Handling of ethylene

Guidelines for Bulk Handling of Ethylene Oxide, London, CIA, 1983... 

Tests Tests shall be conducted as follows Exercise care in the handling of ethylene oxide as it is an explosive and toxic.material. Conduct all tests in a ventilated hood. Use... 

Small shipments of ethylene oxide are made in either compressed gas cylinders up to -0.1 m3 (30 gal) or in 1A1 steel drums (61 gal). Very large shipments >40 m3 (10,000—25,000 gal) are made in insulated, type 105J100W or other DOT approved tank cars. For further information on the shipping and handling of ethylene oxide, see References 9 and 227. 

Several companies have published descriptive bulletins for the safe handling of ethylene oxide, propylene oxide, and butylene oxide. Typical glassware and technical reviews are given in [5,6]. Some physical properties of ethylene and propylene oxides are given in Table I. 

Vinyl acetate homopolymers are simply-made adhesive bases manufactured by addition polymerization in the presence of water and stabilizers. They are made commercially by the batch reactor process or by the Loop reactor continuous process. External plasticizers such as dibutyl phthalate are often added to confer flexibility and to lower the temperature at which they form a film on drying. Higher-quality products may be made by the copolymerization of ethylene with vinyl acetate to form an EVA. This involves the safe handling of ethylene gas under high pressure, and the plant required is more complex and considerably more costly. The Loop process has considerable attraction in the field of pressure polymerization. 

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. 

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). 

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. 

When acetylene is recovered, absorption—desorption towers are used. In the first tower, acetylene is absorbed in acetone, dimethylformarnide, or methylpyroUidinone (66,67). In the second tower, absorbed ethylene and ethane are rejected. In the third tower, acetylene is desorbed. Since acetylene decomposition can result at certain conditions of temperature, pressure, and composition, for safety reasons, the design of this unit is critical. The handling of pure acetylene streams requires specific design considerations such as the use of flame arrestors. 

Due to the low reactivity of ethylene and acetylene as dienophiles, forcing conditions, such as high temperature and high pressure, are necessary for [4 + 2]cycloaddition. The hazards associated with handling acetylene under these conditions are well known and... 

A stream of ethylene is fed into the reactor by use of quaternary LC pumps and subsequently dissolved in a 1.90 ml h toluene stream [1]. Ethylene is handled at 60 °C, well above the critical temperature. Catalyst additions are fed via HPLC-type sample injection valves. Various combinations of precatalysts and activators were sampled and loaded by an autoinjector. Catalyst solutions typically were diluted 20-fold within the micro reactor. 

While (Z)-l,2-bis(phenylsulfonyl)ethylene (140) does not add to dienes such as furan, cyclopentadiene, cyclo-octatetraene, indene and )S-naphthol, ( )-l,2-bis(phenylsulfonyl)ethylene (141) is more reactive and the reaction with furan proceeds at room temperature for 2 h to give the adduct in 95% yield. The reactivity of dienophiles having sulfonyl group in the [4 -t- 2]cycloaddition is shown in equation 103 °X Due to the low reactivity of ethylene and acetylene as dienophiles, forcing conditions, such as high temperature and high pressure, are necessary for [4 -1- 2]cycloaddition. The hazards associated with handling acetylene under these conditions are well known and... 

Hazards attendant on use of ethylene oxide in steriliser chambers arise from difficulties in its subsequent removal by evacuation procedures, owing to its ready absorption or adsorption by the treated material. Even after 2 evacuation cycles the oxide may still be present. Safety is ensured by using the oxide diluted with up to 90% of Freon or carbon dioxide. If high concentrations of oxide are used, an inert gas purge between cycles is essential [7], The main factors in safe handling... 

Olefins plants, for the most part, all have the same basic technology, but the process flows differ with the varied feedstocks that can be used. This chapter will cover in some depth the feeds, the hardware, the reactions, and the variables that can be manipulated to change the amount and mix of products. The physical properties of ethylene and propylene, which present some unique handling problems, will be covered also. 

Referring to the hardware in Figure 5—4, there are much larger facilities required for heavier liquids cracking than for ethane or propane. As you saw in Table 5—1, the yield of ethylene from the heavier feeds is much lower than from ethane. That means that to produce the same amount of ethylene on a daily basis, the gas-oil furnaces have to handle nearly five times as much feed as ethane furnaces. As the design engineer scales up these volumes, he or she has to worry about the size of the cubes necessary to heat up that much feed, the residence times best for each kind of feed, and the best pressure/temper-ature/steam mixture conditions. 

Oxidation of ethyl alcohol was one of the two important commercial routes to acetaldehyde until the 1950s, The other, much older route was the hydration of acetylene. The chemical industry was always after a replacement of acetylene chemistry, not just for acetaldehyde production, but all its many applications. Acetylene was expensive to produce, and with its reactive, explosive nature, it was difficult to handle. In the 1950s, acetylene chemistry and the ethyl alcohol oxidation route were largely phased out by the introduction of the liquid phase direct oxidation of ethylene. Almost all the acetaldehyde produced uses the newer process. 

Ethylene is not irritating to the skin and eyes. The gas has a faintly sweet odor that probably does not provide adequate warning of hazardous concentrations. Owing to the highly flammable and explosive characteristics of ethylene, it should be handled cautiously. ... 

In the 1930s ethylene began to replace acetylene as the primary chemical intermediate, and by the end of the 1940s the transition from acetylene to ethylene as an intermediate was nearly complete. Ethylene is much safer to store and handle, and ethylene now is by far the largest-volume organic chemical produced (80 biUion pounds per year worldwide). 

Since precipitants used for growth were volatile alcohols (methanol, or methanol/ ethylen glycol mixtures) any handling of the crystals was impossible. Even a minor intervention such as sealing the X-ray capillaries shortened the lifetime of crystals drastically to 6-8 hours (Fig. 3) crystals had to be irradiated immediately in their original growth solution. 

Explosibility. Liquid ethylene oxide is stable to detonating agents, but the vapor will undergo explosive decomposition. Pure ethylene oxide vapor will decompose partially however, a slight dilution with air or a small increase in initial pressure provides an ideal condition for complete decomposition. Copper or other acetylide-forming metals such as silver, magpesium, and alloys of such metals should not be used to handle or store ethylene oxide because of the danger of the possible presence of acetylene. Acetylides detonate readily and will initiate explosive decomposition of ethylene oxide vapor. In the presence of certain catalysts, liquid ethylene oxide forms a poly-condensate. 

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