CU-ICAR Hydrogen Infrastructure Final Report

TL;DR: In this paper, the authors proposed an innovation center to accelerate the transition to a hydrogen economy. And the specific objectives of the proposed project were to define the essential attributes of the innovation center; validate the concept with potential partners; and establish a pilot center and demonstrate its benefits via a series of small scale projects.

Abstract: The goal of this project was to establish an innovation center to accelerate the transition to a 'hydrogen economy' an infrastructure of vehicles, fuel resources, and maintenance capabilities based on hydrogen as the primary energy carrier The specific objectives of the proposed project were to: (a) define the essential attributes of the innovation center; (b) validate the concept with potential partners; (c) create an implementation plan; and (d) establish a pilot center and demonstrate its benefits via a series of small scale projects

Summary

1.1. The Need

• Automobiles and trucks, powered by internal combustion engines and fueled by abundant, low cost petroleum, have served as the foundation for the prosperity and growth of their geographically dispersed, yet highly interconnected nation for the past century.
• Recently, the negative impacts of this mode of transportation on their society have become more apparent.
• (1) In addition, increased demand from large developing countries, such as China and India, coupled with finite supplies of petroleum that are increasingly more difficult to recover, will place growing pressure on prices and availability, also known as These impacts include.
• The automotive and fuel industries must transition to a more sustainable fuel source that reduces GHG and pollutant emissions and that enhances their nation's economic and energy security.
• The goal of this project is to support and enhance this transition.

1.2. Project Objective

• The original project objective established in 2008 was to demonstrate a pilot innovation center that would support the Bush Administration's goal of accelerating the transition to a "hydrogen economy" consisting of hydrogen fueled vehicles and fueling infrastructure.
• With the change in Administrations and the move toward vehicle technologies with earlier commercialization opportunities, such as battery electric vehicles and plug-in hybrid electric vehicles, the objective of the project was adjusted to support this change in emphasis.
• The revised objective was to demonstrate key innovation processes for more rapidly and cost effectively transitioning to more sustainable technologies, including but not limited to hydrogen, in the automotive sector.

2. Defining the Innovation Center Attributes

• Initial efforts focused on collecting information on existing innovation centers and incubators to determine the key functions that they perform and key center characteristics.
• Figure 4 provides similar information for the 21 non-profit community based centers.
• In addition to identifying key functions performed by innovation centers, key center characteristics also were identified.
• Based on these data and a review of the literature, two process areas were identified that offered potentially high payoff for the auto and fuels industries and were not duplicative of capabilities already in widespread use within innovation centers.
• The objective of their project was to develop and demonstrate the potential of these two processes in accelerating the transition of the auto and fuels industries to more sustainable, environmentally responsible, and secure vehicles and fuels.

3.1.1. Background

• The innovation process that has served the auto industry well for over 100 years is evolving in response to persistent, external stresses, (2) including:  The impact of auto emissions on air quality and climate change; .
• ( 5) And a subsequent study (6) showed that small companies have recently become the majority of those considered "most innovative.".
• In a rapidly changing market with many competitors and imitators, rapid scale up is key to success.
• The electric powertrain vehicle, which is currently being promoted by governments around the globe as a solution to environmental and fuel security problems, is a good example of where industry-wide open innovation has payoff.

Figure 7 -Electric Vehicle Powertrain Business Model Convergence

• Within this convergence of business models can be found game-changing opportunities that would accelerate the pace of change.
• (10) For example, consumers could realize more value from their plug-in hybrid or all-electric vehicles if they had the opportunity to recharge at any place and time.
• That would extend the electric range of these vehicles independent of the pace of battery improvements.
• Further, the energy supplied to the recharging stations could be derived, at least in part, from distributed and renewable sources.
• And because the renewable energy could be stored on vehicles at the higher value of transportation fuel rather than the lower price of grid electricity, the cost of energy storage, a formidable barrier to renewable electricity, would not inhibit its use.

3.1.2. AutoVenture Forum™ Demonstration

• To better understand how open innovation could be applied to an entire industry, Clemson University and the American Society of Mechanical Engineers (ASME) undertook a proof-of-concept industry-wide, open-innovation network demonstration.
• The authors called this first step the AutoVenture Forum™ (AVF), and its purpose was to accelerate sustainable mobility innovation by linking the fresh ideas and perspectives of entrepreneurs with the technology base, systems integration, manufacturing, and market channels of the established auto industry.
• A network innovation process can bypass the limitations of the more vertically integrated innovation models to realize opportunities like these.
• History and experience suggest that five principles should guide operations: 1. Neutrality.
• Carma Systems, Inc. -develops and markets an integrated m2m telematics vehicle diagnostics monitoring, as well as environmental engine performance hardware and software, device  Celadon Applications -a software development company that focuses on developing software solutions for unmet telematics and infotainment niches for the hybrid and electric vehicle market .

3.1.3. Results and Conclusions

• The response of those participating in the demonstration AVF was overwhelmingly positive.
• Soon after the forum, the AVF team sent a brief e-mail survey to all the participants, simply to test immediate reactions.
• In addition, early responses from the entrepreneurs and comments from the industry participants affirm the value of the connections made.
• To be sure, the longer-term consequences for the automotive innovation cycle remain to be proven.
• But the preliminary and anecdotal results obtained thus far affirm that this proof will be worth the effort to obtain it.

Figures

Figure 1 – Non-Attainment Areas

Figure 2 – Transportation Impacts on GHG Emissions

Figure 16 – Gas Chromatogram after 15 Hour Reaction Time

Figure 31 – Demonstration Fuel System Schematic

Table 6 – Dehydrogenation Results for In-house Catalyst with Reactor Bypass

Table 5 – Dehydrogenation results for HDS-2A Catalyst with Reactor Bypass

Table 13 – Product Peaks for 5% Pd and Neat Fuel at 250oC (T=60 min)

Figure 26 – GC Analysis of 5% Pd Monolith Reactor with Neat Fuel

Figure 13 – Air Products Liquid Carrier Process

Figure 18 – GC Analysis of 1% Pt Monolith and 50/50 Fuel Mix at 220oC

Figure 43 – Fuel System Installation

Figure 10 – Liquid Carrier Molecules Used For Prototype Fuel System Demonstration

Figure 35 – Demonstration Fuel System Test Installation

Figure 17 – H NMR Spectrum for Perhydrofluorene.

Table 8 – Product Peaks after 15 Hour Reaction Time

Figure 27 – GC Analysis of 5% Pd Monolith Reactor with Neat Fuel at 270 °C

Table 14 – Product Peaks for 5% Pd Monolith Reactor at 270°C (T=0 min)

Figure 11 – Experimental Reactor

Figure 21 – GC Analysis of 1% Pd Monolith and 50/50 Fuel Mix at 250oC

Figure 20 – Reaction Products for 5% Pt Monolith and 50/50 Fuel Mix at 220oC

Figure 8 – Auto Company Participants in the Pilot AVF

Full text

CU-ICAR HYDROGEN INFRASTRUCTURE
FINAL REPORT
September 2011
PREPARED BY
Robert Leitner
David Bodde
Dennis Wiese
John Skardon
Bethany Carter
PREPARED FOR
Department of Energy
Golden Field Office
Award No.
DE-FG36-08GO88115
DOE PROJECT OFFICER
James Alkire

CU-ICAR Hydrogen Infrastructure Final Report DE-FG36-08GO88115
ii
Disclaimer
This report was prepared as an account of work sponsored by an agency of the United States
Government. Neither the United States Government nor any agency thereof, nor any of their
employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for
the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed,
or represents that its use would not infringe privately owned rights. Reference herein to any specific
commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does
not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States
Government or any agency thereof. The views and opinions of the authors expressed herein do not
necessarily state or reflect those of the United States Government or any agency thereof.
Acknowledgements
The authors would like to acknowledge the following significant contributions to this project:
 Innovation Center Study – Mr. Manmohan Pozhickal performed the early study of
innovation center attributes.
 AutoVenture Forum – The American Society of Mechanical Engineers (ASME) provided both
financial and staff support to the planning and execution of the AutoVenture Forum. Mr.
Ethan Byler managed the ASME efforts. Ms. Patti Jo Snyder of ASME managed the logistical
arrangements for the first forum. The AVF team would also like to acknowledge the support
provided by USCAR in organizing and hosting the many planning meetings and the
encouragement offered by numerous auto industry executives.
 Test Vehicle Conversion – Conversion of the test vehicles was performed by the Mechanical
Engineering senior design class and graduate students from the Clemson University
International Center for Automotive Research (Frank Richardson, Dave Anderson, Neeraj
Chirmulay, and Harish Kohli).
 Fuel System Controller – Grafton Standifer, a student in the Department of Electrical and
Computer Engineering, performed the design and fabrication of the demonstration fuel
system controller.
 Liquid Carrier and Reactor Testing – Dr. David Bruce and graduate student, Ha Nguyen, of
the Department of Chemical and Biomolecular Engineering provided assistance with all
aspects of the liquid carrier portion of the project.

CU-ICAR Hydrogen Infrastructure Final Report DE-FG36-08GO88115
iii
Table of Contents
1. Introduction .............................................................................................................................................. 1
1.1. The Need ............................................................................................................................................ 1
1.2. Project Objective ................................................................................................................................ 2
2. Defining the Innovation Center Attributes ............................................................................................... 3
3. Key Process Pilot Demonstrations ............................................................................................................ 7
3.1. Industry-Wide Open Innovation Process Demonstration .................................................................. 7
3.1.1. Background ................................................................................................................................. 7
3.1.2. AutoVenture Forum™ Demonstration ........................................................................................ 9
3.1.3. Results and Conclusions ............................................................................................................ 12
3.1.4. Recommendations .................................................................................................................... 13
3.2. Technology Demonstration and Validation Process ........................................................................ 15
3.2.1. Background ............................................................................................................................... 15
3.2.2. Hydrnol Prototype Fuel System Demonstration ....................................................................... 17
3.2.3. Air Products Liquid Carrier Fuel System Demonstration .......................................................... 22
3.2.4. Conclusions and Recommendations ......................................................................................... 49
Works Cited ................................................................................................................................................. 52
List of Figures
Figure 1 – Non-Attainment Areas ................................................................................................................. 1
Figure 2 – Transportation Impacts on GHG Emissions .................................................................................. 2
Figure 3 – Functions Performed by University Based Innovation Centers ................................................... 4
Figure 4 – Functions Performed by Community Based Non-Profit Innovation Centers ............................... 4
Figure 5 – Characteristics of University Based Innovation Centers .............................................................. 5
Figure 6 – Characteristics of Community Based Non-Profit Innovation Centers .......................................... 5
Figure 7 – Electric Vehicle Powertrain Business Model Convergence .......................................................... 8
Figure 8 – Auto Company Participants in the Pilot AVF .............................................................................. 10
Figure 9 – Technology Transition Valley of Death ...................................................................................... 15
Figure 10 – Liquid Carrier Molecules Used For Prototype Fuel System Demonstration ............................ 17
Figure 11 – Experimental Reactor ............................................................................................................... 18
Figure 12 – Process Flow Diagram .............................................................................................................. 20
Figure 13 – Air Products Liquid Carrier Process .......................................................................................... 22
Figure 14 – Gas Chromatogram After 9 Hours Reaction Time.................................................................... 23
Figure 15 – 2,3,4,4a,9,9a-hexahydro-1H-Fluorene Partial Hydrogenation Byproduct .............................. 24
Figure 16 – Gas Chromatogram After 15 Hour Reaction Time ................................................................... 25
Figure 17 – H NMR Spectrum for Perhydrofluorene. ................................................................................. 26
Figure 18 – GC Analysis of 1% Pt Monolith and 50/50 Fuel Mix at 220
o
C .................................................. 28
Figure 19 – GC Analysis of 5% Pt Monolith and 50/50 Fuel Mix at 220
o
C .................................................. 29

CU-ICAR Hydrogen Infrastructure Final Report DE-FG36-08GO88115
iv
Figure 20 – Reaction Products for 5% Pt Monolith and 50/50 Fuel Mix at 220
o
C ...................................... 30
Figure 21 – GC Analysis of 1% Pd Monolith and 50/50 Fuel Mix at 250
o
C ................................................. 30
Figure 22 – Reaction Products for 1% Pd Monolith and 50/50 Fuel Mix at 250
o
C ..................................... 31
Figure 23 – GC Analysis of 5% Pd Monolith and 50/50 Fuel Mix at T=250
o
C ............................................. 32
Figure 24 – Reaction Products for 5% Pd Monolith and 50/50 Fuel Mix at 250
o
C ..................................... 33
Figure25 – Comparison of Fluorene Production Results for Three Monoliths ........................................... 33
Figure 26 – GC Analysis of 5% Pd Monolith Reactor with Neat Fuel .......................................................... 34
Figure 27 – GC Analysis of 5% Pd Monolith Reactor with Neat Fuel at 270 °C ........................................... 35
Figure 28 – Comparison of Diluted and Neat Fuel Test Results .................................................................. 36
Figure 29 – SCIES Hybrid Electric Test Vehicle ............................................................................................ 37
Figure 30 – Fuel System States ................................................................................................................... 38
Figure 31 – Demonstration Fuel System Schematic ................................................................................... 39
Figure 32 – Demonstration Reactor Build-up ............................................................................................. 40
Figure 33 – Fuel System Controller Schematic ........................................................................................... 41
Figure 34 – Demonstration Fuel System ..................................................................................................... 42
Figure 35 – Demonstration Fuel System Test Installation .......................................................................... 43
Figure 36 – Demonstration Fuel System Test Results – Test 1 (T=235
o
C) .................................................. 44
Figure 37 – Demonstration Fuel System Test Results – Test 2 (T=250
o
C) .................................................. 44
Figure 38 – Comparison of Experimental and Demonstration Reactor Test Results (T=250
o
C) ................. 45
Figure 39 – Demonstration Fuel System Test Results – Test 3 (T=270
o
C) .................................................. 46
Figure 40 – Comparison of Experimental and Demonstration Reactor Test Results (T=270
o
C) ................. 46
Figure 41 – Demonstration Fuel System Test Results – Test 4 (Fanfold) .................................................... 47
Figure 42 – Comparison of Demonstration Fuel System Test Results ........................................................ 48
Figure 43 – Fuel System Installation ........................................................................................................... 49
List of Tables
Table 1 – Composition of American Cyanamid Catalysts ........................................................................... 19
Table 2 – Dehydrogenation results for HDS-20A Catalyst (07July2010) ..................................................... 19
Table 3 – Dehydrogenation results for HDS-20A Catalyst (08July2010) ..................................................... 19
Table 4 – Dehydrogenation results for HDS-2A Catalyst ............................................................................ 20
Table 5 – Dehydrogenation results for HDS-2A Catalyst with Reactor Bypass ........................................... 21
Table 6 – Dehydrogenation Results for In-house Catalyst with Reactor Bypass ........................................ 21
Table 7 – Product Peaks After 9 Hours Reaction Time ............................................................................... 24
Table 8 – Product Peaks After 15 Hour Reaction Time ............................................................................... 25
Table 9 – Product Peaks for 1% Pt Monolith and 50/50 Fuel Mix at 220
o
C (T=15 min) ............................. 28
Table 10 – Product Peaks for 5% Pt Monolith and 50/50 Fuel Mix at 220
o
C (T=90 min) ........................... 29
Table 11 – Product Peaks for 1% Pd Monolith and 50/50 Fuel Mix at 250
o
C (T=0 min) ............................ 31
Table 12 – Product Peaks for 5% Pd Monolith and 50/50 Fuel Mix at T=250
o
C (T=30 min)....................... 32
Table 13 – Product Peaks for 5% Pd and Neat Fuel at 250
o
C (T=60 min) ................................................... 34
Table 14 – Product Peaks for 5% Pd Monolith Reactor at 270°C (T=0 min) ............................................... 35
Table 15 – Effect of Temperature on Reactor Performance ....................................................................... 36

CU-ICAR Hydrogen Infrastructure Final Report DE-FG36-08GO88115
1
1. Introduction
1.1. The Need
Automobiles and trucks, powered by internal combustion engines and fueled by abundant, low cost
petroleum, have served as the foundation for the prosperity and growth of our geographically
dispersed, yet highly interconnected nation for the past century. However, recently, the negative
impacts of this mode of transportation on our society have become more apparent. These impacts
include:
 AIR QUALITY AND PUBLIC HEALTH. The US Environmental Protection Agency (EPA) uses six
"criteria pollutants" as indicators of air quality, and has established a maximum
concentration for each of them based on human health concerns. Vehicles are a major
source of several criteria pollutants, including particulate matter, carbon monoxide and
ozone. Despite large reductions in vehicle emissions, approximately 300 counties across the
US, shown in Figure 1, are non-attainment areas today.
Figure 1 – Non-Attainment Areas
 CLIMATE CHANGE. The transportation sector is the second largest source of Greenhouse
Gas (GHG) emissions in the US, and with substantial increases in vehicle demand in large
developing nations, such as China, it is one of the fastest growing sources globally, as shown
in Figure 2.
Source: US EPA Green Book

Frequently asked questions

Q1. What was used to confirm the hydrogenation product as primarily perhydrofluorene?

Proton Nuclear Magnetic Resonance Spectroscopy was used to further confirm the hydrogenation product as primarily perhydrofluorene. 

Q2. What contributions have the authors mentioned in the paper "Cu-icar hydrogen infrastructure final report" ?

In this paper, the authors evaluated the performance of two prototype hydrogen fuel storage technologies and concluded that neither was ready to proceed to the commercialization phase of product development without further research. 

Q3. What have the authors stated for future works in "Cu-icar hydrogen infrastructure final report" ?

The data collected on the two prototype hydrogen fuel storage technologies was adequate to determine that neither was ready to proceed to the commercialization phase of product development without further research. While the level of performance achieved did not reach the level needed to move to the commercialization phase of product development, several promising conclusions were reached, resulting in recommendations for future research. Recommendation – Further studies of catalysts should be performed to determine if a higher rate and higher reaction completion can be achieved. 9 % propylamine reacted, but only 9. 0 % propionitrile produced ; the remainder was unwanted byproducts, including some potentially hazardous byproducts, such as cyanide gas. 

Q4. Why was the demonstration fuel system constructed?

Prior to building the demonstration fuel system, a small, experimental reactor was constructed to aid in selecting the best catalyst and to optimize the reaction conditions. 

Q5. Why did AP find that catalyst efficiency degraded with reactor length?

(16) AP found that catalyst efficiency degraded with reactor length, possibly due to the large volume of hydrogen gas produced (approximately 98% by volume). 

Q6. What is the way to store hydrogen in a vehicle?

Liquid carriers can be stored in conventional fuel tanks that can be conformally mounted, thus simplifying their integration into the vehicle. 

Q7. What was the first step toward building the prototype fuel system?

The first step toward building the Hydrnol fuel system was to select the reactor components, in particular the catalyst, and collect reactor performance data that would allow accurate sizing of the prototype system. 

Q8. What catalyst was used to convert propylamine to propionitrile?

The dehydrogenation of propylamine to propionitrile was repeated under the same reaction conditions, using the second catalyst, HDS-2A. 

Q9. Why are entrepreneurs particularly active at the interface among these traditional business models?

Entrepreneurs are especially active at the interface among these traditional business models because the most attractive opportunities to accelerate the pace of change reside there. 

Q10. Why was the neat fuel used in the demonstration reactor?

neat fuel was chosen for use in the demonstration reactor, and the reactor was designed to provide increased residence time to offset the lower reaction rate of the neat fuel. 

Q11. What is the name of the company that is integrating into electric vehicles?

Consider BYD, for example, the Chinese battery manufacturer that is integrating into electric vehicles with investment from Warren Buffett. 

Q12. What could be used as the hydrogen source for larger engines?

In addition, this fuel system could be used as the hydrogen source for larger engines that use a small quantity of hydrogen to enhance the combustion process. 

Q13. Why was a saturated solution of fluorene needed for the hydrogenation reactions?

a saturated solution of fluorene was desired for the hydrogenation reactions in order to maximize the amount of fluorene hydrogenated. 

Q14. What was the hypothesis that the catalyst would form a film on the catalyst surface?

It was hypothesized that this large volume of gas might form a gas film on the catalyst surface, preventing the liquid from making contact and inhibiting further reaction. 

Q15. What are the three traditional business models that are now being used in the auto industry?

These traditional business models (illustrated in Figure 7) include: Auto companies, once vertically integrated, now requiring innovation by suppliers at all tiers, but still lacking systematic connections with entrepreneurs and new ventures; Energy companies, traditionally commodity energy providers, but increasingly facing competition from “smart” electricity and renewable electricity generated from distributed sources; and Information and communication companies, offering smart devices and systems that manage electric energy onboard vehicles, among energy-using devices, and within smart grids. 

Q16. What was the reaction temperature of the propylamine to propionitrile?

Using the HDS-20A catalyst, the calculated percent conversion of propylamine to propionitrile from two duplicate test runs was extremely low even after the reaction temperature was increased from 513K to 573K, as shown in Tables 2 and 3, despite the endothermicity of the dehydrogenation reaction. 

Q17. What is the process flow diagram for the HDS-20A catalyst?

The process flow diagram, shown in Figure 12, depicts how the flow of the nitrogen-propylamine mixture was regulated through the use of mass flow controllers and three four-way valves.