Post on 07-Jul-2020
環境グリーンプロセスGreen Chemical Processes
Richard Smith東北大学 環境グリーンプロセス学 超臨界流体工学
Supercritical Fluid TechnologySystem Development Division
SMITH
LAB.!
Tohoku University
Department of Chemical Engineering
Graduate School of Environmental Studies
Sendai, Japan
http://www.che.tohoku.ac.jp/~smith/Lab.htm
22 May 2019 1
Supercritical Fluid TechnologySystem Development Division
SMITH
LAB.!Laboratory philosophy...
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Supercritical Fluid
TechnologySystem Development Division
SMITH
LAB.!Outline
1. World population and CO2 emissions
2. World oil supply and demand
3. Carbon-negative oil
4. Supercritical CO2
5. Green chemical processes
6. Concluding Remarks3
Supercritical Fluid TechnologySystem Development Division
SMITH
LAB.!
1. World population and
CO2 emissions
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Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!
7.7
9.8
11.2
2019
2050
2100
Source (2019):
www.un.org/develop
World populationaround 1918 was
1,800,000,000 people
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Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!World Population in 2050
Source (2019):
www.un.org/develop
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Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!
2. World oil supply and demand
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EnergyConsumption
Oil: 32 %Gas: 22 %Coal: 27 %Biomass: 10 %Electricity: 9 %
https://yearbook.enerdata.net/total-energy/world-consumption-statistics.html
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If 1 L of oil (gas/petrol) is totally combusted,
how much CO2 is emitted? (roil = 800 kg/m3)
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If 1 L of oil (gas/petrol) is totally combusted,
how much CO2 is emitted? (roil = 800 kg/m3)
3
3
2 2
2
2
2
2
1 m 800 kg 1 mol1 L 0.85 C (in oil) 0.68 kg C = 0.0566 kmol C
1000 L m 12 g
1 mol C + 1 mol O = 1 mol CO
32 g
kg
0.0566
CO = 0.68 kg C + 1.81 kg O =
kmol O 1.81 kg Omol
2 2.5 kg CO
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If 1 barrel of oil (159 L) is totally combusted,
how much CO2 is emitted?
How much CO2 is emitted if 1 toe (tonne of oil
equivalent) is totally combusted?
(1 toe = 7.33 barrels of oil)
In 2017, CO2 emissions were 36.2 Gigatonnes.
How many Mtoe does this correspond to?
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If 1 barrel of oil (159 L) is totally combusted,
how much CO2 is emitted?
Answer: about 400 kg CO2
How much CO2 is emitted if 1 toe (tonne of oil
equivalent) is totally combusted?
(1 toe = 7.33 barrels of oil)
Answer: about 2900 kg CO2
In 2017, CO2 emissions were 36.2 Gigatonnes.
How many Mtoe does this correspond to?
Answer: about 12483 Mtoe
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Hydraulic fracturing (Fracking) for obtaining shale gas
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Chevron CRUSH process for obtaining shale oil
Chevron's technology for the
Recovery and
Upgrading of Oil from
SHale
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3. Carbon-negative oil
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Can we produce carbon-negative oil?
Enhanced-oil recovery (EOR) -
CO2 aids in oil extraction
1. Primary recovery of oil
2. Secondary recovery of oil
3. Enhanced-oil (EOR) recovery of oil
CO2 - EOR
Adapted from: https://www.iea.org/newsroom/news/2019/april/can-co2-eor-really-provide-carbon-negative-oil.html
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Can we produce carbon-negative oil?
CO2 from coal combustion is used for
CO2 - EOR
Carbon Capture and Utilization (CCU)
Adapted from: https://www.iea.org/newsroom/news/2019/april/can-co2-eor-really-provide-carbon-negative-oil.html
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Can we produce carbon-negative oil?
CO2 from bioenergy is used for
CO2 - EOR
Carbon Capture and Utilization (CCU)
Adapted from: https://www.iea.org/newsroom/news/2019/april/can-co2-eor-really-provide-carbon-negative-oil.html
Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!
4. Supercritical CO2
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Part I: Multidisciplinary instruction
1. Chemical Vocabulary and Essentials2. Systems, Devices and Processes3. Chemical Information and Know-How4. Historical Background and Applications
Part II: Specialized discipline instruction
5. Underlying Thermodynamics and Practical Expressions6. Equations of State and Formulations for Mixtures7. Phase Equilibria and Mass Transfer8. Heat transfer and Finite Difference Methods9. Chemical Equilibria and Reaction Kinetics10. Conclusions and Suggestions for future study
Table of Contents
* Print* Print/eBook* Print/Kindle
http://store.elsevier.com/product.jsp?isbn=9780444522153&pagename=search
Introduction To Supercritical Fluids
A Spreadsheet-based Approach
Richard Smith, Hiroshi Inomata, Cor Peters
Elsevier, 2013
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P
T
solid
gas
liquid
homogeneous
increasing
kinetic energy
increasing
attractive forces
Critical Point
increasing
diffusion
increasing
cohesion
Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!Pressure-Temperature Diagram
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P
T
Solid
Vapor
Liquid
Critical
Point
Pccritical
pressure
Tccritical
temperature
Pttriple point
pressure
Tttriple point
temperature
Psat
vapor pressure
TTemperature
Supercriticalregion
31.1 oC
7.3 MPa
Path withno abruptliquid-vaporphase change
Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!Pressure-Temperature Diagram
Carbon Dioxide (CO2)
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Supercritical CO2 circulating in a cell. An external
temperature gradient causes the supercritical phase
to circulate without mechanical devices.
Sample (blank)
holder
Supercritical
phase (with liquid)
Critical opalescence
(light scattering)back light
S. Yoshikawa, R.L. Smith Jr, H. Inomata, Y. Matsumura, K. Arai, Performance of a Natural Convection
Circulation System for Supercritical Fluids, Journal of Supercritical Fluids, 36 (2005) 70-80.
Group Question – energy of a device
A salesperson claims that an "energy multiplying" device has
just been invented that can continuously multiply energy without
the need for batteries, solar, wave or wind energy. The device
is shown below:
Choose one of the answers below:
(1) Impossible. State why.
(2) Possible. State why.
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Answer: always consider the environment
Transcritical CO2
Heat pumpAnswer: Possible! The system
uses the energy of the environment to
achieve efficient conversion of
electrical
work to thermal energy. 28
自然冷媒ヒートポンプ給湯機
EcoCute was marketed in Japan in May 2001. As of 2009, 2 million units have been sold by more than 26 manufacturers.
To produce 90 oC hot water, an EcoCute consumes 66% less energy than an electric water heater, and costs 80% less than heating water via city gas in Japan. The EcoCute results in more than 50% reductions in CO2 emissions
100 oC 10 MPa
自然冷媒ヒートポンプ給湯機
2014 More than 4 million units installed (Japan)400,000 to 500,000 units installed/year
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1
2
Evaporator
3
4
2
3
41
Heat
Exchanger
ValveCompressor
Liquid
Vapor
W
QC
QH
Environment (20 oC)
Target (cold water to hot water)
fluid compression
(heating)
fluid expansion(cooling)
Electricity
EcoCute Hot Water Heaterwith CO2 as the working fluid
warm CO2
hot CO2
cold CO2
vapor
30
-20
30
80
130
180
-2.0 -1.5 -1.0 -0.5
S [kJ/kg K]
T [
o C]
.
'
Evaporator
Condenser
CompressorExpansion
Valve
1
2
3
4
5 6
W21
Q14
Q32 21
22
23
J K L
Electrical Energy Requirements
W21 3.7 kW
C.O.P. 3.7C.O.P. > 4
tube side
shell side
CO2
q
T2
T3
H2O
Tout
Tin
tube side
shell side
CO2
q
T2
T3
H2O
Tout
Tin
1
23
4
1
2
3
4 4
3 2
2 1
ˆ ˆ
. . .ˆ ˆ
H HC O P
H H
Energy systems-transcritical heating cycles
Transcritical cycles avoid energy-inefficient boiling or condensation31
100Fuel
60 Loss
40 Netelectricity
Powerplant
100
Combustion
20 Loss
80Furnace
Fuel
Heat pump(COP=4)
160
Environment120
ElectricalResistance
Heating(COP=1)
40100Fuel
60 Loss
40 Netelectricity
Powerplant
Electrical resistance
Heat pump
Net heat
Comparison of methods to make hot water
MostEfficient
LeastEfficient
HighestRisk toHumanHealth
32
Access to the programs
http://booksite.elsevier.com/9780444522153/
Excel files3D Grapher files
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Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!
5. Green Chemical Processes
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Supercritical Fluid TechnologySystem Development Division
SMITH
LAB.!Green Chemical Processes
Environmental Impact
Risk = Hazard x Exposure
Martyn Poliakoff, Science 297, 807 (2002)
Traditional:
Green:
Minimize Exposure
Minimize Hazard
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Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!
R.A. Sheldon, Chem & Ind,1997,12; 1992,903
Metric: E-Factor
Low waste per
kg product
High waste per
kg product2 AUGUST 2002 VOL 297 SCIENCE www.sciencemag.org
A large E-factor means much waste is generated
for each kilogram of product
(Waste generated [kg])
(Product produced [kg])E-Factor =
Environmental - Factor
Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!
Solvent substitution methodology
- versatile
- safe
- economical
- widely applicable
Safe Solvent Mixturesinstead of
Hazardous Solventshttp://pubs.acs.org/doi/abs/10.1021/acs.oprd.6b00401
Free – Try the Excel!
OpenAccess!
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Selected Publications on Properties, 2015-2017
Tohoku University/Smith Laboratory + Collaborators
A. Duereh, Y. Sato, R.L. Smith, H. Inomata, Methodology for replacing dipolar aprotic solvents used in API processing with
safe hydrogen-bond donor and acceptor solvent-pair mixtures, Organic Process Research and Development 21(2017)114-124.
Safe Mixed-solvents replace hazardous solvents
API: active pharmaceutical ingredient
HBA: hydrogen bond acceptor
HBD: hydrogen bond donor
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Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!
Catalytic ionic liquids
- efficient
- safe and noncorrosive
- economical
- easily recyclable
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Selected Publications on Biomass, 2015-2017
Tohoku University/Smith Laboratory + Collaborators
H. Guo, A. Duereh, Y. Hiraga, T.M. Aida, X. Qi, R.L. Smith, Perfect recycle and mechanistic role of hydrogen sulfate ionic
liquids as additive in ethanol for efficient conversion of carbohydrates into 5-ethoxymethylfurfural, Chemical Engineering
Journal 323 (2017) 287-294.
Perfect recycle of homogeneous catalyst
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Supercritical Fluid TechnologySystem Development Division
SMITH LAB.!
Hydrogen-less methods
- efficient
- safe
- economical catalysts
- low-energy
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H. Guo, Y. Hiraga, X. Qi, R. L. Smith, Hydrogen Gas-Free Processes for Single-Step Preparation of Transition-Metal Bifunctional
Catalysts and One-Pot g-Valerolactone Synthesis in Supercritical CO2-Ionic Liquid Systems, The Journal of Supercritical Fluids,
(2018), just accepted.
Total synthesis of g-valerolactone without H2 gas
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On Sale Now!http://www.springer.com/us/book/9784431553083
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Supercritical Fluid TechnologySystem Development Division
SMITH
LAB.!6. Concluding remarks
* Carbon dioxide (CO2) can be used to develop
green chemical processes and new low energy
technologies
* Replacement of hazardous solvents with safe
solvent mixtures will lead to new technological
developments
* Chemical processes that use CO2 are essential for
future sustainable development 45
Supercritical Fluid TechnologySystem Development Division
SMITH
LAB.!More Information?
Homepage:
http://www.che.tohoku.ac.jp/~smith/index.html
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