Re: Syn gas to ammonia

[CA...@aol.com]

In a message dated 2/28/2007 9:15:13 A.M. Central Standard Time, rcas...@nexant.com writes:

Syngas (CO+H2), to be converted by water gas shift to H2 for reaction over a catalyst with N2 to ammonia via the ubiquitous Haber process (the largest volume chemical synthesis practiced in the world today, does not “remember” whether it came from natural gas, coal, or biomass. Most ammonia, of course, is promptly reacted to urea (with offgas CO2) or ammonium nitrate (via nitric acid) for more convenient storage, shipment, and application.

Ron and Paul, is ammonia the end product?  Is it for its fertilizer value or some other benefit?

 

Neal

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[Paul Olivier]

Neal,
 
I have been researching ammonia as a fuel, to fuel vehicles.
But I do not yet know enough to comment at this point.
 
Thanks.
Paul

Paul Olivier 
ESR International LLC
5 Thoung Pho Street
Dalat City, Lam Dong Province
Vietnam 

Louisiana tel 1-337-447-4124 (rings in Vietnam) 
Dallas tel 1-214-306-8746 (rings in Vietnam) 
Vietnam mobile 090-6458735 
http://www.esrint.com/ 
http://www.esrla.com/
Skype: xpolivier

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From: CA...@aol.com
Date: Wed, 28 Feb 2007 10:17:44 -0500
Subject: [TALLOW TREE] Re: Syn gas to ammonia
To: iobb...@googlegroups.com

[Cascone, Ronald]

Neal/Paul: The US military has been looking into ammonia fuel for ICEs (besides for fuel cells) for years and a number of private sector entities have programs going.

 

Ron

 

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[Breitenbeck, Gary A.]

The discussion seems to have taken a turn toward futuristic energy alternatives.  This note is an effort to return the focus to feedstock production for biodiesel.  For the short term (i.e., the time I have left on Earth), the immediate need and future of bioenergy lies in powering a vehicle fleet similar to that existing today with alternatives to liquid fossil fuels.  Appropriate alternatives must be cost competitive while complying with clean air regulations.  Biodiesel and ethanol remain current attractive alternatives to liquid fossil fuels.   

 

We will undoubtedly see more electric cars.  This is good as there are many fuels that can be used to produce electricity. The technologies for co-gen facilities and for supplementing coal-fired plants with wood chips,  for example, are well established except for the economic advantages.  Batteries, as mentioned, remain problematic for an electric fleet.  While I strongly support gasification over enzymatic conversion of lignocellulose materials, practical synthesis of liquid fuels from syngas via Fischer-Tropsch remains in the distant future.  We have several researchers focusing full time on improving this process, though they have not yet given any thought to the water, air and waste standards that must be met before this technology contributes significantly to our energy supply.  Storage and handling of lignocellulose (e.g tallow tree clippings) is also problematic.  A pile bigger than a large hay bale can generate enough bioheat to ignite and burn when the wind picks up.  Storing lignocellulose, even with drying, in a warehouse can result in a costly fire that is difficult to extinguish.    

 

The immediate urgent need is for low cost lipid and starch feedstocks.  More biodiesel and ethanol capacity is being built than can be supported with existing feedstocks.  If these facilities can be supplied, their output will begin to address global warming and the mid east crisis immediately. --Gary

[CA...@aol.com]

In a message dated 3/1/2007 2:28:21 P.M. Central Standard Time, GBreit...@agcenter.lsu.edu writes:

The immediate urgent need is for low cost lipid and starch feedstocks.  More biodiesel and ethanol capacity is being built than can be supported with existing feedstocks.  If these facilities can be supplied, their output will begin to address global warming and the mid east crisis immediately. --Gary

Gary, we have been asked to spec out a crush plant for a site in Ghana where 1,000,000 hectares of palm are being planted in former pastures (no trees being cut).  This planting will provide jobs for about 10,000 local people to plant and maintain the crops, as well harvest and transport it.  They will be able to maintain their current grazing and farming activities besides having new employment opportunities.

 

We are considering a biodiesel plant for the site as well, but are being led to other needy areas of West Africa for that phase of the project.

 

We are willing to consider almost any site for a crush plant given economic and political stability for the area, although I must admit we must be somewhat selective with our time and our money.  Gasification is one option for the remaining biomass from such as project.

 

Neal Van Milligen

Kentucky Enrichment Inc

ca...@aol.com

[Breitenbeck, Gary A.]

Sounds like a outstanding project that will make Ghana and the rest of the world better.   You are to be commended for your global vision.  Focusing on the needs of those I know personally is one of my shortcomings. --gary

 

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From: iobb...@googlegroups.com [mailto:iobb...@googlegroups.com] On Behalf Of CA...@aol.com
Sent: Thursday, March 01, 2007 2:38 PM
To: iobb...@googlegroups.com
Subject: [TALLOW TREE] Re: Syn gas to ammonia

 

In a message dated 3/1/2007 2:28:21 P.M. Central Standard Time, GBreit...@agcenter.lsu.edu writes:

[Paul Olivier]

Gary,

 

Over the years my company devoted a lot of time and money to the design of a rotary gasification oven employing two oxy-fuel burners. Once again we are looking at this technology to gasify an organic fraction of automobile and industrial shredders residue that has run through our separators to remove metals and all other inorganic material. The separated organics situate at more than 12,000 BTU/lb.

 

Our problem has always been: what to do with the large amount of hydrogen produced? We then turned our attention to producing ammonia from this hydrogen. This appears to be an exciting option since just about all ammonia in the USA is produced from natural gas. The ammonia infrastructure, with pipelines and storage facilities, is already in place within the USA.

 

My question to you: is ammonia as a fuel still a futuristic concept? Even though ammonia as a fuel might be a few years away, we could sell it in the meantime as a fertilizer. Ammonia as a fuel can go in so many directions. I talked with Mark Holzapple about this question, and he says that ammonia could be used as a fuel in his StarRotor engine.

 

But the storage of Tallow tree biomass is a problem. This biomass cannot be processed in a three-month period. It has to be reduced in volume and stored in such a manner that it will not self-ignite. Let me throw out a suggestion.

 

When green lumber is stored, it does not catch on fire because air is allowed to flow through it. Would it not be possible to compact Tallow tree biomass into relatively small rectangular bales and stack these bales on wooden spacers that would allow air to flow in between the bales? Here we accomplish three things: we prevent combustion, we allow the biomass to shed its moisture over many months, and we reduce its storage volume.

 

Thanks.

Paul

 

Paul A. Olivier

ESR International LLC

 

Louisiana telephone: 1-337-447-4124 (rings Vietnam)

Texas telephone: 1-214-306-8746 (rings Vietnam)

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[CA...@aol.com]

In a message dated 3/2/2007 8:25:01 A.M. Central Standard Time, paul.o...@esrint.com writes:

But the storage of Tallow tree biomass is a problem. This biomass cannot be processed in a three-month period. It has to be reduced in volume and stored in such a manner that it will not self-ignite. Let me throw out a suggestion.

 

When green lumber is stored, it does not catch on fire because air is allowed to flow through it. Would it not be possible to compact Tallow tree biomass into relatively small rectangular bales and stack these bales on wooden spacers that would allow air to flow in between the bales? Here we accomplish three things: we prevent combustion, we allow the biomass to shed its moisture over many months, and we reduce its storage volume.

-------------------------------------------------------------------------------------------------------------------------------

Paul I have put up a million bales of hay, mostly in the small rectangular size of about 30kg each.  The issue with avoiding a barn fire was to keep the moisture content down below 18%.  Higher than that resulted in microbial activity which stimulated spontaneous combustion.  The same issues apply to the 1 tonne bales except that they are so large that significant mold can develop in the interior if not baled properly.  This should not be much of an issue to you though.

 

Allowing free flowing air between the bales would allow further drying to take place and also discourage heat buildup.  I don't think the wooden spacers would be necessary since a loose stack might accomplish the same aeration.  But I don't know for certain since the local humidity in the air might effect all this.

 

We once designed a sawdust fueled hay drying system to allow us to bale wetter hay to avoid a rain storm while harvesting. The blower system was a simple squirrel cage pushing warm air from a plenum into the stacks.  Perhaps this would be the trick you need.

 

Neal

[Breitenbeck, Gary A.]

Paul: your suggestion of producing N fertilizers as an effective means of storing energy and reducing consumption of fossil methane is excellent.  A significant reason for the poor energy balance of corn ethanol is due to the high rates of N fertilizer required for this crop.  I’ve often wondered why the corn belt did not use gasification of DDG and stover to produce ammonia at their ethanol facilities—anhydrous and aqueous ammonia are still used in the midwest.  

 

I would expect that ammonia as a fuel would be highly corrosive to contemporary engines.  Moreover, surely it would result in very large NOx emissions.   We can be certain that Big Oil and Coal will demand all alternative energy processes meet the same stringent requirements that they must meet (e.g., the fuss over the slightly elevated NOx of some biodiesels).   I’ve never been clear on the fate of organic N released in gasification units but presume it converts to N2.  

 

I suspect that methods to safely store CTT biomass can be devised.  Maintaining sufficient aeration certainly is key.   A high fraction of green leaf will always be a problem and it may be necessary to harvest after leaf fall.   I am most aware of the problems associated with sugarcane bagasse, a high C:N material that is used in various fiber products such as ceiling tile.  The industry relies on drying.  A leak in the roof has caused a warehouse to burn to the ground. --gary

 

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From: iobb...@googlegroups.com [mailto:iobb...@googlegroups.com] On Behalf Of Paul Olivier
Sent: Friday, March 02, 2007 8:16 AM
To: iobb...@googlegroups.com
Subject: [TALLOW TREE] Re: Syn gas to ammonia

 

Gary,

 

Over the years my company devoted a lot of time and money to the design of a rotary gasification oven employing two oxy-fuel burners. Once again we are looking at this technology to gasify an organic fraction of automobile and industrial shredders residue that has run through our separators to remove metals and all other inorganic material. The separated organics situate at more than 12,000 BTU/lb.

 

Our problem has always been: what to do with the large amount of hydrogen produced? We then turned our attention to producing ammonia from this hydrogen. This appears to be an exciting option since just about all ammonia in the USA is produced from natural gas. The ammonia infrastructure, with pipelines and storage facilities, is already in place within the USA.

 

My question to you: is ammonia as a fuel still a futuristic concept? Even though ammonia as a fuel might be a few years away, we could sell it in the meantime as a fertilizer. Ammonia as a fuel can go in so many directions. I talked with Mark Holzapple about this question, and he says that ammonia could be used as a fuel in his StarRotor engine.

 

But the storage of Tallow tree biomass is a problem. This biomass cannot be processed in a three-month period. It has to be reduced in volume and stored in such a manner that it will not self-ignite. Let me throw out a suggestion.

 

When green lumber is stored, it does not catch on fire because air is allowed to flow through it. Would it not be possible to compact Tallow tree biomass into relatively small rectangular bales and stack these bales on wooden spacers that would allow air to flow in between the bales? Here we accomplish three things: we prevent combustion, we allow the biomass to shed its moisture over many months, and we reduce its storage volume.

 

Thanks.

Neal

 

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</html

 

[Breitenbeck, Gary A.]

Paul: Can you imagine a fuel cell that uses ammonia rather than H2 to generate an electric current? --gary

[Paul Olivier]

Gary,

 

That is where a lot of thinking is currently going: powering fuels cells with ammonia.

 

Thanks.

Paul

 

Paul A. Olivier

Louisiana telephone: 1-337-447-4124 (rings Vietnam)

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[Paul Olivier]

See comment in blue.

 

Paul A. Olivier

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From: iobb...@googlegroups.com [mailto:iobb...@googlegroups.com] On Behalf Of Breitenbeck, Gary A.
Sent: Friday, March 02, 2007 10:35 PM
To: iobb...@googlegroups.com
Subject: [TALLOW TREE] Re: Syn gas to ammonia

 

Paul: your suggestion of producing N fertilizers as an effective means of storing energy and reducing consumption of fossil methane is excellent.  A significant reason for the poor energy balance of corn ethanol is due to the high rates of N fertilizer required for this crop.  I’ve often wondered why the corn belt did not use gasification of DDG and stover to produce ammonia at their ethanol facilities—anhydrous and aqueous ammonia are still used in the midwest.  

 

There was a time when ammonia was not produced from natural gas.

 

I would expect that ammonia as a fuel would be highly corrosive to contemporary engines.  Moreover, surely it would result in very large NOx emissions.

 

I am confused here. I think ammonia is used to reduce NOx emissions.

I do not have time now to search this, but look for example at http://www.chemithon.com/ammonia.html

 

We can be certain that Big Oil and Coal will demand all alternative energy processes meet the same stringent requirements that they must meet (e.g., the fuss over the slightly elevated NOx of some biodiesels).   I’ve never been clear on the fate of organic N released in gasification units but presume it converts to N2.  

 

A lot of gasifiers produce NOx because they use air. In our gasifier we only inject pure oxygen.

 

I suspect that methods to safely store CTT biomass can be devised.  Maintaining sufficient aeration certainly is key.   A high fraction of green leaf will always be a problem and it may be necessary to harvest after leaf fall.

 

Yes, I imagine harvesting after all leaves have fallen.

[Breitenbeck, Gary A.]

Sorry, Paul.  I thought you were considering combustion of ammonia in internal combustion engines, not its use in a fuel cell.  From personal experience, I can testify that ammonia will ignite with tremendous release of energy under high temperature and pressure.  And yes, NOx and NH3 are highly reactive under ambient conditions.   I was trying to balance the equation    NH3 + O2 (air)  = H2O + N?O? that would invariable result in a residue of NH4OH left in the engine.--Gary

 

I am confused here. I think ammonia is used to reduce NOx emissions.

I do not have time now to search this, but look for example at http://www.chemithon.com/ammonia.html

 

We can be certain that Big Oil and Coal will demand all alternative energy processes meet the same stringent requirements that they must meet (e.g., the fuss over the slightly elevated NOx of some biodiesels).   I’ve never been clear on the fate of organic N released in gasification units but presume it converts to N2.  

 

 

[Cascone, Ronald]

Gary: SOFCs and Molten Carbonate FCs, the high-temperature technologies that are being commercialized for larger-scale, mainly stationary, but also vehicle applications can do this. Unfortunately, for reasons that are expalined in my report, available from Nexant's PERP multiclient program, "Stationary Fuel Cells", there is an un-justified focus on PEMFCs in the auto industry, government, Wall Street, and the press.

 

My information is that the NOx emissions from ammonia-fueled ICEs are low. Remember, ammonia (or urea) is used in catalyic (SCR) and non-catalytic ammonia reduction systems for boiler stacks, world-wide.

 

Also, you are falling for the urban myth that the energy in ammonia fertilizer for corn ethanol is very signifcant. At least you got the methane part right, versus those like Pimental, who keep saying that ammonia is made from petroleum. The US consumes about 6.5 million tons per year of nitrogen in fertilizers to produce about 300 million tons of grains, which are mostly corn, or about 2.2% by weight.  With the typical efficiency of industrial ammonia production from methane in the world today, this means that it takes about 7,500 Btus to provide fertilizer to corn to make a gallon of ethanol, which has a combustion heating value of 84,700 Btus. That is, the synthetic fertilizer energy component of dry mill corn ethanol is, on the average, less than 9%. If you account for the roughly one pound per pound DDGs/ethanol produced, it comes to 4.5% attributable to ethnaol, and if useful CO2 is captured and used commercially, one could argue that the allocation should be yet lower. I would say this is minor. Also, please let's remember that the common practice in the US since the 1940s has been to rotate corn acreage with soybeans, which benefits from their nitrogen fixation and reduces fertilizer needs compared to other crops that are not rotated, despite corn's relatively high nitrogen demand.

 

Ron

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From: iobb...@googlegroups.com [mailto:iobb...@googlegroups.com] On Behalf Of Breitenbeck, Gary A.

Sent: Friday, March 02, 2007 10:41 AM

[Cascone, Ronald]

Paul: I am very encouraged, as partisan of this idea, that you think so. I would appeciate your sharing how you came to this impression.

 

Ron 

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From: iobb...@googlegroups.com [mailto:iobb...@googlegroups.com] On Behalf Of Paul Olivier

Sent: Friday, March 02, 2007 11:03 AM

To: iobb...@googlegroups.com
Subject: [TALLOW TREE] Re: Syn gas to ammonia

Gary,

 

That is where a lot of thinking is currently going: powering fuels cells with ammonia.

 

Thanks.

Paul

 

Paul A. Olivier

Louisiana telephone: 1-337-447-4124 (rings Vietnam)

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[Cascone, Ronald]

No need to speculate. Ammonia is a good egine fuel. Do a Web search. Or, for starts, here is a pretty good review by Vito Agosta, who I know.

 

http://www.memagazine.org/contents/current/webonly/webex710.html

 

Ron

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From: iobb...@googlegroups.com [mailto:iobb...@googlegroups.com] On Behalf Of Breitenbeck, Gary A.

Sent: Friday, March 02, 2007 12:36 PM

[Breitenbeck, Gary A.]

Ron: I can’t be easily persuaded that corn does not use more than its fair share of N and energy, nor that it doesn’t cause a disproportionate among of Ag’s pollution.   It’s simply not fair to divide all grain by N use and conclude that corn is not an N pig.    Corn has one of the highest N requirements and lowest N use efficiencies of any commonly grown row crop.  We can make a soybean crop on 0 N/ac, a cotton crop on 60-80 lbs N, wheat on 50-75 lbs, rice or sorghum on 100-120 but profitable corn will require 180-250 lbs of N/ac.  The credit for a previous soybean crop is insignificant as most producers ignore the ‘1 lb/bu’ rule and apply the full compliment of N.  Frankly, it’s very difficult to show an increase of 25 lbs of residual N after a 25 bu soybean crop.   Moreover, corn only feeds heavily early in the season and leaves behind a good amount of residual nitrate which is subject of loss to the environment.  --Gary

 

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<BR

[Cascone, Ronald]

Gary: Look at your own numbers. The worst case you give is 250 lbs N/acre, but I think 210 is closer to average. You know that yields today in Iowa are at 180 bu/acre and some get over 200, but I'll take 150 as the average I see for feeding dry corn mills over the states. So, 150 bu/acre x 56 lbs /bu = 8,400 lbs/acre, and 100 x 250 / 8,400 = 3.0%. My previous numbers are based on 2.2% by weight - not that different.

 

Comparing N per acre for wheat and corn alone is not relevant and is misleading - look at the diffrences in yield per acre. I believe that corn is the highest yielding grain per acre that we have. However, I do agree with you that we have to re-examine and improve the entire model with respect to nitrogen loss, etc.  

 

My point is not about the quality of the agricultural system, it is about the lie that ammonia energy inputs count big in the energy balance. What else is there - fuel? Ok, when a cultivation/seeding tractor moves down a field, it covers an acre in say, 1/2 mile of travel, and once again for the combine harvesting. I can't imagine that all this could use more than a couple of gallons of diesel fuel per acre on average. We are producing an average of 375 gallons of ethanol on that acre (not to mention the DDGS) - so where is all this energy going? Irrigation? - nonsense!  If we start using the stover for energy as well, the denominator on any of tehse analyses gets much bigger.

 

Ron

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From: iobb...@googlegroups.com [mailto:iobb...@googlegroups.com] On Behalf Of Breitenbeck, Gary A.

Sent: Friday, March 02, 2007 3:05 PM

[Breitenbeck, Gary A.]

Ron: your outrage is understandable.  I’ve sat in on a couple of seminars where this subject was addressed by ag economists (Gallagher from Iowa State comes to mind) from the corn states and therefore presumably sympathetic to the cause.   Can’t say I really followed the details (the economists’ reputation for unreadable slides was well protected), but by consensus they persuaded me of a small yet positive savings in fossil energy through production of alcohol for fuel.  They also showed that alcohol from sugarcane was far more energy efficient (7x vs 1.1-1.4x for corn).  Again, I don’t recollect all their arguments but recall processing energy and N fertilizer were players in the equations. 

 

I did surf ammonia as fuel and am surprised I’ve never heard of this clearly sane alternative to H2.  The brief review by Fiebleman and Strump  was especially informative (http://www.sandia.gov/surface_science/pjf/On_NH3_roles_in_H2_economy.pdf).   Low-temp cracking of NH3 to release H2 for fuel cells or to produce a H2 supplement to improve the efficiency of gasoline powered engines both make wonderful sense. NOx is a primary product of direct ammonia combustion though a catalyst has been used to react non-combusted ammonia with NOx.  This sounds inefficient and risky.  More, there is no way combusting ammonia with O2 in an aluminum cylinder is not going to eat it up high speed.  Steel, especially stainless steel, might fair somewhat better but I wouldn’t want such an engine in my car.   Unlike H2 which is odorless, ammonia is readily detected by the human nose at a couple of ppm.  This is good in that easy leak detection reduces the chances of housewives blowing themselves up, but it does create a bit of a nuisance problem.  Anyone who has worked with anhydrous can testify that minor leaks are difficult to prevent when transferring hoses, etc.  Ammonia clearly merits our attention.--Gary

<BR

[Paul Olivier]

Ron,

 

I read this article, but it sounded too good to be true.

If this is the case, then why not take our Tallow tree biomass and make ammonia?

I think that it would be possible to solve the biomass storage problem.

We can still make biodiesel from the seed.

 

Thanks.

Paul

 

Paul A. Olivier

ESR International LLC

27c Pham Hong Thai, Ward 10

Dalat City

Lam Dong Province

Vietnam

 

Louisiana telephone: 1-337-447-4124 (rings Vietnam)

Texas telephone: 1-214-306-8746 (rings Vietnam)

Mobile: 090-6458735 (in Vietnam)

Mobile: 84-90-6458735 (outside Vietnam)

New website: http://esrint.com/default.aspx

Old Website: http://www.esrla.com/

Skype address: Xpolivier

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<BR

[Lion, Sonoma Co., Cal., USA]

On Mar 1, 12:17 pm, "Breitenbeck, Gary A."

<GBreitenb...@agcenter.lsu.edu> wrote:
> The discussion seems to have taken a turn toward futuristic energy
> alternatives. This note is an effort to return the focus to feedstock
> production for biodiesel. For the short term (i.e., the time I have
> left on Earth), the immediate need and future of bioenergy lies in
> powering a vehicle fleet similar to that existing today with
> alternatives to liquid fossil fuels. Appropriate alternatives must be
> cost competitive while complying with clean air regulations. Biodiesel
> and ethanol remain current attractive alternatives to liquid fossil
> fuels.

None of your assumptions are true. You have a dead-end 20th century
failing lifestyle that you would rather cling to than enter the 21st
century, although we are already 7 years after the 20th century. Your
Levittown suburbia is over. Ecocity is the new prestige address where
everything comes to you (or near enough) and 80% of all commutes are
moot. All three of your big American car companies are on life support
or intensive care. Your American Graffiti small town drag races and
diners are history. It's over. Get used to it. You are choking on
traffic jams right now. Life is hell for more and more people and cars
are not fun anymore. What's good for GM is no longer what's good for
America, and as we found out, never was.

The transportation "fleet" of the future doesn't look like the 1950s.
The last legal gallon of gasoline on Earth will be sold on or before
2048 in 41 years (maybe as short as 10 years), and there will never be
another carbon-fueled vehicle of any kind after that date. How can I
know the exact date? The spreadsheet doesn't lie.

http://hydrogentruth.info/page_04a.html
http://hydrogentruth.info/spreadsheets/scenario_2b.html
http://hydrogentruth.info/spreadsheets/scenario_2b.sxc
http://hydrogentruth.info/spreadsheets/scenario_2b.xls

[Paul Olivier]

Lion,

You may have a lot of interesting ideas, but you speak them out in such an
impolite, harsh and condescending manner that I would kindly ask you not to
participate any further in these discussions. Please find another forum to
vent your anger at this doomed and wretched world.

Gary Breitenbeck is a fine man and a great scientist.

Thanks.
Paul

Paul A. Olivier
ESR International LLC

Louisiana telephone: 1-337-447-4124 (rings Vietnam)
Texas telephone: 1-214-306-8746 (rings Vietnam)

-----Original Message-----
From: iobb...@googlegroups.com [mailto:iobb...@googlegroups.com] On Behalf
Of Lion, Sonoma Co., Cal., USA
Sent: Saturday, March 03, 2007 5:00 PM
To: Chinese Tallow Tree
Subject: [TALLOW TREE] Re: Syn gas to ammonia

[Mike Schuback]

This guy doesn't know how to express himself!!!

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> From: paul.o...@esrint.com
> To: iobb...@googlegroups.com

> Subject: [TALLOW TREE] Re: Syn gas to ammonia

> Date: Sat, 3 Mar 2007 19:22:39 +0700