Novel Initiator For Preparing Alkanesulfonic Acids From Alkane And Oleum

Abstract

A compound of the formula (I)

ALKSO.sub.2OOSO.sub.2OX, wherein ALK is a branched or unbranched alkyl group, especially a methyl, ethyl, propyl, butyl, isopropyl, isobutyl group, or a higher alkyl group, and X=hydrogen, zinc, Aluminium, an alkali or alkaline earth metal.

Claims

1. A mixture comprising a compound having a formula of ALKSO.sub.2OOSO.sub.2OX, wherein ALK is a branched or unbranched alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, or a higher alkyl group, and Xhydrogen, zinc, aluminum, an alkali or alkaline earth metal, and at least one compound selected from the group consisting of ##STR00002##

2. A process for manufacturing a compound having a formula of ALKSO.sub.2OOSO.sub.2OX (Formula I), wherein ALK is a branched or unbranched alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, or a higher alkyl group, and Xhydrogen, zinc, aluminum, an alkali or alkaline earth metal, comprising: reacting a mono-alkali peroxosulfate with an alkanesulfonic acid halide or a methanesulfonic acid halide, and separating the compound according to Formula I from the alkali or alkaline earth halide formed or reacting an alkali mono-alkylperoxosulfonate with chlorosulfonic acid or bromosulfonic acid, and separating the compound according to Formula I from the alkali or alkaline earth halide formed.

3. The process of claim 2 comprising reacting the mono-alkali peroxosulfate with an alkanesulfonic acid halide, wherein the mono-alkali peroxosulfate is a zinc peroxosulfate, an Aluminum peroxosulfate, or an alkaline earth peroxosulfate.

4. The process of claim 2 comprising reacting the alkali mono-alkylperoxosulfonate with chlorosulfonic acid or bromosulfonic acid, wherein the alkali mono-alkylperoxosulfonate is sodium methylperoxosulfonate, zinc mono-alkylperoxosulfonate, Aluminium mono-alkylperoxosulfonate or alkaline earth mono-alkylperoxosulfonate.

5. A process of making a compound comprising preparing an alkanesulfonic acid from a mixture comprising an alkane, oleum, and an initiator, wherein the initiator has a formula of ALK-SO.sub.2OOSO.sub.2OX, wherein ALK is a branched or unbranched alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, or a higher alkyl group, and Xhydrogen, zinc, aluminium, an alkali or alkaline earth metal.

6. The process of claim 5 wherein the alkanesulfonic acid is methanesulfonic acid and the alkane is methane.

7. A process for manufacturing alkanesulfonic acids comprising: providing a solution containing sulfur trioxide/oleum; reacting the solution with an alkane in a reactor; setting the reactor at a pressure of from 1 to 150 bar; preparing an initiator by reacting an alkanesulfonic acid or a solution containing the alkanesulfonic acid with a 30-100% (w/w) hydrogen peroxide solution, wherein the initiator has a formula of ALK-SO.sub.2OOSO.sub.2OX (Formula I), wherein ALK is a branched or unbranched alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, or a higher alkyl group, and Xhydrogen, zinc, aluminium, an alkali or alkaline earth metal adding the initiator to the reactor; controlling the temperature of the reaction mixture at 0-100 C.; and purifying the reaction product.

8. The process of claim 7 wherein adding the initiator to the reactor comprises adding the initiator in a solution that further comprises at least one compound selected from the group consisting of ##STR00003##

9. The process of claim 7 wherein the alkanesulfonic acid is methanesulfonic acid and the alkane is methane.

10. The process of claim 7 wherein the reaction product is purified with distillation or extraction.

11. The process of claim 7 wherein X is H.

12. The process of claim 11 wherein ALK is methyl.

13. The process of claim 7 wherein X is zinc or aluminum.

14. The process of claim 7 wherein X is an alkali or alkaline earth metal.

15. The process of claim 7 wherein ALK is a methyl group.

16. The process of claim 7 wherein ALK is an ethyl group, a propyl group, a butyl group, an isopropyl group, or an isobutyl group.

17. The process of claim 7 wherein ALK is a pentyl group or a higher alkyl group.

18. The process of claim 7 wherein the reactor is reactor II with the process further comprising: a reactor I in which sulfur trioxide and alkane react with the compound of Formula I as initiator, and a distillation apparatus for distilling a product formed in the reactor I, with the reactor II being fluidly connected to reactor I to supply the initiator to reactor I.

19. The process of claim 19 wherein the distillation apparatus is fluidly connected to reactor I, reactor II, and a filling apparatus.

20. The process of claim 18 wherein the alkane is methane.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG. 1 shows schematically, in an exemplary way, a simple system according to the invention for the manufacturing of methanesulfonic acid according to the invention.

[0027] FIG. 2 shows a schematic layout of a preferred device.

DETAILED DESCRIPTION

[0028] The process according to the invention allows for alkane sulfonation, especially methane sulfonation, in a reactor system using oleum with alkane, especially methane, with addition of the compound according to the invention as an initiator. Advantageously, the raw product can be purified by distillation, which already yields a relatively pure alkanesulfonic acid, especially methanesulfonic acid, as a distillate.

[0029] The residue consists of sulfuric acid with a content of up to 10% alkanesulfonic acid, especially methanesulfonic acid (MSA). These distillation bottoms may be used 1) as a solvent for the continuous reaction in the reactor; 2) for the preparation of fresh oleum with pure sulfur trioxide; 3) by reacting hydrogen peroxide (30% to 100% (w/w) solution in water), the compound according to the invention can be prepared, which may be employed as an initiator or precursor for it.

ALKSO.sub.2OH+H.sub.2O.sub.2.fwdarw.ALKSO.sub.2OOH+H.sub.2O.Reaction scheme 1:

[0030] The compound according to the invention is capable of reacting with oleum to form a mixed acid peroxide. This yields the initiator, the compound according to the invention.

ALKSO.sub.2OOH+SO.sub.3.fwdarw.ALKSO.sub.2OOSO.sub.2OH Reaction scheme 2:

[0031] This mixed peroxo anhydride is characterized by a high reactivity as compared to DMSP (dimethylsulfonyl peroxide, H.sub.3CSO.sub.2OOSO.sub.2CH3), which is known from the prior art, for example, and which causes longer reaction times. At the same time, however, the selectivity of the DMSP in view of the formation of side products is obtained. In contrast, peroxodisulfuric acid (Marshall's acid) is very reactive and very little selective. The compound according to the invention combines the selectivity of DMSP with the reactivity of Marshall's acid.

[0032] In the following, the invention is further illustrated in an exemplary way taking the preparation of methanesulfonic acid as an example.

EXAMPLE 1

Preparation of the Initiator Solution

[0033] To a mixture consisting of 90 ml of 100% sulfuric acid and 10 ml of methanesulfonic acid, 3.4 ml of 70% (w/w) hydrogen peroxide is added dropwise with external cooling and intensive stirring.

Synthesis protocol:

[0034] In a 3.75 L autoclave, 1000 g of 36% (w/w) oleum is charged, and the temperature controlled to 50 C. After a pressure of 100 bar of methane gas was set, intensive stirring is performed with a stirrer from the company Parr. Now, the initiator solution is metered dropwise to the solution. The pressure drops to 35 bar within 5 hours. The yield is higher than 90%, based on sulfur trioxide. The reaction product contains 42% (w/w) methanesulfonic acid.

EXAMPLE 2

Preparation of the Initiator Solution

[0035] To a mixture consisting of 90 ml of 100% sulfuric acid and 10 ml of methanesulfonic acid, 3.4 ml of 70% (w/w) hydrogen peroxide is added dropwise with external cooling and intensive stirring.

Synthesis protocol:

[0036] In a 3.75 L autoclave, 1000 g of 36% (w/w) oleum is charged, and the temperature controlled to 35 C. After a pressure of 100 bar of methane gas was set, intensive stirring is performed with a stirrer from the company Parr. Now, the initiator solution is metered dropwise to the solution. The pressure drops to 35 bar within 5 days. The yield is higher than 90%, based on sulfur trioxide. The reaction product contains 42% methanesulfonic acid.

Characterization of monomethylsulfonyl peroxide:

[0037] Using different analytical techniques monomethylsulfonyl peroxide was characterized. Using mass spectroscopy the molecular weight was determined as M191.94 g/mol. The .sup.1H-NMR (D.sub.2SO.sub.4) shows a signal for the Methylgroup at 3.43 ppm. A suitable way in order to measure the peroxide content is titration (Jander, Jahr, Maanalyse, Theorie und Praxis der Titrationen mit chemischen und physikalischen Indikationen, 17. Auflage, Walter de Gruyter GmbH 2009, Berlin).