Industrial Organic Chemistry

Mark Anthony Benvenuto

• Publisher: De Gruyter
• Year: 2017
• Print ISBN: 9783110494464
• eBook ISBN: 9783110491715
• Edition: 1
• Topic: Ciencias físicas
• Subtopic: Ciencia medioambiental

Industrial Organic Chemistry examines all major industrial manufacturing technologies and reaction types with a focus on organic chemistry in general and petroleum refining in particular. The author takes a systematic approach to introducing the most important classes of organic compounds, from the C1 fraction through to polyaromatics and polymers.

The author introduces biological sources for key compounds such as fuel and plastics and compares these bio-based organic materials to the corresponding petroleum-based chemicals.

In addition to the chemistry behind processes in the petroleum, pharma, food and agrochemical industries, this book also discusses related topics such as process selectivity, waste management, and product purification.

1Introduction, overview, and history

1.1Introduction and overview

Throughout history, various cultures have gone through what is called a “Bronze Age” and an “Iron Age,” as the people of those cultures and times learned how to use those two metals. It is only a guess, but a millennium into the future, people of that time may look back and dub the time in which we now live as “the plastics age” or, perhaps, “the oil age.” Like the alloy and elemental metal changing cultures and improving the way of life and quality of life of certain peoples, plastics and the oil from which they come – and the fuels that are derived from crude oil as well – have defined the twentieth century and continue to define the twenty-first.

Simply put, there has never been a time when the entire world has been changed as greatly as it has been by the production of large amounts of several commodity plastics and by the large-scale production of motor fuels. Plastics have been designed to be especially robust, some would say to last “forever.” This has produced a wide variety of materials that have not been seen before in history and that have enabled people to keep food fresh far longer than ever before, have enabled numerous advances in medicine, and have made possible the production of countless end user items now taken for granted in most homes. Likewise, motor fuels and the engines they power have enabled people to travel at faster speeds than ever before. Consider that from the dawn of civilization until the Napoleonic Wars, a person could travel no faster than a horse, if on land, or a sailboat, if on sea. From the middle of the nineteenth century until now, however, a span of less than 200 years, humans have developed the ability to travel as fast as a jet engine can propel them, in large part because of the hydrocarbon-based fuels that run them.

1.2Historical overview

Oil has been known in various parts of the world for millennia but was never widely used in ancient times. It was generally considered a local material, found in the ground in some areas, and was never distilled or separated to any large extent. Most of what is called “oil” throughout history is some material extracted from plants, although from the 1600s onward, whale oil became a large-scale commodity. Olive oil is one such example of a plant oil that was used extensively in the ancient world, or at least that part of it centered on the Roman Empire.

1.2.1The rise of the use of oil in the late 1800s

While oil has seeped to the surface in various parts of the world, such as China and the Middle East, for centuries, it was not developed into a commercial fuel until the nineteenth century. At that time, as mentioned, whale oil was widely used as a fuel in oil lamps, to illuminate homes and some commercial businesses in the night. Thus, by the middle of the nineteenth century, technology had been well developed to harness oils and what became known as kerosene for use in residential and commercial applications, specifically, home and street lamps. This market continued to grow as the population of the developed world continued to grow.

There are competing claims for what is the first oil well, with many in the west claiming that the Drake well near Titusville, Pennsylvania, which began production in 1859 as the first. Since early claims occurred in the 1840s and 1850s, and since the clear fuel derived from crude oil – named kerosene at that time – burned more cleanly than whale oil, the rise of crude oil extraction and distillation corresponds to the decline of the whaling industry. It is not unreasonable to surmise that without this use of oil, where fuel oil from whales had been used before, it is likely that there would be no whales in our oceans today. Humans would have hunted them to extinction.

1.2.2Petroleum consumption in the early 1900s, the First World War

The internal combustion engine had been invented, improved upon, and used in numerous ways by the turn of the twentieth century. Several companies had emerged by that time which produced automobiles, all of them advertising the superiority of such over horse-drawn carriages. Curiously though, all automobiles were not driven by internal combustion engines in the earliest years of the 1900s. Rather, steam-powered automobiles were marketed, as were electric vehicles, the lattermost of which ran on a series of lead-acid batteries. But the power generated by internal combustion engines meant that automobiles that used them became the predominant favorite with owners. The year 1913 for example was the final year in which the Ford Motor Company sold more electric automobiles than internal combustion engine automobiles.

This development of automobiles spurred the demand for motor fuel, but even the mass production of the Model T Ford did not drive up the demand for petrochemical fuel as dramatically as the First World War did. While most of the world’s armies in that conflict used horse-drawn supply vehicles, by the end of the war, the tank had made its debut on the western front, using what was then a massive (and rather inefficient) engine. Beyond this, coal-powered warships were being replaced by oil-powered ships because the combustion efficiency was such that when one compared masses of coal and oil, a ship could sometimes travel twice as far using oil. This war was essentially the first in which hydrocarbon fuels had become a requirement for modern armies and navies.

1.2.3Petroleum consumption during the Second World War

By the outbreak of the Second World War, the armies of various countries had still not converted to entirely mechanized forces, but there had been significant strides made in that direction. The famous Nazi blitzkrieg, or lightning war, through Holland, Belgium, and Luxembourg, and into France, is probably the best known example of a military’s use of equipment that depended on gasoline or diesel fuel. Indeed, in that maneuver, the supply lines stretched so far from the attacking tanks that this logistical problem appears to be a major reason the Blitzkrieg halted when it did.

On a more global scale, the pursuit of oil and the areas from which it can be produced drove the forces of the Nazi Wehrmacht to try to take the Caucasus from the then Soviet Union and drove the forces of the Empire of the Sun to annex large parts of Indonesia. At the same time, leaders of the Allies were courting the leaders of several mid-eastern countries because of the oil available from the Arabian peninsula and present-day Iran.

But oil was not only being refined into gasoline and diesel fuel at this time, it was being separated into component monomers, for a new class of molecules – plastics. To be fair, several plastics have histories that predate the Second World War. Bakelite, a formaldehyde resin, had been known for decades. Nylon had been discovered in the 1930s and was quickly put into service in various applications during the war. As well, synthetic rubber was known before the war but quickly ramped up to industrial scale production when the rubber trees of Southeast Asia fell under the control of the Japanese Empire.

It is fair to say that the Second World War was a bellwether event in the use both of hydrocarbon fuels and synthetic plastics.

1.2.4Post-World War II plastic production

As plastic production rose to an enormous economy of scale, plastics began to compete with traditional materials in an almost uncountable number of ways: plastic versus wood for window sills, plastics versus glass for windows, plastics versus metal for automobile parts to make cars of lighter weight and greater fuel economy, plastics versus leather for shoes and other clothing, and plastics versus cloth for grocery bags. The list does appear almost endless.

In the 1950s, some of the earliest mass-produced plastics were marketed as being materials that would never need to be replaced. But each year, new products were developed, and consumers were urged to buy more and thus to discard their older items. Because plastics have been made to be remarkably durable, their long-term disposal has become an enormous problem [1–7].

Not only have plastics become materials that are used in an ever-widening array of applications, but also, the number of automobiles, trucks, and motorized military vehicles – all of which require gasoline or diesel fuel – mean that ever larger quantities of motor fuels must be found and refined. Even though improvements in engines mean that current vehicles tend to run on less fuel than earlier cars and trucks, the sheer number of them in existence means that tail pipe pollutants such as carbon dioxide and carbon monoxide, as well as other combustion products, continue to be a pollution problem that affects air and water and, to some extent, the land.

1.3World petroleum production

Perhaps obviously, petroleum production is linked to the geologic areas in which oil is locked into the Earth. Since such formations are unevenly distributed throughout the Earth, some nations have become significant producers of oil, and others have become heavy consumers. The Organization of Petroleum Exporting Countries (OPEC) is an organization of nations, all of which have significant reserves of oil, which claims: “to coordinate and unify the petroleum policies of its member countries” [8]. Since the member nations control the production of just under half of the world’s oil, this organization exerts a significant influence over the price of oil [8]. Current OPEC member states are Algeria, Angola, Ecuador, Gabon, Indonesia, Iran Iraq, Kuwait, Libya, Nigeria, Qatar, Saudi Arabia, UAE, and Venezuela [8].

Broadly, petroleum extraction can be divided into onshore and offshore drilling and land-based drilling and extraction. Offshore drilling in what are referred to as littoral waters – generally, waters that are within the boundaries of a specific nation – is often well established simply because these are relatively shallow waters. Offshore drilling in deep water, and especially in waters that have not been claimed by any nation, presents a series of political problems related to jurisdiction and ultimately ownership of the oil that is extracted.

1.4World petroleum use

As discussed above, petroleum use expanded enormously in ...

Table of contents

• Cover
• Title Page
• Copyright
• Preface
• Contents
• 1 Introduction, overview, and history
• 2 Petroleum refining
• 3 The C1 fraction
• 4 The C2 fraction
• 5 The C3 fraction
• 6 The C4 fraction
• 7 The C5–C8 fraction
• 8 Benzene, toluene, xylene
• 9 The higher alkanes
• 10 Further oils and lubricants
• 11 Fuels, biofuels
• 12 Polymers
• 13 Naphthalene and higher polyaromatics
• 14 Coal as a source
• 15 Pharmaceuticals
• 16 Food chemicals and food additives
• 17 Agrochemicals
• Index