US3708542A - Manufacture of dialkyl sulphoxides - Google Patents

Manufacture of dialkyl sulphoxides Download PDF

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Publication number
US3708542A
US3708542A US00094014A US3708542DA US3708542A US 3708542 A US3708542 A US 3708542A US 00094014 A US00094014 A US 00094014A US 3708542D A US3708542D A US 3708542DA US 3708542 A US3708542 A US 3708542A
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dialkyl
sulphide
column
sulphoxide
liquid
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US00094014A
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English (en)
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C Douchet
P Grancher
R Vecchiutti
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides

Definitions

  • the invention relates to an improved process for the manufacture of dialkyl sulphoxides; it is more particularly concerned with obtaining lower alkyl sulphoxides, i.e. those containing from 1 to 4 carbon atoms, and in particular dimethyl sulphoxide.
  • the invention also comprises an installation permitting the new process to be carried into effect.
  • the gaseous or liquid nitrogen peroxide i.e., NO2 and N204
  • liquid dialkyl sulphide reacts with liquid dialkyl sulphide in a column at a temperature between ambient temperature and approximately 80 C., and usually between 20" and 60 C.
  • gaseous NO2 and oxygen are introduced at the bottom of the column, while the liquid dialkyl sulphide enters at the top end thereof.
  • the oxidising gases should be welldispersed within the liquid, so that the volume of gas thus retained by the liquid is at least 7% of the latter.
  • Another process which forms the subject of French Pat.
  • 1,188,561 consists in using NO2 in the form of a solution in dialkyl sulphoxide, or possibly in another solvent, and in thus introducing the solution together with the sulphide to be oxidised at the bottom of the reaction column; this process provides for the re-oxidation of the resultant NO, by contact with the oxygen in a separate reaction zone.
  • the addition No. 73,993 to this patent provides for the treatment of the formed vapor phase, still containing dialkyl sulphide, with an excess of NO2, before the re-oxidation of the NO, so as to avoid any presence of sulphide during this last operation.
  • the present invention remedies the state o-f affairs as it exists at present: it makes possible perfect control of the oxidation of the dialkyl sulphide and higher stability in the conduct of the reaction, with elimination of all dangerous points in the manufacturing cycle. While the yield of pure sulphoxide by the new process is as good as in the best of the prior known processes, it is accompanied by the advantage of a discharging gaseous effluent which is colder and is less charged with sulphide and NO2 than in the known processes.
  • the new process according to the invention for the production of a dialkyl sulphoxide by the oxidation of the corresponding dialkyl sulphide by means of nitrogen peroxide is characterised in that the dialkyl sulphide is diluted with dialkyl sulphoxide, while the nitrogen peroxide is diluted with oxygen, before the oxidation reaction.
  • the degree of dilution of the dialkyl sulphide may vary within wide limits, it is preferable that the liquid which enters the reactor is composed of 0.15 to 3 moles of dialkyl sulphoxide to 1 mole of dialkyl sulphide, or better still of 0.5 to 1.5 moles of sulphoxide to 1 mole of sulphide.
  • these proportions, expressed by weight are about 20 to 380 and preferably 60 to 190 parts of sulphoxide to parts of sulphide.
  • the dilution with oxygen of the N204 intended for the oxidation is preferably such that the molar ratio O2/N2O4 is about 4 to 10 or better still 5 to 8, in the gaseous mixture being used.
  • the adequate proportions of nitrogen peroxide and oxygen are injected in the form of a gaseous mixture at the bottom of a reaction column, the liquid mixture of dialkyl sulphide and dialkyl sulphoxide also being introduced into the lower part of this column.
  • the liquid content of the reaction column is maintained in a thermal state, such that the region where the reactants are injected is at the optimum temperature for the oxidation reaction of sulphide into sulpho-xide, and that, starting from this region and towards the top of the column, the temperature progressively decreases to an intermediate value between the said optimum temperature and ambient temperature.
  • the process according to the invention consists in permitting the reaction medium to become heated to the required temperature, at the point of arrival of the reactants at the bottom of the column, and in suitably cooling all the remainder of the contents of this column.
  • a stable temperature gradient is created, in the sense of a decrease from the bottom towards the top of the reaction column.
  • the preferred temperature at the point of introduction of the reactants is from 45 to 70 C. or better 3 still from 50 to 60 C.; the cooling of the liquid which is above this zone is then such that the temperature does not reach more than about 20 to 40 C. at the top of the column, that is to say, at the point where the liquid leaves the column.
  • One particularly desirable embodiment of the invention consists in dividing Nery finely the gases injected at the bottom of the reactor or column and in ensuring a perfectly intimate Contact between them and the liquid; this can be achieved by the interposition of a plate having very 'ne perforations, or a porous plate, on the inlet for the gases.
  • the gases and vapors escaping from the top of the reaction column are washed in counter-current with the dialkyl sulphoxide produced, which is previously degased and cooled. It is generally suicient for this sulphoxide, thus recycled in the upper part of the column, to be at a temperature of approximately 15 to 30 C., when dimethyl sulphoxide is concerned; it can in particular be at ambient temperature, i.e. 15 to 25 C. As a general rule, the sulphoxide used for this washing operation must be at a temperature below the boiling point of the dialkyl sulphide from which it is derived.
  • the nitrogen peroxide serves as a catalyst or intermediate oxidant and a substance taking up oxygen, in accordance with the reactions:
  • oxidants particularly 110 to 150 atoms of total available oxygen, or better still 120 to 130 atoms, of which about 1/15 to 1/3 are in the form of NO2 and/or N204.
  • the O2/NO2 molar ratio in the gaseous mixture which is employed is preferably about 4 to 10 and especially 5 to 8, as previously indicated.
  • the proportion of nitrogen peroxide, expressed as NO2 is generally from 5 to 20 moles and more particularly 7 to 12 moles, to 100 moles of dialkyl sulphide.
  • the dialkyl sulphoxide produced experiences a degasication, that is to say, the elimination of the volatile compounds which it contains at the outlet of the reactor.
  • it is reheated, usually to a temperature of the order of 60 to 80 C., and passes in counter-current in contact withair.
  • the product thus degasied is divided into two fractions: one of which is cooled and recycled as previously indicated, While the other is neutralised and puried.
  • the new process is particularly adapted to continuous manufacture.
  • the installation according to the invention for carrying into effect the process as described, comprises, in addition to the conventional means, one or more reactors of the column type equipped with means for introduction of gas and liquid at the lower end and cooling means acting over the entire height of the column, from a level situated above the gas and liquid inlets.
  • the bottom region of the column where the gases enter is separated from the remainder of the internal space of the column by a plate perforated with a large number of very small apertures; such a plate can with advantage be formed of a sintered metal; it permits an excellent distribution of the gases, NO2 and oxygen, and of the liquid dialkyl sulphide introduced at the bottom of the column, as they flow upwardly.
  • the reaction column according to the invention is generally equipped with means for the recirculation of the liquid from the top of the column towards the inlet at the bottom of the latter. Quite obviously, it comprises an outlet for unrefined manufactured product in its upper part.
  • the reaction column is surmounted by a scrubbing column, generally lined with ller bodies, in which the gaseous eflluent leaving the reaction medium is scrubbed and cooled by sprinkling with suitably cooled, recycled reaction product.
  • the new installation comprises cooling means in the initial sulphoxide circuit and on a branch line of a fraction of produced sulphoxide.
  • the installation also comprises means for degasifying the manufactured product, these means comprising one or more reheaters.
  • the cooling means referred to above are preferably arranged on a branch line of the manufactured product and are downstream of the degasifying means.
  • 1 represents a source of -liquid dimethyl sulphide
  • 2 is an oxygen gas reservoir
  • 3 is a source of liquid NO2.
  • Represented at 4 is an NO2 vaporiser.
  • the dimethyl sulphide is brought in liquid form to the lower part 5 of a reactor, in the form of a column 5-6.
  • the Oxygen and the nitrogen peroxide, in the form of a gaseous mixture, also reach the bottom 5 of the reactor through the pipeline 2'.
  • the conical portion 5 is terminated at the bottom by a small sleeve 5 at which ends the gas supply pipe 2' ends; the interior of the sleeve 5 is separated from the interior 5 by a porous plate 7 made of sintered metal, which serrves for the ne distribution of the gases in the liquid which is above the plate 7.
  • one or more coolers 8 Installed in the body 6 of the reactor are one or more coolers 8 serving to cause the progressive lowering of the temperature of the reaction medium to a value which is relatively close to ambient temperature, below the region 9 at the top of the column.
  • a discharge conduit 10 comprising a recirculating pump 11, for sending a part of the liquid into conduit 1 through which the fresh dimethyl sulphide reaches the bottom 5 of the column.
  • the discharge pipe 12 Connected to the top of the section 9, filled with Raschig rings, is the discharge pipe 12 for unrefined sulphoxide which is produced.
  • This sulphoxide is taken up by a pump 13, directed into a reheater 14 and is passed to the top of a degasifying tower 15, through which ows an air current introduced through the bottom at 16.
  • the sulphoxide taken up by the pump 17 is divided into two fractions, one passing by way of 18 towards the conventional apparatus for neutralisation and purification purposes, and the other by Way of 19, through a cooler 20, and is recycled through the pipeline 21 to the top of the scrubber 22 which is arranged above the section 9 of the reactor 5-6.
  • the scrubber Z2 contains ller bodies, particularly Raschig rings, and/or plates.
  • the gaseous effluent leaves the apparatus through 23.
  • a process for the manufacture of a dialkyl sulphoxide by oxidation of the corresponding liquid dialkyl sulphide which comprises injecting said dialkyl sulphide, mixed with said dialkyl sulphoxide, and a gaseous mixture of oxygen and nitrogen peroxide into the bottom of a reaction column having a stable temperature gradient established over the entire column, said temperature gradient being such that the bottom of said column is maintained at the optimum temperature for the oxidation reaction of the sulphide and the temperature progressively decreases to an intermediate value between said optimum temperature and room temperature at the top of said column.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treating Waste Gases (AREA)
US00094014A 1969-12-03 1970-12-01 Manufacture of dialkyl sulphoxides Expired - Lifetime US3708542A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR6941635A FR2069896A1 (enrdf_load_stackoverflow) 1969-12-03 1969-12-03

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US3708542A true US3708542A (en) 1973-01-02

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FR (1) FR2069896A1 (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996295A (en) * 1974-07-04 1976-12-07 Produits Chimiques Ugine Kuhlmann Preparation of dimethylsulfoxide by liquid phase reaction of dimethysulfide and hydrogen peroxide
US4113784A (en) * 1977-06-29 1978-09-12 Phillips Petroleum Company Conversion of organic sulfides to corresponding sulfoxides
US6414193B1 (en) * 1999-01-29 2002-07-02 Toray Fine Chemicals Co., Ltd. Process for producing dimethyl sulfoxide
US6414194B1 (en) * 1999-04-23 2002-07-02 Gaylord Chemical Corporation Process and apparatus for making ultra-pure DMSO
US9102600B2 (en) 2013-11-01 2015-08-11 Dmso Solutions, Llc DMSO purification

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3996295A (en) * 1974-07-04 1976-12-07 Produits Chimiques Ugine Kuhlmann Preparation of dimethylsulfoxide by liquid phase reaction of dimethysulfide and hydrogen peroxide
US4113784A (en) * 1977-06-29 1978-09-12 Phillips Petroleum Company Conversion of organic sulfides to corresponding sulfoxides
US6414193B1 (en) * 1999-01-29 2002-07-02 Toray Fine Chemicals Co., Ltd. Process for producing dimethyl sulfoxide
US6414194B1 (en) * 1999-04-23 2002-07-02 Gaylord Chemical Corporation Process and apparatus for making ultra-pure DMSO
US9102600B2 (en) 2013-11-01 2015-08-11 Dmso Solutions, Llc DMSO purification

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Publication number Publication date
FR2069896A1 (enrdf_load_stackoverflow) 1971-09-10

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