text:
No connection to Amazon Web Services. Please retry later.
No connection to Amazon Web Services. Please retry later.
Having the same problem on one of my sites. However, on other sites where AMT was already installed it appears to still be working correctly. I suspect it could be because of a particular theme or plugin. I noticed that the SexyBookmarks plugin will include some of the amtap information in its links... a little weird. Disabling SexyBookmarks didn't fix the problem though.
See my reply to rrhobbs please.
This topic has been closed to new replies.


text:
StartUpHire is the place to find Mobile Software Engineer (iOS/Android) jobs. Review the list of Mobile Software Engineer (iOS/Android) career opportunities to the left. These Mobile Software Engineer (iOS/Android) jobs represent some of the most rewarding careers available.
You can refine your job search for Mobile Software Engineer (iOS/Android) career opportunities by adding a job title, company name, or keyword to the search box above … or click the "Advanced Search" link for more options.
Don't see the employment opportunity you're looking for? Check back soon for more Mobile Software Engineer (iOS/Android) jobs, or sign up for an email alert (link below) to receive periodic updates on new Mobile Software Engineer (iOS/Android) jobs.
We are looking for talented Mobile Software Engineers to make Etsy mobile a delightful, fulfilling experience for everyone, on every device.8/30/2016 Brooklyn, NY Save This Job
at Basis Technology (View all jobs) Bethesda, MD Basis Technology is the leading provider of software solutions for extracting meaningful intelligence from multilingual text and digital devices. Our mission is to improve the process of extracting meaningful intelligence from7/23/2016 Bethesda, MD Save This Job
at Snapchat (View all jobs) Venice, CA Hi Fellow Mobile Software Engineer! Here at Snapchat, we think that mobile is not only the future, but also the present. We work hard to build first-rate iOS and Android apps that help people share authentic moments with friends. What7/31/2016 Venice, CA Save This Job
We're looking for amazing iOS engineers to join our game studio! Â You'll work on new gameplay features, optimizations, improvements, and more for our live titles! Many of our games have been in the App Storeâs top 10 grossing list, and some of our better known gamesSan Francisco, CA Save This Job
PITTSBURGH, PAENGINEERINGFULL-TIME APPLY FOR THIS JOB An iOS expert who will help millions of people learn on a mobile device. Duolingo's software engineers are at the forefront of developing the technologies that improve how millions of people learn. We're looking for ideas to7/5/2016 Pittsburgh, PA Save This Job
Headquarters Disruptor Beam is building a new generation of games for every screen, based on popular universes like Game of Thrones and Star Trek. This is an opportunity to join a rapidly growing company, alongside a veteran team, working with some of the most iconic brands in8/25/2016 Framingham, MA Save This Job
SoundHound is leading the mobile sound search revolution. Join us. SoundHound delights millions of users every day with its famously fast music and voice recognition apps, and is winning awards and praise along the way. Our flagship app for iPhone and Android recently7/14/2016 Santa Clara, CA Save This Job
We're looking for talented Software Engineers to build tools that help independent artists turn their creativity into thriving businesses.8/30/2016 Brooklyn, NY Save This Job
JOB DESCRIPTION: You will utilize your robust technical skills and competencies to design, develop, and maintain several key subsystems for Casenet?s next-generation product, TruCare. Design, develop, and maintain various aspects (i.e. domain model, services, etc.) for key7/10/2016 Bedford, MA Save This Job
at Twilio (View all jobs) San Francisco About the job: The Technical Operations team at Twilio builds and maintains the core internal services platform that powers Twilio and helps us to reach millions of people every day. In this role, you will be responsible for designing and7/28/2016 San Francisco, CA Save This Job
Menlo Park AnchorFree?s mission is to provide secure and private access to the world?s information for every person on the planet. AnchorFree?s Hotspot Shield app is the world?s most popular freedom and privacy platform. Hotspot Shield is the starting point, for mobile and Web8/23/2016 Menlo Park, CA Save This Job
OUR MISSION IS TO BRING THE CERTAINTY OF SCIENCE TO THE ART OF BRAND MARKETING. Tremor Video helps make every advertising moment more relevant for customers. The company?s heritage as custodians of the most recognized advertiser and publisher brands is built on leadership in8/24/2016 San Francisco, CA Save This Job
Livescribe is in the midst of creating a series of mobile apps and an SDK to allow 3rd party app developers to connect with our award winning line of smartpens. We are seeking an experienced Senior Graphics Software Engineer to drive improvements in our content rendering engines7/20/2016 Oakland, CA Save This Job
at AnchorFree Inc. Menlo Park AnchorFree?s mission is to provide secure and private access to the world?s information for every person on the planet. AnchorFree?s Hotspot Shield app is the world?s most popular freedom and privacy platform. Hotspot Shield is the starting point,7/24/2016 Menlo Park, CA Save This Job
Livescribe is in the midst of creating a series of mobile apps and an SDK to allow 3rd party app developers to connect with our award winning line of smartpens. We are seeking an experienced Senior Software Engineer to drive improvements in our data interchange/management7/20/2016 Oakland, CA Save This Job
Engineering Seattle, WA, United States As a Senior Software Engineer, you will use your technical expertise to determine technical feasibility, architecture and design in the development of world-class software products that run on current and future notebook and mobile7/20/2016 Seattle, WA Save This Job
Engineering Development San Jose, CA, United States We are Apigee. We are from the Future. We are looking for you. Are you ready to become an instrumental part of the new digital economy where apps, data and APIs are becoming the very fabric of business? Is innovation in your7/17/2016 San Jose, CA Save This Job
Description: We?re looking for a solid Senior Software Engineer who does not shy away from challenges and opportunities to lead. Were a fun and dynamic startup, with a team of people who work together on everything from the latest front-end technologies to superb database7/14/2016 Washington, DC Save This Job
Resources Jobs Login Product and Technology IN, USA Full Time Email Me This Job Position Summary The Senior Software Engineer is responsible for designing and delivering quality software features to the applications that encompass BidPal's technology products. The Senior5/23/2016 IN Save This Job
Job Description: Work with our audio R&D experts to refine audio technologies and develop software applications that put them into the hands of users. We are looking for an enthusiastic individual who has solid expertise in C++ or C# software application development and working7/9/2016 Los Angeles, CA Save This Job

subset: commoncrawl


text:
Aug 31
Aug 17
Aug 3
Jul 27
Jul 13
"We are not looking for fame or fortune we just want to make a living with music" Doomsday Machine is a Technical Death Metal from Connecticut. The band is made up of Mikael Dugan on vocals, Jimmy Cohaguila on drums, Michael Gibilisco an guitar and piano, and Paul Spak on bass and chords. After listening to a couple of their tunes, which you can download for FREE by following the links to the right, I am forced to say these guys can string together some pretty heavy and melodic riffs! I urge you to venture on over to their land of metal and become a fan! They have a lot of shows coming up, so be sure to check them out when they come to your town! I had a chance to throw some questions their way, and this is what they had to sy.


text:
I set up several recurring events in EM last month and they all appeared in the list for the first instance. But none of them are showing up a second time.
For example, I setup an event on Sept 28 and told it to recur on the fourth Wednesday of the month. It appeared for Sept 28 but the event is not showing up for Oct 26.
EM is set to display all "Future" events on the settings screen.
Is there something I need to change in the template to display recurring events?
Here's the Events page:


text:
Dominican Republic
this wiki
Last updated: 18 February 2016
A workshop participant (right) is introduced to the Global Sun Oven version of a solar box cooker by Louise Meyer.
- See also: Global Calendar of Events and Past events in Dominican Republic
- February 2016: Solar Oven Partners has published its February 2016 newsletter which details their recent solar cooking work in the Dominican Republic. Read more...
- December 2015: Shipping container full of solar ovens arrives in Dominican Republic ready for Solar Oven Partners project. Read more...
- June 2014: Stephan Zech, with Sun and Ice, reports they have just sent 100 parabolic solar cookers to the Dominican Republic.
- March 2014: Recent use of solar cookers in the Dominican Republic - The USAID –TNC's Environmental Protection Program are working together with the US Peace Corps volunteers and PRONATURA (a local NGO) to buffer the energy demands of rural communities. The goal is to reduce poverty, improve the quality of life for rural residents, and restoring the vegetation cover within the country. See more...
- November 2011: Kevin Adair of El Fuego del Sol, reports they are working on a major proposal for USAID for Haiti featuring solar cooking. The request for proposals from USAID appears to be terribly skewed in the direction of low pressure gas (LPG), at the expense of considering other alternatives. There are currently active programs in Haiti and the Dominican Republic promoting solar cookers used in conjunction with alternative fuel efficient stoves. This approach is explained in the Integrated Cooking Method. Read the USAID for HAITI Request for Proposals.
- May 2011: Solar Household Energy (SHE) has begun a cooperative relationship with Grupo Jaragua, a highly respected non-governmental organization in the Dominican Republic, to support a solar cooking initiative. Grupo is aided by a Dominican eco-tourism and solar cooking advocate El Fuego del Sol, which conducts the local assembly and subsidized sale of Sun Oven box cookers in rural communities near the Haitian border. They are also supporting The Nature Conservancy's office in the Dominican Republic to add the integrated cooking method as a component of their reforestation project in Haiti. Read more in the SHE spring update 2011.
- April 2010: Kevin Adair hopes to distribute an additional 300 Global Sun Ovens in the Dominican Republic and Haiti by mid-2010 (photo: Kevin Adair) While shuttling between jobs at a number of resorts in the Dominican Republic, entertainer Kevin Adair witnessed the daily struggles many women go through to collect cooking fuel and the health problems incurred by them and their children due to continuously breathing in smoke from cooking fires. Adair also sensed that the resort vacationers he was entertaining were not being offered opportunities to really experience the people, culture, history, and food of the Dominican Republic. Adair began to address these issues in 2005 when he purchased 40 acres of lush land near Higuey, Altagracia, and formed El Fuego del Sol — a "GeoTourism EcoVillage" that offers alternative travel experiences for individuals and groups looking to delve a bit deeper into the geographical character of the area and its people in an ecologically sustainable way. Partnering with Sun Ovens International, Adair opened Force of the Sun, a Global Sun Oven® manufacturing facility that serves the Dominican Republic and Haiti while providing local jobs that meet fair-trade standards. Visitors to El Fuego del Sol are served traditional meals cooked using a non-traditional fuel source — the sun. They not only taste how wonderful solar-cooked food can be, but also learn about the many health, economic, and environmental benefits of solar cooker use in the region. A requirement of staying at the center is the purchase of a Sun Oven that will be made available to a development organization or a local family in need. In 2007, to expand the reach of this solar cooker distribution program, Force of the Sun began working with Grupo Jaragua, a Dominican nonprofit organization that operates a number of community centers. They developed and continue to use a solar cooker training and purchasing system that involves subsidies and/or volunteer credits. Before a family can purchase or earn a solar cooker, they must learn to use it and cook several meals at the community center. According to Adair, potential solar cooker recipient families must "first cook with the Sun Ovens, preparing food for other volunteers, and do additional community service. … This keeps the Sun Oven from being taken for granted, and familiarizes the recipient with solar cooking techniques well in advance of their receiving a Sun Oven." Next, a reasonable price is set for the subsidized solar cookers. Families are given the opportunity to lower that initial price by keeping a month-long log of wood and propane cooking fuel purchases. A payment plan is then established, wherein the families receive their solar cookers, and pay a weekly amount that is less than the amount of money saved in cooking fuel costs. If the family continues to log fuel purchases, along with solar cooker use, they can submit the journals for additional credits towards the purchase price based on the number of months tracked. The purchase price is further reduced or even waived by volunteering at the community center through activities like reading to children or planting trees. All family members can volunteer, but the men are especially encouraged to participate because they have been shown in this project to be the most hesitant. By requiring that community center meals be cooked with Sun Ovens whenever possible, families that volunteer become accustomed to the food and the solar cooking process. Volunteering to cook at the community center is a great way for families to become familiar with the technology and earn a Sun Oven. Using this distribution model, Adair hopes to provide an additional 300 Sun Ovens by mid-2010. Visit http://www.elFuegodelSol.com to learn how to buy a Sun Oven for a Dominican or Haitian family & Buy a Sun Oven of your own.
- All American Sun Oven® — the durable box-type solar cookers developed by Sun Ovens International — are now being assembled in the Dominican Republic for use there and in Haiti, the Caribbean, and Central America. Kevin Adair, owner of Force of the Sun, says his company offers the ovens for sale at a significant discount to nonprofit organizations. He predicts the company will distribute 50,000 solar cookers regionally in the next three years. Force of the Sun began full production of Global Sun Ovens® in May 2006, and shipped its first cookers to Haiti in June. The factory was designed by solar cooking expert Jack Anderson. Additional space is available for rent to other nonprofits and manufacturers of ecologically sensitive products. Adair believes that by networking with other groups in the Dominican Republic, he will be able to spread the solar cooking idea faster. The company offers training to nonprofits that will distribute solar cookers. Force of the Sun is seeking volunteers to teach solar cooking skills in the Dominican Republic and Haiti. Contact: Kevin Adair, Force of the Sun, Higuey, Dominican Republic. E-mail: firstname.lastname@example.com
For some years, Sophie Jakowska, an associate of the World Conservation Union, has demonstrated the use of solar cookers, in connection with children's exhibits at a new national park. The cookers generated much enthusiasm. Another individual has created a small organization, Estufas Solares Dominicanas, in several towns, with the purpose of demonstrating and promoting cookers. No large-scale project in the nation has been reported.
Archived articles
Climate and culture
Solar Cookers International has rated Dominican Republic as the #24 country in the world in terms of solar cooking potential (See: The 25 countries with the most solar cooking potential). The estimated number of people in Dominican Republic with fuel scarcity but ample sun in 2020 is 1,700,000.
See also:
- Wikipedia article on the climate of Dominican Republic
- Solar cooker dissemination and cultural variables
Possible funders
Articles in the media
- NEW: August 2016: Solar Oven Use in the Dominican Republic Pulitzer Center
Grupo de discusión Facebook
Audio and video
- July 2011:
- August 2009:
Web pages
Manufacturers and vendors
Government agencies
Educational institutions
See also


text:
"Hi my name is Stormi. That's my real name and I get asked that a lot. I'm from Springfield, TN but originally from Pensacola, FL. I am a drummer and hopefully soon getting guitar lessons. Music is my life. I'm an atheist because,…"
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text:
Are you looking for a great experience that will enrich other people's lives while providing you with deep personal satisfaction, personal growth and continued learning? We invite you to become a Bellwood volunteer.
As a Bellwood volunteer, you will be joining a dedicated group of individuals who regularly share their time, energy and experience with our staff members, clients and their families. Many of our volunteers are in recovery and find it rewarding to be involved in the work we do at Bellwood. They are proud to be role models for our clients, and work very hard to hold up the same beacon of hope that guided them through their own treatment program.
To be a Bellwood volunteer, you simply need to contact our coordinator of volunteers. Opportunities may exist in our marketing, research, administration, and IT departments, as well as the client and family programs.
If you are in recovery, you need:
- Three months of uninterrupted post-graduation sobriety if you were a Bellwood client
- One year of proven sobriety if you were not a Bellwood client
- A strong recovery program
- Willingness and honesty
Whether you are a Bellwood graduate, or a family member or individual with personal experience with addiction and recovery, we encourage you to volunteer at Bellwood. Please note that we require a minimum six month commitment and are not able to accommodate individuals seeking short-term volunteer positions.
I have been involved in several different roles as a volunteer at Bellwood for over four years, and have always found each of them to be very rewarding experiences. All of the staff members you work with are of very high quality and really care about the success of clients. The volunteer activities helped keep me grounded and focused on my own recovery. And it's very gratifying when you help others with their treatment and recovery. I'm very grateful to Bellwood for providing me with this opportunity.
- Brian F.
Contact Us
To find out how you can become a Bellwood volunteer, contact our Supervisor of Volunteers at 416-495-0926 extension 112, or email Volunteers.


text:
I'm trying out the WP 3.0
I've set up one blog fine and I'm trying to set up another site.
it's let me add the site - when I click on super admin, Sites... it shows the sites I've made... hoorah... but when I go on network admin it says I have 1 site and 1 user. Is this right?
I can see my second blog but I can't get the template to change or any other info.
I probably shouldn't be doing this sort of thing at 3.30am in the morning :-)
I did want the /blog/ bit - I'm guessing that I just move the wp folder in the main index... right?
I've tried to set up users (it's all me but as two characters so I want an 'admin' which is set up then two 'users' (editors) for each of the blogs. I click on users and it just keeps showing the admin - no new users that I added are listed.
maybe I just need to sleep but any tips would be great - thanks.
I can only create a profile for the plain blog (admin) page but not for the other two.
update: now in the network admin... I have 3 sites and 1 user.
maybe it is just taking time for them to show up?
maybe I should just go to bed now!


text:
Hi, I just installed Fancybox and it is working just fine, except for the window size settings in the Media Settings. I've enabled Fancybox for 'Images & Inline Content' and no matter what values I put into Window size for width, height, and border, nothing changes. The window stays the same size when I load it in the browser.
I've also tried to over-ride the default settings by entering the sizes into the < a > tag, like it says in the FAQ, but that made no difference either.
Everything else seems to work, as I can change colors from the Media Settings, but just not the size.
Also, how do I add padding to the text content? It literally touches the borders of the box.


text:
MOUNT VERNON — In celebration of Music in Our Schools Month, ensembles from the high school band, choir and orchestra performed for the Mount Vernon Board of Education on Monday. The performances, Treasurer Judy Stahl-Reynolds told the News on Tuesday, were "really nice."
Loretta and Norm Lower received the high school Behind the Scenes award and the board applauded the success of a five-year dual enrollment partnership between the high school and Central Ohio Technical College.
The rest of this article is available to Mount Vernon News subscribers. To continue reading, please log in or purchase an e-edition. Login to the e-edition. The article will only be available for thirty (30) days. Try the demo
Pam Schehl: 740-397-5333 or firstname.lastname@example.com and on Twitter, @mountvernonnews


text:
FRI Sessions Now & Later
FRI has a number of resources to make it easy to get FRI content before, during and after the conference. From preview pocasts you can listen to now to IAFC On Demand giving you year-round access to 200 hours of education, we make FRI content easy to access and provide takeaways you can use yourself and share as teaching tools.
A Fresh Perspective in the Fire Service
The FRI conference was amazing. I took away several teaching points for our crews and saw a fresh perspective of the fire service. Although we are steeped in tradition it is refreshing to see so many departments making changes. I look forward to attending this conference again.
– Robert Beam, Paramedic/Firefighter/Acting Captain, Arlington (WA) Fire


text:
When I ripped several DVDs to my xbox, DVD2XBOX split the ISOs of each DVD into two files, ".part 00.iso" and 01. Is there an easy (hopefully quick) way of joining these two files together, without just re-ripping the DVD?
I've tried running the second ISO, and it clicks as if it's trying to load the file, but then nothing happens.
When I put them both in a playlist, and watch the first, once it gets to the end, it ends, tries to play the second, and fails.
I probably should have just ripped them into VOBs & such, but I figured it'd be nice to have ISOs.
Dvd2xbox Splits Iso Images; How To Join Them?
Started by Ck.asdf , Jan 06 2008 12:05 AM
1 reply to this topic
Posted 06 January 2008 - 12:05 AM
Posted 08 March 2008 - 01:10 AM
Set XBMC to stack mode. An option on the left while browsing.
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text:
|Publication number
|Publication type
|Application number
|Publication date
|Aug 3, 2010
|Priority date
|Jan 4, 2005
|Fee status
|Also published as
|Publication number
|Bernard Allen Toseland, Guido Peter Pez, Pushpinder Singh Puri
|Original Assignee
|Air Products & Chemicals, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (27), Non-Patent Citations (9), Referenced by (3), Classifications (30), Legal Events (1)
|External Links: USPTO, USPTO Assignment, Espacenet
This Application is a continuation of application Ser. No. 11/029,059, filed on Jan. 4, 2005, now allowed. The disclosure of application Ser. No. 11/029,059 is hereby incorporated by reference.
This application is related to commonly assigned application having U.S. Ser. No. 10/833,484 and a filing date of Apr. 27, 2004, the subject matter of which is incorporated by reference.
This invention was made with government support under Contract Number DE-FG36-05GO15015 between Air Products and Chemicals, Inc. and the U.S. Department of Energy. The Government has certain rights to this invention.
Hydrogen fueled vehicles, sometimes referred to as the Freedom Car are receiving considerable interest as part of a plan to reduce the reliance on foreign oil and reduce pollution. There are several current designs of hydrogen cars, with one example being a fuel cell powered vehicle commonly called an FCV. In the FCV, hydrogen is supplied to a fuel cell which produces electricity, which is used to power electric motors that propel the vehicle. Another type of hydrogen car is based upon a hydrogen internal combustion engine (HICE). In both designs, hydrogen is the fuel source with water being generated as the combustion byproduct.
A central issue with respect to both types of hydrogen vehicles, i.e., the FCV and HICE vehicles, is one of fuel supply. Not only is there a large infrastructure required for hydrogen dispensation, if one considers all the service stations, production and distribution equipment that are required, but there are issues with respect to fuel handling and use of the fuel on the vehicle itself. Before there can be a progression to dedicated fuel cell propulsion systems and hydrogen internal combustion engines, one must foresee a fuel infrastructure.
Two sources of hydrogen for use in hydrogen cars include the reforming of natural gas (fossil fuels) or from water using electrolysis. Once hydrogen gas is generated it must be stored for subsequent filling of cars or converted into a liquid fuel. Storage of hydrogen gas requires compression and transfer to a cylinder storage vessel. And, if the gaseous hydrogen is stored on the vehicle, such storage cylinders are expensive and they can represent a possible safety hazard in the case of an accident. Alternatively, hydrogen can be stored under low pressure in metal hydride canisters, but, at present, hydride canisters are a lot more expensive than cylinders.
Liquid methanol and other alcohols have been touted as particularly attractive hydrogen sources because they can be catalytically converted over a catalyst allowing pure hydrogen to be released on demand. On site conversion of liquid fuels to gaseous hydrogen overcomes the disadvantages of gaseous storage. Further, fuels such as methanol, and other alcohols are not overly expensive and there is an infrastructure in place today that allows for handling of liquid fuels. Although methanol and alcohols are suitable as a fuel source, they are consumed in the combustion process. In addition, the byproducts of such catalytic conversion, carbon dioxide and water, cannot easily be converted back to a hydrogen source.
Representative patents illustrating hydrogen storage and use are as follows:
Hydrogen Generation by Methanol Autothermal Reforming In Microchannel Reactors, Chen, G., et al, American Institute of Chemical Engineers, Spring Meeting, Mar. 30-Apr. 3, 2003 pages 1939-1943 disclose the use of a microchannel reactor as a means for conducting the endothermic steam-reforming reaction and exothermic partial oxidation reaction. Both reactions are carried out in the gas phase.
Scherer, G. W. et al, Int. J. Hydrogen Energy, 1999, 24, 1157 disclose the possibility of storing and transporting hydrogen for energy storage via the catalytic gas phase hydrogenation and the gas phase, high temperature, dehydrogenation of common aromatic molecules, e.g., benzene and toluene.
US 2004/0199039 discloses a method for the gas phase dehydrogenation of hydrocarbons in narrow reaction chambers and integrated reactors. Examples of hydrocarbons for dehydrogenation include propane and isobutane to propylene and isobutene, respectively. Reported in the publication are articles by Jones, et al, and Besser, et al, who describe the gaseous dehydrogenation of cyclohexane in a microreactor. Jones, et al employ a reported feed pressure of 150 kPa and an exit pressure of 1 Pa.
U.S. Pat. No. 6,802,875 discloses a hydrogen supply system for a fuel cell which includes a fuel chamber for storing a fuel such as isopropyl alcohol, methanol, benzene, methylcyclohexane, and cyclohexane, a catalytic dehydrogenation reactor, a gas-liquid separation device wherein byproduct is liquefied and separated from the gaseous dehydrogenation reaction product, and a recovery chamber for the hydrogen and dehydrogenated byproduct.
The present invention provides an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound initially is in its fully or partially hydrogenated state. It is subsequently catalytically dehydrogenated and the reaction product comprised of hydrogen and byproduct dehydrogenated or partially dehydrogenated organic compound is recovered. The improvement in a route to generating hydrogen via dehydrogenation of the organic compound and recovery of the dehydrogenated or partially dehydrogenated organic compound resides in the following steps:
Significant advantages can be achieved by the practice of the invention and these include:
In the process described herein, the fuel source is an organic compound which can be catalytically dehydrogenated forming carbon-carbon unsaturated bonds under liquid phase conditions at modest temperatures. The fuel source can further be described as one that has a low vapor pressure in order to avoid entrainment and loss of liquid fuel in the hydrogen product. Preferably, the vapor pressure is less than 10 millimeters mercury at 200� C.
In copending application U.S. Ser. No. 10/833,484 having a filing date of Apr. 27, 2004 which has been incorporated by reference, Pi-conjugated (often written in the literature using the Greek letter Π) several molecules are suggested as fuel sources of hydrogen which are in the form of liquid organic compounds. These Pi-conjugated substrates are characteristically drawn with a sequence of alternating single and double bonds. In molecular orbital theory, the classically written single bond between two atoms is referred to as a σ-bond, and arises from a bonding end-on overlap of two dumbbell shaped "p" electron orbitals. It is symmetrical along the molecular axis and contains the two bonding electrons. In a "double" bond, there is, in addition, a side-on overlap of two "p" orbitals that are perpendicular to the molecular axis and is described as a pi-bond (or "Π-bond"). It also is populated by two electrons but these electrons are usually less strongly held, and more mobile. The consequence of this is that these pi-conjugated molecules have a lower overall energy, i.e., they are more stable than if their pi-electrons were confined to or localized on the double bonds.
The practical consequence of this additional stability is that hydrogen storage and delivery via catalytic hydrogenation/dehydrogenation processes are less energy intensive and can be carried out at mild temperatures and pressures. This is represented by the following. The most common highly conjugated substrates are the aromatic compounds, benzene and naphthalene. While these can be readily hydrogenated at, e.g., 10-50 atm. at H2 at ca 150� C. in the presence of appropriate catalysts, extensive catalytic dehydrogenation of cyclohexane and decahydronaphthalene (decalin) at atmospheric pressure is only possible at excessively high temperatures leading to gas phase conditions.
For the purposes of this description regarding suitable organic compounds suitable as hydrogen fuel sources, "extended pi-conjugated substrates" are defined to include extended polycyclic aromatic hydrocarbons, extended pi-conjugated substrates with nitrogen heteroatoms, extended pi-conjugated substrates with heteroatoms other than nitrogen, pi-conjugated organic polymers or oligomers, ionic pi-conjugated substrates, pi-conjugated monocyclic substrates with multiple nitrogen heteroatoms, pi-conjugated substrates with at least one triple bonded group and selected fractions of coal tar or pitch that have as major components the above classes of pi-conjugated substrates, or any combination of two or more of the foregoing.
In one embodiment, the pi-conjugated substrates have a standard enthalpy change of hydrogenation, |ΔH�H2|, to their corresponding saturated counterparts (e.g., the at least partially hydrogenated extended pi-conjugated substrates) of less than about 20 kcal/mol H2 and generally less than 15.0 kcal/mol H2. This value can be determined by combustion methods or by the ab initio DFT method. For purposes of the hydrogenation/dehydrogenation cycle to store and release hydrogen and to re-hydrogenate the substrate, the extended pi-conjugated substrate may exist and be cycled between different levels of full or partial hydrogenation and dehydrogenation as to either the individual molecules or as to the bulk of the substrate, depending upon the degree of conversion of the hydrogenation and dehydrogenation reactions.
The liquid phase pi-conjugated substrates useful according to this invention may also have various ring substituents, such as -n-alkyl, -branched-chain alkyl, -alkoxy, -nitrile, -ether and -polyether, which may improve some properties such as reducing the melting temperature of the substrate while at the same time not adversely interfering with the hydrogenation/dehydrogenation equilibrium. Preferably, any of such substituent groups would have 12 or less carbons. As discussed below in the section on "Pi-conjugated Substrates with Multiple Nitrogen Heteroatoms" alkyl substituents (and it's expected that also alkoxy substituents) will actually favorably slightly lower the modulus of the heat of hydrogenation, ΔH�H2.
Classes of extended pi-conjugated substrates suitable for the processes of this invention are further and more specifically defined as follows:
Extended Polycyclic Aromatic Hydrocarbons (EPAH). For the purposes herein, "extended polycyclic aromatic hydrocarbons" are defined to be those molecules having either (1) a polycyclic aromatic hydrocarbon comprising a fused ring system having at least four rings wherein all rings of the fused ring system are represented as 6-membered aromatic sextet structures; or (2) a polycyclic aromatic hydrocarbon of more than two rings comprising a six-membered aromatic sextet ring fused with a 5-membered ring.
The EPAH molecules represent a particular class of extended pi-conjugated substrates since their pi electrons are largely delocalized over the molecule. While, on a thermodynamic basis, generally preferred are the larger molecules (i.e., those with considerably more than four rings), the value of the standard enthalpy change of hydrogenation, ΔH�H2, and thus the ease of reversible hydrogenation can be very dependent on the "external" shape or structure of the EPAH molecule. Fundamentally, the EPAH molecules that have the highest aromatic resonance stabilization energy will have the lowest modulus (absolute value) of the standard enthalpy of hydrogenation, ΔH�H2. As is taught by E. Clar in "Polycyclic Hydrocarbons" Academic Press, 1964, Chapter 6, it is a general principle that the stability of isomers of fused ring substrates increases with the number of aromatic sextets. For instance anthracene
has one aromatic sextet (conventionally represented by three alternating single and double bonds in a single ring or by an internal circle), as for benzene, while phenanthrene,
has two aromatic sextets, with the result that phenanthrene is more stable by 4.4 kcal/mol (based on the molecules' relative heats of formation).
For an EPAH of a given number of fused rings the structural isomer that is represented with the largest number of aromatic sextets and yet remain liquid at reaction temperatures will be preferred as a hydrogenation/dehydrogenation extended pi-conjugated substrate. Non-limiting examples of polycyclic aromatic hydrocarbons or derivatives thereof particularly useful as a fuel source include pyrene, perylene, coronene, ovalene, picene and rubicene.
EPAH's comprising 5-membered rings are defined to be those molecules comprising a six-membered aromatic sextet ring fused with a 5-membered ring. Surprisingly, these pi-conjugated substrates comprising 5-membered rings provide effective reversible hydrogen storage substrates since they have a lower modulus of the ΔH� of hydrogenation than the corresponding conjugated system in a 6-membered ring. The calculated (PM3) ΔH� for hydrogenation of three linear, fused 6-membered rings (anthracene) is −17.1 kcal/mol H2. Replacing the center 6-membered ring with a 5-membered ring gives a molecule (fluorene, C13H10)
Non-limiting examples of fused ring structures having a five-membered ring include fluorene, indene and acenanaphthylene.
Extended polycyclic aromatic hydrocarbons can also include structures wherein at least one of such carbon ring structures comprises a ketone group in a ring structure and the ring structure with the ketone group is fused to at least one carbon ring structure which is represented as an aromatic sextet. Introducing a hydrogenable ketone substituent into a polyaromatic substrate with which it is conjugated, acceptable heats and hydrogen storage capacities are achievable. Thus for the pigment pyranthrone,
having a standard calculated enthalpy of hydrogenation is −14.4 kcal/mol H2.
Extended Pi-conjugated Substrates with Nitrogen Heteroatoms can also be used as a fuel source. Extended pi-conjugated substrates with nitrogen heteroatoms are defined as those N-heterocyclic molecules having (1) a five-membered cyclic unsaturated hydrocarbon containing a nitrogen atom in the five membered aromatic ring; or (2) a six-membered cyclic aromatic hydrocarbon containing a nitrogen atom in the six membered aromatic ring; wherein the N-heterocyclic molecule is fused to at least one six-membered aromatic sextet structure which may also contain a nitrogen heteroatom.
It has been observed that the overall external "shape" of the molecule can greatly affect the standard enthalpy of hydrogenation, ΔH�. The N heteroatom polycyclic hydrocarbons that contain the greatest number of pyridine-like aromatic sextets will be the most preferred structure and have the lowest modulus of the standard enthalpy of hydrogenation ΔH�H2 structures. The incorporation of two N atoms in a six membered ring (i.e., replacing carbons) provides an even further advantage, the effect on ΔH�H2 depending on the nitrogens' relative positional substitution pattern. A particularly germane example is provided by 1,4,5,8,9,12-hexaazatriphenylene, C18H6N6,
and its perhydrogenated derivative, C12H24N6 system
for which the (DFT calculated) ΔH�H2 of hydrogenation is −11.5 kcal/mol H2 as compared to the (DFT calculated) ΔH�H2 of hydrogenation of −14.2 kcal/mol H2 for the corresponding all carbon triphenylene, perhydrotriphenylene system. Another representative example is pyrazine[2,3-b]pyrazine:
where the (DFT calculated) of ΔH�H2 of hydrogenation is −12.5 kcal/mol H2.
Pi-conjugated aromatic molecules comprising five membered rings substrate classes identified above and particularly where a nitrogen heteroatom is contained in the five membered ring provide the lowest potential modulus of the ΔH�H2 of hydrogenation of this class of compounds and are therefore effective substrates for dehydrogenation in a microchannel reactor under liquid phase conditions according to this invention. Non-limiting examples of polycyclic aromatic hydrocarbons with a nitrogen heteroatom in the five-membered ring fitting this class include the N-alkylindoles such as N-methylindole, 1-ethyl-2-methylindole; N-alkylcarbazoles such as N-methylcarbazole and N-propylcarbazole; indolocarbazoles such as indolo[2,3-b]carbazole; and indolo[3,2-a]carbazole; and other heterocyclic structure with a nitrogen atom in the 5- and 6-membered rings such as N,N′,N″-trimethyl-6,11-dihydro-5H-diindolo[2,3-a:2′,3′-c]carbazole, 1,7-dihydrobenzo[1,2-b:5,4-b′]dipyrrole, and 4H-benzo[def]carbazole.
Extended pi-conjugated substrates with nitrogen heteroatoms can also comprise structures having a ketone group in the ring structure, wherein the ring structure with the ketone group is fused to at least one carbon ring structure which is represented as an aromatic sextet. An example of such structure is the molecule flavanthrone, a commercial vat dye,
a polycyclic aromatic that contains both nitrogen heteroatoms and keto groups in the ring structure, and has a favorable (PM3 calculated) ΔH� of hydrogenation of −13.8 kcal/mol H2 for the addition of one hydrogen atom to every site including the oxygen atoms.
Extended Pi-conjugated Substrates with Heteroatoms other than Nitrogen can also be used as a fuel source and for purposes of this description "extended pi-conjugated substrates with heteroatoms other than nitrogen" are defined as those molecules having a polycyclic aromatic hydrocarbon comprising a fused ring system having at least two rings wherein at least two of such rings of the fused ring system are represented as six-membered aromatic sextet structures or a five-membered pentet wherein at least one ring contains a heteroatom other than nitrogen. An example of an extended pi-conjugated substrate with an oxygen heteroatom is dibenzofuran, C12H8O,
for which the (DFT calculated) ΔH�H2 of hydrogenation is −13.5 kcal/mol H2. An example of a extended pi-conjugated substrate with a phosphorous heteroatom is phosphindol-1-ol:
An example of a extended pi-conjugated substrate with a silicon heteroatom is silaindene:
An example of a extended pi-conjugated substrate with a boron heteroatom is borafluorene:
Non-limiting examples of extended pi-conjugated substrates with heteroatoms other than nitrogen include dibenzothiophene, 1-methylphosphindole, 1-methoxyphosphindole, dimethylsilaindene, and methylboraindole.
Pi-conjugated Organic Polymers and Oligomers Containing Heteroatoms can also be used as a fuel source. For the purposes of this description the, "pi-conjugated organic polymers and oligomers containing heteroatoms" are defined as those molecules comprising at least two repeat units and containing at least one ring structure represented as an aromatic sextet of conjugated bonds or a five membered ring structure with two double bonds and a heteroatom selected from the group consisting of boron, nitrogen, oxygen, silicon, phosphorus and sulfur. Oligomers will usually be molecules with 3-12 repeat units. While there are often wide variations in the chemical structure of monomers and, often, the inclusion of heteroatoms (e.g., N, S, O) replacing carbon atoms in the ring structure in the monomer units, all of these pi-conjugated polymers and oligomers have the common structural features of chemical unsaturation and an extended conjugation. Generally, while the molecules with sulfur heteroatoms may possess the relative ease of dehydrogenation, they may be disfavored in fuel cell applications because of the potential affects of the presence of trace sulfur atoms.
The chemical unsaturation and conjugation inherent in this class of polymers and oligomers represents an extended pi-conjugated system, and thus these pi-conjugated polymers and oligomers, particularly those with nitrogen or oxygen heteroatoms replacing carbon atoms in the ring structure, are a potentially suitable substrate for hydrogenation. These pi-conjugated organic polymers and oligomers may comprise repeat units containing at least one aromatic sextet of conjugated bonds or may comprise repeat units containing five membered ring structures. Aromatic rings and small polyaromatic hydrocarbon (e.g., naphthalene) moieties are common in these conducting polymers and oligomers, often in conjugation with heteroatoms and/or olefins. For example, a heteroaromatic ladder polymer or oligomer containing repeat units such as:
which contains a monomer with a naphthalene moiety in conjugation with unsaturated linkages containing nitrogen atoms.
A pi-conjugated polymer or oligomer formed from a derivatised carbazole monomer repeat unit,
can also be used as a fuel source. Other oligomers that contain 5-membered ring structures with nitrogen atoms are also subject of the present invention. For example, oligomers of pyrrole such as:
which has four pyrrole monomers terminated by methyl groups has an ab initio DFT calculated ΔH�H2 of hydrogenation of −12.5 kcal/mol H2. Other members of this class of pi-conjugated organic polymers and oligomers which are particularly useful according to this invention as extended pi-conjugated substrates are polyindole, polyaniline, poly(methylcarbazole), and poly(9-vinylcarbazole).
Ionic Pi-conjugated Substrates can also be used as fuel source, i.e., a hydrogen source. These ionic pi-conjugated substrates are defined as those substrates having pi-conjugated cations and/or anions that contain unsaturated ring systems and/or unsaturated linkages between groups. Pi-conjugated systems which contain a secondary amine function, HNR2 can be readily deprotonated by reaction with a strong base, such as lithium or potassium hydride, to yield the corresponding lithium amide or potassium amide salt. Examples of such systems include carbazole, imidazole and pyrrole and N-lithium carbazole. Non-limiting examples of ionic pi-conjugated substrates include N-lithiocarbazole, N-lithioindole, and N-lithiodiphenylamine and the corresponding N-sodium, N-potassium and N-tetramethylammonium compounds.
Pi-conjugated monocyclic substrates with multiple nitrogen heteroatoms are another form of hydrogen fuel source. For the purposes of this description "pi-conjugated monocyclic substrates with multiple nitrogen heteroatoms" are defined as those molecules having a five-membered or six-membered aromatic ring having two or more nitrogen atoms in the aromatic ring structure, wherein the aromatic ring is not fused to another aromatic ring. The pi-conjugated monocyclic substrates with multiple nitrogen heteroatoms may have alkyl, N-monoalkylamino and N,N-dialkylamino substituents on the ring. A non-limiting example of a pi-conjugated monocyclic substrates with multiple nitrogen heteroatoms is pyrazine.
Pi-conjugated substrates with triply bonded groups can be used as a fuel source. For the purposes of this description, "pi-conjugated substrates with triply bonded groups" are defined as those molecules having carbon-carbon and carbon-nitrogen triple bonds. The pi-conjugated molecules described thus far comprise atom sequences conventionally written as alternating carbon-carbon single, and carbon-carbon double bonds, i.e., C—C═C—C═C— etc., incorporating, at times, carbon-nitrogen double bonds, i.e., imino groups as in the sequence, C—C═N—C═C—.
An illustration is provided by 1,4-dicyanobenzene:
which can be reversibly hydrogenated to 1,4-aminomethyl cyclohexane:
The enthalpy for this reaction, ΔH�H2, is −16.4 kcal/mol H2.
Table 1a. provides representative extended polycyclic aromatic hydrocarbon substrates, some of which can be used as a liquid hydrogen fuel source or converted to a liquid by incorporating substituents groups such as alkyl groups on the substrate and relevant property data therefor. Comparative data for benzene (1), naphthalene (2, 3), anthracene (46) and phenanthrene (47).
TABLE 1a
ΔHH2 o (300 K)
ΔHH2 o (298 K)
Substrate Structure
aHeat of hydrogenation to form cis-decalin.
bHeat of hydrogenation to form the trans-decalin.
Table 1b shows extended pi-conjugated substrates with nitrogen heteroatoms some of which may be liquids or converted to liquids and thus suited as a hydrogen fuel source. Property data are included.
TABLE 1b
ΔHH2 o (300 K)
ΔHH2 o (298 K)
Substrate Structure
*Calculated and experimental data, both at 150� C.
Table 1c shows extended pi-conjugated substrates with heteroatoms other than nitrogen some of which may be liquids or converted to liquids and thus suited for use as fuels. Property data are included. Comparative data for diphenylsilanes also are shown.
TABLE 1c
ΔHH2 o (300 K)
ΔHH2 o (298 K)
Substrate Structure
Table 1d shows pi-conjugated organic polymers and oligomers some of which may be liquids or converted to liquids and thus suited for use as fuels. Property data are included. Comparative data for phenylene oligomers also are shown.
TABLE 1d
ΔHH2 o (300 K)
ΔHH2 o (298 K)
Substrate Structure
Sometimes one can convert hydrogenated extended pi-conjugated substrates which normally would be solid under reaction conditions to a liquid by utilizing a mixture of two or more components. In some cases, mixtures may form a eutectic mixture. For instance chrysene (1,2-benzophenanthrene, m.p. 250� C.) and phenanthrene, (m.p. 99� C.) are reported to form a eutectic melting at 95.5� C. and for the 3-component system consisting of chrysene, anthracene and carbazole (m.p. 243� C.), a eutectic is observed at 192� C. (Pascal, Bull. Soc. Chim. Fr. 1921, 648). The introduction of n-alkyl, alkyl, alkoxy, ether or polyether groups as substituents on the ring structures of the polycyclic aromatic molecules, particularly the use such substituents of varying chain lengths up to about 12 carbon atoms, often can lower their melting points. But, this may be at some cost in "dead weight" and reduced hydrogen capacity. As discussed above, certain substituents, e.g., nitriles and alkynes, can provide additional hydrogen capacity since each nitrile group can accommodate two molar equivalents of hydrogen.
The dehydrogenation catalysts suited for use in microchannel reactors generally are comprised of finely divided or nanoparticles of metals, and their oxides and hydrides, of Groups 4, 5, 6 and 8, 9, 10 of the Periodic Table according to the International Union of Pure and Applied Chemistry. Preferred are titanium, zirconium of Group 4; tantalum and niobium of Group 5; molybdenum and tungsten of Group 6; iron, ruthenium of Group 8; cobalt, rhodium and iridium of Group 9; and nickel, palladium and platinum of Group 10 of the Periodic Table according to the International Union of Pure and Applied Chemistry. Of these the most preferred being zirconium, tantalum, rhodium, palladium and platinum, or their oxide precursors such as PtO2 and their mixtures, as appropriate.
These metals may be used as catalysts and catalyst precursors as metals, oxides and hydrides in their finely divided form, as very fine powders, nanoparticles or as skeletal structures such as platinum black or Raney nickel, or well-dispersed on carbon, alumina, silica, zirconia or other medium or high surface area supports, preferably on carbon or alumina.
Having described candidates for use a source of hydrogen and their use as fuels for vehicles, their conversion for on site use is described. To facilitate an understanding of the improved step of dehydrogenation of the liquid hydrogen fuel sources described herein, reference is made to
Microchannel reactors, which term is intended by definition to include monolith reactors, are well suited for the liquid phase dehydrogenation process. They offer ability to effect the dehydrogenation of hydrogen fuel sources while obtaining excellent heat transfer and mass transfer. In gas phase dehydrogenation, their main deficiency has been one of excessive pressure drop across the microchannel reactor. Compression of the gaseous reactants comes at a high cost. However, because, in accordance with this invention, the feed to the microchannel reactors is a liquid, the ability to pressurize the reactor becomes easy. One can pump the liquid fuel to a desired reaction pressure. Thus, pressure drop does not become an insurmountable problem as it is in gas phase production of hydrogen. And, as a benefit of the ability to pressurize, it is easy to generate high-pressure hydrogen as a product of the reaction.
Microchannel reactors and monolith reactors are known in the art. The microchannel reactors are characterized as having at least one reaction channel having a dimension (wall-to-wall, not counting catalyst) of 2.0 mm (preferably 1.0 mm) or less, and in some embodiments 50 to 500 μm. The height and/or width of a reaction microchannel is preferably 2 mm or less, and more preferably 1 mm or less. The channel cross section may be square, rectangular, circular, elliptical, etc. The length of a reaction channel is parallel to flow through the channel. These walls are preferably made of a nonreactive material which is durable and has good thermal conductivity. Most microchannel reactors incorporate adjacent heat transfer microchannels, and in the practice of this invention, such reactor scheme generally is necessary to provide the heat required for the endothermic dehydrogenation. Illustrative microchannel reactors are shown in US 2004/0199039 and U.S. Pat. No. 6,488,838 and are incorporated by reference.
Monolith supports which may be catalytically modified and used for catalytic dehydrogenation are honeycomb structures of long narrow capillary channels, circular, square or rectangular, whereby the generated gas and liquid can co-currently pass through the channels. Typical dimensions for a honeycomb monolith catalytic reactor cell wall spacing range from 1 to 10 mm between the plates. Alternatively, the monolith support may have from 100 to 800, preferably 200 to 600 cells per squared inch (cpi). Channels or cells may be square, hexagonal, circular, elliptical, etc. in shape.
In a representative dehydrogenation process, a liquid fuel 2, such as N-ethyl carbazole, is pressurized by means of a pump (not shown) to an initial, preselected reaction pressure, e.g., 1000 psia and delivered via manifold 4 to a plurality of reaction chambers 6 within a first microchannel reactor 8. (Overall dehydrogenation pressures may range from 0.2 to 100 atmospheres.) As shown, dehydrogenation catalyst particles are packed within the reactor chambers 6, although, as an alternative, the catalyst may be embedded, impregnated or coated onto the wall surface of reaction chambers 6. The reaction channel 6 may be a straight channel or with internal features such that it offers a large surface area to volume of the channel.
Heat is supplied to the microchannel reactor by circulating a heat exchange fluid via line 10 through a series of heat exchange channels 12 adjacent to reaction chambers 6. The heat exchange fluid may be in the form of a gaseous byproduct of combustion which may be generated in a hybrid vehicle or hydrogen internal combustion engine or it may be a heat exchange fluid employed for removing heat from fuel cell operation. In some cases, where a liquid heat exchange fluid is employed, as for example heat exchange fluid from a fuel cell, supplemental heat may be added, by means not shown, through the use of a combustion gas or thermoelectric unit. The heat exchange fluid from a PEM (proton exchange membrane) fuel cell typically is recovered at a temperature of about 80� C., which may be at the low end of the temperature for dehydrogenation. By the use of combustion gases it is possible to raise the temperature of the heat exchange fluid to provide the necessary heat input to support dehydrogenation of many of the fuel sources. A heat exchange fluid from fuel cells that operate at higher temperatures, e.g., 200� C. from a phosphoric acid fuel cell, may also be employed.
In the embodiment shown, dehydrogenation is carried out in microchannel reactor 8 at a temperature of generally from about 60 to 300� C., at some pressure of hydrogen. Dehydrogenation is favored by higher temperatures, elevated temperatures; e.g., 200� C. and above may be required to obtain a desired dehydrogenation reaction rate. Because initial, and partial, dehydrogenation of the liquid fuel source occurs quickly, high pressures are desired in the initial phase of the reaction in order to facilitate control of the liquid to gas ratio that may occur near the exit of the reactor chambers. High gas to liquid ratios in reaction chambers 6 midway to the exit of the reactor chambers can cause the catalyst to dry and, therefore reduce reaction rate. In a favored operation, the residence time is controlled such that Taylor flow is implemented, in those cases where the catalyst is coated onto the wall surface of the reactor, or trickling or pulsating flow is maintained in those cases where the catalyst is packed within the reaction chamber. (The pulsing flow regime is described by many references (e.g. Carpentier, J. C. and Favier, M. AlChE J 1975 21 (6) 1213-1218) for convention reactors and for microchannel reactors by Losey, M. W. et al, Ind. Eng. Chem. Res., 2001, 40, p 2555-2562 and is incorporated by reference.) By appropriate control of the gas/liquid ratio, a thin film of liquid organic compound remains in contact with the catalyst surface and facilitates reaction rate and mass transfer of hydrogen from the liquid phase to the gas phase.
After a preselected initial conversion of liquid fuel in microchannel reactor 8 is achieved, e.g. one-third the volume of the hydrogen to be generated, the reaction product comprised of hydrogen and partially dehydrogenated liquid fuel is sent by line 14 to gas/liquid or phase separator 16. Hydrogen is removed at high pressure as an overhead via line 18 and a high pressure partially dehydrogenated liquid fuel source is removed as a bottoms fraction via line 20. High pressure separation is favored to minimize carry over of unconverted liquid hydrocarbon fuel, which typically has a slightly higher vapor pressure than the dehydrogenated byproduct, and contamination of the hydrogen overhead. Advantageously, then the reaction product need not be quenched and thus rendered liquid in order to effect efficient separation of the partially dehydrogenated organic compound from the hydrogen and minimize carryover into the hydrogenated product. This is a favored feature in contrast to those dehydrogenation processes which use reactants such as isopropanol, cyclohexane and decalin where the dehydrogenation reaction products are in the gas phase.
The bottoms from gas/liquid separator 16 in line 20 is combined and charged to reaction chambers 22 in second microchannel reactor 24 at the same or higher temperature in order to maintain reaction rate. The cooled heat exchange fluid is removed from heat exchange channels 6 via line 26 and returned to the fuel cell, if liquid or, if the hydrogen exchange fluid is combustion gas, then it is often vented to the atmosphere via line 28.
On recovery of the bottoms from gas/liquid separator 16, the resulting and partially dehydrogenated liquid fuel may be further reduced in pressure than normally occurs because of the ordinary pressure drop which occurs in microchannel reactor. The pressure in second microchannel reactor 24 is preselected based upon design conditions but in general a pressure of from 30 to 200 psia can be employed for N-ethyl carbazole. The temperature of the previously but partially dehydrogenated liquid fuel in reaction chambers 22 is maintained in second microchannel reactor. Heat to second microchannel reactor 24 is supplied from heat exchange fluid line 10 via manifold 30 to heat exchange channels 31. The use of a lower operating pressure in second microchannel reactor 24 than employed in the first microchannel reactor 8 allows for significant dehydrogenation at the design reaction temperature. Again conversion is controlled in second microchannel reactor in order to provide for a desirable liquid to gas ratio particularly as the reaction product approaches the end of the reaction chamber. The reaction product comprised of hydrogen and further partially dehydrogenation is removed via manifold 32 and separated in gas/liquid separator 34. Hydrogen is removed as an overhead from gas/liquid separator 34 via line 36 and a further dehydrogenated liquid fuel is removed from the bottom of gas/liquid separator 34 via line 38. Heat exchange fluid is withdrawn via line 39 from microchannel reactor 24 and returned to heat exchange fluid return in line 28.
The final stage of dehydrogenation is carried out in third microchannel reactor 40. The partially dehydrogenated liquid fuel in line 38 is introduced as liquid to reaction chambers 42 at the same or higher temperature, based on design. Heat is supplied for the endothermic reaction by heat exchange fluid in line 10 via manifold 44 to heat exchange channels 45. As the dehydrogenation approaches equilibrium in final microchannel reactor 40, i.e., where the final dehydrogenation reaction is carried out at a pressure at the end of the reactor, at or near atmospheric and at even less than atmospheric conditions if this is required to effect the desired degree of dehydrogenation, it is particularly important to maintain Taylor flow or pulsating flow as the case may be. Mass transfer of the hydrogen from the liquid phase to the gas phase at or near atmospheric pressure is quite limited. However, low hydrogen pressures favor completion of the dehydrogenation reaction.
The reaction product from third microchannel reactor 40 is passed to gas/liquid separator 46 via manifold 48 where hydrogen is recovered as an overhead via line 50. The dehydrogenated liquid fuel is recovered as a bottoms fraction from gas/liquid separator 46 via line 52 and ultimately is sent to a hydrogenation facility. Then the dehydrogenated liquid fuel is catalytically hydrogenated and returned for service as a liquid fuel source.
In the event that the hydrogenation product in line 50 contains traces of organic compounds, these may be removed if desired by passing the gas stream through an adsorbent bed (not shown) or an appropriate separator for the trace organic impurity.
Although, the dehydrogenation process has been described employing 3 microchannel reactors, other apparatus designs and operating conditions may be used and are within the context of the invention. The operation parameters are one of process design. The use of multiple reactors, as described, allows for better control of gas/liquid ratios as dehydrogenation of the liquid fuel occurs in the reaction chambers as well as providing for optimized pressures in dehydrogenation of the various organic fuel sources.
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|Citing Patent
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|Chiyoda Corporation
|Method for producing hydrogen aimed at storage and transportation
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|U.S. Classification
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|International Classification
|Cooperative Classification
|European Classification


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Vat(10%) 29 .00 00.00
(3 working days)
Mailing 300 .00 00.00
Insurance 250 .00 00.00
Vat(10%) 55.00 00.00
(To make a currency conversion click on http://www.xe.com)
Immediately after payment of charges and completion of form, we'll send your package. It should be pejorative in taught that payment should be completed first after which we'll pay your Insurance and Notarization fee before Delivery can take place. This is to avoid interception on Express, because we are sending a check with a lump sum of amount. This firm is sentient of British Taxes which must be cleared after confirmation of your payment, Global Express Courier & Diplomatic Company is giving you guarantee that such parcel like yours takes such procedures.
Note:The charges are a little high because of the insurance cover we have undertaken incase of loss, damage or theft of your highly sensitive consignment content. We assume all responsibilities incase of any eventualities. Global Express Courier & Diplomatic Company do not allow Cash on delivery(C.O.D) as all payment must be made in this office before shipment can commence.
This company declined reverse payment for these charges, stating that it is against their professional policy towards ensuring the safe delivery of the check to you. That if a reverse payment is made, and something goes wrong, that we/you cannot sue the courier company or insurance company to recover the full value of the fund as stipulated in the check since payment for insurance cover was not made at point of mailing. With the above reason, reverse payment is ruled out.
Be informed that the winning cheque can only be cleared by you with the provision of your I.D (Driving license/passport). Global Express Courier & Diplomatic Company do not have the authority to cash your check or send your funds via bank-to-bank account. Please take note.
I hope all of this is clearly understood? As soon as I get your response including your completed Delivery Information Request Form I'll give you payment instruction. Send a copy of your Driving license or Passport via express mail or as an attachment via e-mail.
Have your ID card in hand. This will be required by the delivery officer on arrival in your country before handing you your Winning Package. Hope you understand this email and its contents. Please feel free to contact me for any queries/clarification(s).
Send your response to indicate your collection within the next 24hrs, because you only have 10 working days to claim this check BECAUSE OF THE LIMITED TIME BEFORE FUNDS LIQUIDATION and after this period, your cash prize will be deemed to have been forfeited by you and will be reused in the drawings of the next edition as informed from your Lottery Promoter.
George Hilton ESq ..
Customer Service Manager
Tel: +44702...
Thank you & May the good Lord Bless you as you use our services.
12 Ground Floor,Amburst Service, London E8 2BT.
Registered in England and Wales No. 2855735 VAT Registration No. 643 1689 29084
2008 Global Express
This report was posted on Ripoff Report on 01/04/2009 05:39 AM and is a permanent record located here: http://www.ripoffreport.com/r/Global-Express-Courier/London-/Global-Express-Courier-please-tell-me-that-it-is-a-fraud-scam-if-please-tell-a-action-a-407782. The posting time indicated is Arizona local time. Arizona does not observe daylight savings so the post time may be Mountain or Pacific depending on the time of year.
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