Purification ethylene

Kureha and Lummus have similar processes. In these, simplification of the ethylene purification step allows significant reduction in investment cost, refrigeration cost, and compression cost. The cheaper ethylene can then be incorporated into ethylene-route processes for VCM to decided advantage, especially for smaller units. 

Refrigeration systems are extensively used in the chemical industries in low temperature processes such as liquefaction of natural gas, ethylene purification and cryogenic air separation. In these kinds of low temperature systems, heat is rejected from the process by refrigeration to heat sinks being other process streams or refrigeration systems at the expense of mechanical work. The refrigeration systems employed are complex, and energy and capital intensive, and therefore, play a critical role in the overall plant economics. 

Figure 14.1. A simple sequence of distillation columns for ethylene purification.

Ethylene Purity. The ethylene purity in the recycle is a function of feed purity and vent rate. An economic balance between the size of the reactor and ethylene purification facilities results in a recycle purity of 85 per cent and make-up feed of 97 per cent ethylene. 

The bottoms from the demethanizers are sent to the cut treatment for ethylene purification. 

The Sclairtech technology also offers lower cost ethylene as an ethylene feed stream of 85% ethylene and 15% ethane maybe used in the process. The cost savings comes from lower ethylene purification requirements in the ethylene plant. 

Separation processes in petroleum and petrochemical industries are highly energy intensive. Among these processes, ole separations consume the most energy, 0.12 Quad/year (1 Quad = a million billion BTU) (7). Ethylene purification alone required 9 trillion BTU in 1993 (2). Consequently, there is an economic incentive to develop alternative separation processes with lower energy consumption. 

Chitosan-modified silica aerogek have also been tested for chemical catalysis applications, for example, in Ref. [122]. After impregnation of the aerogel with Pd salts and chemical reduction, the resulting model catalyst was tested for the selective hydrogenation of acetylene in the presence of ethylene and superior selectivity for acetylene was found. Such a catalyst system can find use in the gas makeup for polyolefine production (e.g., ethylene purification). Removal of acetylene is important as it is a catalyst poison for commonly used olefin polymerization catalysts. A high selectivity in such a gas makeup catalyst is essential, so that the precious ethylene itself is not hydrogenated. 

Kniel and Slager, Ethylene Purification by Absorption Process, Chem. Eng, Progr., July, 1947, p. 335. 

Hydrolysis yielding terephthaHc acid and ethylene glycol is a third process (33). High temperatures and pressures are required for this currently noncommercial process. The purification of the terephthaHc acid is costly and is the reason the hydrolysis process is no longer commercial. 

Grimm, "Large-Scale Purification of Carbide Acetylene with Special Regard to the Production of Acetaldehyde and Ethylene," OTS Report, PB 35209, U.S. Department of Commerce, 1944. 

Regenerative pyrolysis processing is very versatile it can handle varied feedstocks and produce a range of ethylene to acetylene. The acetylene content of the cracked gases is high and this assists purification. On the other hand, the plant is relatively expensive and requires considerable maintenance because of the wear and tear on the refractory of cycHc operation. 

Most by-product acetylene from ethylene production is hydrogenated to ethylene in the course of separation and purification of ethylene. In this process, however, acetylene can be recovered economically by solvent absorption instead of hydrogenation. Commercial recovery processes based on acetone, dimetbylform amide, or /V-metby1pyrro1idinone have a long history of successfiil operation. The difficulty in using this relatively low cost acetylene is that each 450, 000 t/yr world-scale ethylene plant only produces from 7000 9000 t/yr of acetylene. This is a small volume for an economically scaled derivatives unit. 

Another attractive commercial route to MEK is via direct oxidation of / -butenes (34—39) in a reaction analogous to the Wacker-Hoechst process for acetaldehyde production via ethylene oxidation. In the Wacker-Hoechst process the oxidation of olefins is conducted in an aqueous solution containing palladium and copper chlorides. However, unlike acetaldehyde production, / -butene oxidation has not proved commercially successflil because chlorinated butanones and butyraldehyde by-products form which both reduce yields and compHcate product purification, and also because titanium-lined equipment is required to withstand chloride corrosion. 

Molecular Weight. Measurement of intrinsic viscosity in water is the most commonly used method to determine the molecular weight of poly(ethylene oxide) resins. However, there are several problems associated with these measurements (86,87). The dissolved polymer is susceptible to oxidative and shear degradation, which is accelerated by filtration or dialysis. If the solution is purified by centrifiigation, precipitation of the highest molecular weight polymers can occur and the presence of residual catalyst by-products, which remain as dispersed, insoluble soHds, further compHcates purification. 

In Europe, where an abundant supply of anthracene has usually been available, the preferred method for the manufacture of anthraquinone has been, and stiU is, the catalytic oxidation of anthracene. The main problem has been that of obtaining anthracene, C H q, practically free of such contaminants as carbazole and phenanthrene. Many processes have been developed for the purification of anthracene. Generally these foUow the scheme of taking the cmde anthracene oil, redistilling, and recrystaUizing it from a variety of solvents, such as pyridine (22). The purest anthracene may be obtained by azeotropic distillation with ethylene glycol (23). 

Chlorinated by-products of ethylene oxychlorination typically include 1,1,2-trichloroethane chloral [75-87-6] (trichloroacetaldehyde) trichloroethylene [7901-6]-, 1,1-dichloroethane cis- and /n j -l,2-dichloroethylenes [156-59-2 and 156-60-5]-, 1,1-dichloroethylene [75-35-4] (vinyhdene chloride) 2-chloroethanol [107-07-3]-, ethyl chloride vinyl chloride mono-, di-, tri-, and tetrachloromethanes (methyl chloride [74-87-3], methylene chloride [75-09-2], chloroform, and carbon tetrachloride [56-23-5])-, and higher boiling compounds. The production of these compounds should be minimized to lower raw material costs, lessen the task of EDC purification, prevent fouling in the pyrolysis reactor, and minimize by-product handling and disposal. Of particular concern is chloral, because it polymerizes in the presence of strong acids. Chloral must be removed to prevent the formation of soflds which can foul and clog operating lines and controls (78). 

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. 

Alternatives to oxychlorination have also been proposed as part of a balanced VCM plant. In the past, many vinyl chloride manufacturers used a balanced ethylene—acetylene process for a brief period prior to the commercialization of oxychlorination technology. Addition of HCl to acetylene was used instead of ethylene oxychlorination to consume the HCl made in EDC pyrolysis. Since the 1950s, the relative costs of ethylene and acetylene have made this route economically unattractive. Another alternative is HCl oxidation to chlorine, which can subsequently be used in dkect chlorination (131). The SheU-Deacon (132), Kel-Chlor (133), and MT-Chlor (134) processes, as well as a process recently developed at the University of Southern California (135) are among the available commercial HCl oxidation technologies. Each has had very limited industrial appHcation, perhaps because the equiHbrium reaction is incomplete and the mixture of HCl, O2, CI2, and water presents very challenging separation, purification, and handling requkements. HCl oxidation does not compare favorably with oxychlorination because it also requkes twice the dkect chlorination capacity for a balanced vinyl chloride plant. Consequently, it is doubtful that it will ever displace oxychlorination in the production of vinyl chloride by the balanced ethylene process. 

In the manufacture of ethylene dibromide, gaseous ethylene is brought into contact with bromine by various methods, allowing for dissipation of the heat of reaction (100—102). Eree acids are neutralized and the product maybe fractionally distilled for purification. Typical specifications call for a clear Hquid with 99.5% purity min sp gr (25/25°C), 2.170—2.180 boiling range, 130.4—132.4°C APHA color, 200 max water, 200 ppm max acidity as HCl, 0.0004 wt % max and nonvolatile matter, 0.0050 wt % max. 

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