Phosgene

Phosgene (carbonyl dichloride) is a colorless reactive gas with a bp of 8.2 C, a vapor pressure at 20 C
of 162,000 Pa or 1215 mmHg, and a vapor density of 3.5. Phosgene was first prepared by John Davy
in 1812 by the action of light on a mixture of chlorine and carbon monoxide.

The current scale of world phosgene consumption is 5–6 106 tons y1.
The vast majority of phosgene is utilized at its site of production: only very small quantities are
shipped. Only Van De Mark (now part of SNPE), located in Lockport, N.Y., sells phosgene on the
merchant market. Traditionally, small-scale consumers of phosgene had little choice but to buy it
from Van De Mark. Because of its toxicity, small or zero inventories of phosgene are usually
maintained, although it is easily liquefied.

Phosgene can be prepared from carbon monoxide, from halogenated hydrocarbons, from
carbonaceous materials, from carbon dioxide, carbonyl sulfide or carbon disulfide, and from other
oxygenated compounds [39]. The method based on the chlorination of carbon monoxide is by far
the most important and has been scaled-up for the commercial manufacture of phosgene.

2.1.1 Conventional Manufacturing Processes

Phosgene is produced commercially by the highly exothermic vapor-phase reaction of anhydrous

chlorine gas with high-purity carbon monoxide in the presence of an activated carbon catalyst [1].
The enthalpy of formation is 107.6 kJ mol1, hence efficient heat removal is required.

CO(g) + Cl2(g) -> COCl2(g)

The basic manufacturing process for phosgene has not changed significantly since the 1920s and
comprises the preparation and purification of the raw materials, carbon monoxide and chlorine, the
metering and mixing of these materials, the reaction of the mixed gases over activated charcoal, and
the purification and condensation of the phosgene product. A flow diagram of the process is
illustrated below (Scheme 2.2).

The process is normally operated on a continuous basis, employing a high degree of automation.
Owing to the toxicity of phosgene, extensive safety features are an integral part of the plant design.
The reaction is rapid and nearly quantitative with respect to both raw materials. Traditionally,
phosgene is produced from largescale units running at a steady state, and the product requires
downstream storage. The plants are provided with a safety absorption system, whereby any surplus
phosgene is absorbed and destroyed with a circulating caustic solution. This kind of process is only
well-suited for large users and it engenders a lot of environmental concerns.

Detailed descriptions of the basic manufacturing processes are given in several important references
[40–43].

A summary of recently filed patent applications and granted patents regarding phosgene
preparation is presented in Table 2.1.

Phosgene produced by the traditional processes will typically contain 400–500 ppm by weight
tetrachloromethane (the major world producers claim a CCl4 content of 50–400 ppm). The amount
of tetrachloromethane needs to be evaluated on the basis of the total worldwide production of
phosgene. In relation to the cumulative effect of recycling polycarbonates (the major polymeric
material for which phosgene is a raw material), tetrachloromethane has been shown to have both
significant ozone depletion and global warming potentials. Therefore, there is an interest in
developing phosgene processes in which the amount of tetrachloromethane impurity is minimized.
In the production of polycarbonates from dihydroxylic compounds and phosgene,
tetrachloromethane also causes a yellowing of the material, which is disadvantageous for optical
applications of the polymers; a colorless product can only be achieved when the phosgene has a
CCl4 content <150 ppm [44].

Thus, the development of a process for producing highly pure phosgene has been one goal of
research in this field. On the other hand, extensive industrial research has been dedicated to the
quest for new phosgene-free routes to polycarbonates. Diphenyl carbonate (DPhC) is used as the key
reagent for incorporating the carbonate functionality into polycarbonates by the so-called non-
phosgene route. One of the difficulties associated with this process, however, is making the DPhC.
Currently, DPhC is made from dimethyl carbonate (DMC) by transesterification with phenol (see, for
example, the Enichem process). This reaction is equilibrium-constrained and requires a fairly
complicated processing scheme. The DMC is in turn prepared by oxidative methylation of carbon
monoxide with methanol (as in the Enichem process) as a preferred alternative to obviate the need
for phosgene.

Several efforts have been made to lower the tetrachloromethane content of phosgene to below 150
ppm [44–48]. Examining the patent literature, the major technical improvements have been
focussed on the catalyst; indeed, substitution or modification of the catalyst should have a minimal
impact on the existing manufacturing process and should therefore require the least investment.

In a recent contribution to this field, a process was reported whereby phosgene is manufactured
from chlorine and carbon monoxide under catalysis by a Group III metal halide [47]. The key feature
of this process is that it uses a carbon-free catalyst, principally based on Group III metal (Al or Ga)
halides, which avoids the formation of chlorinated carbon products. The carbon-free catalysts were
applied in the production of nearly CCl4-free phosgene, which contained as little as 1 ppm of the
contaminant. The reported reaction times for a batch reaction system using GaCl3 and GaCl2 (3.7
mol%) as catalyst, e.g. 1.5 h and 1 h, respectively, at 1200 kPa, generating phosgene in 100% yield,
are very promising. Aluminum chloride can also be used as catalyst, but reaction times are
significantly longer. The reaction temperature is very low (below room temperature to 100 C)
compared to those of traditional process. An elegant feature of the process is that the catalyst is
continuously regenerated and activated by resublimation. The process seems to be well-suited for
scale-up and may be operated in either continuous or batch mode. The described process has
important advantages considering the low level of tetrachloromethane contamination (<1 ppm) of
the product, the very mild and highly versatile conditions of operation based on established
chemistry, and the ready availability of the high turnover catalyst.

A further Bayer process yields phosgene with a CCl4 content below 150 ppm by reacting carbon
monoxide and chlorine in the presence of elemental carbon at 30– 80 C at a pressure of 120–400
kPa [44]. Companies such as DuPont [45] and Idemitsu [46] pursue the same approach by treating
charcoal catalysts with 0.1–2.3% of active metals, thereby also producing phosgene with CCl4 levels
<150 ppm. Phosgene manufacture generally takes place in special equipment and plants.

2.1.2 Manufacturing Processes ‘‘On Demand of Consumer’’

Another way of providing consumers on location with phosgene ‘‘on demand’’ is through the use of
Modular Phosgene Generators, which are available in several output sizes ranging from 3–10,000 kg
h1 from Davy Process Technology (DPT), Switzerland [49]. These Modular Generators produce
phosgene from carbon monoxide and chlorine, and consist of two sections, the intrinsic phosgene
generator (Scheme 2.3) and a safety absorption module (for commercial availability, see Section
7.1.1).

A recent publication [50] details the new Novartis Crop Protection Inc. plant (at Monthey,
Switzerland) for the manufacture and use of phosgene in equipment that is considered intrinsically
safe. Indeed, the implementation of ‘‘dynamic reactors’’ for the production of phosgene, which
manufacture and deliver the phosgene to the users on demand as required, without intermediate
storage, has made it possible to strongly reduce the quantities of phosgene contained within the
plant. Furthermore, confinement of the phosgene production, supply, and utilization equipment
within a double envelope makes it possible to collect and destroy any leakage of the phosgene in
dedicated installations [50].