Stream cracking

Hydrogen Hydrogen recovery was the first large commercial membrane gas separation. Polysulfone fiber membranes became available in 1980 at a time when H2 needs were rising, and these novel membranes quickly came to dominate the market. Apphcations include recovery of H2 from ammonia purge gas, and extraction of H2 from petroleum cracking streams. Hydrogen once diverted to low-quality fuel use is now recovered to become ammonia, or is used to desulfurize fuel, etc. H2 is the fast gas. 

Double-bond isomerization was once used in the multistep synthesis of isoprene developed by Goodyear.266-268 2-Methyl-1-pentene produced by the dimerization of propylene was isomerized to 2-methyl-2-pentene over a silica-alumina catalyst at 100°C. The product was cracked to isoprene and methane. Because of the lower cost of isoprene isolated from naphtha or gas oil-cracking streams, synthetic isoprene processes presently are not practiced commercially. 

A typical flow diagram of a two-stage crude oil distillation system is shown in Fig. 18.14. The crude oil is preheated with hot products from the system and desalted before entering the fired heater. The typical feed to the crude-fired heater has an inlet temperature of 550°F, whereas the outlet temperature may reach 657-725°F. Heater effluent enters the crude distillation (CD) column, where light naphtha is drawn off the overhead tower. Heavy naphtha, kerosene, diesel, and cracking streams are sidestream drawoffs from the distillation column. External reflux for the tower is provided by several pumparound streams.12... 

Because many petrochemical operations use cryogenic separation to separate hydrogen in the cracked streams, it is important to maintain the stream free of mercury. Mercury can contaminate naphtha, especially if it is derived from natural gas condensate since traces of mercury can be found in most natural gas". Mercury in naphtha is readily removed using carbon sieve technology. ... 

The preceding information indicates the paths to follow in order to obtain stocks of high octane number by refining. The orientation must be towards streams rich in aromatics (reformate) and in isoparaffins (isomerization, alkylation). The olefins present essentially in cracked gasolines can be used only with moderation, considering their low MONs, even if their RONs are attractive. 

All modern refineries have conversion units, designed to transform black effluent streams into lighter products gas, gasoline, diesel fuel. Among these conversion units, coking processes take place by pyrolysis and push the cracking reaction so far that the residue from the operation is very heavy it is called coke . 

Proportions correspond to the material balance for catalytic cracking in Figure 10.3 showing streams (l)(2)(3)(4) and (5). 

The feedstocks in question are primary distillation streams and some conversion products from catalytic cracking, coking, visbreaking, and residue conversion units. 

These water streams contain mainly dissolved salts ammonium chloride and sulfide, sodium chloride, traces of cyanide, phenols for water coming from catalytic and thermal cracking operations. 

In the United States butadiene was prepared initially from ethanol and later by cracking four-carbon hydrocarbon streams (see Butadiene). In Germany butadiene was prepared from acetylene via the following steps acetylene — acetaldehyde — 3-hydroxybutyraldehyde — 1,3-butanediol — ... 

The Phenox process (254) removes phenol (qv) from the efduent from catalytic cracking in the petroleum industry. Extraction of phenols from ammoniacal coke-oven Hquor may show a small profit. Acetic acid can be recovered by extraction from dilute waste streams (255). Oils are recovered by extraction from oily wastewater from petroleum and petrochemical operations. Solvent extraction is employed commercially for the removal of valuable... 

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. 

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). 

In order to increase the solubiUty parameter of CPD-based resins, vinyl aromatic compounds, as well as other polar monomers, have been copolymerized with CPD. Indene and styrene are two common aromatic streams used to modify cyclodiene-based resins. They may be used as pure monomers or contained in aromatic steam cracked petroleum fractions. Addition of indene at the expense of DCPD in a thermal polymerization has been found to lower the yield and softening point of the resin (55). CompatibiUty of a resin with ethylene—vinyl acetate (EVA) copolymers, which are used in hot melt adhesive appHcations, may be improved by the copolymerization of aromatic monomers with CPD. As with other thermally polymerized CPD-based resins, aromatic modified thermal resins may be hydrogenated. 

The flame-space walls are stainless steel and are water cooled. No mechanical coke scraper is required. A water quench cools the cracked gas stream rapidly at the poiat of maximum acetyleae and this is followed by a secondary water quench. The primary quench poiat can be adjusted for variation ia throughput, to accommodate the depeadeace of acetyleae yield oa resideace time ia the flame space. 

Butanes are recovered from raw natural gas and from petroleum refinery streams that result from catalytic cracking, catalytic reforming, and other refinery operations. The most common separation techniques are based on a vapor—Hquid, two-phase system by which Hquid butane is recovered from the feed gas. 

The success of the process results from the fact that nowhere inside the furnace is heat extracted from the copper-saturated blast furnace buUion through a soUd surface. The problem of accretion formation (metal buUd-up), which has plagued many other attempts to estabUsh a copper dtossing operation of this type, does not arise. In the cooling launder, lead-rich matte and slag accumulate on the water-cooled plates, but these ate designed so that when they ate lifted from the buUion stream, the dross cracks off and is swept into the furnace via the cooled lead pot. 

IFP Process for 1-Butene from Ethylene. 1-Butene is widely used as a comonomer in the production of polyethylene, accounting for over 107,000 t in 1992 and 40% of the total comonomer used. About 60% of the 1-butene produced comes from steam cracking and fluid catalytic cracker effluents (10). This 1-butene is typically produced from by-product raffinate from methyl tert-huty ether production. The recovery of 1-butene from these streams is typically expensive and requires the use of large plants to be economical. Institut Francais du Petrole (IFP) has developed and patented the Alphabutol process which produces 1-butene by selectively dimerizing ethylene. 

The cracked products leave as overhead materials, and coke deposits form on the inner surface of the dmm. To provide continuous operation, two dmms are used while one dmm is on-stream, the one off-stream is being cleaned, steamed, water-cooled, and decoked in the same time interval. The temperature in the coke dmm is in the range of 415—450°C with pressures in the range of 103—621 kPa (15—90 psi). Overhead products go to the fractionator, where naphtha and heating oil fractions are recovered. The nonvolatile material is combined with preheated fresh feed and returned to the furnace. The coke dmm is usually on stream for about 24 hours before becoming filled with porous coke, after which the coke is removed hydraulically. 

The catalyst is employed in bead, pellet, or microspherical form and can be used as a fixed bed, moving bed, or fluid bed. The fixed-bed process was the first process used commercially and employs a static bed of catalyst in several reactors, which allows a continuous flow of feedstock to be maintained. The cycle of operations consists of (/) the flow of feedstock through the catalyst bed (2) the discontinuance of feedstock flow and removal of coke from the catalyst by burning and (J) the insertion of the reactor back on-stream. The moving-bed process uses a reaction vessel, in which cracking takes place, and a kiln, in which the spent catalyst is regenerated and catalyst movement between the vessels is provided by various means. 

Thermal polymerization is not as effective as catalytic polymerization but has the advantage that it can be used to polymerize saturated materials that caimot be induced to react by catalysts. The process consists of the vapor-phase cracking of, for example, propane and butane, followed by prolonged periods at high temperature (510—595°C) for the reactions to proceed to near completion. Olefins can also be conveniendy polymerized by means of an acid catalyst. Thus, the treated olefin-rich feed stream is contacted with a catalyst, such as sulfuric acid, copper pyrophosphate, or phosphoric acid, at 150—220°C and 1035—8275 kPa (150—1200 psi), depending on feedstock and product requirement. 

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. 

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. 

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