Vapor-phase processing

Alkylthiazoles can be oxidized to nitriles in the presence of ammonia and a catalyst. For example, 4-cyanothiazole was prepared from 4-methylthiazole by a one-step vapor-phase process (94) involving reaction with a mixture of air, oxygen, and ammonia at 380 to 460°C. The catalyst was M0O3 and V Oj or M0O3, VjOj, and CoO on an alumina support. 

The reaction of adipic acid with ammonia in either Hquid or vapor phase produces adipamide as an intermediate which is subsequentiy dehydrated to adiponitrile. The most widely used catalysts are based on phosphoms-containing compounds, but boron compounds and siHca gel also have been patented for this use (52—56). Vapor-phase processes involve the use of fixed catalyst beds whereas, in Hquid—gas processes, the catalyst is added to the feed. The reaction temperature of the Hquid-phase processes is ca 300°C and most vapor-phase processes mn at 350—400°C. Both operate at atmospheric pressure. Yields of adipic acid to adiponitrile are as high as 95% (57). 

In 1987, Toray Industries, Inc., announced the development of a new process for making aromatic nitriles which reportedly halved the production cost, reduced waste treatment requirements, and reduced production time by more than two-thirds, compared with the vapor-phase process used by most producers. The process iavolves the reaction of ben2oic acid (or substituted ben2oic acid) with urea at 220—240°C ia the presence of a metallic catalyst (78). 

Liquid- and vapor-phase processes have been described the latter appear to be advantageous. Supported cadmium, zinc, or mercury salts are used as catalysts. In 1963 it was estimated that 85% of U.S. vinyl acetate capacity was based on acetylene, but it has been completely replaced since about 1982 by newer technology using oxidative addition of acetic acid to ethylene (2) (see Vinyl polymers). In western Europe production of vinyl acetate from acetylene stiU remains a significant commercial route. 

Trioxane and Tetraoxane. The cycHc symmetrical trimer of formaldehyde, trioxane [110-88-3] is prepared by acid-catalyzed Hquid- or vapor-phase processes (147—151). It is a colorless crystalline soHd that bods at 114.5°C and melts at 61—62°C (17,152). The heats of formation are — 176.9 kJ/mol (—42.28 kcal/mol) from monomeric formaldehyde and —88.7 kJ/mol (—21.19 kcal/mol) from 60% aqueous formaldehyde. It can be produced by continuous distillation of 60% aqueous formaldehyde containing 2—5% sulfuric acid. Trioxane is extracted from the distillate with benzene or methylene chloride and recovered by distillation (153) or crystallization (154). It is mainly used for the production of acetal resins (qv). 

Vinyl ethers are prepared in a solution process at 150—200°C with alkaH metal hydroxide catalysts (32—34), although a vapor-phase process has been reported (35). A wide variety of vinyl ethers are produced commercially. Vinyl acetate has been manufactured from acetic acid and acetylene in a vapor-phase process using zinc acetate catalyst (36,37), but ethylene is the currently preferred raw material. Vinyl derivatives of amines, amides, and mercaptans can be made similarly. A/-Vinyl-2-pyrroHdinone is a commercially important monomer prepared by vinylation of 2-pyrroHdinone using a base catalyst. 

The hquid-phase processes are more energy efficient than the vapor-phase processes, however, they iacur costiy high pressure equipment investment and also produce waste streams containing used catalyst (213). Both methods produce substantial quantities of by-products which cause refining difficulties. The by-products consist primarily of mesitylene [108-67-8] phorone [504-20-17, and the foUowiag xyUtone isomers (215) ... 

Substantial amounts of 3,3,6,8-tetramethyl-l-tetralone [5409-55-2] are also formed, most notably ia the vapor-phase process (216). This tetralone has been synthesized from isophorone and mesityl oxide and it can thus be assumed to be a product of these two materials ia the isophorone process (217,218). 

Eor vapor-phase processes, the product stream from the nitrator must be separated. The nitroparaffins, excess propane, and NO plus NO2 (which are converted back to HNO ), are recovered. The oxygenated products are removed, but there are generally insufficient amounts for economic recovery. 

The vapor-phase process of SocifitH Chemique de la Grande Paroisse for production of nitroparaffins employs propane, nitrogen dioxide, and air as feedstocks (34). The yields of nitroparaffins based on both propane and nitrogen dioxide are relatively high. Nitric oxide produced during nitration is oxidized to nitrogen dioxide, which is adsorbed in nitric acid. Next, the nitric dioxide is stripped from the acid and recirculated. 

Nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane are produced by a vapor-phase process developed ia the 1930s (2). 

In the Godrej-Lurgi process, olefins are produced by dehydration of fatty alcohols on alumina in a continuous vapor-phase process. The reaction is carried out in a specially designed isothermal multitube reactor at a temperature of approximately 300°C and a pressure of 5—10 kPa (0.05—0.10 atm). As the reaction is endothermic, temperature is maintained by circulating externally heated molten salt solution around the reactor tubes. The reaction is sensitive to temperature fluctuations and gradients, hence the need to maintain an isothermal reaction regime. 

Vapor-Phase Processes. Although vapor-phase alkylation has been practiced since the early 1940s, it could not compete with Hquid-phase processes until the 1970s when the Mobil—Badger vapor-phase ethylbenzene process was introduced (Eig. 4). The process is based on Mobil s ZSM-5 zeohte catalyst (38,52,53). The nonpoUuting and noncorrosive nature of the process is one of its major advantages over the AlCl hquid-phase system. 

Diphenylamine can also be produced by passing the vapors of aniline over a catalyst such as alumina, or alumina impregnated with ammonium fluoride (17). The reaction is carried out at 480°C and about 700 kPa (7 atm). Conversion per pass, expressed as parts diphenylamine per 100 parts of reactor effluent, is low (18—22%), and the unconverted aniline must be recycled. Other catalysts disclosed for the vapor-phase process are alumina modified with boron trifluoride (18), and alumina activated with boric acid or boric anhydride (19). 

The predominant process for manufacture of aniline is the catalytic reduction of nitroben2ene [98-95-3] ixh. hydrogen. The reduction is carried out in the vapor phase (50—55) or Hquid phase (56—60). A fixed-bed reactor is commonly used for the vapor-phase process and the reactor is operated under pressure. A number of catalysts have been cited and include copper, copper on siHca, copper oxide, sulfides of nickel, molybdenum, tungsten, and palladium—vanadium on alumina or Htbium—aluminum spinels. Catalysts cited for the Hquid-phase processes include nickel, copper or cobalt supported on a suitable inert carrier, and palladium or platinum or their mixtures supported on carbon. 

Dehydrogenation. Before the large-scale availabiUty of acetone as a co-product of phenol (qv) in some processes, dehydrogenation of isopropyl alcohol to acetone (qv) was the most widely practiced production method. A wide variety of catalysts can be used in this endothermic (66.5 kj/mol (15.9 kcal/mol) at 327°C), vapor-phase process to achieve high (75—95 mol %) conversions. Operation at 300—500°C and moderate pressures (207 kPa (2.04 atm)) provides acetone in yields up to 90 mol %. The most useful catalysts contain Cu, Cr, Zn, and Ni, either alone, as oxides, or in combinations on inert supports (see Catalysts, supported) (13-16). 

Thermochemical Data. Equilibrium considerations significantly limit alcohol yield at low pressures in the vapor-phase process (116). Consequently, conditions controlling equilibrium constants have been determined and give the following relation, where Tis in K (116,117) ... 

Commercial Manufacture of Pyridine. There are two vapor-phase processes used in the industry for the synthesis of pyridines. The first process (eq. 21) uti1i2es formaldehyde and acetaldehyde as a co-feed with ammonia, and the principal products are pyridine (1) and 3-picoline (3). The second process produces only alkylated pyridines as products. 

A vapor-phase process primarily for ECC off-gas feeds was developed by Sinopec Technology Company based on a 2eoHte catalyst of the Pentasd type (24,25). It reHes on frequent regeneration of the catalyst to minimi2e pretreatment of the ECC off-gas and allows the impurities in the feed gas to react with ben2ene to form by-products. Consequently, the product yield and purity are low. Joint licensing by ABB Lummus Crest and Sinopec was announced in 1994. 

Fig. 2. Schematics of a vapor-phase process that generates thiophene and alkyl thiophenes, where the controHed parameters F = flow and...

Today, the air oxidation of toluene is the source of most of the world s synthetic benzaldehyde. Both vapor- and Hquid-phase air oxidation processes have been used. In the vapor-phase process, a mixture of air and toluene vapor is passed over a catalyst consisting of the oxides of uranium, molybdenum, or related metals. High temperatures and short contact times are essential to maximize yields. Small amounts of copper oxide maybe added to the catalyst mixture to reduce formation of by-product maleic anhydride. 

Vapor-Phase Processing. Optical fiber preforms are prepared by vapor-phase techniques because of the superior clarity of the products. 

Hibemia-Chemie has described a vapor-phase process that passes fresh and recycled 85 wt % phosphoric acid over a catalyst of hydrochloric acid-leached bentonite impregnated with phosphoric acid. Catalyst activity was claimed to remain constant over a period of one year at the following conditions (126) ... 

Gas- or vapor-phase processes Liquid-phase processes ... 

In the vapor-phase process, oxyacylation of ethylene is carried out in a tubular reactor at approximately 117°C and 5 atmospheres. The palla-... 

However, ethylene as a cheap raw material has replaced acetylene for obtaining vinyl chloride. The production of vinyl chloride via ethylene is a three-step process. The first step is the direct chlorination of ethylene to produce ethylene dichloride. Either a liquid- or a vapor-phase process is used ... 

In the direct hydration method, the reaction could be effected either in a liquid or in a vapor-phase process. The slightly exothermic reaction evolves 51.5 KJ/mol. 

Older processes still use the sulfation route. The process is similar to that used for ethylene in the presence of H2SO4, hut the selectivity is a little lower than the modern vapor-phase processes. The reaction conditions are milder than those used for ethylene. This manifests the greater ease with which an isopropyl carhocation (a secondary carhonium ion) is formed than a primary ethyl carhonium ion ... 

In the vapor-phase process, the reaction temperature and pressure are approximately 250°C and 40 atmospheres. Phosphoric acid on Kieselguhr is a commonly used catalyst. To limit polyalkylation, a mixture of propene-propane feed is used. Propylene can be as low as 40% of the feed mixture. A high benzene/propylene ratio is also used to decrease polyalkylation. A selectivity of about 97% based on benzene can be obtained. 

Monochlorohenzene is also produced in a vapor-phase process at approximately 300°C. The hy-product HCl goes into a regenerative oxychlorination reactor. The catalyst is a promoted copper oxide on a silica carrier ... 

A vapor phase process for deparaffmization of light gas oils performed by the BP works in this way The gas oil, boiling range 230-320°C, is passed over a 5-A molecular sieve at 320°C and a pressure of 3.6 bar. The space velocity is 0.63 vol liquid gas oil per vol molecular sieve and per hour, [liquid hourly space velocity (lhsv) = 0.63] the adsorption period takes 6 min. Together with the gas oil vapor 120 vol N2 per vol liquid gas oil is led over the sieve as carrier and purge gas. After the adsorption period the loaded molecular sieve is purged at the same temperature with pure N2 for 6 min. Subsequently, the adsorbed /z-alkanes are desorbed by 1 vol liquid /z-pentane per vol molecular sieve and per hour. The /z-pentane is recovered from the /z-alkane//z-pentane mixture by simple distillation [15]. The IsoSiv process of the Union Carbide Corporation works in a similar way [16]. The purity of the isolated /z-alkanes is >98%. 

Figure 1. Surface grafting by vapor phase process.

Polyethylene (PE) was a commercial LD type (without additives) with a density of 0.92 and polypropylene (PP) was also a commercial material with a density of 0.91. The polvolefin samples were melt pressed to 1 mm thick sheets (plates) which were wiped clean with acetone and used directly for the grafting experiments with the vapor-phase process. 

In the continuous process the solution of sensitizer and monomer forms a thin surface layer on the polymer in which the photoinitiated reaction takes place without affecting the bulk phase of the polymer. In the vapor phase process, the grafting reaction starts at the... 

Figure 3. Reflection infrared spectra (ATR-IR) of a polypropylene-j surface before (A) and after (B) grafting with acrylamide (AM) by the vapor phase process (above). ESCA spectra of the same surface before (dotted lines) and after (full lines) the surface grafting (below).

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