Methanol design

C. M. Gronet, N. S. Lewis, G. Cogan, and J. Gibbons, n-type silicon photoelectrochemistry in methanol Design of a 10.1% efficient semiconductor/liquid junction solar cell, Proc. Natl. Acad. Sci. USA 80, 1152, 1983. 

The important properties of methanol have already been outlined in Chapter 6. Also, reformers for extracting the hydrogen from methanol, designed for mobile applications, have been described already in Section 8.6. Methanol is the man-made carrier of hydrogen that is attracting the most interest among fuel cell developers. 

Figure 2.7 Two alternative reactor designs for methanol production give quite different thermal profiles.

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

Ethylene glycol can be produced by an electrohydrodimerization of formaldehyde (16). The process has a number of variables necessary for optimum current efficiency including pH, electrolyte, temperature, methanol concentration, electrode materials, and cell design. Other methods include production of valuable oxidized materials at the electrochemical cell s anode simultaneous with formation of glycol at the cathode (17). The compound formed at the anode maybe used for commercial value direcdy, or coupled as an oxidant in a separate process. 

Most large-scale industrial methacrylate processes are designed to produce methyl methacrylate or methacryhc acid. In some instances, simple alkyl alcohols, eg, ethanol, butanol, and isobutyl alcohol, maybe substituted for methanol to yield the higher alkyl methacrylates. In practice, these higher alkyl methacrylates are usually prepared from methacryhc acid by direct esterification or transesterification of methyl methacrylate with the desired alcohol. 

The feature that is most usefiil in distinguishing commercial methanol processes from one another is the type of reactor used. The four basic types in use ate shown in Figure 7. There are a variety of proprietary reactor designs commercially available from Hcensors, all of which are either one of these four types or a combination of two among them (17—22). 

Quench Converter. The quench converter (Fig. 7a) was the basis for the initial ICl low pressure methanol flow sheet. A portion of the mixed synthesis and recycle gas bypasses the loop interchanger, which provides the quench fractions for the iatermediate catalyst beds. The remaining feed gas is heated to the inlet temperature of the first bed. Because the beds are adiabatic, the feed gas temperature increases as the exothermic synthesis reactions proceed. The injection of quench gas between the beds serves to cool the reacting mixture and add more reactants prior to entering the next catalyst bed. Quench converters typically contain three to six catalyst beds with a gas distributor in between each bed for injecting the quench gas. A variety of gas mixing and distribution devices are employed which characterize the proprietary converter designs. 

Pectins are subdivided according to their degree of esterification (DE), a designation of the percent of carboxyl groups esterified with methanol. Pectins with DE >50% are high methoxyl pectins (HM pectins) [65546-99-8]-, those with DE <50% are low methoxyl pectins (LM pectins) [9049-34-7]. 

The U.S. Department of Energy has funded a research program to develop the Hquid-phase methanol process (LPMEOH) (33). This process utilizes a catalyst such as copper—zinc oxide suspended in a hydrocarbon oil. The Hquid phase is used as a heat-transfer medium and allows the reaction to be conducted at higher conversions than conventional reactor designs. In addition, the use of the LPMEOH process allows the use of a coal-derived, CO-rich synthesis gas. Typical reactor conditions for this process are 3.5—6.3 MPa (35—60 atm) and 473—563 K (see Methanol). 

Engines are also designed to use either gasoline or methanol and any mixture thereof (132—136). Such a system utilizes the same fuel storage system, and is called a flexible fueled vehicle (EEV). The closed loop oxygen sensor and TWC catalyst system is perfect for the flexible fueled vehicle. Optimal emissions control requires a fuel sensor to detect the ratio of each fuel being metered at any time and to correct total fuel flow. 

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