9 December 2014
TNT – Raw Materials
The booming of the industrial revolution and the technological and scientific advancements of the eighteenth and nineteenth centuries had a profound change in the way our societies and businesses functioned. With the invention of the steam engine, businesses were able to split the manufacturing into smaller steps. The process of manufacturing, which was once completed from the beginning to the end in just one building, was now being divided among various factories which would mass produce parts of the object. These parts would then be sent to another factory, where workers would assemble the final product. And finally, they would transport it globally where the customers would purchase the items at a location close to them. Although, this process increased efficiency, the transparency of the life cycle of the product was lost. In other words, the customer has no idea where, how, when, and who manufactured the product. These products cover a wide range, including TNT. Discovered in 1863 by Joseph Wilbrand 2,4,6-trinitrotoulene, more commonly known as TNT, is a popular explosive still in use today. TNT has a variety of uses from military purposes to industrial purposes. In this paper, I will be exploring the raw materials part of the life cycle, which includes obtaining the raw materials, manufacturing, distributing, using/maintaining, recycling, and finally managing the waste of TNT.
The first step of the life cycle is the obtaining of the raw materials. The materials needed to manufacture TNT are toluene, sulfuric acid, nitric acid, oleum, and water. Toluene, sulfuric acid, nitric acid, and oleum are all produced in various chemical companies. However, the companies from which the chemicals are obtained, depends on the manufacturer. One chemical company that makes these chemicals is the Dominion Chemical Company. Also, each chemical company could have different regulations or specification on how to make the chemicals. The following processes mentioned are from no particular factory. These are rather the general process of producing the chemicals. The first material needed for the production of TNT is toluene. This organic compound can be derived in one of four ways. About eight-seven percent of the total toluene produced comes from catalytic reforming of petroleum. Another nine percent of total toluene produced comes from manufacturing ethylene and propylene. The next one percent comes from coal-tar separation from coke ovens. And the last two percent is a by-product of styrene manufacture. The second material needed for the production of TNT is sulfuric acid. Sulfuric acid is prepared in one of multiple ways. Two of these include, reacting sulfur dioxide with oxygen and then mixing the resultant with water or by reacting nitric oxide with sulfur dioxide and water. The next material needed is oleum. Oleum is produced when, “sulfur trioxide is produced by the contact process is absorbed in concentrated sulfuric acid”. The contact process is a procedure for creating highly concentrated sulfuric acid, which is often used in industrial processes. Because of the way oleum is made, it is often known as fuming sulfuric acid. And the last chemical material that is required to manufacture TNT is nitric acid. The nitric acid is produced industrially using what is known as the Oswald process. There are three steps to the Oswald process. The first step is the, “Catalytic oxidation of ammonia with atmospheric oxygen to yield nitrogen monoxide”. The second step is the, “oxidation of the nitrogen monoxide product to nitrogen dioxide or dinitrogen tetroxide”. And the final step is the, “Absorption of the nitrogen oxides to yield nitric acid”. Nitric acid is the last chemical material needed for the production of TNT. However, the production still requires the supply of water. This supply of water is directly obtained at the site of the TNT production. It is pumped into the factory through the water pipes connecting to the factory. Once the manufacturers obtain all the required materials for the production of TNT, they move on to the manufacturing.
The second step of the life cycle is manufacturing the product. Different manufacturers have various processes in which they make the TNT. In the United States, the largest continuous manufacturer of TNT is Radford Army Ammunition Plant. The first step in the manufacturing process of TNT is nitrating toluene with a mixture of sulfuric acid and nitric acid. This produces mononitrotoluene (MNT). Then, MNT is renitrated using the same mixture to produce dinitrotoluene (DNT). This DNT is then nitrated using an anhydrous mixture of nitric acid and oleum which produces TNT. Afterwards, TNT goes through a process known as sulphitation. This process removes the less stable isomers of TNT. This stabilizes the TNT and prevents any undesired reactions from occurring. This process involves a new material, which is a diluted solution of sodium sulfite. This is the only new material added during this step of the life cycle. The process of manufacturing TNT is known as the “old” process. The Radford Army Ammunition Plant was closed down in 1986, because of an accident that occurred. Up until this accident, the old process of making TNT was used. This old process resulted in a lot of waste and pollution that took a lot of effort and money to contain and take care of. For this reason, a group of people known as Radford’s P2 Team invented a new way of making TNT. This major change from the “old” process to the “new” process was that the toluene raw material was switched out to ONT (orthonitrotoluene). This chemical was much less hazardous and allowed TNT to be virtually hundred percent pure. With this new process, there weren’t any new materials that needed to be added to the manufacturing part of the life cycle.
The third and fourth step are distributing and use/maintenance of the product. As mentioned in the previous paragraph, TNT goes through a sulphitation process that stabilizes the unstable isomers. Because of this stabilization process, the TNT is not as sensitive to temperature, shock, or the kinds of environment it is in. For this reason, TNT does not need to transported or stored with any specific and careful procedures. However, it is important to still take precautions. For example, too high of temperatures, could result in detonation by its own accord. The temperature at which TNT detonates on its own is around eighty degrees Celsius. Therefore as a precaution it is important to store the TNT in an area that does not reach high temperatures or maintain the temperature in the area the TNT is being stored. Since, TNT is used mostly for military purposes, it is shipped to many of the military bases and other military territories around the world. Trucks, train, or plane are some examples of how TNT could be distributed to its customers.
The fifth and sixth steps are recycling and waste management respectively. The fifth step does not exist in the life cycle of the TNT product, because there is no way to recycle the product once it has been used. In other words, once the TNT is detonated, there is no way to reuse the remains of the explosion and make TNT again. For this reason, it is concluded that there is no way to recycle TNT. However, during the manufacturing stage, sulfuric acid, which is diluted, can be recycled and be used again in the process of making TNT. The next step is waste management. There is not any waste to manage after the TNT is used. However, after the production of TNT, there is waste management. The sulphitation process that the TNT goes through produces waste called red water. The rinsing water used to stabilize the TNT during the sulphitation process is what yields the red water output. This requires additional materials necessary to treat the water and to safely dispose of it. However, for the sake of keeping this project related strictly to TNT, we decided not to go further into this part of the process.
As seen from the information give above, TNT is a widely used explosive that is still used by various industries and the military today. It was interesting to research and find out more about what goes into the process of making this product. Along the way, it was really interesting to see how the process of manufacturing and the life cycle of the product were quite invisible to me until we started to research more on the product. For example, my group and I had to look through many different websites to find the manufacturing process of TNT. And also for the raw materials, I had to visit multiple websites before I could find the information I was looking for. This made me think about other products, even mere everyday products, and how their life cycles are invisible to me as well. All in all, not only did I learn about TNT, its raw materials and life cycle, but I also learned that it is important for us to learn about the life cycles of all the products that are being manufactured these days and bring back the visibility of the processes.
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6 December 2014
For the men and women employed at Radford Army Ammunition Plant in Virginia, war is good for business. Radford Army Ammunition Plant (RFAAP) supplies the Department of Defense, in essence the entirety of the United States military, with Trinitrotoluene (TNT); what makes this feat impressive is that RFAAP is the one and only supplier of TNT for the United States Armed Forces (“Radford Army Ammunition Plant”). Not surprisingly, location is a large part of what makes Radford an extremely good place to host an explosives production plant. Not only is RFAAP relatively close to the Department of Defense’s headquarters, the Pentagon, but it is also four hours, 242 miles, from its nearest possible raw material provider, Dominion Chemical Co., and an astounding eleven minutes, 5.4 miles, from the nearest military installation, the National Guard Armory (taken from Google Maps). Given these boundaries, it will be a simple matter to calculate the minimum amount of energy that goes into producing a TNT load. For the idealized lifecycle of a batch of TNT, where less fuel used is more ideal, the major factor is the location of the necessary facilities.
TNT is a fairly complex chemical compound, and its raw materials could hardly be considered “raw” in the sense that they come directly out of the ground. The one possible exception to this trend is TNT’s main ingredient, toluene. Most toluene produced is not made using processes directly intended to yield toluene, as it is a byproduct generated in the production of gasoline (“Toluene”). As such, the use of toluene in TNT could be considered a form of recycling waste materials from a much larger industry. The two-step process that results in nitric acid, though, is done in dedicated production facilities, often alongside TNT’s other two main ingredients. First, ammonia (also made on site) is oxidized under moderate pressure, about 10-13 atm, as well as extremely high temperatures, about 1200 K, resulting in nitrogen oxides (“Nitric Acid” Essential). After this, nitric acid is fully formed when the oxides pass through running water and are absorbed, a process which requires cooling to 310 degrees (“Nitric Acid” Essential). TNT’s last two ingredients, oleum and sulfuric acid, are closely related in that sulfuric acid is an ingredient of oleum and vice versa. Production starts with sulfur, another byproduct of fossil fuel production, which is converted to sulfur dioxide by adding dry air within a 1300 K furnace, then converted to sulfur trioxide in a large, cylindrical fixed-bed reactor, heated to 700 K, and by adding more air to the dioxide, and finally becomes sulfuric acid when the trioxide is reacted with water and heat is dissipated by heat exchangers within the reactor (“Sulfuric Acid” Essential). Oleum is made by dissolving sulfur trioxide in sulfuric acid and can be diluted with water to become sulfuric acid again (“Sulfuric Acid” Wikipedia). In the cases of nitric acid and especially sulfuric acid, which is literally used to make “hundreds of compounds needed by almost every industry” (“Sulfuric Acid” Wikipedia), the actual facilities used in chemical production are essentially very large machines designed for mass production; with knowledge of the raw material production plants and their location comes the means to find which energy sources they use and by what modes of transportation they arrive at Radford.
Within the state of Virginia, there is a wide variety of energy sources available to the chemical manufacturers, although fossil fuel is most likely the only available fuel source for the large vehicles that transport raw materials to Radford Army Ammunition plant. There are nearly as many power plants within the state that offer renewable energy as there are plants that offer non-renewable energy (“List of power stations in Virginia”). Among the offered types of renewable energy are hydroelectric and biomass, while the non-renewable consists of coal, uranium, natural gas and oil (“List of power stations in Virginia”). Thus, it is plausible that the power used for the production of TNT’s raw materials is entirely renewable, with the exception of the fuel used in the furnace for the sulfuric acid production. The same cannot be said for the mode of transportation by which the materials reach RFAAP, though. Dominion Chemical Co. has access to ports, airlines, railroads, and highways (“Company Name – About us”), all of which require fossil fuels to utilize. Because it is shipping chemicals in-state, however, and their destination is only a few hours away, the highway is the most direct and obvious choice. This means that the duty of moving the chemicals falls upon the backs of the large and inefficient semi-truck. On average, these diesel-powered trucks get 6.5 miles per gallon (Berg). As a result, the trip to the TNT plant, 242 miles long, will use approximately 37 gallons of diesel. Following this massive prelude, TNT manufacture can truly begin.
The TNT manufacturing process that takes place in Radford Army Ammunition Plant is yet another string of chemical reactions. RFAAP is capable of producing 50-55 tons of TNT per day (Radford Army 1), which is a staggering 2 tons per hour over a full 24 hour period. Hourly production is certainly higher than 2 tons per hour, though, since the facility and its employees most likely do not work for 24 hours straight without cessation. It seems that TNT manufacture is not a lengthy process, though it requires a decent amount of space for safety reasons; the entire RFAAP campus spans 4600 acres (“Radford Army Ammunition Plant”). As for the TNT, manufacturing is a “3-stage process performed in a series of reactors” (Emission Estimation 3). This process involves mixing chemicals together in large containers, using pumps to introduce the acids and to transfer the product between reactors (Emission Estimation 3). Since no heating or burning is involved, and the machines in the process do nothing besides mix the raw materials together, they most likely use electricity. RFAAP will probably utilize the same energy sources as the raw materials manufacturer in the TNT production process. However, since the process does not utilize a furnace, like sulfuric acid manufacturing, fossil fuel is not a necessary component. Once again, the sole use of renewable energy from Virginia’s hydroelectric and biomass power plants is not removed from the realm of possibilities. When the TNT is finished, only one more energy-consuming step remains, and that is transportation.
Previously, boundaries had been established with the intentions of determining the minimum amount of energy required in TNT’s product lifecycle; the nearby National Guard Armory, one obvious consumer of TNT, fits into these boundaries by being the closest recipient and thus requiring the least fossil fuels to reach. However, depending on how one chooses to define TNT’s life as a product and where that ends, distribution and transportation can end before TNT even leaves the manufacturing plant’s grounds. Although pure TNT blocks of varying size can be found, TNT “is more commonly encountered in synergistic explosive blends comprising a variable percentage of TNT plus other ingredients” (“Trinitrotoluene”). If TNT blends are considered a separate product from TNT, then it is reasonable to assume TNT’s product lifecycle ends when it becomes a raw material for the blend; despite this, tracking of the distribution cycle shall continue. The quickest path to the Armory is by road, a mere 5.4 mile drive that takes 11 minutes according to Google Maps. To deliver as much TNT as possible, the same diesel-powered semi-trucks used in the delivery of the raw materials would be utilized here with their average efficiency of 6.5 miles per gallon (Berg). Therefore, it takes 0.8 gallon of diesel to reach the National Guard Armory. Once it is in the hands of the military consumers, TNT is ready for use with minor preparation. While it does not require any energy (in the same sense that this research pertains to) to use, TNT is a secondary explosive, meaning it requires a more sensitive (easier to explode) initiating explosive in the form of “detonators and percussion caps” (Emission Estimation 2) to activate. Once activated, it produces a large amount of energy over an extremely brief time period. Simply put, there is no reuse, maintenance, or much of anything past this point, not even recycling or waste management; because of its explosive nature, TNT’s product lifecycle ends the moment it is used.
In conclusion, from an energy standpoint the lifecycle of TNT is not a particularly wasteful one. This is due mainly to location of facilities; as Radford Army Ammunition Plant is a manufacturer of vital military supplies, it makes sense that it would be close to military installations. There are civilian manufactures of TNT in the United States whose goods are used, for example, by the mining industry. However, as a weapon, TNT has only one possible origin, and that is Radford. Wherever TNT comes from, though, its lifecycle will end with a bang.
Following is a list of my failures and assumptions. First, here is how I addressed the 6 major sections (Raw Materials, Manufacturing, Processing and Formulation, etc.): because of the nature of TNT’s usage, there is nothing to write about in sections 5, Recycle, or 6, Waste Management. The fundamental acids for TNT production, although considered raw materials in labs and various industries, are not simply “taken out of the ground” (quoted from the Research Paper Writing Tips), and I explained the chemistry to give an idea of what machines are used so I could address my part. Although I simplified the processes, it still took an entire paragraph, so I decided to give the Raw Materials section 2 tidy paragraphs instead of one awkward, extra-large paragraph. The first one handles raw materials and processes, the second handles fuel and energy sources and transportation. I combined sections 3, Distribution, and 4, Use, because they were short. I imply that Radford gets materials from one source, but they most likely come from several plants given the massive TNT output. I know that Dominon Chemical Co., the raw material source, definitely has toluene, nitric and sulfuric acid, but I assume they also have Oleum because of my understanding of sulfuric acid production. I could not find the specific amounts of each raw material needed for a fixed amount of TNT; my estimation is that one truckload of materials will equal one truckload of TNT. I assume the semi-trucks make one-way trips, counting only the fuel it takes to get to each facility. Also, I assume that all semi-trucks use fossil fuel exclusively. I assume that all the heat-intensive processes are powered by electricity except in the case of the furnace. Staying within the boundaries of my research, all the energy used by all the facilities comes from Virginian power plants. I know not whether Radford uses energy provided by renewable or non-renewable sources. I said that TNT is more often encountered in blends, but I did not know how that would affect my product, so I chose to follow the lifecycle of pure TNT. I could find absolutely nothing on the National Guard Armory, except that it was there. The meaning of the word “energy” changes based on context and made my writing about energy in section 4 seem rather unclear, so I feel the need to clarify: the energy needed to activate the TNT is explosive energy generated by an initial explosion, not the same energy with which the rest of my paper deals. Finally, the largest assumption made is that the TNT made here is created through what my Group and I refer to as the old process. The new process is slightly different, and was created by Radford to reduce waste and become more environmentally friendly. My part is not tangibly affected depending on which process is used, except that Oleum is not used in the new process, and toluene is nitrated before becoming a raw material. We chose the old process because there was more information about it.
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December 9, 2014
Professor Christina Cogdell
Wastes and Emissions of TNT
Trinitrotoluene, most commonly referred to as TNT, is known for being an explosive. TNT is mostly associated with war and the military. Radford, a production facility of TNT, emits thousands of toxic chemicals into the environment ever year in order to keep producing TNT. The emissions released from making TNT are far more harmful than regular green house gases. Not only are toxic chemicals released into the air, but they can also spread by water and land. It is highly important to take precaution when dealing with TNT or even living in an environment near an area exposed to this product. Exposure to high levels of these emissions can result in serious health problems. Many people know the main purpose of TNT, but they rarely know how much waste and emissions are created in order to produce TNT.
Along with any production process, there is usually some type of output whether it is waste or byproducts that come out of extracting raw materials. In this case, Radford does not make their raw materials. They actually get their raw materials from other manufacturing facilities. The assumption was made that no toxic byproducts were extracted since raw materials do not primarily come from Radford. Although, there is pollution emitted into the air through the transportation of these materials from one destination to another. The assumption is made that the transportation of these materials takes place in a semi-truck. It was hard finding information on Radford’s raw materials. Most sites only talked about how the process started and what chemicals were needed. There were not any sources that stated if Radford made their raw materials from scratch or if they get them transported to their facility.
Within the last seventy years, a community developed within five miles of the manufacturing facility. This exposed thousands of people in the community to the toxic emissions released by Radford, whether it was air emissions or emissions released into “surrounding waters” (Wikipedia). Emissions to the air come from leaks in equipment and valves, vents, open doors in the building and spills and material handling. Emissions to water occur when toxic substances reach sources of water such as “dams, lakes, rivers, and coastal waters” (NPI). In the old process, one of the first steps to form TNT is nitration. This is when toluene and a mixed acid are nitrated together to form crude TNT. Nitration is a chemical process that takes a nitro group and combines it to an organic chemical compound. From this nitration, nitrogen oxides, sulfur dioxide, and spent acid are produced as byproducts. Spent acid is a “regeneration and production” of sulfuric acid (Wikipedia). This spent acid is the only byproduct that is recycled back into the entire process. It is only recycled back into the nitration step. The other byproducts offer no other use in this process. There is not much recycling of chemicals or products that get used for anything else for the manufacturing and production of TNT.
Products travel many miles to reach consumers whether it involves boat, train, plane, or automobile and produce greenhouse gases. With the assumption that Radford uses semi-trucks to distribute their TNT to consumers, the conclusion can be made that green house gasses are in fact emitted into the air. Semi-trucks use diesel gasoline, which release several pollutants into the air. The pollutants emitted into the air include: volatile organic compounds, THC, CO, NOX (nitrogen oxides), PM10 (regulated pollutant), and PM2.5 (fine particulate) (EPA2008). By looking at table 1 provided, it is clear to see the comparison of emission rates between gasoline and diesel fuel. Heavy-duty diesel vehicles (HDDV) do not seem to release as much green house gases into the environment as heavy-duty gasoline-fueled vehicles do (HDGV). For certain gases though, heavy-duty diesel vehicles do emit more. Table 2 shows the average emission rates of vehicles based on different weight classifications and the type of fuel. In summary, the level of pollution released into the environment reflects on the type of transportation used. Transportation is not the only thing that emits pollutions into the air. There are other things to consider especially when it comes to thinking about the consumers and the precautions they should take.
Every explosion will have a reaction. Many people correlate energy as the ability to do work. Explosions from TNT occur as large amounts of stored energy convert to heat in a “confined” space (Ni). A significant amount of energy is necessary for this process to occur. In fact, one pound of TNT consists of 2723J of energy (Ni). The gas expansion and extreme build up of pressure causes the explosion and forces debris to fly everywhere in its surroundings. The handling of a product like TNT should be handled with caution due to the effects caused by exposure. People expose themselves to TNT simply through breathing, eating, touching, and drinking (DHSS). When exposure occurs, the bloodstream absorbs TNT which then travels to the organs” within the body (DHSS). For humans with high levels of TNT exposure, the chances of developing blood disorders and liver problems increase. This also shows to be true for animals, and unfortunately male animals appeared to experience reproductive problems in addition to the other health issues. Radford’s primary consumer is the military. That makes sense considering the uses for TNT.
The recycling process of TNT regarding chemical, water, and air pollution outputs do not involve many things. No recycling actually takes place after the use of TNT. The old process involves no recycling after the use of TNT. On the other hand, due to yearly enormous amounts of nitrogen oxide and carbon monoxide emitted into the air, Radford created a new system that decreases the amount of toxic airborne emissions by “ten tons”. In order to make this decrease in emissions every year, they started capturing the emissions in an “effective weak nitric acid crystallization process” (Elliott). This change became know as the new process. The main reason for the new process was because they needed a more cost effective way to produce TNT and a way to be more eco-friendly. The emissions created end up sent through a fume abatement tower and carbon monoxide oxidizer, which completely eradicated the step responsible for the “significant quantities” of nitrous oxide (Elliott).
Degradation of TNT occurs mostly in surface soil found in bomb ranges or areas of military and war. For the next step to occur, it needs to reach surface water. The surface water allows the TNT to undergo photolysis at a vast rate. Photolysis is a chemical reaction that breaks down chemical compounds by photons or by the absorption of light (EPA). In this reaction, photodegradation occurs to several degradation products and 1,2,5-trinitrobenzene is the primary one. In addition to degradation, TNT also exhibits biodegradation, but at a less hastily rate in water (EPA). The main products for biodegradation include: 2-amino-4, 6-dinitrotoluene, 2,6-diamino-4-nitrotoluene, and 2,4-diamino-6-nitrotoluene (EPA). TNT contributes to environmental hazards due to the waste produced throughout the formation process. TNT enters the environment through: spills, firing of munitions (war weapons), disposal of ordnance (military weapons and ammunitions), leaks from inadequately sealed impoundments, demilitarization of munitions, and manufacturing and processing facilities (EPA). TNT emissions can be categorized into three sections: air, water, and land. There is no dump for the old process, but there are nitrator vessel dumps in the new process. The nitrator vessel dumps store emissions from the fume abatement tower and the carbon monoxide oxidizer stated earlier. Once they are full, maintenance tanks collect the dumps. There was a failure on finding information on what Radford does with the maintenance tanks after they do their collecting. There was no information that could be found about it, the sources only said that the dumps were collected.
The overall process to produce something like TNT is complex and has many steps to it. Most of the steps are chemical processes. It is interesting that Radford does not make their own raw materials, especially when their starting chemicals need to be pure. It was hard finding information about this part, which is why the assumption was made that semi-trucks are probably used to transport the needed raw materials to Radford, from wherever they order from. The emissions that Radford releases definitely impact the surrounding environment. The amounts released from the old process were way too high, therefore they needed to find a new process to decrease the emissions and become more eco-friendly. That is very important because they are affecting people’s lives. Exposure to these toxins can really damage a person’s health. The new process was better because it proved to be more cost effective. Radford was able to recycle a byproduct as well as market it towards mining manufacturers. There was difficulty in finding information relating to this because most sources were not specifying which process they were referring to, either the old or the new. TNT requires huge amounts of energy to get an explosion. The debris from the explosions go into surrounding areas and contaminate water sources. The only thing recycled from the production process is a form of sulfuric acid. Most byproducts are just waste. The hardest part about this product was the fact that the life cycle of TNT is short. There is not much left TNT does after it is used by the consumer. Most of it is just emitted into the environment and nothing gets recycled. There are a lot of things that go into making TNT that many people do not realize. They do not think about the amount of waste and emissions that are produced and released, the recycling if anything, and what happens after it is used.
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