Sunday, June 26, 2016

Manufacture of Sulfur - IV

In our last post, we saw how Sicily was slowly losing dominance in the sulfur trade and how Britain became a major sulfur producer using the Claus process. In today's post, we will look at how the United States started dominating the business of sulfur production.

In the mid-1800s, the United States was producing sulfur, but only in small quantities. There were sulfur mines found in the Western United States, in Wyoming, Colorado, Texas, Utah, Nevada and California, but the total production of these mines couldn't keep up with demand and therefore, the US also imported a lot of sulfur from Sicily. Then, in 1867, a large sulfur deposit was discovered in Calcaseiu Parish, Louisiana by workers employed by the Lousiana Petroleum and Coal Oil Company (LPCO). Unlike the other places in the US, where the sulfur was found on the surface or close to it, this particular sulfur deposit was buried deep underground in a salt dome, covered by a layer of quicksand. Two years later, a geologist, Professor Eugene Hilgard, from the University of Mississippi, was brought in to study this deposit and he realized that this deposit was large enough to offer an alternative to sulfur imported from Sicily, although mining it would be a challenge. Professor Hilgard later moved to the University of California, Berkeley in 1875 and became Professor of Agricultural chemistry there, where he later studied wine making and his research was responsible for California becoming a major wine maker in the world today.

Meanwhile, LPCO officials decided to go ahead and try to mine the sulfur out of their discovery, but they could not do it because they only had licenses to mine coal and oil, not sulfur. Therefore, they sold their rights to another company, which sold it to another and so on. The problem was that while everyone knew that the sulfur deposit was there, no one knew how to get it out of the ground. Unlike the other sulfur mines, this one was located deep underground and there was a layer of quicksand in between and pockets of deadly hydrogen sulfide gas, that made mining the sulfur underneath impossible. Numerous attempts made in the 1870s and 1880s failed with the loss of many lives.

The solution to getting to this deposit was discovered in 1890 by Herman Frasch, a German-born American chemist.

Herman Frasch
Click on the image to enlarge. Public domain image.

Herman Frasch was born in Oberrot bei Gaildorf, Wurttemberg, Germany in 1851. At the age of sixteen, he migrated to the United States in 1868 and arrived in Philadelphia, where he joined the College of Pharmacy and began increasing his knowledge of chemistry. One of his first inventions was discovering how to separate tin from steel cans. Previously, tin had to be imported from Britain and the cost was passed down to anyone who bought a tin can. Later, he got interested in the field of industrial chemistry, specifically driven by the oil industry. He came up with a process of purifying paraffin wax, which was a waste by-product in oil refining until then, and after his invention, it could be used in many industries, such as waterproofing, candle manufacturing, preserving food etc. 

Then in 1885, he came up with a process to remove excess sulfur from oil. Oil with a large amount of sulfur in it was called "skunk oil" or "sour oil" because of its smell and poor burning characteristics, which made it unusable and very hard to sell. As it happened, the Standard Oil Company owned by John D. Rockefeller had found a large oil field in Ohio, where the oil had a lot of sulfur content in it, therefore he brought Herman Frasch in to solve the issue. The Frasch process he developed in 1888 to extract the sulfur from the oil was a huge success on an industrial scale. Previously, Rockefeller could only get about 16 cents per barrel, but after using the process developed by Frasch, he could sell it for over $1 per barrel. Considering that there were millions of barrels of oil sold, this made Rockefeller very rich. As Herman Frasch was also paid in shares of Standard Oil, he became very rich as well!

Incidentally, as modern laws for automobiles mandate using unleaded gasoline, oil refineries use sulfur extraction units to remove sulfur from crude oil to produce unleaded gasoline.

However, Herman Frasch wasn't done yet. He set his sights on the sulfur deposit that was found in Louisiana back in 1867 and bought some land there. But as luck would have it, the area containing the sulfur was not on his property. He took out multiple patents for his newly developed Frasch process in 1890 and 1891, formed the Union Sulfur Company in 1892 and then signed a contract with his neighbors to mine sulfur from their land. In 1894, the sulfur was successfully brought to the surface for the first time.

The Frasch Process. Click on the image to enlarge. Public domain image.

The Frasch process consists of using three concentric tubes, which are drilled through the earth into the sulfur deposit. The walls of the outer tube keep the quicksand from collapsing into the hole. Water is heated under pressure to produce superheated water (about 340 °F or 171 °C), which is then pumped in through the outer tube under high pressure. This heat is enough to melt the sulfur, which has a melting point of around 240 °F (or 115 °C). The molten sulfur flows through the middle tube, but since sulfur has a greater density than water, the water pressure is often insufficient to bring the sulfur to the surface. Therefore, hot air is pumped through the inner tube, which causes the molten sulfur to form a froth and reduces its density, which allows it to be pushed up towards the surface. All other substances have a higher melting point and remain underground. The sulfur obtained by this method is very pure (99.7% or greater) and needs no further refinement. The molten sulfur is then pumped into large containers and allowed to solidify in open air and the blocks are then broken up and directly loaded onto rail cars.

One major problem with this method was the cost of fuel for heating the water, but this problem was overcome in 1901 when oil was discovered a short distance away in Spindletop, Texas, which provided cheap fuel oil for the entire region and made the production of sulfur economically competitive with other sources. Due to the booming growth of sulfur mining, a small town was formed in the area around where Frasch built his mine, appropriately named Sulphur, Louisiana! The town of Sulphur still exists today and an elementary school there is named after Herman Frasch.

As a result of this process, the Union Sulfur Company became one of the top sulfur producing companies in the world and the United States displaced Italy as the world's leading sulfur producer. In 1903, Sicily had exported over 157,000 tons of sulfur to the US and 106,000 tons in 1904, but by 1906, they only exported 7000 tons, as the rest was made up by the Union Sulfur Company in America! The mighty Anglo-Sicilian Sulfur Company (ASSC) demanded that Union Sulfur stay out of Europe and demanded a share of the US market, but they didn't know Herman Frasch very well. His process gave him a huge manufacturing cost advantage over ASSC and Union Sulfur started dropping their price to the point where ASSC could not compete any more. By 1907, ASSC was out of business. In 1911, Frasch's patent for his process expired and other American companies in Texas and Louisiana started producing sulfur from salt domes all over the Gulf Coast of the United States.

The Frasch process dominated the world markets until about 1970 or so, when sulfur recovered as a by-product of oil refining and natural gas production (the Claus process we studied in our previous post) became significant again. The last US Frasch sulfur mine closed in 2000, but the process is still used in Mexico and Poland today.

Tuesday, June 21, 2016

Manufacture of Sulfur - III

In our last post, we saw how sulfur was extracted and purified in Italy (mainly Sicily) and then further purified in England for the purposes of manufacturing gunpowder. Up to the end of the nineteenth century, Italy was the main source of sulfur for both Europe and America. Therefore, both the British and the French tried to secure their supplies from Italy. In particular, the British managed to secure very favorable trading rights with Sicily in the early 1800s, thanks to rescuing their ruler from Napoleon Bonaparte's invasion. Soon, British, French and American merchants were all trying to get a piece of the Sicilian export market, with British merchants having the most control generally. Many of these British merchants were originally wine merchants, who got into the sulfur trade since they already had well-established transport networks and marketing connections with other regions of the world. There was a brief hiccup in 1839, when a French company named TAC (Taix, Aycard & Company, named after its two founders, Aime Taix and Arsene Aycard) managed to convince the ruler of Sicily, Ferdinand II, to grant them a monopoly and thereby increase the price of sulfur worldwide. This action caused many countries to manufacture sulfur from pyrites and import from other sources (such as Iceland) and nearly caused a war in 1840, before diplomatic efforts succeeded in negotiating a settlement. Nevertheless, sulfur produced from pyrites took a share of the market.

Then in 1883, Carl Friedrich Claus, working in London, patented a process called the Claus process, that allowed recovering sulfur from hydrogen sulfide gas. By 1887, Alexander Chance and C.F. Chance modified his process to process sulfur from the left over waste of the Leblanc process (which was used to manufacture soda ash (sodium carbonate), useful for glass, textile and soap industries). Until then, the waste product of the Leblanc process, which is calcium sulfide, was simply thrown into heaps outside the plant. The Claus-Chance process first converts the calcium sulfide to hydrogen sulfide, using water and carbon dioxide, and then extracts the sulfur from the hydrogen sulfide gas using the Claus process. Therefore, all those heaps of waste calcium sulfide that were thrown out earlier, could be used to extract the sulfur from them.

A pile of Sulfur produced by the Claus process in Vancouver, Canada. Click on the image to enlarge.
Image licensed under Creative Commons Share Alike 1.0 License by LeonardG.

Using the Claus-Chance process, England became the second largest sulfur producer in the world by the early 1890s.

The British also attempted to form a cartel to control the Sicilian industry, almost 55 years after the attempt made by the French Company TAC. The Anglo-Sicilian Sulfur Company (ASSC) was formed in 1896, which gained control of about 2/3rd of Sicily's export. In particular, they made some huge sales in the American marketplace, shipping it to many well known companies in the US.

However, there was danger to the Anglo-Sicilian Sulfur Company from an American invention that we will study about in our next post: the Frasch process. Sicily was exporting over 177,000 tons to the American market in 1902, 106,000 tons in 1904, and two years later, it dropped to 7000 tons thanks to the new process invented in America! In fact, in 1906 Sicily was no longer the global dominant producer of sulfur, being replaced by sulfur produced in Louisiana and Texas, which was cheaper and purer, and the Anglo-Sicilian Sulfur Company was out of business a couple of years later.

However, while the Claus-Chance process went into decline, the Claus process did not go away entirely. In fact, it is still around today and is the dominant method of producing sulfur today, as there is plenty of hydrogen sulfide gas from other sources, especially from oil and natural gas fields and from crude oil refineries.

We will study the Frasch process in our next post.



Sunday, June 19, 2016

Manufacture of Sulfur - II

In our last post, we saw how the Chinese extracted sulfur from pyrites (fool's gold) and used it in gunpowder. In some parts of the world though, particularly in regions containing hot springs and volcanoes, elemental sulfur occurs naturally on the surface of the earth. Some famous locations are Sicily in southern Italy, the Romagna region in northern Italy, some islands in Japan (Iwo Jima, for one), the Ijen volcano complex in Indonesia etc. Today, we will study how sulfur was extracted from these regions in the past centuries.

Naturally occurring sulfur at the edge of a crater on Vulcano Island, Sicily, Italy.

A miner carrying away blocks of sulfur on Kawah Ijen, Indonesia. Click on the image to enlarge.
Image licensed under a Creative Commons license
By Jean-Marie Hullot - originally posted to Flickr as Kawah Ijen, CC BY-SA 2.0, https://commons.wikimedia.org/w/index.php?curid=8753232

Mining for sulfur from Sicily and Romagna regions in Italy dates back to at least Roman times. After the 14th century, as gunpowder technology began to develop throughout Europe, the demand of sulfur began to increase. Several gunpowder mills began to appear near the sulfur mines. In the 19th century, 75% of the world's sulfur production came from Sicily alone, and 5% more from the Romagna region. This meant that Italy accounted for both the 1st and 2nd largest producers of sulfur in the world in the 19th century.

The traditional way of extracting sulfur during the Roman times to the middle ages was to melt it in open pits. Sulfur from Sicilian deposits generally contained from 12% to 50% sulfur, with the other impurities being mainly gypsum and limestone. However, to melt the sulfur, fuel is needed and wood was a luxury in those volcanic regions. Hence, sulfur was used as a fuel as well and was used to melt itself! The earliest recovery technique consisted of placing the crude sulfur in conical mounds over and open pit and covering it with earth. The bottom of the sulfur was set on fire, melting the rest of what remained on the pile, which could be extracted. However, this process wasted a good portion of the sulfur (about 33% was recovered and 67% was wasted) and over the centuries, miners exhausted the sulfur deposits on the surface and had to start digging tunnels into the hillsides to extract the sulfur deposits.

During the Middle Ages, a better technique emerged, using clay pots to distill the sulfur. There was at least two pots employed, called Doppioni (which means "double" in Italian), which were connected by a clay pipe. The crude sulfur was placed in one pot, which was heated on a fire using wood or coke as a fuel. The sulfur would evaporate and the fumes would be led into the other pot via the pipe, where it would condense and be poured into wooden moulds. Meanwhile, the slag remaining in the first pot would be unloaded. Later on, the pots were produced using cast iron. This technique was mainly used in the Romagna region and not in Sicily, because of the way that land mining rights laws were in the two regions.

Instead, in 19th century Sicily, they simply improved on the melting techniques and came up with melting furnaces called Calcarelli and Calcaroni. The main difference between these two was that the Calcaroni was a larger furnace and soil was added to the top of the sulfur heap inside it, to control the combustion.

It consists of a round open-topped furnace, lined with firebrick, with an inclined floor. Calcarelli furnaces tended to be smaller and were typically about 2 meters (6.6 feet) in diameter, whereas Calcaroni type furnaces were larger and about 10-30 meters (about 33-100 feet) in diameter. A cone-shaped pile of sulfur was built up, and in the case of the Calcaroni furnace, a cover plug of soil was put on top of the sulfur. A flame was applied from the top and part of the sulfur burned away, which produced enough heat to melt the rest, which would then flow down the sloping floor and could be collected from a hole in the bottom (appropriately called morte, the Italian word for "death"). The Calcarelli type furnaces would yield about 1/3rd of the sulfur from the ore and took about 2 days to finish the process, only processing a few tons at a time. The larger Calcaroni type furnaces could extract about 50-65% of the sulfur and took about 60-90 days to complete, producing about 200 tons of sulfur per batch. Nevertheless, these were highly polluting furnaces and the sulfur dioxide fumes would destroy any vegetation in the neighborhood, which is why Italian laws prohibited building these furnaces less than 3 km. (2 miles) from any town and only allowed these furnaces to run at certain times of the year so that they wouldn't interfere with growing crops. These furnaces were more inefficient than the Doppioni, but were widely used in Sicily because they allowed large scale processing for cheap.

An improved kiln was invented in 1880 by Robert Gill, a British engineer working for the Gibellini Sulphur Company. A Gill kiln consists of a series of cone shaped chambers (typically two to six chambers) which are connected sequentially and the heat from the first chamber is used to preheat and set fire to the second one and the heat from the second one is used to preheat and set fire to the third one and so on. Each chamber has an inclined floor and is provided with several openings: one for adding the crude sulfur, another for a pipe to bring in the hot gases, another for a pipe to take out the combustion gases to a main chimney, a tap hole at the bottom to extract the molten sulfur and another adjustable hole to adjust the airflow needed for combustion.

The main innovation of this type of furnace was to reuse the combustion gases from one chamber to heat the net chamber and so on, which reduced the amount of sulfur fumes, allowing a Gill furnace to work continuously through the year. Typical wastage was only around 7-10% of the sulfur and this furnace was widely adopted in Italy -- by 1890, Gill's furnace was used in about 12% of Sicily's production, but by 1905, it was used for about 65% of the sulfur produced by Sicily.

The sulfur produced varied in quality and was generally exported to other distilleries, primarily to Marseilles, France, but also to smaller refineries owned by gunpowder mills, such as Waltham Abbey, where it could be further refined. At Waltham Abbey, best quality Sicilian sulfur came in with about 3-5% of impurities. It was distilled in a large iron pot, provided with two tubes at right angles to each other: The larger tube (about 15 inches diameter) communicated to a large dome-shaped subliming chamber, the smaller tube (about 5 inches diameter) entered an iron pot, which received the distilled sulfur. This tube was surrounded a jacket cooled with water. Valves could be opened or closed in the tubes to connect to or cut off the distilling vessel. The distilling vessel was heated till the sulfur boiled and the valves were initially manipulated so that vapors were sent to the subliming chamber, where the sulfur would deposit on the interior surface as small crystals (called the "flowers of sulfur"). After a while, the other valve would be opened and the vapors sent through the condenser, which would then liquify the sulfur. The liquid sulfur would be allowed to cool a bit, but not enough to solidify. Then it would be ladled into moist wooden molds to solidify into "stick sulfur". The "flowers of sulfur" contained a small percentage of sulfuric acid, formed by the action of the air on the sulfur and therefore, wasn't suitable for the manufacture of gunpowder. The "stick sulfur", on the other hand, was very pure and only needed to be ground up into powder to be used in gunpowder.

The Sicilian monopoly on sulfur production slowly started to decrease at the end of the 19th century, due to an invention by a German-born American chemist in Louisiana. We will study his process in our next post.


Monday, June 13, 2016

Manufacture of Sulfur - I

In our last couple of posts, we looked at some historical methods used to produce charcoal, one of the key ingredients of black powder. In today's post, we will look at some methods used to extract the third ingredient of black powder, namely sulfur (also spelled as "sulphur" if you speak British English).

As we've seen previously, the saltpeter (potassium nitrate) provides the oxygen needed for the gunpowder to burn rapidly, and the charcoal (carbon) provides the fuel. So what's the role of sulfur then? The sulfur helps to reduce the ignition temperature of gunpowder. Strictly speaking, it is possible to manufacture gunpowder using only saltpeter and charcoal, but the result needs sparks at a higher temperature to ignite. This is why sulfur was added to black powder to increase the reliability of ignition on early firearms such as matchlocks, wheellocks, flintlocks etc. If there is no sulfur in the black powder, then the chance of misfiring on these early firearms increases quite a bit. However, the presence of sulfur is also responsible for most of the smoke produced by burning black powder.

 Interestingly, a mixture of saltpeter and sulfur, but no charcoal, does not burn at all, although sulfur alone burns well in air and saltpeter is an oxidizer.

Sulfur has been known since ancient times and has been mentioned in texts of ancient Egypt, Greece, India, China, Italy etc. It is even mentioned in the Bible as "brimstone". Sulfur is a pretty common element and occurs in many minerals, as well as in natural state (elemental sulfur). When it occurs in natural state, this is typically around hot springs and volcanic regions in many parts of the world (e.g. Sicily, Indonesia, Japan, etc.) It also occurs in minerals such as pyrites (fool's gold). One more source of elemental sulfur is salt domes in many regions of the world. 

Sulfur found naturally on the ground from the island of Vulcano in Italy.
Click on the image to enlarge. Public domain image.

In China, the common source of sulfur in ancient times was from pyrites. This is a mineral that contains both iron and sulfur and commonly occurs in various places around the world. It was known since ancient times because of its property of giving off sparks, when struck with a piece of flint or a steel rod. This is why pyrites were also used in early wheel lock firearms. Even before firearms were invented, travelers would carry a small piece of pyrite and one of flint with them and strike them together to start a fire. There is evidence that using pyrite and flint as a portable fire-starter has been in use since at least the Upper Paleolithic era. In fact, the word "pyrite" derives from the Greek word for fire (pyr)

Three samples of pyrites. Click on the image to enlarge.

Pyrites are also known as "fool's gold", since their shiny nature has fooled many people into believing that they have found some mineral containing gold in it.

We have good accounts of how sulfur was extracted from pyrites in China. One book by Song Yingxing in 1637, describes the process: About 250 kg. (550 lbs.) of pyrites was surrounded by 500 kg. (1100 lbs.) of coal in a brick kiln, and a hole was left on top of the pile. The pile was then ignited at the base and left to burn for 10 days. The sulfur would form a yellow vapor that came out of the top of the pile and this could be condensed into solid sulfur crystals by covering the top of the pile with a simple earthenware bowl, as seen in the image below.

Ancient Chinese process to make sulfur from pyrites. Click on the image to enlarge. Public domain image.

There is evidence that the technique of extracting sulfur from pyrites was known to the Chinese, since at least the 3rd century. This process was somewhat wasteful in the amount of sulfur extracted from the pyrites, but since pyrites were plentiful in China, it was very commonly used there. 

In Europe, the main source of sulfur for many centuries was the island of Sicily, where sulfur occurs in its natural state (we will study its extraction in the next post) and was mined since Roman times at least. However, in 1839, the Sicilian deposits came under the control of a French company, which raised the price about three-fold. This led to a number of countries reverting back to extracting sulfur from pyrites, until the price dropped again.

In the next post, we will look at how sulfur was extracted in Europe since ancient times until the middle of the nineteenth century.

Saturday, June 11, 2016

Historical Manufacture of Charcoal - II

In our last post, we looked at the charcoal manufacturing process, as it was done from the 14th to the early 20th century. In today's post, we will look at some variations of the process.

As we saw in the last post, charcoal manufactured for the purposes of gunpowder had to be of a higher quality with uniform charring. Therefore it was manufactured in smaller batches using iron cylinders to heat the wood, instead of heating up large heaps. Our last post also described the process in England, where they used small iron cylinders, each holding about 80 lbs. of wood, being placed inside a furnace and heated. In today's post, we will study some variants of this basic method.

Instead of using fixed carbonizing cylinders, many black powder factories in England started switching towards using movable cylinders in the 19th century. Each furnace was provided with two cylinders, so that one could be refilled while the contents of the other were being carbonized. Each filled cylinder would be run into the furnace on rails, with the rails supporting them over the fire. An elaborate system of pipes and valves was used to distribute the gases and the wood distillation byproducts (wood gas, tar, volatile chemicals etc.), so that they could be redirected back to any one of the furnaces, or allowed to escape through the chimney.

The advantages of this process were:

  1. Uniformity of the charcoal being produced.
  2. The gases produced by distilling the wood could be reused to additionally heat the furnace, thereby saving on fuel costs
  3. The charcoal was cooled down out of contact with the air, which took away the possibility of the charcoal catching fire.
In some British factories, vertical movable cylinders were used instead. The advantages of this were that more cylinders could be fired at the same time and the moving of the cylinders to the cooling room was easier.

In Sweden, some factories used rotating cylinders, with each cylinder being rotated 90 degrees on its horizontal axis every 30 minutes. This allowed the heat to act upon each side evenly and this process gave a more uniform carbonization and saved fuel as well.

Another method of carbonizing wood used superheated steam to do the job. Pressurized steam was produced by passing water through a coil of wrought iron heated by a fire. For the production (from dogwood) of charbon roux (brown charcoal) containing 70% carbon, the temperature of the steam had to be around 280° Fahrenheit; by using steam heated to about 350°, charcoal containing about 77% carbon could be produced, and by heating both the cylinders and the steam to about 450° fahrenheit, charcoal of about 89% carbon content could be produced. The charcoal produced by this method was very uniform in composition, but the method was later abandoned because it gave a larger yield of charbon roux, but not so much black charcoal, as the ordinary method of carbonization using iron cylinders; and the lightly-burnt charcoal was only required for sporting powders. Also, the cost of production of charcoal using superheated steam apparatus was greater.

In 1887, one Mr. H. Guttler of Reichenstein, Germany, invented a process of carbonizing wood (he received British patent # 8929 on June 22nd, 1887 for his idea "Improvement in the Manufacture of Charcoal for Explosives and other Purposes, and Apparatus for that Purpose"). His idea consisted of putting the material to be carbonized into a suitable air-tight cylinder fitted with a pressure gauge and pyrometer and using an arrangement of two furnaces to heat it. One is a normal charring furnace and the other is a producer-furnace, which produces carbon dioxide gas by blowing air through burning coke using a fan. The heated carbon dioxide gas is then piped into the cylinder (similar to the superheated steam process we saw above) and the carbonization takes place. The pressure of the carbon dioxide in the cylinder can be varied as needed. The temperature is regulated by admitting cold air to the muffle and by varying the supply of heated gas into the cylinder. After the charring is completed, cooled carbon dioxide is passed through the charcoal, which rapidly cools and absorbs the carbon dioxide in its pores. The advantage of this process over using superheated steam was that it didn't leave the charcoal produced in a moist state, which the steam process did. It could also be used to produce charcoal from cheaper materials such as wood cuttings, pulp, straw, peat etc. Another advantage was that since it used carbon dioxide instead of air, the charcoal produced could not spontaneously ignite.

In the next post, we will look at the historical production methods of the third ingredient of gunpowder: sulfur.

Wednesday, June 8, 2016

Historical Manufacture of Charcoal

After spending the last few weeks studying the history of saltpeter manufacturing around the world, we will spend some time today studying another component of gunpowder: charcoal. We actually studied this topic briefly when studying about black powder many months ago. We will revisit this topic in more detail today.

Strictly speaking, the chemical element that is used for gunpowder is carbon, which is supplied by the charcoal. The carbon acts as a fuel in the gunpowder.

Since the very early days of firearms, it was found that the quality of charcoal is a pretty important factor in the quality of the gunpowder produced. Therefore the process of manufacturing high quality charcoal was regarded as a closely-guarded state secret. Charcoal made by burning wood in heaps or kilns is not very suitable for gunpowder. Instead, to make high quality charcoal, the wood must be selected very carefully and burned uniformly in ovens or iron vessels. The procedure to do so hadn't changed very much from the fourteenth to the twentieth century. We will look at the process used at Waltham Abbey in England, during the early 20th century.

First, the choice of wood for making charcoal for gunpowder: Soft and light woods are preferred, as they leave less ash. At one time, the charcoal for black powder in England was exclusively made from alder wood, but later other soft woods were also used. In England, dogwood was extensively used, especially for small grain powders, and for larger grain powders, alder and willow wood were used, with straw charcoal being used for brown powders used in heavy ordnance; In America, cottonwood, redwood, soft pine and western cedar trees were used; In Germany, alder and willow were mostly used; in Austria, hazel and alder; in Switzerland, hazel trees; in France, dogwood was exclusively used in military and sporting powders, but as it became more difficult to procure, alder, poplar and lime were tried out; in Russia, alder was commonly used; in Spain, yew, oleander, willow, hemp stems and vine; in Italy, hemp stems were used mostly.

The trees chosen were usually between two and  ten years old. The trees were generally cut down in spring for a few reasons. First, this is the time when trees are the most full with sap, which means the sap is very watery and contains less dissolved salts in it, thereby producing less ash. The second reason is that trees cut down in spring are easiest to separate the wood from the bark, which is good because the tree bark contains a large portion of the ash produced. The wood was seasoned for at least 1.5 to 3 years, to allow most of the sap in it to dry out. The method of doing this varied by location and type of wood. For instance, in Germany, it was customary to keep the wood inside sheds in Dresden, but at Spandau, they kept the wood out in the open. In England, dogwood was covered with thatch, but the willow and alder woods were dried out in the open.

After drying, the wood was split into pieces about 3 feet long by 1 inch thick. These pieces were placed in iron cylindrical cases called slips. Each cylinder was about 2 feet in diameter and 3.5 feet long. The lid was fastened to each slip, with two openings (about 4 inches diameter) being left in the bottom of each slip. The slips were then placed in horizontal cylinders, the end of the slip with the openings going to the further end of the cylinder, in which end there were openings corresponding to those in the slips. The cylinders were then lifted with pulleys into a furnace, where they could be heated as uniformly as possible. The cylinders were placed such that the furnace flames surrounded the cylinder entirely, so the heat acted upon the whole surface as much as possible. The higher the temperature and the longer the heating time, the lower was the percentage of hydrogen and oxygen in the charcoal, which made it harder and more difficult to ignite. Therefore the type of wood and the type of gunpowder that the charcoal was meant to be used for, determined how long the cylinders were heated. For instance, to make R.F.G (Rifle Fine Grain) powder or M.G. (Machine Gun powder for Nordenfelt guns) powder in Waltham Abbey, dogwood was heated for abuot 4 hours. Alder and willow for R.L.G (Rifle Large Grain) powder was heated for 3.5 to 4 hours and for P grade gunpowder, it was heated for 6 hours. Smaller cylinders were used, to make the composition of the charcoal more uniform, since high temperature is not needed to carry the heat to the center of the wood pile in each cylinder. However, the use of small cylinders reduces the efficiency and raises the cost of production. In England, most cylinders were only large enough to hold about 80 lbs. of wood. Incidentally, for a given temperature, slow carbonization produces much more charcoal than quick carbonization at the same temperature.  Also, the lower the temperature used for carbonization, the lower the temperature at which the charcoal burns. Therefore charcoal made at 260-280 degrees centigrade burns at around 340-360 degrees centigrade, whereas charcoal made at 950 degrees burns at around 1900 degrees.

As the cylinders were heated, the volatile chemicals and tar in the wood would be released by the decomposition of the wood. Normally, these gases could be condensed by using a condenser and used to make useful chemicals like lime acetate and wood spirit. However, charcoal produced by gunpowder mills were generally on a much smaller scale that the charcoal used for metallurgy, therefore it was not considered to be worth the effort to do so. Instead, the gases were removed via a pipe and fed back into the furnace, where they could be burnt. Doing this saved a considerable amount of fuel, thereby reducing costs. When the wood was sufficiently charred, the color of the flame would change to a bluish violet, indicating the formation of carbonic oxides. At this point, the furnace is opened and the cylinder is taken out using pulleys and replaced by a fresh cylinder. The cylinder taken out was placed in a larger cylinder with a tight fitting lid and allowed to cool for about 4 hours, until all the fire in the wood could be extinguished. It is necessary to do this cooling out of contact with the air, otherwise the charcoal could catch fire. The charcoal was then emptied into smaller cylinders and carefully picked by hand to ensure that it is properly and evenly burnt. It was cooled in the smaller cylinders for about one to two weeks, to reduce the danger of spontaneous combustion (caused by the charcoal absorbing oxygen from the air), before being sent to be ground.

Charcoal intended for firearms use was generally jet black in color and so soft that it could not even scratch a copper plate. The following table shows an analysis of the charcoal produced for different powder grades:

Note that the Spanish Hemp Charcoal has a higher percentage of ash than the others. This is because it was manufactured by burning the charcoal in pits holding about 0.5 to 1 ton of wood each (unlike in England, where each cylinder only held about 80 lbs of wood). Also in the Spanish method, when the wood had carbonized enough, the pit was covered with a woolen cloth upon which earth was placed, which accounts for the higher percentage of ash produced.

Inferior quality charcoal was generally used for powders shipped to Africa and Brazil, since the locals there seemed to value the shiny quality of the black powder rather than its shooting properties.

In our next post, we will look at some variations of this process used by factories in England, Sweden and elsewhere.


Monday, June 6, 2016

The History of Saltpeter - XIX

In the second half of the nineteenth century, people began to look for other sources of natural nitrates besides the plains of India. Today, we will study natural nitrates from South America, called Chile Saltpeter or Peru Saltpeter or soda niter.

A sample of Chile Saltpeter. Click on the image to enlarge. Public domain image.

Unlike the saltpeter we've been studying so far, which is potassium nitrate, chile saltpeter is sodium nitrate. It occurs naturally in the Atacama desert, which lies between Peru and Chile. The first shipment of Chile saltpeter to Europe arrived in England in 1820 or 1825, but they could not find any buyers and therefore dumped it at sea, so that they didn't have to pay a customs toll. However, by the time of the Crimean war (1854-1855), the demand for saltpeter was so much that the existing sources from Europe and India couldn't keep up and it became profitable to ship South American saltpeter to Europe. There is a good reason why this stuff was called "white gold".

There are a few theories about how the saltpeter forms there. The classic explanation is that in the Tarapaca region in the Atacama desert, which is a dry desert that experiences a little rainfall every six or seven years, when the rain falls, it floods the plain. However, the plain slopes gently towards the coast hills and as there is no outlet for the water, it collects there and evaporates in the desert's arid conditions, and all the nitrate that was dissolved from the entire plain is deposited in a relatively narrow area. A more modern theory states that the Andes climate was warmer and wetter about 20 million years ago and nitrates, iodine and chromium deposits were leached from the ground water. About 10 million years ago, as the Andes and the coast mountains began to grow higher and higher, the climate shifted to desert and forced the groundwater to evaporate, leaving behind the nitrates. Sea spray and fog from the ocean also drop small amounts of nitrates on the surface.

Originally, the areas where most of the deposits were concentrated belonged to Peru and Bolvia: specifically Peru's Tarapaca region and Bolivia's coastal region of Antofagasta. Mining concessions were granted to Chilean and the British companies to mine these areas. Then the Peruvians and the Bolivians attempted to control the British and Chilean companies by imposing new taxes on them. This led to the War of the Pacific (1879-1883) which ended with Chile capturing both the Tarapaca and Antofagasta regions. By the 1890s, Chile was supplying a whole lot of Chile saltpeter to the world. 

Sodium nitrate can be converted to potassium nitrate by interacting with the chloride of potassium, which could be made from kelp, wood ash, or later, from carnallite, which is a mineral that occurs in huge deposits in Europe and America, particularly in Carlsbad, New Mexico, Paradox Basin in Colorado and Utah, Stassfurt in Germany and the Perm Basin in Russia.

In a heated and concentrated mother liquor, sodium nitrate (about 95% pure from the chile saltpeter) and potassium chloride (greater than 80% purity, from the carnallite) are dissolved. Due to the chemical reactions, the solution can now contain four possible salts: sodium chloride, potassium chloride, sodium nitrate and potassium nitrate. As it happens, when the temperature of the solution is high, potassium nitrate has the highest rate of solubility (i.e. it dissolves easily in water), but sodium chloride has the least solubility. At low temperatures, potassium nitrate has the least solubility. This fact is exploited to filter out the crystals of the other salts out. The liquid is boiled for about half an hour to complete the reaction as much as possible and convert most of the salts to sodium chloride and potassium nitrate. Then it is run through a filter into shallow cooling tanks and the solution is kept stirred while it cools, so that the potassium nitrate may form smaller crystals. The crystals are then drained and washed with the liquors from the next crystallization using a centrifuge. The crystals still contain a fair amount of sodium chloride, so they are purified by washing in cold water, which dissolves most of the sodium chloride, but leaves most of the potassium nitrate undissolved, which reduces the percentage of sodium chloride to below 0.05 percent. Then the remaining potassium nitrate crystals are dried and ready to be used for gunpowder production.

During the First World War, demand for Chilean nitrate exports skyrocketed. Before 1914, only one-fifth of Chilean nitrates were used for explosives, but after the war started, almost four-fifth of all nitrate exports were used for military purposes. Before the war, Germany was the largest market for Chilean saltpeter. For example, in 1912, Germany imported 37.9 % of all Chile saltpeter exports, England had 5.7% and the rest of Europe had 31.6%, which means that Germany alone imported more than all of Europe combined! The United States imported about 23.6% of Chile saltpeter exports during the same year. At the beginning of World War I, German Admiral Maximilian Reichsgraf von Spee commanded a fleet of ships off the coast of Chile in an attempt to disrupt Chile saltpeter supplies to everyone else. After the German fleet was destroyed in the Battle of the Falkland Islands, the exports to Britain resumed. Germany was blockaded from accessing Chilean saltpeter from 1915 onwards, leading to the United States and the UK becoming the largest markets for Chilean saltpeter. Because of this, Germany was forced to discover a method to produce synthetic nitrates. The first breakthrough came from Fritz Haber, who discovered a way to produce ammonia from nitrogen and hydrogen in the air and water (neither of which could be blockaded by the allies). Then Wilhelm Ostwald discovered a method to convert ammonia to nitric acid and from then on, Germany's military industry was free from its dependency on Chilean saltpeter. In fact, if it weren't for these two discoveries, the shortage of munitions would have forced Germany to end the war by 1915, instead of prolonging it till 1918. 

Ultimately though, the German innovations forced the decline of the Chilean saltpeter mining industry, as more and more countries began to produce synthetic nitrates using the techniques that they pioneered. At one time, Chile saltpeter accounted for 50% of Chile's Gross National Product, but by the time the 1940s rolled around, it had fallen to practically 0. Of the 170 or so "nitrate towns" that were formed in the Atacama desert to mine for nitrates, only one of them remains open today, the town of Maria Elena.