The 35th International Technical Conference on Clean Coal & Fuel Systems  

Clearwater, Florida, USA

June 6 to 10, 2010

TECHNICAL TOPIC:

INDUSTRIAL COAL USE: CHEMICAL LOOPING

CHAIRED BY: Dr Marie Anheden

EFFECT OF PRESSURE ON COPPER/COPPER-OXIDE SYSTEM FUNCTIONING AS AN OXYGEN

CARRIER IN CHEMICAL LOOPING COMBUSTION

Richard Baraki, Graduate Student, Department of Chemical Engineering, The University of Utah
50 S Central Campus Drive, MEB, Rm 3290, Salt Lake City, Utah, USA 84112, richard.baraki@utah.edu

Kevin R. Tucker, Undergraduate Student, Department of Chemistry, The University of Utah,

315 S 1400 E Salt Lake City, Utah, USA, 84112, k.tucker@utah.edu

Gabor Konya, Postdoctoral Research Associate, Department of Chemistry, The University of Utah,
315 S 1400 E Salt Lake City, Utah, USA, 84112, konya@chem.utah.edu

Terry A. Ring, Professor, Department of Chemical Engineering, The University of Utah

50 S Central Campus Drive, MEB, Rm 3290, Salt Lake City, Utah, USA 84112, t.ring@utah.edu

Edward M. Eyring,, Professor, Department of Chemistry, The University of Utah

315 S 1400 E Salt Lake City, Utah, USA, 84112, eyring@chem.utah.edu

Adel F. Sarofim, Presidential Professor, Department of Chemical Engineering, The University of Utah
50 S Central Campus Drive, MEB, Rm 3290, Salt Lake City, Utah, USA 84112, sarofim@reaction-eng.com

Chemical Looping Combustion (CLC) is a promising technology that will utilize more efficient

harvesting of energy along with decreasing emissions into the atmosphere. CLC is flameless and

the fuel has no direct contact with the air. Flameless combustion allows less emittance of

pollutants into the atmosphere. The only emissions are H2O and CO2. CLC uses two basic

reactions in this process. An oxidation step, and a reduction step. The oxygen may come from

air, or a purified oxygen supply. The oxygen is combined in the oxidation step with a metal to

form a metal oxide. Typically the metal is either Ni or Cu, however there are a numbe of other

metals that are being explored in research. Once the metal oxide is formed it is transferred to the

fuel reactor where a hydrocarbon based fuel consumes the oxygen from the metal oxide and

returns it back to a metallic state where the metal can be recycled and oxidized again. In the
transitions between reactors the carrier does not necessarily need to fully oxidize or reduce

before making the transition to the other reactor. This task can be analyzed from a cost benefit

approach.

Figure 1, (Chemical Looping Combustion)

Copper is a very promising metal. The advantages of copper lie in it’s two oxidation states. The

first oxide that forms is copper(I) oxide, Cu2O, the next oxide formed is copper(II) oxide, CuO.

Once the CuO is formed, the exposure to a non-oxidizing environment between our observed

experimental range 850°C and 985°C, the copper oxide will spontaneously decompose into a

new copper oxide, Cu2O. This trait makes copper a preferred oxygen carrier, because faster

switching times can be implemented. With this information follow up research was conducted

using various pressure conditions.

Based on the …………. Increasing the pressure during the oxidation step should increase the

rate of oxidation by the square root of the pressure in atmospheres For example if the reaction

was conducted under the pressure condition 25 atm the rate of oxidation, i.e. reaction rate should

increase by 5 times. The plot shown below is a plot of a copper sample weighing approx 200mg

and oxidized at different pressure conditions.

Experemental Procedure

To conduct the experiements a High pressure Thermogravimetric analysis device is used (HP-

TGA). Once the sample is loaded the chamber on the device is closed and purged of air for

several minutes using compressed nitrogen. Once the nitrogen has purged the chamber of the

HP-TGA the temperature ramp from approximately 21 C to 950 C is initiated. The ramp rate is

conducted at 25C/min. During the temperature ramp, if the given experiment calls for a pressure

increase the pressure would be built in the chamber using nitrogen. Once temperature reaches

950C and pressure is constant at desired pressure, a gas switch takes place going from nitrogen

to air in the reaction chamber. The oxidation starts here once the air diffuses to the sample

surface.

Operating conditions of experiments

Temperature=constant= 950C
Reaction gas= constant= ½ liter per min
Sample size= approximately 200mg
Pressure= varies between 0psig-367.5psig (atmospheric pressure condition-25atm)
The plot is a mass % verse time. Using mass % allows adjustment to the minute change between
the sample’s mass from one experiemtn to the next. The stoichiometric gain of Cu  CuO is
125.178%.
 A t m o s p h e ric
25 a tm o s p h e r e s
16 a tm o s p h e r e s
9 a tm o s p h e re s

120
M a s s (% )

100

0 2 00 0 40 00 6000

T im e (s e c )

After looking at the plot it is very evident that pressure is hindering the reaction. It is slowing the

gas switching time, time taken for air to hit the sample, and the reaction rate as well. The plots

below represent a compilation of expanded versions of the same plot above, that display

switching time.

A tm ospheric Atm ospheric

105 25 atm ospheres 105 25 atm ospheres
16 atm ospheres 16 atm ospheres
9 atm ospheres 9 atm ospheres
104 104

103 103
M ass (% )
M ass (% )

102 102

101 101

100 100

99 99
0 200 400 600 800 1000 0 200 400 600 800 1000

Tim e (sec) Tim e (sec)

 Atm ospheric A tm ospheric
105 25 atm ospheres 105 25 atm ospheres
16 atm ospheres 16 atm ospheres
9 atm ospheres 9 atm ospheres
104 104

103 103
M ass (% )

M ass (% )
102 102

101 101

100 100

99 99
0 200 400 600 800 1000 0 200 400 600 800 1000
Tim e (sec) T im e (sec)

With these plots that show switching times individually, we can easily see that the design of the HP-TGA

is not ideal. The time taken for the sample to be exposed to the air is almost a linear relationship. As the

pressure goes up the time it takes to switch gases goes up, as the plot shows below.

900

800

700

600

500

400

300

200

100

0
0 5 10 15 20 25 30

The plot arises many questions regarding the response function of the HP-TGA.
 25 atm
16 atm
8 9 atm
atm ospheric condition

O 2 C oncentration (% ) (% )
6

0
0 2000 4000 6000 8000 10000 12000
Tim e (seconds)

This step from pure copper to the full CuO state is a difficult transition that requires a lot of

work to explain. The step from Cu  Cu(I) is nearly impossible to explain unless your reaction

is performed with no more than a few Cu atoms and the exact corresponding stoichiometric

amount of oxygen. So consequently the kinetics and nature of the oxidation is analyzed from

Cu  Cu(II). This reaction as expected what is currently trying to be

Overall oxidation 2 Cu(s) + O2(g)↔ 2 CuO(s)

Cu → Cu(I) 4Cu(s) + O2(g)↔ 2Cu2O(s)

Cu(I) → Cu(II) 2Cu2O(s) + O2(g)↔ 4 CuO(s)