Industrial-scale

A microelectrode is an electrode with at least one dimension small enough that its properties are a fimction of size, typically with at least one dimension smaller than 50 pm [28, 29, 30, 31, 32 and 33]. If compared with electrodes employed in industrial-scale electrosynthesis or in laboratory-scale synthesis, where the characteristic dimensions can be of the order of metres and centimetres, respectively, or electrodes for voltannnetry with millimetre dimension, it is clear that the size of the electrodes can vary dramatically. This enonnous difference in size gives microelectrodes their unique properties of increased rate of mass transport, faster response and decreased reliance on the presence of a conducting medium. Over the past 15 years, microelectrodes have made a tremendous impact in electrochemistry. They have, for example, been used to improve the sensitivity of ASV in enviroiunental analysis, to investigate rapid... 

On the industrial scale oxygen is obtained by the fractional distillation of air. A common laboratory method for the preparation of oxygen is by the decomposition of hydrogen peroxide. H Oj, a reaction catalysed by manganese(IV) oxide ... 

On the industrial scale it is produced in large quantities for the manufacture of sulphuric acid and the production methods are dealt with later. It was once estimated that more than 4 000 000 tons of sulphur dioxide a year entered the atmosphere of Britain from the burning of coal and oil. 

Sulphur trioxide is used on an industrial scale for sulphonating organic compounds. 

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

On the industrial scale, bromine is obtained from sea water by using the displacement reaction with chlorine (the reaction by which bromine was discovered) ... 

Cobalt compounds have been in use for centuries, notably as pigments ( cobalt blue ) in glass and porcelain (a double silicate of cobalt and potassium) the metal itself has been produced on an industrial scale only during the twentieth century. Cobalt is relatively uncommon but widely distributed it occurs biologically in vitamin B12 (a complex of cobalt(III) in which the cobalt is bonded octahedrally to nitrogen atoms and the carbon atom of a CN group). In its ores, it is usually in combination with sulphur or arsenic, and other metals, notably copper and silver, are often present. Extraction is carried out by a process essentially similar to that used for iron, but is complicate because of the need to remove arsenic and other metals. 

Industrial scale polymer forming operations are usually based on the combination of various types of individual processes. Therefore in the computer-aided design of these operations a section-by-section approach can be adopted, in which each section of a larger process is modelled separately. An important requirement in this approach is the imposition of realistic boundary conditions at the limits of the sub-sections of a complicated process. The division of a complex operation into simpler sections should therefore be based on a systematic procedure that can provide the necessary boundary conditions at the limits of its sub-processes. A rational method for the identification of the subprocesses of common types of polymer forming operations is described by Tadmor and Gogos (1979). 

All these highly complex compounds are produced on the industrial scale from microorganisms. Only the S-lactams are modified chemically after the isolation from the fermentation broth. We shall describe these partial syntheses as well as some typical synthetic sequences of academic total syntheses. 

Cyclooctatetraene can be obtained on an industrial scale by metal carbonyl catalyzed thermal tetramerization of acetylene. If cyclooctatetraene is UV-irradiated at low temperature in the presence of acetone, it is reversibly rearranged to form semibullvalene (H.E. Zimmerman, 1968, 1970). 

Like the chlorination of methane chlorination of ethane is carried out on an industrial scale as a high temperature gas phase reaction... 

Athene formation requires that X and Y be substituents on adjacent carbon atoms By mak mg X the reference atom and identifying the carbon attached to it as the a carbon we see that atom Y is a substituent on the p carbon Carbons succeedmgly more remote from the reference atom are designated 7 8 and so on Only p elimination reactions will be dis cussed m this chapter [Beta (p) elimination reactions are also known as i 2 eliminations ] You are already familiar with one type of p elimination having seen m Section 5 1 that ethylene and propene are prepared on an industrial scale by the high temperature dehydrogenation of ethane and propane Both reactions involve (3 elimination of H2... 

At one time acetaldehyde was prepared on an industrial scale by this method Modern methods involve direct oxidation of ethylene and are more economical... 

The conjugated diene 1 3 butadiene is used m the manufacture of synthetic rubber and IS prepared on an industrial scale m vast quantities Production m the United States is currently 4 X 10 Ib/year One industrial process is similar to that used for the prepara tion of ethylene In the presence of a suitable catalyst butane undergoes thermal dehy drogenation to yield 1 3 butadiene... 

When applied to the synthesis of ethers the reaction is effective only with primary alcohols Elimination to form alkenes predominates with secondary and tertiary alcohols Diethyl ether is prepared on an industrial scale by heating ethanol with sulfuric acid at 140°C At higher temperatures elimination predominates and ethylene is the major product A mechanism for the formation of diethyl ether is outlined m Figure 15 3 The individual steps of this mechanism are analogous to those seen earlier Nucleophilic attack on a protonated alcohol was encountered m the reaction of primary alcohols with hydrogen halides (Section 4 12) and the nucleophilic properties of alcohols were dis cussed m the context of solvolysis reactions (Section 8 7) Both the first and the last steps are proton transfer reactions between oxygens... 

In general this method is limited to the preparation of symmetrical ethers m which both alkyl groups are primary Isopropyl alcohol however is readily available at low cost and gives high enough yields of diisopropyl ether to justify making (CH3)2CHOCH(CH3)2 by this method on an industrial scale... 

Manufacture. Furfuryl alcohol has been manufactured on an industrial scale by employing both Hquid-phase and vapor-phase hydrogenation of furfural (56,57). Copper-based catalysts are preferred because they are selective and do not promote hydrogenation of the ring. 

A photochemical partial synthesis of aldosterone (19) made the hormone available on an industrial scale for the first time (114). Corticosterone acetate (51 acetate) is treated with nitrosyl chloride in pyridine at 20°C to yield the 11-nitrite (115). Irradiation of (115) leads to rearrangement with formation of the C g-oxime (116). Removal of the oxime residue with nitrous acid furnishes aldosterone (19) in excellent yield. 

Strain-Gauge Load Cells. The majority of industrial scales today use strain-gauge load cells as the weighing element. The strain-gauge load cell is a device which, when a force is appHed to it, gives an electrical output proportional to the appHed load. 

Technical Publication, National Industrial Scale Association, Birmingham, Ala. 

The subject has been reviewed (37,38). Water may be added to the feed to suppress methyl acetate formation, but is probably not when operating on an industrial scale. Water increase methanol conversion, but it is involved in the unavoidable loss of carbon monoxide. A typical methanol carbonylation flow sheet is given in Figure 2. 

The plutonium usually contains isotopes of higher mass number (Fig. 1). A variety of industrial-scale processes have been devised for the recovery and purification of plutonium. These can be divided, in general, into the categories of precipitation, solvent extraction, and ion exchange. 

Industrial-scale adsorption processes can be classified as batch or continuous (53,54). In a batch process, the adsorbent bed is saturated and regenerated in a cychc operation. In a continuous process, a countercurrent staged contact between the adsorbent and the feed and desorbent is estabhshed by either a tme or a simulated recirculation of the adsorbent. 

J. A. Johnson and A. R. Oroskar, "Sorbex Technology for Industrial Scale Separation," iu H. G. Karge and J. Weitkamp, eds.. Zeolites as Catalysts,... 

Until recently most industrial scale, and even bench scale, bioreactors of this type were agitated by a set of Rushton turbines having about one-thind the diameter of the bioreactor (43) (Fig. 3). In this system, the air enters into the lower agitator and is dispersed from the back of the impeller blades by gas-fiUed or ventilated cavities (44). The presence of these cavities causes the power drawn by the agitator, ie, the power requited to drive it through the broth, to fall and this has important consequences for the performance of the bioreactor with respect to aeration (35). k a has been related to the power per unit volume, P/ U, in W/m and to the superficial air velocity, in m/s (20), where is the air flow rate per cross-sectional area of bioreactor. This relationship in water is... 

The effect of increasing column diameter is to increase the tendency for circulation, and hence to increase the axial mixing (62,63). However, extremely few measurements of axial mixing at the industrial scale are available, so large-scale contactor design must still rely quite heavily on empirical experience with the particular type of equipment. 

Eor design of a large-scale commercial extractor, the pilot-scale extractor should be of the same type as that to be used on the large scale. Reflable scale-up for industrial-scale extractors still depends on correlations based on extensive performance data collected from both pilot-scale and large-scale extractors covering a wide range of Hquid systems. Only limited data for a few types of large commercial extractors are available in the Hterature. 

Other Spinning Processes. The following examples are of scientific interest but have not been employed on an industrial scale. 

Nutsche Filter. The nutsche filter (Fig. 8) is simply an industrial-scale equivalent of the laboratory Buckner funnel. Nutsche filters consist of cylindrical or rectangular tanks divided into two compartments of roughly the same size by a horizontal medium supported by a filter plate. Vacuum is apphed to the lower compartment, into which the filtrate is collected. It is customary to use the term nutsche only for filters that have sufficient capacity to hold the filtrate from one complete charge. The cake is removed manually or sometimes by reslurrying. 

Product innovation absorbs considerable resources in the fine chemicals industry, in part because of the shorter life cycles of fine chemicals as compared to commodities. Consequently, research and development (R D) plays an important role. The main task of R D in fine chemicals is scaling-up lab processes, as described, eg, in the ORAC data bank or as provided by the customers, so that the processes can be transferred to pilot plants (see Pilot PLANTS AND microplants) and subsequently to industrial-scale production. Thus the R D department of a fine chemicals manufacturer typically is divided into a laboratory or process research section and a development section, the latter absorbing the Hon s share of the R D budget, which typically accounts for 5 to 10% of sales. Support functions include the analytical services, engineering, maintenance, and Hbrary. 

In the laboratory or process research section a laboratory procedure for a fine chemical is worked out. The resulting process description provides the necessary data for the determination of preliminary product specifications, the manufacture of semicommercial quantities in the pilot plant, the assessment of the ecological impact, an estimation of the manufacturing cost in an industrial-scale plant, and the vaHdation of the process and determination of raw material specifications. 

The development section serves as an intermediary between laboratory and industrial scale and operates the pilot plant. A dkect transfer from the laboratory to industrial-scale processes is stiH practiced at some small fine chemicals manufacturers, but is not recommended because of the inherent safety, environmental, and economic risks. Both equipment and plant layout of the pilot plant mirror those of an industrial multipurpose plant, except for the size (typically 100 to 2500 L) of reaction vessels and the degree of process automation. 

A similar technique to the Bureau of Mines trommel process called pellet flocculation has been used in Japan on a number of substrates on an industrial scale (47) using equipment made by the Ebara-Infilco Co. Combinations of inorganic salts such as lime with polyacrylamides are used as flocculants. 

Disposal. Fluorine can be disposed of by conversion to gaseous perfluorocarbons or fluoride salts. Because of the long atmospheric lifetimes of gaseous perfluorocarbons (see Atmospheric models), disposal by conversion to fluoride salts is preferred. The following methods are recommended scmbbing with caustic solutions (115,116) reaction with soHd disposal agents such as alumina, limestone, lime, and soda lime (117,118) and reaction with superheated steam (119). Scmbbing with caustic solution and, for dilute streams, reaction with limestone, are practiced on an industrial scale. 

Fluoroaromatics are produced on an industrial scale by diazotization of substituted anilines with sodium nitrite or other nitrosating agents in anhydrous hydrogen fluoride, followed by in situ decomposition (fluorodediazoniation) of the aryldiazonium fluoride (21). The decomposition temperature depends on the stabiHty of the diazonium fluoride (22,23). A significant development was the addition of pyridine (24), tertiary amines (25), and ammonium fluoride (or bifluoride) (26,27) to permit higher decomposition temperatures (>50° C) under atmospheric pressure with minimum hydrogen fluoride loss. 

Explosions have been reported during preparation of duoronitroaromatics by the Halex reaction on a laboratory or industrial scale (9-duoronitroben2ene (65) 2,4-dinitroduoroben2ene (66) 2,4-diduoronitroben2ene (67) and l,5-diduoro-2,4-dinitroben2ene (68). 

The conversion of coal to gas on an industrial scale dates to the early nineteenth century (14). The gas, often referred to as manufactured gas, was produced in coke ovens or similar types of retorts by simply heating coal to vaporize the volatile constituents. Estimates based on modem data indicate that the gas mixture probably contained hydrogen (qv) (ca 50%), methane (ca 30%), carbon monoxide (qv) and carbon dioxide (qv) (ca 15%), and some inert material, such as nitrogen (qv), from which a heating value of approximately 20.5 MJ/m (550 Btu/fT) can be estimated (6). 

TiH2 is prepared on an industrial scale by dkect combination of hydrogen and the metal (sponge, ingot, scrap, etc) at 200—650°C, followed by cooling in an H2 atmosphere. An alternative method is the reduction of the oxide using calcium hydride under hydrogen ... 

A considerable amount of carbon is formed in the reactor in an arc process, but this can be gready reduced by using an auxiUary gas as a heat carrier. Hydrogen is a most suitable vehicle because of its abiUty to dissociate into very mobile reactive atoms. This type of processing is referred to as a plasma process and it has been developed to industrial scale, eg, the Hoechst WLP process. A very important feature of a plasma process is its abiUty to produce acetylene from heavy feedstocks (even from cmde oil), without the excessive carbon formation of a straight arc process. The speed of mixing plasma and feedstock is critical (6). 

Farbwerke Hoechst AG and Hbls AG have cooperated in the development of industrial-scale plasma units up to 10,000 kW (7). Yields of acetylene of 40—50 wt % with naphtha feedstock, and about 27 wt % with cmde oil feedstock, have been obtained. Acetylene concentration in the cracked gas is in the 10—15 vol % range. 

Hoechst WHP Process. The Hoechst WLP process uses an electric arc-heated hydrogen plasma at 3500—4000 K it was developed to industrial scale by Farbwerke Hoechst AG (8). Naphtha, or other Hquid hydrocarbon, is injected axially into the hot plasma and 60% of the feedstock is converted to acetylene, ethylene, hydrogen, soot, and other by-products in a residence time of 2—3 milliseconds Additional ethylene may be produced by a secondary injection of naphtha (Table 7, Case A), or by means of radial injection of the naphtha feed (Case B). The oil quenching also removes soot. 

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