Liquid-phase hydrogenation process

The technique commercially used for this process is a rapid agitation of two liquid phases, one essentially hydrogen fluoride and one essentially hydrocarbon. The reaction apparently takes place rapidly at the liquid-liquid interface. Reaction also takes place in either of the liquid phases but at a much slower rate. With aromatic compounds reaction takes place rapidly and homogeneously in either a hydrocarbon liquid phase or a hydrogen fluoride liquid phase. 

The bridge between gas-phase and electrochemical hydrogenation, namely liquid-phase hydrogenation, has been mentioned earlier. The scope of such processes is outlined in books such as those by Augustine, Rylander, " and Freifelder, as well as Sokol skii s work or in published Conference Proceedings. Qualitatively, this affords a fascinating comparison between... 

Isopropyl alcohol can be partially oxidized by a noncatalytic, liquid-phase process at low temperatures and pressure to produce hydrogen peroxide [7722-84-1] and acetone (24—26). 

Allied-Signal Process. Cyclohexanone [108-94-1] is produced in 98% yield at 95% conversion by liquid-phase catal57tic hydrogenation of phenol. Hydroxylamine sulfate is produced in aqueous solution by the conventional Raschig process, wherein NO from the catalytic air oxidation of ammonia is absorbed in ammonium carbonate solution as ammonium nitrite (eq. 1). The latter is reduced with sulfur dioxide to hydroxylamine disulfonate (eq. 2), which is hydrolyzed to acidic hydroxylamine sulfate solution (eq. 3). 

Deviations from Raonlt s law in solution behavior have been attributed to many charac teristics such as molecular size and shape, but the strongest deviations appear to be due to hydrogen bonding and electron donor-acceptor interac tions. Robbins [Chem. Eng. Prog., 76(10), 58 (1980)] presented a table of these interactions. Table 15-4, that provides a qualitative guide to solvent selection for hqnid-hqnid extraction, extractive distillation, azeotropic distillation, or even solvent crystallization. The ac tivity coefficient in the liquid phase is common to all these separation processes. 

Liquid phase processes, such as hydrogenation, halogenation, oxidation, nitration, kylation, and so on... 

The illustrated unit can be used to study vapor-phase reforming of kerosene fractions to high octane gasoline, or hydrogenation of benzene, neat or in gasoline mixtures to cyclohexane and methylcyclopentane. In liquid phase experiments hydrotreating of distillate fractions can be studied. The so-called Solvent Methanol Process was studied in the liquid phase, where the liquid feed was a solvent only, a white oil fraction. 

A route to phenol has been developed starting from cyclohexane, which is first oxidised to a mixture of cyclohexanol and cyclohexanone. In one process the oxidation is carried out in the liquid phase using cobalt naphthenate as catalyst. The cyclohexanone present may be converted to cyclohexanol, in this case the desired intermediate, by catalytic hydrogenation. The cyclohexanol is converted to phenol by a catalytic process using selenium or with palladium on charcoal. The hydrogen produced in this process may be used in the conversion of cyclohexanone to cyclohexanol. It also may be used in the conversion of benzene to cyclohexane in processes where benzene is used as the precursor of the cyclohexane. 

The effect of physical processes on reactor performance is more complex than for two-phase systems because both gas-liquid and liquid-solid interphase transport effects may be coupled with the intrinsic rate. The most common types of three-phase reactors are the slurry and trickle-bed reactors. These have found wide applications in the petroleum industry. A slurry reactor is a multi-phase flow reactor in which the reactant gas is bubbled through a solution containing solid catalyst particles. The reactor may operate continuously as a steady flow system with respect to both gas and liquid phases. Alternatively, a fixed charge of liquid is initially added to the stirred vessel, and the gas is continuously added such that the reactor is batch with respect to the liquid phase. This method is used in some hydrogenation reactions such as hydrogenation of oils in a slurry of nickel catalyst particles. Figure 4-15 shows a slurry-type reactor used for polymerization of ethylene in a sluiTy of solid catalyst particles in a solvent of cyclohexane. 

Figure 8-6. The Hoechst AG process for producing 2-ethylhexanol from n-butyraldehyde (1) Aldol condensation reactor, (2) separation (organic phase from liquid phase), (3) hydrogenation reactor, (4) distillation column.

Older methods use a liquid phase process (Figure 10-11). ° New gas-phase processes operate at higher temperatures with noble metal catalysts. Using high temperatures accelerates the reaction (faster rate). The hydrogenation of benzene to cyclohexane is characterized by a highly exothermic reaction and a significant decrease in the product volume... 

Figure 10-11. The Institut Francais du Petiole process for the hydrogenation of benzene to cyclohexane " (1) liquid-phase reactor, (2) heat exchanger, (3) catalytic pot (acts as a finishing reactor when conversion of the main reactor drops below the required level), (4) high-pressure separator, (5) stabilizer.

In the chemical process industry molybdenum has found use as washers and bolts to patch glass-lined vessels used in sulphuric acid and acid environments where nascent hydrogen is produced. Molybdenum thermocouples and valves have also been used in sulphuric acid applications, and molybdenum alloys have been used as reactor linings in plant used for the production of n-butyl chloride by reactions involving hydrochloric and sulphuric acids at temperatures in excess of 170°C. Miscellaneous applications where molybdenum has been used include the liquid phase Zircex hydrochlorination process, the Van Arkel Iodide process for zirconium production and the Metal Hydrides process for the production of super-pure thorium from thorium iodide. 

In stirred-slurry reactors, momentum is transferred to the liquid phase by mechanical stirring as well as by the movement of gas bubbles. Small particles are used in most cases, and the operation is usually carried out in tank reactors with low height-to-diameter ratios. The operation is in widespread use for processes involving liquid reactants, either batchwise or continuous— for example, for the batchwise hydrogenation of fats as referred to in Section II. 

Life as we know it depends on this existence of water as a liquid. Biochemical processes require free movement of chemicals, which cannot occur in the solid phase. Biochemical stmctures contain many interlocking parts that would not be stable in the gas phase. Thus, the liquid phase is best suited for life. Moreover, water is an excellent solvent, particularly for molecules that can form hydrogen bonds. As we describe in Chapter JA, the molecular building blocks of living matter are rich in groups that form hydrogen bonds. This allows biological molecules to be synthesized, move about, and assemble into complex structures, all in aqueous solution. 

TS-1-catalyzed processes are advantageous from the environmental point of view as the oxidant is aqueous hydrogen peroxide, which turns into water, and the reactions are operated in liquid phase under mild conditions, showing very high selectivity and yields, thus reducing problems and the costs of by-product treatments. Confinement of the metal species in the well-defined MFl pore system endows TS-1 with shape selectivity properties analogous to enzymes. For these features the application of the terms mineral enzyme or zeozyme to TS-1 is appropriate [42]. 

The catalysts most frequently used are based on noble metals (mainly palladium and platinum) on various supports, or on nickel catalysts (mainly Raney type). Hydrogenations are generally performed in the liquid phase, under relatively mild conditions of temperature and pressure (1—40 bar). Most processes are performed batch-wise using powder catalysts in stirred tank or loop-type reactors with sizes up to 10 m . 

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