WO2013186305A1 - Procédé pour la préparation d'un sulfonate d'oléfine interne - Google Patents

Procédé pour la préparation d'un sulfonate d'oléfine interne Download PDF

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Publication number
WO2013186305A1
WO2013186305A1 PCT/EP2013/062258 EP2013062258W WO2013186305A1 WO 2013186305 A1 WO2013186305 A1 WO 2013186305A1 EP 2013062258 W EP2013062258 W EP 2013062258W WO 2013186305 A1 WO2013186305 A1 WO 2013186305A1
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Prior art keywords
internal olefin
nucleophile
base
process according
containing solution
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PCT/EP2013/062258
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English (en)
Inventor
Robert Moene
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Shell Internationale Research Maatschappij B.V.
Shell Oil Company
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Publication of WO2013186305A1 publication Critical patent/WO2013186305A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids

Definitions

  • the present invention relates to a process for preparing an internal olefin sulfonate.
  • nucleophile is water or hydroxide ion. In a case where the nucleophile is water or hydroxide ion.
  • alkene sulfonic acids are converted into alkene
  • EP0446971A1 discloses that suitable other nucleophiles are aliphatic or aromatic (thio ) alcohols or alkoxides thereof, (capped)
  • EP0446971A1 discloses that after the reaction with the nucleophile the product thus obtained can be converted into a surface active ionic form by reaction with a base, for example sodium hydroxide (NaOH) .
  • a base for example sodium hydroxide (NaOH)
  • the reaction product would comprise an alkoxy alkane sulfonic acid.
  • a subsequent treatment with a base can be performed resulting in alkoxy alkane sulfonate.
  • such treatment with a base would also convert any alkene sulfonic acid into the corresponding sulfonate.
  • the nucleophile is used in a molar excess over the compounds which need to be converted. Further, said reaction with a nucleophile may be performed in a solvent for the nucleophile, as also disclosed in
  • EP0446971A1 (e.g. n-hexane) .
  • EP0446971A1 e.g. n-hexane
  • nucleophile if such solvent is used, is still present in the reaction mixture which should be separated therefrom.
  • the presence of such nucleophile or solvent may have a detrimental effect on the properties of the final
  • nucleophile and solvent may be separated from the reaction mixture after treatment with a base as discussed above.
  • An object of the present invention is to provide a process for preparing an internal olefin sulfonate which is more efficient than known processes for preparing internal olefin sulfonates, in respect of the removal of remaining nucleophile and any solvent for the
  • the present invention relates to a process for preparing an internal olefin sulfonate, comprising sulfonating an internal olefin into sulfonated internal olefin, reacting sulfonated internal olefin with a nucleophile, with the proviso that the nucleophile is not water or hydroxide ion, and contacting the thus obtained reaction mixture with a base containing solution under reduced pressure.
  • the present invention results in that (i) the step of contacting the reaction mixture obtained by reacting sulfonated internal olefin with a
  • nucleophile other than water or hydroxide ion, with a base containing solution, and (ii) the step of removing remaining nucleophile and any solvent for the
  • nucleophile are performed at the same time, since the pressure at which this is performed is a reduced
  • the process of the present invention is a process for preparing an internal olefin sulfonate (IOS) from an internal olefin.
  • IOS internal olefin sulfonate
  • an internal olefin and an IOS comprise a mixture of internal olefin molecules and a mixture of IOS molecules,
  • internal olefin refers to a mixture of internal olefin molecules whereas "internal olefin molecule” refers to one of the components from such internal olefin.
  • IOS or “internal olefin sulfonate” as such refers to a mixture of IOS molecules whereas "IOS molecule” or “internal olefin sulfonate molecule” refers to one of the components from such IOS.
  • Branched IOS molecules are IOS molecules derived from internal olefin molecules which comprise one or more branches.
  • Linear IOS molecules are IOS molecules derived from internal olefin molecules which are linear, that is to say which comprise no branches (unbranched internal olefin molecules) .
  • An internal olefin may be a mixture of linear internal olefin molecules and branched internal olefin molecules.
  • an IOS may be a mixture of linear IOS molecules and branched IOS molecules.
  • an internal olefin or IOS may be characterised by its carbon number, branched content and/or molecular weight.
  • said average carbon number is determined by multiplying the number of carbon atoms of each internal olefin molecule or IOS molecule by the weight fraction of that molecule and then adding the products, resulting in a weight average carbon number.
  • the average carbon number may be determined by GC
  • branched content is determined by dividing the amount of branched molecules by the total amount of branched and unbranched molecules.
  • the branched content may be determined by GC analysis.
  • said average molecular weight is determined by multiplying the
  • molecular weight of each internal olefin molecule or IOS molecule by the mole fraction or weight fraction of that molecule and then adding the products, resulting in a number average or weight average molecular weight, respectively.
  • the molecular weight may be determined by GC analysis.
  • sulfonate is prepared from an internal olefin in a process comprising sulfonation followed by reaction with a nucleophile and finally by contacting the reaction mixture with a base containing solution.
  • an internal olefin is sulfonated.
  • the internal olefin may have an average carbon number of from 5 to 40, suitably 10 to 35, more suitably 15 to 30, most suitably 18 to 24.
  • the branched content of the internal olefin used in the sulfonation step may be of from 0.1 to 30 wt.%, preferably 1 to 25 wt . % .
  • Branches in the above-mentioned internal olefin molecules may include methyl, ethyl and/or higher
  • molecular weight branches including propyl branches.
  • molecular weight for the internal olefin may vary within wide ranges, such as from 200 to 600, suitably 250 to 500, more suitably 300 to 400 g/mole.
  • An IOS molecule is made from an internal olefin molecule whose double bond is located anywhere along the carbon chain.
  • Internal olefin molecules may be made by double bond isomerization of alpha-olefin molecules whose double bond is located at a terminal position. Generally, such isomerization results in a mixture of internal olefin molecules whose double bonds are located at different internal positions. The distribution of the double bond positions is mostly thermodynamically
  • the mixture resulting from alpha-olefin isomeration may likewise comprise that minor amount of unreacted
  • the amount of alpha-olefins in the internal olefin may be up to 5%, for example 1 to
  • the amount of paraffins in the present invention is 4 wt . % based on total composition. Further, in the present invention, the amount of paraffins in the present invention is 4 wt . % based on total composition. Further, in the present invention, the amount of paraffins in the present invention is 4 wt . % based on total composition. Further, in the present invention, the amount of paraffins in the present invention is 4 wt . % based on total composition. Further, in the present invention, the amount of paraffins in the present invention.
  • internal olefin may be up to 15 wt.%, for example up to 12 wt.% based on total composition.
  • Suitable processes for making an internal olefin include those described in US5510306, US5633422,
  • the internal olefin is contacted with a sulfonating agent. Reaction of the sulfonating agent with an internal olefin leads to the formation of cyclic intermediates known as beta-sultones , which can undergo isomerization to
  • the sulfonating agent may be sulfur trioxide (SO 3 ), sulfuric acid or oleum, of which sulfur trioxide is preferred.
  • the mole ratio of sulfonating agent to internal olefin may be 0.5:1 to 2:1, more suitably 0.8:1 to 1.8:1, most suitably 1:1 to 1.6:1.
  • the sulfur trioxide is preferably provided as a gas stream comprising a carrier gas and the sulfur trioxide.
  • the carrier gas may be air or an inert gas, such as nitrogen.
  • the concentration of sulfur trioxide in said gas stream may be 1 to 10 vol.%, more suitably 2 to 8 vol.%, most suitably 2 to 7 vol.%, based on the volume of the carrier gas.
  • the sulfonation reaction with SO 3 is preferably carried out in a film reactor, for example a "falling- film reactor", where the olefin feed is continuously fed onto the inside surfaces of a tube and gaseous SO 3 is fed into the tube to react with the (falling) olefin film in a controlled manner.
  • the reactor may be cooled with a cooling means, which is preferably water, having a temperature preferably not exceeding 90 °C, especially a temperature in the range of from 10 to 70 °C, more suitably 20 to 60 °C, most suitably 20 to 55 °C, for example by flowing the cooling means at the outside walls of the reactor.
  • the present process may be carried out batchwise, semi-continuously or continuously, preferably
  • the sulfonation step may be carried out batchwise, semi-continuously or continuously.
  • the sulfonation step is carried out
  • nucleophile is not water or hydroxide ion.
  • a nucleophile is a molecule capable of attacking a positive centre or a positively polarized site in e.g. another molecule.
  • Suitable nucleophiles in the present invention may be selected from the group consisting of aliphatic and aromatic (thio) alcohols and alkoxides thereof, (capped) polyethylene glycols and propylene glycols and their alkoxides, aliphatic and aromatic amines and the amides thereof, ammonia and heterocyclic nitrogen compounds.
  • aliphatic and aromatic (thio) alcohols and alkoxides thereof capped
  • nucleophile in the present invention is selected from the group consisting of aliphatic and aromatic
  • propylene glycols and aliphatic and aromatic amines, most preferably aliphatic alcohols and aliphatic amines. It is preferred to react the sulfonated internal olefin, comprising sultones such as beta-sultones , with a
  • nucleophile which is selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-pentanol, triethylene glycol mono-methyl ether, ethanolamine, n- butylamine, sodium n-propyl thiolate, sodium ethoxide and sodium phenolate, more preferably methanol, ethanol, propanol, isopropanol, n-pentanol, triethylene glycol mono-methyl ether, ethanolamine and n-butylamine .
  • the reaction product would comprise an alkoxy alkane sulfonic acid, part of which may have been
  • the nucleophile in the reaction of sulfonated internal olefin with the nucleophile, is used in a molar excess over said sulfonated internal olefin to ensure a complete conversion of said sulfonated internal olefin.
  • sulfonated internal olefin is of from greater than 1:1 to 1.6:1, more preferably 1.05:1 to 1.5:1, most preferably 1.1:1 to 1.4:1. Further, such amount of the nucleophile may be used that the mole ratio of the nucleophile to sulfonating agent is of from greater than 1:1 to 1.6:1, more preferably 1.05:1 to 1.5:1, most preferably 1.1:1 to 1.4:1.
  • the step wherein the nucleophile is reacted with sulfonated internal olefin in the present process may be carried out batchwise, semi-continuously or continuously. Preferably, said step is carried out continuously.
  • CSTR continuously stirred tank reactor
  • plug flow reactor may be used in this step.
  • any remaining nucleophile may be neutral or may have a negative charge.
  • the nucleophile is an alkoxide, it will have a negative charge. In both cases, such remaining nucleophile has to be removed.
  • a solvent for the nucleophile especially in a case where the nucleophile is negatively charged.
  • Suitable solvents for the nucleophile are disclosed in EP0446971A1, the disclosure of which is incorporated herein by reference.
  • lithium ethoxide is the nucleophile which is added in a solvent mixture of n-hexane and tetrahydrofuran .
  • solvent for the nucleophile is used in the present invention, then after the reaction of sulfonated internal olefin with the nucleophile, also such solvent remains in addition to any remaining nucleophile.
  • the reaction product comprises an alkoxy alkane sulfonic acid.
  • a subsequent treatment with a base is needed.
  • the reaction mixture obtained by reacting sulfonated internal olefin with the nucleophile is contacted with a base containing solution.
  • containing solution implies that the base is dissolved in a solvent, thereby forming said solution, when the base is contacted with said reaction product.
  • Said solvent is thus a solvent for the base, which solvent is preferably water.
  • the base to be used may be a water soluble base, which is preferably selected from the group consisting of hydroxides, carbonates and bicarbonates of an alkali metal ion, such as sodium or potassium, or of ammonium ion, and amine compounds. Suitable examples are sodium hydroxide and sodium carbonate, most suitably sodium hydroxide.
  • the solvent for the base is water.
  • an aqueous solution of a water soluble base, such as described hereinabove, especially sodium hydroxide is used as the base
  • the reaction in this step is generally carried out with an excessive molar amount of base. It is preferred that the final internal olefin sulfonate product is not acidic because this may lead to corrosion of process equipment and/or to disintegration of the internal olefin sulfonate. Therefore, it is preferred that the final internal olefin sulfonate product contains a certain amount of base, for example 0.1 to 2 wt . % based on 100% of the active matter. This may be achieved by choosing the amount of base to be added such that the molar ratio of (i) the amount of base fed to the step wherein the reaction mixture, obtained by reacting sulfonated
  • the amount of sulfonating agent (e.g. SO 3 ) fed to the sulfonation step is higher than 1, suitably higher than 1 up to 1.4, more suitably 1.1 to 1.3.
  • the base and the solvent for the base may be added separately.
  • the base is added as part of a solution as described above. Additional solvent may be added separately in addition to such base containing solution. If the base is added as part of a solution, the concentration of the base in such solution, based on total solution, is suitably at most 60 wt.%, more
  • the temperature at which the treatment with the base containing solution in the present process is carried out may vary within wide ranges, for example 0 to 250 °C.
  • treatment time may also vary within wide ranges, for example 5 minutes to 4 hours.
  • containing solution in the present process is carried out may be carried out batchwise, semi-continuously or continuously. Preferably, said step is carried out continuously.
  • the internal olefin sulfonates may be synthesized in a way as described by Van Os et al . in "Anionic Surfactants: Organic Chemistry", Surfactant Science Series 56, ed. Stacke H.W., 1996, Chapter 7:
  • Olefin sulfonates pages 367-371, the disclosure of which is incorporated herein by reference.
  • reactor should be used in the step of the treatment with the base containing solution that allows for the treatment to take place under reduced pressure.
  • reduced pressure within the present specification means that the pressure is lower than atmospheric pressure. Further, preferably, the temperature is sufficiently high for remaining
  • a suitable reactor for this step is a film evaporator, preferably a wiped film evaporator
  • the temperature and pressure in this step are chosen such that the solvent for the base containing solution, which solvent is preferably water as discussed above, is not separated and removed or is separated and removed to only a small extent. It is therefore preferred that the nucleophile is more volatile than said solvent for the base containing solution. This means that at a given pressure, the temperature is suitably maintained below the boiling point of said solvent for the base containing solution, but at or above the boiling point of said remaining nucleophile and any solvent for the nucleophile.
  • the pressure is of from 0.01 bar to lower than 1 bar, more preferably of from 0.05 bar to lower than 1 bar, most preferably of from 0.05 bar to 0.5 bar.
  • said pressure is at most 0.9 bar, more preferably at most
  • said pressure is at least 0.01 bar, more preferably at least 0.03 bar, more preferably at least 0.05 bar, more preferably at least 0.07 bar, most preferably at least 0.09 bar.
  • the temperature in this step is preferably of from 0 to lower than 100 °C, more preferably of from 10 to lower than 100 °C, more preferably of from 15 to lower than 100 °C, more
  • any nucleophile and possibly said solvent for the nucleophile that remain after the reaction of sulfonated internal olefin with the nucleophile are removed in the same step wherein the treatment with the base containing solution is carried out. Therefore, advantageously, no separate step for removing said nucleophile and solvent is needed. Doing both steps simultaneously is more efficient than having to perform both steps one after another. Thus, enormous savings in throughput time and operational costs may be obtained .
  • the internal olefin sulfonate (IOS) product may be diluted, for example by adding additional solvent (e.g. water), for example in case one wishes to facilitate the handling of that product in the application for which the IOS product is intended, for example in the application as a surfactant.
  • additional solvent e.g. water
  • IOS internal olefin sulfonate
  • sulfonate may be used as a surfactant in any kind of process, for example in a method of chemical Enhanced Oil Recovery (cEOR) for maximising the yield of hydrocarbons (oil) from a subterranean reservoir.
  • cEOR chemical Enhanced Oil Recovery

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention porte sur un processus pour la préparation d'un sulfonate d'oléfine interne, comprenant la sulfonation d'une oléfine interne en oléfine interne sulfonée, la réaction de l'oléfine interne sulfonée avec un nucléophile, à condition que le nucléophile ne soit pas l'eau ou l'ion hydroxyde, et la mise en contact du mélange réactionnel ainsi obtenu avec une solution contenant une base sous pression réduite.
PCT/EP2013/062258 2012-06-13 2013-06-13 Procédé pour la préparation d'un sulfonate d'oléfine interne WO2013186305A1 (fr)

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EP12171761.5 2012-06-13

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10035746B2 (en) 2015-05-07 2018-07-31 Rhodia Operations Process for the decarboxylative ketonization of fatty acids or fatty acid derivatives
US11267781B2 (en) 2016-11-08 2022-03-08 Rhodia Operations Method for making end compounds from internal ketones issued from the decarboxylative ketonization of fatty acids or fatty acid derivatives

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755429A (en) * 1971-10-12 1973-08-28 Procter & Gamble Process for the preparation of sulfonated detergent composition
US4183867A (en) 1977-08-25 1980-01-15 The Lion Fat & Oil Co. Method for preparation of internal olefin sulfonate
US4248793A (en) 1979-09-26 1981-02-03 The Lion Fat & Oil Co., Ltd. Process for the production of internal olefin sulfonate
EP0293913A1 (fr) * 1987-06-04 1988-12-07 Raschig AG Procédé de préparation de composés éthane sulfoniques, le cas échéant substitués
EP0351928A1 (fr) 1988-07-20 1990-01-24 Shell Internationale Researchmaatschappij B.V. Procédé pour la préparation de sulfonates d'oléfines internes
EP0446971A1 (fr) 1990-01-12 1991-09-18 Shell Internationale Researchmaatschappij B.V. Procédé pour la préparation d'acides sulfoniques et/ou de sulfonates substitués
US5510306A (en) 1993-12-29 1996-04-23 Shell Oil Company Process for isomerizing linear olefins to isoolefins
US5648585A (en) 1993-12-29 1997-07-15 Murray; Brendan Dermot Process for isomerizing linear olefins to isoolefins
US5849960A (en) 1996-11-26 1998-12-15 Shell Oil Company Highly branched primary alcohol compositions, and biodegradable detergents made therefrom
EP0830315B1 (fr) 1995-06-07 1999-09-08 Shell Oil Company Procede de preparation de ferrierite

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755429A (en) * 1971-10-12 1973-08-28 Procter & Gamble Process for the preparation of sulfonated detergent composition
US4183867A (en) 1977-08-25 1980-01-15 The Lion Fat & Oil Co. Method for preparation of internal olefin sulfonate
US4248793A (en) 1979-09-26 1981-02-03 The Lion Fat & Oil Co., Ltd. Process for the production of internal olefin sulfonate
EP0293913A1 (fr) * 1987-06-04 1988-12-07 Raschig AG Procédé de préparation de composés éthane sulfoniques, le cas échéant substitués
EP0351928A1 (fr) 1988-07-20 1990-01-24 Shell Internationale Researchmaatschappij B.V. Procédé pour la préparation de sulfonates d'oléfines internes
EP0446971A1 (fr) 1990-01-12 1991-09-18 Shell Internationale Researchmaatschappij B.V. Procédé pour la préparation d'acides sulfoniques et/ou de sulfonates substitués
US5510306A (en) 1993-12-29 1996-04-23 Shell Oil Company Process for isomerizing linear olefins to isoolefins
US5633422A (en) 1993-12-29 1997-05-27 Shell Oil Company Process for isomerizing linear olefins to isoolefins
US5648585A (en) 1993-12-29 1997-07-15 Murray; Brendan Dermot Process for isomerizing linear olefins to isoolefins
US5648584A (en) 1993-12-29 1997-07-15 Shell Oil Company Process for isomerizing linear olefins to isoolefins
EP0830315B1 (fr) 1995-06-07 1999-09-08 Shell Oil Company Procede de preparation de ferrierite
US5849960A (en) 1996-11-26 1998-12-15 Shell Oil Company Highly branched primary alcohol compositions, and biodegradable detergents made therefrom

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Surfactant Science Series", vol. 56, 1996, MARCEL DEKKER, INC., article "Anionic Surfactants: Organic Chemistry"
VAN OS ET AL.: "Surfactant Science Series", vol. 56, 1996, article "Anionic Surfactants: Organic Chemistry", pages: 367 - 371

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10035746B2 (en) 2015-05-07 2018-07-31 Rhodia Operations Process for the decarboxylative ketonization of fatty acids or fatty acid derivatives
US11267781B2 (en) 2016-11-08 2022-03-08 Rhodia Operations Method for making end compounds from internal ketones issued from the decarboxylative ketonization of fatty acids or fatty acid derivatives

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