Setting the scene: Biomass to Chemicals

• Fossil feedstocks constitute essential pillars of the

economy in modern society. They are the primary
source of energy, accounting for three-quarters of the
world’s energy supply.
• Moreover, the refining of crude oil (45% of the fossil raw
materials) generates fuels and a wide variety of products
that improve the quality of our everyday life.
• Nevertheless, because of the accelerated consumption of
these finite resources and the associated rise in
anthropogenic CO2 emissions, scientists have been
exploring more sustainable sources of energy, fuels, and
chemicals over the past years
• Biomass has received particular attention because it
represents the only abundant source of renewable
organic carbon that can reduce our reliance on fossil
feedstocks

• Biomass allows for a wide variety of chemical

transformations, and its more even distribution and
accessibility around the world with respect to fossil
reserves should set a better scenario to minimize price
fluctuations and the raising of socioeconomic conflicts.

• Among the various types of biomass, lignocellulose is

regarded as the main raw material of the future
biorefinery. This is essentially related to its nonedible
nature, which implies no competition with food.
Total consumption of oil in the United States compared with the potential
harvested biomass divided into its main uses.
• Since the carbon content in biomass is only half of
that in crude oil, even considering full conversion
and selectivity, two times more biomass than crude
oil would be necessary to generate an equivalent
amount of transportation fuels

• On the other hand, the available lignocellulose

could fully replace the fossil feedstock for the
manufacture of commodity chemicals and polymer
• In the first half of the 20th century, fermentation was
industrially practiced to produce a number of bulk
organic alcohols and acids.

• Three main catalytic routes for biomass-to-chemicals

have emerged in the recent past:
1. Gasification
2. Pyrolysis
3. Hydrolysis

• Heterogeneous catalysis possesses a tremendous

potential for rendering feasible and economic
biobased conversion processes.
Routes for the production of chemicals from fossil feedstocks (left to center) and
biomass (right to center).
Toward a Greener Industry:
Liquid-phase Conversion of Biomass
Introduction
• Biomass to liquid is a process by which liquid
biofuels are produced from biomass.

• Lignocellulose provides the basis for this fuel such

as straw, wood, energy crops, agricultural waste –
nearly all sorts of solid biomass in the world can be
considered for the production of BTL biofuel.
Benefits of BTL Fuels
• Better quality
• Lower CO2 emissions
• Zero emission of particulate matter
• Low NOx emissions
• An adjustable product quality (octane and cetane
number)
1-Fischer–Tropsch Process
• The Fischer–Tropsch process is used to produce
synfuels from gasified biomass.

• While biodiesel and bio-ethanol production so far

only use parts of a plant i.e. oil, sugar, starch or
cellulose, BTL production uses the whole plant
which is gasified by gasification.

• The result is that for BTL, less land area is required

per unit of energy produced compared with
biodiesel or bioethanol
2-Flash Pyrolysis
• Flash pyrolysis produces bio-oil, char and gas at
temperatures between 350 and 550°C and
residence times <1s (also called anhydrous
pyrolysis).

3-Catalytic Depolymerization
• Catalytic depolymerization uses heat and catalysts
to separate usable diesel fuel from hydrocarbon
wastes.
BIOMASS-TO-LIQUID (CURRENT
PROCESS)
• Currently, the major biomass-to-liquid production
processes are gas-to-liquid conversion and
pyrolysis.
– Both processes employ heat and chemical reactions
to convert biomass into fuels, chemicals and power.
– The products of both processes are cleaner and more
efficient than the solid biomass from which they
were derived.

• Another benefit is that biomass-to-liquid processes

can convert types of biomass such as wood and
agricultural residues that are difficult to handle
using other biofuel production processes
Pyrolysis
• In this process, liquid is obtained by thermo-
chemical conversion at low temperature and high
pressure using a catalyst in the presence of
hydrogen.

• In the direct liquefaction, the biomass is converted

into a liquid fuel without a synthetic gas being
produced in-between.
– This promises a considerable improvement in thermal
efficiency compared with the synthesis gas process.
The Fischer–Tropsch Synthesis
• FTS is a process where a gas mixture of H2 and CO
(synthesis gas or syngas) is converted into hydrocarbons
by using a transition metal catalyst, typically iron or
cobalt.

– The hydrocarbon products are formed via a

polymerization mechanism

– The key to the process are catalysts

1- Syngas formation:
𝑂𝑙𝑑 ℎ𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛 + 𝑂𝑥𝑦𝑔𝑒𝑛 → 𝑆𝑦𝑛𝑔𝑎𝑠

2- F-T reaction:
𝑆𝑦𝑛𝑔𝑎𝑠 → 𝑁𝑒𝑤 𝐻𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛 + 𝑊𝑎𝑡𝑒𝑟

3- Refining:
𝑁𝑒𝑤 ℎ𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛 → 𝐹𝑢𝑒𝑙𝑠, 𝐶ℎ𝑒𝑚𝑖𝑐𝑎𝑙𝑠, 𝑒𝑡𝑐.
Main steps of BTL production of fuels.
Reaction mechanism
• The Fischer–Tropsch process involves a series of chemical
reactions that produce a variety of hydrocarbons, ideally
having the formula (CnH(2n+2)).
• The more useful reactions produce alkanes as follows:

2𝑛 + 1 𝐻2 + 𝑛𝐶𝑂 → 𝐶2 𝐻(2𝑛+2) + 𝑛𝐻2 𝑂

– where n is typically 10-20

– The formation of methane (n = 1) is unwanted
– Most of the alkanes produced tend to be straight-chain, suitable as diesel
fuel.
– Competing reactions give small amounts of alkenes, as well as alcohols
and other oxygenated hydrocarbons
Reactions in Fischer–Tropsch Synthesis
Schematic line-up of the integrated BTL plant.
Routes for the conversion of biomass into liquid fuels. Red arrows refer to thermal routes,
green arrows refer to biological routes, and blue arrows refer to catalytic routes
• Problem 1:
– The F-T synthesis unit is highly sensitive to impurities
and the direct integration of biomass gasification and F–T
synthesis is not possible.
• Tar
• Volatile species such as NH3, HCl
• Sulfur compounds
• Fine particles and ash

• Solution:
– An intermediate gas-cleaning system is used between
biomass gasification and F-T synthesis unit.
• Problem 2:
– Since biomass contains higher amounts of oxygen
compared to coal, the syngas delivered from
lignocellulosic sources is typically enriched in CO (H2/CO
= 0.5), and F–T synthesis requires syngas with a H2/CO
ratio closer to 2.

• Solution:
– By providing sufficient water co-feeding, the H2/CO ratio
can be adjusted by means of an intermediate water gas-
shift (WGS: CO + H2O  CO2 + H2) reactor situated
between the gasifier and the F–T unit.
Applications
• BTL: biomass-to-liquid. A synthetic fuel with similar
fuel properties as conventional diesel

• SNG: synthetic natural gas. A possible replacement of

natural gas

• DME: dimethyl ether. A fuel with similar properties as

LPG (liquid petroleum gas)

• Ethanol

• Methanol
CATALYSTS FOR THE F-T SYNTHESIS
• A variety of catalysts can be used for the Fischer–Tropsch
process, but the most common are the transition metals
cobalt, iron, and ruthenium.

– Nickel can also be used, but it tends to favor methane

formation

– Ruthenium is too expensive, leaving cobalt and iron as the

only viable metals for industrial applications.

– Cobalt catalysts are more active than iron on a per gram

basis
Cobalt Catalysts
• Cobalt catalysts are more active for Fischer–Tropsch
synthesis when the feedstock is natural gas.
– Natural gas has a high hydrogen to carbon ratio, so the
water-gas-shift is not needed for cobalt catalysts

• Limitations:
– The temperature range cobalt catalysts can be operated in
is fairly narrow (200–240°C) as higher temperatures will
lead to a high selectivity toward methane.

– Sintering can also become a significant problem at higher

temperatures as solid-state diffusion becomes faster

– Cobalt only displays a negligible water gas shift (WGS)

activity
Iron Catalysts
Iron catalysts can be used under two different process regimes

• Low Temperature Fischer–Tropsch (LTFT):

– T: 200–240°C
– P: 20–45 bar
– The main product is heavy paraffinic wax (C10–C100)

• High temperature Fischer–Tropsch (HTFT):

– T: 300–350°C
– P: 20–40 bar
– Yields hydrocarbons in the C1 to C15 range, with a large
fraction of light olefins
Main catalyst families employed in the conversion of bioderived molecules described in terms of suitability to
perform different types of reaction (orange boxes) versus main benefits and drawbacks (green boxes).
References
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Chemicals from Conception toward Industrial Reality: Lessons
Learned and To Be Learned, ACS Catal. 2 (2012) 1487−1499

• P. K. Swain, L. M. Das and S. N. Naik, Biomass to liquid: A

prospective challenge to research and development in 21st century,
Renewable and Sustainable Energy Reviews 15 (2011) 4917– 4933

• J. C. Serrano-Ruiza and J. A. Dumesic, Catalytic routes for the

conversion of biomass into liquid hydrocarbon transportation fuels,
Energy Environ. Sci., 4 (2011) 83-99

• A. H. Lillebø, A. Holmen, B. C. Enger and E. A. Blekkan, Fischer–

Tropsch conversion of biomass-derived synthesis gas to liquid fuels,
WIREs Energy Environ 2 (2013) 507–524
Thank you