Coke formers

The structures of the aromatics listed in Table 4.1 are shown in Figs. 4.2 (coke formers) and 4.3 (char formers). Some of the most important aromatics are the following... 

The coke-former aromatic hydrocarbons listed in Table 4.1 and shown in Fig. 4.2, i.e., naphthalene, einthracene, and acenaphtalene, are linear with a coplanar structure that has no preferred growth direction. This structural feature and the formation of a mesophase mentioned in Sec. 2.3 are the major factors in the easy conversion of theturbostratic structure into well-ordered graphite planes.1 1... 

Graphitization of Aromatics. As mentioned above, not ail aromatic hydrocarbons form coke. Some, such as phenanthrene and biphenyl, do not graphitize and are considered char formers. These compounds are branched aromatics (as opposed to the linear structure of the coke-former aromatics) with a preferred axisof growth asshown in Fig. 4.3. Thischaracteristic prevents the formation of extensive graphitic planes and of a liquid mesophase.l l... 

A new countercurrent continuous centrifugal extractor developed in the former USSR (214) has the feature that mechanical seals are replaced by Hquid seals with the result that operation and maintenance are simplified the mechanical seals are an operating weak point in most centrifugal extractors. The operating units range between 400 and 1200 mm in diameter, and a capacity of 70 m /h has been reported in service. The extractors have been appHed in coke-oven refining (see Coal conversion processes), erythromycin production, lube oil refining, etc. 

As the economic value of coproducts has decreased, it has become more difficult to provide capital for environmental controls on air emissions and wastewater streams such as toxic phenoHc effluents from chemical recovery operations. Some former coke and manufactured gas sites may require remediation to clean up contaminated soil and groundwater. These difficulties will force the shutdown of some operations and discourage recovery of coproducts in future installations. 

When energy alternatives are available, a compromise between cost and quaHty is often realized. Blending of coals can be used to achieve more desirable quaHties. For example, lignite from the former Yugoslavia has been blended with, and even substituted for, the highly caking Rasa coal used for coke production in the iron (qv) and steel (qv) industries. 

The dehydrogenation of the mixture of m- and -ethyltoluenes is similar to that of ethylbenzene, but more dilution steam is required to prevent rapid coking on the catalyst. The recovery and purification of vinyltoluene monomer is considerably more difficult than for styrene owing to the high boiling point and high rate of thermal polymerization of the former and the complexity of the reactor effluent, which contains a large number of by-products. Pressures as low as 2.7 kPa (20 mm Hg) are used to keep distillation temperatures low even in the presence of polymerization inhibitor. The finished vinyltoluene monomer typically has an assay of 99.6%. 

Bitumen is a hydrogen-deficient oil that is upgraded by carbon removal (coking) or hydrogen addition (hydrocrackiag) (2,4). There are two methods by which bitumen conversion can be achieved by direct heating of mined tar sand and by thermal decomposition of separated bitumen. The latter is the method used commercially, but the former has potential for commercialisation (see Fuels, SYNTHETIC). 

Catalytic Pyrolysis. This should not be confused with fluid catalytic cracking, which is used in petroleum refining (see Catalysts, regeneration). Catalytic pyrolysis is aimed at producing primarily ethylene. There are many patents and research articles covering the last 20 years (84—89). Catalytic research until 1988 has been summarized (86). Almost all catalysts produce higher amounts of CO and CO2 than normally obtained with conventional pyrolysis. This indicates that the water gas reaction is also very active with these catalysts, and usually this leads to some deterioration of the olefin yield. Significant amounts of coke have been found in these catalysts, and thus there is a further reduction in olefin yield with on-stream time. Most of these catalysts are based on low surface area alumina catalysts (86). A notable exception is the catalyst developed in the former USSR (89). This catalyst primarily contains vanadium as the active material on pumice (89), and is claimed to produce low levels of carbon oxides. 

By far the most important sulfide is CS2, a colourless, volatile, flammable liquid (mp — 111.6°, bp 46.25°, flash point —30°, autoignition temperature 100°, explosion limits in air 1.25 50%). Impure samples have a fetid almost nauseating stench due to organic impurities but the purified liquid has a rather pleasant ethereal smell it is very poisonous and can have disastrous effects on the nervous system and brain. CSt was formerly manufactured by direct reaction of S vapour and coke in He or steel retorts at 750 1000°C but, since the early 1950s, the preferred synthesis has been the catalysed reaction between sulfur and natural gas ... 

The isolation of zinc, over 90% of which is from sulfide ores, depends on conventional physical concentration of the ore by sedimentation or flotation techniques. This is followed by roasting to produce the oxides the SO2 which is generated is used to produce sulfuric acid. The ZnO is then either treated electrolytically or smelted with coke. In the former case the zinc is leached from the crude ZnO with dil H2SO4, at which point cadmium is precipitated by the addition of zinc dust. The ZnS04 solution is then electrolysed and the metal deposited — in a state of 99.95% purity — on to aluminium cathodes. 

The "conventional" methods for the preparation of SiC and Si3N4, the high temperature reaction of fine grade sand and coke (with additions of sawdust and NaCl) in an electric furnace (the Acheson process) for the former and usually the direct nitridation of elemental silicon or the reaction of silicon tetrachloride with ammonia (in the gas phase or in solution) for the latter, do not involve soluble or fusible intermediates. For many applications of these materials this is not necessarily a disadvantage (e.g., for the application of SiC as an abrasive), but for some of the more recent desired applications soluble or fusible (i.e., proces-sable) intermediates are required. 

Phenolsolvan A process for extracting phenols from coke-oven liquor and tar acids from tar by selective solvent extraction with di-isopropyl ether (formerly with -butyl acetate). Developed by Luigi in 1937. 

Sulfiban A process for removing hydrogen sulfide from coke-oven gases by scrubbing with monoethanolamine. Developed by the Bethlehem Steel Corporation and B. S. B. Process Systems and tested in a demonstration plant of the former company in the mid 1970s. Not commercialized. 

MgO is a basic metal oxide and has the same crystal structure as NiO. As a result, the combination of MgO and NiO results in a solid-solution catalyst with a basic surface (171,172), and both characteristics are helpful in inhibiting carbon deposition (171,172,239). The basic surface increases C02 adsorption, which reduces or inhibits carbon-deposition (Section ALB). The NiO-MgO solid solution can control the nickel particle sizes in the catalyst. This control occurs because in the solid solution NiO has strong interactions with MgO and, as indicated by TPR data (26), the former oxide can no longer be easily reduced. Consequently, only a small amount of NiO is expected to be reduced, and thus small nickel particles are formed on the surface of the solid solution, smaller than the size necessary for coke formation. Indeed, the nickel particles on a reduced 16.7 wt% NiO/MgO solid-solution catalyst were too small to be observed by TEM (171). Furthermore, two additional important qualities stimulated the selection of MgO as a support its high thermal stability and low cost (250,251). 

English Method,—It has already been pointed out that from thermal chemical reasons, the coke through which the steam is passing in the manufacture of water gas should be at about 1000° C. in order to obtain good results, and that as a result of the reaction between the coke and steam, the temperature of the former falls, necessitating the addition of heat to the coke mass, in order to keep up the efficiency of the process. 

Coke does not offer the same potential environmental issues as other petroleum products (Chapter 10 and above). It is used predominantly as a refinery fuel unless other uses for the production of a high-grade coke or carbon are desired. In the former case, the constituents of the coke that will release environmentally harmful gases such as nitrogen oxides, sulfur oxides, and particulate matter should be known. In addition, stockpiling coke on a site where it awaits use or transportation can lead to leachates as a result of rainfall (or acid rainfall) which are highly detrimental. In such a case, application of the toxicity characteristic leaching procedure... 

Coke-oven tars Former CVR tars Low tempera-t ure tars Lurgi tars... 

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