WO2009058654A1 - Procédé de fabrication d'alcoxysulfates d'alcools secondaires - Google Patents

Procédé de fabrication d'alcoxysulfates d'alcools secondaires Download PDF

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Publication number
WO2009058654A1
WO2009058654A1 PCT/US2008/080918 US2008080918W WO2009058654A1 WO 2009058654 A1 WO2009058654 A1 WO 2009058654A1 US 2008080918 W US2008080918 W US 2008080918W WO 2009058654 A1 WO2009058654 A1 WO 2009058654A1
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Prior art keywords
paraffins
catalyst
acid
secondary alcohol
alcohols
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PCT/US2008/080918
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English (en)
Inventor
Maria Celeste Colantonio
Howard Lam Ho Fong
Andrew David Horton
Jan Hermen Hendrik Meurs
Thomas Carl Semple
Sanne Wijnans
Arie Van Zon
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Shell Oil Company
Shell Internationale Research Maatschappij B.V.
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Publication of WO2009058654A1 publication Critical patent/WO2009058654A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • This invention relates to a process for producing secondary alcohol alkoxy sulfates from carbon monoxide and hydrogen .
  • a large variety of products useful, for instance, as nonionic surfactants, wetting and emulsifying agents, solvents and chemical intermediates are prepared by the addition reaction (alkoxylation reaction) of alkylene oxides (epoxides) with organic compounds having one or more active hydrogen atoms.
  • alkylene oxides epoxides
  • organic compounds having one or more active hydrogen atoms For example, particular mention may be made of the alcohol ethoxylates prepared by the reaction of ethylene oxide with aliphatic alcohols of 6 to 30 carbon atoms.
  • Such ethoxylates, and to a lesser extent corresponding propoxylates and compounds containing mixed oxyethylene and oxypropylene groups, are widely employed as nonionic detergent components in cleaning and personal care formulations .
  • Sulfated alcohol alkoxylates have a wide variety of uses as well, especially as anionic surfactants.
  • Sulfated higher secondary alcohol ethoxylates (SAES) offer comparable properties in bulk applications relative to anionics like linear alkyl benzene sulfonates and primary alcohol ethoxy sulfates, as well as methyl ester sulfonates.
  • SAES secondary alcohol ethoxylates
  • These materials may be used to produce household detergents including laundry powders, laundry liquids, dishwashing liquids and other household cleaners, as well as lubricants and personal care compositions and as surfactants for (dilute) surfactant flooding of oil wells and as surfactant components used in e.g.
  • alkoxylated alcohols suitable for enhanced oil recovery.
  • One typical method of preparing alkoxylated alcohols is by hydroformylating an olefin into an oxo-alcohol, followed by alkoxylation of the resulting alcohol by reaction with a suitable alkylene oxide such as ethylene oxide or propylene oxide.
  • a suitable alkylene oxide such as ethylene oxide or propylene oxide.
  • primary alcohol alkoxylates When primary alcohol alkoxylates are made, this is a three step process because olefins have to be made either by oligomerization of ethylene (which tends to be relatively expensive) or by dehydrogenation of paraffins.
  • Secondary alcohol alkoxylates may be made in a two step process because secondary alcohols may be produced directly from paraffins.
  • Secondary alcohols may be made directly from paraffins by oxidation using boric acid as a catalyst.
  • the boron reagent is not a catalyst as it is consumed in the reaction. Its function is to protect the oxygenate (sec-alcohol) by reaction to give an oxidation- resistant borate ester.
  • the boric acid does act as a "catalyst" because its secondary function is to increase the oxidation rate .
  • Borate esters of the secondary alcohols are formed and may be separated from the paraffins by distillation when the carbon number (number of carbon atoms in the alcohol chain) of the alcohol is 14 or less. When the carbon number is 15 or more, the distillation temperature required is equal to or above the decomposition temperature of the borate ester and therefore conventional distillation techniques may not be effective. It would, however, be useful to be able to make secondary alcohols, secondary alcohol alkoxylates and secondary alcohol alkoxy sulfates with carbon numbers of 15 or more.
  • DMC catalyst in the presence of contaminating diols or triols the required amount of DMC catalyst may be so high that it is no longer economically viable to leave it in the end-product, considering the levels of heavy metal, such as cobalt, which would then end up in the final product, e.g. a household detergent.
  • Another hurdle for the application of the DMC catalyst is the presence of sodium hydroxide in the secondary alcohol, since this base has been used in the hydrolysis of the borate ester of the secondary alcohols. It is also known that water and basic contaminants, such as sodium hydroxide or potassium hydroxide, reduce or even impede the activity of the DMC catalyst and therefore these contaminants should be removed from the secondary alcohol as meticulously as possible via extraction and/or topping and tailing.
  • This invention provides a process for making secondary alcohol alkoxy sulfates which comprises: (a) reacting carbon monoxide and hydrogen under Fischer-Tropsch conditions in the presence of a Fischer-Tropsch catalyst to produce a reaction mixture comprising paraffins, (b) contacting the paraffins with oxygen in the presence of an oxidation catalyst to produce secondary alcohols, (c) contacting the secondary alcohols with an alkylene oxide in the presence of a double metal cyanide catalyst to produce secondary alcohol alkoxylates, and (d) sulfating the secondary alcohol alkoxylates .
  • the carbon number of the paraffins and secondary alcohols is 9 or more, preferably 9 to 30, and the oxidation catalyst may be a boric acid derivative, preferably dehydrated orthoboric acid or metaboric acid. Since the molecular weight of the borate esters of the secondary alcohols may be over three times higher than that of the unreacted paraffins, these components may be separated from the unreacted paraffins by application of conventional means such as vacuum distillation.
  • the carbon number of the paraffins and secondary alcohols is 15 or more, preferably 15 to 30, and the oxidation catalyst may be a boric acid derivative, preferably metaboric acid.
  • the average molecular weight of the borate esters of the secondary alcohols may be more than three times higher than that of the unreacted paraffins, these components may be separated from the unreacted paraffins by separation techniques such as high-vacuum flashing or stripping, using a wiped film evaporator, solvent-solvent extraction or by application of membrane separation techniques, such as dialysis using a latex rubber membrane and heptane as the eluens .
  • the saponification of the borate ester is carried out with an aqueous base.
  • the hydrolysis step is replaced by transesterification with a low boiling alcohol, such as methanol or ethanol .
  • a low boiling alcohol such as methanol or ethanol .
  • the low boiling trimethylborate or triethylborate may be easily boiled off from the secondary alcohol.
  • the ethoxylation is carried out in one single step using a double metal cyanide catalyst (DMC) in such low amounts that a secondary alcohol ethoxylate product is produced containing preferably less than 10 ppm cobalt metal and 20 ppm zinc metal.
  • DMC double metal cyanide catalyst
  • Fig. 1 is a graph which compares the secondary alcohol content as a function of time when a paraffin made according to the present invention is oxidized as opposed to when a paraffin from kerosene is oxidized.
  • hydrocarbons may be prepared by reacting carbon monoxide and hydrogen under suitable conditions.
  • the preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen at elevated temperature and pressure in the presence of a suitable catalyst is known as the Fischer-Tropsch hydrocarbon synthesis.
  • Catalysts used in this hydrocarbon synthesis are normally referred to as Fischer-Tropsch catalysts and usually comprise one or more metals from Groups 8, 9 and 10 of the Periodic Table of Elements, optionally together with one or more promoters, and a carrier material.
  • iron, nickel, cobalt and ruthenium are well known catalytically active metals for such catalysts and can be used in the present process. Processes and catalysts for this reaction are described in U.S. Patent No. 7,105,706 which is herein incorporated by reference in its entirety.
  • the catalyst may preferably also comprise a porous carrier material, in particular a refractory oxide carrier.
  • a refractory oxide carrier include alumina, silica, titania, zirconia or mixtures thereof, such as silica-alumina or physical mixtures such as silica and titania.
  • Particularly suitable carriers are those comprising titania, zirconia or mixtures thereof.
  • the catalyst is a cobalt-based Fischer-Tropsch catalyst.
  • titania carriers are preferred, in particular titania which has been prepared in the absence of sulfur-containing compounds.
  • This carrier may further comprise up to about 50% by weight of another refractory oxide, typically silica or alumina. More preferably, the additional refractory oxide, if present, constitutes up to 20% by weight, even more preferably up to 10% by weight, of the carrier.
  • a cobalt-based Fischer-Tropsch catalyst comprises about 1-100 parts by weight of cobalt (calculated as element) , preferably about 3-60 parts by weight and more preferably about 5-40 parts by weight, per 100 parts by weight of carrier. These amounts of cobalt refer to the total amount of cobalt in elemental form and can be determined by known elemental analysis techniques.
  • the catalyst may comprise one or more promoters known to those skilled in the art.
  • Suitable promoters include manganese, zirconium, titanium, ruthenium, platinum, vanadium, palladium and/or rhenium.
  • the amount of promoter, if present, is typically between about 0.1 and about 150 parts by weight (calculated as element) , for example between about 0.25 and about 50, more suitably between about 0.5 and about 20 and even more suitably between about 0.5 and about 10, parts by weight per 100 parts by weight of carrier.
  • the Fischer-Tropsch catalyst may be an iron-based Fischer-Tropsch catalyst.
  • suitable iron-based Fischer-Tropsch catalysts include those disclosed in United States Patent 6,740,683 which is herein incorporated by reference in its entirety.
  • Alternative iron-based Fischer-Tropsch catalysts include those used in the so-called "Synthol" process. Details of catalysts used in the Synthol process can be found in Frohning et al in Falbe; Chemical Feedstocks from Coal; Chapter 8; Fischer-Tropsch Process, pages 309-432, John Wiley & Sons, 1982. In particular, page 396 discloses details of Synthol catalyst preparation.
  • the Fischer-Tropsch process conditions applied in step (a) of the present process may typically involve a temperature in the range from about 125 to about 350 0 C, or from about 150 to about 250 0 C, or from about 160 to about 230 0 C, and a pressure in the range from about 500 up to about 15,000 kPa abs, or from about 5500 to about 14,000 kPa abs .
  • Step (a) of the present process may be operated at the pressures conventionally applied, i.e. up to about 8000 kPa abs., suitably up to about 6500 kPa abs.
  • the Fischer-Tropsch process conditions applied in step (a) of the present process are preferably those as disclosed in United States Patent 6,740,683, about 200 to about 300 0 C and about 1000 to about 10,000 kPa abs .
  • Hydrogen and carbon monoxide may typically be fed to the reactor at a molar ratio in the range from about 0.5 to about 4, preferably from about 0.5 to about 3, more preferably from about 0.5 to about 2.5 and especially from about 1.0 to about 1.5. These molar ratios are preferred for the case of a fixed bed reactor.
  • the Fischer-Tropsch reaction step (a) may be conducted using a variety of reactor types and reaction regimes, for example a fixed bed regime, a slurry phase regime or a fluidized bed regime. It will be appreciated that the size of the catalyst particles may vary depending on the reaction regime they are intended for. It is within the normal skills of the skilled person to select the most appropriate catalyst particle size for a given reaction regime.
  • the skilled person is capable to select the most appropriate conditions for a specific reactor configuration and reaction regime.
  • the preferred gas hourly space velocity may depend upon the type of reaction regime that is being applied.
  • the gas hourly space velocity is chosen in the range from about 500 to about 2500 Nl/l/h (normal-litres/litre/hour,) .
  • the gas hourly space velocity is chosen in the range from about 1500 to about 7500 Nl/l/h.
  • this hydrocarbon fraction may be hydrotreated and separated into one or more hydrocarbon fractions comprising from about 95 to about 100% by weight, preferably from about 99 to about 100% by weight, of paraffins .
  • the separation may involve a distillation treatment. Conventional distillation techniques may be used.
  • the separation step may involve fractional distillation, but the separation step may also comprise a combination of distillation with another separation treatment, such as condensation and/or extraction.
  • the catalyst and process conditions in step (a) are selected such that the hydrocarbon fraction obtained in step (a) comprises a Ci 0 to Cn hydrocarbon fraction, a C i2 to C i3 hydrocarbon fraction or a combination of these two hydrocarbon fractions .
  • the hydrocarbon fraction may contain from about 99 to about 100% by weight of paraffins.
  • the catalyst and process conditions are selected to produce a Ci 4 to Ci 5 and a Ci 6 to Ci 8 hydrocarbon fraction or a combination of these two hydrocarbon fractions.
  • hydrocarbon fraction means a portion of the Fischer-Tropsch (FT) reaction product which boils within a certain temperature range. Said portion comprises a mixture of compounds synthesized in the Fischer- Tropsch reaction such as paraffins, olefins and alcohols. The compounds in a particular hydrocarbon fraction each have boiling points within the boiling point range for that hydrocarbon fraction .
  • FT Fischer-Tropsch
  • hydrocarbon fractions which comprise paraffins and olefins having from 9 to 18 carbon atoms and hydrocarbon fractions having from 10 to 13 carbon atoms and hydrocarbon fractions having from 10 to 11 carbon atoms and hydrocarbon fractions having from 12 to 13 carbon atoms and hydrocarbon fractions having from 14 to 18 carbon atoms and hydrocarbon fractions having from 14 to 15 carbon atoms and hydrocarbon fractions having from 16 to 18 carbon atoms.
  • Narrow cut fractions are particularly preferred because after oxidation of the paraffins, the separation between the secondary alcohols and the diols (by-product) is easier because there is no boiling point overlap.
  • Paraffins and olefins having the same number of carbon atoms, n tend to have boiling points within about 5 ° C or less of each other. Therefore hydrocarbon fractions can also be described in terms of the number of carbon atoms present in the paraffins and olefins contained therein. Hence a “C 9 " hydrocarbon fraction will generally comprise paraffins having 9 carbon atoms and olefins having 9 carbon atoms . Suitable hydrocarbon fractions herein may be designated as “C 9 ", "Ci 0 ", “Cn”, “Ci 2 ", “Ci 3 “, “Ci 4 ", “Ci 5 “, “Ci 6 “, “Ci 7 " hydrocarbon fractions .
  • suitable hydrocarbon fractions may comprise a mixture of paraffins and olefins having a wider range of carbon atom numbers (and hence having a wider boiling point range) .
  • other such hydrocarbon fractions suitable for use herein include the C 8 -Ci 0 , Cn-Ci 2 , Ci 3 -Ci 4 and Ci 5 -Ci 6 hydrocarbon fractions.
  • the Cn-Ci 2 hydrocarbon fraction will tend to comprise a mixture of paraffins and olefins having from 11-12 carbon atoms, in addition to alcohols having from 9-10 carbon atoms.
  • the Cn-Ci 2 hydrocarbon fraction may additionally comprise paraffins, olefins and alcohols of higher or lower carbon number, depending on the boiling point range of the fraction.
  • hydrocarbon fractions can be used individually as feed to oxidation step (b) , but two or more of these fractions may also be combined into a feed stream to the oxidation step (b) .
  • the process of the present invention is particularly suitable when using Ci 0 -Cn hydrocarbon streams, Ci 2 -Ci 3 hydrocarbon streams, Ci 4 -Ci 5 hydrocarbon streams and C 1 6-C 1 8 hydrocarbon streams or mixtures thereof.
  • Narrow cut fractions particularly preferred because after oxidation of the paraffins, the separation between the secondary alcohols and the diols (by-product) is easier because there is no boiling point overlap.
  • the crude products from the FT reaction probably should not be used in the Bashkirov oxidation.
  • Co-produced olefins are expected to have a negative effect on the selectivity and rate of the oxidation.
  • Co-produced alcohols may be allowed because they may be separated from paraffins and olefins after borate ester formation by membrane separation.
  • the crude FT products of a gas to liquids plant generally contain paraffins, (alpha) olefins and alcohols of high molecular weight as the main products. They are subsequently hydrogenated and/or (hydro) cracked to the desired saturation level and mol weight distribution. These saturated products are distilled. Paraffin Oxidation
  • the paraffins may be oxidized in the presence of a weak acid, preferably boric acid.
  • a weak acid preferably boric acid.
  • Boric acid is preferred because it leads to high selectivity of alcohol formation and it catalyzes alcohol formation at a fast rate.
  • Boric acids which can be used in the present invention include orthoboric acid, metaboric acid (dehydrated boric acid), and boric oxide, as well as boric esters. Each of these boric acid forms will readily form esters with the secondary alcohols, whereas boric esters will transesterify with secondary alcohols.
  • Metaboric acid is preferred because it is easily formed from orthoboric acid by dehydration, its esters are more resistant to further oxidation and are easily hydrolyzed or transesterified, the concomitant boric acid or borate derivative may be efficiently recycled, and it is finely divided and has less tendency to agglomerate and deposit on the reactor walls .
  • Metaboric acid may be formed from orthoboric acid by dehydration. Boric anhydride gives the least fouling due to being a high melting finely divided solid. Orthoboric and metaboric acids may be heated slowly in paraffin under N 2 to produce a non-fouling boron compound.
  • At least a portion of the feed paraffins may be mixed with boric acid to form a slurry. This slurry may then be dehydrated to form metaboric acid. The dehydration may take place at a temperature of from about 140 to about 160 0 C over a period of from about 0.1 to about 2 hours.
  • the dehydrated slurry of metaboric acid and paraffins and also the portion of the feed paraffins which was not mixed with the acid are introduced into an oxidation reactor.
  • Oxidizing gas is also added to the reactor.
  • the oxidizing gas may be air or an inert gas such as nitrogen with a low concentration of oxygen.
  • the rate of oxidation may be controlled by limiting the amount of oxygen absorbed. This can be done by limiting the air flow, operating with air at reduced pressures to limit the amount of oxygen absorbed, or by using a gas with a low oxygen content. It is preferred to use an inert gas, such as nitrogen, with an oxygen content of from about 2 to about 8 volume percent.
  • the oxidation reaction may be carried out at a temperature from about 150 to 175°C. Above 175°C, the reaction is difficult to control. Preferred temperatures for use herein range from about 160 to about 175°C.
  • the reaction is generally carried out at relatively low pressures. The pressure may range from about 100 to about 300 kPa abs .
  • the length of time of the oxidation has an effect on the conversion of the paraffins to the secondary alcohols.
  • the oxidation may continue for from about 2 to about 4 hours .
  • the reaction of the alcohols with the metaboric acid to form borate esters of the alcohols is reversible. Water may be removed during the oxidation to drive the reaction to produce more esters .
  • the oxidation reaction mixture is then distilled to remove unreacted paraffins and other low boiling compounds.
  • the operating conditions will depend upon the carbon number of the feed paraffins and the borate esters produced.
  • the paraffins may be recycled after being washed with caustic followed by water washing.
  • the separation by distillation is straightforward.
  • the separation may be carried out by application of high vacuum flashing or stripping, using a wiped film evaporator or by application of membrane separation techniques, such as dialysis using a latex rubber membrane and heptane as the eluens .
  • the next step is hydrolysis of the borate esters to form alcohols and boric acid.
  • Water is added to the borate ester mixture at elevated temperature, preferably of from about 90 to about 100 0 C over a period of from about 1 to about 3 hours.
  • the alcohols may be separated by decantation of the aqueous boric acid phase.
  • the boric acid in the aqueous phase may be crystallized out and recycled.
  • the hydrolysis of the borate esters forms crude alcohols which contain residual organic acids, boric acid, and organic esters. These are removed by saponification by reaction of this mixture with a base at a temperature of from about 90 to about 100 0 C for from about 1 to about 3 hours.
  • the base may be caustic soda, sodium hydroxide, potassium hydroxide, etc.
  • the mixture is allowed to settle and the base (aqueous) layer is removed. This may be repeated more than once.
  • the remaining organic material may then be washed with water at a temperature of from about 80 to about 100 0 C to separate the alcohols. Multiple water washing steps may be used.
  • the water washed material may then be subjected to two distillations. One distillation removes the lower boiling components and the other distillation removes the higher boiling components.
  • the final recovered product is a secondary alcohol.
  • transesterification of the borate esters with volatile alcohols may be employed for liberating the higher alcohols from the borate ester.
  • volatile alcohols such as methanol or ethanol
  • the volatile methyl or ethyl esters of boric acid are subsequently boiled off.
  • Organic esters and acids contained in the crude secondary alcohols are removed by saponification and subsequent extraction and washing with water.
  • the water washed material may then be subjected to two distillations (topping and tailing) . One distillation removes the lower boiling components and the other distillation removes the higher boiling components.
  • the final recovered product is the secondary alcohol.
  • membrane separation techniques may be employed to separate the liberated secondary alcohol from trialkyl borate and to separate the secondary alcohol from its further contaminants .
  • the secondary alcohol alkoxylates may be prepared by a process comprising reacting a secondary alcohol with an alkylene oxide in the presence of a multi, usually double, metal cyanide (DMC) catalyst .
  • DMC metal cyanide
  • the alkoxylation reaction in the invention may be conducted in a generally conventional manner.
  • the catalyst may initially be mixed with liquid secondary alcohol.
  • the mixture of catalyst and liquid secondary alcohol may be contacted, preferably under agitation, with alkylene oxide reactant, which is typically introduced in gaseous form, at least for the lower alkylene oxides.
  • alkylene oxide reactant which is typically introduced in gaseous form, at least for the lower alkylene oxides.
  • the order in which the reactants and catalyst are contacted has not been found to be critical to the invention.
  • the two reactants are utilized in quantities which are predetermined to yield an alkoxylate product of the desired mean or average adduct number.
  • the average adduct number of the product is not critical to this process. Such products commonly have an average adduct number in the range from less than one to 30 or greater.
  • the quantities are selected to produce an ethoxylate containing an average of 3 to 7 ethylene oxide (EO) groups per molecule of the ethoxylate.
  • EO ethylene oxide
  • suitable and preferred process temperatures and pressures for purposes of this invention are the same as in conventional alkoxylation reactions between the same reactants, employing conventional catalysts.
  • a temperature of at least about 90 0 C, particularly at least about 120 0 C and most particularly at least about 130 0 C, may be utilized to achieve sufficient rate of reaction, while a temperature of about 250 0 C or less, particularly about 210 0 C or less, and most particularly about 190 0 C or less, typically is desirable to minimize degradation of the product.
  • the process temperature can be optimized for given reactants, taking such factors into account .
  • Superatmospheric pressures e.g., pressures between about 170 and about 1000 kPa abs, may be used as long as the pressure is sufficient to maintain the secondary alcohol substantially in the liquid state.
  • alkoxylation may then be suitably conducted by introducing alkylene oxide into a reactor containing the secondary alcohol and the catalyst.
  • the partial pressure of a lower alkylene oxide reactant is preferably limited, for instance, to about 400 kPa abs or less, and/or the reactant is preferably diluted with an inert gas such as nitrogen, for instance, to a vapor phase concentration of about 50 volume percent or less.
  • the reaction may, however, be safely accomplished at greater alkylene oxide concentration, greater total pressure and greater partial pressure of alkylene oxide if suitable precautions, known in the art, are taken to manage the risks of explosion.
  • a total pressure of from about 400 to about 900 kPa abs with an alkylene oxide partial pressure of from about 200 to about 500 kPa abs may be advantageously used.
  • the time required to complete this step of the process according to the invention is dependent both upon the degree of alkoxylation desired (i.e., upon the average alkylene oxide adduct number of the product) as well as upon the rate of the alkoxylation reaction (which is, in turn, dependent upon temperature, catalyst quantity and nature of the reactants) .
  • a typical reaction time may be from about 1 to about 24 hours, preferably from about 1 to about 4 hours.
  • the product may be cooled.
  • catalyst may be removed from the final product, although catalyst removal is not necessary to the process of the invention.
  • Catalyst residues may be removed, for example, by filtration, precipitation, or extraction.
  • a number of specific chemical and physical treatment methods have been found to facilitate removal of catalyst residues from a liquid product. Such treatments include contact of the alkoxylation product with strong acids such as phosphoric and/or oxalic acids or with solid organic acids such as NAFION H+ or AMBERLITE IR 120H acids; contact with alkali metal carbonates and bicarbonates; contact with zeolites such as Type Y zeolite or mordenite; or contact with certain clays.
  • such treatments are followed by filtration or precipitation of the solids from the product. In many cases filtration, precipitation, or centrifugation is most efficient at elevated temperature.
  • secondary alcohols (and their alkoxylates and alkoxysulfates) having from 9 to 30 carbon atoms, with C9 to C24 secondary alcohols considered more preferred and C9 to C20 C ] _Q to C]_3 and C]_4 to C]_g secondary alcohols considered highly preferred and C]_i to C]_3 C]_4 to C16 ⁇ 15 to C]_7 and C]_g to C]_g secondary alcohols considered most preferred, including mixtures thereof, such as a mixture of C9 and C20 secondary alcohols.
  • the secondary alcohols may be of branched or straight chain structure depending on the intended use.
  • secondary alcohols which may be made herein include 2-undecanol, 2-hexanol, 3-hexanol, 2-heptanol, 3- heptanol, 2-octanol, 3-octanol, 2-nonanol, 2-decanol, 4- decanol, 2-dodecanol, 2-tetradecanol, 2-hexadecanol, and mixtures thereof.
  • Suitable alkylene oxide reactants for use herein include an alkylene oxide (epoxide) reactant which comprises one or more vicinal alkylene oxides, particularly the lower alkylene oxides and more particularly those in the C2 to C4 range.
  • alkylene oxides are represented by formula (I)
  • each of the R ⁇ , R ⁇ , R ⁇ and R ⁇ moieties is individually selected from the group consisting of hydrogen and alkyl moieties.
  • Reactants which comprise ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof are more preferred, particularly those which consist essentially of ethylene oxide and propylene oxide.
  • Alkylene oxide reactants consisting essentially of ethylene oxide are considered most preferred from the standpoint of commercial opportunities for the practice of alkoxylation processes, and also from the standpoint of the preparation of products having narrow-range ethylene oxide adduct distributions.
  • the catalyst used for the preparation of the alkoxylate composition of the present invention is a double metal cyanide catalyst. Any double metal cyanide catalyst suitable for use in alkoxylation reactions can be used in the present invention.
  • Conventional DMC catalysts are prepared by reacting aqueous solutions of metal salts and metal cyanide salts or metal cyanide complex acids to form a precipitate of the DMC compound.
  • the DMC catalysts used herein are particularly suitable for the direct ethoxylation of secondary alcohols. It is particularly useful to be able to directly ethoxylate secondary alcohols since secondary alcohols may be derived from relatively cheap feedstocks such as paraffins produced by oxidation using Fischer-Tropsch technologies as described above .
  • the catalyst may be used in an amount which is effective to catalyze the alkoxylation reaction.
  • the catalyst may be used at a level such that the level of solid DMC catalyst remaining in the final alkoxylate composition is in the range from about 1 to about 1000 ppm (wt/wt) , preferably of from about 5 to about 200 ppm (wt/wt) , more preferably from about 10 to about 100 ppm (wt/wt) .
  • the DMC catalysts used in the present invention are very active and hence exhibit high alkoxylation rates. They are sufficiently active to allow their use at very low concentrations of the solid catalyst content in the final alkoxylation product composition.
  • the catalyst can often be left in the alkoxylated alcohol composition without an adverse effect on product quality.
  • the ability to leave catalysts in the alkoxylated alcohol composition is an important advantage because commercial alkoxylated alcohols currently require a catalyst removal step.
  • the concentration of the residual cobalt in the final alkoxylate composition is preferably below about 10 ppm (wt/wt) .
  • suitable metal salts and metal cyanide salts are, for instance, described in U.S. Patents Nos . 5,627,122 and 5,780,584, which are herein incorporated by reference in their entirety.
  • suitable metal salts may be water- soluble salts suitably having the formula M(X' ) n ', in which M is selected from the group consisting of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV) , Sr(II) , W(IV), W(VI), Cu(II), and Cr(III) .
  • M is selected from the group consisting of Zn(II) , Fe(II) , Co(II) , and Ni(II) , especially Zn(II) .
  • X' is preferably an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate.
  • the value of n' satisfies the valency state of M and typically is from 1 to 3.
  • suitable metal salts include, but are not limited to, zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetate, zinc benzoate, zinc nitrate, iron (II) chloride, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt (II) thiocyanate, nickel (II) formate, nickel (II) nitrate, and the like, and mixtures thereof.
  • Zinc halides, and particularly zinc chloride are preferred.
  • the metal cyanide salt may be a water-soluble metal cyanide salt having the general formula (Y) a ⁇ M' (CN)J 3 I (A' ) Q I in which M' is selected from the group consisting of Fe(II) , Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III) , Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V) .
  • M' is selected from the group consisting of Co(II), Co(III), Fe(II), Fe(III) , Cr(III), Ir(III) , and Ni(II) , especially Co(II) or Co(III) .
  • the water-soluble metal cyanide salt may contain one or more of these metals.
  • Y is an alkali metal ion or alkaline earth metal ion, such as lithium, sodium, potassium and calcium.
  • A' is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate.
  • Suitable water-soluble metal cyanide salts may include, for example, potassium hexacyanocobaltate (III) , potassium hexacyanoferrate (II) , potassium hexacyanoferrate (III ) , calcium hexacyanocobaltate (III) and lithium hexacyano- iridate(III) .
  • a particularly preferred water-soluble metal cyanide salt for use herein is potassium hexacyanocobaltate (III) .
  • DMC catalysts useful in the process of this invention may be prepared according to the processes described in U.S. Published Patent application No. 2005/0014979, which is herein incorporated by reference in its entirely.
  • DMC catalysts may be prepared in the presence of a low molecular weight organic complexing agent such that a dispersion is formed comprising a solid DMC complex in an aqueous medium.
  • the organic complexing agent used should generally be reasonably to well soluble in water.
  • Suitable complexing agents are, for instance, disclosed in U.S. Patent No. 5,158,922, which is herein incorporated by reference in its entirely, and in general are water-soluble heteroatom- containing organic compounds that can complex with the double metal cyanide compound.
  • suitable complexing agents may include alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides, and mixtures thereof.
  • Combining both aqueous reactant streams may be conducted by conventional mixing techniques including mechanical stirring and ultrasonic mixing. Although applicable, it is not required that intimate mixing techniques like high shear stirring or homogenization are used.
  • the reaction between metal salt and metal cyanide salt may be carried out at a pressure of from about 50 to about 1000 kPa abs and a temperature of from about 0 to about 80 0 C. However, it is preferred that the reaction be carried out at mild conditions, i.e. a pressure of about 50 to about 200 kPa abs and a temperature of from about 10 to about 40 0 C.
  • an extracting liquid may be added to the dispersion of solid DMC complex in aqueous medium, in order that the DMC catalyst particles may be efficiently and easily separated from the aqueous phase without losing any catalytic activity .
  • Suitable extracting liquids are described in U.S. Patent No. 6,699,961, which is herein incorporated by reference in its entirely.
  • a suitable extracting liquid should meet two requirements: firstly it should be essentially insoluble in water and secondly it must be capable of extracting the DMC complex from the aqueous phase.
  • the extracting liquid can, for instance, be an ester, a ketone, an ether, a diester, an alcohol, a di-alcohol, a (di)alkyl carbamate, a nitrile or an alkane.
  • An especially preferred extracting liquid for use herein is methyl tert-butyl ether.
  • the extracting liquid is added under stirring and stirring is continued until the liquid has been uniformly distributed through the reaction mixture. After the stirring has stopped the reaction mixture is allowed sufficient time to settle, i.e. sufficient time to separate into two phases: an aqueous bottom layer and a layer floating thereon containing the DMC catalyst dispersed in the extracting liquid.
  • the next part of the catalyst preparation process is for the aqueous layer to be removed. Since the aqueous layer forms the bottom layer of the two phase system formed, this may be easily accomplished by draining the aqueous layer via a valve in the bottom part of the vessel in which the phase separation occurred. After removal of the aqueous phase, the remaining phase contains the solid DMC catalyst particles which are dispersed or finely divided in the extracting compound and which are subsequently recovered.
  • the catalyst recovery step may be carried out in various ways .
  • the recovery procedure may involve mixing the DMC catalyst with complexing agent, optionally in admixture with water, and separating DMC catalyst and complexing agent/water again, e.g. by filtration, centrifugation/decantation or flashing. This procedure may be repeated one or more times. Eventually, the catalyst may be dried and recovered as a solid.
  • the recovery step may comprise adding a water/complexing agent to the DMC catalyst layer and admixing catalyst layer and water/complexing agent (e.g. by stirring) , allowing a two phase system to be formed and removing the aqueous layer.
  • This procedure may be repeated one to five times after which the remaining catalyst layer may be dried and the catalyst may be recovered in solid form (as a powder) or, alternatively, a liquid alcohol/polyol may be added to the catalyst layer and a catalyst suspension in liquid alcohol is formed, which may be used as such.
  • the alcohol/polyol added may be any liquid alcohol/polyol which is suitable to serve as a liquid medium for the DMC catalyst particles.
  • the DMC catalyst is used for catalyzing the alkoxylation reaction of alcohols, it is preferred to use an alcohol/polyol which is compatible with the alkoxylated alcohols to be produced and which will not have any negative effect on the final alkoxylated alcohol produced when present therein in trace amounts .
  • suitable polyols include polyols such as polyethylene glycol and polypropylene glycol.
  • the organic complexing agent may be removed from the catalyst slurry. This may be achieved by any means known in the art to be suitable for liquid-liquid separation.
  • a preferred method for the purpose of the present invention is flashing off the complexing agent at atmospheric conditions or under reduced pressure. Flashing under reduced pressure is preferred, because this enables separation at a lower temperature which reduces the risk of thermal decomposition of the DMC catalyst.
  • the DMC catalyst may be recovered as a slurry in liquid alcohol/polyol .
  • the advantage of such a slurry is that it is storage stable and may, for instance, be stored in a drum. Moreover, dosing of the catalyst and its distribution through the alkoxylation medium is greatly facilitated by using a catalyst slurry.
  • the secondary alcohol alkoxylates may be sulfated using one of a number of sulfating agents including sulfur trioxide, complexes of sulfur trioxide with (Lewis) bases , such as the sulfur trioxide pyridine complex and the sulfur trioxide trimethylamine complex, chlorosulfonic acid and sulfamic acid.
  • the sulfation may be carried out at a temperature preferably not above about 80 0 C.
  • the sulfation may be carried out at temperature as low as about -20 0 C, but higher temperatures are more economical.
  • the sulfation may be carried out at a temperature from about 20 to about 70 0 C, preferably from about 20 to about 60 0 C, and more preferably from about 20 to about 50 0 C.
  • Sulfur trioxide is the most economical sulfating agent.
  • the secondary alcohol alkoxylates may be reacted with a gas mixture which in addition to at least one inert gas contains from about 1 to about 8 percent by volume, relative to the gas mixture, of gaseous sulfur trioxide, preferably from about 1.5 to about 5 percent volume.
  • gas mixtures having less than 1 percent by volume of sulfur trioxide but the space-time yield is then decreased unnecessarily.
  • Inert gas mixtures having more than 8 percent by volume of sulfur trioxide in general may lead to difficulties due to uneven sulfation, lack of consistent temperature and increasing formation of undesired byproducts .
  • other inert gases are also suitable, air or nitrogen are preferred, as a rule because of easy availability.
  • the reaction of the secondary alcohol alkoxylate with the sulfur trioxide containing inert gas may be carried out in falling film reactors .
  • Such reactors utilize a liquid film trickling in a thin layer on a cooled wall which is brought into contact in a continuous current with the gas.
  • Kettle cascades for example, would be suitable as possible reactors.
  • Other reactors include stirred tank reactors, which may be employed if the sulfation is carried out using sulfamic acid or a complex of sulfur trioxide and a (Lewis) base, such as the sulfur trioxide pyridine complex or the sulfur trioxide trimethylamine complex. These sulfation agents would allow an increased residence time of sulfation without the risk of ethoxylate chain degradation and olefin elimination by (Lewis) acid catalysis.
  • the molar ratio of sulfur trioxide to alkoxylate may be 1.4 to 1 or less including about 0.8 to about 1 mole of sulfur trioxide used per mole of OH groups in the alkoxylate and latter ratio is preferred.
  • Sulfur trioxide may be used to sulfate the alkoxylates and the temperature may range from about -20 0 C to about 50 0 C, preferably from about 5 0 C to about 40 0 C, and the pressure may be in the range from about 100 to about 500 kPa abs .
  • the reaction may be carried out continuously or discontinuously .
  • the residence time for sulfation may range from about 0.5 seconds to about 10 hours, but is preferably from 0.5 seconds to 20 minutes.
  • the sulfation may be carried out using chlorosulfonic acid at a temperature from about -20 0 C to about 50 0 C, preferably from about 0 0 C to about 30 0 C.
  • the mole ratio between the alkoxylate and the chlorosulfonic acid may range from about 1:0.8 to about 1:1.2, preferably about 1:0.8 to 1:1.
  • the reaction may be carried out continuously or discontinuously for a time between fractions of seconds (i.e., 0.5 seconds) to about 20 minutes.
  • the liquid reaction mixture may be neutralized using an aqueous alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, an aqueous alkaline earth metal hydroxide, such as magnesium hydroxide or calcium hydroxide, or bases such as ammonium hydroxide, substituted ammonium hydroxide, sodium carbonate or potassium hydrogen carbonate.
  • the neutralization procedure may be carried out over a wide range of temperatures and pressures. For example, the neutralization procedure may be carried out at a temperature from about 0 0 C to about 65°C and a pressure in the range from about 100 to about 200 kPa abs .
  • the neutralization time may be in the range from about 0.5 hours to about 1 hour but shorter and longer times may be used where appropriate.
  • the oxidation was performed in a 2-litre glass reactor equipped with a double turbine stirrer, overhead cooler, thermostat bath (Julabo F30) , and a safety relief valve of 500 kPa abs.
  • the inlet gas flows were measured by mass flow controllers (Brooks Instruments, 5850TR) , and controlled by constant pressure valves (Testcom 500) and safety relief valves.
  • the off-gas flow was controlled by a backpressure valve and measured by a gas meter (Ritter TG3) .
  • the off-gas line was connected to a cold-trap and oxygen analyzer (M&C, PMA 225) .
  • the maximum operating window of this unit was 500 kPa abs at 180 0 C.
  • the reactor was charged with 1200 ml (888.2g) Ci 0 -Ci 3 paraffin (GC analysis gives typically 11 wt% decane, 32 wt% undecane, 31 wt% dodecane and 25 wt% tridecane, of which approximately 5 wt% are predominantly methyl-branched C 1 0-C 1 3 paraffins; GC x GC analysis: 250 mg/kg total mono-naphthenes, 10 mg/kg total di-naphthenes and 0 mg/kg total mono-aromatics) and 32.23 g B 2 O 3 (Sigma-Aldrich, 99.98%) .
  • the reactor was heated under a reduced N 2 flow. At 110 0 C it was pressurized to 150 kPa abs by increasing the N 2 flow to 200 Nl/hr. Subsequently, the reactor temperature was increased to 170 0 C, while stirred (1000 rpm) .
  • both the reactor temperature and pressure remained stable, part of the N 2 flow was replaced stepwise by a mixed gas flow (4.94 vol% O 2 in N 2 ) to start the oxidation reaction. Table 1 shows the reaction conditions used.
  • the conversion was aimed at 15-20% to obtain good selectivity towards secondary alcohols.
  • the reactor temperature increased slightly (3°C) as a result of the exothermic oxidation reaction.
  • the reaction was terminated after 180 minutes by reducing the O 2 / N 2 flow to zero.
  • the reactor pressure was slowly reduced and the reactor was cooled to room temperature under a N 2 flow.
  • the reactor mixture and reflux fraction were collected (809.5 g and 88.97 g, respectively) .
  • the reflux fraction consisted of an organic layer and a water layer.
  • the organic layer (-72 g) contained predominantly decane and undecane (approximately 50 wt% and 40 wt%, respectively) . Little primary or secondary alcohols were found ( ⁇ 0.2 wt%) .
  • the main contaminants were C 2 to C 7 acids ( ⁇ 1 wt%) .
  • the water layer in the reflux fraction (-16 g) contained C 2 to C 7 acids and C 2 to C 4 lactones.
  • the sample was extracted with diethyl ether to enable qualitative analysis of water layer) . Based on gas chromatography results, the overall conversion to primary and secondary monoalcohols was about 17 wt%.
  • Distillation of the reaction mixture (809.5 g) was performed in a wiped film evaporator.
  • the feed was preheated to 50 0 C in order to decrease viscosity.
  • the wall temperature was heated to about 130 0 C (the temperature of the heating oil was 170 0 C) and the temperature of the cold finger was 4-6 0 C.
  • the vacuum during the distillation was 2- 6 Pa abs .
  • the internals were rotated at 200 rpm.
  • Example Ib The distillate fractions C 3 and C 4 were combined (the so-called "purified alcohol mixture", designated Example Ib) and used for ethoxylation .
  • the final yield of this purified alcohol mixture was 39.7 g.
  • Gas chromatography showed that the purified alcohol mixture (Example Ib) having an average molecular weight of 182, contained predominantly secondary Cn, Ci 2 and C 1 3 alcohols (92 wt%) .
  • small amounts of secondary Cio alcohol (1.4 wt%) and primary Cg to C i2 alcohols (1.8 wt%) were present.
  • the main contaminants were Cn to Ci 3 ketones ( ⁇ 1.25 wt%) , paraffins ( ⁇ 0.25 wt%) and Ci 0 to Ci 2 diols ( ⁇ 0.25 wt%) .
  • Example 1C Ethoxylation
  • Ethoxylation was performed in a lab scale apparatus using a 250ml Schlenk flask equipped with magnetic stirring bar and bubble counter.
  • the flask was filled with the alcohol mixture of Example Ib (36.0 g) , DMC catalyst (7-8 mg as solid catalyst, prepared essentially according to Example 1 of co-pending U.S. Published Application Serial No. 2005/0014979, which is herein incorporated by reference) , and toluene (7 ml) .
  • the mixture was flushed with N 2 at 130 0 C for 20 minutes to remove the toluene and possible light contaminants (e.g. water) .
  • a small amount of alcohol evaporated during this step and 35.66 g (196 mmol) of alcohol remained.
  • ethylene oxide (EO) was introduced at such a rate that no gas passed the bubble counter. After an initial uptake due to saturation of the alcohol with EO, an induction period of 45 minutes was observed before the catalyst became active. Then the EO uptake was rapid and 62.15 g of EO was consumed within 3.5 hours. Based on this weight increase the average length of ethoxylate chains was estimated to be 7.2 equivalents of EO. Reducing the EO flow to zero stopped the reaction and the flask was flushed with N 2 for 1 hour to remove residual EO.
  • EO ethylene oxide
  • Example Ic yellow oil, opaque at room temperature
  • HPLC high performance liquid chromatography
  • ICP-MS inductively coupled plasma mass spectrometry
  • Example Ic Based on the peak intensities of the ethoxylate end-groups compared to the carbons within the ethoxylate chain, the average chain length was estimated to be equivalent to 6.8 EO units for Example Ic. HPLC measurements gave an average chain length of 7.2 EO units and an amount of free alcohols of approximately 1.9 %wt . Detailed HPLC results of Example Ic on the EO distribution are given in Table 6.
  • the amounts of trace metals in the final product of Example Ic have been determined by ICP-MS to be in the range of 4-7 ppm for cobalt and 11-19 ppm for zinc, respectively .
  • 3-Octanol and 2-dodecanol were used as internal standards (ISTD) for GC analysis of the LDF- and HDF-based samples, respectively.
  • ISD internal standards
  • LDF- and HDF-based samples the retention times of the linear paraffins, branched paraffins, linear secondary alcohols and most of the linear primary alcohols are known. Furthermore, several ketones, acids and lactones were identified and diols were indicated. Identification of these products was based on Gas chromatography-mass spectrometry (GC-MS) analysis of pure reference samples. Since retention times may shift due to ageing of the GC-column, they have not been specified here.
  • GC-MS Gas chromatography-mass spectrometry
  • Measurement of the average number of moles of EO per mole of secondary alcohol and the residual amount of secondary alcohol of the distribution of the ethoxylated secondary alcohol was performed by 13 C-NMR spectroscopy using a 300 or a 400 MHz apparatus.
  • concentration of cobalt and zinc remaining in the product composition in mg/kg was measured by Inductively Coupled Plasma - Mass Spectroscopy (ICP-MS) .
  • the detection limit for cobalt and zinc is 0.5 mg/kg.
  • GC Gas Chromatography
  • the technique for these GC measurements involves introducing a known amount of the alcohol ethoxylate product into a sealed vial, which is thermostated and held for 20 minutes at 50 0 C to allow equilibrium between the gas and liquid phases. After thermostating is complete, the product composition vapour is automatically injected into the Capillary Gas Chromatography apparatus.
  • a fused silica, 50 m x 0.32 mm internal diameter, 1.0 ⁇ m film CpSiI 5CB is used as the carrier gas. Detection is performed by flame ionization. The calibration is performed using the standard addition method at 2 levels.
  • Example 2b The reaction mixture was distilled three times in the wiped film evaporator to remove the unreacted paraffin. After the three distillations less than 1.5 wt% of HDF paraffins remained in the residue. Hydrolysis and fractional distillation were carried out similarly to Example IB. Two purified secondary alcohol fractions were isolated, designated Example 2b and Example 2b' .
  • the light fraction, Example 2b, (52.5 g, having an average molecular weight of 225) consisted mainly of Ci 4 -Ci 6 alcohols (89 wt%) .
  • the main contaminants were paraffins (-1.5 wt%) , Ci 3 to Ci 7 ketones (-1 wt%) and Ci 3 to Ci 5 diols ( ⁇ 0.5 wt%) .
  • Example 2b' (45.1 g, having an average molecular weight of 241) consisted mainly of Ci 5 -Ci 7 alcohols (89 wt%) .
  • the main contaminants were paraffins ( ⁇ 1 wt%) , Ci 3 to Ci 7 ketones ( ⁇ 1 wt%) and Ci 3 to Ci 6 diols ( ⁇ 4 wt%) .
  • Examples 2b and 2b' have been ethoxylated to a 2-EO level in a lab-scale apparatus using a 250-ml Schlenk flask equipped with a magnetic stirring bar and a bubble counter.
  • the flask was filled with 50.05 g of Example 2b, 8 mg of DMC as solid catalyst (prepared essentially according to Example 1 of co-pending U.S. Published Application Serial No. 2005/0014979, which is herein incorporated by reference) , and toluene (7 ml) .
  • the mixture was flushed with nitrogen at 130 0 C for 20 minutes to remove toluene and possible light contaminants, such as water.
  • ethylene oxide (EO) was introduced at such a rate that no gas passed the bubble counter.
  • EO ethylene oxide
  • an induction period of 40 minutes was observed before the DMC catalyst became active.
  • the EO uptake was rapid and 20.88 g of EO was consumed within 2.5 hours. Based on this weight increase the average length of ethoxylate chains was estimated to be 2.1 equivalents of EO.
  • Reducing the EO flow to zero stopped the reaction and the flask was flushed with nitrogen for 1 hour to remove the residual EO.
  • the resulting product (70.9 g) designated sample 2c, was analyzed by 13 C- NMR to have an average EO-chain length of about 2.
  • Sample 2c was subjected to sulfation. Sulfation was carried out with gaseous sulfur trioxide in a glass falling film reactor approximately one meter in length and 5 mm in diameter. Sulfur trioxide was generated by passing sulfur dioxide in dry air over a heated catalyst bed containing vanadium pentoxide. The hot stream of SO3 in air was cooled by a heat exchanger, and then admitted to the thin film reactor at approximately 1 gram of S0 3 /minute. The secondary alcohol ethoxylate (sample 2c) was pumped to the falling film reactor at 3.8 grams/minute to give a S03/ethoxylate molar ratio of 0.80. A nitrogen flow of 16 normal liters per minute was used to generate a thin liquid film.
  • the temperatures of the three zones of the reactor column were controlled at 25°C using circulator baths.
  • the product sulfate was collected at the bottom of the falling film column in a solution of sodium hydroxide mixed in a blender. A ratio of 1.2 moles NaOH/mole of sulfate was employed.
  • the product was analyzed and found to contain 27 wt% active matter. UOM (unreacted organic matter) was 4.7 wt% and sulfate content was 0.17 wt% .
  • Petrepar 147 gives 26 wt% n-tetradecane; 61 wt% n- pentadecane; 10 wt% n-hexadecane; 1 wt% n-heptadecane; ⁇ 0.5 wt% >n-heptadecane; 0.5 wt% branched Ci 4 -Ci 7 paraffins; 1 wt% total mono- and di-naphthenes and about 500 mg/kg of total mono-aromatics .
  • samples were taken every 30 minutes, until the oxidations had progressed for 180 minutes.
  • the total secondary alcohol content, as determined by GC after hydrolysis of each sample is given in Figure 1 as a function of time to establish the induction period and the rate of secondary alcohol formation (paraffin oxidation) .
  • the average number of moles of EO per molecule was 7.0, the level of free alcohol was 0.7 wt% (both according to HPLC) and the level of 1,4-dioxane was ⁇ 5 mg/kg (by GC), using the methods as described in Example ID.
  • the ethoxylate distribution as obtained by HPLC is shown in Table 6 below.
  • Example 4 was repeated except that before the EO was added, 1 ml toluene was added and the mixture stripped with nitrogen at 130 ° C (to remove water) . Then to the remaining reaction mixture (9.3 g) EO was added, which reacted immediately. EO dosing was stopped after the consumption of 16.1 g.
  • the average number of moles of EO per molecule was 6.5, the level of free alcohol was 1.1 wt% and the level of 1,4- dioxane was ⁇ 10 mg/kg, using the same methods as used in Example 4.
  • the E0-distribution (by HPLC) is shown in Table 6 below.
  • Example 6 (comparative) The preparation of an ethoxylate derived from the secondary alcohol, 2-undecanol, and having an average of about 7 EO groups per molecule, produced by acid catalysis using hydrogen fluoride / boric acid
  • a magnetically stirred PTFE bottle was charged with 15.2 g of 2-undecanol (>98% pure, purchased from FLUKA A. G., Switzerland) , 2.0 g of a 5 % solution of HF (wt/wt) in 2- undecanol and 20 mg of orthoboric acid (purchased from Aldrich) .
  • the total amount of 2-undecanol was 17.2 g (0.1 mol) .
  • 31.0 g (0.705 mol) of ethylene oxide was bubbled through the solution at such a rate that the bubbles were consumed before reaching the surface (at atmospheric pressure) .
  • the temperature rapidly increased and was maintained at about 70 0 C by external cooling.
  • the ethoxylate distribution of the DMC catalyzed ethoxylation of secondary alcohols mixture of Example Ib, leading to the product of Example Ic is about as narrow as those of the DMC catalyzed ethoxylation of the secondary alcohol, 2-undecanol, of comparative Examples 4 and 5, and of the HF/boric acid catalyzed ethoxylation of the secondary alcohol, 2-undecanol, of comparative Example 6.
  • the 1,4-dioxane formation is almost absent, whereas upon acid catalyzed ethoxylation ethoxylate chain degradation occurs with concomitant formation of large amounts of 1,4-dioxane.

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Abstract

L'invention porte sur un procédé de fabrication d'alcoxysulfates d'alcools secondaires qui consiste : (a) à faire réagir du monoxyde de carbone et de l'hydrogène dans des conditions de Fischer-Tropsch en présence d'un catalyseur de Fischer-Tropsch pour obtenir un mélange réactionnel comportant des paraffines, (b) à mettre en contact les paraffines avec de l'oxygène en présence d'un catalyseur d'oxydation pour obtenir des alcools secondaires, (c) à mettre en contact les alcools secondaires avec un oxyde d'alkylène en présence d'un catalyseur cyanure métallique double pour obtenir des alcoxylates d'alcools secondaires, et (d) à sulfater les alcoxylates d'alcools secondaires.
PCT/US2008/080918 2007-10-29 2008-10-23 Procédé de fabrication d'alcoxysulfates d'alcools secondaires WO2009058654A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131719A1 (fr) 2010-04-23 2011-10-27 Basf Se Procédé d'extraction du pétrole avec utilisation de composés tensio-actifs, en particulier à base d'alkylalcoxylates à teneur en alcool secondaire en c35
WO2014165424A1 (fr) 2013-04-03 2014-10-09 Shell Oil Company Procédé de préparation d'alcools en c10 à c30
CN107168062A (zh) * 2017-05-31 2017-09-15 国网河南省电力公司电力科学研究院 一种超临界燃煤机组协调控制系统中的负荷预测方法
WO2021171209A1 (fr) * 2020-02-28 2021-09-02 Oxiteno S.A. Indústria E Comércio Faible production de 1,4-dioxane lors de la sulfatation d'un mélange éthoxylé préparé à l'aide d'un catalyseur dmc
WO2022128561A1 (fr) 2020-12-16 2022-06-23 Unilever Ip Holdings B.V. Compositions détergentes
CN117550954A (zh) * 2023-11-09 2024-02-13 江苏赛科化学有限公司 一种烷烃氧化制仲醇的加工工艺

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Publication number Priority date Publication date Assignee Title
US3966828A (en) * 1973-12-26 1976-06-29 Texaco Inc. Secondary alcohol process
US6255275B1 (en) * 1996-12-06 2001-07-03 Nippon Shokubai Co., Ltd. Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition
US7105706B2 (en) * 2003-12-11 2006-09-12 Shell Oil Company Process for the preparation of an alkoxylated alcohol composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3966828A (en) * 1973-12-26 1976-06-29 Texaco Inc. Secondary alcohol process
US6255275B1 (en) * 1996-12-06 2001-07-03 Nippon Shokubai Co., Ltd. Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition
US7105706B2 (en) * 2003-12-11 2006-09-12 Shell Oil Company Process for the preparation of an alkoxylated alcohol composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131719A1 (fr) 2010-04-23 2011-10-27 Basf Se Procédé d'extraction du pétrole avec utilisation de composés tensio-actifs, en particulier à base d'alkylalcoxylates à teneur en alcool secondaire en c35
WO2014165424A1 (fr) 2013-04-03 2014-10-09 Shell Oil Company Procédé de préparation d'alcools en c10 à c30
CN107168062A (zh) * 2017-05-31 2017-09-15 国网河南省电力公司电力科学研究院 一种超临界燃煤机组协调控制系统中的负荷预测方法
WO2021171209A1 (fr) * 2020-02-28 2021-09-02 Oxiteno S.A. Indústria E Comércio Faible production de 1,4-dioxane lors de la sulfatation d'un mélange éthoxylé préparé à l'aide d'un catalyseur dmc
WO2022128561A1 (fr) 2020-12-16 2022-06-23 Unilever Ip Holdings B.V. Compositions détergentes
CN117550954A (zh) * 2023-11-09 2024-02-13 江苏赛科化学有限公司 一种烷烃氧化制仲醇的加工工艺

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