microwave cracking of ethane for ethylene production
TRANSCRIPT
Microwave Cracking of Ethane
for Ethylene Production
Morgana Fall, Frank Cabe, Holly Shulman
Ceralink Inc.
Troy, New York
Eric Wagner, Gary Eagleson, Ravi Lal
Technip
Claremont, California
Presented at the 24th Annual Ethylene Producers Conference
April 3rd, 2012
Houston, TX
Outline
Background
Experimental Conditions
Results and Discussion
Summary
Acknowledgments
Ceralink Overview Troy, New York
Engineering Laboratories Advanced Materials Laboratory
Materials Testing Services
Microwave Technology Center (MTC)
Materials Engineering Services
Process Development & Scale-up
Specialized Equipment Building
Materials Analysis
Manufacturing Consulting
Technology Commercialization
Commercial and Government Projects
Technip Participated in the Lab Work
& Performed the SPYRO Modeling
Microwave Process
Ethane + Ar travel through 10mm inner diam quartz tube
Pass through hot zone: 6.4 mm thick surfa-guide
Microwave energy heats thin carbon film
hot enough to crack ethane (750-1150 °C range)
Control temperature through power application
Static
Mixer Mass Flow
Controllers
Ar
C2H6
Quartz
Tube
Gas
Chromatograph
Injection
Port
Exhaust Microwave equipment
Thermal Cracking of Ethane
6.3mm –tall hot zone
• Orange glow within surfa-guide
• Localized hot zone
• Carbon deposited inside quartz tube
• Microwave heats carbon
Hot zone
Experimental Conditions
Ethane Feed Rate
25 - 100 SCCM
Argon Feed Rate
10 - 100 SCCM
Pressure
Function of Feed Rate: 15 – 55 Torr
Higher Pressure Operation Possible in Principle
Temperature
Estimated to be in the range 1000 – 1100 °C
Measured Yields
TCD Gas Chromatograph
Detected Components:
H2, CH4, C2H2, C2H4, C2H6
Low Ethane Conversions
H/C of Measured Effluent 3.0 – 3.1
Limited Byproduct Formation (Feed H/C = 3.0)
High Ethane Conversions
H/C of Measured Effluent: 3.2 – 3.3
Expect Mostly Formation of C3H6 (from SPYRO)
Experimental Data
2.9
3
3.1
3.2
3.3
3.4
3.5
3.6
0 20 40 60 80 100
Me
asu
red
H/C
in E
fflu
en
t
Ethane Conversion
Gas Chromatography Measured H/C of Effluent
SPYRO ® Yield Simulations
Normally used for Industrial Operations
ISO Extension Allows Laboratory Simulations
No Reactor Geometry Specified
Inputs
Flow and Composition of Ethane and Argon
Outlet Pressure as Measured: 15 – 55 torr
Residence Time (Vacuum) ~ 0.001 Seconds
Isothermal Temperature
Varied to Match Measured Ethane Conversion
Results and Discussion
0
10
20
30
40
50
60
70
80
90
100
800 850 900 950 1000 1050 1100 1150 1200
Eth
ane
Co
nve
rsio
n
Temperature (oC)
SPYRO® Predicted Ethane Conversion at 42 Torr and 0.001 Seconds Residence Time
SPYRO® Simulations
0
10
20
30
40
50
60
70
0 20 40 60 80 100
Yie
ld (
wt%
)
Ethane Conversion
SPYRO® Predicted Ethylene Yield at 42 Torr and 0.001 Seconds Residence Time
YC2H4
SPYRO® Simulations
0
5
10
15
20
25
0 20 40 60 80 100
Yie
ld (
wt%
)
Ethane Conversion
SPYRO® Predicted Yields at 42 Torr and 0.001 Seconds Residence Time
YH2
YCH4
YC2H2
SPYRO Yields – Normalize SPYRO SPYRO Lab
Component Full Norm C2 Data H2 3.6 3.8 5.6
CH4 6.6 6.9 4.5 C2H2 1.5 1.6 1.9 C2H4 47.5 49.8 50.0 C2H6 36.3 38.0 38.0
Subtotal C2- 95.4 100.0 100.0
MAPD 0.2 - - C3H6 3.5 - - C3H8 0.1 - - C4's 0.7 - - C5+ 0.1 - -
Subtotal C3+ 4.6 0.0 0.0
Total 100.0 100.0 100.0
Experimental Results
0
1
2
3
4
5
6
7
8
9
0 20 40 60 80 100
Hyd
roge
n Y
ield
(w
t%)
Ethane Conversion
Comparison of SPYRO® Predicted and Measured Hydrogen (H2) Yield
SPYRO
LAB H2
Experimental Results
0
5
10
15
20
25
0 20 40 60 80 100
Met
han
e Y
ield
(w
t%)
Ethane Conversion
Comparison of SPYRO® Predicted and Measured Methane (CH4) Yield
SPYRO
LAB CH4
Experimental Results
0
2
4
6
8
10
12
14
16
18
0 20 40 60 80 100
Ace
tyle
ne
Yie
ld (
wt%
)
Ethane Conversion
Comparison of SPYRO® Predicted and Measured Acetylene (C2H2) Yield
SPYRO
LAB C2H2
Experimental Results
0
10
20
30
40
50
60
70
80
0 20 40 60 80 100
Eth
yle
ne
Yie
ld (
wt%
)
Ethane Conversion
Comparison of SPYRO® Predicted and Measured Ethylene (C2H4) Yield
SPYRO
LAB C2H4
Discussion
Data in Good Agreement with SPYRO®
Use SPYRO to Predict Industrial Performance
Microwave Energy Input
Microwaves Supply Heat Only
Neither Helps nor Hinders Pyrolysis
Apply Microwaves to Conventional Conditions
Pressure ~ 2 bar abs
Coil Outlet Temperature (COT) ~ 850 °C
Expect Yields to be Similar to Conventional Cracking
Industrial Design
Conventional Process
Burn Fuel to Create Temperature Driving Force
If COT ~ 850 °C, Tbridgewall ~ 1180 °C
Excess Energy Recovered From Fluegas
Feed Preheating
Byproduct Steam Production
Microwave Process
Burn Fuel to Create Electricity to Make Microwaves
No Combustion of Fuel (Locally)
No Temperature Driving Force Required
Only Supply Heat of Reaction
Example: 100 MWth Reactor Duty
Conventional Process - Combustion
Burn Fuel ~ 240 MWth LHV Basis in Furnace
Steam ~ 61 MWth Transferred to Export Steam
Microwave Conversion from Electricity
~ 71% Efficiency In Magnetron
~ 45% Efficiency At Power Plant LHV Basis
Fuel Burned at Power Plant ~ 313 MWth LHV
Limited Steam Produced at Reactor
Summary
Microwave Cracking Demonstrated
Cracking of ethane CH4, C2H2, C2H4,
Similar conversion selectivity compared to SPYRO
Short residence time (~0.001 sec)
The Microwave Cracking Process
Possibility of selectively heating reaction volume
May allow novel reactor designs
Future Work
Continued Testing Will be Required:
Experiments at Elevated Pressure
Steam as Dilution Gas Instead of Argon
GC Analysis to Include C3+
Apply Concept to Industrial Design Improve Heat Balance
Microwave Produces Little Byproduct Steam
Smaller “Furnace” footprint
Reactor Design – Different Constraints
Higher Throughput Per Reactor Tube
Reactor Tube Material Considerations
Acknowledgments
This material is based upon work supported by the
Department of Energy under Award Number
DE-EE0003469.
Thanks to Dr. James Carnahan of Edison Laboratories
Special thanks to Eric Wagner and Gary Eagleson of
Technip USA, Inc. in Claremont, California