Catalyst, alumina phosphoric acid

Trickle bed reaction of diol (12) using amine solvents (41) has been found effective for producing PDCHA, and heavy hydrocarbon codistiUation may be used to enhance diamine purification from contaminant monoamines (42). Continuous flow amination of the cycloaUphatic diol in a Hquid ammonia mixed feed gives >90% yields of cycloaUphatic diamine over reduced Co /Ni/Cu catalyst on phosphoric acid-treated alumina at 220°C with to yield a system pressure of 30 MPa (4350 psi) (43). 

Isomerization of ethylene oxide to acetaldehyde occurs at elevated temperatures ia the presence of catalysts such as activated alumina, phosphoric acid, and metallic phosphates (75). Iron oxides also catalyze this reaction. Acetaldehyde may be found as a trace impurity ia ethylene oxide. 

Other workers also report studies on alkylation of aromatics over silica-alumina (63). Ivanov el al. alkylated coal-tar aromatics with olefins in the presence of aluminum chloride-hydrogen chloride and obtained a product suitable for use as a lubricating oil (143). Topchiev and Paushkin have reported high yields in the alkylation of isopentene with propylene in the presence of a catalyst containing phosphoric acid and boron trifluoride (395). 

Dehydration and dehydrogenation combined utilizes dehydration agents combined with riuld dehydrogenation agents. Included in this class of catalysts are phosphoric acid, silica-magnesia, sihca-alumina, alumina derived from aluminum chloride, and various metal oxides. 

Supported the catalysts used in this case are silica aluminas, phosphoric acid deposited on kieselguhr, or boron trifluoride deposited on modified alumina. 

A number of works have been reported on the alkylation of phenol with methanol over metal oxides as catalyst. Generally, alkylation over acidic oxides such as silica-alumina, phosphoric acid and Nafion-H give mainly anisole and a mixture of three isomers of cresol. On the other hand, basic metal oxides sudi as MgO and Mg-containing mixed oxides favor alkylation at ortho positions. This reaction is industrially important since the reaction product, 2,6-xylenol, is a monomer for good heat-resisting resin. 

Acid-Gatalyzed Synthesis. The acid-catalysed reaction of alkenes with hydrogen sulfide to prepare thiols can be accompHshed using a strong acid (sulfuric or phosphoric acid) catalyst. Thiols can also be prepared continuously over a variety of soHd acid catalysts, such as seoHtes, sulfonic acid-containing resin catalysts, or aluminas (22). The continuous process is utilised commercially to manufacture the more important thiols (23,24). The acid-catalysed reaction is commonly classed as a Markownikoff addition. Examples of two important industrial processes are 2-methyl-2-propanethiol and 2-propanethiol, given in equations 1 and 2, respectively. 

Dutch State Mines (Stamicarbon). Vapor-phase, catalytic hydrogenation of phenol to cyclohexanone over palladium on alumina, Hcensed by Stamicarbon, the engineering subsidiary of DSM, gives a 95% yield at high conversion plus an additional 3% by dehydrogenation of coproduct cyclohexanol over a copper catalyst. Cyclohexane oxidation, an alternative route to cyclohexanone, is used in the United States and in Asia by DSM. A cyclohexane vapor-cloud explosion occurred in 1975 at a co-owned DSM plant in Flixborough, UK (12) the plant was rebuilt but later closed. In addition to the conventional Raschig process for hydroxylamine, DSM has developed a hydroxylamine phosphate—oxime (HPO) process for cyclohexanone oxime no by-product ammonium sulfate is produced. Catalytic ammonia oxidation is followed by absorption of NO in a buffered aqueous phosphoric acid... 

Dehydration of ethanol has been effected over a variety of catalysts, among them synthetic and naturally occurring aluminas, siUca-aluminas, and activated alumina (315—322), hafnium and 2irconium oxides (321), and phosphoric acid on coke (323). Operating space velocity is chosen to ensure that the two consecutive reactions. 

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

Manufacture. Much of the diethyl ether manufactured is obtained as a by-product when ethanol (qv) is produced by the vapor-phase hydration of ethylene (qv) over a supported phosphoric acid catalyst. Such a process has the flexibiHty to adjust to some extent the relative amounts of ethanol and diethyl ether produced in order to meet existing market demands. Diethyl ether can be prepared directly to greater than 95% yield by the vapor-phase dehydration of ethanol in a fixed-bed reactor using an alumina catalyst (21). 

Activated alumina and phosphoric acid on a suitable support have become the choices for an iadustrial process. Ziac oxide with alumina has also been claimed to be a good catalyst. The actual mechanism of dehydration is not known. In iadustrial production, the ethylene yield is 94 to 99% of the theoretical value depending on the processiag scheme. Traces of aldehyde, acids, higher hydrocarbons, and carbon oxides, as well as water, have to be removed. Fixed-bed processes developed at the beginning of this century have been commercialized in many countries, and small-scale industries are still in operation in Brazil and India. New fluid-bed processes have been developed to reduce the plant investment and operating costs (102,103). Commercially available processes include the Lummus processes (fixed and fluidized-bed processes), Halcon/Scientific Design process, NIKK/JGC process, and the Petrobras process. In all these processes, typical ethylene yield is between 94 and 99%. 

Hydration and dehydration employ catalysts that have a strong affinity for water. Alumina is the principal catalyst, but also used are aluminosihcates, metal salts and phosphoric acid or its metal salts on carriers, and cation exchange resins. 

The reactor is a vessel with beds of solid catalyst. Most commercial processes use a catalyst called kieselguhr, which is phosphoric acid deposited on a silica/alumina pellet. Because of the weight of the pellets, supported beds at multiple levels in the vessel are used so the bottom layers wont be crushed.-... 

Note that ethylbenzene is a derivative of two basic organic chemicals, ethylene and benzene. A vapor-phase method with boron trifluoride, phosphoric acid, or alumina-silica as catalysts has given away to a liquid-phase reaction with aluminum chloride at 90°C and atmospheric pressure. A new Mobil-Badger zeolite catalyst at 420°C and 175-300 psi in the gas phase may be the method of choice for future plants to avoid corrosion problems. The mechanism of the reaction involves complexation of the... 

Gas-phase oxidation of glycerol has been less investigated than liquid-phase oxidation it occurs via a two-step catalyzed reaction involving first the dehydration of glycerol into acrolein, catalyzed by an acid, and then its oxidation. The same reactions can be conducted in two distinct reactors, in which the first step can be carried out with an acid catalyst such as phosphoric acid over alumina [107]. Then acrolein is oxidized to acrylic acid with a conventional alumina-supported Mo/V/Cu/O catalyst. 

Low temperatures in the alkylation reaction zone favor the isomerization of butylene-1 to butylene-2 during the alkylation reaction. Where low temperatures are not used for economic reasons, however, as is the case with many HF alkylation units, this isomerization is sometimes carried out in a separate unit and the isomerized product then charged to the alkylation unit. Catalysts for this isomerization reaction are phosphoric acid and silica-alumina. Some polymer is usually made when isomerizing with these catalysts, but when the polymer production is limited to diisobutylene, it will be alkylated to produce the trimethylpentanes. Any polymer made from normal butylenes, however, is an inferior feed for alkylation units. When this type of polymer is made, it is usually removed by fractionation before charging the isomerized butylene feed to the alkylation unit. 

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