Recovery of 3,4-epoxy-1-butene by extractive distillation

Distillation: processes – separatory – Adding material to distilland except water or steam per se – Organic compound

Reexamination Certificate

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C203S057000, C203S058000, C203S060000, C203S062000, C203S063000, C203S070000, C549S541000

Reexamination Certificate

active

06582565

ABSTRACT:

FIELD OF THE INVENTION
This invention relates to a process for the recovery and purification of 3,4-epoxy-1-butene (epoxybutene). More specifically, the present invention relates to the separation by extractive distillation of epoxybutene from crude mixtures with close-boiling, pinched, or azeotrope-forming compounds. The invention disclosed herein is of particular interest and utility in the recovery and purification of epoxybutene from mixtures comprising aliphatic and aromatic hydrocarbons containing five to seven carbon atoms having boiling points between about 20° C. and 11 5° C.
DESCRIPTION OF PRIOR ART AND BACKGROUND OF INVENTION
U.S. Pat. Nos. 4,897,498, 4,950,773, and 5,618,954 disclose gas phase epoxidation processes for the production of epoxybutene from molecular oxygen and 1,3-butadiene using silver-based catalysts. U.S. Pat. No. 5,362,890 describes a gas-phase epoxidation process for the production of epoxybutene in which a C2 to C6 paraffinic hydrocarbon is used as gas-phase reaction diluent in order to improve heat transfer and increase the safe oxygen levels in the epoxidation reactor. These patents further disclose that liquid 1,3-butadiene and liquid n-butane/1,3-butadiene mixtures are particularly favorable solvents for the absorptive recovery of epoxybutene from the gaseous effluent of the epoxidation reactor. An epoxide-rich absorbent obtained from the bottom of the absorption column typically comprises 1 to 40 mole percent epoxybutene, 1 to 10 mole percent water, and 30 to 98 mole percent n-butane and 1,3-butadiene. This epoxide-rich absorbent is subjected to further processing steps, i.e., decantation and distillations in order to recover substantially pure epoxybutene and n-butane and 1,3-butadiene that is substantially free of epoxybutene, i.e., less than 5000 ppm by volume of epoxybutene. Since n-butane and 1,3-butadiene have normal boiling points of 0° C. and −2° C., respectively, and do not form close-boiling, pinched, or azeotropic mixtures with epoxybutene, the distillation separations disclosed therein can be accomplished in simple single feed rectification columns.
U.S. Pat. No. 5,945,550 discloses a gas-phase epoxidation process for the production of epoxybutene in which one or more C4 to C10 paraffinic hydrocarbons having high autoiginition temperatures are used as gas-phase reaction diluents in order to improve heat transfer, increase the safe oxygen levels, and substantially increase space-time yield in the epoxidation reactor. Although clearly advantageous for improving reactor performance, many of such C5 to C7 alkane diluents having boiling points between about 20° C. and about 115° C. form close-boiling, pinched, or azeotropic mixtures with epoxybutene. Such mixtures are not amenable to production of epoxybutene in high purity and high recovery in simple single-feed rectification columns.
Furthermore, many alkyl and aryl hydrocarbons, with boiling points between about 20° C. and about 115° C., are useful as absorbents for the recovery of epoxybutene from gas-phase reactor effluents, as extractants of epoxybutene from aqueous streams, and as reaction media for further derivatization of epoxybutene. Examples of such alkyl and aryl hydro-carbons include but are not limited to benzene, toluene, isopentane, n-pentane, n-hexane, n-heptane, and 2,2-dimethylbutane. These compounds also form close-boiling, pinched, or azeotropic mixtures with epoxybutene and thus cannot be separated effectively in simple single-feed rectification columns. Thus there is a need for a process to effectively separate such compounds from epoxybutene.
Relative volatility, &agr;, is defined as the ratio of the equilibrium vapor and liquid compositions of the two components to be separated. Thus,
α
=
y
1
x
1
y
2
x
2
(
1
)
where y
i
is the mole fraction of component i in the vapor phase and x
i
is the mole fraction of the component i in the liquid phase. The normal convention in the art is to define the lower boiling pure component as component 1 and the higher boiling pure component as component 2.
In an azeotropic system, the relative volatility will vary from greater than unity to less than unity as one passes through the azeotropic composition. At mole fractions of the lower boiling component less than the azeotropic composition the relative volatility is greater than unity, while at mole fractions greater than the azeotropic composition the relative volatility is less than unity. At the azeotropic composition, the relative volatility of the components forming the azeotrope is unity. In other words, the vapor and liquid compositions are identical. Since distillation works by differences in vapor and liquid compositions, no further separation is possible by simple distillation once the azeotropic composition is reached, even with an infinite number of equilibrium stages.
In a pinched or close-boiling binary system that shows positive deviations from ideal liquid behavior, the relative volatility will vary from greater than unity at low concentrations of the lower boiling component to close to unity at high concentrations of the lower boiling component. Thus, near the pinch point, the composition of the vapor and liquid phases approach each other, and a large number of equilibrium stages is required for further separation.
Table I shows the effect of relative volatility (&agr;) on theoretical stage requirements in terms of the number of theoretical equilibrium stages required at total reflux for the given degree of separation or purity. In Table I, Separation Purity refers to the mole fraction separation purity of both products.
TABLE I
Relative Volatility
1.00
1.02
1.1
1.2
1.4
1.5
2.0
3.0
Separation Purity
Theoretical Stages at Total Reflux
0.999

697
144
75
40
33
19
12
0.995

534
110
57
30
25
14
9
0.990

463
95
49
26
22
12
7
0.98

392
81
42
22
18
10
6
0.95

296
61
31
16
14
8
4
0.90

221
45
23
12
10
5
3
Rarely is it economical or practical to operate a distillation column with more than about 60 theoretical (typically 70 to 120 actual stages). Thus, for situations where both high purity and high recovery are required, the relative volatility should be greater than about 1.2.
Extractive distillation is a method of separating close boiling, azeotropic, or pinched compounds from each other by conducting the distillation in a two-feed, multi-staged, rectification column in the presence of an added liquid or liquid mixture, said liquid(s) having a boiling point higher than the compounds being separated. The extractive agent or solvent is introduced near the top of the column, above the primary feed stage where the components to be separated are introduced. Since the extractive agent is chosen to be higher boiling than the components to be separated, the agent remains largely in the liquid phase throughout the sections of the column below the stage upon which it is fed. Extractive distillation operates by the exploitation of the selective solvent-induced enhancements or moderations of the liquid-phase nonidealities of the components to be separated. The solvent selectively alters the activity coefficients of the components being separated, thus making a greater degree of separation possible than in the absence of the extractive agent. At the bottom of the extractive distillation column, the less volatile component in the presence of the selected solvent and the extractive distillation solvent itself are removed continuously from the column. The usual methods of separation of these two components are by a second single feed distillation, cooling and phase separation, or solvent extraction. Although the principles of extractive distillation are well-known in the art, there are no a piori methods of determining the efficacy of extractive agents for a given separation, even for those ordinarily skilled in the art.
The usual method of evaluating the efficacy of extractive distillation agents is to measure the change in relative volatility of the compounds to be separated in the absence and presence of the extractive disti

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