Olefin feedstocks

Catalytic oxidation is the most important technology for the conversion of hydrocarbon feedstocks (olefins, aromatics and alkanes) to a variety of bulk industrial chemicals.1 In general, two types of processes are used heterogeneous, gas phase oxidation and homogeneous liquid phase oxidation. The former tend to involve supported metal or metal oxide catalysts e.g. in tne manufacture of ethylene oxide, acrylonitrile and maleic anhydride whilst the latter generally employ dissolved metal salts, e.g. in the production of terephthalic acid, benzoic acid, acetic acid, phenol and propylene oxide. 

Feedstock Olefin-rich Qs Olefin- rich FCC LCN Coker LN... 

Upstream of the refornjiing unit, the feedstock undergoes hydrotreatment so as to eliminate impliritles such as S, N, olefins, and metals which are all catalyst poisons. 

The performance of the adsorptive section of such a combination in a commercial installation is shown in Table 4. The feedstock includes components, and olefins are recovered at about 94% efficiency. 

The olefin product contains 1.1% of residual / -paraffins. Essentially similar results have been obtained in commercial operations on Cg—C q and C g feedstocks. The desorbents used are generally hydrocarbon mixtures of lower boiling range than the feed components. The concentrated olefin stream may then be used for production of detergent alcohols. 

Olefin Sources. The choice of feedstock depends on the alcohol product properties desired, availabiUty of the olefin, and economics. A given producer may either process different olefins for different products or change feedstock for the same appHcation. Feedstocks beheved to be currentiy available are as follows. 

The Dimersol process (Erench Petroleum Institute) produces hexenes, heptenes, and octenes from propylene and linear butylene feedstocks. This process is reported to produce olefin with less branching than the corresponding polygas olefins. BASE practices this process ia Europe. 

A.luminum Jilkyl Chain Growth. Ethyl, Chevron, and Mitsubishi Chemical manufacture higher, linear alpha olefins from ethylene via chain growth on triethyl aluminum (15). The linear products are then used as oxo feedstock for both plasticizer and detergent range alcohols and because the feedstocks are linear, the linearity of the alcohol product, which has an entirely odd number of carbons, is a function of the oxo process employed. Alcohols are manufactured from this type of olefin by Sterling, Exxon, ICI, BASE, Oxochemie, and Mitsubishi Chemical. 

Catalytic Oligomeri tion. Shell Chemical provides C —C linear internal olefin feedstock for detergent oxo alcohol production from its SHOP... 

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. 

In most of the rest of the world the olefins industry was originally based on naphtha feedstocks. Naphtha is the dominant olefins feedstock in Europe and Asia. In the middle 1980s several large olefins complexes were budt outside of the United States based on gas Hquids feedstocks, most notable in western Canada, Saudi Arabia, and Scotiand. In each case the driving force was the production of natural gas, perhaps associated with cmde oil production, which was in excess of energy demands. 

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. 

Olefin Feedstock Selection. The selection of feedstock and severity of the cracking process are economic choices, given that the specific plant has flexibiUty to accommodate alternative feedstocks. The feedstock prices are driven primarily by energy markets and secondarily by supply and demand conditions ia the olefins feedstock markets. The prices of iadividual feedstocks vary widely from time to time as shown ia Figure 2, which presents quarterly prices of the various feedstocks ia the United States from 1978 through 1991 ia dollars per metric ton (1000 kg) (4). 

Fig. 2. Quarterly olefin feedstock prices, 1978—1991, for (D) ethane (+) propane (<)) light naphtha, and (A) naphtha.

The feedstocks used ia the production of petroleum resias are obtaiaed mainly from the low pressure vapor-phase cracking (steam cracking) and subsequent fractionation of petroleum distillates ranging from light naphthas to gas oil fractions, which typically boil ia the 20—450°C range (16). Obtaiaed from this process are feedstreams composed of atiphatic, aromatic, and cycloatiphatic olefins and diolefins, which are subsequently polymerized to yield resias of various compositioas and physical properties. Typically, feedstocks are divided iato atiphatic, cycloatiphatic, and aromatic streams. Table 2 illustrates the predominant olefinic hydrocarbons obtained from steam cracking processes for petroleum resia synthesis (18). 

About 35% of total U.S. LPG consumption is as chemical feedstock for petrochemicals and polymer iatermediates. The manufacture of polyethylene, polypropylene, and poly(vinyl chloride) requires huge volumes of ethylene (qv) and propylene which, ia the United States, are produced by thermal cracking/dehydrogenation of propane, butane, and ethane (see Olefin polymers Vinyl polymers). 

Interest in synthetic naphthenic acid has grown as the supply of natural product has fluctuated. Oxidation of naphthene-based hydrocarbons has been studied extensively (35—37), but no commercially viable processes are known. Extensive purification schemes must be employed to maximize naphthene content in the feedstock and remove hydroxy acids and nonacidic by-products from the oxidation product. Free-radical addition of carboxylic acids to olefins (38,39) and addition of unsaturated fatty acids to cycloparaffins (40) have also been studied but have not been commercialized. 

The 0x0 process is employed to produce higher alcohols from linear and branched higher olefins. Using a catalyst that is highly selective for hydroformylation of linear olefins at the terminal carbon atom. Shell converts olefins from the Shell higher olefin process (SHOP) to alcohols. This results in a product that is up to 75—85% linear when a linear feedstock is employed. Other 0x0 processes, such as those employed by ICI, Exxon, and BASE (all in Europe), produce oxo-alcohols from a-olefin feedstocks such alcohols have a linearity of about 60%. Enichem, on the other hand, produces... 

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