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pyrolysis-oil-upgrading pdf
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New and old building blocks
for bio-based chemical
industry
F.Trifirò Facoltà Chimica
Industriale Bologna
BIOMASS
•Straw and manure from farming
•Energy crops from farming
•Wastes from the food industry
•Wastes from households and industry
•Sludges from sewer plants
•Aquatic biomass
•Organic wastes and organic products from the
woodworking industry
•Methane from anaerobic fermentation of wastes
from animal farming
•Oily wastes (spent coffee,waste cooking oil)
Chemical conversion technologies
Herbaceous crops Tree crops
Annual Perennial
Thermo-chemical conversion
Ligno-cellulosic (combustion, pyrolysis, gasification)
Bio-chemical conversion
Carbohydrate (bio-gasification, fermentation)
Chemical conversion
Oils (esterification)
Second(next) generation biofuels
• 1) bioethanol from fermentation of
lignocellulosic wastes
• 2) biogas(CH4) from anaerobic fermentation
of animal wastes
• 3) production of ethanol, methanol,
hydrogen, Fischer-Tropsch fuels , DME,
from gasification of lignocellulosic wastes
• 4) bio-oil from pyrolysis of lignocellulosic
wastes
Next generation of building
blocks for the chemical industry
• Ethanol
• Methanol
• Syn-gas
• l-lactic acid
• Glycerol
• Olefins(ethylene .propylene ,butenes)
• Aromatics
• Fatty acids
• Succinic acid
FROM BIOMASS TO
CHEMICALS
THROUGH :
1) Physical methods
2) (Bio)chemical transformations in one
stage
3) (Bio)chemical transformations in two
or more stages
4) Pyrolysis
5) Gasification
6) Pyrolysis +gasification
Physical methods
THEY SEPARATE AND ISOLATE THE DIFFERENT
COMPONENTS OF BIOMASS LEAVING
UMMODIFIED THEIR STRUCTURE
RAW MATERIALS MORE EASY TO TRANSPORT
EXAMPLES
THE PRODUCTION :
OF POLYSSACARIDES ( CELLULOSE, STARCH, AGAR
ALGINATE , CHITIN, INULIN )
OF DISACCARIDES( LACTOSE AND SUCROSE ),
OF TRIGLYCERIDES, NATURAL RUBBER,
OF FLAVOURS AND FRAGRANCES AND
FARMACEUTICALS
ONE STEP (BIO)CHEMICAL
MODIFICATION
ONE STEP MODIFICATIONS OF COMPONENTS
SEPARATED BY PHYSICAL METHODS
EXAMPLES PRODUCTION OF:
CELLULOSE AND STARCH DERIVATES , GLUCOSE
AND FRUCTOSE,GLYCEROL, FATTY ACIDS
ETHANOL, CITRIC ACID, GLUTAMMIC ACID AND
LACTIC ACID BY FERMENTATION
LACTULOSE, LACTILOL AND LACTOBIONIC ACID BY
ISOMERIZATION, HYDROGENATION AND OXIDATION,
RESPECTIVELY, OF LACTOSE
TWO OR MORE STEPS
MODIFICATIONS
EXAMPLES
ETHYLENE FROM ETHANOL
SORBITOL AND MANNITOL BY HYDROGENATION
OF GLUCOSE AND FRUCTUOSE
VITAMIN C IN SEVERAL STEPS FROM GLUCOSE
FATTY ALCOHOLS AND AMMINES FROM
TRIGLYCERIDES
ALKYL POLYGLUCOSIDES FROM GLUCOSE
AND FATTY ALCOHOLS
Thermochemical conversions
Of lignocellulosic wastes
I Pyrolysis of biomass
II Gasification of biomass
III Pyrolyis+Gasification
I V Gas upgrading by reforming:
processes,
Thermochemical
conversions
Without O2 O2 in defect O2 in excess
D P G C
A O
R Y S M
Y R I
B
F
I O I U
N L F S
C T
G Y A I
S T O
I N
I O
S N
100 200 300 650 900 Temp
°C
PYROLYSIS
IT IS THE THERMAL DEGRADATION OF A BIOMASS IN
ABSENCE OF OXIDANT WITH AN ENDOTHERMIC
PROCESS
( THE HEAT IS FURNISHED FROM COMBUSTION OF
AN OTHER FUEL OR OF THE GASEOUS FRACTION)
THE PROCESS IS REALIZED AT TEMPERURE BETWWEN
400-800oC WITH FORMATION OF THREE FRACTIONS
1) GASEOUS FRACTION(15% -30%): CO, H2, CO2,
LIGHT HYDROCARBONS
2) LIQUID FRACTION (50-60% ): H20, HYDROCARBONS
AND OXYGENATES
3) SOLID FRACTION (: 20-30%): BITUMINOUS OR
ANTRACITIC COAL
Bio – oil properties
Property Pyrolysis Oil Diesel Heavy Fuel Oil
Density at 15°C (Kg/m3) 1220 854 963
%C 48.5 86.3 86.1
%H 6.4 12.8 11.8
%O 42.5 0.0 0.0
%S 0.0 0.9 2.1
Viscosity at 50°C (cSt) 13 2.5 351
Flash point (°C) 66 70 100
Pour point (°C) -27 -20 21
Ash (wt.%) 0.13 <0.01 0.03
S (wt.%) 0.0 0.15 2.5
Water (wt.%) 20.5 0.1 0.1
LHV (MJ/kg) 17.5 42.9 40.7
Acidity (pH) 3 - -
Bio-oil properties
1) Immiscibility. Due to its high water content, the pyrolysis oil is not
miscible with fossil fuels.
2) Low Ignition. The high water content is also detrimental for ignition.
3) Corrosion. Organic acids in the oils are highly corrosive.
4) Erosion. Char in the liquid can block injectors or erode turbine
blades.
5) Instability. Over time, the reactivity of some components in the oils
leads to formation of larger molecules (polymerization) that result in
high viscosity.
Bio – oil applications
Pyrolysis Bio-oil Gasifier
Pre-treated biomass
Engine
Extraction
Upgrading
Chemicals Power & Heat
(CHP)
Transport fuels
Bio – oil upgrading
Some upgrading methods, to improve the stability of the
pyrolysis oil, by removing oxygen and water thus increasing
the burning properties such:
1) catalytic hydrotreating
2) steam reforming are used.
3) Reactive pyrolysis( processes carried out into a
reactive atmosphere, i.e. hydrogen, to directly obtain
an upgraded bio-oil).
Reactive Pyrolysis
►
► Reactive pyrolysis (or hydropyrolysis) is carried
out in a pressurized H2 atmosphere, in presence of
catalysts, to obtain an upgraded bio-oil that can be
streamed in a gas turbine or blended with diesel
fuels, since hydrogen converts all the oxygenated
and polyaromatic compounds
Pyrolysis for Liquids
Biomass
heat
Combustion
Pyrolisis ΔH°>0
550°C, no O2
Gases
H2,CO,CH4,C2
Char
Vapours Condensation Liquid
Bio-oil
Catalytic
de-oxigenation
Stable
bio-oil
Chemicals from bio-oil
• Food flavouring and essences
• Specialty chemicals for Pharmaceuticals
and synthons
• Fertilizers
• Environmental chemicals
• Polyphenols for Resins with CH2O
• Fuels
GASIFICATION
-PRODUCTION OF BIO-GAS
Gasification is the conversion by partial
oxidation at elevated temperature of a
carbonaceous feedstock into,
non-condensable gas together with several
contaminants such as particulate, tars, alkali
metals, nitrogen compounds and ash residue
COMPOSITION OF THE GAS
The constituents of the produced gas
(tars and salts included) strictly
depends on:
1) the biomass type
2) the gasifying conditions
3) the presence of catalysts
Components of gas after the
gasifier
CH4 (7-10%)
light hydrocarbons (2-4%)
CO (10-13%)
H2(10-13%)
CO2(25-30%)
H2O ( 35-45)%
Ash(0,1-2%)
Gasification main
parameters
• Pressure 1-30Atm
• Temperature 760-800oC
• Gaseous media: Air,O2, O2- H2O ,O2-CO2
• Reactors: Upcraft Fixed bed, Downcraft
fixed bed, Circulating fluid bed ,bubbling
fluid bed
• Type of catalysts and their localization
( inside the gasifier or downstream )
Why it is necessary a catalyst
in gasification ?
• To reduce tars
• To eliminate NH3
• To reform methane
The properties of a catalyst
The catalyst, to eventually put inside the
gasifier, should have the following properties:
1. effective in the removal of tars
2. capable of reforming methane, also
providing a suitable syngas ratio for the
intended process
3. resistant to deactivation as a result of
carbon fouling and sintering
4. easily regenerated
5. resistant to abrasion and attrition
6. be cheap
Coupled pyrolysis- gasification
Coupled pyrolysis gasification
►Pyrolysis oil is relatively free of
contaminants, so in the gasifier
excessive gas cleaning may be avoided
Two stages gasification
process
-In the flash pyrolysis step a large part of the contaminants
are already removed and therefore is avoided excessive gas
cleaning
-By using a thermal gasification instead of catalytic
problems concerning deactivation are by- passed
-The use of high gasification temperatures results
in a tar free gas
- Pyrolysis gasification can be geographically decoupled
FSH C.I.
Pyrolysis and gasification
Biomass (chopping and
drying)
COMPOSITION
•Organics (C4-C5, BTX..) 60%
Fast pyrolisis
Heat 1 bar, 500°C, τ = few sec •Char 16%
Gases •Water 11%
Oil & Char
H2,CO,CH4,C2 •GAS (CH4 CO, H2) 13%
Entrained flow gasification Organics + CHAR 75-80%
1 bar, τ = 1-2 sec
Can go to gasification
Syngas
CO + H2
Gas cleaning with heat
recovery
Methanol FT Diesel
DME H2
Gas Upgrading
RM PROX
WGS
POX
Clean
gas
H2, CO2
H2, CO
RM: Reforming,
POX: Partial Oxidation,
WGS: Water Gas Shift,
PROX: Preferential oxidation
Syngas production
SRM (Steam Reforming)
CH4 + H2O CO + 3H2 (ΔH0298=250.1 kJ/mol)
POX (Partial Oxidation)
CH4 + ½ O2 CO + 2H2 (ΔH0298=−35.7 kJ/mol)
ATR (Autothermal Reforming)
combining reforming and combustion is an
attractive technology for syngas production,
especially for large plants
10 % CO
Water Gas Shift
Necessary step to produce a hydrogen
enriched stream
CO + H2O CO2 + H2 (WGS: ΔH0298=-41 kJ/mol)
HTS
Fe3O4-Cr2O3 CO + 3 H2 CH4 + H2O (Methanation: ΔH0298=-206
kJ/mol)
300-400°C
2 CO CO2 + C (Boudouard: ΔH0298=-172
kJ/mol)
3 % CO
► Fe3O4-Cr2O3 are stable up to 50 ppm of
LTS
CuZnO/Al2O3 H2S, however are active at T>300°C and very
200-300°C sensitive to aging (sintering of magnetite
crystallites)
► Instead, CuZnO/Al2O3 are sensitive to few
0.5 % CO
ppm of H2S
Fuels by thermal conversion of
wastes
• We have four alternatives in order to
produce fuels by thermal conversion of
wastes
• 1) production of bio-oil
• 2) up-grading of bio-oil
• 3) gasification of bio oil and further
chemical transformation(upgrading)
• 4) gasification of wastes and further
chemical transformation(upgrading)
From syngas to fuels and
chemicals
• Fuels from syngas : PROX ( H2)
• Fuels from syngas : Fischer Tropsch (diesel oil)
• Fuels from syngas: CH3OH,DME and gasoline
• Building blocks for chemical industries from
syngas
F-T Diesel
H2, CO PROX H2, CO2 FC *
0.5 % CO 5-10 ppm
200°C 80°C
CH3OH Preferential Oxidation
CO + ½ O2 CO2 ΔH0298=-254 kJ/mol
H2 + ½ O 2 H2O ΔH0298=-242 kJ/mol
Catalysts: promoted Pt on alumina
More recently: Au based catalysts
DME
Gasoline
* Fuel Cell: H2 + ½ O2 H2O + e-
Products of Fischer- Tropsch
The FT reaction always produces a wide range of
hydrocarbon products,i.e., paraffins, olefins as
well as oxygenated products such as
aldehydes, alcohols and fatty acids.
The carbon numbers of the products range from
one to over a hundred .At high temperatures,
aromatics and ketones are also produce,.
The FT process, produces large amounts of the
valuable linear alpha olefins (at higher
temperatures) as well as long chain linear
paraffins (at lower temperatures).
FSH
Fischer-Tropsch Synthesis
C.I.
Naphtha (20%)
Syngas Fischer-Tropsch WAX
generation SYnthesis Upgrading
Middledistillate
(80%)
Process Yield (1) : 55- 65 %
Fom syngas to fuel
via Fischer-Tropsch
Off-
Off-gas
to recycle
Water Products
Separation
Syn-gas Hydro-
unit cracking
Fischer-Tropsch
Reactor
Currently, there are two FT operating
modes: high and low-temperature FT
processes
I
From Syngas to olefins
• The different technologies
SDTO
DME
SYNGAS
CH3OH OLEFINS
MTO
BIOMASS MTG MTP
PROPYLENE
GASOLINE
CHRISGAS:
Clean Hydrogen-rich Synthesis Gas,
Methanol
Biomass and waste
DME
Gasification H2
Reforming Synthesis Gas
-
FischerTropsch
Natural Gas
Synthesis of methanol
• CO+2H2 CH3OH ΔH298k=-90.6kJmol-1
• Methanol synthesis is the second largest
process after ammonia which use catalysts at
high pressure
• The mechanism is believed to be
• CO+H2O-> CO2+H2 ΔH298k=-41.2kJmol-1
• CO2+2H2->CH3OH+H2O ΔH298k= -49kJmol-1
Two steps process for DME
DME one step
From syngas to DME
• The catalyst applied is a proprietary dual-function
catalyst, catalyzing both steps (i.e., methanol and DME
synthesis) in the sequential reaction. Significant
advantages arise by permitting the methanol synthesis,
the water–gas shift, and the DME synthesis reaction to
take place simultaneously. The synthesis of DME from
synthesis gas involves three reactions:
• CO2+3 H2->CH3OH+H2O
• CO+H2O-> CH3OH
• 2 CH3OH ->2CH3OCH3 +H2O
Mobil MTG
.. The complex reaction sequence can be
represented as follows :
• 2CH3OH→(CH3)2O+H2O
• (CH3)2O→(CH2)2 +H2O
• Light olefins → Heavier olefins
• Heavy olefins → Aromatics, alkanes, cycloalkanes
• For 100 g of methanol consumed, the
stoichiometric yields are 43.75 g of hydrocarbons
and 56.25 g of water.
From MTG to MTO
It is possible to modify the MTG process in order to
obtain only the olefins by operating on these
factors:
1)Operating at high temperature
2)Using zeolites with lesser acid strength
3) Using a zeolite with narrow pore width
From ZSM5 to H SAPO 34 ,8 membered ring
silicoalluminophosphate
Methanol to olefins
• There are three types of methanol-to-olefins
processes available.
• 1) The UOP/HYDRO Methanol to Olefins
(MTO) process, which produces propylene and
ethylene with minimal other by-products in
Norway
• 2) The Lurgi’s “methanol-to-propylene
(MTP)” process, which produces propylene and
gasoline. Will start in Cina
• 3) Dalian Institute of Chemical Physics
(DICP) from syngas to dimethylether to
olefins (SDTO) has done some work in this area
and is close to commercializing its own
technology .
Advantages of MTO versus
cracking
1) Direct use of ethylene and propylene in chemical grade
products with greater than 98% purity using a flow scheme
that does not require expensive ethylene/ethane or
propylene/propane splitters.
2) Limited production of by-products ( H2,CH4 diolefins
acetylenes ) compared to a steam cracker, which results
in a simplified product recovery section.
3) Easy integration into existing naphtha cracker
facilities due to low paraffin (ethane and propane ) yields.
4) Flexibility to change the propylene to ethylene
product weight ratio from 0.77 to 1.33.
via Dimethyl Ether to Olefins
Process (SDTO)
• In the mid-1990s, DICP was awarded two patents in the
United States concerned with the conversion of
methanol/dimethyl ether (DME) to light olefins. These
patents are the basis for the syngas via dimethyl ether to
olefin process (SDTO). Compared with the MTO
process, SDTO directly converts synthesis gas to DME
with high carbon monoxide conversion, thus exhibiting
greater efficiency than the MTO process. Other special
features of the SDTO process include: Bifunctional metal
(Cu, Zn, etc.)-zeolite catalysts have been developed,
which can convert syngas very selectively to DME with
high carbon monoxide (CO) conversion (this reaction is
far more favorable thermodynamically than methanol
synthesis from syngas
SDTO
• 50t(methanol)/d unit for the conversion of
methanol to lower olefins, with a methanol
conversion of close to 100%, and a selectivity to
lower olefins(ethylene, propylene and butylenes)
of higher than 90%. by utilizing a proprietary
SAPO-34 catalyst system and a recycling
fluidized bed reaction system for the production
of lower olefins from methanol, is the first unit in
the world having a capacity of producing nearly
ten thousand tons lower olefins (ethylene
,propylene and butenes per year.
The near future
biomass
From renewables feedstocks to chemicals
Lignocellulosics Hemicellulose Furfurol
Renewable Grains Starch Glucose Ethanol
feedstocks
Sugar crops Carbohydrates Sucrose Lactic acid
Oil crops TriglyceridesFatty acids Fatty alcohols
Terpenes
ETHANOL
BY FERMENTATION OF BIOMASS
PRODUCTS
ETHANOL ETHYLENE
ETHANOL ACETIC ACID
ETHANOL AROMATIC ETHYLATION
ETHANOL ETHYLENE GLYCOL
METHANOL
FROM SYNTHESIS GAS
PRODUCTS
METHANOL OLEFINS
METHANOL DIMETHYLETHER ALTERNATIVE DIESEL
METHANOL FOR FUEL CELL
METHANOL ACETIC ACID
METHANOL FORMALDEHYDE
FROM TRYGLICERIDES TO
CHEMICALS
-BY TRANSESTERIFICATION WITH MEHANOL
AT 50C WITH BASIC CATALYSTS METHYL FATTY ESTERS
ADDITIVE FOR FUELS AND FUEL
-BY HYDROLYSIS AT 230oC AT 32 ATM FATTY ACIDS
AND GLICERIN
- BY HYDROGENATION AT 225 oC 50 ATM FATTY
ALCOHOLS BIODEGRADABLE SURFACTANTS
-BY DEHYDRATATION OF FATTY ALCHOOLS AT 400o C
OLEFINS TO PRODUCE LUBRICANTS
-BY EPOXIDATION OR DIMERIZATION OF OLEFINS
TO PRODUCE VALUABLE CHEMICALS
LACTIC ACID
LACTIC ACID IS PRODUCED BY FERMENTATION
FROM SUCROSE OR FRUCTOSE
CHEMICAL ROUTE 1)VIA ADDITION OF HCN TO
CH3CHO AND SUCCESSIVE HYDROLYSIS
2) BY SELECTIVE OXIDATION OF 1-2
PROPANDIOL
PRODUCTS
ETHYL LACTATE BIODEGRADABLE SOLVENT
L- LACTIC ACID CHIRAL BUILDING BLOCK
LACTIC ACID ACRYLIC ACID ( GREEN ROUTE)
L- LACTIC ACID BIODEGRABLE POLYMER
L LACTIC ACID EMULSIFIERS
VALORIZATION OF
GLYCEROL
OXIDATION OF GLICEROL TO GLYCARIC ACID
WITH Pd CATALYSTS
OXIDATION OF GLICEROL TO DIYIDROXYACETONE
WITH Pt-Bi CATALYSTS
DEHYDRATATION TO ACROLEIN
Oxidation products of glycerol
O
O O
HO OH
OH
HO glyoxylic acid O
O
O
glycolic acid hydroxyacetone
HO OH
OH
HO
O
oxalic acid dihydroxyaceton
O
OH
HO OH HO OH
O OH
O O
pyruvic acid glycerol
tartronic acid
O
HO OH OH
HO OH
O
O O
hydroxypyruvic acid
HO OH glyceric acid
O O
mesoxalic acid
Conclusions
• 1) Synthesis of old building blocks
• Ethylene, propylene, aromatics, hydrogen,
syngas
• 2) Synthesis of new building blocks
• Ethanol,methanol, glycerol , l-lactic acid
• 3) Synthesis of additives for fuels
• Ethanol, ETBE, biodiesel, green diesel
