Boron Nanoparticles in Fuels and Combustion Flow-Tube Calorimetry

Objectives
Develop a novel calorimetric method to measure the relative heats of combustion for hydrocarbon based fuels Determine whether boron nanoparticle suspensions can increase the overall heat liberated by these modified fuels

Why Boron ?
Boron has a uniquely large volumetric energy density Boron is cheap Boron is easily converted from micron sized particles to nanoparticles using ball milling. The milling process is can be scaled up to larger mills

Energy Density of Boron

B(s) +
3/ 4 O2(g)

1/2 B2O3(s)

H = -636.75 kJ/mol H = -4163.2 kJ/mol

2C6H14(l) + 19O2(g) 14H2O (g) + 12CO2(g)

160 140 120 100 80 60 40 20 0

volumetric energy density, kJ/mL specific energy density, kJ/g

Gasoline

Jet Fuel

EtOH

Mg

http://www.codata.org/resources/databases/key1.html

H2

Al

Li

Milling
In a N2 glovebox 2g of micron sized boron particles 160g of 1/8 TC balls 1ml of oleic acid ~35 ml of hexanes TC milling Jar Milled for a total of 12 hours

Benchtop Shaker Mill

Boron

2mg/ml boron in hexanes

Loading
The loading of the boron suspensions is determined by hexane evaporation at ambient conditions
It is easily re-suspended in other hydrocarbons

63 mg/ml loading

2mg/ml loading

Turbulent Flame Measurements

Hexanes turbulent flame measurements
1400 1200 1000 Temp. Deg C 800 102109_hex_turb_01 600 400 200 0 102109_hex_turb_02 102109_hex_turb_03

Average Temp: 1145oC

0 10 20 time (s) 30 40 50

Turbulent Flame measurements

Kerosene Turbulent Flame Measurements
2000 1800 1600 1400 Temp Deg C 1200 1000 800 600 400 200 0 0 10 20 Time (s) 30 40 50 102109_kero_turb_01 102109_kero_turb_02 102109_kero_turb_03 102109_kero_turb_04 102109_kero_turb_05 102109_kero_turb_06

Viscosity of Kerosene @ 15oC: 2.1-2.2 Cp o Viscosity of Hexanes @ 25 C : .241 Cp

http://www.gates.com/brochure.cfm?brochure=2625&location_id=3046 Landolt-Brnstein - Group IV Physical Chemistry Numerical Data and Functional Relationships in Science and Technology

Why Flow-Tube Calorimetry?

Direct turbulent flame temperature measurements are not feasible.
S(Pt/Rd) thermocouple 0oC - 1450oC C(W/Rh) thermocouple 0oC - 2320oC (easily oxidized)

We want to know the turbulent flame output for application in jet engines

What is Flow-Tube Calorimetry

Flow-tube calorimetry transfers the heat generated by a turbulent flame to a known amount of water (~9740ml) using coiled tubing, while stirring the water for real-time temperature monitoring. Fuel is metered in at a constant flow rate (12.5ml/min) Oxygen is metered at a constant pressure behind the burner (8psi)

Delevan Spray Technologies

http://www.delavaninc.com/siphon.htm

Experimental setup

Experimental setup

Initial Data from Mark I Calorimeter

Hexanes vs. Ethanol
90 80 70 60 Temp Deg C 50 40 30 20 10 0
y = 0.0178x + 33.115 y = 0.0161x + 36.347

Ethanol T= 11.5oC o Hexanes T= 15.4 C 11.5/15.4= 0.747

EtOH water temp EtOH exhaust temp Hex water Temp Hex Exhaust Temp extrap Hex extrap Etoh Linear (extrap Hex) Linear (extrap Etoh)

Theoretical: HC(Ethanol) = 1366.8 KJ/mol HC(Hexanes)= 4163.2 KJ/mol Total fuel: 18.75 ml Experimental: Ethanol: 438.7 KJ Hexanes: 593.3 KJ 438.7/593.3= .739

200

400 Time (s)

600

800

Thats 1.0% from theoretical!!

Handbook of Chemistry and Physics 83rd Edition

Mark II Calorimeter
Pilot Flame replaced by a 120V 10,000V transformer as an ignition source, which is now controlled by LabView The igniter and nozzle were inserted into a barrel, fits tightly into the inlet The fuel valve was replaced with LabView controlled valve A spillway was added for ease of water transfer and accuracy Temperature is now monitored in LabView with an Omega Dpi32-C24 A valve was added to the O2 line so that the calorimeter may be purged

LabView Front panel

Data from Mark II Calorimeter

Hexanes Calorimetry at 3psi O2
34 y = -0.0009x + 31.213 32 y = -0.0015x + 32.8 y = -0.0016x + 32.86 30 y = -0.0013x + 32.861

temp deg C

28

T= 9.3oC
o T= 10.7 C

102709_hex_01 extrap_01

26

102709_hex_02 extrap_02

24

Std. dev= .047

T= 10.8oC
o T= 10.8 C

102709_hex_03 extrap_03 102709_hex_04 extrap_04

22

-50

20

50

100

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300

350

400

450

500

time (s)

Data from Mark II Calorimeter

Hexanes Calorimetry at 8psi O2
33 31 29 27 Temp deg C 25 23 21 19 17 15 y = -0.0014x + 31.172 y = -0.0013x + 31.91 y = -0.0014x + 31.808 y = -0.0013x + 31.446

T= 13.1oC Std. dev= .179 T= 13.5 C T= 13.2 C T= 13.5 C

o o o

102709_hex_8psi_01 extrap_01 102709_hex_8psi_02 extrap_02 102709_hex_8psi_03 extrap_03 102709_hex_8psi_04 extrap_04

-50

50

100

150

200 Time (s)

250

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450

Data from Mark II Calorimeter

Kerosene Calorimetry at 8psi O2
35 33 31 29 27 Temp deg C 25 23 21 19 17 15 y = -0.0017x + 32.711 y = -0.0011x + 32.485 y = -0.0014x + 32.556

T= 14.5oC Std. dev= .058 T= 14.4oC T= 14.4oC

102709_kero_8psi_01 extrap_01 102709_kero_8psi_03 extrap_03 102709_kero_8psi_04 extrap_04

-50

50

100

150

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Data from Mark II Calorimeter

Kerosene Calorimetry at 8psi O2
31 29

27

y = -0.0012x + 28.517 y = -0.0011x + 28.315

25 temp Deg C

y = -0.001x + 28.12

23

T= 10.3oC Std. dev= .152 T= 10.2oC

o T= 10.0 C

102709_etoh_8psi_01 extrap_01 102709_etoh_8psi_02 extrap_02 102709_etoh_8psi_03 extrap_03

21

19

17

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15

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Data from Mark II Calorimeter

Ratio of Hexanes to Ethanol is 3.65% from theoretical Ratio of Hexanes to Kerosene is 15.45% from theoretical

Data from Mark II Calorimeter

Boron/Oleic acid in Hexanes Planetary Mill Supernatents
33 31 29 27 Temp deg C 25 23 21 19 17 15 y = -0.0015x + 31.467 y = -0.0013x + 31.102

T= 13.1oC T= 12.9 C
o

102808_BOH_sup_plan_01 extrap_01 102809_BOH_sup_plan_02 extra_02

-50

50

100

150

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Data from Mark II Calorimeter

Boron/Oleic acid in Hexanes Planetary Mill 63 mg/ml
34 32 y = -0.0015x + 32.237 30

Temp deg C

28

26

T= 10.6oC

102808_BOH_sup_plan_01 extrap_01

24

22

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Conclusions
Combustion flow-tube calorimetry is useful in making relative measurements of turbulent hydrocarbon combustion flames Boron suspended in hydrocarbons is still being investigated, with respect to increasing the heat of combustion of turbulent flames.