THE GREEN REVOLUTION FOR CHEMISTRY

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THE GREEN REVOLUTION FOR CHEMISTRY

• ACTUALITY AND PERSPECTIVES

C.GESSA AND F.TRIFIRO
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HOW TO TRANSFORMBIOMASS IN CHEMICAL PRODUCTS ?

• 2) WHAT ARE THE DRIVEN FORCES FOR THE USE OF
  BIOMASS AS FEEDSTOCKS FOR THE CHEMICAL INDUSTRY?

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WHAT WE HAVE LEARNED FROM THESE TWO DAYS
IT IS NOT POSSIBLE TO GENERALIZE WITH SENTENCES
LIKE THE FOLLOWINGS BIOMASS AS FEEDSTOCKS FOR
CHEMICAL INDUSTRY ARE LESSER POLLUTANT, MORE
BIODEGRADABLE , MORE SUSTAINABLE , MORE
ENVIROMENTAL BENIGN, MORE (LESSER) EXPENSIVE ,
MORE AVAILABLE, LESSER TOXIC THAN THOSE DERIVED
FROM FOSSIL FUELS. WE HAVE FIRST TO
ELABORATE, A LIFE CYCLE ASSESMENT
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ECONOMICAL ASPECTS IN THE PRODUCTION OF BIODIESEL
IT IS POSSIBLE TO DECREASE THE PRICE OF
BIODIESEL, IF IT IS POSSIBLE TO USE THE COPRODUCT
GLYCEROL AND TO RECOVER THE SEVERAL BY
PRODUCTS. EXAMPLE FROM PALM OIL THE RECOVERY
OF CAROTENES, ( PRO VITAMIN A, PREVENT
XEROPHTHALMIA ANTI-CANCER ANTI-OXIDANT) VITAMIN
E , STEROLS COENZIME Q SQUALENE PHOSPHOLIPIDES
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CURRENT FEEDSTOCKS FOR THE CHEMICAL INDUSTRY
1)OIL FOR THE PRODUCTION OF ETHYLENE,
PROPYLENE, BUTADIENE, BENZENE, TOLUENE AND
XYLENES 2)NATURAL GAS FOR THE PRODUCTION OF
SYNGAS(COH2) , METHANOL , HYDROGEN 3)CARBON
FOR THE PRODUCTION OF ANTHRACENE AND NAFTHALENE
4)BIOMASS FOR THE PRODUCTION OF NATURAL
POLYMERS( CELLULOSE AND RUBBER), SEVERAL FINE
CHEMICALS AND PHARMACEUTICALS
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EMERGING FEEDSTOCKSFOR THE CHEMICAL INDUSTRY
1)NATURAL GAS ?METHANOL TO OLEFINS ?LOW ALKANES
TO OLEFINS ?LOW ALKANES TO INTERMEDIATES 2)BIOMAS
S
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FOSSIL RESOURCES
TOTAL USE ( COALOILGAS) 7,3GTOE TOTAL
AVAILABLE
121 GTOE
GAS
850 GTOE
COAL
OIL 143 GTOE
GTOE 109 TON OIL EQUIVALENT
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FARMING
FOOD CROPS
CONSTRAINTS
RESEARCH
REASONS
NEW TECHNOLOGIES ?
NEW CROPS?
NON FOOD CROPS
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REASONS

• EXHAUSTION OF FOSSIL SOURCES
• SURPLUS OF FOODS
• ENVIROMENTAL SUSTAINABILITY
• INDUSTRIAL INTEREST

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CONSTRAINTS

• FEEDSTOCK SQUALITY
• FEEDSTOCKS PRICE
• CONTINOUS FEEDSTOCK SUPPLY
• TRANSFORMATION TECHNOLOGY
• POLITICAL CONSTRAINTS

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SURPLUS OF FOOD PRODUCTION(1990)
WORLD POPULATION FOOD PRODUCTION 5
109 PEOPLE 4.3
109 TON

x106ton increase

from 1996 CEREALS
1800
83 ROOT TUBERS
580 18 VEGETABLES
265
123 SUGAR BEET- SUGAR CANE 100
110 FRUITS
330
78 PRODUCTS FROM LIVERSTOCKS 715
65 FISHING
95 170 THIS
AMOUNT MIGHT ASSURE A RIGHT DIET TO 6.109PEOPLE (
2350KCAL/DAY)
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SURPLUS FOOD PRODUCTION
THE PROBLEM THE DISTRIBUTION OF FOODS IS NOT
UNIFORM IN THE WORLD DIET AVERAGE IN DEVELOPED
COUNTRIES IS 3132 kCAL/DAY/PERSON
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SCENARIO 2040 (9.109 PEOPLE
AGRICULTURAL SOILS AVAILABLE ARABLE 2.8 109
ha LAND REQUIRED TO FEED 1.8
109ha WORLD POPULATION

• SOILS FOR
• a)GRAIN 143. 106 ha
• MILK, 445. 106ha
• MEAT
• c)OIL.FATS, 750.106ha
• SUGAR, FRUITS
• VEGETABLES
• 1,338.106ha

REMAINING FOR 1.0 109 ha CARBON
FARMING
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RENEWABLE RESOURCES
TOTAL BIOMASS 170.109 t/y TOTAL USE
7.1.109t/y
WOOD 3.2.109 t/y GRAIN 1.9.109t/y OIL SEEDS
2.0.109t/y SUGARS,FRUITS ROOTS ETC
4.0.109t/y 3.1.109 t/y FOOD
NON FOOD PRODUCTION
PRODUCTION
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NON FOOD PRODUCTION
OILS/FATS SUGARS
VEGETABLE FIBERS 18.0.106t/y
112.106t/y 23.0 .106t/y

LIPOCHEMISTRY 33 LUBRIFICANTS 6.0 DETERGENTS
60 INKS-PAINTS 1.0
FEEDING CHEMISTRY 35
65
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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)
Pyrolisis 5) Gasification
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PHYSICAL METHODS
THEY SEPARATE AND ISOLATE THE DIFFERENT
COMPONENTS OF BIOMASS LEAVING UMMODIFIED THEIR
STRUCTURE
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

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ONE STEP (BIO)CHEMICAL MODIFICATION
ONE STEP MODIFICATIONS OF COMPONENTS SEPARATED BY
PHYSICAL METHODS
EXAMPLES ?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
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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
• THE ANTIARRYTHMIC QUINIDINE IN TWO STEPS FROM
• QUININE

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PYROLYSIS-PRODUCTION OF BIO-CRUDE
?DECOMPOSITION AT TEMPERATURE BETWEEN 500-800C
IN ABSENCE OR WITH LOW AMOUNT OF OXYGEN TO
PRODUCE ?LIQUID ORGANIC FRACTIONS SIMILAR THOSE
ONES OBTAINED FROM PETROLEUM
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GASSIFICATIONPRODUCTION OF BIO-GAS

• ?CONTROLLED COMBUSTION AROUND 1000C
• TO PRODUCE SYNTHESIS GAS
• FROM SYNTHESIS GAS
• ?TO HYDROGEN,
• ?TO METHANOL
• TO LIQUID FUEL VIA FISCHER TROPSCH
• REACTIONS

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FROM RENEWABLES FEEDSTOCKS TO CHEMICALS
Lignocellulosics
Hemicellulose
Furfurol
Glucose
Renewable feedstocks
Grains
Starch
Ethanol
Sugar crops Carbohydrates Sucrose Lactic
acid
Oil crops
Triglycerides
Fatty acids Fatty alcohols
Terpenoid crops? Terpenes
Algae
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THE NEED OF ALTERNATIVE UNIT OPERATIONS

• MEMBRANE TECHNOLOGIES
• MULTIPHASE REACTORS
• SOLID LIQUID EXTRACTION
• MANAGING SOLID POWDER (GASIFICATION, MOVING BED,
  FLUID BED,PNEUMATIC TRANSPORT)
• FILTRATION
• SIEVING, GRINDING
• FLUID SUPERCRITICAL EXTRACTION
• CHROMATOGRAPHY

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THE ROLE OF BIO AND OF CHEMICAL CATALYSIS

• THEY ARE NOT COMPETITIVE BUT INTEGRATED

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BASE CHEMICALS PRODUCED BY FERMENTATION PRODUCT
NUTRIENT TYPE OF
REACTION ETHANOL CARBOHYDRATES
ANAEROBIC BUTANOL YEAST
ANAEROBIC CITRIC ACID
SUCROSE AEOROBIC LACTIC
ACID SUCROSE
ANAEROBIC SUCINNIC ACID GLUCOSE
ANAEROBIC
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FROM TRYGLICERIDES TO CHEMICALS

• -BY TRANSESTERIFICATION WITH MEHANOL
• AT 50C WITH BASIC CATALYSTS ? METHYL FATTY ESTERS
  ADDITIVE FOR FUELS AND FUEL
• -BY HYDROLYSIS AT 230C AT 32 ATM ? FATTY ACIDS
  AND GLICERIN
• - BY HYDROGENATION AT 225 C 50 ATM ? FATTY
  ALCOHOLS BIODEGRADABLE SURFACTANTS
• -BY DEHYDRATATION OF FATTY ALCHOOLS AT 400 C ?
  OLEFINS TO PRODUCE LUBRICANTS
• BY EPOXIDATION OR DIMERIZATION OF OLEFINS?
• TO PRODUCE VALUABLE CHEMICALS

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CATALYSIS IN CARBOHYDRATES CONVERSION

Biocatalysts Chemiocatalysts OXIDATION

HYDROGENATION -
HYDROLYSIS

ESTERIFICATION
ISOMERIZATION
ALKYLATION

CYCLIC OLIGOMERIZATION
- CYCLIC ETHERIFICATION -
NITRATION
-

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GENETIC MODIFICATIONS
TOWARDS AGROCHEMCALS
MAKING PLANT RESISTANT
TOWARDS DISEASES AND PEST
HIGH STEARIC SOY BEAN
INDUCING PLANT TO MAKE OTHER MATERIALS
HIGH LAURIC RAPE SEED OIL
B CAROTENE AND IRON CONTAINING RICE
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ENVIROMENTAL SUSTAINABILITY

• OF RENEWABLE RESOURCES
• MORE EASY BIODEGRADABLES
• C02 EMISSIONNEUTRAL FOR GREENHOUSE EFFECT
• LESS AMOUNT OF POLLUTANTS
• LESS AMOUNT OF PESTICIDES AND FERTILIZERS
• INCREASE THE PLANT SPECIES FOR CROP ROTATION

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PRODUCTS MORE BENIGN FOR THE ENVIROMENT
FROM METHYL ESTERS OF FATTY ACIDS ?SURFACTANTS
IN ALTERNATIVE TO ALCHYLBENZENE SULPHONATES
?LUBRICANTS IN ALTERNATIVE TO MINERAL
OILS ?SOLVENTS IN ALTERNATIVE TO CHLORINATE
SOLVENTS
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COMPARISON OF PRODUCTION COST OF SURFACTANTS
MES METYLESTER SULPHONATE LAS
ALCHYLBENZENE SULPHONATE RAW MATERIAL
MES LAS S
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11 ALCHYLBENZENE
809 METHYLESTER
374 INORGANICS
68 57 TOTAL RAW MATERIALS 454
877 UTILITIES
40 21 OTHER COSTS
31 30 TOTAL
COSTS 525
928
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COMPARIOSN BETWEEN MES AND LAS
MES
LAS RAW MATERIAL
LESSER ENERGY LESSER N0x
S0x C0 VOC
HIGHER WASTEWATER
LESSER SOLID WASTE
COMPARABLE
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PRICES OF SOME INDUSTRIAL SOLVENTS
SOLVENT
/Kg METHYL ESTER OF SOYA
0.60-0.90 METHYLENE CHLORIDE
0.60 METHYLETHYLCHE
TONE
0.92 TRICHLOROETHYLENE
1.30 N-
METHYLPIRROLIDONE
3.40 PERCHLOETHYLENE
0.70
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FUTUR KEY CHEMICALS

• LACTIC ACID
• METHANOL
• ETHANOL

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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
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METHANOL
FROM SYNTHESIS GAS
PRODUCTS METHANOL ? OLEFINS METHANOL ?
DIMETHYLETHER ALTERNATIVE DIESEL METHANOL? FOR
FUEL CELL METHANOL? ACETIC ACID METHANOL?
FORMALDEHYDE
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ETHANOL
BY FERMENTATION OF BIOMASS
PRODUCTS ETHANOL? ETHYLENE ETHANOL
?ACETIC ACID ETHANOL?AROMATIC ETHYLATION ETHANOL?
ETHYLENE GLYCOL
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CONCLUSIONS
MAIN ADVANTAGES BESIDES RENEWABILITY OF
EMPOLYING RAW MATERIALS ISSUED FROM CROPS AND
BIOMAS ARE ?HIGH MOLECULAR FUNCTIONALITY
?BIODEGRADABILITY ?THE NATURAL LABLE WHICH IS
RETAINED FROM THE INITIAL FEEDSTOCK TO THE END
PRODUCT THE PRIORITY MUST BE
GIVEN TO ? THEIR TRANSFORMATION TO HIGH VALUE
ADDED INTERMEDIATES AND FINE CHEMICAL ?OTHER
BIOMASS ( WASTES) CAN BE DEGRADATED TO SMALL
MOLECULES THROUGH FERMENTATION OR GASIFICATION
ALSO FOR ENERGY PRODUCTION