Process cracking

1 Steam thermal) cracking for lower olefins, A typical naphtha for cracking has a carbon number range from 4 to 12 or more. The uncatalysed cracking reaction is carried out within tubes in a furnace enclosure at near atmospheric pressure (less than 3 atm). Steam makes up 30-45% w/w of the total feed to improve heat transfer, reduce the partial pressure of hydrocarbons (thermodynamically desirable) and remove carbon by the reaction 

Cracking temperatures were traditionally 750-850°C, but temperatures up to 900°C (high severity cracking) are becoming more common, in conjunction with shorter residence times (about 0 1 second). 

The table on p. 358 shows typical overall yield patterns (%w/w), with ethane/propane recycle, for a number of cracker feedstocks n-butane gives high ethylene yields, isobutane more propylene and methane. In all cases, the cracker product stream is cooled rapidly to below 400°C to minimize further reactions. After further cooling and separation of condensed hydrocarbons and water, the gases (H2,Ci—CJ are compressed, scrubbed with aqueous alkali to remove CO2 and other acidic contaminants, and dried over solid beds. Thereafter, the C2 and C3 alkanes and alkenes are separated by distillations at pressures up to 3 5 atm., with refrigerated condensers for the early columns in the train. Selective hydrogenation to remove acetylenes and dienes (most frequently over a 

The C4 fraction from the cracking of naphtha contains appreciable quantities of 1, 3-butadiene, and represents the major source of this material in western Europe and Japan (section 12.9.1). 

Finally, the gasoline fraction, frequently referred to as pyrolysis gasoline , is usually rich in aromatics, particularly benzene.  

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Table 10.13 provides some characteristic data relative to the steam cracking process. 

Other compounds which may be found in crude oil are metals such as vanadium, nickel, copper, zinc and iron, but these are usually of little consequence. Vanadium, if present, is often distilled from the feed stock of catalytic cracking processes, since it may spoil catalysis. The treatment of emulsion sludges by bio-treatment may lead to the concentration of metals and radioactive material, causing subsequent disposal problems. 

ElexibiHty allows the operator to pick and choose the most attractive feedstock available at a given point in time. The steam-cracking process produces not only ethylene, but other products as weU, such as propylene, butadiene, butylenes (a mixture of monounsaturated C-4 hydrocarbons), aromatics, etc. With ethane feedstock, only minimal quantities of other products ate produced. As the feedstocks become heavier (ie, as measured by higher molecular weights and boiling points), increasing quantities of other products are produced. The values of these other coproduced products affect the economic attractiveness and hence the choice of feedstock. 

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). 

Catalytic Processes. A second group of refining operations which contribute to gas production are the catalytic cracking processes, such as fluid-bed catalytic cracking, and other variants, in which heavy gas oils are converted into gas, naphthas, fuel oil, and coke (5). 

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). 

Cycloaliphatic Diene CPD—DCPD. Cycloatiphatic diene-based hydrocarbon resias are typically produced from the thermal or catalytic polymerization of cyclopeatadieae (CPD) and dicyclopentadiene (DCPD). Upon controlled heating, CPD may be dimerized to DCPD or cracked back to the monomer. The heat of cracking for DCPD is 24.6 kJ / mol (5.88 kcal/mol). In steam cracking processes, CPD is removed from C-5 and... 

The quantity of coproduct acetylene produced is sensitive to both the feedstock and the severity of the cracking process. Naphtha, for example, is cracked at the most severe conditions and thus produces appreciable acetylene up to 2.5 wt % of the ethylene content. On the other hand, gas oil must be processed at lower temperature to limit coking and thus produces less acetylene. Two industry trends are resulting in increased acetylene output (/) the ethylene plant capacity has more than doubled, and (2) furnace operating conditions of higher temperature and shorter residence times have increased the cracking severity. 

Visbreaking. Viscosity breaking (reduction) is a mild cracking operation used to reduce the viscosity of residual fuel oils and residua (8). The process, evolved from the older and now obsolete thermal cracking processes, is classed as mild because the thermal reactions are not allowed to proceed to completion. 

The feedstock, usuaHy consisting of propylene and butylenes (various isomers of C Hg) from cracking processes, may even consist of selective olefins for dimer, trimer, or tetramer production ... 

Aliphatics. Methane, obtained from cmde oil or natural gas, or as a product from various conversion (cracking) processes, is an important source of raw materials for aliphatic petrochemicals (Fig. 10) (see Hydrocarbons). Ethane, also available from natural gas and cracking processes, is an important source of ethylene, which, in turn, provides more valuable routes to petrochemical products (Fig. 11). 

During the cracking process, the hydrolyzate is depolymerized in the presence of strong base or acids to yield cycHc monomers, primarily octamethylcyclotetrasdoxane (D and decamethylcyclopentasdoxane (D ), which are distilled from the reaction mixture. The ttifunctional by-products remain in the pot and are periodically removed. 

Economic considerations in the 1990s favor recovering butadiene from by-products in the manufacture of ethylene. Butadiene is a by-product in the C4 streams from the cracking process. Depending on the feedstocks used in the production of ethylene, the yield of butadiene varies. Eor use in polymerization, the butadiene must be purified to 994-%. Cmde butadiene is separated from C and C components by distillation. Separation of butadiene from other C constituents is accomplished by salt complexing/solvent extraction. Among the solvents used commercially are acetonitrile, dimethyl acetamide, dimethylform amide, and /V-methylpyrrolidinone (13). Based on the available cmde C streams, the worldwide forecasted production is as follows 1995, 6,712,000 1996, 6,939,000 1997, 7,166,000 and 1998, 7,483,000 metric tons (14). As of January 1996, the 1995 actual total was 6,637,000 t. 

Oxychlorination reactor feed purity can also contribute to by-product formation, although the problem usually is only with low levels of acetylene which are normally present in HCl from the EDC cracking process. Since any acetylene fed to the oxychlorination reactor will be converted to highly chlorinated C2 by-products, selective hydrogenation of this acetylene to ethylene and ethane is widely used as a preventive measure (78,98—102). 

Thermal Asphalt. Thermal asphalt products are in low supply because the thermal process has been virtually replaced by catalytic cracking processes. Thermal pitches, because of their high viscosity temperature susceptibiHty, are very hard at ordinary temperatures (Table 9), but become quite... 

Catalytic Cracking. This is a refinery process that produces a mixture of butylenes and butanes with very small amounts of butadiene. The specific composition of the mixture depends on the catalyst and process conditions. Most catalytic cracking processes employ temperatures about... 

The most dominant catalytic process in the United States is the fluid catalytic cracking process. In this process, partially vaporized medium-cut petroleum fractions called gas oils are brought in contact with a hot, moving, freshly regenerated catalyst stream for a short period of time at process conditions noted above. Spent catalyst moves continuously into a regenerator where deposited coke on the catalyst is burnt off. The hot, freshly regenerated catalyst moves back to the reactor to contact the hot gas oil (see Catalysts, regeneration). 

The specific rate is expected to have an Arrhenius dependence on temperature. Deactivation by coke deposition in cracking processes apparently has this kind of correlation. 

Koszman, I., Antifoulant Additive for Steam-Cracking Process, U.S. Patent 3,531,394, Sept. 29, 1970. Hochman, R. F, Fundamentals of the Metal Dusting Reaction, Proceedings, Fourth International Congress on Metallic Corrosion, NACF (1971). 

Separation of raw feedstock. The pyrolysis of petroleum feedstream is carried out at 650-900°C at normal pressure in the presence of steam. The so-called steam-cracking process involves carbon-carbon splitting of saturated, unsaturated and aromatic molecules. The following steam-cracker fractions are used as raw materials to produce hydrocarbon resins. 

The catalytic cracking processes, as well as most other refinery catalytic processes, produce coke which collects on the catalyst surface and diminishes its catalytic properties. The catalyst, therefore, needs to be regenerated continuously or periodically essentially by burning the coke off the catalyst at high temperatures. 

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