Selective catalyst

Furfural can be oxidized to 2-furoic acid [88-14-2] reduced to 2-furanmethanol [98-00-0] referred to herein as furfuryl alcohol, or converted to furan by decarbonylation over selected catalysts. With concentrated sodium hydroxide, furfural undergoes the Cannizzaro reaction yielding both 2-furfuryl alcohol and sodium 2-furoate [57273-36-6]. 

Propylene Oxidation. The propylene oxidation process is attractive because of the availabihty of highly active and selective catalysts and the relatively low cost of propylene. The process proceeds in two stages giving first acrolein and then acryUc acid (39) (see Acrolein and derivatives). 

Dehydrogenation of Propionates. Oxidative dehydrogenation of propionates to acrylates employing vapor-phase reactions at high temperatures (400—700°C) and short contact times is possible. Although selective catalysts for the oxidative dehydrogenation of isobutyric acid to methacrylic acid have been developed in recent years (see Methacrylic ACID AND DERIVATIVES) and a route to methacrylic acid from propylene to isobutyric acid is under pilot-plant development in Europe, this route to acrylates is not presentiy of commercial interest because of the combination of low selectivity, high raw material costs, and purification difficulties. 

Shape selective catalysts, such as ZeoHtes of the H-ZSM-5 type, are capable of directing alkyl groups preferentially to the para position (18). The ratio of the catalyst to the substrate also plays a role ia controlling the regiochemistry of the alkylations. For example, selective alkylation of anilines at the para position is achieved usiag alkylatiag ageats and AlCl ia equimolar ratio (19). 

MPa (15—20 atm), 300—400 kg benzene per kg catalyst per h, and a benzene ethylene feed ratio of about 30. ZSM-5 inhibits formation of polyalkjlated benzenes produced with nonshape-selective catalysts. With both ethylene sources, raw material efficiency exceeds 99%, and heat recovery efficiency is high (see Xylenes and ethylbenzene). 

The selective alkylation of toluene with methanol to produce -xylene as a predominant isomer can be achieved over shape-selective catalysts (99—101). With a modified ZSM-5 zeoHte catalyst, more than 99% -xylene in xylene isomers can be produced at 550°C. This -xylene concentration exceeds the equiHbrium concentration of 23% (99). The selective synthesis of -xylene using relatively low cost toluene is economically attractive however, this technology was not commercialized as of 1991. 

The same four operating steps are used with the complex batch reactor as with the simple batch reactor. The powerhil capabiUties of the complex batch reactor offset their relatively high capital cost. These reactors can operate at phenol to alkene mole ratios from 0.3 to 1 and up. This abiUty is achieved by designing for positive pressure operation, typically 200 to 2000 kPa (30 to 300 psig), and for the use of highly selective catalysts. Because these reactors can operate at low phenol to alkene mole ratios, they are ideal for production of di- and trialkylphenols. 

The main by-products ia the dehydrogenation reactor are toluene and benzene. The formation of toluene accounts for the biggest yield loss, ie, approximately 2% of the styrene produced when a high selectivity catalyst is used. Toluene is formed mostly from styrene by catalytic reactions such as the foUowiag ... 

The benzene—toluene fraction is further fractionated in a small column, not shown in Figure 5, to recover benzene for recycle to the alkylation unit and toluene for sale. This toluene can be converted to benzene by hydrodealkylation but the high selectivity catalyst has reduced the formation of toluene in the dehydrogenation reactor to the point where the cost of installing a hydrodealkylation unit is difficult to justify even in a large styrene plant. 

Concerning the reduction of NO, automobile three-way catalysts exhibit a property called selectivity. Catalyst selectivity occurs when several reactions are thermodynamically possible but one reaction proceeds at a faster rate than another. In the case of a TWC catalyst, CO, HC, and ... 

Polypropylenes produced by metallocene catalysis became available in the late 1990s. One such process adopts a standard gas phase process using a metallocene catalyst such as rac.-dimethylsilyleneto (2-methyl-l-benz(e)indenyl)zirconium dichloride in conjunction with methylaluminoxane (MAO) as cocatalyst. The exact choice of catalyst determines the direction by which the monomer approaches and attaches itself to the growing chain. Thus whereas the isotactic material is normally preferred, it is also possible to select catalysts which yield syndiotactic material. Yet another form is the so-called hemi-isotactic polypropylene in which an isotactic unit alternates with a random configuration. 

This is an endothermic reaction in which a volume increase accompanies dehydrogenation. The reaction is therefore favoured by operation at reduced pressure. In practice steam is passed through with the ethylbenzene in order to reduce the partial pressure of the latter rather than carrying out a high-temperature reaction under partial vacuum. By the use of selected catalysts such as magnesium oxide and iron oxide a conversion of 35-40% per pass with ultimate yields of 90-92% may be obtained. 

This process does produce HCN as a by-product in small quantities. Puranik et al. (1990) report on work to develop an improved, more selective catalyst, and on coupling the ammoxidation process with a second reactor in which a subsequent oxycyanation reaction would convert the by-product HCN to acrylonitrile. 

Evans et al. reported that the his(oxazolinyl)pyridine (pybox) complex of copper(II) 17 is a selective catalyst of Diels-Alder reactions between a-bromoacrolein or methacrolein and cydopentadiene affording the adducts in high enantioselectivity [23] (Scheme 1.30). Selection of the counter-ion is important to achieve a satisfactory reaction rate and enantioselectivity, and [Cu(pyhox)](ShFg)2 gave the best result. This catalyst is also effective for the Diels-Alder reaction of acrylate dieno-philes (vide infra). 

The chiral BIN0L/Ti(0-i-Pr)4 combination has also been used as a very enantio-selective catalyst for the cyclocondensation of polyfluoroalkylaldehydes with Danishefsky s diene leading to polyfluoroalkyldihydropyrenones in moderate yields (35-60%) and with high ee (90-98.5% ee) [20]. 

Conversion processes are either thermal, where only heat is used to effect the required change, or catalytic, where a catalyst lowers the reaction activation energy. The catalyst also directs the reaction toward a desired product or products (selective catalyst). 

To improve the yield of mono- and dimethylamines, a shape selective catalyst has been tried. Carhogenic sieves are microporous materials (similar to zeolites), which have catalytic as well as shape selective properties. Comhining the amorphous aluminum silicate catalyst (used for producing the amines) with carhogenic sieves gave higher yeilds of the more valuable MMA and DMA. ... 

Oxidizing toluene to benzaldehyde is a catalyzed reaction in which a selective catalyst limits further oxidation to benzoic acid. In the first step, benzyl alcohol is formed and then oxidized to benzaldehyde. Further oxidation produces benzoic acid ... 

Catalyst A higher level of rare earth or an increase in the matrix content. Switch to a more coke-selective catalyst. 

Install high efficiency Feed Nozzles Lower Preheat Temperature Inject Naphtha Quench to Riser Increase Stripping and Dispersion Steam Switch to a Coke Selective Catalyst... 

Que and coworkers reported on a similar monomeric iron complex, formed with the BPMEN ligand but without acetic acid [128]. This complex was able to epoxidize cyclooctene in reasonably good yield (75%), but at the same time a small amount of the ris-diol (9 %) was formed. This feature observed with this class of complexes has been further studied and more selective catalysts have been prepared. Even though poor levels of conversion are often obtained with the current... 

In conclusion, the above summary of oxidation methods shows that there is still room for further improvements in the field of selective olefin epoxidation. The development of active and selective catalysts capable of oxidizing a broad range of olefin substrates with aqueous hydrogen peroxide as terminal oxidant in inexpensive and environmentally benign solvents remains a continuing challenge. 

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