Catalyst automation

Adequate description of many catalysts will require a large number of bits of data since they are usually rather complicated materials rather than simple chemicals. Attempts at tMs were just beginning by ICC 1, but now, one expects authors to give specific surface areas and some details of the porosity of their catalysts. Automation of the former tedious point by point measiirement of the N2 adsorption isotherm has greatly facilitated this. 

HT technology for catalysts-automated synthesis and testing appears to be reasonably adapted to date, but further improvements are expected for HT catalysts characterization, which is still restricted to costly and in general ex-situ spectroscopic techniques. These tools would provide the new catalyst descriptors needed to improve the ability to predict catalytic performances without testing. 

Resoles. Like the novolak processes, a typical resole process consists of reaction, dehydration, and finishing. Phenol and formaldehyde solution are added all at once to the reactor at a molar ratio of formaldehyde to phenol of 1.2—3.0 1. Catalyst is added and the pH is checked and adjusted if necessary. The catalyst concentration can range from 1—5% for NaOH, 3—6% for Ba(OH)2, and 6—12% for hexa. A reaction temperature of 80—95°C is used with vacuum-reflux control. The high concentration of water and lower enthalpy compared to novolaks allows better exotherm control. In the reaction phase, the temperature is held at 80—90°C and vacuum-refluxing lasts from 1—3 h as determined in the development phase. SoHd resins and certain hquid resins are dehydrated as quickly as possible to prevent overreacting or gelation. The end point is found by manual determination of a specific hot-plate gel time, which decreases as the polymerization advances. Automation includes on-line viscosity measurement, gc, and gpc. 

Bosch and co-workers devised laboratory reactors to operate at high pressure and temperature in a recycle mode. These test reactors had the essential characteristics of potential industrial reactors and were used by Mittasch and co-workers to screen some 20,000 samples as candidate catalysts. The results led to the identification of an iron-containing mineral that is similar to today s industrial catalysts. The researchers recognized the need for porous catalytic materials and materials with more than one component, today identified as the support, the catalyticaHy active component, and the promoter. Today s technology for catalyst testing has become more efficient because much of the test equipment is automated, and the analysis of products and catalysts is much faster and more accurate. 

Important physical properties of catalysts include the particle size and shape, surface area, pore volume, pore size distribution, and strength to resist cmshing and abrasion. Measurements of catalyst physical properties (43) are routine and often automated. Pores with diameters <2.0 nm are called micropores those with diameters between 2.0 and 5.0 nm are called mesopores and those with diameters >5.0 nm are called macropores. Pore volumes and pore size distributions are measured by mercury penetration and by N2 adsorption. Mercury is forced into the pores under pressure entry into a pore is opposed by surface tension. For example, a pressure of about 71 MPa (700 atm) is required to fill a pore with a diameter of 10 nm. The amount of uptake as a function of pressure determines the pore size distribution of the larger pores (44). In complementary experiments, the sizes of the smallest pores (those 1 to 20 nm in diameter) are deterrnined by measurements characterizing desorption of N2 from the catalyst. The basis for the measurement is the capillary condensation that occurs in small pores at pressures less than the vapor pressure of the adsorbed nitrogen. The smaller the diameter of the pore, the greater the lowering of the vapor pressure of the Hquid in it. 

Catalyst testing and evaluation have been revolutionized by computers, automated test reactors, and analytical methods. With modem equipment, researchers can systematically prepare and screen many catalysts in a short time and efftciendy deterrnine, not only the initial catalytic activity and selectivity, but also the stabiUty and the appearance of trace products that may indicate some new catalytic properties worthy of further development. 

The operational characteristics of the older Berty reactors are described in Berty (1974), and their use in catalyst testing in Berty (1979). Typical uses for ethylene oxide catalyst testing are described in Bhasin (1980). Internal recycle reactors are easy to run with minimum control or automation. 

On the other hand, when workers are seriously under-loaded, they might not be very alert to changing process conditions. Many of the problems of plant automation are common to other situations of task underload. To increase the level of activity in monitoring tasks, additional tasks can be assigned, such as calculating the consumption of fuels, the life of a catalyst, the efficiency of the furnace and so on. Meister (1979) provides a summary of research on team organization. 

In principle, it is possible to fully automate the procedure (2) and software can be written to obtain the results to an operator spemFied precision, as the error equations are available. Unfortunately, this online procedure is sometimes difficult with catalysts because most supported metal catalysts contain only the order of one percent or less of metal, the peaks are broad due to the small size of the crystallites, and the large amount of support gives strong background scattering which has features of its own. Visual inspection of the data is often necessary prior to processing. 

The catalysts were tested for their CO oxidation activity in an automated microreactor apparatus. The catalysts were tested at space velocities of 7,000 -60,000 hr . A small quantity of catalyst (typically 0.1 - 0.5 g.) was supported on a frit in a quartz microreactor. The composition of the gases to the inlet of the reactor was controlled by mass flow controllers and was CO = 50 ppm, CO2 = 0, or 7,000 ppm, HjO = 40% relative humidity (at 25°C), balance air. These conditions are typical of conditions found in spacecraft cabin atmospheres. The temperature of the catalyst bed was measured with a thermocouple placed half way into the catalyst bed, and controlled using a temperature controller. The inlet and outlet CO/CO2 concentrations were measured by non-dispersive infrared (NDIR) monitors. 

The catalyst testing was carried out in a gas phase downflow stainless steel tubular reactor with on-line gas analysis using a Model 5890 Hewlett-Packard gas chromatograph (GC) equipped with heated in-line automated Valeo sampling valves and a CP-sD 5 or CP-sil 13 capillary WCOT colunm. GC/MS analyses of condensable products, especially with respect to O-isotopic distribution, was also carried out using a CP-sil 13 capillary column. For analysis of chiral compounds, a Chirasil-CD capillary fused silica column was employed. 

High-throughput screening of molecular catalysts using automated liquid handling, injection and microdevices, Ghimia 56, 11 (2002) 621-626. 

Depending on the reaction temperature and reaction time, tetrahydroisoquinoline 357 afforded different mixtures of 1,2,3,4,11,11 a-hcxahydro-6//-pyrazino[ 1,2-3]isoquinolines 358-361 and tetracyclic compound 362 (Scheme 30) <2005JA16796>. Each of the individual diastereoisomers 358-361 could be transformed into the compound 362. z7r-3//,4a//-3-Phcnylpcrhydropyra/ino[ 1,2-7]isoquinoline-l,4-dione was prepared via automated parallel solid-phase synthesis on Kaiser oxime resin <1998BML2369>. l,2,3,5,6,7-Hexahydropyrido[l,2,3-r/f ]quinoxaline-2,5-dionc was obtained by catalytic hydrogenation of ethyl 3-(2-oxo-l,2,3,4-tetrahydro-5-quinoxalinyl)acrylate in the presence of TsOH over 5% Pd/C catalyst under 40 psi of hydrogen <1996JME4654>. 

Jacobsen proposed a related heterogeneous catalyst in which the complex is bound via an ester linkage to commercial hydroxymethylpolystyrene beads. Such catalysts are of value not only in large-scale processes, but also in the combinatorial automated synthesis of libraries of new compounds.180... 

To exploit the numerous applications for floating catalyst VGCF in engineered plastics, production rates are projected to be on the order of several pounds per hour from a single tube reactor. Demonstration experiments on a small scale have shown feasibility of accomplishing the desired rate of production. Economic production of such quantities will involve recapture of energy in the heated unreacted gas which exits the reactor, as well as automated collection, debulking, and preform fabrication systems. 

Solid-supported technologies are already well established methods in medicinal chemistry and automated synthesis. Over the last couple of years new trends have evolved in this field which are of utmost importance as they have the potential to revolutionize the way chemical synthesis especially for library production is performed. Microchip-based synthesis technologies and multistep sequences with solid-supported catalysts or reagents in flow-through systems are only two spectacular examples. A new approach is the use of solid-supported systems for the scale-up of chemical reactions thereby enabling the rapid and smooth transition from discovery to development units. 

Figure 3.1 shows a typical laboratory flow reactor for the study of catalytic kinetics. A gas chromatograph (GC, lower shelf) and a flow meter allow the complete analysis of samples of product gas (analysis time is typically several minutes), and the determination of the molar flow rate of various species out of the reactor (R) contained in a furnace. A mass spectrometer (MS, upper shelf) allows real-time analysis of the product gas sampled just below the catalyst charge and can follow rapid changes in rate. Automated versions of such reactor assemblies are commercially available. 

A second strategy relies on parallel experimentation. In this case, the same experimental step is performed over n samples in n separated vessels at the same time. Robotic equipment such as automated liquid-handlers, multi-well reactors and auto-samplers for the analysis are used to perform the repetitive tasks in parallel. This automated equipment often works in a serial fashion as, for example, a liquid handler with a single dispensing syringe filling the wells of a microtiter plate, one after another. However, the chemical formation of the catalyst or the catalytic reaction are run at the same time, assuming that their rate is slow compared to the time needed to add all the components. The whole process appears parallel for the human user whose intervention is reduced. 

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