Separation of alkenes from close-boiling alkanes

Abstract

An extractive distillation process for separatin at least one C.sub.4 -C.sub.10 alkene (monoolefin) from at least one close-boiling alkane employs a solvent mixture of (a) at least one saturated alcohol (preferably cyclohexanol) and either (b1) at least one sulfolane (preferably cyclotetramethylene sulfone) or (b2) at least one glycol compound (preferably tetraethylene glycol) or (b1)+(b2).

Description

BACKGROUND OF THE INVENTION

This invention relates to the separation of alkenes (monoolefins) from close-boiling alkanes (paraffins) by extractive distillation.

Extractive distillation is a well known technique for separating mixtures of components having a relative volatility close to unity (i.e., having nearly equal volatility and having nearly the same boiling point). It is difficult to separate the components of such mixtures by conventional fractional distillation. In extractive distillation, a solvent is introduced into a distillation column above the entry point of the feed mixture which is to be separated. The solvent affects the volatility of the higher boiling feed component(s) sufficiently to facilitate the separation of the various feed components by distillation and exits with the bottoms fraction, as has been described in the article entitled "Extractive Distillation Saves Energy" by Ian Sucksmith, Chemical Engineering, June 28, 1982, pages 91-95. Other literature sources on extractive distillation techniques include the "Handbook of Separation Techniques for Chemical Engineers" by Philip A. Schweitzer, McGraw-Hill Book Company, 1979, pages 1-135 to 1-143; and Perry's Chemical Engineers Handbook, 6th Edition, McGraw-Hill Book Company 1984, pages 13-53 to 13-57.

SUMMARY OF THE INVENTION

It is an object of this invention to provide a process for separating alkenes from close-boiling alkanes by extractive distillation employing a selective solvent (also referred to as extractant or entrainer). Other objects and advantages will be apparent from the detailed description of the invention and the appended claims.

In accordance with this invention, a process for separating at least one alkene containing 4-10 carbon atoms per molecule from at least one close-boiling alkane by extractive distillation of a feed comprising (preferably consisting essentially of) said at least one alkene and said at least one close-boiling alkane employs a solvent comprising (preferably consisting essentially of):

(a) at least one saturated alcohol selected from the group consisting of alkanols and cycloalkanols (latter preferred), wherein said alcohol contains 5-9 carbon atoms and 1 OH group per molecule, and

either (b1) at least one sulfolane compound as defined by Formula 1 in U.S. Pat. No. 4,053,369, wherein said sulfolane compound contains 4-8 carbon atoms per molecule,

or (b2) at least one glycol compound having the general chemical formula of

HO--[CHR.sup.1 --CHR.sup.2 --O].sub.n --CHR.sup.1 --CHR.sup.2 --OH, wherein n can be 0, 1, 2, 3, or 4, and R.sup.1 and R.sup.2 can be independently selected from the group consisting of hydrogen and the methyl group;

or both (b1) and (b2), as defined above.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 illustrates the extractive distillation process of this invention.

DETAILED DESCRIPTION OF THE INVENTION

In an extractive distillation process, an agent (called "solvent" or "extractant" or "entrainer") is added to a feed mixture of components to be separated so that the relative volatilities of the components of the mixture are changed such that a sufficient difference in volatility of the components results and effective separation by distillation becomes possible. The added solvent is usually chosen so as to exhibit high "selectivity" regarding the components to be separated. Selectivity is a term related to the change in volatilities of components in the mixture caused by the presence of the solvent. The larger the difference in relative volatility of the components in the mixture, the easier the separation of the components by fractional distillation becomes. Therefore, a solvent of high selectivity is a solvent which causes great differences between the relative volatilities of the components in a mixture, and will allow for the separation of components in a mixture with fewer distillation stages, lower amount of reflux and higher product purity. The term "close-boiling" as used herein, means that the alkene(s) and the alkane(s) contained in the feed have nearly the same boiling point at atmospheric pressure.

In the process of this invention, any hydrocarbon feed which contains at least one alkene containing 4-10 carbon atoms per molecule and at least one close-boiling alkane (preferably containing 4-10 carbon atoms per molecule) can be used in the extractive distillation process of this invention. Preferably, the boiling points (at atmospheric pressure conditions, i.e., at about 1 atm.) of the alkene(s) and of the alkane(s) to be separated by extractive distillation process of this invention, are in the range of from about 20.degree. to about 350.degree. F., more preferably about 100.degree.-300.degree. F. Generally, the boiling points of the alkene(s) and of the alkane(s)differ by about 0.2.degree.-10.degree. F. (preferably about 0.5.degree.-5.degree. F.), at about 1 atm.

Preferably, the monoolefin (alkene) content in the feed is about 10-95 weight-% (more preferably about 20-80 weight-%), and the alkane content is about 5-90 weight-% (more preferably about 20-80 weight-%).

Non-limiting examples of suitable feed alkanes are n-butane, isobutane, n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,4-dimethylpentane, 2,2,3-trimethylbutane, n-octane, 2-methyloctane, n-nonane, n-decane and the like, and mixtures thereof; in particular n-heptane.

Non-limiting examples of suitable alkenes are 1-butene, 2-butene, 2-methylpropene (isobutene), 1-pentene, 2-pentene, 2-methyl-1-butene, 1-hexene, 2-hexene, 3-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-1-pentene, 2,3-dimethyl-1-butene, 1-heptene, 2-heptene, 3-heptene, 2-methyl-1-hexene, 2-methyl-2-hexene, 3-methyl-2-hexene, 3-methyl-3-hexene, 3,3-dimethyl-1-pentene, 1-octene, 2-octene, 3-octene, 2-methyl-1-heptene, 1-nonene, 2-nonene, 3-nonene, 1-decene, 2-decene, and the like, and mixtures thereof; preferably 2-heptene, in particular cis-2-heptene.

Non-limiting examples of alcohols which are suitable as component (a) of the solvent are: cyclopentanol, 2-methylcyclopentanol, 3-methylcyclopentanol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,3-dimethylcyclohexanol, cycloheptanol, 2-methylcycloheptanol, 3-methylcycloheptanol, 4-methylcycloheptanol, 2,3-dimethylcycloheptanol, n-hexanol, 2-methyl-1-hexanol, 3-methyl-1-hexanol, 3-methyl-2-hexanol, n-heptanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 3-methyl-2-heptanol, 2,3-dimethyl-1-heptanol, n-octanol, mixtures thereof, and the like. Presently preferred is cyclohexanol.

Non-limiting examples of sulfolanes which are suitable as component (b1) of the solvent are: unsubstituted sulfolane (cyclotetramethylene sulfone; also referred to as 2,3,4,5-tetrahydrothiophene-1,1-dioxide), 2-methylsulfolane, 3-methylsulfolane, 2,3-dimethylsulfolane, 2,4-dimethylsulfolane, 2-ethylsulfolane, 2,3,4,5-tetramethylsulfolane, and the like, and mixtures thereof. Presently preferred is unsubstituted sulfolane (cyclotetramethylene sulfone).

Non-limiting examples of glycol compounds which are suitable as component (b2) are: ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol, and mixtures thereof. Presently preferred is tetraethylene glycol.

Any suitable weight ratio of component (a) to component (b1) or (b2) or (b1)+(b2) in the solvent (also called extractant or entrainer) can be employed in the extractive distillation process of this invention. Preferably, the weight ratio of component (a) to component (b1) or (b2) or (b1)+(b2) is in the range of from about 0.1:1 to about 20:1, more preferably from about 0.2:1 to about 5:1. When a combination of (b1)+(b2) is used, any weight ratio of (b1):(b2) is feasible, preferably one being in the range of from about 0.01:1 to about 100:1.

Any suitable weight ratio of the solvent to the hydrocarbon containing feed mixture can be employed. Generally, the solvent to feed weight ratio is in the range of from about 1:1 to about 40:1, preferably in the range of from about 5:1 to about 20:1.

Any suitable reflux ratio (i.e., the weight ratio of the portion of condensed vapor which is returned to the distillation column to the portion of condensed vapor which is withdrawn as distillate product) can be employed in the extractive distillation process of this invention. Generally the reflux ratio is in the range of from about 0.1:1 to about 100:1, preferably in the range of from about 0.5:1 to about 50:1, more preferably in the range of from about 1:1 to about 20:1.

Any suitable feed entry location can be selected. Generally the feed entry location is in the range of from about 2 to about 70 percent of the total height of the packed or trayed column, measured upward from the bottom of the column, preferably in the range of from about 5 to about 60 percent, more preferably in the range of from about 7 to about 70 percent.

Any suitable solvent entry location can be selected. Generally the solvent entry location is in the range of from about 50 to about 99 percent of the total height of the packed or trayed column (i.e., within the upper half of the column), preferably in the range of from about 70 to about 99 percent, more preferably in the range of from about 80 to about 99 percent.

Any suitable temperature in the reboiler vessel (containing primarily the higher boiling feed components and the solvent) can be employed. The temperature is generally in the range of from about 100.degree. to about 400.degree. F., preferably in the range of from about 150.degree. to about 320.degree. F. The extractive distillation column is generally heated (more near the bottom, and less near the top). Generally, the temperature at the top of the column where the vapor exists into the condenser is in the range of from about 100.degree. to about 300.degree. F., preferably in the range of from about 150.degree. to about 250.degree. F. Solvent and feed are generally preheated (generally to a temperature close to the column temperature of the corresponding entry point) before they are introduced into the column. Any suitable pressure can be employed during the extractive distillation. Generally the pressure is about 5 to about 100 psig, preferably about 8 to about 20 psig.

The overhead distillate product (withdrawn from the top of the column) generally contains a smaller volume percentage of the alkene(s) than the feed and a larger volume percentage of alkane(s) than the feed. Generally, the bottoms product (a portion of which can be reheated and recycled to the lower portion of the column) contains more of the alkene(s) than the feed, and less of the alkane(s) than the feed. Furthermore, the bottoms product contains essentially all of the added solvent, which can be separated from the other bottoms product components by distillation or other suitable separating means and then be recycled to the extractive distillation column.

Any suitable total column height, packed column height, column diameter and number of trays in the extraction distillation column can be employed. The exact dimensions and column designs depend on the scale of the operation, the exact feed composition, the exact solvent composition, the desired recovery and degree of purity of the various product, and the like, and can be determined by those having ordinary skills in the art.

The invention can be better understood by reference to FIG. 1 and the following description of a preferred embodiment of the invention. The feed mixture comprising alkene(s) and close-boiling alkane(s) is introduced through conduit 10 to a fractionation zone such as multi-stage distillation column 12. The temperature of the feed mixture flowing through conduit 10 can be adjusted as needed by controlling heat exchanger 14 so as to add heat to or remove heat from the feed mixture. Solvent from solvent storage 6 is introduced to distillation column 12 through conduit 8, and an overhead stream enriched in alkane(s) is withdrawn from an upper portion of distillation column 12 through conduit 16. This overhead stream can be completely passed to storage or to other processing units or, as is often the case, the overhead stream can be partially or totally condensed, with a portion thereof being returned to the fractionation zone as reflux. The overhead stream passing through conduit 16 is condensed in condenser 22 to yield a condensed overhead stream. A portion of the condensed overhead stream can be returned to distillation column 12 as reflux through conduit 18, while the remainder of the condensed overhead stream is yielded as product or passed to other processing units through conduit 20.

A bottoms stream is withdrawn from a lower portion of the fractionation zone represented by distillation column 12 through conduit 24. A portion of the fluids withdrawn from the bottom of distillation column 12 may be heated and returned to distillation column 12. For example, a portion of the bottoms product stream can be withdrawn through conduit 25, heated in reboiler 26 and then passed back to a lower portion of distillation column 12 through conduit 27.

Operating conditions in heat exchanger 14, condenser 22 and reboiler 26 can be controlled and interfaced with solvent flow through conduit 8, feed mixture flow through conduit 10, reflux flow through conduit18 and bottoms stream flow through conduit 24 such that the feed mixture introduced into distillation column 12 will be fractionated to yield an overhead stream which is enriched in alkane(s) and a bottoms stream predominantly comprising the alkene(s) and the solvent.

The bottoms stream passing through conduit 24 can be passed to storage, used in other processes or, preferably, passed to another fractionation zone, such as distillation column 29. Any adjustments to the temperature of the bottoms stream passing through conduit 24 necessary for efficient fractionation in distillation column 29 can be made by appropriately adjusting heat exchanger 28. An overhead stream predominantly comprising alkene(s) is withdrawn from an upper portion of distillation column 29 through conduit 30. This overhead stream can be at least partially condensed in condenser 32. A portion of the overhead stream withdrawn from condenser 32 can be returned through conduit 34 as reflux for distillation column 29, with the remainder of the overhead stream being withdrawn as product, i.e., alkene(s) of high purity (preferably higher than 95%), through conduit 36.

A bottoms stream predominantly comprising the solvent is withdrawn from a lower portion of distillation column 29 through conduit 38. A portion of this bottoms stream is preferably routed back to solvent storage 6 and then recycled to distillation column 12, while another portion of the bottoms stream is heated in a reboiler (not shown) and returned to the lower portion of column 29. From time to time, impurities which may build up in the solvent can be removed from the system by removing a small purge stream through conduit 40. Solvent lost through the purge stream or through other processing losses may be made up by a makeup stream passing through conduit 42 and into solvent storage 6.

The following examples are presented to further illustrate the invention and are not to be considered unduly limiting the scope of this invention.

EXAMPLE I

This example demonstrates the superiority as solvent of a cyclohexanol/tetraethylene glycol mixture versus cyclohexanol alone or tetraethylene glycol alone in the extractive distillation of an alkene/alkane feed.

To a hydrocarbon mixture of 50 weight-% cis-2-heptene and 50 weight-% n-heptane was added an extractive solvent (either cyclohexanol or tetraethylene glycol or a mixture of 25 weight-% cyclohexanol and 75 weight-% tetraethylene glycol) at various solvent:feed weight ratios. The total mixture (including the extractive solvent) was heated under reflux conditions for about 20-30 minutes in a distillation flask equipped with a reflux condenser. Then a small sample was withdrawn by means of a septum from the flask containing the liquid phase of the equilibrium system, and a sample of the condensed vapor was withdrawn by means of a septum located just below the reflux condenser. Both samples were analyzed, and the mole fractions of cis-2-heptene and n-heptane in the liquid phase and in the vapor phase were determined by means of a gas chromatograph. The relative volatility R was calculated as follows: ##EQU1## wherein Y1 and Y2 are the mole fractions of n-heptane and cis-2-heptene, respectively, in the vapor phase; and X1 and X2 are the mole fractions of n-heptene and cis-2-heptene, respectively, in the liquid phase. Test results are summarized in Table I.

TABLE I______________________________________ RelativeSolvent:Feed Added VolatilityWeight Ratio Solvent R______________________________________5:1 TEG.sup.1 1.105:1 Cyclohexanol 1.175:1 Cyclohexanol + TEG.sup.2 1.237:1 TEG.sup.1 1.147:1 Cyclohexanol 1.187:1 Cyclohexanol + TEG.sup.2 1.28______________________________________ .sup.1 tetraethylene glycol .sup.2 mixture of 25 weight % Cyclohexanol and 75 weight % tetraethylene glycol.

Based on the test results in Table I, it is concluded that cyclohexanol/tetraethylene glycol mixtures would be more effective than tetraethylene glycol or cyclohexanol alone as solvent in the extractive distillation of feeds containing C.sub.4 -C.sub.10 alkenes and close-boiling alkane(s), in particular at commercially most feasible solvent: feed weight ratios of about 5:1 and higher. Additional tests (not herein described in detail) indicated that the TEG/cyclohexanol solvent mixture can be successfully used in the extractive distillation of a mixed feed which contains 4-methyl-1-pentene and n-hexane.

EXAMPLE II

This example demonstrates the superiority as solvent of a cyclohexanol/sulfolane mixture versus cyclohexanol alone or sulfolane alone in the extractive distillation of an alkene/alkane feed.

Tests were carried out substantially in accordance with the procedure described in Example I, except that unsubstituted sulfolane (cyclotetramethylene sulfone, hereinafter referred to as "sulfolane") and a solvent mixture of 50 weight-% cyclohexanol and 50 weight-% sulfolane were used. Test results are summarized in Table II.

TABLE II______________________________________Solvent:Feed Added RelativeWeight Ratio Solvent Volatility R______________________________________5:1 Sulfolane 1.175:1 Cyclohexanol 1.175:1 Cyclohexanol + Sulfolane 1.277:1 Sulfolane 1.207:1 Cyclohexanol 1.187:1 Cyclohexanol + Sulfolane 1.30______________________________________

Based on test results in Table II, it is concluded that cyclohexanol/sulfolane mixtures would be more effective than cyclohexanol or sulfolane alone as solvent in the extractive distillation of feeds C.sub.4 -C.sub.10 alkene(s) and close-boiling alkane(s), especially at a solvent: feed ratio of about 5:1 and higher.

Reasonable variations, modifications and adaptations for various usages and conditions can be made within the scope of the disclosure and the appended claims, without departing from the scope of this invention.

Claims

1. A process for separating at least one alkene containing 4-10 carbon atoms per molecule from at least one close-boiling alkane by extractive distillation of a feed consisting essentially of said at least one alkene and said at least one alkane in the presence of a solvent consisting essentially of a mixture of

(a) at least one saturated alcohol selected from the group consisting of alkanols and cycloalkanols containing 5-9 carbon atoms and 1 OH group per molecule, and

(b1) at least one sulfolane compound containing 4-8 carbon atoms per molecule;

wherein said extractive distillation process produces (i) an overhead distillate product which contains a smaller volume percentage of said at least one alkene and a larger volume percentage of said at least one alkane than said feed, and (ii) a bottoms product which contains said solvent and a larger volume percentage of said at least one alkene and a smaller volume percentage of said at least one alkane than said feed; and wherein said at least one alkene is separated from said solvent and recovered from said bottoms product.

2. A process in accordance with claim 1, wherein said at least one saturated alcohol is a cycloalkanol.

3. A process in accordance with claim 1, wherein said at least one saturated alcohol is cyclohexanol and said at least one sulfolane compound is cyclotetramethylene sulfone.

4. A process in accordance with claim 1, wherein the weight ratio of component (a) to component (b1) in said solvent is in the range of from about 0.1:1 to about 20:1.

5. A process in accordance with claim 1, wherein said at least one alkane in said feed contains 4-10 carbon atoms per molecule.

6. A process in accordance with claim 1, wherein said at least one alkene in said feed is cis-2-heptene, and said at least one alkane is n-heptane.

7. A process in accordance with claim 1, wherein the weight ratio of said solvent to said feed is in the range of from about 5:1 to about 20:1.

8. A process in accordance with claim 1, wherein said feed boils at a temperature in the range of from about 20.degree. F. to about 350.degree. F., at a pressure of about 1 atm.

9. A process in accordance with claim 1, wherein the boiling point of said at least one alkene and the boiling point of said at least one alkane differ from 0.2.degree. to about 10.degree. F., at a pressure of about 1 atm.

10. A process for separating at least one alkene containing 4-10 carbon atoms per molecule from at least one close-boiling alkane by extractive distillation of a feed consisting essentially of said at least one alkene and said at least one alkane in the presence of a solvent consisting essentially of a mixture of

(a) at least one saturated alcohol selected from the group consisting of alkanols and cycloalkanols containing 5-9 carbon atoms and 1 OH group per molecule, and

(b2) at least one glycol compound having the general chemical formula of

HO--[CHR.sup.1 --CHR.sup.2 --O].sub.n --CHR.sup.1 --CHR.sup.2 --OH,

wherein n can be 0, 1, 2, 3, or 4, and R.sup.1 and R.sup.2 can be independently selected from the group consisting of hydrogen and methyl;

wherein said extractive distillation process produces (i) an overhead distillate product which contains a smaller volume percentage of said at least one alkene and a larger volume percentage of said at least one alkane than said feed, and (ii) a bottoms product which contains said solvent and a larger volume percentage of said at least one alkene and a smaller volume percentage of said at least one alkane than said feed; and wherein said at least one alkene is separated from said solvent and recovered from said bottoms product.

11. A process in accordance with claim 10, wherein said at least one saturated alcohol is a cycloalkanol.

12. A process in accordance with claim 10, wherein said at least one glycol compound is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.

13. A process in accordance with claim 10, wherein said at least one saturated alcohol is cyclohexanol and said at least one glycol compound is tetraethylene glycol.

14. A process in accordance with claim 10, wherein the weight ratio of component (a) to component (b2) in said solvent is in the range of from about 0.1:1 to about 20:1.

15. A process in accordance with claim 10, wherein said at least one alkane in said feed contains 4-10 carbon atoms per molecule.

16. A process in accordance with claim 10, wherein said at least one alkene in said feed is cis-2-heptene, and said at least one alkane is n-heptane.

17. A process in accordance with claim 10, wherein the weight ratio of said solvent to said feed is in the range of from about 5:1 to about 20:1.

18. A process in accordance with claim 10, wherein said feed boils at a temperature in the range of from about 20.degree. F. to about 350.degree. F., at a pressure of about 1 atm.

19. A process in accordance with claim 10, wherein the boiling point of said at least one alkene and the boiling point of said at least one alkane differ from 0.2.degree. to about 10.degree. F., at a pressure of about 1 atm.

20. A process for separating at least one alkene containing 4-10 carbon atoms per molecule from at least one close-boiling alkane by extractive distillation of a feed consisting essentially of said at least one alkene and said at least one alkane in the presence of a solvent consisting essentially of a mixture of

(a) at least one saturated alcohol selected from the group consisting of alkanols and cycloalkanols containing 5-9 carbon atoms and 1 OH group per molecule,

(b1) at least one sulfolane compound containing 4-8 carbon atoms per molecule, and

(b2) at least one glycol compound having the general chemical formula of

HO--[CHR.sup.1 --CHR.sup.2 --O].sub.n --CHR.sup.1 --CHR.sup.2 --OH,

wherein n can be 0, 1, 2, 3, or 4, and R.sup.1 and R.sup.2 can be independently selected from the group consisting of hydrogen and methyl;

wherein said extractive distillation process produces (i) an overhead distillate product which contains a smaller volume percentage of said at least one alkene and a larger volume percentage of said at least one alkane than said feed, and (ii) a bottoms product which contains said solvent and a larger volume percentage of said at least one alkene and a smaller volume percentage of said at least one alkane than said feed; and wherein said at least one alkene is separated from said solvent and recovered from said bottoms product.

21. A process in accordance with claim 20, wherein said at least one saturated alcohol is a cycloalkanol.

22. A process in accordance with claim 21, wherein said at least one sulfolane compound is cyclotetramethylene sulfone.

23. A process in accordance with claim 22, wherein said at least one glycol compound is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.

24. A process in accordance with claim 20, wherein the weight ratio of component (a) to components (b1)+(b2) in said solvent is in the range of from about 0.1:1 to about 20:1.

25. A process in accordance with claim 20, wherein said at least one alkane in said feed contains 4-10 carbon atoms per molecule.

26. A process in accordance with claim 20, wherein said at least one alkene in said feed is cis-2-heptene, and said at least one alkane is n-heptane.

27. A process in accordance with claim 20, wherein the weight ratio of said solvent to said feed is in the range of from about 5:1 to about 20:1.

28. A process in accordance with claim 20, wherein said feed boils at a temperature in the range of from about 20.degree. F. to about 350.degree. F., at a pressure of about 1 atm.