Process for fine purification of 1-butenic streams

1. A process for preparing 1-butenic fractions having less than 2000 ppm of isobutene based on the 1-butene from technical mixtures of C 4 hydrocarbons I which contain at least 1-butene and from 2000 ppmw to 8% by mass of isobutene based on the content of 1-butene, comprising the process steps of

a) reacting at least a portion of the isobutene present in a technical mixture I with ethanol in a series of at least one reaction zone or a series of at least two reaction zones in the presence of an acidic catalyst to give ethyl tert-butyl ether,

b) transferring a reactor effluent II of a last reaction zone of said series into a thermal removal in which a fraction III comprising ethyl tert-butyl ether and a fraction IV which comprises 1-butene and ethanol are obtained, and

c) removing said ethanol from fraction IV to obtain a 1-butenic fraction V, and optionally

d) removing any C 4 hydrocarbons other than 1-butene or isobutene which are present in the fraction IV in at least one further separating step to obtain a 1-butenic fraction VI,

wherein a reaction in a first reaction zone in step a) is carried out with an at least threefold molar excess of ethanol based on said isobutene present in mixture I.

2. The process according to claim 1 , wherein said technical mixture of C 4 hydrocarbons I which has a content of 1-butene of greater than 50% by mass is used.

3. The process according to claim 1 , wherein said technical mixture of C 4 hydrocarbons I comprises isobutane, n-butane and/or 2-butenes, and the ethanol-depleted 1-butenic fraction V obtained in process step c) is separated in a further process step d) into a fraction VI which comprises 1-butene and into at least one further stream which comprises at least one compound selected from isobutane, n-butane and 2-butenes.

4. The process according to claim 1 , wherein said 1-butenic fraction V and/or said 1-butenic fraction VI comprise less than 0.5% by mass of 2-butenes.

5. A process according to claim 1 , wherein acid-catalyzed etherification in stage a) is carried out in such a way that at least one reaction zone is designed as a reactive distillation.

6. A process according to claim 1 , wherein acid-catalyzed etherification in stage a) is carried out in such a way that the last reaction zone is designed as a reactive distillation, in which step b) is also carried out.

7. A process according to claim 1 , wherein acid-catalyzed etherification in stage a) is carried out in such a way that no reaction zone is designed as a reactive distillation.

8. A process according to claim 1 , wherein an extraction is carried out in stage c) and the extractant used is selected from the group consisting of water or an aqueous solution.

9. A process according to claim 1 , wherein residual amounts of ethanol present in fractions V or VI are scrubbed out with water in a further extraction step.

10. A process according to claim 1 , wherein said technical mixture I has a content of polyunsaturated compounds of less than or equal to 20 ppm by mass.

11. A process according to claim 1 , wherein polyunsaturated hydrocarbons are present in said technical mixture of C 4 hydrocarbons I which are catalytically hydrogenated in an additional purification stage which is inserted upstream of one or more of process steps a), b), c) or d).

12. A process according to claim 11 , wherein said polyunsaturated compounds are hydrogenated in at least two reaction stages, at least the last reaction stage being carried out in the presence of 0.05 to 100 ppmw of CO.

13. A process according to claim 1 , wherein said acidic catalyst is an ion exchange resin.

14. A process according to claim 1 , wherein reaction in step a) is carried out at a temperature of 30 to 70° C.

15. A process according to claim 1 , wherein reaction in step a) is carried out at a temperature in at least one reaction zone of 30 to 50° C. and a catalyst which has an acid capacity of greater than 3 to 5.5 mol/kg is used, or reaction in step a) is carried out at a temperature of 51 to 70° C. and a catalyst which has an acid capacity of 0.5 to 3 mol/kg is used.

16. A process according to claim 1 , wherein the reaction in step a) is carried out before the distillation step b) with an LHSV of 0.3 to 2.5 m 3 /(m 3 CAT h).

17. A process according to claim 1 , wherein reaction in a first reaction zone in step a) is carried out with a 10- to 15-fold excess of ethanol in relation to the isobutene present in the mixture I.