Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-07-20
2003-07-22
Trinh, Ba K. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S541000
Reexamination Certificate
active
06596882
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method of recovering and purifying 3,4-epoxy-1-butene (epoxybutene) from an epoxidation effluent gas obtained by the vapor phase, catalytic, partial oxidation of 1,3-butadiene (butadiene) with molecular oxygen in the presence of a silver catalyst. More specifically, the present invention relates to a method of recovering epoxybutene from an epoxybutene-laden reaction product gas by absorption into a water-miscible solvent. This invention also relates to a method of separating epoxybutene from the solvent and other reaction by-products by a novel combination of distillation and decantation steps.
BACKGROUND OF THE INVENTION
Ethylene oxide (EO) and 1,2-epoxy-3-butene both are produced by processes which involve the catalytic, partial oxidation of the corresponding olefin, i.e., ethylene and butadiene, with oxygen in the presence of a silver catalyst. See, for example, U.S. Pat. Nos. 2,773,844 and 3,962,136, and 4,356,312 for ethylene oxide oxidation and U.S. Pat. Nos. 4,897,498, 4,950,773, and 5,081,096 for butadiene oxidation. Considerable effort has been devoted to the development of efficient methods for recovering these epoxides, particularly EO, from the reaction product gas and subsequent purification of the epoxide.
According to U.S. Pat. Nos. 3,745,092 and 3,964,980, and Dever et al
Ethylene Oxide
, in
Kirk-Othmer Encyclopedia of Chemical Technology
, 4
th
Ed., 1994, pages 929-930, EO is recovered and purified according to the following procedure. A reaction product gas typically containing 0.5 to 5% EO, obtained by the vapor phase, catalytic oxidation of ethylene with molecular oxygen in the presence of a silver catalyst, is introduced to an EO absorption tower wherein it is contacted counter-currently with an absorbent comprised primarily of water which absorbs the ethylene oxide. The absorber typically is maintained at a temperature of 5 to 40° C. and a pressure of 10 to 30 bar absolute (bara).
The EO-laden absorbent then is transferred to a distillation (stripping) column wherein vaporous EO is recovered from the upper section or top of the tower at a temperature of 85 to 140° C. by steam stripping at reduced pressure. The water remaining after the distillation of EO is recycled to the absorption tower for reuse. EO reacts readily with water under absorption and distillation conditions to form ethylene glycol, which can react further to form diethylene glycol, triethylene glycol, and higher oligomers. Although ethylene glycol is a valuable and marketable chemical, diethylene glycol and higher oligomers have much less commercial demand and, thus, normally are undesirable by-products. Formation of ethylene glycol oligomers can be controlled to some extent by limiting ethylene glycol concentration in the recycled water to the absorber. Typical levels are less than 10 weight per cent ethylene glycol in the recycled absorber water.
The crude EO vapor recovered in the stripper overhead comprises EO as the main component, as well as impurities such as water, argon, nitrogen, carbon dioxide, methane, ethane and ethylene, formaldehyde, and acetaldehyde. This crude EO vapor is fed to a second distillation (stripping) column from which the light or low-boiling components, e.g., nitrogen, carbon dioxide, argon, methane, ethane, and ethylene, are removed from the upper section or top of the column. A partially purified EO is removed from the lower section or base of the second stripping column and is transferred to the mid-section of a refining column for final purification. U.S. Pat. Nos. 5,529,667 and 3,418,338 disclose the use of extractive distillation with water as a solvent in either the second stripping column or the refining column to reduce the level of aldehyde impurities in the final purified ethylene oxide product.
By employing the above-described procedure, EO purities of greater than 99.5 mole per cent are possible. Although the water-based processing procedure functions effectively for EO recovery and purification, it cannot be employed equally efficaciously for the recovery and purification of epoxybutene. Firstly, whereas ethylene oxide is completely and infinitely miscible with water, epoxybutene is only sparingly miscible with water. At 25° C. the solubility of epoxybutene in water is only about 5 to 6 weight percent. As a result, water is a very poor absorbent for epoxybutene. High water to epoxybutene ratios, i.e., upward of 50/1 to 150/1, are required to ensure complete absorption of epoxybutene from the butadiene oxidation effluent. The use of such ratios is prohibited by the cost of the equipment and energy required.
Secondly, EO is a relatively low-boiling component compared to water, i.e., normal boiling point of 10.4° C. versus 100° C., respectively, and does not form an azeotrope with water. Thus, EO can be distilled readily from water by simple fractional distillation techniques as described above for the conventional EO recovery scheme. However, epoxybutene is much more hydrophobic than EO oxide and forms a minimum-boiling azeotrope with water. High purity epoxybutene cannot be obtained by the simple fractional distillation techniques employed for EO recovery.
Other methods proposed for recovery of EO from ethylene oxidation effluents likewise are not effective or are uneconomical for epoxybutene recovery and purification. For example, U.S. Pat. No. 3,948,621 discloses a method of separating EO and carbon dioxide simultaneously from a mixed gas obtained from catalytic oxidation of ethylene using methanol as an absorbent. As with water, epoxybutene forms a minimum-boiling azeotrope with methanol and thus epoxybutene and methanol cannot be separated readily by simple fractional distillation.
U.S. Pat. Nos. 4,437,938 and 4,437,939 disclose methods using supercritical or near supercritical carbon dioxide and water at the same time as absorbents. EO is first absorbed into water as in conventional recovery methods. The EO-rich aqueous absorbent is contacted with (near) supercritical carbon dioxide, and EO is extracted to the carbon dioxide solvent. The carbon dioxide is separated from EO by distillation under reduced pressure. The carbon dioxide is recompressed before recycling as the extraction solvent. This method, however, has many drawbacks. First, the required amount of (near) supercritical carbon dioxide is approximately 35 times the amount of EO to be absorbed therein, which requires large equipment. The extraction is carried out at high pressures, i.e., 86 bara, while the distillation step is carried out at lower pressure, i.e., about 0.1 to 2 bara. The wide pressure differential results in high compression costs and thus does not provide an economical solution.
U.S. Pat. Nos. 4,221,727 and 4,233,221 discloses an EO recovery method that uses ethylene carbonate as an absorbent for EO. Ethylene carbonate has many advantages as an absorbent. The absorption affinity of ethylene carbonate for EO is higher than that of water. The vapor pressure of ethylene carbonate is quite low, i.e., normal boiling point of 239° C., so losses into the recycle gas are minimal. Moreover, ethylene carbonate is stable and does not react directly with EO. The process disclosed in U.S. Pat. No. 4,233,221, however, has the following drawbacks for EO and epoxybutene recovery. The most preferred temperature range for operation of conventional absorption of EO with water is 5 to 40° C. The melting point of ethylene carbonate is 39° C., so ethylene carbonate would be a solid over almost all of the preferred temperature range. In order to avoid solidification, it is necessary to operate the absorber and other processing equipment substantially above, i.e., at least 10 to 20° C., above the melting point of ethylene carbonate. This is much higher temperature than an operation using water. The absorbing power of the ethylene carbonate correspondingly decreases so that the amount of circulating absorbent must be increased, reducing the economic utility of the process.
U.S. Pat. No. 5,559,255 describes the use of propylene c
Barnicki Scott Donald
Briley Steven Edward
Hamilton Jackie Lee
Kline Robert Sterling
Stavinoha, Jr. Jerome Leonard
Blake Michael J.
Eastman Chemical Company
Graves, Jr. Bernard J.
Trinh Ba K.
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