Catalysts, types

A range of catalysts can be used for the selective hydrogenation step depending on the composition of the cracked gasoline  

TABLE 5.1 Main Polymers made by Coordination Polymerization 

High density polyethylene (HOPE) Linear low density polyethylene (LLDPE) Isotactic polypropylene (iPP) Syndiotactic polypropylene (sPP) tram-1,4-Polyisoprene Syndiotactic polystyrene (sPS) Cyclooleflns Ethylene-propylene copolymers Styrene-ethylene copolymers cw -1,4-polybutadiene rrarw -1,4-Poly isoprene Random ethylene-a-olefin copolymers Ethylene-propylene rubber (EPR) Ethylene-propylene-diene copolymers (EPDM) 

The last part of this chapter deals with coordination polymerization kinetics and mechanism, mathematical models at different scales, as well as some analyses on the supported catalyst particle breakup and growth. 

Polymerization by coordination is one of the most versatile methods to produce a variety of polymers. Stereoregularity is one of the outstanding characteristics of the coordination polymerization that relies on the use of catalytic systems based on organometallic or coordination complexes of special structures and symmetries to make highly stereospecific polymers. 

The Phillips-type catalyst, first reported by Hogan in the early 1950s at the Phillips Petroleum Co., is defined as chromium oxide (Cr03) supported on activated mixtures of silica and alumina particles with a ratio Si/Al = 87 13. Usually, the support particles have high surface area around 

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Molecular Weight Distribution. In industry, the MWD of PE resins is often represented by the value of the melt flow ratio (MER) as defined in Table 2. The MER value of PE is primarilly a function of catalyst type. Phillips catalysts produce PE resins with a broad MWD and their MER usually exceeds 100 Ziegler catalysts provide resins with a MWD of a medium width (MFR = 25-50) and metallocene catalysts produce PE resins with a narrow MWD (MFR = 15-25). IfPE resins with especially broad molecular weight distributions are needed, they can be produced either by using special mixed catalysts or in a series of coimected polymerization reactors operating under different reaction conditions. 

MAO is a relatively expensive chemical its price in 1994 was about 450/kg of 30 wt % MAO solution, but projected to decrease to about 200/kg (28). Continuous efforts to replace MAO have resulted in the development of co-catalysts containing mixtures of MAO and trimethyl aluminum (29) as well as new co-catalyst types (30,31). Another approach is to prepare MAO directiy in a polymeriza tion reactor by co-feeding into it trimethyl aluminum and water (32). 

Producer Location Trade name Catalyst type... 

The cure rate of a sihcone sealant is dependent on the reactivity of the cross-linker, catalyst type, catalyst level, the diffusion of moisture into the sealant, and the diffusion of the leaving group out of the sealant. For one-part sealants, moisture diffusion is the controlling step and causes a cured skin to form on the exposed sealant surface and progress inward. The diffusion of moisture is highly dependent on the temperature and relative humidity conditions. 

There is an enormous volume of Hterature available on the appHcations for supported catalysts. Examples are compiled here based on important synthesis methods and industrial uses. The organization is according to specific reactions and appHcations rather than according to catalyst type. 

Primary Variables. The most obvious variables are those whose effects on performance are to be evaluated directiy these ate the variables that, most likely, created the need for the investigation in the first place. Such variables may be quantitative, such as catalyst concentration, temperature, or pressure, or they may be quaUtative, such as method of preparation, catalyst type, or batch of material. 

Quahtative variables can be broken down into two categories. The first consists of those variables whose specific effects ate to be compared directiy eg, comparison of the effect on performance of two proposed preparation methods or of three catalyst types. The requited number of conditions for such variables is generally evident. Such variables are sometimes referred to as fixed effects or Type I variables. 

Polymer Structure. Isopiene can undergo 1,4-, 1,2-, oi 3,4-addition polymerisation depending on the catalyst type and conditions, lesultiag ia several structures ... 

Operating Temperature. The operating temperature needed to achieve a particular VOC destmction efficiency depends primarily on the species of pollutants contained in the waste stream, the concentration of the pollutants, and the catalyst type (14). One of the most important factors is the hydrocarbon species. Each has a catalytic initiation temperature which is also dependent on the type of catalyst used (14). 

NO removals of 90% are achievable. The primary variable is temperature, which depends on catalyst type (38). The principal components of an SCR... 

Variables It is possible to identify a large number of variables that influence the design and performance of a chemical reactor with heat transfer, from the vessel size and type catalyst distribution among the beds catalyst type, size, and porosity to the geometry of the heat-transfer surface, such as tube diameter, length, pitch, and so on. Experience has shown, however, that the reactor temperature, and often also the pressure, are the primary variables feed compositions and velocities are of secondary importance and the geometric characteristics of the catalyst and heat-exchange provisions are tertiary factors. Tertiary factors are usually set by standard plant practice. Many of the major optimization studies cited by Westerterp et al. (1984), for instance, are devoted to reactor temperature as a means of optimization. 

Catalyst type Coal minerals Coal minerals Coal minerals Supported aKZO-aO-60 aKZO-aO-60... 

Correlations have been used as a tool for catalyst selection studies. Predictions of the product yields and qualities possible with various catalysts can provide the necessary information for a refiner to study the economics of switching catalysts, for instance. With a good idea of the profitability of changing catalyst types, the refinery can justify such a change in his cat crackings operation. 

Troublesome amounts of C and Q acetylenes are also produced in cracking. In the butadiene and isoprene recovery processes, the acetylenes in the feed are either hydrogenated, polymerized, or extracted and burned. Acetylene hydrogenation catalyst types include palladium on alumina, and some non-noble metals. 

Metal Catalyst Catalyst type Preparation method Temp. (°Q Carbon source Ref. 

When potassium fluoride is combined with a variety of quaternary ammonium salts its reaction rate is accelerated and the overall yields of a vanety of halogen displacements are improved [57, p 112ff. Variables like catalyst type and moisture content of the alkali metal fluoride need to be optimized. In addition, the maximum yield is a function of two parallel reactions direct fluorination and catalyst decomposition due to its low thermal stability in the presence of fluoride ion [5,8, 59, 60] One example is trimethylsilyl fluoride, which can be prepared from the chloride by using either 18-crown-6 (Procedure 3, p 192) or Aliquot 336 in wet chlorobenzene, as illustrated in equation 35 [61],... 

The reaction occurs at approximately 80-130°C using the proper catalyst. Many catalysts have been tried for this reaction, and there is an indication that the best catalyst types are those of the tertiary amine and quaternary ammonium functionalized resins. This route produces ethylene glycol of a high purity and avoids selectivity problems associated with the hydrolysis of ethylene oxide. 

As with HjS, the distribution of sulfur among the other FCC products depends on several factors, which include feed, catalyst type, conversion, and operating conditions. Feed type and residence time are the most significant variables. Sulfur distribution in FCC products of several feedstocks is shown in Table 2-4. Figure 2-9 illustrates the sulfur distribution as a function of the unit conversion. 

The 300-ton inventory unit in Example 3-2 is changing catalyst type and planning to add 3.5 tons per day of new catalyst. Determine the percent of changeover after 60 days of operation. Assume a retention factor of 0.7. 

Catalytic coke is a byproduct of the cracking of FCC feed to lighter products. Its yield is a function of conversion, catalyst type, and hydrocarbon/catalyst residence time in the reactor. 

Many factors influence delta coke, including quality of the FCC feedstock, design of the feed/catalyst injection system, riser design, operating conditions, and catalyst type. The following is a brief discussion of these factors ... 

Gaseous emissions (CO, NO, SO, particulates) have been regulated at local and national levels. The quantity of these emissions is directly related to the quality of the FCC stocks, operating conditions, catalyst type, and mechanical conditions of the unit. Processing heavy feeds will release a greater amount of SO, NO, and particulates. 

The shape of the kinetic curves depends on the catalyst type and polymerization conditions (ethylene pressure, temperature, concentration of inhibitors in reaction medium) (89, 97, 98). The types of the kinetic curves obtained. at ethylene polymerization under various conditions are presented in Fig. 1. 

In practice, one proceeds as follows. The value of bh >s determined for the reaction with a series of acids of similar structure, that is, for carboxylic acids or ammonium ions, etc. Limiting the data to a single catalyst type improves the fit. since the inclusion of data for a second ype of acid catalyst might define a close but not identical line. This means that Ga may be somewhat different for each catalyst type. A plot of log(kBH/p) versus log(A BH(7//i) is then constructed. This procedure most often results in a straight line, within the usual —10-15 percent precision found for LFERs. One straightforward example is provided by the acid-catalyzed dehydration of acetaldehyde hydrate,... 

A proposed mechanism for silyl ether displacement is shown in Scheme 6.14. In the first step, the fluoride anion converts the trimethyl siloxy group into a phe-nolate salt. In the following step, the phenolate anion attacks the activated fluoro monomer to generate an ether bond. The amount of catalyst required is about 0.1-0.3 mol%. Catalyst type and concentration are crucial for this reaction. 

Although the actual reaction mechanism of hydrosilation is not very clear, it is very well established that the important variables include the catalyst type and concentration, structure of the olefinic compound, reaction temperature and the solvent. used 1,4, J). Chloroplatinic acid (H2PtCl6 6 H20) is the most frequently used catalyst, usually in the form of a solution in isopropyl alcohol mixed with a polar solvent, such as diglyme or tetrahydrofuran S2). Other catalysts include rhodium, palladium, ruthenium, nickel and cobalt complexes as well as various organic peroxides, UV and y radiation. The efficiency of the catalyst used usually depends on many factors, including ligands on the platinum, the type and nature of the silane (or siloxane) and the olefinic compound used. For example in the chloroplatinic acid catalyzed hydrosilation of olefinic compounds, the reactivity is often observed to be proportional to the electron density on the alkene. Steric hindrance usually decreases the rate of... 

Both of the above-mentioned catalyst types get the anions into the organic phase, but there is another factor as well. There is evidence that sodium and potassium salts of many anions, even if they could be dissolved in organic solvents, would undergo reactions very slowly (dipolar aprotic solvents are exceptions) because in these solvents the anions exist as ion pairs with Na or and are not free to attack the substrate (p. 443). Fortunately, ion pairing is usually much less with the quaternary ions and with the positive cryptate ions, so the anions in these cases are quite free to attack. Such anions are sometimes referred to as naked anions. 

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