Transportation Fuels from Biomass : A sustainable Alternative for Energy Needs

Dr A K Gupta Ex. Scientist G , Indian Institute of Petroleum, Dehradun, INDIA

Background

About 100 years ago, the economy was primarily based on Biomass or Carbohydrates In 1920s a shift towards Fossil Fuels started This trend accelerated after World war II Presently Fossil fuels have become the energy and chemical commodity backbone of both developed and developing Nations.

Due to abundant availability and favourable economics, Fossil fuels (crude oil, Natural gas and Coal) energy resources still dominated the market. Concerns for environment, and depletion of fossil fuel reserves have evoked serious deplates all over the world

This has led to search for ecofriendly and sustainable alternative fuels. increased efforts for energy conservation and improving energy efficiency.

For developing countries like India, where the economy is largely agricultural based biofuels such as Biodiesel, ethanol, biomass derived fuels, biogas and bio-syn gas are becoming increasingly important as future fuels.

Biomass can provide alternative to Fossil resources

Strengths of biomass

Available in abundant quantities Can significantly enhance our energy independence and security Can reduce use of imported oil and increase reliability of energy supplies Can improve balance of Trade deficit
Other benefits include Productive use of agricultural, Municipal and forest wastes Lower Emissions of Green House gases and pollutants Growth of Rural Economy

Potential Biomass Resourcess

Agricultural Residues Forest Residues Primary mill residues Sludge (manure & Biosolids) Biogas (Landfill, digester and sewage gas) Other wastes (e.g. Organic fraction of MSN) Micro algae

Bioconversion processes
FEEDSTOCK

PROCESS
ANAEROBIC DIGESTION

FUELS
METHANE

COPRODUCTS

SLUDGE

WET BIOMASS, SEWAGE, MANURE, ALGAE, WASTE LIQUORS

MICROBIAL DIGESTION ACID HYDROLYSIS FERMENTATION

HYDROGEN

SLUDGE

SUGARS

ALCOHOLS; ETHANOL, ETC.

PROTEIN, SLUDGE

ANAEROBIC DIGESTION

COMPOST HUMUS, CO2, H2O

Pyroconversion processes
FEEDSTOCK PROCESS
DESTRUCTIVE DISTILLATION

FUELS
CHARCOAL (METHANOL) CHARS, OILS, GASSES

COPRODUCTS

WOOD CHEMICALS

PYROLYSIS DRY BIOMASS MUNICIPAL WASTE WOOD AND FARM RESIDUES O2-PARTIAL SYNTHESIS COMBUSTION GAS CO + H2 AIR PARTIAL COMBUSTION

HYDROLIQUEFACTION

OILS

METHANE AMMONIA METHANOL

LOW BTU GAS

TOTAL COMBUSTION

HEAT, STEAM, ELECTRICITY

MINERAL ASH

Current and future biofuels

Bio-alchols and ethers Methanol, Ethanol, butanol, ETBE, MTBE Vegetable oils, Biodiesel Biogas- SNG, bio-methane Gasification products- Syn gas Bio-mehane steam reformed products- Syn gas Pyrolysis oil Bio-syn gas based Liquid fuels- F-T fuels, Methanol, DME Hydrogen MicroAlgae based biodiesel and liquid fuels

Bio-ethanol

Conventionally produced via fermentation of sugars derived from sugar crops. Can also be produced from starch and biomass via hydrolysis followed by fermentation. Bio-ethanol is suitable as gasoline blending component The cost of ethanol from biomass is higher ~ $ 1.27 / gal

Bioethanol

Future Research is focussed on reducing the cost of production through improvements in fermentation technology, using low cost feed stocks, and new biocatalysts. The process patented by IIP, Dehradun uses a Thermophilic bacteria which directly converts starch into ethanol in high yields.

Biodiesel

Biodiesel is methyl/ethyl esters of Fatty acids. Biodiesel can be used in blends with diesel or as such in IC engines. It produces less tail pipe emmissions and improves lubricity of diesel.

Biodiesel

Conventionally produced via transesterification of vegetable oils, waste oils and animal fat using alkali catalysts such as NaOH, KOH, MeONa etc. Alkali catalysts based processes are not suitable for feed stocks containing high FFA and generate large effluents as waste. 1.5 -2 times costler than diesel

Biodiesel

More Research is needed to reduce the cost of biodiesel, use of cheaper feed stocks with high FFA, and reduce effluents. Recently, Studies have been reported in: -Transesterification in supercritical MeOH - Use of heterogeneous catalysts (metal oxides, phosphates, zeolites etc. Most of the heterogeneous catalysts are also not suitable for high FFA containing feed stocks

Biodiesel: new developments

Axens, France process uses a silicate catalyst for transesterification of low FFA oils. IIP, Dehradun has patented a heterogeneous catalyst which simultaneously catalyses transesterification of glycerides and esterification of FFA, thereby giving high yields even with low quality oils containing high FFA.

Substitute natural gas (SNG) from Biomass

What is SNG ? SNG is subtitute natural gas derived from biomass/ organic wastes. Since it is obtained from renewable resources it is also known as green gas

SNG Production:

There are four options for producing SNG fro biomass/ waste organic matter (MSW): 1. 2. 3. 4. SNG production by upgrading Biomass from Anaerobic Digestion SNG production by combined biomass gasification/methanation process. SNG production by biomass hydrogasification process Cogeneration as well as stand-alone production of F-T liquids and SNG

SNG production..

Development status:

Anaerobic digestion is a well established technology for waste treatment, and generally available on commercial scale. Millions of anaerobic digesters (commonly known as biogas plants) have been built around the world, most of which are very small, built in developing countries. Large scale digesters have been built in France, Germany, and Belgium for treating Municipal Solid waste (MSW) and farm based digesters dotted around Europe. In UK use of land fill gas is significant. The technology is fully commercial.

SNG production by combined biomass gasification/methanation process:

Biomass Gasification
Steam(O2)

Gas Clean-up

Methanation

Gas conditioning

SNG SNG production by combined biomass gasification/ methanation process

SNG production by biomass hydrogasification process:

Hydrogen and biomass are fed to the reactor operating at 30 bar and 800-850oC. Due to exothermic reactions this reactor can be operated autothermally. ( Example Deutshe Montan Tehnologies (DMT) Gas Clean-up Gas Final conditioning Methanation SNG

Bioma Hydross gasification H2 (rich) gas

SNG co-production by conversion of biomass through Fischer-Tropsch/metanation:

In this process syn gas produced in the gasifier is converted to liquid fuel by once through F-T process. The off gas is from F-T process which contains unconverted CO and H2 and methane produced in gasification and C1 C4 hydrocarbons produced in F-T synthesis is upgraded by methanation and CO2 removal.

Cogeneration as well as stand-alone production of F-T liquids and SNG

F-T liquids Biomass Gasification F-T Synthesis Methanation CO2 removal CO2 Gasification Biomass F-T synthesis F-T SNG CO2 liquids removal CO2

SNG

Gasification

Methanation

Potential Alternative Bio-syngas applications

Base chemicals Aromatics (BTX) nOlefins (Ethylene, propylene, butenes, Butadiene)

n

Transportation fuels Methanol nSubstitute for CNG nGasoline (MTG process) nDimethyl Ether (DME) nFischer-Tropsch (FT) diesel nMixed Alcohols
n n

Substitute Natural Gas (SNG)

n

Power production

Syn gas (Bio-syn gas)from biomass

Syn gas is a mixture of CO and H2 Biosyn gas can be produced by gasification of biomass. It can also be produced by steam reforming of SNG obtained from anaerobic digestion of biomass Currently, Bio Syn gas to liquid fuels is one of the most researched area

Boi-oils from biomass

Fast Pyrolysis, a thermal process, is used to produce pyrolysis oil ( Bio-oil) Bio-oils are not suitable as transportation fuels but can be upgraded Bio-oils can be used in power plants.

Bio-oils
Upgrading Bio-oils to Transportation fuels: - Microemulsion with 5-30% bio-oil in diesel with emulsifiers. - Deoxigenation : -hydrotreatment over Co-Mo/NiMo catalysts - Catalytic cracking over zeolite catalysts Upgrading bio-oils to transportation fuels is not economical

H2 From Biomass
Biomass conversion technologies can be divided into two categories.
1. 2.

Direct production routes (simplicity of process). Conversion of storable intermediates (additional production steps, distributed production of intermediates, lower transportation costs of biomass, larger-scale H2 production facilities.) Both categories involve thermochemical and biological routes.

Pathways From Biomass to H2

Biomass

Thermochemical Gasification H2/CO

Bio-shift High Pressure Aqueous

Pyrolysis
Sever e

CH4/CO2

Synthesis

CH4/CO2

CH1.4O.6

Reforming CH3OH/CO2 Reforming shift Shift Reforming shift shift H2/CO2 H2/CO2 H /CO H2/CO2 H2/CO2 H2/C 2 2

H2

Pathways from Biomass to

Biomass

Biological
Anaerobic Digestion CH4/CO2 Fermentation CH3CH2OH/CO2 Bio-shift Reforming shift Photobiology H2/CO2 H2/O2 H2/CO2

Metabolic Processing

Reforming shift Pyrolysis H2/CO2

H2/C

Direct Production of H2 From Biomass

Gasification coupled with water-gas shift is the most widely practiced process route for biomass to H2. Thermal, steam and partial oxidation gasification technologies are under development around the world. Feedstocks include both dedicated crops and agricultural and forest product residues of hardwood, softwood and herbaceous species.

Direct Solar Gasification

Several investigators have examined the use of solar process heat for gasification or organic solid wastes to produce H2.
Studies have shown favourable economic projections for solar gasification of carbonaceous materials such as agricultural waste to produce syn gas for producing H2.

Supercritical Conversion of Biomass

Aqueous conversion of whole biomass to H2 under low temperature supercritical conditions in another area of investigation in recent years. Corrosion, pumping of biomass slurry, improvement in heating rates, heat transfer, commercial reactor system development are some of the problems need attention.

Pyrolysis to Hydrogen and Carbon or Methanol

This is a high temperature two-step process involving
(i) Conversion of biomass to methane (ii) Thermal decomposition of methane to H2 and clean carbon-black Typical overall stoichiometry is: CH1.44 O0.66 + C + 0.6 H2 + 0.66 H2O The process is called Hydrocarb process In another process Carnol Process methanol is produced with H2 CH1.44 O0.66 + 0.30 CH4 0.64 C + 0.66 CH3OH

ISSUES

Since H2 content in Biomass is low the yield of H2 is low (Approx. 6% vs. 25% of CH4) Energy content of biomass is also low due to 40% O2 content. Low energy content of biomass is inherent limitation of the process since over half of H2 from biomass comes from splitting of water in steam reforming.
continued

ISSUES

Even at reasonable high efficiency, production of H2 from biomass is not presently economically competitive with natural gas steam reforming without the advantage of high-value co-products, very low cost biomass and potential environmental incentives. There are no completed technology demonstrations.

Microalgae

Micro algae are single-celled plants that contain photosynthetic machinery driven by the Suns energy to combine CO2 and water to form variety of products. These are low input high yield feed stocks to produce biofuels. It produces 30 times more energy per acre land than land crops such as soyabean.

Algae to liquid fuels

Dry algae contains as high as 50-60% lipids and hydrocarbons. Oil is extracted from dry algae by solvents Algae oil is converted to biodiesel Oil cake can be gasified to produce syn gas which can be used to produce liquid fuels( diesel and gasoline) via F-T process Cost of production of biodiesel from microalgae is ~ $ 3.50/gal

Conclusions:

Awide range of transportation fuels, which can reduce our vulnerabilityto disruption in fuel supplies and improve our balance of trade deficit, can be produced from biomass. Biomass based fuels are little costlier than fossil fuels Biofuels are more eco-friendly than fossil fuels. There is need for focused R&D to reduce cost and quality of biomass based fuels

Thanks