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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

				
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