Olefin refinery

Polygas Olefins. Refinery propylene and butenes are polymerized with a phosphoric acid catalyst at 200°C and 3040—6080 kPa (30—60 atm) to give a mixture of branched olefins up to used primarily in producing plasticizer alcohols (isooctyl, isononyl, and isodecyl alcohol). Since the olefins are branched (75% have two or more CH groups) the alcohols are also branched. Exxon, BASE, Ruhrchemie (now Hoechst), ICl, Nissan, Getty Oil, U.S. Steel Chemicals (now Aristech), and others have all used this olefin source. 

Methane as an abundant natural resource chemical could partially substitute for both olefins (refinery ethylene and propene) and carbon monoxide. 

The initial manufacture of chemicals from petroleum raw materials was the manufacture of alcohols from olefinic refinery gases by the Standard Oil Co. (N.J.) in 1919 (60), Other pioneering efforts in the field involved synthesis of chemicals from hydrocarbon gases by Carbide and Carbon and the manufacture of oxygenated chemicals from natural gas by Cities Service Oil Co., dating from 1926 (61),... 

We cite isomerization of Cs-Ce paraffinic cuts, aliphatic alkylation making isoparaffinic gasoline from C3-C5 olefins and isobutane, and etherification of C4-C5 olefins with the C1-C2 alcohols. This type of refinery can need more hydrogen than is available from naphtha reforming. Flexibility is greatly improved over the simple conventional refinery. Nonetheless some products are not eliminated, for example, the heavy fuel of marginal quality, and the conversion product qualities may not be adequate, even after severe treatment, to meet certain specifications such as the gasoline octane number, diesel cetane number, and allowable levels of certain components. 

ALKANOLAMNES - ALKANOLAMINES FROM OLEFIN OXIDES AND ALETONIA] (Vol 2) -in petroleum refining [PETROLEUM - REFINERY PROCESSES, SURVEY] (Voll8)... 

Olefins are produced primarily by thermal cracking of a hydrocarbon feedstock which takes place at low residence time in the presence of steam in the tubes of a furnace. In the United States, natural gas Hquids derived from natural gas processing, primarily ethane [74-84-0] and propane [74-98-6] have been the dominant feedstock for olefins plants, accounting for about 50 to 70% of ethylene production. Most of the remainder has been based on cracking naphtha or gas oil hydrocarbon streams which are derived from cmde oil. Naphtha is a hydrocarbon fraction boiling between 40 and 170°C, whereas the gas oil fraction bods between about 310 and 490°C. These feedstocks, which have been used primarily by producers with refinery affiliations, account for most of the remainder of olefins production. In addition a substantial amount of propylene and a small amount of ethylene ate recovered from waste gases produced in petroleum refineries. 

Since the early 1980s olefin plants in the United States were designed to have substantial flexibiHty to consume a wide range of feedstocks. Most of the flexibiHty to use various feedstocks is found in plants with associated refineries, where integrated olefins plants can optimize feedstocks using either gas Hquids or heavier refinery streams. Companies whose primary business is the production of ethylene derivatives, such as thermoplastics, tend to use ethane and propane feedstocks which minimize by-product streams and maximize ethylene production for their derivative plants. 

Fig. 1. Typical refinery—olefin plant complex. Courtesy of Shell Oil Co.

LPG recovered from natural gas is essentially free of unsaturated hydrocarbons, such as propylene and butylenes (qv). Varying quantities of these olefins may be found in refinery production, and the concentrations are a function of the refinery s process design and operation. Much of the propylene and butylene are removed in the refinery to provide raw materials for plastic and mbber production and to produce high octane gasoline components. 

Butene. Commercial production of 1-butene, as well as the manufacture of other linear a-olefins with even carbon atom numbers, is based on the ethylene oligomerization reaction. The reaction can be catalyzed by triethyl aluminum at 180—280°C and 15—30 MPa ( 150 300 atm) pressure (6) or by nickel-based catalysts at 80—120°C and 7—15 MPa pressure (7—9). Another commercially developed method includes ethylene dimerization with the Ziegler dimerization catalysts, (OR) —AIR, where R represents small alkyl groups (10). In addition, several processes are used to manufacture 1-butene from mixed butylene streams in refineries (11) (see BuTYLENEs). 

All lation. The combination of olefins with paraffins to form higher isoparaffins is termed alkylation (qv). Alkylate is a desirable blendstock because it has a relatively high octane number and serves to dilute the total aromatics content. Reduction of the olefins ia gasoline blendstocks by alkylation also reduces tail pipe emissions. In refinery practice, butylenes are routinely alkylated by reaction with isobutane to produce isobutane—octane (26). In some plants, propylene and/or pentylenes (amylenes) are also alkylated (27). 

The hydrocarbon cracking operations that generate feed olefins generally do not produce sufficient isobutane to satisfy the reaction requirements. Additional isobutane must be recovered from cmde oil or natural gas Hquids or generated by other refinery operations. A growing quantity of isobutane is produced by the isomerization of / -butane [106-97-8]. 

Propylene has many commercial and potential uses. The actual utilisation of a particular propylene supply depends not only on the relative economics of the petrochemicals and the value of propylene in various uses, but also on the location of the supply and the form in which the propylene is available. Eor example, economics dictate that recovery of high purity propylene for polymerisation from a smaH-volume, dilute off-gas stream is not feasible, whereas polymer-grade propylene is routinely recovered from large refineries and olefins steam crackers. A synthetic fuels project located in the western United States might use propylene as fuel rather than recover it for petrochemical use a plant on the Gulf Coast would recover it (see Euels, synthetic). 

The largest use of NMP is in extraction of aromatics from lube oils. In this appHcation, it has been replacing phenol and, to some extent, furfural. Other petrochemical uses involve separation and recovery of aromatics from mixed feedstocks recovery and purification of acetylenes, olefins, and diolefins removal of sulfur compounds from natural and refinery gases and dehydration of natural gas. 

The ethylene feedstock used in most plants is of high purity and contains 200—2000 ppm of ethane as the only significant impurity. Ethane is inert in the reactor and is rejected from the plant in the vent gas for use as fuel. Dilute gas streams, such as treated fluid-catalytic cracking (FCC) off-gas from refineries with ethylene concentrations as low as 10%, have also been used as the ethylene feedstock. The refinery FCC off-gas, which is otherwise used as fuel, can be an attractive source of ethylene even with the added costs of the treatments needed to remove undesirable impurities such as acetylene and higher olefins. Its use for ethylbenzene production, however, is limited by the quantity available. Only large refineries are capable of deUvering sufficient FCC off-gas to support an ethylbenzene—styrene plant of an economical scale. 

Extraction Solvent. Dimethyl sulfoxide is immiscible with alkanes but is a good solvent for most unsaturated and polar compounds. Thus, it can be used to separate olefins from paraffins (93). It is used in the Institute Fransais du Pntrole (IFF) process for extracting aromatic hydrocarbons from refinery streams (94). It is also used in the analytical procedure for determining polynuclear hydrocarbons in food additives (qv) of petroleum origin (95). 

Butylenes are C Hg mono-olefin isomers 1-butene, <7j -2-butene, trans-2-huX.en.e and isobutylene (2-methylpropene). These isomers are usually coproduced as a mixture and are commonly referred to as the fraction. These fractions are usually obtained as by-products from petroleum refinery and petrochemical complexes that crack petroleum fractions and natural gas Hquids. Since the fractions almost always contain butanes, it is also known as the B—B stream. The linear isomers are referred to as butenes. 

Polymers account for about 3—4% of the total butylene consumption and about 30% of nonfuels use. Homopolymerization of butylene isomers is relatively unimportant commercially. Only stereoregular poly(l-butene) [9003-29-6] and a small volume of polyisobutylene [25038-49-7] are produced in this manner. High molecular weight polyisobutylenes have found limited use because they cannot be vulcanized. To overcome this deficiency a butyl mbber copolymer of isobutylene with isoprene has been developed. Low molecular weight viscous Hquid polymers of isobutylene are not manufactured because of the high price of purified isobutylene. Copolymerization from relatively inexpensive refinery butane—butylene fractions containing all the butylene isomers yields a range of viscous polymers that satisfy most commercial needs (see Olefin polymers Elastomers, synthetic-butylrubber). 

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