Marja Lajunen Green Chemistry
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Green Chemistry
6.4.2006
Green Chemistry for Sustainable Production Prof. Marja Lajunen University of Oulu Department of Chemistry
Waste minimization and resources use optimization, April 3rd-7th, 2006
1
”If mankind is to survive, we shall require a substantially new manner of thinking.” Albert Einstein (18791955) Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
2
1
Green Chemistry
6.4.2006
Green chemistry for sustainable production Content What is green chemistry? Green chemistry methods in sustainable production Ionic liquids Microwave-assisted synthesis Applications of suitable production Waste minimization and resources use optimization, April 3rd-7th, 2006
3
Green chemistry Background: Chemistry has improved our everyday life in many ways • Health care, drugs, clean water, safe food, better appliances • Resulted in a better health and longer life: from 47 years in 1900 to 65 years in 2000 Population Division of the Department of Economic and Social Affairs of the United Nations Secretariat, World Prospects: Theuse 2004 Revision and World Urbanization WastePopulation minimization and resources 4 Prospects: The 2003 Revision, http://0-esa.un.org.portia.nesl.edu:80/unpp optimization, April 3rd-7th, 2006
Marja Lajunen
2
Green Chemistry
6.4.2006
Advances also created problems • Environmental disasters all over the world 1956 - Japan, Minamata Bay, mercury poisoning 1976 - USA, Massachusetts: Argo Merchant 1976 - Italy, Seveso, dioxin release 1977 - USA, New York, City of Niagara Falls 1978 - France, North Atlantic, oil tanker Amoco Cadiz 1982 - USA, Missouri, Town of Times Beach 1984 - India, Bhopal, Union Carbide pesticide plant 1989 - USA, Alaska, oil tanker Exxon Valdez
Waste minimization and resources use optimization, April 3rd-7th, 2006
5
Wake-up of the society by Rachel Carson (1907-1964) • Effects of DDT
Cl Cl
Cl Cl C C H
Cl
para-dichlorodiphenyltrichloroethane (DDT)
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
6
3
Green Chemistry
6.4.2006
Consequences: Understanding and awareness of the environmental issues increased Focus on environmental laws and regulations
Waste minimization and resources use optimization, April 3rd-7th, 2006
120 110 100 90 80 70 60 50 40 TA FWCA BPA
30 NBRA
20 RHA
AA
WA IA
NPS
MBCA
YA
10 1870 0
1880
1890
1900
1910
1920
1930
7
AMFA ARPAA AQ AJA A ASBCAA ESAA-AECA FFRAA FEAPRA IRA NAWCA NWPAA CODRA/NMSPAA FCRPA MMPAA RCRAA APA WQA WLDI SWDA CERCLA CZMIA NWPA COWLDA FWLCA MPRSAA CAAA ARPA MPRSAA CWA SMCRA SWRCA SDWAA BLBA HMTA FWPCA MPRSA ESA CZMA TAPA NCA FEPCA PWSA FRRRPA MMPA SOWA DPA AQA FCMHSA FOIA WRPA AFCA FHSA WSRA NFMUA EA AEPA FIFRA PAA NHPA RCFHSA WLDA FWCAA FAWRA FWA AEA NLRA WPA
1940
1950
1960
1970
1980
1990
EPACT FFCA CERFA CRAA PPA PPVA IEREA ANTPA GLCPA ABA CZARA WRDA EDP OPA RECA CAAA GCRA GLFWRA HMTUSA NEEA SDWAA SARA BLRA ERDDAA EAWA NOPPA PTSA UMTRCA ESAA QGA NCPA TSCA FLPMA RCRA NFMA CZMAA NEPA EQIA CAA EPA EEA OSHA FAWRAA NPAA
2000
P.T Anastas and J.C. Warner, Green Chemistry: Theory and Practice, Oxford University Press, 1998. Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
8
4
Green Chemistry
6.4.2006
Resulted in... Increased testing of chemical substances to determine their hazard • Understanding on the molecular basis of hazards • Physical hazards, global hazards, and toxicological ones • Treating hazard as simply another physical/chemical property Waste minimization and resources use optimization, April 3rd-7th, 2006
9
Results from testing of chemicals began to grow in scientific and industrial circles • Knowledge about chronic toxicity, bioaccumulation and carcinogenicity increased (direct toxicity) • Indirect toxicity: acidic rain and snowfall, greenhouse effect and ozone depletion
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
10
5
Green Chemistry
6.4.2006
Seeking of replacements, substitutes, or alternatives for toxic compounds A new term was introduced in 1990 by Paul Anastas and John Warner in contex of The U.S. Pollution Prevention Act
Green chemistry the use of chemistry for pollution prevention Waste minimization and resources use
11
optimization, April 3rd-7th, 2006
Organization for Economic Cooperation and Development (OECD) defined in 1998 Sustainable chemistry initiative to encourage the development of environmentally benign chemicals Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
12
6
Green Chemistry
6.4.2006
Definition GREEN CHEMISTRY: The design of chemical products and processes that reduce and/or eliminate the use and generation of hazardous substances
P.T Anastas and J.C. Warner, Green Chemistry: Theory and andresources Practice, Waste minimization useOxford University Press, 1998. 13 optimization, April 3rd-7th, 2006
Twelve Principles of Green Chemistry 1. Prevention is preferable to treatment/control 2. Atom Economy 3. Less Hazardous Chemical Syntheses 4. Designing Safer Chemicals 5. Safer Solvents and Auxiliaries 6. Design for Energy Efficiency 7. Use of Renewable Feedstocks 8. Reduce Derivatives 9. Catalysis 10. Design for Degradation 11. Real-time Analysis for Pollution Prevention 12. Inherently Safer Chemistry for Accident Prevention P.T Anastas and J.C. Warner, Green Chemistry: Theory and Practice, Oxford University Press, 1998. Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
14
7
Green Chemistry
6.4.2006
Green chemistry is... Interdisciplinary • • • • • • •
Economics Engineering Political science Ethics and psychology Environmental science Chemistry Biology Waste minimization and resources use optimization, April 3rd-7th, 2006
15
Green chemistry is... A way of dealing with risk Risk = Hazard x Exposure • Green chemistry focuses on reducing environmental risk by reducing hazard • By reducing hazard, it is possible to lower both direct and Waste minimization and resources use 16 indirect optimization, costsApril 3rd-7th, 2006
Marja Lajunen
8
Green Chemistry
6.4.2006
Green chemistry in a nutshell Reduce waste Reduce the consumption of resources and use renewable resources Reduce energy consumption Waste minimization and resources use optimization, April 3rd-7th, 2006
17
Major problems of processes Inefficient processes Solid waste Heavy metals Solvent waste
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
18
9
Green Chemistry
6.4.2006
Alternative solvents
Solventless system Water Supercritical Fluids Ionic liquids
Waste minimization and resources use optimization, April 3rd-7th, 2006
19
A new solvent Ionic liquids (ILs): • They are salts • Their melting point is below the boiling point of water • They are totally in ionic form
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
20
10
Green Chemistry
6.4.2006
Synonyms for ionic liquids ¾Molten salts ¾Room temperature ionic liquids (RTIL’s) ¾Low-temperature molten salts ¾Ambient-temperature molten salts ¾Liquid organic salts Waste minimization and resources use optimization, April 3rd-7th, 2006
21
Typical cationic parts of ILs
Large organic cations Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
22
11
Green Chemistry
6.4.2006
Common anionic parts of ILs CH3COO-, CF3COO-, F-, Cl-, Br-, I-, BF4-, PF6-, NO3-, AlCl4-, FeCl4-, NiCl3-, ZnCl3-, SnCl5-
Mostly inorganic, multiatomic anions
Waste minimization and resources use optimization, April 3rd-7th, 2006
23
Common ionic liquids
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
24
12
Green Chemistry
6.4.2006
Important properties of ILs ¾ Excellent solvents for organic, inorganic as well as polymeric materials ¾ Wide liquid range (~300 °C) ¾ High thermal stability ¾ High electrochemical stability ¾ Practically non-volatile (very low vapour pressure) ¾ Very polar ¾ Hydrophilic or hydrophobic and air stable Waste minimization and resources use
25
optimization, April 3rd-7th, 2006
Properties for sustainable processes Non-flammable and non-explosive Highly solvating (low volumes required) Recyclable Catalysts as well as solvents Increase reaction rates, selectivities and yields Substitutes for Volatile Organic Compounds (VOC) Waste minimization and resources use to prepare Easy to buy or simple
26
optimization, April 3rd-7th, 2006
Marja Lajunen
13
Green Chemistry
6.4.2006
Waste minimization and resources use optimization, April 3rd-7th, 2006
27
Ionic liquid applications Analytical Synthesis and catalysis Process Engineering Electrochemical Energy Biotechnology Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
28
14
Green Chemistry
6.4.2006
Process Engineering Extraction Separation Membrane technology Extractive destillation
Waste minimization and resources use optimization, April 3rd-7th, 2006
29
Desulfurization & denitrogenation ILs show selective absorption of sulfur and nitrogen from fuels Absorption capacity highly dependent on the IL Applied to the removal of SO2 Waste minimization resources Jess et al. Chem. Commun. (2001) and 2494; Chenuseet al. Energy & Fuels April 3rd-7th, 2006 Res. (2004) 614; Han 18 (2004) 1862; Zhangoptimization, et al. Ind. Eng. Chem. t l A Ch I t Ed 43 (2004) 2415
Marja Lajunen
30
15
Green Chemistry
6.4.2006
Biotechnology Enzyme catalysis Protein synthesis Biomass processing
Waste minimization and resources use optimization, April 3rd-7th, 2006
31
Biomass processing Some ILs dissolve cellulose Water precipitates cellulose Functionalization of cellulose fibers
Swatloski et al. J. Am. Chem. Soc. 124 (2002) 4974; Zhang, et al. Biomacromol. 5 (2004) 266; Turner et al. Biomacromol. 5 (2004) 1379; Mantz et al. J. Am. Chem. Soc. 126 (2004) 14350; Zhu et al. Green Chem. 8 (2006) 325.
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
32
16
Green Chemistry
6.4.2006
Industrial applications Acid scavenging • BASILTM process
Methanol carbonylation • Eastman methanol carbonylation
Waste minimization and resources use optimization, April 3rd-7th, 2006
33
BASILTM process Cl P + 2 R-OH + 2 N Cl
OEt P + 2 OEt
N
N
N
+ H
Cl-
N- Methylimidazole
The BASILTM process (Biphasic Acid Scavenging utilizing Ionic Liquids) HCl is formed during the synthesis Scavenging with a tertiary amine results in a thick, non-stirrable slurry 1-Methylimidazole as an acid scavenger, an ionic liquid is formed: 1-methylimidazolium chloride (HMIM Cl)
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
The BASIL reactor. Upper phase, the solvent-free pure product; lower phase, ionic liquid. PHOTO 34 BASF REPRODUCED BY COURTESY OF
17
Green Chemistry
6.4.2006
Eastman methanol carbonylation C H 3 OH
+
• Old process: – Product flashed (65 psig, 166 °C) – Rh catalyst precipitates (loss of catalyst, plugging)
CO
C H 3 COOH
• IL process: – Product distilled at 90 °C – Rh catalyst stable and stays in solution Gerald Tustin, Eastman Company
Waste minimization and resources use optimization, April 3rd-7th, 2006
35
Conclusions IL can have a strong influence on the outcome of a chemical or physical process IL must be carefully chosen to suit the application Properties of IL is determined by the choise of anion and cation Understanding both IL and application ILs fit with GC Principles 1, 5, Waste minimization and resources use optimization, April 3rd-7th, 2006 9, and 12
Marja Lajunen
36
18
Green Chemistry
6.4.2006
Activation of a chemical reaction or process
Thermal heating
– Slow, inefficient
Microwave
irradiation – Fast, effective
Wall transparent to MW energy
Reactants/solven t absorb MW energy
Local superheating
Heating by conduction
Heating by microwaves
Waste minimization and resources use optimization, April 3rd-7th, 2006
37
What are microwaves? A form of electromagnetic energy Frequency 300 – 300 000 MHz
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
38
19
Green Chemistry
6.4.2006
Microwaves... They have very low energy (0,037 kcal/mol) only molecular rotation happens
They move at the speed of light
Waste minimization and resources use optimization, April 3rd-7th, 2006
39
Dielectric heating A mechanism by which matter absorbs microwave energy Dipoles move and orient according to the direction of the electric field
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
40
20
Green Chemistry
6.4.2006
Dielectric heating... Dipolar molecules cannot follow the rapidly changing electric field Phase shifts and dielectric losses result Field energy is transferred to the medium Electrical energy is converted into kinetic or thermal energy = molecular friction Waste minimization and resources use optimization, April 3rd-7th, 2006
41
Therefore... Heating effect of MW is Purely kinetic effect Instant superheating
Oscillating dipoles
Ionic conduction
dipoles rotate
ions move Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
42
21
Green Chemistry
6.4.2006
Solvent and MW Solvent a crucial factor in MW activation • Polarity and absorbing ability dependent on constant ε’(permittivity) Dipole moment μ = Qr Dielectric loss ε’’ (the amount of input MW energy lost to the sample) Tangent δ= ε’’/ε’ (loss tangent) Dielectric relaxation time Dielectric
Waste minimization and resources use optimization, April 3rd-7th, 2006
43
Tangent loss The ability of matter to convert microwave energy into thermal energy at a given frequency and temperature tan δ = ε’’/ε’
ε’’ = dielectric loss ε’ = dielectric constant
Dielectric
loss describes best the coupling efficiency of a particular solvent Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
44
22
Green Chemistry
6.4.2006
Solvent categories Heat very quickly
Heat very efficiently but they require more time
Heat over their b.p but it takes much longer time
B. Hayes Microwave Synthesis Chemistry at the Speed of Light, CEM Publishing, 2002.
Waste minimization and resources use optimization, April 3rd-7th, 2006
45
Heating ability [emim][PF6], ionic liquid (high absorber) Hexane, bp. 69 °C nonpolar (low)
Acetone, bp. 56 °C polar (medium) B. Hayes Microwave Synthesis Chemistry at the Speed of Light, CEM Publishing, 2002.
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
46
23
Green Chemistry
6.4.2006
Safety Work only with an equipment designed for its specific use
Hot spot
Domestic microwave oven MW reactor Waste minimization and resources use optimization, April 3rd-7th, 2006
47
Reactor cavity A single-mode reactor • Power 300-400 W W/ml
field density 0.90
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
48
24
Green Chemistry
6.4.2006
Operation
Waste minimization and resources use optimization, April 3rd-7th, 2006
49
Benefits of the microwave-assisted reaction
Faster reactions Better yields Cleaner reactions Greener chemistry
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
50
25
Green Chemistry
6.4.2006
% Acceptance
The use of MW technique •50 •40
Medicinal Chemistry
•30
Academia •20
Process Development •10
Production Scale 2000 2008
2001
Single Mode Reactors
2002
2003
2004
Flow Thru Reactors
Automation Options
2005
2006
2007
Production Scale Flow Reactor
Sub Ambient Waste minimization and resources use Reactors optimization, April 3rd-7th, 2006
Dr. Mike Collins 51 CEO, CEM corporation
Iso-octane synthesis dime rization, red uctio n
2 iso -b utyle ne
iso -o cta ne
Preparation of iso-octane, an additive of gasoline • Synthesis performed in ionic liquid
MSc. Johanna Kärkkäinen, Prof. Marja Lajunen, Dept of Chemistry Waste minimization and resources use
52
optimization, April 3rd-7th, 2006
Marja Lajunen
26
Green Chemistry
6.4.2006
Esterification of polyols Peracetylated alcohols in ionic liquids by using microwave activation • Detergents, paper chemicals O
Ac2O R OH n BMIMCl
R
O
R' n
MSc. Janne Asikkala, Prof. Marja Lajunen, Dept. of Chemistry Waste minimization and resources use optimization, April 3rd-7th, 2006
53
α-Hydroxyketones and aldehydes Preparation of multifunctional model compounds, which fit into the binding pocket of triose phosphatate isomerase (TIM) O -O
OP
T IM
O
OH O
D ihy d ro x y ac e ton e p ho s ph ate ( D H A P)
O -O
QuickTime™ ja TIFF (LZW) pakkauksen purkuohjelma tarvitaan elokuvan katselemiseen.
OP
O
O OH
D -g ly c er ald eh y d e-3 -p ho s ph a te (D G AP )
MSc. Matti Vaismaa, Prof. Marja Lajunen, Dept. of Chemistry Waste minimization and resources use
54
optimization, April 3rd-7th, 2006
Marja Lajunen
27
Green Chemistry
6.4.2006
Functionalization of carbon nanotubes New properties by chemical modification in ionic liquid
QuickTime™ ja TIFF (ei pakattu) pakkauksen purkuohjelma tarvitaan elokuvan katselemiseen.
• CNTs: diameter few nanometers, length millions nm, metallic or semiconductive, 100 times stronger than steel, stiff as dimond BUT insoluble in any common solvent.
QuickTime™ ja TIFF (ei pakattu) pakkauksen purkuohjelma tarvitaan elokuvan katselemiseen.
MSc. Heli Leinonen, Prof. Marja Lajunen, Dept. of Chemistry Waste minimization and resources use optimization, April 3rd-7th, 2006
55
A. Hirsch Angew. Chem. Int. Ed. 41 (2002) 1853.
MW activation in use Solution, solid phase or solventless reactions Homogeneous or heterogeneous solutions • Transition metal catalysis, Lewis acids, other insoluble salts
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
56
28
Green Chemistry
6.4.2006
Solventless reaction •
Reagents absorbed on the surface of mineral oxide
Waste minimization and resources use optimization, April 3rd-7th, 2006
57
• Phase transfer reactions – Phase transfer reactions
• Plain reagents
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
58
29
Green Chemistry
6.4.2006
Organometallic reactions • Heck reaction
• Stille coupling
Waste minimization and resources use optimization, April 3rd-7th, 2006
59
Cycloadditions
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
60
30
Green Chemistry
6.4.2006
Microwave technique is... • A breakthrough technology, whose use is rapidly evolving • Suitable for reactions/processes requiring heating • Used in medical industry ca. in 90 % of drug development studies • Saves energy and time • GREEN (GC Waste Principles minimization and resources5 use and 6)
61
optimization, April 3rd-7th, 2006
Thank you for your attention! Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
62
31
6.4.2006
Green Chemistry for Sustainable Production Prof. Marja Lajunen University of Oulu Department of Chemistry
Waste minimization and resources use optimization, April 3rd-7th, 2006
1
”If mankind is to survive, we shall require a substantially new manner of thinking.” Albert Einstein (18791955) Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
2
1
Green Chemistry
6.4.2006
Green chemistry for sustainable production Content What is green chemistry? Green chemistry methods in sustainable production Ionic liquids Microwave-assisted synthesis Applications of suitable production Waste minimization and resources use optimization, April 3rd-7th, 2006
3
Green chemistry Background: Chemistry has improved our everyday life in many ways • Health care, drugs, clean water, safe food, better appliances • Resulted in a better health and longer life: from 47 years in 1900 to 65 years in 2000 Population Division of the Department of Economic and Social Affairs of the United Nations Secretariat, World Prospects: Theuse 2004 Revision and World Urbanization WastePopulation minimization and resources 4 Prospects: The 2003 Revision, http://0-esa.un.org.portia.nesl.edu:80/unpp optimization, April 3rd-7th, 2006
Marja Lajunen
2
Green Chemistry
6.4.2006
Advances also created problems • Environmental disasters all over the world 1956 - Japan, Minamata Bay, mercury poisoning 1976 - USA, Massachusetts: Argo Merchant 1976 - Italy, Seveso, dioxin release 1977 - USA, New York, City of Niagara Falls 1978 - France, North Atlantic, oil tanker Amoco Cadiz 1982 - USA, Missouri, Town of Times Beach 1984 - India, Bhopal, Union Carbide pesticide plant 1989 - USA, Alaska, oil tanker Exxon Valdez
Waste minimization and resources use optimization, April 3rd-7th, 2006
5
Wake-up of the society by Rachel Carson (1907-1964) • Effects of DDT
Cl Cl
Cl Cl C C H
Cl
para-dichlorodiphenyltrichloroethane (DDT)
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
6
3
Green Chemistry
6.4.2006
Consequences: Understanding and awareness of the environmental issues increased Focus on environmental laws and regulations
Waste minimization and resources use optimization, April 3rd-7th, 2006
120 110 100 90 80 70 60 50 40 TA FWCA BPA
30 NBRA
20 RHA
AA
WA IA
NPS
MBCA
YA
10 1870 0
1880
1890
1900
1910
1920
1930
7
AMFA ARPAA AQ AJA A ASBCAA ESAA-AECA FFRAA FEAPRA IRA NAWCA NWPAA CODRA/NMSPAA FCRPA MMPAA RCRAA APA WQA WLDI SWDA CERCLA CZMIA NWPA COWLDA FWLCA MPRSAA CAAA ARPA MPRSAA CWA SMCRA SWRCA SDWAA BLBA HMTA FWPCA MPRSA ESA CZMA TAPA NCA FEPCA PWSA FRRRPA MMPA SOWA DPA AQA FCMHSA FOIA WRPA AFCA FHSA WSRA NFMUA EA AEPA FIFRA PAA NHPA RCFHSA WLDA FWCAA FAWRA FWA AEA NLRA WPA
1940
1950
1960
1970
1980
1990
EPACT FFCA CERFA CRAA PPA PPVA IEREA ANTPA GLCPA ABA CZARA WRDA EDP OPA RECA CAAA GCRA GLFWRA HMTUSA NEEA SDWAA SARA BLRA ERDDAA EAWA NOPPA PTSA UMTRCA ESAA QGA NCPA TSCA FLPMA RCRA NFMA CZMAA NEPA EQIA CAA EPA EEA OSHA FAWRAA NPAA
2000
P.T Anastas and J.C. Warner, Green Chemistry: Theory and Practice, Oxford University Press, 1998. Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
8
4
Green Chemistry
6.4.2006
Resulted in... Increased testing of chemical substances to determine their hazard • Understanding on the molecular basis of hazards • Physical hazards, global hazards, and toxicological ones • Treating hazard as simply another physical/chemical property Waste minimization and resources use optimization, April 3rd-7th, 2006
9
Results from testing of chemicals began to grow in scientific and industrial circles • Knowledge about chronic toxicity, bioaccumulation and carcinogenicity increased (direct toxicity) • Indirect toxicity: acidic rain and snowfall, greenhouse effect and ozone depletion
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
10
5
Green Chemistry
6.4.2006
Seeking of replacements, substitutes, or alternatives for toxic compounds A new term was introduced in 1990 by Paul Anastas and John Warner in contex of The U.S. Pollution Prevention Act
Green chemistry the use of chemistry for pollution prevention Waste minimization and resources use
11
optimization, April 3rd-7th, 2006
Organization for Economic Cooperation and Development (OECD) defined in 1998 Sustainable chemistry initiative to encourage the development of environmentally benign chemicals Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
12
6
Green Chemistry
6.4.2006
Definition GREEN CHEMISTRY: The design of chemical products and processes that reduce and/or eliminate the use and generation of hazardous substances
P.T Anastas and J.C. Warner, Green Chemistry: Theory and andresources Practice, Waste minimization useOxford University Press, 1998. 13 optimization, April 3rd-7th, 2006
Twelve Principles of Green Chemistry 1. Prevention is preferable to treatment/control 2. Atom Economy 3. Less Hazardous Chemical Syntheses 4. Designing Safer Chemicals 5. Safer Solvents and Auxiliaries 6. Design for Energy Efficiency 7. Use of Renewable Feedstocks 8. Reduce Derivatives 9. Catalysis 10. Design for Degradation 11. Real-time Analysis for Pollution Prevention 12. Inherently Safer Chemistry for Accident Prevention P.T Anastas and J.C. Warner, Green Chemistry: Theory and Practice, Oxford University Press, 1998. Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
14
7
Green Chemistry
6.4.2006
Green chemistry is... Interdisciplinary • • • • • • •
Economics Engineering Political science Ethics and psychology Environmental science Chemistry Biology Waste minimization and resources use optimization, April 3rd-7th, 2006
15
Green chemistry is... A way of dealing with risk Risk = Hazard x Exposure • Green chemistry focuses on reducing environmental risk by reducing hazard • By reducing hazard, it is possible to lower both direct and Waste minimization and resources use 16 indirect optimization, costsApril 3rd-7th, 2006
Marja Lajunen
8
Green Chemistry
6.4.2006
Green chemistry in a nutshell Reduce waste Reduce the consumption of resources and use renewable resources Reduce energy consumption Waste minimization and resources use optimization, April 3rd-7th, 2006
17
Major problems of processes Inefficient processes Solid waste Heavy metals Solvent waste
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
18
9
Green Chemistry
6.4.2006
Alternative solvents
Solventless system Water Supercritical Fluids Ionic liquids
Waste minimization and resources use optimization, April 3rd-7th, 2006
19
A new solvent Ionic liquids (ILs): • They are salts • Their melting point is below the boiling point of water • They are totally in ionic form
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
20
10
Green Chemistry
6.4.2006
Synonyms for ionic liquids ¾Molten salts ¾Room temperature ionic liquids (RTIL’s) ¾Low-temperature molten salts ¾Ambient-temperature molten salts ¾Liquid organic salts Waste minimization and resources use optimization, April 3rd-7th, 2006
21
Typical cationic parts of ILs
Large organic cations Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
22
11
Green Chemistry
6.4.2006
Common anionic parts of ILs CH3COO-, CF3COO-, F-, Cl-, Br-, I-, BF4-, PF6-, NO3-, AlCl4-, FeCl4-, NiCl3-, ZnCl3-, SnCl5-
Mostly inorganic, multiatomic anions
Waste minimization and resources use optimization, April 3rd-7th, 2006
23
Common ionic liquids
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
24
12
Green Chemistry
6.4.2006
Important properties of ILs ¾ Excellent solvents for organic, inorganic as well as polymeric materials ¾ Wide liquid range (~300 °C) ¾ High thermal stability ¾ High electrochemical stability ¾ Practically non-volatile (very low vapour pressure) ¾ Very polar ¾ Hydrophilic or hydrophobic and air stable Waste minimization and resources use
25
optimization, April 3rd-7th, 2006
Properties for sustainable processes Non-flammable and non-explosive Highly solvating (low volumes required) Recyclable Catalysts as well as solvents Increase reaction rates, selectivities and yields Substitutes for Volatile Organic Compounds (VOC) Waste minimization and resources use to prepare Easy to buy or simple
26
optimization, April 3rd-7th, 2006
Marja Lajunen
13
Green Chemistry
6.4.2006
Waste minimization and resources use optimization, April 3rd-7th, 2006
27
Ionic liquid applications Analytical Synthesis and catalysis Process Engineering Electrochemical Energy Biotechnology Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
28
14
Green Chemistry
6.4.2006
Process Engineering Extraction Separation Membrane technology Extractive destillation
Waste minimization and resources use optimization, April 3rd-7th, 2006
29
Desulfurization & denitrogenation ILs show selective absorption of sulfur and nitrogen from fuels Absorption capacity highly dependent on the IL Applied to the removal of SO2 Waste minimization resources Jess et al. Chem. Commun. (2001) and 2494; Chenuseet al. Energy & Fuels April 3rd-7th, 2006 Res. (2004) 614; Han 18 (2004) 1862; Zhangoptimization, et al. Ind. Eng. Chem. t l A Ch I t Ed 43 (2004) 2415
Marja Lajunen
30
15
Green Chemistry
6.4.2006
Biotechnology Enzyme catalysis Protein synthesis Biomass processing
Waste minimization and resources use optimization, April 3rd-7th, 2006
31
Biomass processing Some ILs dissolve cellulose Water precipitates cellulose Functionalization of cellulose fibers
Swatloski et al. J. Am. Chem. Soc. 124 (2002) 4974; Zhang, et al. Biomacromol. 5 (2004) 266; Turner et al. Biomacromol. 5 (2004) 1379; Mantz et al. J. Am. Chem. Soc. 126 (2004) 14350; Zhu et al. Green Chem. 8 (2006) 325.
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Industrial applications Acid scavenging • BASILTM process
Methanol carbonylation • Eastman methanol carbonylation
Waste minimization and resources use optimization, April 3rd-7th, 2006
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BASILTM process Cl P + 2 R-OH + 2 N Cl
OEt P + 2 OEt
N
N
N
+ H
Cl-
N- Methylimidazole
The BASILTM process (Biphasic Acid Scavenging utilizing Ionic Liquids) HCl is formed during the synthesis Scavenging with a tertiary amine results in a thick, non-stirrable slurry 1-Methylimidazole as an acid scavenger, an ionic liquid is formed: 1-methylimidazolium chloride (HMIM Cl)
Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
The BASIL reactor. Upper phase, the solvent-free pure product; lower phase, ionic liquid. PHOTO 34 BASF REPRODUCED BY COURTESY OF
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Green Chemistry
6.4.2006
Eastman methanol carbonylation C H 3 OH
+
• Old process: – Product flashed (65 psig, 166 °C) – Rh catalyst precipitates (loss of catalyst, plugging)
CO
C H 3 COOH
• IL process: – Product distilled at 90 °C – Rh catalyst stable and stays in solution Gerald Tustin, Eastman Company
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Conclusions IL can have a strong influence on the outcome of a chemical or physical process IL must be carefully chosen to suit the application Properties of IL is determined by the choise of anion and cation Understanding both IL and application ILs fit with GC Principles 1, 5, Waste minimization and resources use optimization, April 3rd-7th, 2006 9, and 12
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Green Chemistry
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Activation of a chemical reaction or process
Thermal heating
– Slow, inefficient
Microwave
irradiation – Fast, effective
Wall transparent to MW energy
Reactants/solven t absorb MW energy
Local superheating
Heating by conduction
Heating by microwaves
Waste minimization and resources use optimization, April 3rd-7th, 2006
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What are microwaves? A form of electromagnetic energy Frequency 300 – 300 000 MHz
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Green Chemistry
6.4.2006
Microwaves... They have very low energy (0,037 kcal/mol) only molecular rotation happens
They move at the speed of light
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Dielectric heating A mechanism by which matter absorbs microwave energy Dipoles move and orient according to the direction of the electric field
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Green Chemistry
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Dielectric heating... Dipolar molecules cannot follow the rapidly changing electric field Phase shifts and dielectric losses result Field energy is transferred to the medium Electrical energy is converted into kinetic or thermal energy = molecular friction Waste minimization and resources use optimization, April 3rd-7th, 2006
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Therefore... Heating effect of MW is Purely kinetic effect Instant superheating
Oscillating dipoles
Ionic conduction
dipoles rotate
ions move Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
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Green Chemistry
6.4.2006
Solvent and MW Solvent a crucial factor in MW activation • Polarity and absorbing ability dependent on constant ε’(permittivity) Dipole moment μ = Qr Dielectric loss ε’’ (the amount of input MW energy lost to the sample) Tangent δ= ε’’/ε’ (loss tangent) Dielectric relaxation time Dielectric
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Tangent loss The ability of matter to convert microwave energy into thermal energy at a given frequency and temperature tan δ = ε’’/ε’
ε’’ = dielectric loss ε’ = dielectric constant
Dielectric
loss describes best the coupling efficiency of a particular solvent Waste minimization and resources use optimization, April 3rd-7th, 2006
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Green Chemistry
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Solvent categories Heat very quickly
Heat very efficiently but they require more time
Heat over their b.p but it takes much longer time
B. Hayes Microwave Synthesis Chemistry at the Speed of Light, CEM Publishing, 2002.
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Heating ability [emim][PF6], ionic liquid (high absorber) Hexane, bp. 69 °C nonpolar (low)
Acetone, bp. 56 °C polar (medium) B. Hayes Microwave Synthesis Chemistry at the Speed of Light, CEM Publishing, 2002.
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Green Chemistry
6.4.2006
Safety Work only with an equipment designed for its specific use
Hot spot
Domestic microwave oven MW reactor Waste minimization and resources use optimization, April 3rd-7th, 2006
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Reactor cavity A single-mode reactor • Power 300-400 W W/ml
field density 0.90
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Green Chemistry
6.4.2006
Operation
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Benefits of the microwave-assisted reaction
Faster reactions Better yields Cleaner reactions Greener chemistry
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Green Chemistry
6.4.2006
% Acceptance
The use of MW technique •50 •40
Medicinal Chemistry
•30
Academia •20
Process Development •10
Production Scale 2000 2008
2001
Single Mode Reactors
2002
2003
2004
Flow Thru Reactors
Automation Options
2005
2006
2007
Production Scale Flow Reactor
Sub Ambient Waste minimization and resources use Reactors optimization, April 3rd-7th, 2006
Dr. Mike Collins 51 CEO, CEM corporation
Iso-octane synthesis dime rization, red uctio n
2 iso -b utyle ne
iso -o cta ne
Preparation of iso-octane, an additive of gasoline • Synthesis performed in ionic liquid
MSc. Johanna Kärkkäinen, Prof. Marja Lajunen, Dept of Chemistry Waste minimization and resources use
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optimization, April 3rd-7th, 2006
Marja Lajunen
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Green Chemistry
6.4.2006
Esterification of polyols Peracetylated alcohols in ionic liquids by using microwave activation • Detergents, paper chemicals O
Ac2O R OH n BMIMCl
R
O
R' n
MSc. Janne Asikkala, Prof. Marja Lajunen, Dept. of Chemistry Waste minimization and resources use optimization, April 3rd-7th, 2006
53
α-Hydroxyketones and aldehydes Preparation of multifunctional model compounds, which fit into the binding pocket of triose phosphatate isomerase (TIM) O -O
OP
T IM
O
OH O
D ihy d ro x y ac e ton e p ho s ph ate ( D H A P)
O -O
QuickTime™ ja TIFF (LZW) pakkauksen purkuohjelma tarvitaan elokuvan katselemiseen.
OP
O
O OH
D -g ly c er ald eh y d e-3 -p ho s ph a te (D G AP )
MSc. Matti Vaismaa, Prof. Marja Lajunen, Dept. of Chemistry Waste minimization and resources use
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optimization, April 3rd-7th, 2006
Marja Lajunen
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Green Chemistry
6.4.2006
Functionalization of carbon nanotubes New properties by chemical modification in ionic liquid
QuickTime™ ja TIFF (ei pakattu) pakkauksen purkuohjelma tarvitaan elokuvan katselemiseen.
• CNTs: diameter few nanometers, length millions nm, metallic or semiconductive, 100 times stronger than steel, stiff as dimond BUT insoluble in any common solvent.
QuickTime™ ja TIFF (ei pakattu) pakkauksen purkuohjelma tarvitaan elokuvan katselemiseen.
MSc. Heli Leinonen, Prof. Marja Lajunen, Dept. of Chemistry Waste minimization and resources use optimization, April 3rd-7th, 2006
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A. Hirsch Angew. Chem. Int. Ed. 41 (2002) 1853.
MW activation in use Solution, solid phase or solventless reactions Homogeneous or heterogeneous solutions • Transition metal catalysis, Lewis acids, other insoluble salts
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Solventless reaction •
Reagents absorbed on the surface of mineral oxide
Waste minimization and resources use optimization, April 3rd-7th, 2006
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• Phase transfer reactions – Phase transfer reactions
• Plain reagents
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Organometallic reactions • Heck reaction
• Stille coupling
Waste minimization and resources use optimization, April 3rd-7th, 2006
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Cycloadditions
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Microwave technique is... • A breakthrough technology, whose use is rapidly evolving • Suitable for reactions/processes requiring heating • Used in medical industry ca. in 90 % of drug development studies • Saves energy and time • GREEN (GC Waste Principles minimization and resources5 use and 6)
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optimization, April 3rd-7th, 2006
Thank you for your attention! Waste minimization and resources use optimization, April 3rd-7th, 2006
Marja Lajunen
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