smith supercritical fluid technology system …smith/img/green_processes_2019-v2...group question...

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


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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


SMITH

LAB.!

1. World population and

CO2 emissions

4


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

5


SMITH LAB.!World Population in 2050

Source (2019):

www.un.org/develop

6


SMITH LAB.!

2. World oil supply and demand

8

10

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)

12

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

16

Hydraulic fracturing (Fracking) for obtaining shale gas

17

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

19

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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CO2 from coal combustion is used for

CO2 - EOR

Carbon Capture and Utilization (CCU)


21


CO2 from bioenergy is used for

CO2 - EOR

Carbon Capture and Utilization (CCU)



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

23

P

T

solid

gas

liquid

homogeneous

increasing

kinetic energy

increasing

attractive forces

Critical Point

increasing

diffusion

increasing

cohesion


SMITH LAB.!Pressure-Temperature Diagram

24

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


SMITH LAB.!Pressure-Temperature Diagram

Carbon Dioxide (CO2)

25

26

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.

27

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

33


SMITH LAB.!

5. Green Chemical Processes

34

35


SMITH

LAB.!Green Chemical Processes

Environmental Impact

Risk = Hazard x Exposure

Martyn Poliakoff, Science 297, 807 (2002)

Traditional:

Green:

Minimize Exposure

Minimize Hazard

36


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


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!

38

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

39


SMITH LAB.!

Catalytic ionic liquids

- efficient

- safe and noncorrosive

- economical

- easily recyclable

40

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

41


SMITH LAB.!

Hydrogen-less methods

- efficient

- safe

- economical catalysts

- low-energy

42

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

43

On Sale Now!http://www.springer.com/us/book/9784431553083

44


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


SMITH

LAB.!More Information?

Homepage:

http://www.che.tohoku.ac.jp/~smith/index.html

46

smith supercritical fluid technology system …smith/img/green_processes_2019-v2...group question...

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