Industrial aldehydes

Aldehydes and ketones are among the most important of all compounds, both in biochemistry and in the chemical industry.. Aldehydes are normally prepared in the laboratory by oxidation of primary alcohols or by partial reduction of esters. Ketones are similarly prepared by oxidation of secondary alcohols or by addition of diorganocopper reagents to acid chlorides. 

Over the last 40 years the economic importance of industrial aldehyde production has led chemists and engineers to propose new and alternative ways to further optimize hydroformylation technologies. Particular attention in these attempts was always given to new concepts by which to combine the molecular defined, homogeneous nature of hydroformylation catalysis with cleverer ways to separate products and catalyst after reaction. Many of the reported strategies have focused on the... 

Tween 20 Atlas Chemical Industries aldehyde and naphthalene sulphonic acid Polyoxyethylene sorbitan... 

The industrial process for preparing the reagent usually permits a little hydrolysis to occur, and the product may contain a little free calcium hydroxide or basic chloride. It cannot therefore be employed for drying acids or acidic liquids. Calcium chloride combines with alcohols, phenols, amines, amino-acids, amides, ketones, and some aldehydes and esters, and thus cannot be used with these classes of compounds. 

The reaction of trivalent carbocations with carbon monoxide giving acyl cations is the key step in the well-known and industrially used Koch-Haaf reaction of preparing branched carboxylic acids from al-kenes or alcohols. For example, in this way, isobutylene or tert-hutyi alcohol is converted into pivalic acid. In contrast, based on the superacidic activation of electrophiles leading the superelectrophiles (see Chapter 12), we found it possible to formylate isoalkanes to aldehydes, which subsequently rearrange to their corresponding branched ketones. 

Extensive studies on the Wacker process have been carried out in industrial laboratories. Also, many papers on mechanistic and kinetic studies have been published[17-22]. Several interesting observations have been made in the oxidation of ethylene. Most important, it has been established that no incorporation of deuterium takes place by the reaction carried out in D2O, indicating that the hydride shift takes place and vinyl alcohol is not an intermediate[l,17]. The reaction is explained by oxypailadation of ethylene, / -elimination to give the vinyl alcohol 6, which complexes to H-PdCl, reinsertion of the coordinated vinyl alcohol with opposite regiochemistry to give 7, and aldehyde formation by the elimination of Pd—H. 

Many low molecular weight aldehydes and ketones are important industrial chem icals Formaldehyde a starting material for a number of plastics is prepared by oxida tion of methanol over a silver or iron oxide/molybdenum oxide catalyst at elevated temperature... 

A number of aldehydes and ketones are prepared both m industry and m the lab oratory by a reaction known as the aldol condensation which will be discussed m detail in Chapter 18... 

Hydroformylation (Section 17 5) An industrial process for prepanng aldehydes (RCH2CH2CH=0) by the reaction of terminal alkenes (RCH=CH2) with carbon monoxide Hydrogenation (Section 6 1) Addition of H2 to a multiple bond... 

Common catalyst compositions contain oxides or ionic forms of platinum, nickel, copper, cobalt, or palladium which are often present as mixtures of more than one metal. Metal hydrides, such as lithium aluminum hydride [16853-85-3] or sodium borohydride [16940-66-2] can also be used to reduce aldehydes. Depending on additional functionahties that may be present in the aldehyde molecule, specialized reducing reagents such as trimethoxyalurninum hydride or alkylboranes (less reactive and more selective) may be used. Other less industrially significant reduction procedures such as the Clemmensen reduction or the modified Wolff-Kishner reduction exist as well. 

Aldehydes fiad the most widespread use as chemical iatermediates. The production of acetaldehyde, propionaldehyde, and butyraldehyde as precursors of the corresponding alcohols and acids are examples. The aldehydes of low molecular weight are also condensed in an aldol reaction to form derivatives which are important intermediates for the plasticizer industry (see Plasticizers). As mentioned earlier, 2-ethylhexanol, produced from butyraldehyde, is used in the manufacture of di(2-ethylhexyl) phthalate [117-87-7]. Aldehydes are also used as intermediates for the manufacture of solvents (alcohols and ethers), resins, and dyes. Isobutyraldehyde is used as an intermediate for production of primary solvents and mbber antioxidants (see Antioxidaisits). Fatty aldehydes Cg—used in nearly all perfume types and aromas (see Perfumes). Polymers and copolymers of aldehydes exist and are of commercial significance. 

Chemical Properties. A combination of excellent chemical and mechanical properties at elevated temperatures result in high performance service in the chemical processing industry. Teflon PEA resins have been exposed to a variety of organic and inorganic compounds commonly encountered in chemical service (26). They are not attacked by inorganic acids, bases, halogens, metal salt solutions, organic acids, and anhydrides. Aromatic and ahphatic hydrocarbons, alcohols, aldehydes, ketones, ethers, amines, esters, chlorinated compounds, and other polymer solvents have Httle effect. However, like other perfluorinated polymers,they react with alkah metals and elemental fluorine. 

In the early 1920s Badische Arulin- und Soda-Fabrik aimounced the specific catalytic conversion of carbon monoxide and hydrogen at 20—30 MPa (200—300 atm) and 300—400°C to methanol (12,13), a process subsequendy widely industrialized. At the same time Fischer and Tropsch aimounced the Synth in e process (14,15), in which an iron catalyst effects the reaction of carbon monoxide and hydrogen to produce a mixture of alcohols, aldehydes (qv), ketones (qv), and fatty acids at atmospheric pressure. 

Substances other than enzymes can be immobilized. Examples include the fixing of heparin on polytetrafluoroethylene with the aid of PEI (424), the controUed release of pesticides which are bound to PEI (425), and the inhibition of herbicide suspensions by addition of PEI (426). The uptake of anionic dyes by fabric or paper is improved if the paper is first catonized with PEI (427). In addition, PEI is able to absorb odorizing substances such as fatty acids and aldehydes. Because of its high molecular weight, PEI can be used in cosmetics and body care products, as weU as in industrial elimination of odors, such as the improvement of ambient air quaHty in sewage treatment plants (428). 

Autooxidation. Liquid-phase oxidation of hydrocarbons, alcohols, and aldehydes by oxygen produces chemiluminescence in quantum yields of 10 to 10 ° ein/mol (128—130). Although the efficiency is low, the chemiluminescent reaction is important because it provides an easy tool for study of the kinetics and properties of autooxidation reactions including industrially important processes (128,131). The light is derived from combination of peroxyl radicals (132), which are primarily responsible for the propagation and termination of the autooxidation chain reaction. The chemiluminescent termination step for secondary peroxy radicals is as follows ... 

Ligand-Modified Rhodium Process. The triphenylphosphine-modified rhodium oxo process, termed the LP Oxo process, is the industry standard for the hydroformylation of ethylene and propylene as of this writing (ca 1995). It employs a triphenylphosphine [603-35-0] (TPP) (1) modified rhodium catalyst. The process operates at low (0.7—3 MPa (100—450 psi)) pressures and low (80—120°C) temperatures. Suitable sources of rhodium are the alkanoate, 2,4-pentanedionate, or nitrate. A low (60—80 kPa (8.7—11.6 psi)) CO partial pressure and high (10—12%) TPP concentration are critical to obtaining a high (eg, 10 1) normal-to-branched aldehyde ratio. The process, first commercialized in 1976 by Union Carbide Corporation in Ponce, Puerto Rico, has been ficensed worldwide by Union Carbide Corporation and Davy Process Technology. 

The switch from the conventional cobalt complex catalyst to a new rhodium-based catalyst represents a technical advance for producing aldehydes by olefin hydroformylation with CO, ie, by the oxo process (qv) (82). A 200 t/yr CSTR pilot plant provided scale-up data for the first industrial,... 

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