Alth, Constructing & Maintaining Your Well & Septic System [water well books often discuss cable tool and rotary drilling]Kurlansky, Salt : A World History.Encyclopedia Americana (note articles on "Petroleum", "Gas, Fuel," "Geophysical Exploration," "Wells and Well Sinking," "Artesian Well," "Pumps," "Tanker," "Oil Sand,"
"Oil Shale," "Paleontology," "Rocks-Petrology," "Coal Liquefaction," "Salt Dome,"
"Salt," "Pipeline," "Tanker," "Asphalt")
I have been informed that Grantville has both the 1911 Encyclopedia Britannica and a more recent
edition.While it is not in the Mannington Public Library, I would be very surprised if none of the local Oil and Gas Festival buffs owned a copy of McKain"s Where it all began: the story of the people and places where the oil & gas industry began: West Virginia and Southeastern Ohio (1994).
Works Consulted by the Author (starred references are of particular interest) Petroleum Geology and Prospecting Lalicker, Principles of Petroleum Geology (1949) North, Petroleum Geology (1985) Crump, Our Oil Hunters (1948)
Gould, Covered Wagon Geologist (1959) *Pearson, Surface Marks of Oil Deposits (1920) *Hager, Practical Oil Geology (1951) Ver Wiebe, Oil Fields in the United States (1930) Dobrin, Introduction to Geophysical Prospecting (1976) Nettleton, Geophysical Prospecting for Oil (1940) King, Stratigraphic Oil and Gas Fields: Cla.s.sification, Exploration Methods, and Case
Histories (1972)
Moody, Petroleum Exploration Handbook; a Practical Manual Summarizing the Application of Earth Sciences to Petroleum Exploration (1961)Cunningham-Craig, Oil Finding (1921)*Ver Wiebe, How Oil is Found (1951)Egloff, Earth Oil (1933)Levorsen, Geology of Petroleum (1967)Lalicker, Principles of Petroleum Geology (1949)*Tiratsoo, Petroleum Geology (1951).Hobson and Tiratsoo, Introduction to Petroleum Geology (1975)Blakey, Oil on Their Shoes: Petroleum Geology to 1918 (1985)
Petroleum Engineering (Drilling and Production) Thomas, Principles of Hydrocarbon Reservoir Simulation Muskat, Physical Principles of Oil Production (1949)Crichlow, Modern Reservoir Engineering: a simulation approach (1977)Pirson, Oil Reservoir Engineering (1958)Clark, Elements of Petroleum Reservoirs (1960)*Brantly, History of Oil Well Drilling (1971)*American Petroleum Inst.i.tute, History of Petroleum Engineering (1961)(HPE)Inst.i.tute of Petroleum, "Oil, A Natural Resource"
Oil Economics Grayson, Decisions under Uncertainty : Drilling Decisions by Oil and Gas Operators (1979) Harbaugh, Probability Methods in Oil Exploration (1977) Thompson, Oil Property Evaluation (1984) Campbell, Oil Property Evaluation (1959)
American Oil History *Williamson and Dunn, The American Petroleum Industry (1963) (2 vols.; v. 1. The Age of Illumination, 1859-1899. v. 2. The Age of Energy, 1899-1959.)*Olien and Olien, Easy Money (1990)*Fanning, Rise of American Oil (1948)Donahue, Wildcatter: The Story of Michael T. Halbouty and the Search for Oil (1983)Mallison, The Great Wildcatter (1953)Ezell, Innovations in Energy: the Story of Kerr-McGee Franks, Early Oklahoma Oil-A Photographic History 1859-1936 (1981)*Giddens, Early Days of Oil (1948)Giddens, Pennsylvania Petroleum, 1750-1872 (1947)Rister, Oil! t.i.tan of the Southwest (1949)Roberts, Salt Creek, Wyoming; the story of a great oil field (1956)Rundell, Jr., Oil in West Texas and New Mexico: A Pictorial History of the Permian Basin (1982)Tennent, The Oil Scouts: Reminiscences of the Night Riders of the Hemlocks 1915 (1986)Hughes, Oil in the Deep South (1993)Latta, Black Gold in the Joaquin (1949)Welty and Taylor, Black Bonanza (1958)Clark, The Last Boom (1972)O"Connor, The Oil Barons: Men of Greed and Grandeur (1971)White, Formative Years in the Far West: a history of Standard Oil Company of California and predecessors through 1919 (1976)Franks and Lambert, Early Louisiana and Arkansas oil : a photographic history, 19011946 (1982)*Clark, The Oil Century (1955)Clark and Halbouty, Spindletop (1952)Marcossan, Isaac F., The Black Golconda: The Romance of Petroleum (1923-4)Presley, Saga of Wealth: The Rise of the Texas Oilmen (1934)Getty, My Life and Fortunes Abels, The Rockefeller Billions (1965)Knowles, First Pictorial History of the American oil and Gas Industry, 1859-1983 (1983) West Virginia Geological and Economic Survey, "History of WV Mineral Industries - Oil and Gas"
Storage and Transportation *Wilson, Oil Across the World (1946).
Labouret, "A World Athirst for Oil; from Square-Rigger to Supertanker," UNESCO Courier, June, 1984
European Oil Fields Scholle, "Petroleum-Related Medals and Tokens" Oil Museum *Harvard Business School, Oil"s First Century (1959) (HBS) Tiratsoo, Petroleum Geology 121-139 (1951)Implications for Oil Potential in the Rhine Graben"
Nigeria Nigerian Oil Fields photo of inland drilling barge in Nigeria www.nigerianoil-gas.com/industryprofile/index.htm and www.nigerianoil-gas.com/industryprofile/niger-detla-fields.htm Trinidad and Venezuela Barbour, "Privateers and Pirates of the West Indies," American Historical Review, vol 16, No. 3 (Apr., 1911), 529-566.Porter and Prince, Frommer"s Caribbean 2004 (p. 661) Lonely Planet, Chaitan, "A Gravity Investigation of the Pitch Lake of Trinidad and Tobago,"
"History of Trinidad"s Oil" Tiratsoo, Petroleum Geology pp. 250-69 (1951).Seaman, "Trinidad"s Pitch Lake""How Ancient People and People Before the Time of Oil Wells Used Petroleum," Trevelyan, Sir Walter Raleigh (2002)Lacey, Sir Walter Raleigh (1973)
Other Regions Al-Ha.s.san and Hill, Islamic Technology: An Ill.u.s.trated History (1986)Tiratsoo, Petroleum Geology (1951)Yergin, The Prize: The Epic Quest for Oil, Money, and Power (1992)Temple, The Genius of China: 3,000 Years of Science, Discovery and Invention (1986)
General Oil and Gas Industry Boatright, Folklore of the Oil Industry (1963) *Anderson, Fundamentals of the Petroleum Industry (1984) *Ball, The Fascinating Oil Business (1965) Deaton, U.S. Patent No. 2,299,803 American Oil & Gas Historical Society (museum links) Malkamaki, Blake, "Oil History: An Index to Early Petroleum Historical Sites"
Oil and Gas Museum, Parkersburg, WV *Pees, Oil History *"Petroleum," 1911 Encyclopedia Britannica
General Geology Levin, The Earth Through Time (1991) Cooper, A Trip Through Time: Principles of Historical Geology (1986) Gilluly, Principles of Geology (1968) Chesterman, Audubon Society Field Guide to North American Rocks and Minerals (1979)
General History, History of Technology James and Thorpe, Ancient Inventions: Wonders of the Past (1994).
Teresi, Lost Discoveries (2002) "A Brief History of New Sweden in America"
"Cast Iron Pipe through the Ages,"
Gies, Cathedral, Forge and Waterwheel: Technology and Invention in the Middle Ages
(1994).
Clarkson, "History of Alsace and Lorraine"
*Kurlansky, Salt: A World History (2002) "Animal Treadmills on the Farm"
Vogel, "A Short History of Animal-Powered Machines: What Goes Around Comes
Around, and Does Useful Work" Natural History (March 2002) Miscellaneous Chemlink, Benzene *West Virginia Library Catalog gateway (includes Mannington Public Library) History of Mining in Cape Breton Coal Tar MSDS USE Map *Encyclopedia Americana *1911 Encyclopedia Britannica *current Encyclopedia Britannica
How To Keep Your Old John Deere Plowing: Diesel Fuel Alternatives For Grantville 1631-1639
by Allen W. McDonnell.
The Ring of Fire has left many of the farms around Grantville scrambling to train enough horses for the fall harvest. About half of the tractors that came through the Ring Of Fire were designed to burn gasoline and with the help of the agriculture department they will be converted to use pressurized natural gas in its place in 1631. Grantville has an abundance of natural gas; therefore, this conversion will put half of the modern equipment back into service for the first year. The tractors that are the topic of this article are farm size tractors, not the smaller lawn tractors people with large yards like to use for mowing their gra.s.s. The small lawn tractors are mostly gasoline, powered but with conversion to run on natural gas they will come in handy for a lot of other jobs outside the farming industry. Examples of those alternate uses include the drawing of wagons and carriages designed for horses or serving as stationary PTO sources to operate machinery where electricity is not easily available.
With the exception of the old steam tractor, which was being rebuilt for the county fair, the rest of the tractors that came through the Ring of Fire are diesel engined machines. These diesel machines are st.u.r.dy beasts of burden; some of them are 30 years old and still running well. Several of the farms have their own diesel fuel storage tanks and can keep their equipment in the field with a little extra effort. In addition to petroleum diesel in these farm grade tanks, some isolated farms and homes outside of town use heating oil #2 in oil furnaces. Heating oil #2 is almost identical to farm grade diesel fuel #2 and burns quite well in diesel engines.
The question of how to keep these diesel tractors and the modern diesel trucks and cars also in the area fueled is the central focus of this article. Four different fuel alternatives and one fuel additive are explored. First is the petroleum diesel that came through the Ring of Fire and additives to it, including propane. Direct use of biologically derived oil is a second method, and the easiest short-term solution. Third, for the long run beginning in late 1634 the most likely method will be to burn crude diesel refined from petroleum sources. This crude diesel is easy to make once petroleum is available. Until that time, however, it would be a waste to let the diesel engines in Grantville sit idle. Finally, there is bio-diesel, which is a form of diesel fuel made from biologically derived oil.
Two methods are available to extend the petroleum derived diesel in up-time tanks. The first method is mixing. Any diesel engine, modern or archaic, will function quite well on a mix of 75% petroleum refined diesel and 25% light vegetable oil. Of course, this presumes the availability of cheap vegetable oil, which may be problematic in seventeenth-century Germany. The second alternative, if a competent mechanic is available, is to add propane injection to the diesel engine. Propane injection, also known as fumigation, will give an increase in diesel combustion efficiency. The propane acts as a combustion catalyst during the power stroke of the cylinder. If you are not a good mechanic let an expert do the conversion, otherwise you may get the propane amount too high and cause severe engine damage. When a turbo-charged diesel engine is properly fumigated with propane it will get a boost in torque and fuel economy resulting from the more complete combustion of the liquid fuel. Typical tractor engines are not turbo-charged and will only receive a small boost in efficiency from propane fumigation; many diesel farm trucks and pick-up trucks on the other hand are turbo-charged and would greatly benefit. No information is available on propane fumigation for engines that burn unrefined plant or animal oils; however with diesel or bio-diesel the engine boost amounts to a 10% increase in fuel economy. Combined with a 25% light vegetable oil mix in the fuel, this will total up as a 38% increase in fuel economy per unit of petroleum derived diesel used. The propane tanks used for this fumigation are generally the same ones found on backyard barbecue grills. With proper treatment some propane can be recovered from raw natural gas and used to refill these tanks if the knowledge and ability to install them on the diesels is available.
One of the most surprising things to come to light in researching this article was how easy it is to produce propane and butane from raw natural gas. Both propane and butane may be adapted to power gasoline engines where they provide 80% of the range of an equal volume of gasoline. This is an increase in range of 240 to 1 over low-pressure natural gas. To refine butane and propane out of raw natural gas you can follow any of several methods. The easiest one to explain is condensation.
Butane vaporizes at just below the freezing point of water, and propane vaporizes at about 45 degrees F below that. Using a metal coil run through a freezer you can condense butane out of the raw natural gas at about 10 degrees below freezing. The liquefied butane is separated out through a drip tube and stored in a regular propane cylinder like those used on portable backyard barbecues. When removed from the freezer, the butane will naturally warm to ambient temperature but will remain a liquid in the tank due to vapor pressure. If sufficient (probably cascaded) freezing is available, the partially refined natural gas can then be fed through a second condensing coil in a much colder freezer at about 30 C where the propane condenses. The propane may also be stored as a liquid under pressure in another tank. Natural gas in the eastern USA averages about 10% butane-propane-ethane and 90% methane. Using the freezing condenser method above refines about 2% butane and 4% propane by volume from the raw natural gas.
The second method to conserve up-time diesel works best with older diesel engines, but with a relatively simple heating set it will work for modern diesel engines as well. The newer machines in the diesel group can run on straight vegetable oil (SVO), or the animal equivalent, with a simple tank and fuel system heater added. These modifications involve installing a simple resistance heating element in the fuel tank, very similar to the ones used in engine blocks for winter weather. This can even be an electric heating pad fastened onto the bottom of the fuel tank. When the engine is not running, the heating element can be connected to an electrical outlet, to maintain a hot liquid oil temperature in the fuel tank and fuel system. While the engine is running, the waste heat from the liquid cooling system takes over. A copper tube is wrapped around the exterior of the fuel tank and attached to the tractor cooling system between the engine block and the radiator. This copper tube forces the hot engine coolant to circle the fuel tank several times before going to the radiator and maintains the oil as a hot liquid.
Hot and thin waste cooking oil or fresh vegetable oil burns just fine in older diesel engines; those that predate late twentieth-century pollution controls can be expected to have zero problems. Lighter oils such as corn or soybean oil work best. If the oil is kept sufficiently hot and thin; tallow, b.u.t.ter or lard can also be used as fuel. If bio-diesel or stockpiles of fossil fuel derived diesel are available, it is recommended that a small diesel tank be added to the newer equipment. This will allow the more refined fuel to be utilized when starting the engine and bringing it up to full power. Once at full power, one can switch to the biologically derived unmodified fuel oil. About five minutes prior to shutting down the engine, it should be switched back to the refined fuel. While these modifications are not mandatory, they do ensure that the equipment will have very little problem with clogged fuel injectors. The refined fuel serves as a fuel system cleaner during startup and shutdown, purging the lines and filter. Using refined fuel in this supplemental tank requires less than one percent of the total fuel supply for the newer vehicle and keeps the fuel pump and filter full of refined fuel when the equipment is shut off. This in turn helps prevent any pitting or premature wear that in some rare cases may be caused by free fatty acids that are present in all unrefined biologically derived fuel oils. Of course, again, this technique is dependent on the availability of animal or vegetable fats.
The third supply of fuel for the up-time diesel engines that came through the Ring of Fire will be crudely refined from down-time petroleum, most likely the Wentz oil fields. These oil fields are well known. Drilling for petroleum in this location has begun in 1633. Modern style multiple fractional distilling however, is several years in the future and only the much cruder pot distilling method will be available for several years. Pot distilled diesel fuel is very crude compared to that which came through the Ring of Fire with Grantville. The older diesel equipment, both the farm tractors and older farm trucks, can burn this crude diesel with minimal problems. The more modern heavy equipment, cars, and turbo-charged trucks on the other hand will suffer if they must use it. Crudely refined diesel tends to be high sulfur and it also has a broader range of chemicals in its mix. The turbo-charged engines of the late twentieth century are specifically designed to produce low exhaust emissions burning highly refined fuel with very low sulfur content and do not run well on crude diesel. To a small extent removing pollution controls on these engines will help, however the fuel filter and pump systems will be very hard to duplicate or modify until Grantville has built up an extensive manufacturing capability. Added to these difficulties is the expense of hauling either the crude petroleum or crudely refined diesel from the Wentz area to Grantville. This adds even more cost and complexity to the task of keeping the modern diesel engines of Grantville operational. The available hauling methods amount to wagons loaded with heavy oil barrels hauled over dirt pathways, with the option of using a barge for portions of the trip. All of the loading, hauling, unloading and reloading involved, when combined with wages and supplies for the teamsters and fodder for the livestock, make this process slow, complicated and expensive.
The medium-term solution to the general diesel fuel supply problem and the medium- to long-term solution for the modern diesel equipment is to create an alternative to the crude pot distilled diesel that will be coming from the Wentz petroleum fields down-time in 1634 and later. Bio-diesel can fill the gap during the period between 1634 when the crude refinery will be available and the projected fractional distillery five to ten years in the future.
What is bio-diesel? Regular cooking oil, no matter if it is vegetable oil or pork drippings, consists of triglyceride molecules. A triglyceride molecule consists of three fatty acid molecules that are bound to one glycerol molecule. The longer the fatty acid molecules, the more viscous the oil is. To make biodiesel the triglyceride molecules have to be broken down to separate out the glycerol, which is a useful byproduct of the whole process but not a good thing to burn in a modern computer-controlled diesel engine. The easiest method of separating the glycerol from the triglyceride molecule is to break it down with a catalyst and subst.i.tute another alcohol molecule for the glycerol molecule. Most recent tractors and modern diesel farm trucks can have problems burning raw cooking oil; these engines work much better when operating on bio-diesel fuel.
Feedstocks to be used to manufacture bio-diesel will not be cheap to acquire. There is very little waste oil and fat to make fuel from. Most fats are eaten. Transportation costs in the 1630"s were extremely high, effectively doubling the cost of any raw materials transported a long distance due to taxes, tolls and labor expenses. One possible plant oil source in 1631-1633 will be the traditional seed crops grown by the local farmers as livestock feed. This leads to resource compet.i.tion for any food crop such as oats or rice and it is believed that they will be only minor sources for biological oils. In 1631 linseed oil averaged 40 guilders per aum in Amsterdam, with one aum roughly equal to 30 gallons. With a monetary exchange rate of 50 to 1, a gallon of linseed oil in Amsterdam would cost $60.00, or about $120.00 per gallon by the time it is transported to Grantville.
The most economic animal derived oils in 1631-1633 will be cod liver oil, which sold for 60 guilders per tun, with one tun roughly equal to 252 gallons, or just over 4 gallons per guilder. This gives a price of about $11.91 in Amsterdam or $25.00 per gallon delivered in Grantville. As a final example tallow, made from the fat of cattle and sheep, sold for 16 guilders per 100 pounds. One gallon weighs six pounds so each gallon costs just over 1 guilder in Amsterdam and would be about twice that in Grantville, $100.00 per gallon.
While many people like the idea of corn oil because corn is available in Grantville, at the 2004 minicon the West Virginia extension agent explained that the Mannington area was a gra.s.s-based agriculture and that corn was not grown in Marion county. Corn crops will have to be built up from small amounts of seed, which will take years. Additionally, other oil crops have a much higher yield. Corn has an average yield of 18 gallons of oil per acre while pumpkin seeds yield 57 gallons per acre. Sunflowers seeds yield 102 gallons and pecans 191!
While the corn and sunflowers used in this example are modern hybrids with very good yield per acre, that would likely decline over the course of years. Pumpkins on the other hand are bred for size and weight, not seed content, and should remain fairly constant.
Another biological oil source is cow"s milk. This can be made into b.u.t.ter at a ratio of about 21 pounds of milk to 1 pound of b.u.t.ter. Cow"s milk weighs about 8 pounds per gallon and this means that for every 3.5 gallons of fresh milk you get 1 pound of b.u.t.ter. Six pounds of b.u.t.ter yields about a gallon of biodiesel. A good down-time milking cow will yield about 1 gallon a day of milk when in season. Therefore, every cow in the pasture has the potential to produce about 8 ounces of bio-diesel per day while in season. Because down-time milk is a seasonal product the local people are not conditioned to getting b.u.t.ter with every meal as the up-timers do. To entice them to sell the b.u.t.ter instead of eating it will be expensive, but not impossible. A package deal could be made to purchase the cooking oil, the pork drippings, and the lard given off by cooked beef or mutton along with the b.u.t.ter. To make it attractive for the down-time farmers up-timers would need to offer a moderate income, otherwise they will eat the b.u.t.ter and grease. The added benefit to down-time farmers of having up-time farmers help with planting and harvest will also encourage them to provide oil and some b.u.t.ter.
Animal fats tend to have longer fatty acid molecules and hence are thicker than most plant oils. Some common examples of this are tallow, lard, pork drippings and b.u.t.ter. On the contrary side, some plant oils like coconut oil are very thick in their own right, but few of these are present in Europe in the seventeenth century. Much more common will be linseed oil, which is made by pressing the seeds from the flax plant that is grown throughout northern Europe to provide flax for linen cloth. Any viable sunflower or safflower seeds that made it through the Ring of Fire will need to be conserved and planted; they yield considerable oil and the pressed seeds make good livestock feed after the oil has been extracted. Corn, soybeans and cottonseeds are also good sources of vegetable oil but do not yield as much per acre as sunflower seeds. Making bio-diesel from any of these biological oil supplies will require a moderate knowledge of chemistry. The high school chemistry teacher, his lab a.s.sistants and Frank Stone all would be able to follow the simple recipes given in this article and produce a product that would burn correctly in modern diesel engines.
Most people who "home brew" bio-diesel use methyl alcohol, also known as methanol, because it is cheap and is the easiest alcohol to use. Methanol is made industrially by combining natural gas, heat and steam through a series of catalytic chambers. The end result is a very pure form of methanol which can be burned in modified Otto-cycle engines, used as an industrial solvent, or used as the starting point in manufacturing products like bio-diesel fuel. Methanol is being produced down-time, and is a major component of the fuel for the down-time air force.
Larger bio-diesel processing plants usually use ethanol, also known as moonshine, because it is easy to produce on an industrial scale. Ethanol is much less toxic than methanol if it is accidentally spilled or the vapors are inhaled. Methanol is a nerve poison. It can cause blindness followed by death if it is swallowed, absorbed through the skin, or the vapor is inhaled. Ethanol used in the bio-diesel process must be 199 proof or higher. You cannot just distill it; you have to dry it completely afterwards. Fortunately, you can dry ethanol to 199 proof by straining it through a tank filled with diatomaceous earth. The diatomaceous earth can be reused indefinitely. After a batch of moonshine is fully dried out the earth is gently heated and the water is driven off as low energy steam. When the heated diatomaceous earth stops steaming the heat is removed immediately and it is allowed to cool before more distilled ethanol is poured through it for drying. Methanol is not as sensitive to water contamination and if all you have is 190 proof moonshine you might be able to force the process to work by subst.i.tuting 40% methanol in the process, but there are no guarantees.
Diatomaceous earth is also known as kieselguhr and has been mined in Thuringia since at least the 1860"s. It consists of the fossil remains of millions of nearly microscopic water plants that form beds of tiny seash.e.l.ls. It is almost pure silicon dioxide; the same stuff sand is made from, but with hollow centers. This makes diatomaceous earth very absorbent, and an excellent filter. It was be the preferred material used by Alfred n.o.bel in the late nineteenth century in the manufacture of dynamite up-time.
Two different catalysts can be used for the bio-diesel conversion process and both are commonly called lye. Cleaning lye (NaOH), also known as sodium hydroxide, is very slowly and carefully added to the methanol to form a compound called methoxide. Alternatively potash (KOH), also known as pota.s.sium hydroxide, can be used and is available by dripping boiling hot water through wood ashes and through a filter, then evaporating off the water to leave crystalline pota.s.sium hydroxide.
Bio-diesel is made by subst.i.tuting the glycerol in biologically derived oil with light alcohol molecules such as methanol or ethanol. Because it is a subst.i.tution process you get the same volume of materials out as you put in. Biological oil and alcohol go in, bio-diesel, glycerol and a little soap come out.
Small Batch Process Beware! The methoxide reaction is exothermic. It releases large quant.i.ties of heat and if done too quickly will release deadly methanol vapor or explode in your mixing chamber. For unused oil the average ratio of lye to methanol is 3.5 g sodium hydroxide lye or 4.9 g pota.s.sium hydroxide to 200 ml of methanol per liter of oil. Pota.s.sium hydroxide is less reactive than sodium hydroxide so you need 1.4025 times as much. 1.4 works fine for the small batches you would be making at home. When the methoxide solution is slowly added to the heated oil and stirred, the lye acts as a catalyst. It strips the fatty acids from the triglyceride molecules in sequence by reacting with the fatty acids directly. The process creates first one free fatty acid and a duoglyceride molecule, then a second free fatty acid and a monoglyceride molecule, and then ultimately a third free fatty acid and a free glycerol molecule. As each of the free fatty acids separates, it is in a reactive state and quickly binds with one of the methanol molecules in the mix, forming a methyl ester molecule.
If too much lye is added to the mix it will attack the methyl ester molecules once all of the glycerides have been broken down into glycerol and free fatty acids. In a normal reaction with fresh oil most of the lye will mix with the glycerol, which is denser than the methyl ester solution and naturally separates into layers after the stirring is stopped. The methoxide and oil mixture is stirred for an hour while being kept at a moderate temperature of 130 degrees Fahrenheit, which is the temperature of hot water straight out of your average hot water heater. Much hotter than this and the methanol will boil out of the mix. This results in poisoning and also means it will not be available to react with the free fatty acids in the mix to form methyl ester. Any of the above mentioned biologically derived fats are appropriate for this use.
If you are using oil that has been kept at high temperatures for an extended period of time, such as waste fryer oil, it will have a lower pH level. In this case you would need to increase the lye portion in the methoxide solution to compensate for the increased acidity of the used oil. To do this most accurately you would need a pH meter or simple litmus paper, which should be available before the end of 1632. As a general rule you will need a 20% increase in lye for used cooking oil and the end product will contain more soap than you would get with fresh oil. For recycled used cooking oil you need to not only increase the lye concentration 20%, it is also helpful to dry out the used cooking oils as much as possible. This is done by heating the used oil to about 190 degrees Fahrenheit and maintaining that temperature for 15 minutes to drive off all suspended water in the oil. Make sure you allow the oil to cool to 130 degrees Fahrenheit before adding the methoxide or the methanol will vaporize back out and poison you. Having too much methanol in the mix results in more methanol in the crude glycerin, but does not cause any problems as a result. Having too much lye does cause problems. When in doubt err on the low side for the lye component and increase the agitation or stirring time from 60 minutes to 90 minutes.
After an hour of mixing allow the mixture to cool to room temperature and stand for 12 hours. If you did everything correctly you will have light straw-colored liquid on the top of the settling tank and darker, thicker liquid in the bottom of the tank. If you have a proper settling tank with a spigot drain on the bottom, drain the glycerol mix into another container. If the tank does not have a drain, use a siphon pump to draw the liquid off the top of the tank into suitable containers, making sure to stop above the glycerin layer. This is the raw bio-diesel. More cautious people will wash the bio-diesel before utilizing it to remove the small percentage of free fatty acids, lye and soap that are suspended in it. If you wish to wash the bio-diesel, simply add a small quant.i.ty of water, about a quart per gallon, and bubble air through from the bottom of the container. The water will mix thoroughly with the raw bio-diesel causing bubbles to form on the top and the water to change to a milky color from absorbed impurities. To thoroughly wash the raw fuel you should wash it for several hours, let it settle, and drain the milky water from the bottom of the tank. Replace the dirty water with fresh water and bubble the tank for several more hours. Repeat as needed until the water returns to a clear color after the liquid separates. The top of the tank is bio-diesel solution and it is ready to use in your modern equipment exactly as is.
Once the raw bio-diesel is removed from the mixing tank, the mixture of lye, methanol, soap and glycerol, remaining at the bottom, is crude glycerin. Using a sealed still, gently heat the crude glycerin and capture the vapors distilled off in a cooling chamber. This will be about 20% of the total volume of methanol used in the methoxide mix. Through more difficult processing the lye can also be separated from the glycerol as a soap compound leaving nearly pure glycerol. Glycerol is a very valuable byproduct. It is nontoxic, tastes sweet, and can be used in a wide range of products from soap to diabetic friendly sweetener. It is also the foundation for nitroglycerin types of explosives. Glycerol can even be burned in modified kerosene lanterns giving off light and heat without the bad smells or indoor air pollution. It can also be added to crude jell soap as a conditioner.
For the near-term future most of the bio-diesel available in 1632 will be made by the small batch process given above. Once capital is raised for construction, a large batch industrial scale plant could be built to keep Grantville supplied with nontoxic bio-diesel made with the ethanol process. The ethanol process for making bio-diesel is somewhat more difficult as it requires more precise temperature and mixing processes to work correctly. This will only happen if petroleum derived diesel remains unavailable, as the most economic sources of biological oils will remain waste cooking oils and b.u.t.ter purchased from local farms for about $2.00 per gallon. The farmers will gain spending cash while giving up a seasonal resource that they could not transport to market for a profit.
The industrial process The first step in creating bio-diesel with ethanol is to prevent soap formation during the process. Soap is one of the by-products of the small batch process for brewing up bio-diesel. Soap is a chemical compound formed when the metal component of the lye, sodium or pota.s.sium binds with a free fatty acid and loosely attaches itself to a methyl or ethyl ester in the bio-diesel. These molecules in turn bind with water during the washing stage and draw the attached bio-diesel out of the solution. A similar process occurs when you use soap to wash your hands and body. The metal ions bind the water to the natural oils secreted by your skin as well as the dirt that is sticking to these oils. Raw soap does this so well that it will make your skin dry and chapped in short order. One of the first remedies for this problem with raw soap was to mix 20% pure glycerol into the formula, which acts as a conditioner and has the added benefit of being a disinfectant.
The first stage of the industrial process prevents the soap formation by eliminating the free fatty acid component, which is bound to the metal ions at the start of the soap chain of reactions. This is done by adding 98% pure sulfuric acid to the incoming oil. Any solution of less than 95% pure sulfuric acid will not work well for this process. Sulfuric acid in a lead acid vehicle battery is only concentrated to 50% but in the industrial processing plant they will make their own acid. At all costs avoid using other acids for the first stage. If you were to use nitric acid for instance, it would bind with the glycerol to form nitroglycerin and likely destroy not only the processing plant but a good piece of territory around it. Because you are using very dry sulfuric acid you must make sure the oil is as dry as possible by simply heating it and driving the water out before you add the sulfuric acid. If the oil has more than .5% water in solution it will derail the reaction, so the solution must be very dry. Once the oil is fully dry allow it to cool to 95 degrees Fahrenheit. Make sure that all of the solids in the oil such as lard or b.u.t.ter are completely melted. Add 12% pure ethanol by volume to the oil and mix for 5 minutes. Maintain the temperature and continue stirring while slowly adding 1 ml concentrated sulfuric acid per liter of oil. Stir at temperature for 60 minutes, remove the heat source and continue stirring for an additional 60 minutes as the solution slowly cools. Move the solution to the settling tank and let it settle for 12 hours.
Prepare sodium ethoxide by mixing pure 199 proof ethanol with pota.s.sium hydroxide. This is impractical for home use because the sodium hydroxide does not dissolve easily in ethanol, but for the industrial plant, sustained temperature and agitation of the mix will result in the compound needed. The pota.s.sium ethoxide mix is made at a ratio of 3.5 grams pf lye to 350 ml of ethanol per liter of oil undergoing processing. After 12 hours of settling, warm the oil mixture to dissolve the solid fats and mix at a low speed. Once the solids are dissolved, add 175 ml of pota.s.sium ethoxide solution per liter of oil, but do it slowly. The pota.s.sium ethoxide will neutralize the sulfuric acid creating pota.s.sium sulfide in the process.
The processing plant then raises the temperature of the neutralized oil mixture to 140 degrees Fahrenheit and maintains this temperature throughout the remainder of the process. An additional 175 ml per liter of pota.s.sium ethoxide is added to the oil mixture while stirring continuously for 30 minutes while maintaining heat. Allow the mixture to settle for 10 minutes. At the end of the settling period, the plant drains the settled glycerol from the bottom of the mixing chamber and removes the glycerin to the soap processing portion of the bio-diesel plant. Resume mixing for an additional 15 minutes. Then the processing vat repeats the settling and draining procedure. As the glycerin is settled out of the reaction chamber and drained off, the mixture will become lighter in color until it achieves a straw yellow color. At this point the mixing and heating are stopped and the product is allowed to settle for 60 minutes. After this long settling period the residual glycerin is drained off and the raw bio-diesel is transferred to the washing chamber. A very weak phosphoric acid water solution is used to wash the raw bio-diesel through three stages. The water is stirred with the raw bio-diesel for 60 minutes and then allowed to settle out for another 10 minutes between draining and water changes. After the third wash the refined bio-diesel is filtered through diatomaceous earth filters and placed in storage containers for sale.
Conclusion Feedstock for all of these processes will be expensive, and even using the oil collected for a fee does not change that fact. After 1634 petroleum derived diesel will be more economical to produce than biodiesel. In 1631 and 1632 the citizens of Grantville will have feedstocks of up-time fuel to consume, and these can be stretched with the addition of local waste oil at a ratio of 75% petroleum diesel to 25% waste cooking oil. By 1633 these up-time supplies will be exhausted, even with careful conservation and boosting through addition of local waste oils. This is the crucial year when bio-diesel would be most valuable to Grantville since it can be manufactured with relatively simple technology. Key materials for the process such as methanol, ethanol, and pota.s.sium hydroxide (lye) will already be in production for use as a gasoline fuel subst.i.tute and for soap manufacture. Diatomaceous earth will most likely have been found and quarried because it is located inside Thuringia. It is easy for an amateur geologist to identify and is useful for many industrial processes as an absorbent or as a filter. If a supply of diatomaceous earth does not get discovered before 1633, the safer ethanol process can be set aside in favor of the methanol process. Of fresh biologically derived supplies only cod liver oil, a by-product of the intensive north Atlantic cod fishing by the maritime nations, will remain cheap for the near- and medium-term future of 1631-1634. Buying b.u.t.ter from down-time farmers will supplement this source with a moderate economic cost, but is only available in quant.i.ty about 5 months of the year. With adequate supplies of the feedstock materials one competent up-timer using a 55 gallon oil drum, a low fire, thermometer, and stir stick should be able to make 100 gallons of bio-diesel per week, along with 20 gallons of glycerol and a gallon of soap. An amateur up-timer using the recipe given in this article would be able to make at least 45 gallons if they take extra time and caution at each step of the process.
In conclusion, without shorting any other critical resource, a small batch bio-diesel facility would give Grantville the crucial supply of fuel it will need in late 1632 through early 1634 to keep its diesel farm equipment and heavy mine trucks available for use. Due to the costs of transporting any of the materials for long distances, bio-diesel will only be economically feasible in localized areas such as in Grantville and in Magdeburg where the up-time diesel engines are positioned. Bio-diesel cannot compete with petroleum diesel except for this narrow window of time when highly refined fossil fuel is not available, but may be a vital fuel supply during that period of time. Additionally, liquid butane and liquid propane production is within the reach of Grantville from their natural gas supplies and can be used to power up time gasoline engines, and extend the fuel life of uptime diesel engines.
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