Confidential A European Project supported within the Seventh Framework Programme for Research and Technological Development CATALYTIC CONVERSIONS of BIOSOURCED RAW MATERIALS : HETEROGENEOUS CATALYSIS Wolfgang Hoelderich TCHK , RWTH-Aachen EuroBioRef Summer School Utilization of Biomass for the Production of Chemicals and Fuels Castro Marina , Lecce ,Italy September 18th -24th ,2011, Wolfgang f F Hoelderich TCHK , RWTH -Aachen
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Confidential A European Project supported within the Seventh Framework Programme for Research and Technological Development
CATALYTIC CONVERSIONS of BIOSOURCED
RAW MATERIALS :
HETEROGENEOUS CATALYSIS
Wolfgang Hoelderich TCHK , RWTH-Aachen
EuroBioRef Summer School Utilization of Biomass for the Production
of Chemicals and Fuels
Castro Marina , Lecce ,Italy
September 18th -24th ,2011,
Wolfgang f F Hoelderich
TCHK , RWTH -Aachen
Confidential
World’s most pressing environmental issues
Global
climate change
Sustainable
energy
production
Food
production
Depletion of
non-renewable
resources
Dissipation of
toxic materials
Green chemistry and engineering
Alternative
Feedstocks
Alternative
Reagents
Alternative
Solvents
Alternative
Products
Alternative
Catalysts
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Conference in Rio de Janeiro 1992
The sustainable use of renewable
natural resources is one aim in the
Agenda 21 of the Rio de Janeiro
concept for the 21st century
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Strengths Weaknesses
Petrochemistry
• Known technology
• Existing plants
• Simple chemistry
• Pollution
• Functionalisation
• Depleted resources
Alternative
feedstocks
• Low environmental impact
• Functionalisation
• Non-Toxic
• Biodegradable
• Domestic feedstock
• Natural variability
• Seasonal cost
• Complexity
• Unknown technology
• Technology evaluation
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However, this field is not as new as it is assumed sometimes:
-10 mio t/a of cellulose and pulp from wood;
-15 mio t/a of fibers from cotton;
-10 mio t/a of fats and oils used in chemical industry e.g for surfactants,
detergents, lubricants;
- X mio t/a of alcohol by fermentation; think of wine and beer
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Renewable Feedstock
Recently, there is the new trend to use renewable sources
for the synthesis of value added chemicals
as well as
for the chemical modification of renewable feedstock
to produce new materials with favorable properties
such as surface activity and biodegradability
as well as
to produce already existing materials in a cheaper and ecologically
safer way than before.
A field of sustainable, green chemistry!
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• The utilization of renewable feedstock found increasing interest
over recent years due to economic as well as ecological reasons.
• That helps:
- to use the overcapacities of our agricultural economy.
- to save resources such as crude oil and gas as well as energy.
- to produce biodegradable products such as polymers, lubricants.
- to use readily and “cheaply?” available starting materials for the
synthesis of chemicals.
The nature is the architect of the carbon framework !
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• Renewable raw materials contribute with 10% to the feedstock
consumption of the chemical industry in Germany and the USA.
• Recently, the National Research Council of the USA estimated
for the year 2020 that 25% of the production of organic chemicals
will originate from renewable feedstock. A German politician of the Green
Party spoke about 40% until 2020 .
• At present, approximately 51% of the renewables used in Germany are fats
and oils, 43% based on carbohydrates and 6% based on proteins.
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Coal
2.2%
Gas
7.6%
Petroleum
82.1%
Renewable Feed
8.0%
Annual total consumptionof
organic raw materials is ca
22.4 mio. tons
8% of renewable feedstock
contribute to approx. 20% of
value of chemicals production
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Renewable Feed
1.8 Mio. t
Petroleum
18.4 Mio. t
Gas
1.7 Mio. t
Coal
0.5 Mio. t
Annual total consumptionof
organic raw materials is ca.
22.4 mio. tons
8% of renewable feedstock
contribute to about 20% of
value of chemical production
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The nature is the architect of the carbon framework
One uses readily and “cheaply?” available starting materials found in nature
for the synthesis of chemicals .
Not starting anymore from ethylene / propylene and aromatics to build
up the carbon framework . Starting on a higher synthesis level !!
For example : campholenic aldehyde from pinene epoxide
p-cymene from limonene and pinene
mango fruit aroma from limonene and pinene
grape fruit aroma from limonene and pinene
acrolein and acrylic acid from glycerol as C3 unit
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p-Cymene is used: as solvent and perfume ingredient,
as intermediate for p-cresol
(antioxidant 2,6-di-tert-butyl-p-cresol)
production route based on petroleum feedstock
H3C
after distillation of the o-isomer m/p-cymene-isomers separation according to
the Cymex-process (UOP) using molecular sieve as an appropriate sorbent and
toluene as desorption media
m/p-cresol isomers separation by partial crystallization of m-cresol under
elevated pressure according to Sumitomo Chemical Corp.
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- e. g.: catalyst Pd/SiO2 (D-11-10), T = 300°C, WHSV = 3 h-1
in the presence of 1,5 NL H2/h
yield = 98% for a very long service time (> 800h)
W. F. Hoelderich and coworkers
Appl .Catal. A: General 158 (1997), 145
Appl. Catal. A: General 163 (1997), 31
Appl. Catal. A: General 188 (1999), 287
Appl. Catal. A: General 171 (1998), 1
Catal. Lett. 52 (1998), 7
Stud. Surf. Sci. Catal. 121 (1998), 191
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alpha-limonene
37%
p-cymene
11%
other terpenes
4%
terpinolene
13%
gamma-
terpinene
4%
1,8-cineole
1%
alpha-terpinene
6%
camphene
6%
alpha-pinene
18%
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crude sulfate terpentine (CST)
cheapest and major source of terpenes
by-product from pulp and paper industry produced during pulp digestion
in Kraft paper mill
15-20 ct / kg compared to 26 ct / kg for toluene and >100 ct / kg for propylene
exact CST composition depending on the geographical origin of the wood
from a Kraft paper mill in La Tuque, Canada, 90% out of -pinene (65%) and
-pinene (25%)
Overall result :
CST conversion/pinene conversion over Pd/SiO2 (D-11-10) is a nice
example for the catalytic bi-functionality
cheap biodegradable resource can replace petrochemical feedstock
double catalyst bed ZnO and Pd/SiO2 (D-11-10) makes the use
S-containing terpenes mixtures manageable
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limonene 8-alkoxy-1-p-menthene -pinene R = alkyl- 8-alkoxy-1-p-menthenes used as flavours and fragrances, as additives for pharmaceuticals and agricultural chemicals, in food industry and in synthesis of fine chemicals Homogeneous catalysts: HCl, H2SO4, p-toluene sulfonic acids, and Lewis acids such as AlCl3, BF3-etherate Heterogeneous catalysts: acidic cation exchange resins, mordenite, clinopthilolite, ferrierite