OLIGOBUTYL BENZENE SULFONATE FOR LUBRICANTS AND FUELS

Abstract

The present invention relates to a method for preparing an oligobutyl benzene sulfonate comprising the steps of oligomerization of a butene mix comprising 1-butene and 2-butene to produce an alkene blend which comprises oligobutenes with a molecular weight of 220 to 2000 g/mol, alkylation of benzene with the alkene blend to produce an oligobutyl benzene, sulfonation of the oligobutyl benzene to produce a oligobutyl benzene sulfonic acid, and neutralizing the oligobutyl benzene sulfonic acid to produce the oligobutyl benzene sulfonate. The invention also relates to the oligobutyl benzene sulfonate obtainable by the method; to the oligobutyl benzene sulfonic acid obtainable by the method; to the oligobutyl benzene obtainable by the method; to the lubricant comprising the oligobutyl benzene sulfonate; to a fuel comprising the oligobutyl benzene sulfonate; and to a use of the oligobutyl benzene sulfonate as lubricant additive or fuel additive.

Claims

1.-17. (canceled)

18. A method for preparing an oligobutyl benzene sulfonate comprising the steps of i) oligomerization of a butene mix comprising 1-butene and 2-butene to produce an alkene blend which comprises oligobutenes with a molecular weight of 220 to 2000 g/mol, ii) alkylation of benzene with the alkene blend to produce an oligobutyl benzene, iii) sulfonation of the oligobutyl benzene to produce an oligobutyl benzene sulfonic acid, and iv) neutralizing the oligobutyl benzene sulfonic acid to produce the oligobutyl benzene sulfonate.

19. The method according to claim 18, wherein the oligobutenes have a molecular weight from 220 to 1000 g/mol, 220 to 700 g/mol, 220 to 500 g/mol, or 220 to 350 g/mol.

20. The method according to claim 18, wherein the butene mix contains from 20 to 99 wt %, based on the total olefin content, of 1-butene and 2-butene.

21. The method according to claim 18, wherein the butene mix comprises: from 0.5 to 5% by weight of isobutane, from 5 to 20% by weight of n-butane, from 20 to 40% by weight of trans-2-butene, from 10 to 20% by weight of cis-2-butene, from 25 to 55% by weight of 1-butene, and from 0.5 to 5% by weight of isobutene.

22. The method according to claim 18, wherein the butene mix is obtainable from a raffinate II.

23. The method according to claim 18, wherein the alkene blend comprises C.sub.16 alkenes, C.sub.20 alkenes, and C.sub.24 alkenes.

24. The method according to claim 18, wherein the alkene blend comprises: 20-85 wt % of the C.sub.16 alkenes, 5-30 wt % of the C.sub.20 alkenes, and 2-20 wt % of the C.sub.24 alkenes.

25. The method according to claim 18, wherein the alkene blend comprises terminal unsaturated C.sub.16 alkenes, terminal unsaturated C.sub.20 alkenes, and terminal unsaturated C.sub.24 alkenes.

26. The method according to claim 18, wherein the alkene blend is obtainable by oligomerization in the presence of a nickel containing heterogenous catalyst.

27. The method according to claim 18, wherein the sulfonic acid group in the oligobutyl benzene sulfonic acid is in para position to the oligobutyl group.

28. An oligobutyl benzene sulfonate obtainable by the method as defined in claim 18.

29. The oligobutyl benzene sulfonate according to claim 28, in form of a neutral or overbased alkali metal salt, earth alkali metal salt or ammonium salt.

30. A oligobutyl benzene sulfonic acid obtainable by the method as defined in claim 18.

31. A oligobutyl benzene obtainable by the method as defined in claim 18.

32. A lubricant comprising the oligobutyl benzene sulfonate as defined in claim 28.

33. A fuel comprising the oligobutyl benzene sulfonate as defined in claim 28.

34. A use of the oligobutyl benzene sulfonate as defined in claim 28 as lubricant additive or fuel additive.

Description

EXAMPLES

Example 1Oligomerization of Butene Mix

[0392] An alkene blend is prepared starting from a butene mix which is obtained from a raffinate II stream. The butene mix comprises about [0393] isobutane: 3% by weight [0394] n-butane: 15% by weight [0395] isobutene: 2% by weight [0396] 1-butene: 30% by weight [0397] trans-2-butene: 32% by weight [0398] cis-2-butene: 18% by weight.

[0399] The butene mix is oligomerized in the presence of a nickel containing heterogenous catalyst in an isothermally operated reactor having a length of about 1.5 m and a diameter of 30 mm at 20 bar and 80 C.

[0400] The nickel containing heterogenous catalyst is a material which is produced as described in WO1995/14647 in the form of pellets (5 mm5 mm). The composition in % by weight of the active components is typically: 50% by weight of NiO, 12.5% by weight of TiO.sub.2, 33.5% by weight of SiO.sub.2, 4% by weight of Al.sub.2O.sub.3.

[0401] The throughput is 0.75 kg of raffinate II/(I(cat)h). The reaction is carried out without recirculation of C.sub.4-hydrocarbons. The C.sub.4 conversion, based on the butenes comprised in the raffinate II is about 52.0% by weight. The selectivity in % by weight in the alkene blend is as follows: C.sub.8 alkenes: 76.9; C.sub.12 alkenes: 18.4 and C.sub.16 and higher alkenes: 4.7.

[0402] 2.0 kg of this alkene blend are subjected to fractionation over an 80 cm packed column (wire-mesh coils) with a reflux ratio of 1:5 to yield: [0403] 1.45 kg Fraction A (comprising mainly C.sub.8 alkenes) with boiling interval 100-130 C. at 950 mbar [0404] 0.35 kg Fraction B (comprising mainly C.sub.12 alkenes) with boiling interval 100-130 C. at 950 mbar [0405] 0.18 kg Fraction C (comprising mainly C.sub.16 and higher alkenes) in the distillation bottom.

[0406] According to GC analysis, Fraction C consists of 7% C.sub.12 alkenes, 70% C.sub.16 alkenes, 17% C.sub.20 alkenes, and 6% C.sub.24 and higher alkenes.

Example 2Alkylation of Benzene With Fraction C Alkene Blend

[0407] An oligobutyl benzene is prepared starting from benzene and Fraction C of Example 1, which contains the following oligobutenes: [0408] 7% C.sub.12 alkenes [0409] 70% C.sub.16 alkenes [0410] 17% C.sub.20 alkenes, and [0411] 6% C.sub.24 and higher alkenes.

[0412] The alkylation catalyst is a zeolite and the Friedel-Crafts alkylation is successfully made to produce the corresponding oligobutyl benzene.

Example 3-Alkylation of Benzene With Alkene Blend of Fraction B and C

[0413] An oligobutyl benzene is prepared starting from benzene and a mixture of Fraction B and Fraction C of Example 1, which contains the following oligobutenes: [0414] 38% C.sub.12 alkenes [0415] 43% C.sub.16 alkenes [0416] 13% C.sub.20 alkenes, and [0417] 6% C.sub.24 and higher alkenes.

[0418] The alkylation catalyst is a zeolite and the Friedel-Crafts alkylation is successfully made to produce the corresponding oligobutyl benzene.

Example 4Sulfonation of Oligobutylbenzene of Example 2

[0419] An oligobutyl benzene sulfonic acid is prepared by sulfonation of the oligobutyl benzene from Example 2. The sulfonation is effected by reacting the oligobutyl benzene with sulfur trioxide. The sulfonic acid group is mainly in para position to the oligobutyl group, which can be determined by H-NMR.

Example 5Sulfonation of Oligobutylbenzene of Example 3

[0420] An oligobutyl benzene sulfonic acid is prepared by sulfonation of the oligobutyl benzene from Example 2. The sulfonation is effected by reacting the oligobutyl benzene with sulfur trioxide. The sulfonic acid group is mainly in para position to the oligobutyl group, which can be determined by H-NMR.

Example 6Sulfonates by Neutralization

[0421] The oligobutyl benzene sulfonic acid from Example 4 is neutralized with equimolar amounts of [0422] calcium hydroxide to yield oligobutyl benzene sulfonate calcium salt. [0423] magnesium carbonate to yield oligobutyl benzene sulfonate magnesium salt.

[0424] To make overbased sulfonates the oligobutyl benzene sulfonic acid from Example 4 is is neutralized with a molar excess of [0425] calcium hydroxide to yield overbased oligobutyl benzene sulfonate calcium salt. [0426] magnesium carbonate to yield overbased oligobutyl benzene sulfonate magnesium salt.

Example 7Sulfonates by Neutralization

[0427] The oligobutyl benzene sulfonic acid from Example 5 is neutralized with equimolar amounts of [0428] calcium hydroxide to yield oligobutyl benzene sulfonate calcium salt. [0429] magnesium carbonate to yield oligobutyl benzene sulfonate magnesium salt.

[0430] To make overbased sulfonates the oligobutyl benzene sulfonic acid from Example 5 is is neutralized with a molar excess of [0431] calcium hydroxide to yield overbased oligobutyl benzene sulfonate calcium salt. [0432] magnesium carbonate to yield overbased oligobutyl benzene sulfonate magnesium salt.