June 23, 2009

Catalytic Converters: An Introduction to the Science and Environmental Concerns

Catalytic Converters:
An Introduction to the Science and Environmental Concerns

by Carter Lavin

Introduction:

Devices used in the decontamination of air can be divided into two general categories based on their methods of purification: physical and chemical. Catalytic converters utilize chemical reactions between the catalyst and the pollutant to remove the contamination. While they have the advantage of logistical simplicity, high efficiency and scalability, which makes them ideal for treating exhaust from internal combustion engines, these devices have their drawbacks that make their net worth debatable. They primarily work by converting highly dangerous pollutants into benign substances or less dangerous pollutants. They are not an ideal technical solution to air pollution as they cannot fully eliminate contamination, just decrease its threat, but their expanded use may result in lowering pollution levels. However, due to the energy intense and environmentally damaging nature of refining the necessary materials and constructing catalytic converters, extensive environmental life-cycle analyses must be done in order to determine if they have a net environmental gain and should be encouraged to be spread to new applications.

While the understanding of catalytic science has been largely neglected until the later half of the 20th century, catalytic technology has been used extensively since 1904 when Fritz Haber first synthesized ammonium using an iron oxide as the catalyst (Maugh). The use of catalytic processes to purify air started getting studied more in depth as the 1950s brought about the beginning of environmental concern in the United States and regulations on air pollution (Piver). When the United States passed its first federal regulation on air pollution control, the Air Pollution Control Act of 1955, industries like refining, power generation and automotive started to receive pressure to work to limit pollution, which lead to the increase of investment in research and development of many technologies including catalytic converters (EPA, Maugh). However, as further understanding of the details of what occurs in a catalytic reaction have not yielded great technological applications, the majority of research has focused on surface area sciences (Maugh).

How they function:

There are two types of catalytic reactions that take place in a catalytic converter: reduction catalysts and oxidation catalysts, and they both work on the concept of transform pollutants into less harmful substances. Reduction catalysts are the first stage in the purification process where the converter utilizes a catalyst, usually a precious metal like platinum or rhodium. These precious metals break apart the chemical bonds of nitric oxides by making stronger bonds with the nitrogen than the nitrogen was bonded to the oxygen. Thus, the nitrogen leaves its bond with oxygen to bond with the catalyst, while the left over oxygen atoms bond with each other and form the highly stable oxygen molecule of O2. The diatomic oxygen molecule will not re-bond with the nitrogen as the valence of the oxygen molecule is completely filled with the double bond so a great deal of energy is needed to disassociate the double bond and allow the oxygen to reform with the nitrogen. The nitrogen atoms that are bonded to the catalyst will then bond with each other to form N2, then release the catalyst and continue to flow to the second part of the catalytic converter (Twigg).

The second part of the converter, the oxidation catalyst, has the opposite type of reaction as the reduction catalyst. In the oxidation catalyst, the remaining pollutants, generally carbon monoxide and hydrocarbons are burned to encourage bonding between the carbon and hydrogen atoms of the pollutants and the oxygen in the environment to produce carbon dioxide and water. This phase has the potential of creating unintended molecules if the pollutants in the air coming from the engine react with other substances in the air such as sulfur or parts of the catalyst. The second phase is important to purifying the airflow as the primary combustion process, which occurs in the engine, may result in incomplete combustion which creates toxins like carbon monoxide and various hydrocarbons. While the two types of reactions in catalytic converters are complete opposites, one creating chemical bonds and the other of breaking them, they are improved with similar construction techniques and are part of the same whole.

Increasing the time allowed for a chemical reaction to occur increases its efficiency. In the case of catalytic converters, this can be achieved by slowing down air flow or increasing the converter’s surface area. While slowing the air flow is possible in industrial uses due to venting controls, it is difficult to achieve in regards to transit as maintaining a certain level of air flow is vital to increasing combustion efficiency in the engine which in turn reduces the amount of carbon monoxide and hydrocarbons. If the air flow in the system were slowed to augment the pollutant’s time in the catalytic converter, engine combustion efficiency would decrease thereby creating a higher need to use the converter so it would be self-defeating. Surface area can be increased by expanding the size of the catalytic converter, but as they are reliant upon precious metals like platinum, this could drastically increase their cost. Also, in its main application, transit, space is a limited variable as the converter needs to fit on the automobile. The way most manufactures increase surface area in a cost effective manner is by constructing the converter to house a porous, honeycomb-like structure with many groves (Maugh). By maximizing the amount of surface area exposed of the catalyst, the need for more of the catalytic material is lowered which is very desirable due to the high cost of the precious metals involved.

The catalytic processes in air decontamination can be applied to a wide variety of pollution sources like factories and power plants. However, the high cost of the catalysts, the precious metals, and their potential to be made into a relatively small size makes them economically unsuitable for large scale applications but useful for transit. Also, there is a large selection of other, similarly efficient but less costly, methods to purify air in industrial processes such as sedimentation chambers, filters, absorption chambers so catalytic reactions are generally not selected for industrial processes. Meanwhile, most other methods of air pollution are neither as scalable nor portable as catalytic converters and so they have become the de facto exhaust treatment technology on automobiles.

Disadvantages, Logistical and Environmental:

The disadvantages of catalytic converters are in their physical limitations and their byproducts from their use and manufacturing. All other types of air purifying methods can only function within certain parameters and catalytic converters are no exception. As the catalytic process is dependent on the exposure of the reactants, efficiency can be reduced greatly and the reaction can be stopped if a physical barrier is created between the reactants due to sedimentation build up. This requires some sort of cleaning to remove the sedimentation which adds to the cost of devices in both added materials and loss of time they can be used efficiently. Also, the temperature within the converters must be maintained below high extremes to prevent deterioration of the catalysts, a task which is can be difficult as the chemical reaction that takes place is generally exothermic and the reaction takes place using combustion exhaust.

Converters are relatively sensitive to different types of fuels that may contain substances that can cause sedimentation build up or “catalyst poisoning.” The issue of different fuel types poisoning catalysts received attention in the 1980s as world-wide supplies of “sweet” crude oil, oil with low sulfur content, became depleted causing a shift in use to “sour” crude oil which contains more sulfur and trace metals that can poison catalysts (Cohn). The change in fuel type required a change in catalytic converter design and refining techniques of the fuel to make them more compatible to converters. As the depletion of sour crude oil continues and as alternative fuels like biodiesel, ethanol, and oil shale become adopted, more retooling of catalytic converters will be needed as well as new refining techniques for the variety of fuels to properly adapt the catalysts and their design to the fuel change and prevent catalytic poisoning.

From an environmental standpoint, there are two great disadvantages to catalytic converters. The first and most obvious in terms of air pollution is that they convert harmful contaminants to less harmful ones. This does not mean that their byproducts are harmless; they are simply less harmful in regards to certain parameters. Catalytic converters can be used to oxidize the toxin carbon monoxide or hydrocarbons to form the less immediately dangerous compound of carbon dioxide, which is formed with both types of pollutants, and water, which is only in the case of hydrocarbons. They may also be used to convert the smog inducing compounds of nitric oxides into the greenhouse gas of nitrous oxide. Thus, catalytic converters transform a local air pollutant, a contaminant that mainly damages the area near its point of emission, to locally benign greenhouse gases which are global pollutants. The end product of these greenhouse gases has always been an expected result of the use of catalytic converters and until recently, it was not considered a problem. However, now that the dangers of greenhouse gases in regards to climate change have started to be understood, the aggregated benefit of catalytic converters is being brought into question (Wald).

The second great issue with using catalytic reactions to decontaminate air in terms of an overall environmental standpoint is that the extraction process of the precious metals needed in these reactions is very destructive. To reach ores containing platinum, companies used mechanized drills and explosives to create holes in mountains. The generated waste rock can cause mine tailings and contaminate the local ecosystem. Mine tailings contaminate watersheds as erosion brings toxic sediments like lead or arsenic from the waste into rivers and streams. Some companies, like the Stillwater Mining Company, the only platinum and palladium mining company in the United States, backfill their emptied mine shafts with waste rock and sand to limit mine tailings (Mined). This process does not completely eliminate mine tailings, sources of contamination of watersheds, but it does help protect the tailings erosion which is the primary cause of the dispersion of their toxins (Arizona). However, the vast majority of platinum mining occurs in South Africa where environmental regulations are more lax than in the United States and so this positive technique is likely not widely used resulting in higher levels of environmental poisoning from these tailings.

Once the ore is extracted, it needs to be concentrated, smelted, and refined into a useable product. Due to the relatively high melting point of platinum, a simple technique to refine the ore is to melt all the other impurities, a process that requires temperatures over 1000° Celsius (Metal). Sustaining these temperatures requires high levels of energy which are likely created from burning fossil fuels which contribute to local air pollution and climate change. The issues with smelting is not restricted to the pollution from the energy source, this can theoretically be overcome by adapting renewable energy sources, another issue with the smelting process is it melts or even vaporizes toxic elements that can contaminate air, water and soil. For example, if the smelting process results in incomplete combustion, it has been found that dioxin-like compounds may form (Jordan). These waste products could be recaptured and possibly separated for use, but this would require more mechanization and higher economic costs. Another technique used in refining platinum, which is also used in the gold mining process, is that of applying strong acids to the ores as the precious metals are impervious to their effect. However, this results in a slurry of liquid toxins that have been extracted from the ore and currently there is not an effective way of disposing this waste.

 Once the ore is refined into a useable level of purity of platinum it then needs to be shipped to a factory to create it into the final product, usually a catalytic converter, which is then shipped to an automotive factory and installed (Metal). Here ends the bulk of the environmental impact of the catalytic converters, with the caveat that each added weight to a vehicle, however small increases its fuel consumption as the vehicle needs to transport a heavier mass. While this final stage of manufacturing and transporting the end product is common throughout the globalized economy, it is important to keep in mind so as to calculate the total environmental cost of this air purifying device.  

These environmental issues stem from the basic principle that in order to manufacture any product designed to decontaminate, especially one reliant on rare precious metals, there is an environmental cost from each stage of the product’s life. Catalytic reactions are used to purify the air, but in their fabrication, they cause soil, water and air contamination and in their use, they convert local carbon-based pollutants to global pollutants. While there are many social justice implications of this issue, that of transferring pollution from one comparatively wealthy region to another poorer region, and of passing the burden of a regional decision to be a burden on the world, that is not the focus of this paper.

 A severe and more directly relevant issue is that of the overall environmental impact of the converters. As it is difficult to make a comparison between different types of pollution such as between air and water pollution, we should focus on the total effect on air quality of catalytic converters. And while a full investigation of a life-cycle environmental cost-benefit analysis of catalytic converters is beyond this paper, it is import to investigate to see if the amount of pollutants they take from vehicle exhaust in their life time is greater than the amount of air pollutants required in their fabrication before we can suggest their expanded use.  

Possible Improvements:

Reduction catalysts may be able to be improved to convert nitric oxides into the separate compounds of nitrogen and oxygen which are non pollutants, but it is physically impossible for oxidation catalysts to convert a hydrocarbon or carbon monoxide to a more benign substance than the greenhouse gas carbon dioxide. There inability to make carbon molecules into a completely innocuous substance is not a failing within the technology, but rather a reflection of the fundamental issue with burning carbon fuels. Catalytic converters that are used to purify air contaminated with nitric oxides must be improved to eliminate the formation of nitrous oxide, which is 300 times more potent than carbon dioxide as a greenhouse gas (Wald). If this change is effected, catalytic converting technology will be nearly perfected and as benign as possible. If further environmental protection is desired, it must come from reducing the need to use these catalysts or improving manufacturing techniques and not from improving the technology itself.

Improvements can be made in the expanded use of catalytic converters and current legal reforms in California are working to foster this diffusion (Barringer). While catalytic converters are nearly always used in automobiles and used in various forms of heavy industry, they are not used in smaller applications of engines such as lawn mowers. These smaller, gasoline or diesel powered devices are responsible for emitting far greater quantities of pollutants than cars or trucks per unit of fuel due to their lack of regulation in terms of fuel efficiency and emissions. Although there is currently a regulation battle of the broader application of catalytic converters, if passed pollution levels of carbon monoxide, hydrocarbons and smog will drop in California. However as the use of lawn mowers and similar small-scale engines are less prevalent than automobile use, the drop in pollution levels following the adoption of new regulation will probably be less precipitous than the drop caused by the Clean Air Act. This case of new lawn mower regulation is just one example of how the use of catalytic converters can be spread to curtail end point pollution in a wider application than is currently used.

Conclusion:

            Catalytic technology use for decontaminating air is a scientifically simple concept. In its most common form, the automotive catalytic converter, catalysts are used to complete the previously uncompleted combustion in order to eliminate carbon monoxide and hydrocarbons in exhaust and they are used to break the bonds between nitrogen and oxygen in harmful nitric oxides to allow them to reform as diatomic nitrogen or oxygen molecules. As environmental concern for cleaner air has grown, governmental regulation has encouraged private industry to invest in this technology and to maximize efficiency they have expanded research in surface area sciences. This effective investment and adaptation of the technology has resulted in drops in the occurrence and gravity of smog; however, they have increased emissions of climate change inducing greenhouse gasses. Their wide use came as a result of growing environmental concerns in the developed world to solve their air pollution problems, but their adaptation has increased air, water and soil pollution problems in other, poorer, parts of the world as well as exacerbated the growing global threat of climate change. Further technological development and deployment of catalysts to purify air at more emission points could reduce local air pollution where adapted, but this would come at the expense of air quality in other parts of the world and further the ecological disaster of climate change. In terms of catalytic air decontamination, the question is not how can we better use this technology to improve air quality in the region, but rather does the continued use of this technology provide an overall improvement in global environmental quality?


Bibliography:

Barringer, Felicity. "A Greener Way to Cut the Grass Runs Afoul of a Powerful Lobby." New York Times 24 Apr. 2006.

Cohn, J.G. Catalytic Converters for Exhaust Emission Control of Commercial Equipment Powered by             Internal Combustion Engines.” Environmental Health Perspectives, Vol. 10, (Apr., 1975),                     pp. 159-164. Published by: Brogan & Partners

"History of the Clean Air Act." 19 Dec. 2008. Environmental Protection Agency. 18 June 2009 <http://www.epa.gov/air/caa/caa_history.html>.

Jordan, I., R. Pieters, L. Q. Quinn, J. P. Giesy, P. D. Jones, M. B. Murphy, and H. Bouwman. "The                 contribution of dioxin-like compounds from platinum mining and processing samples." Minerals             Engineering 20 (2007): 191-93.

Maugh, Thomas H. “Catalysis: ‘No Longer a Black Art’.” Science, New Series, Vol. 219, No. 4584 (Feb. 4, 1983), pp. 474-477. Published by: American Association for the Advancement of Science

"Mine Tailings." University of Arizona Superfund Basic Research Program (SBRP). 2008. 20 June 2009             <http://superfund.pharmacy.arizona.edu/Mine_Tailings.php>.

“Palladium- Metal Comparisons.” Palladium: Metal of the 21st Century. 2008. Stillwater Palladium. 19 June 2009 < http://www.stillwaterpalladium.com/metal_comparison.html>

Piver, Warren T. “Potential Dilemma: The Methods of Meeting Automotive Exhaust Emission                         Standards of the Clean Air Act of 1970.” Environmental Health Perspectives, Vol. 8, (Aug.,                 1974), pp. 165-190. Published by: Brogan & Partners

"Stillwater Palladium: How Palladium is Mined.” Palladium: Metal of the 21st Century. 2008. Stillwater Palladium. 19 June 2009 < http://www.stillwaterpalladium.com/mining.html>.

Twigg, Martyn T. "Controlling automotive exhaust emissions: success and underlying science."                         Philisophical Transactions of the Royal Society 363 (2005): 1013-033.

Wald, Matthew. “ E.P.A. Says Catalytic Converter is Growing Cause of Global Warming.” New York Times 29 May. 1998

June 19, 2009

Think Global, Act Local: Carbon Monoxide vs. Carbon Dioxide

I'm currently working on a paper on catalytic converters and I'm stuck on a dilemma they present. A catalytic converter is something that purifies air through a chemical reaction that changes polluting molecules into something more innocuous. They are most commonly used to oxidize carbon monoxide to make carbon dioxide and to oxidize nitric oxides into nitrous oxide. This cuts down on smog and carbon monoxide poisoning. The kicker is that it does that by converting these local pollutants into greenhouse gasses which are global pollutants. It's just buggering thy neighbor.

So when it comes to ideas like Agenda 21 which propose "Think Global, Act Local" what are we supposed to do? With this mentality it seems the proper course of action would be to say that local pollution is the lesser of two evils and that we should take catalytic converters off of our cars and trucks. The issue with that is that damages from local pollutants are far more acute than global ones as you are putting a more toxic element in a smaller area.

As the EPA official Wylie J. Barbour said in a 1998 interview with the New York Times on the subject, "You've got people trying to solve one problem, and as it is not uncommon, they've created another." Some problems are fundamental to an issue, burning things causes pollution period. You can dress it up however you want to, purify it, filter it, but you'll still contaminate something somewhere along the line. The most effective way to combat this fundamental issue is to cut down on consumption. Efficiency is a great thing and should be improved upon, but when we start complicating things, we start getting more unwanted outputs.

This dilemma cannot really be solved, as neither of the two outcomes is all that great, but we can eliminate the choice all together is we "Simplify, Simplify, Simplify"- Henry David Thoreau

May 25, 2009

Solar Train in Arizona- A Smart Move

Imagine a state where the residents of its too largest cities have no way of getting back and forth except by a crammed highway. Imagine a state famous for its renewable energy potential but the only way of traveling the 120 miles between its most important cities was to burn imported fossil fuels. Sounds like a solar powered train would be the way to go to fix that egregious transportation oversight, and that's exactly the plan of the newly formed Silver Bullet LLC based in Tucson Arizona. They are planning to build a high-speed solar powered train to the will go from Tucson to Phoenix Arizona in "about 30 minutes. I am glad to hear that when they say "high-speed" train they are not aiming for being just fast enough to be a "high-speed" train, but they are seeking to go nearly twice as fast as the minimum speed requirement by European Union standards and 2.6 times faster than the American standard*.

Also they are doing this while being nearly carbon neutral from a power standpoint^. But first the concept picture which is a thing of beauty.
Solar bullet

Talk about slick. A very interesting feature is the photovoltaic canopy. I asked Ray Wright, one of the business partners on the project, why did they decided to go for the line instead of one aggregated location. He said the the linear system drastically cuts power losses from transmission and that they are investigating the net effects on cost and logistics of security and maintenance. He suggests it will probably be easier for automated cleaning of the panels this way, but that they are still looking into it. Also he says there is a larger advantage in this which is that you do not need to convert the energy from DC (what solar and wind energy always produce) to AC (which is what our grid uses)** thus avoiding conversion losses as well as transmission losses. Some commentators on the Treehugger article on the subject said that the panels should be next to the tracks and not in a canopy to lower construction costs, but I would imagine that that would put them in far greater risk of damage.

Of course there is always the question of how do you store the energy. Mr. Wright explained that,

Storage technology is one of the keys. Hybrid energy units are to be co-located every mile. combination of very maintainable super capacitor/battery storage units will provide local stored energy each mile, thus the vehicle does not carry that as a primary weight. The vehicles would have a small backup diesel generator system for emergency operation. In emergency mode, the vehicle would be able to operate effectively, just not at top speeds and be as green as under normal operations. A third level of redundancy would be the grid ties at major junction points. These points during normal operation are used to dump excess power to local communities.


An important thing to remember about pv technology is that it functions with light, not with heat. In fact, most solar cells have efficiency loses if it's too hot out which I bet will be a concern of the Silver Bullet. Then again, they seem to be committed to the line of power generation idea which can only work with PV, not with solar-thermal.

Operation is planned to start in 2018, and hopefully they'll have worked out the kinks in their plans and have gone forward to build something that will help Arizona have a brighter future.


*And I always thought we Americans we more obsessed with the newest, biggest and fastest thing, I guess we don't include infrastructure.
^Not a materials standpoint as it'll take a lot of energy to make the metals used for the tracks and trains. Of course it's less material than expanding the I-10, the highway that connects the cities.
**For more info on the AC vs DC front, read up about the War of Currents

April 29, 2009

Thaumatopoea pityocampa and Gary Larson

Gary Larson, the creator of the comic The Far Side, once wrote a book called There’s a Hair in My Dirt, in which a young worm learns about nature and his place in it from his father worm. Father worm tells his son about the young maiden Harriet who took an adventure into the woods, loved nearly everything she saw and understood none of it. I had a similar experience with a few friends in the Sierras de Francia the other month and only last week did I learn that. 

As we were hiking in the woods by the Castilla y Leon and Extremadura border, my friends and I stumbled upon a long line of caterpillars that seemed to be crossing the path in a single-file line. We all marveled at the strange behavior of the seemingly cute insects and stopped and watched them for a while as they processed across the path. Some of them fell out of line and my friend’s Arnika and Karel felt bad for them, picked them up and tried to help them get back to their spot. After watching for a bit more we decided to continue our journey and see how they were doing on our way back. When we got back to the point a few hours later we saw that they had been clumped in a pile in the middle of the path and squashed. We were sad to see that our little friends were massacred in such a manner and decided that it was probably a bunch of nogoodnics who didn’t appreciate nature.

How wrong we were. The other day in my Forest Protection class, I learned the nature of the insects. They were Thaumatopoea pityocampa known as the Pine Processionary for their behavior and they are one of the worst plagues that hit Spanish forests every year. They are defoliators and while they do not directly kill the tree, they eat all the leaves and weaken it to the point where something else kills it easily. People are also generally highly allergic to them and the video we watched strongly warned us never to touch them with bare skin. Arnika and Karel learned that the hard way as they both had rashes for the several weeks after our hike. If you do see them, you are supposed to crush the one in front, as she is the only female and she is leading them all to food. Without her, all the males will descend into chaos and wander aimlessly. You are also supposed to try to corral them together and stomp on them all if you can, which was the fate of the ones we saw.

Dscn1791

That adventure re-iterated a very important lesson about nature and how we relate to it. Gary Larson explained our fault nicely in the book There’s a Hair in My Dirt through Father Worm so I will let him close this post out with his message:

"You see," Father Worm began," Harriet loved Nature. But loving nature is not the same as understanding it. And Harriet not only misunderstood the things she saw- vilifying some creatures while romanticizing others- but also her own connection to them." Father Worm paused, his eyes narrowing, "Ah, connections, Son. That's the fateful key that Harriet missed, the key to understanding the natural world."

April 21, 2009

Promises of Exciting Themes to Come: Teaser

Hey everyone, sorry for not updating recently, I was on Semana Santa vacation, but now I'm back. I won't be able to post frequently in the upcoming week or so as finals are soon approaching so I need to study.

But I wanted to give you all a teaser of themes I will soon post about:
The difference between loving nature and knowing about nature, my adventure with a caterpillar
City bike rental programs in Catalonia (including both the French and Spanish parts) as well as bike infrastructure
The Spanish AVE
Anti-fur protest in Salamanca (with pictures and reflection on my possible hypocrisy due to my stance on bullfighting)
Streetfilms depiction of Bogata in contrast to Bogatanos ideas of the city
Recycling in Girona
Organic food conference in Argeles Sur Mer France
Sustainable and unsustainable cherries in Castilla y Leon and Andalucia
and my favorite- Profesional Worm Coposting!

Get pumped!

Also, Earth Day is coming up, go green, plant a garden!