Cracker stream

The major aromatics (organics having at least one ring structure with six carbon atoms) manufactured include benzene, toluene, xylene, and naphthalene. Other aromatics manufactured include phenol, chlorobenzene, styrene, phthalic and maleic anhydride, nitrobenzene, and aniline. Benzene is generally recovered from cracker streams at petrochemical plants and is used for the manufacture of phenol, styrene, aniline, nitrobenzene, sulfonated detergents, pesticides such as hexachlorobenzene, cyclohexane (an important intermediate in synthetic fiber manufacture), and caprolactam, used in the manufacture of nylon. Benzene is also used as a general purpose solvent. 

The Hj/400°FVT streams from each system are sent to separate flash drums where the bulk of the Cj and lighter material is removed. The virgin and cat cracker streams from the flash drums go to separate debutanizers while the Powerformer stream goes to an absorber-deethanizer followed by a debutanizer. The Q and lighter overhead streams from the virgin and cat cracker debutanizers are sent to this absorber- deethanizer for final deethanization. In the flow scheme shown this tower does not have a separate lean oil. It is called an absorber-deethanizer because the Powerformer stream serves in part to absorb the Cj and C4 components in the streams from the debutanizers. A separate lean oil stream is added in cases where higher Q and Q recoveries are justified. 

Following is a discussion about the by-products from the various naphtha cracker streams ... 

The oxyfunctionalization of linear alkanes at the terminal position is one of the major challenges of catalysis in the case of n-hexane, oxidation at the two terminal C atoms would lead to AA. However, there is a little amount of n-hexane in cracker streams, because it is easily converted to benzene. Therefore, sourcing of this hydrocarbon would be a challenge. 

Today, more butadiene (BD) is produced from butene (another C4) through steam cracking of naphtha gas oil (a byproduct of ethylene/propylene production). Through extractive distillation of this C4 cracker stream, the butadiene is obtained. Com-... 

Today more butadiene is produced from butene (another C4) through steam cracking of naphtha gas oil from ethylene/propylene production (it is a byproduct of eth-ylene/propylene production). Through extractive distillation of this C4 cracker stream, the butadiene is obtained. Commonly the yield achieved forBD is dependent on the quality of the feedstocks used for ethylene production. Usually the heavier the feedstock, the greater the BD production. Reportedly, the lighU feedstock only yields about one-fifth the yield of butadiene compared to the heavy feedstock. 

Figure 2.8 shows the essential features of a refinery catalytic cracker. This particular reaction is accompanied hy the deposition of carhon on the surface of the catalyst. The fiuidized-hed reactor allows the catalyst to he withdrawn continuously and circulated to a fiuidized regenerator, where the carhon is burnt ofi" in an air stream, allowing regenerated catalyst to he returned to the cracker. 

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. 

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 other significant industrial route to /-butyl alcohol is the acid cataly2ed hydration of isobutylene (24), a process no longer practiced in the United States. Raffinate 1, C-4 refinery streams containing isobutylene [115-11-7], / -butenes and saturated C-4s or C-4 fluid catalytic cracker (ECC) feedstocks (23)... 

The C4 stream from steam crackers, unlike its counterpart from a refinery, contains about 45% butadiene by weight. Steam crackers that process significant amounts of Hquid feedstocks have satellite faciUties to recover butadiene from the stream. Conventional distillation techniques are not feasible because the relative volatihty of the chemicals in this stream is very close. Butadiene and butylenes are separated by extractive distillation using polar solvents. 

A typical feed to a commercial process is a refinery stream or a steam cracker B—B stream (a stream from which butadiene has been removed by extraction and isobutylene by chemical reaction). The B—B stream is a mixture of 1-butene, 2-butene, butane, and isobutane. This feed is extracted with 75—85% sulfuric acid at 35—50°C to yield butyl hydrogen sulfate. This ester is diluted with water and stripped with steam to yield the alcohol. Both 1-butene and 2-butene give j -butyl alcohol. The sulfuric acid is generally concentrated and recycled (109) (see Butyl alcohols). 

The various sources of isobutylene are C streams from fluid catalytic crackers, olefin steam crackers, isobutane dehydrogenation units, and isobutylene produced by Arco as a coproduct with propylene oxide. Isobutylene concentrations (weight basis) are 12 to 15% from fluid catalytic crackers, 45% from olefin steam crackers, 45 to 55% from isobutane dehydrogenation, and high purity isobutylene coproduced with propylene oxide. The etherification unit should be designed for the specific feedstock that will be processed. 

Although the avadabihty of butane—butylene streams containing high concentrations of isobutylene from steam crackers will increase and possibly make these technologies attractive, these same steam crackers also produce recoverable amounts of isoprene direcdy, particularly from heavier feedstocks. 

Additive inhibitors have been developed to reduce the contaminant coke produced through nickel-cataly2ed reactions. These inhibitors are injected into the feed stream going to the catalytic cracker. The additive forms a nickel complex that deposits the nickel on the catalyst in a less catalyticaHy active state. The first such additive was an antimony compound developed and first used in 1976 by Phillips Petroleum. The use of the antimony additive reportedly reduced coke yields by 15% in a commercial trial (17). 

Basic Yield Data. This is a good place to start asking questions. If the process uses a catalytic reaction, do the yields represent new catalyst or catalyst regenerated a number of times For a thermal reaction like an olefin plant steam cracker, questions might be asked about on-stream time between decokings. Therefore, how much contingency is there in the specified number of crackers required ... 

The teed to the cat cracker in a typical refinery is a blend of gas oils from such operating units as the crude, vacuum, solvent deasphalting, and coker. Some refiners purchase outside FCC feedstocks to keep the FCC feed rate maximized. Other refiners process atmospheric or vacuum residue in their cat crackers. In recent years, the trend has been toward heavier gas oils and residue. Residue is most commonly defined as the fraction of feed that boils above 1,050°F (565 C). Each FCC feed stream has different distillation characteristics. 

The overhead stream from the debutanizer or stabilizer is a mix of C, s and C4 s, usually referred to as LPG (liquefied petroleum gas). It is rich in olefins, propylene, and butylene. These light olefins play an important role in the manufacture of reformulated gasoline (RFG). Depending on the refinery s configuration, the cat cracker s LPG is used in the following areas ... 

Table El4.1 A shows various feeds and the corresponding product distribution for a thermal cracker that produces olefins. The possible feeds include ethane, propane, debutanized natural gasoline (DNG), and gas oil, some of which may be fed simultaneously. Based on plant data, eight products are produced in varying proportions according to the following matrix. The capacity to run gas feeds through the cracker is 200,000 lb/stream hour (total flow based on an average mixture). Ethane uses the equivalent of 1.1 lb of capacity per pound of ethane propane 0.9 lb gas oil 0.9 lb/lb and DNG 1.0.

In the purification section of an ethane cracker, the gas can be handled in one of two ways. In order to fractionate the streams, they must be liquefied. Since they are all light gases, liquefaction can be done either by increasing the pressure in a compressor or by reducing the temperature to very low points in something called a cold box. The ethane cracker in Figure 5—2 shows the compressor option. (Even then, the streams have to be cooled to assure they liquefy.)... 

The reasons for the three grades are very practical. For the first two, refinery and chemical, that s the way they re made. Refinery grade propylene streams are generally by-products of a refinery s cat cracker, and the propane/propylene ration is determined by the way the cat cracker is run to make gasoline, not propylene. Chemical grade propylene is usually produced in a naphtha or gas oil cracker. The ratio of propylene and propane is about 92 8 over most of the operating conditions. 

The first serious notice of C4 hydrocarbons came with the development of refinery cracking processes. When catalytic cracking became popular, refiners were faced with disposing of a couple of thousand barrels per day of a stream containing butane, butylenes, and small amounts of butadiene. Their first thought was to burn it all as refinery fuel, but then they developed the alkylation process. With that, they could undo some of the molecule shatter that took place in the crackers and reassemble some of the smaller pieces as alkylate, a high-octane gasolinerblending component. 

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