COGENERATION POSIBILITIES

WITH THE ARGENTINEAN

MODULAR NUCLEAR POWER

REACTOR CAREM

“Technical Meeting to Examine the Techno-

Economics Opportunities for Non-Electric

Applications of Small and Medium Sized or

Modular Reactors”

“May, 29th - 31st 2017”

Vienna - Austria

G.G. Fouga, D. Nassini, H.E. Nassini, A.E. Bohé

fouga@cab.cnea.gov.ar

Non-Electric Applications of Small and Medium

Sized or Modular Reactors.

The wide “spectrum” of current reactors can cover all applications

I. Khamis. Non-Electric Applications of Nuclear Energy.

02/20

CAREM Nuclear Reactor

CAREM Nuclear Reactor

Under Construction

(Videos) CAREM Nuclear Reactor

Characteristic (Videos)

IAEA SMR Booklet 2014

03/20

Gasification involves the possibility of co-generation of electricity,

chemicals and fuels in the same energy facility.

Gasification

Gasification refers to a thermo-chemical process that converts solid

carbonaceous fuels into either fuel gas (usually containing CH4 and

some N2) or syngas (containing mainly H2 and CO).

C(s) + H2O(g) → H2(g) + CO(g)

C(s) + CO2(g) → 2CO(g)

C(s) + 2H2(g) → CH4(g)

H = 159.7 KJ/mol

H = 118.9 KJ/mol

H = -87.4 KJ/mol

2 2 2(2 ) n nnCO n H C H nH O

2 2 1 2(2 ) ( 1)n nnCO n H C H OH n H O

2 2 2 2(2 1) n nnCO n H C H nH O

Alkenes

Alcohols

Paraffins

04/20

Pyrolysis

Reactor

Tar +

Pyrolysis gas

Solid Fuel

Gasifier

Reactor

Char

Gasifying agent

Steam; CO2

Syngas

Gasification

Gasification is a

two-step process

Step 1: Pyrolysis Step 2: Gasification

Volatile

components of solid

fuels are rapidly

released

At T

between

300 and

500 ºC

Coal

Asphaltites

petroleum coke

Biomass, etc.

Composed of

fixed carbon

and mineral

matter

Rate-

limiting

step

05/20

The two-stage

gasification concept

makes full use of the

high-value aromatic

compounds contained

in the solid fuels.

In this way one can

co-produce tar and

fuel gas or syngas,

(poly-generation).

Gasification

Gasification also involves the possibility of using a wide range of “feed

stocks” including low-cost fuels like: petroleum coke, biomass and also

municipal waste.

06/20

Sub-bituminous coal: Rio Turbio

Ortho-Asphaltite: F4

Meta-Asphaltite: EM

Argentinean

Natural Solid

Fuels

Evaluated

Asphaltites are complex

mixtures containing

compounds ranging from non-

polar aliphatic and naphthenic

hydrocarbons to highly polar

aromatic molecules.

Natural Solid Fuels Deposits in Argentina

Coal Asphaltites Peat

H2O Volatile

Material

Fixed

Carbon Ash +

Char

Natural

Solid

Fuels

Pirólisis

+ +

Determinati

on

HT in air.

(105 °C)

HT in Ar.

(950 °C)

% of Char –

% of Ash

HT in air.

(950 °C)

ASTM

standard

ASTM

D3173 – 03

ASTM

D3175 – 07

ASTM

D3174 – 04

07/20

Determination Coal

(Río Turbio)

Asphaltites

EM (Meta) F4 (Ortho)

Moisture (wt%) 3.5 11.47 0.26

Volatile Matter (wt%) 36.4 26.18 58.97

Fixed carbon (wt%) 51.2 68.67 40.57

Ash (wt%) 12.3 5.13 0.46

Density (g·cm3) 1.107 0.679 0.412

CT 59.8 64.3 78.0

NT 2.78 3.27 2.92

ST 0.86 2.36 4.5

Calorific Power kJ/kg 25104 24895 39472

Experimental Program

Objective: characterize the behaviour of Argentine solid

carbonaceous fuels under typical pyrolysis and gasification

conditions, to identify the most suitable operational

parameters in nuclear-assisted two-stage gasifiers.

Scope: Theoretical and experimental studies designed to get

the necessary information about the fundamental

mechanisms and kinetic parameters of pyrolysis and

gasification reactions, on laboratory scale.

08/20

Experimental Setup for Pyrolysis 09/20

Effects of pyrolysis conditions as temperature,

heating rate and holding time on:

Fixed bed reactor

Microstructure and gasification reactivity of chars.

Yield and composition of the evolved tar and

pyrolysis gas.

Drop tube reactor

Fixed bed reactor after pyrolysis

Experimental Setup for Pyrolysis

“Kinetics of the Gasification of a Rio Turbio Coal Under Different

Pyrolysis Temperatures”. G. De Micco, A. Nasjleti, A.E. Bohé. Fuel 95

(2012) 537–543.

“Effects of pyrolysis conditions on the structure of chars prepared

from an Argentine asphaltite”. D. Nassini, G. G. Fouga, H. E. Nassini,

A. E. Bohé. Fuel 182 (2016) 623–631

Pyrolysis heat treatments at temperatures above 500-600 ºC produce a significant reordering

of the carbonaceous char matrix, increasing the crystalline carbon fraction and consequently

decreasing their reactivity.

Initial Asphaltite sample Asphaltite char after pyrolysis

at 950ºC during 60 minutes

0 200 400 600 800 1000-60

-50

-40

-30

-20

-10

0

F4

Rio Turbio

EM

LHR: 4 °C/min

Mass: 10 mg

Temperature (°C)

M

/Mi

(%)

10/20

Experimental Setup for Gasification with CO2 11/20

THERMOGRAVIMETRIC ANALYSIS SYSTEM: This equipment is applied to

follow the kinetic of gasification reaction by measuring the temporal evolution of

relative mass changes of the char.

The gasification rate, R, is evaluated as:

(t) is the reaction degree at time t,

m0 is the initial char mass,

m(t) is the char mass at time t,

mash is residual mass at the end of the gasification reaction.

𝛼 𝑡 =𝑚0 −𝑚 𝑡

𝑚0 −𝑚𝑎𝑠ℎ

𝑅 =𝑑𝛼

𝑑𝑡= −

1

𝑚0 −𝑚𝑎𝑠ℎ∙𝑑𝑚

𝑑𝑡

0 600 1200 1800 2400 3000 3600 4200 4800

0.0

0.2

0.4

0.6

0.8

1.0

20 (l·h-1

)

15 (l·h-1

)

10 (l·h-1

)

5 (l·h-1

)

T: 950 °C

PCO2: 80 kPa

Mi: 10 mg

Tiempo (seg)

0 900 1800 2700 3600 4500 5400

0.0

0.2

0.4

0.6

0.8

1.0

1 mg

2,5 mg

5 mg

10 mg

20 mg

40 mg

T: 950 °C

PCO2: 80 kPa

Caudal: 5 ls/h

Alf

a

Tiempo (seg)

Efecto de la Masa

0 1800 3600 5400 7200

0.0

0.2

0.4

0.6

0.8

1.0

80 kPa

70 kPa

60 kPa

50 kPa

40 kPa

20 kPa

10 kPa

T: 950 °C

Caudal: 5 ls/h

Masa: 2,5 mg

Alf

a

Tiempo (seg)

CO2 Flow Mass PCO2

2.4 2.8 3.2 3.6 4.0 4.4 4.8-8.0

-7.6

-7.2

-6.8

-6.4

-6.0

-5.6

-5.2

= 0,8

= 0,7

= 0,6

= 0,5

= 0,4

= 0,3

7654321

ln (PCO2(g))

-l

n t(

)

8.0x10-4

8.5x10-4

9.0x10-4

9.5x10-4

4

5

6

7

8

9

10775 °C

825 °C

800 °C

850 °C

950 °C

925 °C

875 °C900 °C

Ln

t

1/T

0 3600 7200 10800 14400 18000 21600

0.0

0.2

0.4

0.6

0.8

1.0

950 °C

925 °C

900 °C

875 °C

850 °C

825 °C

800 °C

775 °C

PCO2: 80 kPa

Caudal: 10 ls/h

Masa: 2,5 mg

Alf

a

Tiempo (seg)

Efecto de la Temperatura

Temperature Det. Ea:

185 kj/mol Order: 0,5

12/20 EM Asphaltite Gasification

2

3

2

15 0.5185

1 1.1x10 exp CO

d kJ molRate P

dt R T

“Kinetic Study of Argentinean Asphaltite Gasification Using Carbon

Dioxide as Gasifying Agent”. G.G. Fouga, G. De Micco, and A.E. Bohé.

Fuel. Vol. 90, (2011), pp 674 - 680. ISSN: 0016-2361.

Río Turbio Coal Gasification 13/20

Mass PCO2

CO2 Flow

Temperature effect Ea: 190 kj/mol Order: 0,85

“Coal Gasification Studies Applied to H2 Production”. G. De Micco,

G.G. Fouga and A.E. Bohé. International Journal of Hydrogen Energy.

Vol. 35, Issue 11, 2010, pp 6012-6018.

14/20

0 60 120 180 240 300 360 420 480 540 600

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0T = 1400 ºC

Mass = 1 mg

pCO2 = 1 atm

CO2

Flow

9 L/h

8 L/h

6 L/h

4 L/h

2 L/h

Time (seg)CO2 Flow 0 120 240 360 480 600 720

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0 Experimental coditions:

T = 1400 ºC

CO2(g) Flow = 6 L/h

pCO2= 1 atm

Char Mass

1 mg

2 mg

4 mg

10 mg

15 mg

20 mg

Time (s)

Mass

0 1800 3600 5400 7200 9000 10800 12600 14400

0.0

0.2

0.4

0.6

0.8

1.0

1 atm

0,82 atm

0,90 atm

0,64 atm

0,27 atm

T= 1300 °C

Q CO2= 6 Lh

-1

mo= 2 mg

0,18 atm

0,36 atm

0,45 atm

0,55 atm

0,73 atm

Time (s)

PCO2

-2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5-9.5

-9.0

-8.5

-8.0

-7.5

-7.0

-6.5

-6.0

-5.5

-5.0

-4.5

0,091 atm

0,364 atm

0,455 atm

0,637 atm

0,819 atm

0,546 atm

0,728 atm

0,91 atm

0,273 atm

0,182 atm

ln(pCO2)

-ln

(t)

= 0,2

= 0,3

= 0,4

= 0,5

= 0,6

= 0,7= 0,8

Order: 1

0 1800 3600 5400 7200 9000

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.01150 °C 1100 °C

1200 °C

1250 °C

1300 °C

1350 °C

1400 °C

Time (s)

0.00060 0.00064 0.00068 0.00072

5.0

5.5

6.0

6.5

7.0

7.5

8.0ln

( t

)

T-1(K

-1)

Temperature

effect Ea: 183 kj/mol

F4 Asphaltite Gasification

“Gasification for Practical Applications”. ISBN 980-953-307-245-1.

Chapter Number 2. “Gasification Studies on Argentine Solid Fuels”.

Fouga, G. G., De Micco, G., Nassini H. E. & Bohé A. E. Editorial InTech.

Experimental Setup for Gasification with Steam

The gasification with steam needs a more complex

experimental setup: it consist of a steam generator,

a gasification reactor and a water condenser;

coupled in series with a GC and a FTIR.

15/20

Analysis setup for gaseous components. 16/20

Gas Chromatograph CG/MS

Perkin Elmer. Model Clarus 600/680

TCD: H2; METANIZER-FID: CO, CO2

Infrared Spectrometer

Perkin Elmer, Model: Spectrum 400

Gas cell

nCO(t) is the number of CO(g) moles formed from the beginning until time t.

nCO(tf) is the number of total moles formed during the whole reaction. 𝛼 𝑡 =

𝑛𝐶𝑂 𝑡

𝑛𝐶𝑂 𝑡𝑓

Gasification

reaction kinetics

Peak

areas

Characterised

CO(g) concentration

In chromatograms

registered every 5 minutes

Steam vs CO2 Gasification

These results show that Argentinean solid carbonaceous fuels tested are

susceptible to be gasified since their reactivities are comparable with

those of low-rank coals used in large-scale gasifiers.

H2O GASIFICATION CO2 GASIFICATION

17/20

Reactivity Rank Rate (E) > Rate (RT) > Rate F4

Fluidized bed reactor for solid fuel gasification

Parameter FBR

Int 25,8 mm

Bed mass 40 g

Height of the bed 5 cm

Height of the bed (mfc) 8 cm

Rmf 30 l/min

∆Pfr No detected

18/20

Concluding Remarks 19/20

For this purpose, a theoretical and experimental program on laboratory

scale is underway with the objective of characterizing the behaviour of

selected feed materials under typical pyrolysis and gasification conditions.

Coal gasification assisted by nuclear energy is a promissory process to

utilize the residual heat from a nuclear reactor providing heat and steam for

the natural solid fuels pyrolysis and gasification reactions respectively

These studies allow to get relevant information about the reaction

mechanisms and kinetic parameters of the pyrolysis and the gasification

reactions, in order to be used in large-scale gasifier design.

The research program included the development of specially-designed

experimental setups for gasification using CO2 and steam as gasifying

agents.

Thank you for your attention!!!

20/20

http://www.barilocheturismo.gob.ar/es/home

Bariloche - Argentina