PROCESS FOR THE PRODUCTION OF OLIGOMERIZED OLEFINS

Abstract

A process for the production of oligomerized olefins comprising the following steps: purification of an organic composition (OC1) in at least one adsorber to obtain an organic composition (OC2); oligomerization of organic composition (OC2) in the presence of a catalyst to obtain an organic composition (OC3); distillation of organic composition (OC3) in a distillation column (D1) to obtain an organic composition (OC4) from the upper part of (D1) and an organic composition (OC5) from the lower part of (D1); hydrogenation of organic composition (OC4) to obtain an organic composition (OC1 1) and regeneration of an adsorber (A1) employing organic composition (OC11) as regeneration media.

Claims

1. A process for the production of oligomerized olefins comprising the following steps a) to e): a) purification of an organic composition (OC1) comprising at least one alkane, at least one olefin and at least one compound containing oxygen and/or sulfur wherein (OC1) is fed into at least one adsorber in order to obtain an organic composition (OC2) comprising at least one alkane, at least one olefin and a reduced amount of at least one compound containing oxygen or sulfur compared to the respective amount in organic composition (OC1), b) oligomerization of organic composition (OC2) in the presence of a catalyst, wherein at least one of the olefins of (OC2) is at least partially oligomerized, obtaining an organic composition (OC3) comprising a reduced amount of at least one olefin and an increased amount of at least one oligomerized olefin, compared to the respective amounts in (OC2); c) distillation of organic composition (OC3) in a distillation column (D1), wherein i) an organic composition (OC4) is obtained from the upper part of (D1) and (OC4) comprises at least one alkane, at least one olefin and a reduced amount of at least one oligomerized olefin compared to the respective amount in (OC3), ii) an organic composition (OC5) is obtained from the lower part of (D1) and (OC5) comprises at least 80% by weight, preferably at least 95% by weight of the at least one oligomerized olefin present in organic composition (OC3); d) hydrogenation of organic composition (OC4) to obtain an organic composition (OC11) comprising at least one alkane and a further reduced amount of the at least one olefin or of the at least one oligomerized olefin compared to organic composition (OC4), and e) regeneration of an adsorber (A1) employing organic composition (OC11) as regeneration media.

2. The process according to claim 1, wherein i) the oligomerization according to step b) is a dimerization, or ii) the olefin in the organic composition (OC2) is butene, which is at least partially dimerized to octene.

3. The process according to claim 1, wherein the at least one adsorber in step a) is an adsorber (A1) and at least one further adsorber (A2) is present in the process, and adsorber (A2) is regenerated according to step e).

4. The process according to claim 3, wherein the adsorbers (A1) and (A2) are operated in parallel and (A1) is in operation mode according to step a), while (A2) is in regeneration mode according to step e).

5. The process according to claim 1, wherein prior to step d) an additional step f) is carried out, comprising f) distillation of organic composition (OC4) in a distillation column (D2), wherein i) an organic composition (OC2a) is obtained from the upper part of (D2) and (OC2a) comprises at least one alkane and an reduced amount of at least one olefin compared to the respective amount in (OC2), (OC3) or (OC4), with use of (OC2a) rather than (OC4) in the subsequent steps; ii) an organic composition (OC6) is obtained from the lower part of (D2) and (OC6) comprises at least 80% by weight of the olefins present in (OC2), (OC3) or (OC4).

6. The process according to claim 1, wherein prior to step b), an additional step g) is carried out, comprising g) feeding organic composition (OC2) into a further adsorber (SA), to further lower the amount of sulfur containing compounds in order to obtain an organic composition (OC7), wherein the amount of sulfur containing compounds is lower than in (OC2), with use of (OC7) rather than (OC2) in the subsequent steps.

7. The process according to claim 1, wherein the organic compositions (OC1) and (OC2) additionally comprise at least one diene and prior to step b), an additional step h) is carried out, comprising h) at least partial conversion of residual dienes in organic composition (OC2), into monoolefins by selective monohydrogenation, to obtain an organic composition (OC8) wherein the amount of dienes is lower and the amount of monoolefins higher compared to the amount in (OC2), with use of (OC8) rather than (OC2) in the subsequent steps.

8. The process according to claim 1, wherein the organic composition (OC1) additionally comprises at least one halogen or halogen-containing compound, and prior to step a) an additional step i) is carried out, comprising i) feeding organic composition (OC1) into a chloride adsorber (ClA) in order to obtain an organic composition (OC9) wherein the amount of halogen, or the amount of halogen-containing compounds, is lowered compared to (OC1), with use of (OC9) rather than (OC1) in the subsequent steps.

9. The process according to claim 1, wherein the organic composition (OC1) additionally comprises water and prior to step a) an additional step j) is carried out, comprising j) lowering the water content in organic composition (OC1), obtaining an organic composition (OC10), with use of (OC10) rather than (OC1) in subsequent steps.

10. The process according to claim 1, wherein organic composition (OC11) comprises butane and butene.

11. The process according to claim 1, wherein i) the alkane in organic composition (OC1) is butane and the olefin in (OC1) is butene, or ii) the organic compositions (OC1), (OC2), (OC7), (OC8), (OC9), and (OC10) comprise linear and branched alkanes or olefins, or iii) the organic compositions (OC3) and (OC5) comprise octene, or iv) the organic composition (OC1) comprises at least 20 wt-% of the at least one olefin, or at least 20 wt-% of the at least one alkane, or v) the organic composition (OC3) comprises at least 5 wt-% of octane, or vi) the organic composition (OC1) comprises at most 1 wt-% of compounds containing oxygen or sulfur, or vii) the organic composition (OC1) comprises at least 15 wt-ppm of at least one compound containing oxygen or sulfur, or viii) the organic composition (OC2) comprises not more than 10 wt-ppm of compounds containing oxygen or sulfur, or ix) the organic composition (OC3) comprises not more than 5 wt-ppm of compounds containing oxygen or sulfur, or x) the organic composition (OC8) comprises not more than 1 wt-% of dienes, or at least 20 wt-% of monoolefins, or xi) the organic composition (OC9) comprises not more than 50 wt-ppm of halogen or halogen containing compounds, or xii) the organic composition (OC4) comprises at least 20 wt-% alkane, and not more than 5 wt-% oligomerized olefin, preferably octene, or xiii) the water content in the organic composition (OC10) is lower than 5 wt-ppm, or xiv) organic composition (OC11) comprises not more than 1000 wt-ppm olefin, or xv) organic composition (OC2a) comprises at least 96 wt-% butane and not more than 4 wt-% butene.

12. The process according to claim 1, wherein the oligomerization in step b) is carried out i) with a catalyst comprising 10 to 70 wt-% NiO, 5 to 30 wt-% TiO.sub.2 or ZrO.sub.2, 0 to 20 wt-% A10, 20 to 40 wt-% SiO.sub.2 and 0.01 to 1 wt-% of an alkali metal oxide, or ii) at a pressure of 10 to 300 bar, or iii) at a temperature of 20 to 280° C., or iv) adiabatically, without additional measures taken for cooling by a heat exchange medium, or v) in a fixed bed process.

13. The process according to claim 1, wherein distillation column (D1) or distillation column (D2) serve the purpose of removing iso-butane and the respective organic composition fed into (D1) or (D2) comprises butane or butene.

14. The process according to claim 7, wherein no additional carbon monoxide is added.

15. The process according to claim 1, wherein the adsorbent in the absorbers (A1) or (A2) is based on a molecular sieve or aluminum oxide, or the absorbers can be employed for the adsorption of compounds containing oxygen or sulfur out of organic compositions.

16. The process according to claim 5, wherein step a) is carried out prior to step b), step b) is followed by step c), step c) is followed by step f), step f) is followed by step d) and step d) is followed by step e).

17. The process according to claim 6, step a) is followed by step g), step g) is carried out prior to step b), step b) is followed by step c), step c) is followed by step f), step f) is followed by step d) and step d) is followed by step e).

18. The process according to claim 7, wherein step a) is followed by step g), step g) is followed by step h), step h) is followed by step b), step b) is followed by step c), step c) is followed by step f), step f) is followed by step d) and step d) is followed by step e).

19. The process according to claim 8, wherein step i) is carried out prior to step a), step a) is followed by step g), step g) is followed by step h), step h) is followed by step b), step b) is followed by step c), step c) is followed by step f), step f) is followed by step d) and step d) is followed by step e).

20. The process according to claim 9, wherein step j) is carried out prior to step i), step i) is carried out prior to step a), step a) is followed by step g), step g) is followed by step h), step h) is followed by step b), step b) is followed by step c), step c) is followed by step f), step f) is followed by step d) and step d) is followed by step e).

21. The process according to claim 10, wherein (OC11) comprises at least 96 wt-% butane and not more than 4 wt-% butene.

22. The process according to claim 11, wherein i) the olefin in (OC1) comprises butene or the alkane in (OC1) comprises butane, or ii) the diene in (OC8) comprises not more than 1% of butadiene or (OC8) comprises butane as monoolefin, or iii) (OC4) comprises at least 96 wt-% butane and not more than 4 wt-% butane.

Description

FIGURES

[0156] FIGS. 1 to 3 illustrate certain aspects of the invention. For the sake of clarity not all applicable components and embodiments are drawn in one and/or all figures. Embodiments shown in different figures may be combined with each other and do not exclude the incorporation of further components within the limits of the disclosure of the specification.

[0157] FIG. 1 illustrates the most basic assembly of the present invention. Organic composition (OC1) comprising at least one alkane and/or at least one olefin and at least one compound containing oxygen and/or sulphur is fed into adsorber (A1), run in operation mode, in order to obtain an composition (OC2) comprising at least one alkane and/or at least one olefin and a reduced amount of at least one compound containing oxygen and/or sulphur compared to the respective amount in organic composition (OC1).

[0158] The organic composition (OC2) is subsequently fed into an oligomerization reactor (OR) wherein at least one of the olefins is at least partially oligomerized, obtaining an organic composition (OC3) comprising a reduced amount of at least one olefin and an increased amount of at least one oligomerized olefin, compared to the respective amounts in (OC2).

[0159] Organic composition (OC3) is fed into distillation column (D1) and an organic composition (OC4) comprising at least one alkane, at least one olefin and an reduced amount of at least one oligomerized olefin compared to the respective amount in (OC3) is obtained from the upper part of (D1). From the lower part of (D1) an organic composition (OC5) is obtained comprising at least 80% by weight, preferably at least 95% by weight of the at least one oligomerized olefin present in organic composition (OC3).

[0160] (OC4) is subjected to a hydrogenation in a hydrogenation reactor (HR) yielding an organic composition (OC11) comprising at least one alkane and a further reduced amount of the at least one olefin and the at least one oligomerized olefin compared to organic composition (OC4).

[0161] Organic composition (OC11) is used as regeneration media in adsorber (A1) only when (A1) is operated in regeneration mode. (OC11B) leaving the adsorber during regeneration mode (dotted arrow), preferably at the opposite side of its entrance in the adsorber (A1), may comprise a higher amount of compounds containing oxygen and/or sulphur than the organic composition (OC11) fed into the adsorber.

[0162] FIG. 2 shows an embodiment of the invention in which two adsorbers (A1) and (A2) are incorporated in the process operated in parallel. One adsorber may be operated in operation mode at the same time as the other adsorber is run in regeneration mode When the respective adsorber is operated in regeneration mode organic composition (OC11) is fed into the adsorber. When the adsorber is operated in operation mode, organic composition (OC1) is fed into the adsorber.

[0163] In FIG. 3 the embodiment in FIG. 1 is extended by further process steps. Before being fed into adsorber (A1) organic composition is dewatered in a dewatering unit (DW) resulting in an organic composition (OC10) with a lower water content compared to (OC1), subjected to a chlorine removal procedure in chlorine adsorber (CIA) yielding organic composition (OC9) with a lower chlorine content compared to (OC10).

[0164] (OC9) is subsequently passed through adsorber (A1).

[0165] Organic composition (OC2) is routed through a sulfur adsorber (SA) to obtain an organic composition (OC7) wherein the amount of sulfur containing compounds is lower than in (OC2).

[0166] (OC7) is fed into a diene mono-hydrogenation reactor (DMHR) in order to lower the content of dienes, resulting in an organic composition (OC8) being used in the oligomerization step in oligomerization reactor (OR).

[0167] Instead of organic composition (OC4), an organic composition (OC2a) comprising at least one alkane and a reduced amount of at least one olefin compared to the respective amount in (OC2), (OC3) or (OC4) is subjected to hydrogenation in hydrogenation reactor (HR). (OC2a) is the result of a distillation of (OC4) in a distillation column (D2) and obtained in the upper part of the column, besides an organic composition (OC6) obtained in the lower part of the column comprising at least 80% by weight, preferably at least 90% by weight of the olefins present in (OC2), (OC3) or (OC4).