
Catalytic Decomposition in Fluidized Bed Reactor CNT + H2
Specialty
Chemicals
Smart Tailored Biorefinery
Organic
Acids
CO + H2 CH3OH CH3OCH3
CH4
Tri--Reforming
Electricity
DME Syn Gas
Olefins, Paraffin, Aromatics Non-oxidative
Direct Conversion
Fuels
Chemicals
Gaseous
Products
CO, H2, CH4
Dehydration
Lignin
O2
CO2 H2O
Catalytic Decomposition in Fluidized Bed Reactor CNT + H2
Specialty
Chemicals
Alpha
Olefins
Methanol
Range of
Chemicals
& Polymer
Precursors
Smart Tailored Biorefinery
Organic
Acids
CO + H2 CH3OH CH3OCH3
CH4
Tri--Reforming
Electricity
DME Syn Gas
Olefins, Paraffin, Aromatics Non-oxidative
Direct Conversion
Fuels
Chemicals
Gaseous
Products
CO, H2, CH4
Dehydration
Lignin
O2
CO2 H2O
Catalytic Decomposition in Fluidized Bed Reactor CNT + H2
Specialty
Chemicals
Alpha
Olefins
Industrial Flue Gases
Methanol
Range of
Chemicals
& Polymer
Precursors
Concept of Smart Tailored Biorefinery
Organic
Acids
CO + H2 CH3OH CH3OCH3
CH4
Tri--Reforming
Electricity
DME Syn Gas
Olefins, Paraffin, Aromatics Non-oxidative
Direct Conversion
Fuels
Chemicals
Gaseous
Products
CO, H2, CH4
Dehydration
Lignin
O2
CO2 H2O
Catalytic Decomposition in Fluidized Bed Reactor CNT + H2
Specialty
Chemicals
Alpha
Olefins
Industrial Flue Gases
Natural
Gas, Coal
Methanol
Algae Non-Edible
Oil
Linear
Alkanes,
Diesel
Pyrolysis Oil
CO+H2O
WGS At elevated Pressure
-CO2, -H2
Social
Sustainability
Environmental
Sustainability
Economical
Sustainability
Raw
Materials End
Products
Smart
Biorefinery
Process Intensification
Wood and Non Wood
Biomass
Paint, Polymers, Rubbers,
Detergents, Paints, Surfactants,
Biofuel
Environmental Sustainability
• Use of residual Biomasses
• Preservation of forests and water
• Minimal Discharge and reduction
of CO2
Social Sustainability
• Food for people, not for cars
• Local farming and supply of
biomass
• Local products and use of products
Economic Sustainability
• Highly profitable
• Low operating and investment
costs
• Many high quality products
Smart Tailored Biorefinery: A sustainable approach
Main driver for establishment of bio refineries : SUSTAINALBITY
Summary and Way Forward
• Biorefineries can provide a significant contribution to sustainable
development, generating value to sustainable biomass use and
producing a range of biobased products (food, feed, materials,
chemicals, fuels, power, and/or heat) at the same time.
• This requires optimal biomass conversion efficiency, thus minimizing
feedstock requirements while at the same time strengthening economic
viability of (e.g., agriculture, forestry, chemical and energy) market
sectors.
• The use of smart biorefinery concepts in the biobased economy will
allow the production of green fuels and chemicals from biomass next to
food and feed.
• R & D on Biorefinery concepts are in progress like green biorefinery
(valorisation of grass), small-scale biorefinery and valorisation of algae.
Acknowledgement: Green Catalytic Reaction Engineering Laboratory
