Heavy-ends removing

EDC from the oxychlorination process is less pure than EDC from direct chlorination and requires purification by distillation. It is usually first washed with water and then with caustic solution to remove chloral and other water-extractable impurities (103). Subsequently, water and low boiling impurities are taken overhead in a first (light ends or heads) distillation column, and finally, pure, dry EDC is taken overhead in a second (heavy ends or product) column (see Fig. 2). 

Although there are minor differences in the HCl—vinyl chloride recovery section from one vinyl chloride producer to another, in general, the quench column effluent is distilled to remove first HCl and then vinyl chloride (see Eig. 2). The vinyl chloride is usually further treated to produce specification product, recovered HCl is sent to the oxychlorination process, and unconverted EDC is purified for removal of light and heavy ends before it is recycled to the cracking furnace. The light and heavy ends are either further processed, disposed of by incineration or other methods, or completely recycled by catalytic oxidation with heat recovery followed by chlorine recovery as EDC (76). 

By-products from EDC pyrolysis typically include acetjiene, ethylene, methyl chloride, ethyl chloride, 1,3-butadiene, vinylacetylene, benzene, chloroprene, vinyUdene chloride, 1,1-dichloroethane, chloroform, carbon tetrachloride, 1,1,1-trichloroethane [71-55-6] and other chlorinated hydrocarbons (78). Most of these impurities remain with the unconverted EDC, and are subsequendy removed in EDC purification as light and heavy ends. The lightest compounds, ethylene and acetylene, are taken off with the HCl and end up in the oxychlorination reactor feed. The acetylene can be selectively hydrogenated to ethylene. The compounds that have boiling points near that of vinyl chloride, ie, methyl chloride and 1,3-butadiene, will codistiU with the vinyl chloride product. Chlorine or carbon tetrachloride addition to the pyrolysis reactor feed has been used to suppress methyl chloride formation, whereas 1,3-butadiene, which interferes with PVC polymerization, can be removed by treatment with chlorine or HCl, or by selective hydrogenation. 

The delayed coking feed stream of residual oils from various upstream processes is first introduced to a fractionating tower where residual lighter materials are drawn off and the heavy ends are condensed. The heavy ends are removed and heated in a furnace to about 900 to 1,000 F and then fed to an insulated vessel called a coke drum where the coke is formed. When the coke drum is filled with product, the feed is switched to an empty parallel drum. Hot vapors from the coke drums, containing cracked lighter hydrocarbon products, hydrogen sulfide, and ammonia, are fed back to the fractionator where they can be treated in the sour gas treatment system or drawn off as intermediate products. 

In two stage units, it is often economical to distill more gas oil in the vacuum stage and less in the atmospheric stage than the maximum attainable. Gas formed in the atmospheric tower bottoms piping at high temperatures tends to overload the vacuum system and thereby to reduce the capacity of the vacuum tower. The volume of crude vaporized at the flash zone is approximately equal to the total volume of distillate products. Of course, the vapor at this point contains some undesirable heavy material and the liquid still contains some valuable distillate products. The concentration of heavy ends in the vapor is reduced by contact with liquid on the trays as the vapor passes up the tower. This liquid reflux is induced by removing heat farther up in the tower. 

Developed by Allied Chemical Company, this process is selective toward removing sulfur compounds. Levels of CO2 can be reduced bv annroximately 85%. This process may be used economically when there a ligh acid-gas partial pressures and the absence of heavy ends in iJic gas., but it will not normally meet pipeline gas requirements. This proc also removes water to less than 7 Ib/MMscf. DIPA can be added to I... 

Some radioactive bromine (half-life 36 hours), in the form of ammonium bromide, was put into a brine stream as a radioactive tracer. At another plant 30 km away, the brine stream was electrolyzed to produce chlorine. Radioactive bromine entered the chlorine stream and subsequently concentrated in the base of a distillation column, which removed heavy ends. This column was fitted with a radioactive-level controller. The radioactive bromine affected the level controller, which registered a low level and closed the bottom valve on the column. The column became flooded. There was no injury, but production was interrupted. 

Water connections to a shell-and-tube condenser must always be arranged so that the end covers can easily be removed for inspection, cleaning, and repair of the tubes. Heavy end covers require the use of lifting tackle, and supports above the lifting points should be provided on installation to facilitate this work. 

In the hydroformylation of lower alkenes using a modified cobalt catalyst complex separation is achieved by distillation. The ligands are high-boiling so that they remain with the heavy ends when these are removed from the alcohol product. Distillation is not possible when higher alcohols or aldehydes are produced, because of decomposition of the catalyst ligands at the higher temperatures required. Rhodium complexes can usually also be removed by distillation, since these complexes are relatively stable. 

Trace hydrocarbons that may be regarded as contaminants may be determined by the gas chromatographic methods already discussed. Heavier hydrocarbons in small amounts may not be removed completely from the column. If accurate information is required about the nature and amount of heavy ends, temperature programming or a concentration procedure may be used. 

HPT Research, Inc., has developed the ionic state modification (ISM) process for the treatment of acid mine drainage (AMD). ISM is an ex situ treatment technology that uses magnets, electricity, and proprietary chemical to precipitate heavy metals, remove sulfate ions, and neutralize acidity from AMD and industrial wastewaters. The end products of the process are a metal hydroxide sludge, a calcium sulfate sludge, and treated liquid effluent. The vendor claims that the metal hydroxide sludge may have some value as an ore, the calcium sulfate may be used as an agricultural additive to soils, and the liquid effluent is free of metal contamination and has low sulfate concentrations. 

Most atmospheric columns contain from 30 to 50 fractionation trays. For each sidestream desired, about five to eight trays are required, plus additional trays above and below the primary trays. The various sidestreams collected from the distillation column contain lighter boiling products that must be removed. Smaller reboiling units are used to remove lighter products and direct them back into the distillation column as vapor. Also, refluxing units are sometimes employed to condense and remove heavy end products from collected fractions. These condensed heavier products are reintroduced into the lower trays. 

The unwanted heavy ends, which are removed as a bottom product and sent to cracking coil stock... 

This effluent then goes to a condenser where aldehydes and by-products drop out this mixture is removed in a separator. The liquid stream from the separator contains appreciable amounts of dissolved gases, mainly propylene and propane. A product stripping column distills these out. The liquid stream from this stripper goes through two distillation columns in series that remove iso- and n-butyraldehyde as overhead products, respectively. A small stream that contains heavy by-products formed in the reactor leaves the bottom of the second column. This stream can be combined with the heavy ends stream from the n-butanol column and valuable aldehydes and alcohols recovered for recycle. The iso-butyraldehyde overhead product from the first aldehyde column may be hydrogenated and sold as a low cost solvent, cracked to synthesis gas and recycled to the oxo reactors, or burned as fuel. 

Removing light and heavy-end impurities is compulsory before other separations. 

Figure 3.5 Alternative methods for removing heavy-ends.

Once the synthetic crude oils from coal and oil shale have been upgraded and the heavy ends converted to lighter distillates, further refining by existing processes need not be covered in detail except to note the essential character of the products. The paraffinic syncrude from oil shale yields middle distillates which are excellent jet and diesel fuel stocks. The principal requirements are removal of nitrogen to the extent necessary for good thermal stability of the fuels and adjustment of cut points to meet required pour or freeze points, limited by the presence of waxy straight-chain paraffins. The heavy naphtha from shale oil can be further hydrotreated and catalytically reformed to acceptable octane number, but with considerable loss of volume because of the only moderate content of cyclic hydrocarbons, typically 45-50%. On the other... 

Effect of EBP. By decreasing the FBP, the naphtha concentration of n-paraffms and naphthenes increased as a result of the removal of the aromatics-rich heavy end of the base naphtha. Above FBP 149°C, only Cg components were removed. Below this temperature the Cg aromatics were affected, and first of all the xylenes (Figure 2). Because of a higher boiling point, o-xylene is the first Cg aromatic component to be removed from the naphtha when the FBP is lowered. Ethylbenzene is the last Cg aromatic component to be removed due to a lower boiling point (136.2 °C, compared with 138-144 C for the xylenes). 

---