Other Hydrocarbons

Our experience with cyclopropanes has been limited. There is not very much data, but, in this case (in contrast to the alkenes and alkynes), it is difficult to parameterize to that which is available. Because of the very fragmentary nature of the results, they will not be discussed further here. 

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Identification of normal paraffins by chromatography presents no special problems with the exception of biodegraded crudes, they are clearly distinguished. The problem encountered is to quantify, as shown in Figure 3.14, the normal paraffin peaks that are superimposed on a background representing other hydrocarbons. 

Alkylation combines lower-molecular-weight saturated and unsaturated hydrocarbons (alkanes and alkenes) to produce high-octane gasoline and other hydrocarbon products. Conventional paraffin-olefin (alkane-alkene) alkylation is an acid-catalyzed reaction, such as combining isobutylene and isobutane to isooctane. 

Alkynes resemble alkanes and aUcenes m their physical properties They share with these other hydrocarbons the properties of low density and low water solubility They are slightly more polar and generally have slightly higher boiling points than the corre spondmg alkanes and alkenes... 

Acetylene and terminal alkynes are more acidic than other hydrocarbons They have s of approximately 26 compared with about 45 for alkenes and about 60 for alkanes Sodium amide is a strong enough base to remove a proton from acetylene or a terminal alkyne but sodium hydroxide is not... 

In general arenes resemble other hydrocarbons in their physical properties They are nonpolar insoluble in water and less dense than water In the absence of polar sub stituents mtermolecular forces are weak and limited to van der Waals attractions of the induced dipole/mduced dipole type... 

Section 11 9 The physical properties of arenes resemble those of other hydrocarbons... 

Carboxylate groups are hydrophilic ( water loving ) and tend to confer water sol ubility on species that contain them Long hydrocarbon chains are lipophilic ( fat loving ) and tend to associate with other hydrocarbon chains Sodium stearate is an example of an amphiphilic substance both hydrophilic and lipophilic groups occur within the same molecule... 

The principal direct appHcation of furfural is as a selective solvent. It is used for separating saturated from unsaturated compounds in petroleum refining, for the extractive distillation of butadiene and other hydrocarbons in the manufacture of synthetic mbber and for the production of... 

Commercial production of acetic acid has been revolutionized in the decade 1978—1988. Butane—naphtha Hquid-phase catalytic oxidation has declined precipitously as methanol [67-56-1] or methyl acetate [79-20-9] carbonylation has become the technology of choice in the world market. By-product acetic acid recovery in other hydrocarbon oxidations, eg, in xylene oxidation to terephthaUc acid and propylene conversion to acryflc acid, has also grown. Production from synthesis gas is increasing and the development of alternative raw materials is under serious consideration following widespread dislocations in the cost of raw material (see Chemurgy). 

Although the selectivity of isopropyl alcohol to acetone via vapor-phase dehydrogenation is high, there are a number of by-products that must be removed from the acetone. The hot reactor effluent contains acetone, unconverted isopropyl alcohol, and hydrogen, and may also contain propylene, polypropylene, mesityl oxide, diisopropyl ether, acetaldehyde, propionaldehyde, and many other hydrocarbons and carbon oxides (25,28). 

Many catalytic systems have been described acidic solutions of mercuric salts are the most generally used. This process has long been superseded by more economical routes involving oxidation of ethylene or other hydrocarbons. 

Benzene [71-43-2] toluene [108-88-3] xylene [1330-20-7] and solvent naphtha are separated from the light oil. Benzene (qv), toluene (qv), and xylene are useful as solvents and chemical intermediates (see Xylenes and ethylbenzene). The cmde light oil is approximately 60—70% ben2ene, 12—16% toluene, 4—8% xylenes, 9—16% other hydrocarbons, and about 1% sulfur compounds (5) (see BTX processing). 

Natural gas is by far the preferred source of hydrogen. It has been cheap, and its use is more energy efficient than that of other hydrocarbons. The reforming process that is used to produce hydrogen from natural gas is highly developed, environmental controls are simple, and the capital investment is lower than that for any other method. Comparisons of the total energy consumption (fuel and synthesis gas), based on advanced technologies, have been discussed elsewhere (102). 

Direct hydrohquefaction of biomass or wastes can be achieved by direct hydrogenation of wood chips on treatment at 10,132 kPa and 340 to 350°C with water and Raney nickel catalyst (45). The wood is completely converted to an oily Hquid, methane, and other hydrocarbon gases. Batch reaction times of 4 hours give oil yields of about 35 wt % of the feed the oil contains about 12 wt % oxygen and has a heating value of about 37.2 MJ /kg (16,000 Btu/lb). Distillation yields a significant fraction that boils in the same range as diesel fuel and is completely miscible with it. 

The term gasohol has come into wide usage to identify, generally, a blend of gasoline and ethanol, with the latter derived from grain. The term may also be appHed to blends of methanol or other alcohols in gasolines or other hydrocarbons, without regard to sources of components. 

Fuel. Natural gas is used as a primary fuel and source of heat energy throughout the iadustrialized countries for a broad range of residential, commercial, and iadustrial appHcations. The methane and other hydrocarbons react readily with oxygen to release heat by forming carbon dioxide and water through a series of kinetic steps that results ia the overall reaction,... 

Several studies of spherical and cylindrical detonation in acetylene—oxygen and acetylene—air mixtures have been reported (82,83). The combustion and oxidation of acetylene are reviewed extensively in Reference 84. A study of the characteristics and destmctive effects of detonations in mixtures of acetylene (and other hydrocarbons) with air and oxygen-enriched air in earthen tuimels and large steel pipe is reported in Reference 81. 

The alkanes have low reactivities as compared to other hydrocarbons. Much alkane chemistry involves free-radical chain reactions that occur under vigorous conditions, eg, combustion and pyrolysis. Isobutane exhibits a different chemical behavior than / -butane, owing in part to the presence of a tertiary carbon atom and to the stability of the associated free radical. 

The butane-containing streams in petroleum refineries come from a variety of different process units consequently, varying amounts of butanes in mixtures containing other light alkanes and alkenes are obtained. The most common recovery techniques for these streams are lean oil absorption and fractionation. A typical scheme involves feeding the light hydrocarbon stream to an absorber-stripper where methane is separated from the other hydrocarbons. The heavier fraction is then debutanized, depropanized, and de-ethanized by distillation to produce C, C, and C2 streams, respectively. Most often the stream contains butylenes and other unsaturates which must be removed by additional separation techniques if pure butanes are desired. 

Almost all of the cyclohexane that is produced in concentrated form is used as a raw material in the first step of nylon-6 and nylon-6,6 manufacture. Cyclohexane also is an excellent solvent for cellulose ethers, resins, waxes (qv), fats, oils, bitumen, and mbber (see Cellulose ethers Resins, natural Fats AND FATTY OILS Rubber, NATURAL). When used as a solvent, it usually is in admixture with other hydrocarbons. However, a small amount is used as a reaction diluent in polymer processes. 

The manufacture of the highly pure ketene required for ketenization and acetylation reactions is based on the pyrolysis of diketene, a method which has been employed in industrial manufacture. Conversion of diketene to monomeric ketene is accompHshed on an industrial scale by passing diketene vapor through a tube heated to 350—600°C. Thus, a convenient and technically feasible process for producing ketene uncontaminated by methane, other hydrocarbons, and carbon oxides, is available. Based on the feasibiHty of this process, diketene can be considered a more stable form of the unstable ketene. 

Hexyllithium. Hexyllithium [21369-64-2] soluble in hexane and other hydrocarbons in high concentrations. 

Nitrations are highly exothermic, ie, ca 126 kj/mol (30 kcal/mol). However, the heat of reaction varies with the hydrocarbon that is nitrated. The mechanism of a nitration depends on the reactants and the operating conditions. The reactions usually are either ionic or free-radical. Ionic nitrations are commonly used for aromatics many heterocycHcs hydroxyl compounds, eg, simple alcohols, glycols, glycerol, and cellulose and amines. Nitration of paraffins, cycloparaffins, and olefins frequentiy involves a free-radical reaction. Aromatic compounds and other hydrocarbons sometimes can be nitrated by free-radical reactions, but generally such reactions are less successful. 

Mechanism. The NO2 mechanism has been accepted since about 1950 for the nitration of most aromatic hydrocarbons, glycerol, glycols, and numerous other hydrocarbons in which mixed acids or highly concentrated nitric acid are used. The mechanism has been discussed in detail and critically analy2ed (1). NO2 attacks an aromatic compound (ArH) as follows ... 

Absolute. This is concentrated extract obtained by treatment of a concrete or other hydrocarbon-type extract of a plant or plant part with ethanol. It is usually Hquid and should be totally soluble in alcohol. By this method, waxes, hydrocarbons (including terpenoid), as well as most of the odorless material of the concrete are removed from the extract. 

SASOL. SASOL, South Africa, has constmcted a plant to recover 50,000 tons each of 1-pentene and 1-hexene by extractive distillation from Fischer-Tropsch hydrocarbons produced from coal-based synthesis gas. The company is marketing both products primarily as comonomers for LLDPE and HDPE (see Olefin polymers). Although there is still no developed market for 1-pentene in the mid-1990s, the 1-hexene market is well estabhshed. The Fischer-Tropsch technology produces a geometric carbon-number distribution of various odd and even, linear, branched, and alpha and internal olefins however, with additional investment, other odd and even carbon numbers can also be recovered. The Fischer-Tropsch plants were originally constmcted to produce gasoline and other hydrocarbon fuels to fill the lack of petroleum resources in South Africa. 

Other hydrocarbons. They have been used as corrosion inhibitors in glycol heat-exchanger fluids (antifree2es) and as volatile corrosion inhibitors for steel (see Corrosion and corrosion inhibitors). They also stabilize sulfur trioxide. 

Commercial polystyrenes are normally rather pure polymers. The amount of styrene, ethylbenzene, styrene dimers and trimers, and other hydrocarbons is minimized by effective devolatilization or by the use of chemical initiators (33). Polystyrenes with low overall volatiles content have relatively high heat-deformation temperatures. The very low content of monomer and other solvents, eg, ethylbenzene, in PS is desirable in the packaging of food. The negligible level of extraction of organic materials from PS is of cmcial importance in this appHcation. 

Benzene is a natural component of petroleum, but the amount of benzene present ia most cmde oils is small, often less than 1.0% by weight (34). Therefore the recovery of benzene from cmde oil is uneconomical and was not attempted on a commercial scale until 1941. To add further compHcations, benzene cannot be separated from cmde oil by simple distillation because of azeotrope formation with various other hydrocarbons. Recovery is more economical if the petroleum fraction is subjected to a thermal or catalytic process that iacreases the concentration of benzene. 

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