The ICI Process

ICI produced gasoline. Coal was slurried with heavy oil (bp 400 0) and 2% of an iron oxide catalyst (later an improved stannous oxalate catalyst was used) and hydrogenated at 420 C and 250 atm. Dnring operation in the tall, narrow reactor the slnrry was agitated by the upward flow of hydrogen. The ratio of hydrogen to slnrry was about 1000, with a residence time of up to 2 h. 

TABLE 2.15. Coal and Creosote Hydrogenation Process and Catalysts. 

First stage (liquid phase) 47% coal/heavy oil slurry Creosote 375 C 

Note One of the first eatalysts was sulfided ZnO/MgO/MoOs, whieh gave low yields. Replaced with WS2, which produced low-octane gasoline. Two vapor phase reactors in series used WSj in the first, with either WS2 on Terrana clay (fuller s earth) or 10% FeFa onkieselguhr in the second to produce high-octane gasoline. 

Originally Bergius felt that coal hydrogenation could not be catalyzed because the large quantities of sulfur present would poison the catalysts. He added luxmasse simply to absorb sulfur from the products although, coincidentally, the combination of iron oxide with titania and alumina was an excellent choice of catalyst. Since his first tests, however, the industrial use of the process has depended on catalysts that were developed more or less empirically. It was soon realized that the processes involved in hydrogenating coal were more complex than the simple reactions described by Sabatier and Ipatieff. Different catalysts such as iron oxide or iron snlfide, probably with traces of other metal oxides, were reqnired. These catalysts could be used in the presence of snUhr and were, in fact, even more active when sulfided. Several studies reported that iron, nickel, cobalt, tin, zinc, and copper chlorides were effective catalysts and claimed that aimnoninm molybdate was particularly active. 

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Figure 5-2. The ICI process for producing synthesis gas and ammonia (1) desulfurization, (2) feed gas saturator, (3) primary reformer, (4) secondary reformer, (5) shift converter, (6) methanator, (7) ammonia reactor.

Gas phase hydration, on the other hand, is carried out at temperatures above 200°C and approximately 25 atmospheres. The ICI process employs WO3 on a silica carrier as catalyst. 

In the Discussion period, it was emphasised that C02 played an important role in the ICI process for methanol synthesis. Tom Wilkie, the Science Correspondent of The Independent newspaper, was present and the following day, 22 August 1990, the following headline appeared in the newspaper ... 

Figure 17.20. Control of temperature in multibed reactors so as to utilize the high rates of reaction at high temperatures and the more favorable equilibrium conversion at lower temperatures, (a) Adiabatic and isothermal reaction lines on the equilibrium diagram for ammonia synthesis, (b) Oxidation of SOz in a four-bed reactor at essentially atmospheric pressure, (c) Methanol synthesis in a four bed reactor by the ICI process at 50 atm not to scale 35% methanol at 250°C, 8.2% at 300°C, equilibrium concentrations.

Combining whole-cell biocatalysis and radical polymerization, researchers at Imperial Chemical Industries (ICI) published a chemoenzymatic route to high-molecular-weight poly(phenylene) [86], This polymer is used in the fibers and coatings industry. However, since it is practically insoluble, the challenge was to make a soluble polymer precursor that could first be coated or spun, and only then converted to poly(phenylene). The ICI process starts from benzene, which is oxidized by Pseudomonas putida cells to cyclohexa-3,5-diene-l,2-diol (see Figure 5.17). The... 

A 1,000 ton/day methanol plant, using a Winkler type gasifier adapted to burn wood chips and to use the ICI process for synthesis, requires the following consumption of ingredients per ton of methanol ... 

Most modern processes are low pressure processes. Plant capacities range from 150-3000 tons/day. The plants differ mainly in reactor design and, interrelated with this, in the way the heat produced by the reaction is removed. In the ICI process an adiabatic reactor is used with a single catalyst bed. The reaction is quenched by adding cold reactant gas at different heights in the catalyst bed. The temperature profile in the bed has a sawtooth profile. A flow scheme of the ICI process is given in Fig. 2.20. 

The Lurgi LPM process involves the same basic steps as the ICI processes. The two processes differ mainly in their reactor designs and the way in which the produced heat is removed as shown in Figure 12.18. The ICI design consists of a number of adiabatic catalytic beds, and cold gas is used to cool the reactant gases between the beds. The highest temperature is reached in the first catalyst bed. The Lurgi... 

As with the Commercial Solvents process, essentially all plants using this process have been replaced by new processes. In fact, in the United States only three processes are used for the manufacture of methanol. Of the total U.S. capacity, 63.3% is based on the Lurgi process 34.8% is based on the ICI process. 

LDPE was the first commercial PE, being introduced by Imperial Chemical Industries in 1938 [1-3]. Based on free-radical chemistry conducted at high pressure, the ICI process produces a wide variety of short- and long-chain branches. Even the branches can have branches, a structure sometimes described as "fuzz-ball" architecture. The structure hinders the entangling of the polymer molecule with neighbors, which profoundly influences the behavior of the material during and after molding. 

The Union Carbide Company in the United States and BASF (Badische) in Germany developed processes using tubular reactors. These processes give products that differ in molecular weight and branching from the ICI process. 

The second group of the batch type of solid layer techniques are those with moving melts. Here again, three processes must be named the MWB-Sulzer, nowadays called Sulzer falling film (CH-PS 1967 U.S. 1985), the ICI-process (GB-PS 1964), and the BASF-process (DE-PS 1976), which is now distributed by the Kvaerner company. In all processes, the crystallization takes place on the inside of tubes, which are cooled from the outside. The melt coming from a feed tank is continuously circulated through the tubes until the crystal coat at the walls is thick enough, i.e., until... 

The ICI process is an example of neutralization at atmospheric pressure. Nitric acid feed is preheated by part of the vapors produced in the neutralizer and is then split into two streams. Recycled, undersized product is dissolved in one stream, conditioning material in the other. The recombined streams are added to a two stage neutralizer along with ammonia and recirculated solution to give 87 to 89% ammonium nitrate feed for evaporation. The C I—Girdler-Cominco process is similar in principle the Pintsch-Bamag (23) process uses a two-stage neutralizer without recirculation. 

The conversion of methanol to hydrocarbons is the most studied reaction of oxygenates over microporous solids, for both commercial and academic reasons. Methanol can be generated from syngas over copper- and zinc-based catalysts using the ICI process, and syngas can be prepared from methane, which is a readily available resource. Under the correct economic conditions, methanol conversion reactions can provide an important route to higher... 

Commercial production started at ICI in 1938, and in 1940 polyethylene production had reached 100 tons which were utilized in early wire and cable applications to build radar systems and other applications to support the war effort. One could argue that these first 100 tons of polyethylene may have been the most important polyethylene ever manufactured. Toward the end of the war, British annual production was about 1,500 tons. In 1943, the great military significance of polyethylene led both the Union Carbide and DuPont corporations to license the ICI process and begin the manufacture of polyethylene in the United States. 

A larger heat recovery efficiency relative to the ICI process of 98% vs 86%, due to external steam raising This advantage probably will be much less pronounced if compared to the Lurgi process, as also Ledakowicz et al [l73] point out ... 

ICI introduced the low-pressure methanol proeess with a queneh reaetor system. The ICI process is the most widely used, and therefore there are many quench reactors in methanol serviee. Other reaetor systems have been developed over the years to improve upon the thermodynamics of the system, including pseudoisothermal reactors as used by Liir and Linde and intercooled reaetors as used by Topsoe and Kellogg. These reactors are described in Section 3.2.5. 

The only large-scale commercial SCP facility in the Western countries using methanol as a substrate was the 50,000 ton per year plant in England operated by ICI, but this plant shut down for economic reasons. Phillips Petroleum has a SCP technology called Provesteen, with a protein content of about 62%, and there are reports they are planning to build a 10,000 t/year SCP plant in China (People s Republic). Reports indicate the former Soviet Union at present has a SCP capacity of 1.0 million ton, but using a low-grade carbohydrate base and normal paraffins, which result in protein contents of 53 and 60%, respectively. SCP based on methanol via the ICI process produces a protein content of 72%. 

Case d shows that stoichiometric carbon dioxide production can also be achieved by using an excess of process air. However, in this case it becomes necessary to introduce an extra gas separation process step in order to remove the excess nitrogen which is introduced with the excess air. As explained in Sect. 6.5.3.2.3, several process schemes exist where excess process air is used, and the excess nitrogen is removed in dedicated units. Processes using excess process air are the Braun process, the ICI processes, and several process schemes of minor importance. 

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