From carbon monoxide and

Even though form amide was synthesized as early as 1863 by W. A. Hoffmann from ethyl formate [109-94-4] and ammonia, it only became accessible on a large scale, and thus iadustrially important, after development of high pressure production technology. In the 1990s, form amide is mainly manufactured either by direct synthesis from carbon monoxide and ammonia, or more importandy ia a two-stage process by reaction of methyl formate (from carbon monoxide and methanol) with ammonia. 

Two-Step Process. The significant advantage of the two-step process is that it only requkes commercial-grade methyl formate and ammonia. Thus the cmde product leaving the reactor comprises, in addition to excess starting materials, only low boiling substances, which are easily separated off by distillation. The formamide obtained is of sufficient purity to meet all quaUty requkements without recourse to the costiy overhead distillation that is necessary after the dkect synthesis from carbon monoxide and ammonia. 

The estimated capacity of formamide was approximately 100,000 t/yr worldwide in 1990. In 1993, there are only three significant producers BASE in Germany is the leading manufacturer. Smaller quantities of formamide are produced in the former Czechoslovakia (Sokolov) and Japan (Nitto) by direct synthesis from carbon monoxide and ammonia. Most of the formamide produced is utilized direcdy by the manufacturers. The market price for formamide (ca 1993) is about 2.00/kg. 

Reforming is completed in a secondary reformer, where air is added both to elevate the temperature by partial combustion of the gas stream and to produce the 3 1 H2 N2 ratio downstream of the shift converter as is required for ammonia synthesis. The water gas shift converter then produces more H2 from carbon monoxide and water. A low temperature shift process using a zinc—chromium—copper oxide catalyst has replaced the earlier iron oxide-catalyzed high temperature system. The majority of the CO2 is then removed. 

Nitric acid oxidation is used where carbohydrates, ethylene glycol, and propylene are the starting materials. The diaLkyl oxalate process is the newest, where diaLkyl oxalate is synthesized from carbon monoxide and alcohol, then hydrolyzed to oxahc acid. This process has been developed by UBE Industries in Japan as a CO coupling technology in the course of exploring C-1 chemistry. 

The sodium formate process is comprised of six steps (/) the manufacture of sodium formate from carbon monoxide and sodium hydroxide, (2) manufacture of sodium oxalate by thermal dehydrogenation of sodium formate at 360°C, (J) manufacture of calcium oxalate (slurry), (4) recovery of sodium hydroxide, (5) decomposition of calcium oxalate where gypsum is produced as a by-product, and (6) purification of cmde oxahc acid. This process is no longer economical in the leading industrial countries. UBE Industries (Japan), for instance, once employed this process, but has been operating the newest diaLkyl oxalate process since 1978. The sodium formate process is, however, still used in China. 

Fig. 1. Manufacture of phosgene from carbon monoxide and chlorine.

An interesting development in the use of metal carbonyl catalysts is the production of hydrocarbons from carbon monoxide and hydrogen. The reaction of carbon monoxide and hydrogen in a molten solution of sodium chloride and aluminum chloride with It4(CO) 2 a catalyst yields a mixture of hydrocarbons. Ethane is the primary product (184). 

Tn the synthesis of methane from carbon monoxide and hydrogen, it is desired to operate the reactor or reactors in such a way as to avoid carbon deposition on catalyst surfaces and to produce high quality product gas. Since gas compositions entering the reactor may vary considerably because of the use of diluents and recycle gas in a technical operation, it is desirable to estimate the effects of initial gas composition on the subsequent operation. Pressure and temperature are additional variables. 

A number of such processes were established before the second World War in Germany, Japan, and France for the production of hydrocarbon mixtures in the liquid fuel range (P2). This way of manufacturing automotive fuels is now uneconomical in most areas, but related processes may be utilized for the production of various chemicals, such as paraffinic waxes or oxygenated compounds. (The manufacture of methanol from carbon monoxide and hydrogen, usually by catalytic reaction in fixed-bed gas-particle operation, is an important process of this type.)... 

The formation of polyesters from carbon monoxide and propylene oxide using a cobalt catalyst may involve an alternate coordination on the metal and an insertion of monomers into the carbon-transition metal bond240. ... 

Methyl alcohol, CH2OH, also called wood alcohol or wood spirit, since it was formerly obtained from the destructive distillation of wood. It has also been synthesised from carbon monoxide and hydrogen or by fermentation of various sugar containing crops. Used as a part replacement for petrol in Gasohol to deliver a more environmentally friendly fuel, i.e., from renewable resources. 

Lapidus, A., Krylova, A., Kazanskii, V., Borovkov, V., and Zaitsev, A. 1991. Hydrocarbon synthesis from carbon monoxide and hydrogen on impregnated cobalt catalysts. Part I. Physico-chemical properties of 10% cobalt/alumina and 10% cobalt/ silica. Appl. Catal. 73 65-81. 

With reference to the homogeneous catalyst systems thus far reported for the synthesis of hydrocarbons/chemicals from carbon monoxide and hydrogen, only the anionic rhodium systems of Union Carbide show any appreciable shift activity. With neutral species of the type M3(CO)12 (M = Ru or Os), only small quantities of carbon dioxide are produced under the synthesis conditions (57). 

However, since the goal of this work was the synthesis of alcohols from olefins via hydrohydroxymethylation (75, 76), little attention was given to developing a shift-catalyst per se. Pettit has recently reexamined some of this work and shown that, by careful control of the pH of the reaction mixture, systems based on either Fe(CO)5 or Cr(CO)6 can be developed for the production of either formic acid or methanol from carbon monoxide and water (77, 78). Each of these latter systems involves the formation of metal hydride complexes consequently, molecular hydrogen is also produced according to the shift reaction [Eq. (16)]. 

Pier-Mittasch A high-pressure, catalytic process for making methanol from carbon monoxide and hydrogen. Developed by M. Pier and A. Mittasch at BASF in the 1920s. 

Following the first observations by Heck that Pd(OAc)2 can substitute a hydrogen atom in ethylene by a carbomethoxy group [50], Stille and James have discovered that the [Pd - Cu] couple catalyzes the incorporation of a COOMe group arising from carbon monoxide and methanol [51]. Most of the reactions with an alkene end up with a diester or a methoxyester, copper being used in stoichiometric quantities. Cyclic alkenes give preferentially diesters (Scheme 7). 

Several important chemical reactions for the conversion of coal to methane are shown in Table 2. Steam conversion involves the reaction of coal with steam to produce hydrogen and carbon monoxide. Hydrogen conversion is a reaction in which coal and hydrogen react to form methane. Oxygen conversion produces hydrogen and carbon monoxide by partial oxidation of coal. Methan-ation involves a reaction in which methane and water are produced from carbon monoxide and hydrogen. The water gas shift reaction between carbon monoxide and steam produces carbon dioxide and hydrogen. 

So far, no reference has been made to the presence of more than one phase in the reactor. Many important chemicals are manufactured by processes in which gases react on the surface of solid catalysts. Examples include ammonia synthesis, the oxidation of sulphur dioxide to sulphur trioxide, the oxidation of naphthalene to phthalic anhydride and the manufacture of methanol from carbon monoxide and hydrogen. These reactions, and many others, are carried out in tubular reactors containing a fixed bed of catalyst which may be either a single deep bed or a number of parallel tubes packed with catalyst pellets. The latter arrangement is used, for exjimple, in the oxidation of ethene to oxiran (ethylene oxide)... 

The reactions studied were the catalytic formation of methane from carbon monoxide and hydrogen (according to Sabatier (34), normal pressure), the catalytic hydrogenation of unsaturated hydrocarbons and also of unsaturated fatty acids ( fat hardening according to Normann (35)). Here again, a certain analogy was established between... 

When the carbon dioxide is replaced with carbonyl sulfide, generated in situ from carbon monoxide and sulfur, 4-thioxo-2-quinazolinones 818 are produced <2000HAC428>. 

An industrial process to produce methanol from carbon monoxide and hydrogen was developed by BASF in 1923 using a zinc oxide-chromia catalyst.361 362 Since this catalyst exhibited relatively low specific activity, high temperature was required. The low equilibrium methanol concentration at this high temperature was compensated by using high pressures. This so-called high-pressure process was operated typically at 200 atm and 350°C. The development of the process and early results on methanol synthesis were reviewed by Natta 363... 

In Ihe 1990s. formamide is mainly manufactured cither by direct synthesis from carbon monoxide and ammonia, or more importantly in a two-stage process by reaction of methyl formate (front carbon monoxide and methanol) with ammonia. 

Phosgene is used in the production of diisocyanates, starting materials for polyurethanes, and in other organic syntheses. Commercially, phosgene is obtained from carbon monoxide and chlorine... 

The production of phosgene, COCl2, from carbon monoxide and chlorine is believed to take place by the following mechanism ... 

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