Processing Economics

A very important but rather complex application of surface chemistry is to the separation of various types of solid particles from each other by what is known as flotation. The general method is of enormous importance to the mining industry it permits large-scale and economic processing of crushed ores whereby the desired mineral is separated from the gangue or non-mineral-containing material. Originally applied only to certain sulfide and oxide ores. 

It was not until the twentieth century that furfural became important commercially. The Quaker Oats Company, in the process of looking for new and better uses for oat hulls found that acid hydrolysis resulted in the formation of furfural, and was able to develop an economical process for isolation and purification. In 1922 Quaker announced the availability of several tons per month. The first large-scale appHcation was as a solvent for the purification of wood rosin. Since then, a number of furfural plants have been built world-wide for the production of furfural and downstream products. Some plants produce as Httie as a few metric tons per year, the larger ones manufacture in excess of 20,000 metric tons. 

Catalyst recovery is a major operational problem because rhodium is a cosdy noble metal and every trace must be recovered for an economic process. Several methods have been patented (44—46). The catalyst is often reactivated by heating in the presence of an alcohol. In another technique, water is added to the homogeneous catalyst solution so that the rhodium compounds precipitate. Another way to separate rhodium involves a two-phase Hquid such as the immiscible mixture of octane or cyclohexane and aliphatic alcohols having 4—8 carbon atoms. In a typical instance, the carbonylation reactor is operated so the desired products and other low boiling materials are flash-distilled. The reacting mixture itself may be boiled, or a sidestream can be distilled, returning the heavy ends to the reactor. In either case, the heavier materials tend to accumulate. A part of these materials is separated, then concentrated to leave only the heaviest residues, and treated with the immiscible Hquid pair. The rhodium precipitates and is taken up in anhydride for recycling. 

Plasteins ate formed from soy protein hydrolysates with a variety of microbial proteases (149). Preferred conditions for hydrolysis and synthesis ate obtained with an enzyme-to-substrate ratio of 1 100, and a temperature of 37°C for 24—72 h. A substrate concentration of 30 wt %, 80% hydrolyzed, gives an 80% net yield of plastein from the synthesis reaction. However, these results ate based on a 1% protein solution used in the hydrolysis step this would be too low for an economical process (see Microbial transformations). 

With the avadabihty of polymerization catalysts, extensive efforts were devoted to developing economical processes for manufacture of isoprene. Several synthetic routes have been commercialized. With natural mbber as an alternative, the ultimate value of the polymer was more or less dictated by that market. The first commercial use of isoprene in the United States started in 1940. It was used as a minor comonomer with isobutylene for the preparation of butyl mbber. Polyisoprene was commercialized extensively in the 1960s (6). In the 1990s isoprene is used almost exclusively as a monomer for polymerization (see ELASTOLffiRS,SYNTHETic-POLYisoPRENE). 

Table 1. Grade of Ore for Economic Processing and Estimated World Reserves...

Naphthenic acids are normal constituents of nearly all cmde oils, but not all cmdes contain sufficient quantities of usable acids to make recovery an economic process. Heavy cmdes from geologically young formations have the highest acid content, and paraffinic cmdes usually have low acid content. 

Synthesis. Exploratory research has produced a wide variety of odorants based on natural stmctures, chemicals analogous to naturals, and synthetic materials derived from available raw materials and economical processing. As in most areas of the chemical industry, the search for new and useful substances is made difficult by the many materials that have been patented and successfully commercialized (4). In the search for new aroma chemicals, many new materials are prepared for screening each year. Chemists who perform this work are involved in a creative exercise that takes its direction from the commercial sector in terms of desirable odor types and specific performance needs. Because of economic limitations, considerations of raw material costs and available processing methods may play a role eady in the exploratory work. 

Although phosphine [7803-51-2] was discovered over 200 years ago ia 1783 by the French chemist Gingembre, derivatives of this toxic and pyrophoric gas were not manufactured on an industrial scale until the mid- to late 1970s. Commercial production was only possible after the development of practical, economic processes for phosphine manufacture which were patented in 1961 (1) and 1962 (2). This article describes both of these processes briefly but more focus is given to the preparation of a number of novel phosphine derivatives used in a wide variety of important commercial appHcations, for example, as flame retardants (qv), flotation collectors, biocides, solvent extraction reagents, phase-transfer catalysts, and uv photoinitiators. 

A number of 2eohtic materials have been claimed to cataly2e this reaction and reaction temperatures are on the order of 200—350°C with pressures as high as 18000 kPa (2600 psi) reported. This is a low conversion process and recycle of the unconverted starting materials is necessary to provide an economical process. Amination of ethylene to produce ethylamines cataly2ed by ammonium iodide is reported, but not beheved to be practiced commercially (15,16). Alkyl Halide Amination (Method 7). The oldest technology for pioducing amines is the reaction of ammonia with an alkyl hahde. This... 

Arc wire utilizes two continuously fed 1.6-mm dia intersecting wires with a d-c arc maintained between the wire tips as they meet. Compressed gas (usually air) strips the molten metal from the tips and forms a directional spray stream. This process is widely used to spray most metals. Arc wire is the most economical process because of the wire feedstock. Moreover, it utilizes - 10% of the thermal energy of the other spray processes (0.4 vs 6.6 kWh/kg using stainless steel) because of the direct arc heating of the wire tips. 

Passing a stream of nitrogen at 95—100°C through a reaction mixture of ethyl ether and 30 wt % oleum prepared at 15°C results in the entrainment of diethyl sulfate. Continuous operation provides a >50% yield (96). The most economical process for the manufacture of diethyl sulfate starts with ethylene and 96 wt % sulfuric acid heated at 60°C. The resulting mixture of 43 wt % diethyl sulfate, 45 wt % ethyl hydrogen sulfate, and 12 wt % sulfuric acid is heated with anhydrous sodium sulfate under vacuum, and diethyl sulfate is obtained in 86% yield the commercial product is >99% pure (97). 

Modifications and improvements to the basic process have been made to reduce the quantity of waste products (21,22) in the wet chemical process, to recover HF, and to economically process low Ta, high Nb containing raw materials (23). Several alternative extraction media have been reported in the hterature. Most, except for tributylphosphate (TBP) (24) and tri- -octylphosphine oxide (TOPO) (25), have never been used in industry. 

Benzoic Acid. Ben2oic acid is manufactured from toluene by oxidation in the liquid phase using air and a cobalt catalyst. Typical conditions are 308—790 kPa (30—100 psi) and 130—160°C. The cmde product is purified by distillation, crystallization, or both. Yields are generally >90 mol%, and product purity is generally >99%. Kalama Chemical Company, the largest producer, converts about half of its production to phenol, but most producers consider the most economic process for phenol to be peroxidation of cumene. Other uses of benzoic acid are for the manufacture of benzoyl chloride, of plasticizers such as butyl benzoate, and of sodium benzoate for use in preservatives. In Italy, Snia Viscosa uses benzoic acid as raw material for the production of caprolactam, and subsequendy nylon-6, by the sequence shown below. 

Reichsteia and Grbssner s second L-ascorbic acid synthesis became the basis for the iadustrial vitamin C production. Many chemical and technical modifications have improved the efficiency of each step, enabling this multistep synthesis to remain the principal, most economical process up to the present (ca 1997) (46). L-Ascorbic acid is produced ia large, iategrated, automated faciUties, involving both continuous and batch operations. The process steps are outlined ia Figure 7. Procedures require ca 1.7-kg L-sorbose/kg of L-ascorbic acid with ca 66% overall yield ia 1977 (55). Siace 1977, further continuous improvement of each vitamin C production step has taken place. Today s overall ascorbic acid yield from L-sorbose is ca 75%. In the mid-1930s, the overall yield from L-sorbose was ca 30%. 

Around 1800, the attack of chromite [53293-42-8] ore by lime and alkaU carbonate oxidation was developed as an economic process for the production of chromate compounds, which were primarily used for the manufacture of pigments (qv). Other commercially developed uses were the development of mordant dyeing using chromates in 1820, chrome tanning in 1828 (2), and chromium plating in 1926 (3) (see Dyes and dye intermediates Electroplating Leather). In 1824, the first chromyl compounds were synthesized followed by the discovery of chromous compounds 20 years later. Organochromium compounds were produced in 1919, and chromium carbonyl was made in 1927 (1,2). 

Compact brazed aluminum plate-fin heat exchangers can be used in most cryogenic hydrogen purification apphcations. The use of these relatively low cost heat exchangers, combined with low separation energy requirements, results in a highly economical process for hydrogen purification. 

The need for a large number of stages and for the special equipment makes gaseous diffusion an expensive process. The three United States gaseous diffusion plants represent a capital expenditure of close to 2.5 x 10 dollars (17). However, the gaseous diffusion process is one of the more economical processes yet devised for the separation of uranium isotopes on a large scale. 

For years this was the process used to manufacture alizarin (19) although it was claimed that a more economical process would result if 2-chloroanthraquinone was used instead of silver salt (20). In 1870, the market price for 100% synthetic alizarin was 200 German marks, but by 1912 it had fallen to 5—6 marks, thereby sounding the death of natural alizarin (21). Also, dyers welcomed synthetic alizarin since it was 100% 1,2-dihydroxyanthraquinone natural alizarin always contained varying amounts of other polyhydroxyanthraquinones. 

Other Derivatives. Ethylene carbonate, made from the reaction of ethylene oxide and carbon dioxide, is used as a solvent. Acrylonitrile (qv) can be made from ethylene oxide via ethylene cyanohydrin however, this route has been entirely supplanted by more economic processes. Urethane intermediates can be produced using both ethylene oxide and propylene oxide in their stmctures (281) (see Urethane polymers). 

The decision to cathodically protect reinforced concrete structures depends on technical and economic considerations. Cathodic protection is not an economic process for small area displacements of the concrete due to corrosion of the reinforcing steel arising from insufficient concrete covering. On the other hand, the... 

As a first step in the selection process, the applicability of the various solidification/ stabilization processes for specific contaminants can be determined using Table 12. Since these waste treatment systems vary widely in their applicability, cost, and pretreatment requirements, many are limited as to the types of waste that can be economically processed. Waste characteristics such as organic content, inorganic content, viscosity and... 

Georgescu-Roegen, N. (1971). The Entropy and the Economic Process. Cambridge, MA Harvard University Press. 

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