Process space-time yield

Meyer et al. examined the formation of rose oxide by the oxidation ofdtronellol with singlet oxygen in a temperature-resistant glass (Borofloat) microreactor [9]. A 10 mL P-citronellol-ethanol solution with Ru(T>py)3Cl2 is circulated through the microchannel reactor (hold-up volume 0.27 mL). Products are identified by H PLC analysis. After an irradiation time of 40 min, space-time yields of 0.8 mmol L min are obtained. In a comparable batch process, space-time yields are 10 times lower. 

Determination of the actual cost of a hydrogenation process is difficult. Among the factors entering into the determination are catalyst cost, catalyst life, cost of materials, capital investment, actual yield, space-time yield, and purification costs, Considerable data are needed to make an accurate evaluation. 

Biocatalysts in nature tend to be optimized to perform best in aqueous environments, at neutral pH, temperatures below 40 °C, and at low osmotic pressure. These conditions are sometimes in conflict with the need of the chemist or process engineer to optimize a reaction with respect to space-time yield or high product concentration in order to facilitate downstream processing. Furthermore, enzymes and whole cells are often inhibited by products or substrates. This might be overcome by the use of continuously operated stirred tank reactors, fed-batch reactors, or reactors with in situ product removal [14, 15]. The addition of organic solvents to increase the solubility of substrates and/or products is a common practice [16]. 

The catalytic single-step Alfen process has a good space-time yield, and the process engineering is simple. The molecular weight distribution of the olefins of the single-step process is broader (Schulz-Flory type of distribution) than in the two-step Alfen process (Poisson-type distribution) (Fig. 2). As a byproduct 2-alkyl-branched a-olefins also are formed, as shown in Table 6. About... 

Heat transfer problems become more severe as reaction rates are increased and water-to-monomer ratios are reduced. In addition, as reactor sizes are increased for improved process economics, the amount of wall heat transfer surface area per unit volume will drop and result in a lower reactor space-time yield. 

As an example for continuous process design, 2-keto-3-deoxy-D lycero-D-galacto-nonosouate (KDN) (S) has been produced on a 100-g scale from D-mannose and pyruvate using a pilot-scale EMR at a space-time yield of 375 gl d and an overall crystallized yield of 75% (Figure 10.6) [47]. Similarly, L-KDO (6) can be synthesized from L-arabinose [48]. 

The transformation from batch to continuous processing, the safe operation with bromine at temperatures over 170°C and the decrease of reaction time, i.e. increase of space-time yields, were drivers for the development here. 

An increase from 2 to 5 bar total pressure increases the space-time yield by about 20% (15 vol.-% ethylene, 85 vol.-% oxygen, 2-20 bar 0.235-3.350 s 11 h ) [4], At higher pressures, 10 and 20 bar, a decrease activity is observed. Since industrial processes occur at up to 30 bar, at first sight this result is surprising. The decreasing activity with pressure was partially explained by catalyst deactivation, probably as a consequence of the longer residence times applied. 

GP 3] [R 3b] The space-time yield of chemical micro processing was a factor of five larger than that of a conventional fixed-bed reactor (Figure 3.35) (0.4% 1-butene in air 0.1 MPa 400 °C) [103]. This is due to the shorter residence time needed in the micro reactors for the same conversion as in the fixed bed. Differences from the fixed bed become smaller when operating at very high conversion, up to 95%. 

Partial methane oxidation comprises very high rates so that high space-time yields can be achieved (see original citations in [3]). Residence times are in the range of a few milliseconds. Based on this and other information, it is believed that syngas facilities can be far smaller and less costly in investment than reforming plants. Industrial partial oxidation plants are on the market, as e.g. provided by the Syntroleum Corporation (Tulsa, OK, USA). Requirements for such processes are operation at elevated pressure, to meet the downstream process requirements, and autothermal operation. 

The design optimization of an electrolytic cell aims at a high throughput with a low energy consumption at the lowest feasible cost. The throughput of an electrochemical reactor is measured in terms of the space time yield, Yt, defined as the volumetric quantity of the metal produced per unit time per unit volume of the process reactor. This quantity is expressed as ... 

Similarly, whole-cell Lactobacillus kefir DSM 20587, which possesses two alcohol dehydrogenases for both asymmetric reduction steps, was applied in the reduction of tert-butyl 6-chloro-3,5-dioxohexanoate for asymmetric synthesis of ft rf-butyl-(31 ,5S)-6-chloro-dihydroxyhexanoate (Figure 7.5), a chiral building block for the HMG-CoA reductase inhibitor [ 17]. A final product concentration of 120 him and a specific product capacity of 2.4 mmol per gram dry cell were achieved in an optimized fed-batch process. Ado 99% was obtained for (3R,5S)- and (3.S, 55)-te/ f-butyl-6-chloro-dihydroxyhexanoate with the space-time yield being 4.7 mmolL-1 h-1. 

Application of this system in the continuous transfer-hydrogenation reaction of acetophenone gave a stable conversion of about 87%, an ee of 94%, and a space-time yield of 255 g L"1 d"1. A continuous dosage of isopropoxide was necessary in order to compensate for deactivation caused by traces of water in the feed stream. Under these circumstances a TTON of 2360 was reached. Comparison of this system with an enzymatic process showed that both approaches offer different advantages and are therefore complementary. 

With the RCH/RP process, it is possible to hydroformylate propene up to pentenes with satisfying space time yields. On the other hand, heavier aldehydes such as Cio (iso-decanal) or higher from the hydroformylation of nonene(s), decenes, etc. can not be separated from the oxo catalysts by conventional means such as distillation due to thermal instability at the required temperatures and thus especially needs the careful aqueous-biphasic separation technique. There are numerous attempts to overcome the problem of low reactivity of higher alkenes which is due to low miscibility of the alkenes in water [26,27b, 50a,58d]. These proposals can briefly be summarized as ... 

Using the high-p,T microreactor processing, the Kolbe-Schmitt synthesis was completed within less than 1 min at comparable yields, i.e., a reaction time reduced by a factor of approximately 2,000 was achieved (see Fig. 6). This corresponds to an increase in space-time yield by a factor of 440. 

In addition, many other aspects must be considered when developing a catalytic reaction for industrial use these include catalyst separation, stability and poisoning, handling problems, space-time yield, process sensitivity and robustness, toxicity of metals and reagent, and safety aspects, as well as the need for high-pressure equipment. 

Substrate and product inhibition. Few academic researchers are familiar with this phenomenon as they usually mn their hydrogenations at low substrate concentrations and low SCR. However, for industrial applications the space-time yield of a reaction - the amount of product per unit reactor volume per time unit - is quite important. Clearly, the higher the substrate concentration the higher the space-time yield and the more economic the process. More often than not, either substrate or product inhibition becomes a problem when the substrate concentration is increased to 10 wt% or more. 

In this case history, the control of the TMRaa (adiabatic Time-to-Maximum-Rate) is to be achieved in a semi-continuous reactor process by the dynamic optimization of the feed rate. Here it is desired to have the highest possible space-time-yield STY and it is necessary to achieve a thermally safe process (Keller, 1998). The reaction involves the addition of a sulfur trioxide on a nitro-aromatic compound... 

Organic synthesis, the powerful chemistry developed by humankind, still often uses a simple step-by-step approach to convert a starting material A into a final product D, in which intermediate products B and C are isolated and purified for each next conversion step (Fig. 13.1). Catalytic steps are mostly combined with stoichiometric steps in the preparation of precursors or in the further downstream processing. Obvious disadvantages are low space-time yields (kg L-1 h-1), laborious recycle loops and large amounts of waste. 

By adding up to 36% ethylene glycol to the aqueous catalyst phase, the space-time yield could be boosted up to approx. 3 mt m-3 h-1 for propene hydroformylation, a factor of 20 in comparison to the conventional two-phase process without changing the reaction conditions. Because of this surprising speed-up, higher alpha-olefins up to 1-octene are converted with high to acceptable space-time yield (Fig. 22). Up to date this process is not commercialized, but has been tested in a continuous pilot plant. 

With this system we converted 135 mM styrene (relative to the total liquid volume) to styrene oxide in 10 h at a cell dry weight of around lOg/L aqueous phase, with an average activity of 152 U/L total liquid volume. This corresponds to a space-time yield of 1.1 g (5)-styrene oxide per liter and hour. These are the highest specific activities reported thus far for a microbial epoxidation process. ... 

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