Paraffins process chemistry

Catalytic hydrocracking is a flexible process for the conversion of heavy, hydrogen-deficient oils into lighter and more-valuable produets. Part of its flexibility is its ability to handle a wide range of feeds, from heavy aromatics to paraffinic crudes and cycle stocks. The ability to extend this flexibility to customized product slates depends on the ability to control and manipulate the process chemistry, which is, in turn, enhanced by a rigorous representation of fte process chemistry. This motivates the present interest in a heavy paraffin hydrocracking kinetics model. 

The scope of oxidation chemistry is enormous and embraces a wide range of reactions and processes. This article provides a brief introduction to the homogeneous free-radical oxidations of paraffinic and alkylaromatic hydrocarbons. Heterogeneous catalysis, biochemical and hiomimetic oxidations, oxidations of unsaturates, anodic oxidations, etc, even if used to illustrate specific points, are arbitrarily outside the purview of this article. There are, even so, many unifying features among these areas. 

Chemistry. Chemical separation is achieved by countercurrent Hquid— Hquid extraction and involves the mass transfer of solutes between an aqueous phase and an immiscible organic phase. In the PUREX process, the organic phase is typically a mixture of 30% by volume tri- -butyl phosphate (solvent) and a normal paraffin hydrocarbon (diluent). The latter is typically dodecane or a high grade kerosene (20). A number of other solvent or diluent systems have been investigated, but none has proved to be a substantial improvement (21). 

Sulfochlorination of Paraffins. The sulfonation of paraffins using a mixture of sulfur dioxide and chlorine in the presence of light has been around since the 1930s and is known as the Reed reaction (123). This process is made possible by the use of free-radical chemistry and has had limited use in the United States. Other countries have had active research into process optimization (124,125). 

Another current development in the use of F-T chemistry in a three-phase slurry reactor is Exxon s Advanced Gas Conversion or AGC-21 technology (Eidt et al., 1994 Everett et al., 1995). The slurry reactor is the second stage of a three-step process to convert natural gas into a highly paraffinic water-clear hydrocarbon liquid. The AGC-21 technology, as in the Sasol process, is being developed to utilize the large reserves of natural gas that are too remote for economical transportation via pipelines. The converted liquid from the three-step process, which is free of sulfur, nitrogen, nickel, vanadium, asphaltenes, polycyclic aromatics, and salt, can be shipped in conventional oil tankers and utilized by most refineries or petrochemical facilities. 

Petrochemical-derived alcohols use a wider range of chemistry but, in each case, an olefin is the starting point. The olefins maybe derived from n-paraffins which give internal olefins, or more linear a-olefins from ethylene oligomerisation. The olefins are converted to alcohols using the oxo process (see Figure 4.16). 

Here we will describe the main aspects of the chemistry involved in selected zeolite-catalyzed processes in the field of oil refining and petrochemistry, such as short paraffin aromatization, skeletal isomerization of n-paraffins and n-olefins, isoparaffin/olefin alkylation, and catalytic cracking. 

The development of modem chemistry in the past thirty years dearly demonstrates that oil and natural gas are the ideal raw materials for the synthesis of most mass-consumption chemicals. In addition to the fact that they have been and still are very widely available, they are formed espedally in the case of oil, of a wide variety of compounds providing access to a multitude of possible hydrocarbon structures. The biological and physicochemical processes that contributed to their formation have furnished, apart from a certain quantity of aromatic hydrocarbons, a large proportion of saturated hydrocarbons (paraffins and naphthenes). In fact, these compounds generally display low reactivity, so that it is not easy to obtain the desired finished products. This is why the production of these derivatives entails a sequence of chemical operations which, in practice, require the combination of the facilities in which they take place within giant petrochemical complexes. 

Early work in this field was conducted prior to the availability of powerful radiation sources. In 1929, E. B. Newton "vulcanized" rubber sheets with cathode-rays (16). Several studies were carried out during and immediately after world war II in order to determine the damage caused by radiation to insulators and other plastic materials intended for use in radiation fields (17, 18, 19). M. Dole reported research carried out by Rose on the effect of reactor radiation on thin films of polyethylene irradiated either in air or under vacuum (20). However, worldwide interest in the radiation chemistry of polymers arose after Arthur Charlesby showed in 1952 that polyethylene was converted by irradiation into a non-soluble and non-melting cross-linked material (21). It should be emphasized, that in 1952, the only cross-linking process practiced in industry was the "vulcanization" of rubber. The fact that polyethylene, a paraffinic (and therefore by definition a chemically "inert") polymer could react under simple irradiation and become converted into a new material with improved properties looked like a "miracle" to many outsiders and even to experts in the art. More miracles were therefore expected from radiation sources which were hastily acquired by industry in the 1950 s. 

The SMB technology was developed by UOP and its major field of application is in the area of binary separations. For example, SMB has been used in the chemical industry for several separations known as SORBEX processes [1-3], which include, among others, the PAREX process for p-xylene separation from a Cs aromatic fraction [4], the OLEX process for the separation of olefins from paraffins, the SAREX process to separate fructose from glucose [4] and the MOLEX process [5]. Simulated moving bed is being used particularly for separation of enantiomers from racemic mixtures or from the products of enantioselective synthesis [6,7]. It has been used for the production of fine chemicals, and petrochemical intermediates, such as Cg-hydrocarbons [8], food chemistry such as fatty acids [2], or certain sugars from carbohydrate mixtures [8] and protein desalination [9]. 

Multitubular reactors are mainly used in gas-phase partial oxidation processes, such as the air oxidation of light olefins, paraffins, and aromatics. Examples of chemistries where these reactors are used include the partial oxidation of methanol to formaldehyde, ethylene to ethylene oxide, ethylene and acetic acid to vinyl acetate, propylene to acrolein and acrylic acid, butane to maleic anhydride, isobutylene to methacrolein and methacrylic acid, and o-xylene to phthalic anhydride. An overview of the multitubular reactor process for the partial oxidation of n-butane to maleic anhydride is given here. 

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