Handbook of Industrial Chemistry and Biotechnology

The first oil shock that occurred at the end of 1973 with the Yom Kippur war served to pinpoint the crisis which world chemicals were already undergoing.

There is an ongoing emphasis on chemical process safety as a result of highly publicized accidents such as the recent BP Deep Water Horizon well blow out in the Gulf of Mexico that resulted in a fire and explosion that killed 11 people and a massive leak of oil that caused catastrophic damage to the environment and economy of the Gulf Coast. Public awareness of these accidents has provided a driving force for industry to improve its safety record. There has also been an increasing amount of government regulation.

The preceding chapter explored many technical aspects of chemical process safety and some safety management systems that form the foundation of a comprehensive emergency preparedness program. Clearly, the first step in preparing for emergencies is to identify and mitigate the conditions that might cause them. This process starts early in the design phase of a chemical facility, and continues throughout its life. The objective is to

prevent

emergencies by eliminating hazards wherever possible.

The discipline of statistics is the study of effective methods of data collection, data summarization, and (data based, quantitative) inference making in a framework that explicitly recognizes the reality of nonnegligible variation in real-world processes and measurements.

Literature sources on green chemistry and green engineering are numerous. The objective of this chapter is to familiarize readers with some of the green engineering and chemistry concepts, approaches, and tools. In order to do this, the chapter is organized into five sections as follows.

Every student of chemistry, material science, and chemical engineering should be schooled in catalysis and catalytic reactions. The reason is quite simple; most products produced in the chemical and petroleum industry utilize catalysts to enhance the rate of reaction and selectivity to desired products. Catalysts are also extensively used to minimize harmful byproduct pollutants in environmental applications. Enhanced reaction rates translate to higher production volumes at lower temperatures with smaller and less exotic materials of construction necessary. When a highly selective catalyst is used, large volumes of desired products are produced with virtually no undesirable byproducts. Gasoline, diesel, home heating oil, and aviation fuels owe their performance quality to catalytic processing used to upgrade crude oil.

Environmental chemical determinations are identifications and measurements of the concentrations of elements, compounds, or ions in environmental media. In a chemical determination equal importance is given to the correct identification of the substance, and to its accurate and precise measurement. There has been a tendency in some environmental work to place more emphasis on making accurate and precise measurements, and to give less attention to ascertaining the correctness of the identification of the substance being measured.

Research in nanotechnology has seen an explosive growth during the past decade, fueled by significant investment in research and development and the appearance of a cornucopia of consumer-based products. As of August 2009, an inventory conducted by the Project on Emerging Nanotechnologies has identified over 1,000 nanotechnology consumer products [1]. Based on current growth rates, it is estimated that nano-related goods could be in the range of $1–2.5 trillion market by 2015 globally.

Nanoscience and nanotechnology are transforming materials science in a broad way, in a manner similar to polymer chemistry’s transformation of materials science over the preceding century. The continuous development of novel nanostructured materials and the extensive study of physicochemical phenomena at the nanoscale are creating new approaches to innovative technologies that are constantly resulting in products with a wide range of applications [1–5].

Synthetic organic chemicals are produced by the transformation of carbonaceous feedstocks into functionalized molecules through one or more chemical reactions. Such transformations are accomplished at vast industrial scales and the resulting products permeate every aspect of modern society. The molecules produced find use largely as monomers for polymer synthesis of ubiquitous plastics, or as task-specific ingredients for a myriad of applications as divergent as paint leveling agents to food preservatives. Advances in technology, significant increases in energy efficiency, as well as the utilization of fossil-fuel derived starting materials has resulted in unprecedented economy of scale and relatively stable product costs in spite of large relative increases in the price of oil and natural gas. The section entitled “Chemical Raw Materials and Feedstocks” covers the most important carbonaceous feedstocks currently utilized in the chemical processing industries; all derived from fossil-fuel based raw materials.

This chapter discusses the role of chemistry within the pharmaceutical industry [1–3]. Although the focus is upon the industry within the United States, much of the discussion is equally relevant to pharmaceutical companies based in other first-world nations such as Japan and those in Europe. The primary objective of the pharmaceutical industry is the discovery, development, and marketing of safe and efficacious drugs for the treatment of human disease. However, drug companies do not exist as altruistic, charitable organizations. As with other shareholder-owned corporations within a capitalistic society, drug companies must earn profits in order to remain viable. Profits from the enterprise finance the essential research and development that leads to new drugs designed to address unmet medical needs. Thus, there exists a tension between the dual goals of enhancing the quality and duration of human life and that of increasing stockholder equity. Much has been written and spoken in the lay media about the high prices of prescription drugs and the hardships these place upon the elderly and others of limited income. Consequently, some consumer advocate groups support governmental imposition of price controls on ethical pharmaceuticals in the United States, such as those that exist in a number of other countries. However the out-of-pocket dollars spent by patients on prescription drugs must be weighed against the more costly and inherently risky alternatives of surgery and hospitalization, which can often be obviated by drug therapy. Consideration must also be given to the enormous expense associated with the development of new drugs. It typically takes 10 or more years from the inception of a drug in the laboratory to registrational approval and marketing at an overall cost which is now estimated to be in excess of $800 million and increasing, a figure that includes the opportunity costs of failed development campaigns. Only 1 out of 10,000–20,000 compounds prepared as potential drug candidates ever reach clinical testing in humans and the attrition rate of those that do is >80%, a success rate that has been stubbornly difficult to change despite advances in improving candidate quality and significant increases in investment in research and development. The expense of developing a promising drug grows steadily further through the pipeline it progresses; clinical trials can be several orders of magnitude more costly than the preclinical development of a compound. While the sales of drugs that complete clinical trials and reach the shelves of pharmacies can eventually recoup their developmental expenses many times over if successful, many fail to do so and the cost of the drugs that fail is never recovered.

The first conversion of naturally occurring fibers into threads strong enough to be looped into snares, knit to form nets, or woven into fabrics is lost in prehistory. Unlike stone weapons, such threads, cords, and fabrics—being organic in nature—have in most part disappeared, although in some dry caves traces remain. There is ample evidence to indicate that spindles used to assist in the twisting of fibers together had been developed long before the dawn of recorded history. In that spinning process, fibers such as wool were drawn out of a loose mass, perhaps held in a distaff, and made parallel by human fingers. (A maidservant so spins in Giotto’s

The Annunciation to Anne

, ca.

ad

1306, Arena Chapel, Padua, Italy [1].) A rod (spindle), hooked to the lengthening thread, was rotated so that the fibers while so held were twisted together to form additional thread. The finished length then was wound by hand around the spindle, which, in becoming the core on which the finished product was accumulated, served the dual role of twisting and storing and, in so doing, established a principle still in use today. (Even now, a “spindle” is 14,400 yards of coarse linen thread.) Thus, the formation of any threadlike structure became known as spinning, and it followed that a spider spins a web, a silkworm spins a cocoon, and manufactured fibers are spun by extrusion, although no rotation is involved.

It is difficult if not impossible to determine when mankind first systematically applied color to a textile substrate. The first colored fabrics were probably nonwoven felts painted in imitation of animal skins. The first dyeings were probably actually little more than stains from the juice of berries. Ancient Greek writers described painted fabrics worn by the tribes of Asia Minor. But just where did the ancient craft have its origins? Was there one original birthplace or were there a number of simultaneous beginnings around the world?

Adhesives have been used successfully in a variety of applications for centuries. Today, adhesives are more important than ever in our daily lives, and their usefulness is increasing rapidly. In the past few decades there have been significant advances in materials and in bonding technology. People now routinely trust their fortunes and their lives to adhesively bonded structures and rarely think about it.

Plastic (adj.) is defined by Webster [1] as “capable of being molded or modeled (e.g., clay) … capable of being deformed continuously and permanently in any direction with-out rupture.” Plastic (n.) a plastic substance;

specifically

: any of numerous organic synthetic or processed materials that are mostly thermoplastic or thermosetting polymers of high molecular weight and that can be made into objects, films, or filaments.

The word “rubber” immediately brings to mind materials that are highly flexible and will snap back to their original shape after being stretched. In this chapter a variety of materials are discussed that possess this odd characteristics. There will also be a discussion on the mechanism of this “elastic retractive force.” Originally, rubber meant the gum collected from a tree growing in Brazil. The term “rubber” was coined for this material by the English chemist Joseph Priestley, who noted that it was effective for removing pencil marks from paper. Today, in addition to Priestley’s natural product, many synthetic materials are made that possess these characteristics and many other properties. The common features of these materials are that they are made up of long-chain molecules that are amorphous (not crystalline), and the chains are above their glass transition temperature at room temperature.

Agrochemical Industry comes under life science segment of Chemical Industry and deals with production and distribution of pesticides and fertilizers to increase the crop yields. As Pharmaceuticals are meant for life, Agrochemicals are for livelihood.

Petroleum makes the world go around. In the realm of global economics and politics, that statement is hard to dispute. Petroleum is uniquely versatile. When wisely handled, it is safe and clean. It is still abundant, and it can be stored for years at a time simply by leaving it in the ground. Under ambient conditions, it is a liquid and relatively noncompressible, so it can be carried across oceans in large tankers or pumped through pipelines hundreds of miles long. Its distilled products have high energy densities. Fifteen gallons of gasoline can move a 3,300-lb automobile across 350 flat miles at 65 miles per hour. (In metric units, those values are 57 L, 1,480 kg, 565 km, and 105 kph.) We transform petroleum into thousands of useful substances: fuels, lubricants, and chemicals with exceedingly different properties—from baby oil to pesticides, from adhesives to laxatives, from artificial sweeteners to sulfuric acid (Tables 18.1 and 18.2).

The United States contains about 23% of the world’s coal reserves, with Russia, China, Australia, and India each having more than 5% of the reserves. Coal represents over 90% of US proven reserves of fossil fuels. Recoverable reserves of US coal are estimated to be 227 Gt (billion tons; all numbers quoted are in metric tons). Bituminous coals (with a heating value of 23.26–34.89 MJ/kg) comprise nearly one-half of total US coal reserves. Eastern US coals are generally bituminous. Western and southwestern US coals are mainly subbituminous (with a heating value of 20.93–27.91 MJ/kg) and lignite (with a heating value of 18.61–23.26 MJ/kg). Coal is a major source of energy for electric power production and process heat and can serve as a source of synthetic fuels and feedstock for the petrochemical industry.

Natural gas is a naturally occurring mixture of simple hydrocarbons and nonhydrocarbons that exists as a gas at ordinary pressures and temperatures. In the raw state, as produced from the earth, natural gas consists principally of methane (CH

4

) and ethane (C

2

H

4

), with fractional amounts of propane (C

3

H

8

), butane (C

4

H

10

), and other hydrocarbons, pentane (C

5

H

12

) and heavier. Occasionally, small traces of light aromatic hydrocarbons such as benzene and toluene may also be present.

The objective of the nuclear industry is to produce energy in the forms of heat from either fission reactions or radioactive decay and radiation from radioactive decay or by accelerator methods. For fission heat applications, the nuclear fuel has a very high specific energy content that currently has two principal uses, for military explosives and for electricity generation. As higher temperature reactors become more widely available, the high temperature heat (>900°C) will also be useful for making chemicals such as hydrogen. For radiation applications, the emissions from radioactive decay of unstable nuclides are employed in research, medicine, and industry for diagnostic purposes and for chemical reaction initiation. Radioactive decay heat is also employed to generate electricity from thermoelectric generators for low-power applications in space or remote terrestrial locations. Radiation produced from accelerator-based sources is used for geologic investigation (e.g., identifying oil deposits), materials modification, and contrast imaging of dense media (e.g., security inspections in commercial shipping). Fuel from the first atomic pile is shown in Fig. 21.1.

Nitrogen products are among the most important chemicals produced in the world today. The largest quantities are used as fertilizers, but nitrogen products also find very important uses in the manufacture of nylon and acrylic fibers, methacrylate and other plastics, foamed insulation and plastics, metal plating, gold mining, animal feed supplements, and herbicides.

Phosphates, compounds of the element phosphorous, are produced from relatively abundant supplies of phosphate rock.

Fertilizers provide plants with the nutrients they need for their growth and development. Plants live, grow, and reproduce by taking up water and nutrients, carbon dioxide from the air, and energy from the sun. Apart from carbon, hydrogen, and oxygen, which collectively make up 90–95% of the dry matter of all plants, other nutrients needed by plants come essentially from the media in which they grow—essentially in the soil. The other nutrients are subdivided into primary nutrients (nitrogen, phosphorus, and potassium) and secondary nutrients (calcium, magnesium, and sulfur). In addition, plants also need other nutrients in much smaller amounts, and they are referred to as micronutrients (boron, chlorine, copper, iron, manganese, molybdenum, and zinc).

Sulfur is one of the few elements that is found in its elemental form in nature. Typical sulfur deposits occur in sedimentary limestone/gypsum formations, in limestone/anhydrite formations associated with salt domes or in volcanic rock [1]. A yellow solid at normal temperature, sulfur becomes progressively lighter in color at lower temperatures and is almost white at the temperature of liquid air. It melts at 114–119°C (depending on crystalline form) to a yellow liquid which turns orange as the temperature is increased. The low viscosity of the liquid begins to rise sharply above 160°C, peaking at 93 Pas at 188°C, and then falling as the temperature continues to rise to its boiling point of 445°C. This and other anomalous properties of the liquid state are due to equilibria between the various molecular species of sulfur which includes small chains and rings.

There are very many inorganic salts, but only one of them, sodium chloride, is commonly referred to by the simple name “salt.” Sodium chloride is ubiquitous, and more that 14,000 uses have been tabulated [1]. It is a raw material in the production of many chemicals, including chlorine, caustic soda (sodium hydroxide), synthetic soda ash (sodium carbonate), sodium chlorate, sodium sulfate, and metallic sodium. Indirectly, it is also used to produce many other sodium salts and the very useful hydrochloric acid.

Industrial gases may actually be used as gases, liquids, or cryogenic liquids. Industrial users generally accept them as those gases used primarily in their pure form in large quantities. Most of the gases we consider to be industrial gases have been in use for many years. Processes for the cryogenic separation of the air gases were developed as early as 1895, with commercial production of oxygen beginning in 1902. Nitrous oxide was used as an anesthetic as early as 1799. Carbon dioxide had been identified as a specific substance by 1608. Methane has been used as an energy source since the 1700s. Other gaseous compounds commonly used today for specific manufacturing processes (e.g., electronics/semiconductors, plastics) are discussed in other chapters of this Handbook related to those processes.

Wood along with the outer portion of tree trunk (bark) [1] (Fig. 28.1) represents the bulk of forestry biomass materials and has been utilized by humans since antiquity. Trees provided a source of many products required by early humans such as food, medicine, fuel, and tools. For example, the bark of the willow tree, when chewed, was used as a painkiller in early Greece and was the precursor of the present-day aspirin. The leaf extracts and nuts from Gingo trees have been used in traditional Chinese medicines for thousands of years. Wood served as the primary fuel in the United States until about the turn of the nineteenth century, and even today over one-half of the wood now harvested in the world is used for heating fuel.

Change is constant in the coatings market. As mergers, acquisitions, and partnerships take shape, consolidation and globalization remain prominent. The 80/20 rule (20% of the firms accounting for 80% of business) takes effect as the need for regulatory and environmental compliance continues to plague the market. In 1975, the United States alone supported about 2,000 coatings companies. Today, there are less than half that many.

Fermentation products have penetrated almost every sector of our daily lives. They are used in ethical and generic drugs, clinical and home diagnostics, defense products, nutritional supplements, personal care products, food and animal feed ingredients, cleaning and textile processing, and in industrial applications such as fuel ethanol production. Even before knowing about the existence of microorganisms, for thousands of years ancient people routinely used them for making cheese, soy sauces, yogurt, and bread. Although humans have used fermentation as the method of choice for manufacturing for a long time, it is only now being recognized for its potential towards sustainable industrial development.

All life processes, whether plant, animal, or microbial, depend upon a complex network of enzyme-catalyzed chemical reactions for cellular growth and maintenance [1, 2]. As catalysts, enzymes facilitate reactions by enabling alternate reaction mechanisms with lower activation energy, but in no way modify the thermodynamic equilibrium constant or the free energy change of a chemical transformation. They generate enormous kinetic rate accelerations, often exceeding factors of 10

12

-fold relative to the rate of the uncatalyzed reaction. Enzymes are capable of performing many different chemistries, can be produced on a large scale, and typically operate at ambient temperatures and near neutral pH [3–5]. These attributes have captured the attention of generations of scientists and engineers alike and enabled the dramatic growth of the enzyme industry over the past century.

The biotechnology and pharmaceutical industries have seen a recent surge in the development of biological drug products manufactured from engineered mammalian cell lines. Since the hugely successful launch of human tissue plasminogen activator in 1987 and erythropoietin in 1988, the biopharmaceutical market has grown immensely. Global sales in 2003 exceeded US $30 billion [1]. Currently, a total of 108 biotherapeutics are approved and available to patients (Table 32.1). In addition, 324 medically related, biotechnology-derived medicines for nearly 150 diseases are in clinical trials or under review by the US Food and Drug Administration [2]. These biopharmaceutical candidates promise to bring more and better treatments to patients. Compared to small molecule drugs, biotherapeutics show exquisite specificity with fewer off-target interactions and improved safety profiles. Protein engineering technologies have advanced to create protein drugs with improved efficacy, specificity, stability, pharmacokinetics, and solubility. Strategies that have been employed to implement these changes include mutagenesis, recombination, and other directed evolution methods, as well as rational design and structure-based computational approaches [3–7]. These advanced protein engineering technologies are creating novel drug designs and clever treatment strategies that are fuelling the biopharmaceutical market growth.

In its simplest terms, biomass is all the plant matter found on our planet. Biomass is produced directly by photosynthesis, the fundamental engine of life on earth. Plant photosynthesis uses energy from the sun to combine carbon dioxide from the atmosphere with water to produce organic plant matter. More inclusive definitions are possible. For example, animal products and waste can be included in the definition of biomass. Animals, like plants, are renewable; but animals clearly are one step removed from the direct use of sunlight. Using animal rather than plant material thus leads to substantially less efficient use of our planet’s ultimate renewable resource, the sun. So, we emphasize plant matter in our definition of biomass. It is the photosynthetic capability of plants to utilize carbon dioxide from the atmosphere that leads to its designation as a “carbon neutral” fuel, meaning that it does not introduce new carbon into the atmosphere. In reality—as discussed later in the description of life cycle assessments of biomass use—we find that biomass fuels are not quite carbon neutral, because somewhere in the life cycle of their production, conversion, and distribution, some fossil energy carbon is released.

Biotechnology

has been defined by various groups and broadly includes technologies that utilize living organisms or parts of biological systems. The nurture of man and animals, and provision of replenishable industrial materials, typically includes: (1) growing selected species or their genetic modifications; (2) harvest, preprocess storage, conversion into useful products, and protection until use; and (3) utilization or disposal of byproducts and wastes in the most beneficial or least-cost manner. Specific actions may be taken to suppress residual enzymes and contaminating microorganisms that could degrade product value. Also,

remediation

(restoration) of air and water used in processing to near-pristine condition often is mandated today.

Sugar and starch are among the most abundant plant products available, and large industries exist worldwide to extract and process them from agricultural sources. The world production of sugar (sucrose from cane and beet) in 2007/2008 was 170.4 million metric tons, raw value [1], with 20.7% being beet sugar and 79.3% cane sugar. The proportion of beet sugar to cane sugar has fallen steadily since about 1971, when it constituted 42.8% of total sugar production [2]. The decline in beet sugar proportion represents not so much a decline in beet production, which has remained in the range of 33–39 million metric tons, but rather a continued increase in cane sugar production from around 72 million metric tons in 1991 to 134 million metric tons in 2008. The total production of world sugar has risen dramatically since 1971/1972, when it was 71.7 million tons [3].

The origin of the word “soap” is traced to sacrificial Mount Sapo of ancient Roman legend. The mixture of fat and wood ashes that reacted to form soap was carried by rain to the banks of the Tiber River and was found as a clay deposit useful for cleaning clothes [1].

The average citizen in today’s world gives little thought to the important role that commercial explosives play in their lives and how their use is linked to our standard of living and our way of life. Explosives provide the energy required to give us access to the vast resources of the earth for the advancement of civilization. In 2010, the Mineral Information Institute estimated that the average baby born in America will need the following quantities of minerals, metals, and fuels in their lifetime: copper—932 lb; salt—31,779 lb; clays—12,121 lb; zinc—544 lb; stone, sand, and gravel—1,100,000 lb; petroleum—72,499 gal; lead—777 lb; other minerals and metals—43,822 lb: natural gas—5.93 million ft

3

; cement—41,181 lb; iron ore—14,530 lb; bauxite (aluminum)—4,040 lb; coal—542,968 lb; phosphate rock—15,152 lb; and gold—1.383 troy oz [1]. Availability of all of these materials, which total 2.9 million lb/individual, depends on the use of explosives.

Energy consumption in the world has increased significantly over the past 20 years. In 2008, worldwide energy consumption was reported as 142,270 TWh [1], in contrast to 54,282 TWh in 1973; [2] this represents an increase of 262%. The surge in demand could be attributed to the growth of population and industrialization over the years. In 2009, energy consumption was reported as 140,700 TWh, a slight decrease (1.1%) when compared to 2008 due to the world financial crisis [1], while in 2010 there was a rise in the consumption to 149,469 TWh, due to the recovery of the economy at that time [3]. Conversely, the total supply of energy in the world had caught up with the consumption as shown in Table 38.1 [2, 4]. Approximately 10–14% of the total energy supply in the world is delivered as electric energy. In addition, the amount of power supplied by renewables had increased over the years, from 37 TWh in 1973 to 612 TWh in 2008 (as shown in Table 38.1), which represents a growth of 94%. However, the total amount of energy available from renewables based on current technology could reach up to 834,280 TWh (distributed as: 53.2% solar, 20.0% wind, 16.7% geothermal, 8.4% biomass, and 1.7% hydropower); [5] that is, 5.7 times the world energy supply in 2008. Nevertheless, renewable sources of energy such as solar and wind are intermittent and only abundant in certain regions, which causes a limitation on the use and distribution of such sources of energy. An undersized world energy surplus (based on a total energy balance including supply, consumption, and losses) is usually reported annually; a comprehensive analysis is presented in the literature [2].