Scale laboratory

This section reviews the criteria for hazards testing of reactions on a small scale, particularly whether the experiments should be run in an open laboratory or in a high-pressure cell. 

The first step is the evaluation of thermodynamic and kinetic data by quantitative energy calculations and qualitative considerations as discussed in Chapter 2. The results may provide a satisfactory answer as to whether the reaction can be performed in the open laboratory or requires a high-pressure cell arrangement on the small scale. Further evaluations are required for scale-up. Toxicity, corrosivity, type of apparatus, size, and other criteria must also be considered. 

FIGURE 3.24. Flow Sheet to Determine Proper Site for Reactivity Testing (Laboratory or High-pressure Cell). 

Credible cases are identified when the probability of decomposition is low. Energy calculations of known or proposed chemical reactions and side reactions are carried out to determine a more likely level of energy release than the worst-case scenario. Therefore, it is necessary to define the most energetic reactions. Enthalpies of reaction are calculated, followed by calculations of the adiabatic temperature rise of the system and the corresponding pressure rise. 

The sensitivity to impact can be determined as described in Chapter 2. Impact sensitivities below 60 J for solids and 10 J for liquids are considered positive hazards. 

The situation changes somewhat when the costs of operation and of the material being purified are taken into account. The reason is that unless a touching band separation is being carried out, there is always a certain loss of crude material which is not recovered in the pure product fractions. Where the cost of this crude is low, this is of little consequence. In contrast, if the cost of the crude product is very high, the losses of crude can become overwhelmingly important. This can be illustrated by consideration of two scenarios - a laboratory scale purification and an industrial scale operation. 

In this example we take a purification of 200 g of material. If we assume some typical parameters, this quantity of material may be purified in 27 runs at a load of 7.5 g per run using a column 8 cm in diameter. If each chromatogram takes 

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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 a laboratory scale, hydrotliennal syntliesis is usually carried out in Teflon-coated, stainless-steel autoclaves under autogenous pressure. A typical syntliesis mixture consists of up to four major constituents, a T-atoni source (silicon and aluminium, otlier elements may also be incoriiorated as indicated above), a solvent (almost exclusively... 

For most laboratory scale reductions of aldehydes and ketones catalytic hydro genation has been replaced by methods based on metal hydride reducing agents The two most common reagents are sodium borohydride and lithium aluminum hydride... 

Fig. 7. A bead filter, one of many types of biological filters, shown in association with a laboratory-scale recirculating water system. Small plastic beads inside the fiber glass chamber provide surface area for colonisation by bacteria that convert ammonia to nitrate.

After development of a new process scheme at laboratory scale, constmction and operation of pilot-plant faciUties to confirm scale-up information often require two or three years. An additional two to three years is commonly required for final design, fabrication of special equipment, and constmction of the plant. Thus, projections of raw material costs and availabiUty five to ten years into the future become important in adopting any new process significantly different from the current technology. 

In the simplest case, the feed solution consists of a solvent A containing a consolute component C, which is brought into contact with a second solvent B. Eor efficient contact there must be a large interfacial area across which component C can transfer until equiHbrium is reached or closely approached. On the laboratory scale this can be achieved in a few minutes simply by hand agitation of the two Hquid phases in a stoppered flask or separatory fuimel. Under continuous flow conditions it is usually necessary to use mechanical agitation to promote coalescence of the phases. After sufficient time and agitation, the system approaches equiHbrium which can be expressed in terms of the extraction factor S for component C ... 

The development of the novel Davy-McKee combined mixer—settler (CMS) has been described (121). It consists of a single vessel (Fig. 13d) in which three 2ones coexist under operating conditions. A detailed description of units used for uranium recovery has been reported (122), and the units have also been studied at the laboratory scale (123). AppHcation of the Davy combined mixer electrostatically assisted settler (CMAS) to copper stripping from an organic solvent extraction solution has been reported (124). 

Eor evaluation of flocculants for pressure belt filters, both laboratory-scale filters and filter simulators are available (52,53) in many cases from the manufacturers of the full-scale equipment. The former can be mn either batchwise or continuously the simulators require less substrate and are mn batchwise. The observed parameters include cake moisture, free drainage, release of the cake from the filter cloth, filter blinding, and retention of the flocculated material during appHcation of pressure. 

Fluorine was first produced commercially ca 50 years after its discovery. In the intervening period, fluorine chemistry was restricted to the development of various types of electrolytic cells on a laboratory scale. In World War 11, the demand for uranium hexafluoride [7783-81-5] UF, in the United States and United Kingdom, and chlorine trifluoride [7790-91 -2J, CIF, in Germany, led to the development of commercial fluorine-generating cells. The main use of fluorine in the 1990s is in the production of UF for the nuclear power industry (see Nuclearreactors). However, its use in the preparation of some specialty products and in the surface treatment of polymers is growing. 

Tetrafluoroethylene was first synthesized in 1933 from tetrafluoromethane, CF, in an electric arc furnace (11). Since then, a number of routes have been developed (12—18). Depolymerization of PTFE by heating at ca 600°C is probably the preferred method for obtaining small amounts of 97% pure monomer on a laboratory scale (19,20). Depolymerization products contain highly toxic perfluoroisobutylene and should be handled with care. 

Some additives have the ability to lower the pour point without lowering the cloud point. A number of laboratory scale flow tests have been developed to provide a better prediction of cold temperature operability. They include the cold filter plugging point (CFPP), used primarily in Europe, and the low temperature flow test (LTFT), used primarily in the United States. Both tests measure flow through filter materials under controlled conditions of temperature, pressure, etc, and are better predictors of cold temperature performance than either cloud or pour point for addithed fuels. 

Combinatorial Hbraries are limited by the number of sequences that can be synthesized. For example, a Hbrary consisting of one molecule each of a 60-nucleotide sequence randomized at each position, would have a mass of >10 g, weU beyond the capacity for synthesis and manipulation. Thus, even if nucleotide addition is random at all the steps during synthesis of the oligonucleotide only a minority of the sequences can be present in the output from a laboratory-scale chemical DNA synthesis reaction. In analyzing these random but incomplete Hbraries, the protocol is efficient enough to allow selection of aptamers of lowest dissociation constants (K ) from the mixture after a small number of repetitive selection and amplification cycles. Once a smaller population of oligonucleotides is amplified, the aptamer sequences can be used as the basis for constmcting a less complex Hbrary for further selection. 

Ra.don Sepa.ra.tion, Owing to its short half-life, radon is normally prepared close to the point of use in laboratory-scale apparatus. Radium salts are dissolved in water and the evolved gases periodically collected. The gas that contains radon, hydrogen, and oxygen is cooled to condense the radon, and the gaseous hydrogen and oxygen are pumped away. 

If the hGH is exported to the culture medium the product can easily be collected by removal of the cells from the culture medium by centrifiigation. Purification of hGH from the culture medium is faciUtated by low amounts of contaminating proteins present. In fact, it has been shown that hGH can be purified on a laboratory scale by a single purification step on a reversed-phase hplc column (43). Mammalian cells growing in tissue culture have also been used as hosts to produce hGH, which is exported into the culture media (44). 

L bor toiy. Hydrogen is produced on a laboratory scale from the action of an aqueous acid on a metal or from the reaction of an alkah metal... 

These reactions can be carried out at room temperature. Hydrogen gas can also be produced on a laboratory scale by the electrolysis of an aqueous solution. Production of hydrogen through electrolysis is also used industrially. This involves the following reaction at the cathode of the electrochemical cell ... 

Newer techniques that are responding to the need for atomic level imaging and chemical analysis include scanning tunneling microscopes (STMs), atomic force microscopes (AFMs) (52), and focused ion beams (FIBs). These are expected to quickly pass from laboratory-scale use to in-line monitoring apphcations for 200-mm wafers (32). 

Cyanide Wastes. Ozone is employed as a selective oxidant in laboratory-scale synthesis (7) and in commercial-scale production of specialty organic chemicals and intermediates such as fragrances, perfumes (qv), flavors, antibiotics (qv), hormones (qv), and vitamins (qv). In Japan, several metric tons per day (t/d) of piperonal [120-57-0] (3,4-methylenedioxybenzaldehyde) is manufactured in 87% yield via ozonolysis and reduction of isosafrole [93-16-3], Piperonal (or heHotropine [120-57-0]) has a pleasant odor and is used in perfumery. Oleic acid [112-80-1/, CH3(CH2 )7CH—CH(CH2 ). C02H, from tall oil (qv) is ozonated on a t/d scale to produce pelargonic, GgH2yG02H, and azelaic, H02G(GH2)yG02H, acids. Oleic acid also is ozonated in Japan... 

Synthesis. The most important starting material for rhodium compounds is rhodium(III) chloride hydrate [20765-98-4], RhCl3 nH2 O. Other commercially available starting materials useful for laboratory-scale synthesis include [Rh2(0000113)4] [5503-41 -3], [Rh(NH3)201]0l2 [13820-95-6], [Rh20l2(0O)4] [32408-34-7], and [Rh20l2(cod)2] [12092-47-6]. 

Synthesis. The principal starting material for synthesis of iridium compounds is iridium trichloride hydrate [14996-61-3], IrCl3-a H2 0. Another useful material for laboratory-scale reactions is [Ir20l2(cod)2] [12112-67-3]. 

Synthesis. The most common staiting materials for palladium complexes are PdCl2 [7647-10-1] and [PdClJ [14349-67-8]. Commercially available materials useful for laboratory-scale synthesis iuclude [Pd2(OOCCH2)J [3375-31-3] [PdCl2(NCCgH )] [14220-64-5] [Pd(acac)2] [14024-61-4] [PdCl2(cod)] [12107-56-1], and [Pd(P(CgH5)3)J [14221-01-3]. 

Oa the laboratory scale, potassium can be prepared by the foUowiag reactions, however, these reactions are not easily adaptable to a commercial scale. 

Batch vs Continuous Reactors. Usually, continuous reactors yield much lower energy use because of increased opportunities for heat interchange. Sometimes the savings are even greater in downstream separation units than in the reaction step itself Especially for batch reactors, any use of refrigeration to remove heat should be critically reviewed. Batch processes often evolve Httle from the laboratory-scale glassware setups where refrigeration is a convenience. 

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