WO2010062605A1 - Sulfonates d’alkylaryle avec niveaux de sulfone réduits, et procédés de préparation associés - Google Patents

Sulfonates d’alkylaryle avec niveaux de sulfone réduits, et procédés de préparation associés Download PDF

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Publication number
WO2010062605A1
WO2010062605A1 PCT/US2009/062230 US2009062230W WO2010062605A1 WO 2010062605 A1 WO2010062605 A1 WO 2010062605A1 US 2009062230 W US2009062230 W US 2009062230W WO 2010062605 A1 WO2010062605 A1 WO 2010062605A1
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alkylaryl
feedstock
sulfonic acid
sulfonate
alkylaromatic
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PCT/US2009/062230
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English (en)
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Gregory P. Dado
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Stepan Company
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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
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • 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
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising

Definitions

  • the presently described technology relates generally to the sulfonation of alkyl aromatic compounds and mixtures thereof, such as, for example, detergent-range linear alkylbenzenes, wherein the sulfonation is achieved utilizing sulfur trioxide (SO 3 ) with conversion of aromatic feedstock, preferably high conversion, and with reduced levels of sulfone formation relative to conventional and known processing. More specifically, the presently described technology relates to the use of neutralized salts of sulfonated products of alkylaromatic feedstock as sulfone inhibitors in the SO 3 sulfonation of the alkylaromatic feedstock. In some preferred embodiments, the feedstock for the preparation of the sulfone inhibitors is the same feedstock that is to be sulfonated in the presence of the sulfone inhibitor.
  • the SO 3 sulfonation of alkylaromatic feedstocks for example detergent-range linear alkylbenzenes (LAB) is typically conducted on continuous processing equipment such as falling film reactor units. These reactors provide a means of controlling the intimate contact of feedstock with gaseous SO 3 diluted in dry air, thereby providing short mass diffusion lengths and rapid heat removal. Such processing also enables high throughput while maintaining product quality.
  • the application of falling film sulfonation to the conversion of alkylaromatic feedstocks into alkylaryl sulfonic acids has been described by W. H. de Groot in Sulphonation Technology in the Detergent Industry, Kluwer Academic Publishers, Dordrecht, The Netherlands: 1991 ; and G. P. Dado, et. al. in Sulfonation and Sulfation, Kirk-Othmer Encyclopedia of Chemical Technology, 5th ed, Wiley-lnterscience, Hoboken, NJ: 2005.
  • the initial contact of gaseous SO 3 with alkylaromatic feedstocks results in acid products that are comprised of sulfonic acids, pyro-acids (e.g., transient adducts of sulfonic acids and SO 3 ), unreacted aromatic feedstock, unsulfonatable feedstock components (e.g., parrafins), sulfuric acid or H 2 SO 4 -oleum, sulfonic anhydrides, and sulfones.
  • Sulfonic anhydrides are formed in reactions that are formally the conversion of two moles of LAB plus three moles of SO 3 to produce one mole of sulfonic anhydride plus one mole of sulfuric acid.
  • Sulfones are formed in reactions that are formally the conversion of two moles of LAB plus two moles of SO 3 to produce one mole of sulfone plus one mole of sulfuric acid.
  • the initially produced acid derived from a detergent linear alkylbenzene feedstock in a commercial SO 3 sulfonation process may be comprised of, for example, about 85-92% of sulfonic acid.
  • Sulfones and other free oil components can impart deleterious effects to the properties and performance of sulfonates by, for example, decreasing viscosities and decreasing formulation stability.
  • an acid aging step In commercial practice, it is common for an acid aging step to be conducted after the initial contact of SO 3 with aromatic feedstock. This aging step provides time for the reactions between pyro-acids and oleum with unreacted aromatic feedstock to increase overall conversion to sulfonic acid product. It has been demonstrated that the level of sulfonic anhydrides decrease substantially during acid aging, but that sulfones levels decrease only very minimally.
  • a small amount of water for example, about 0.3 to 1 % by weight, is typically added to the acid composition in order to hydrolyze any remaining sulfonic anhydrides to sulfonic acids and to stabilize the product against color degradation.
  • Sulfone generation during the processing of linear alkylbenzene sulfonic acid is known to be promoted by excessive temperature during processing.
  • generation of sulfones has been shown under certain conditions to increase as the molar amount of SO 3 relative to aromatic feedstock approaches and surpasses one equivalent (See Moreno et al., 2003).
  • the conversion of linear alkylbenzene feedstocks to sulfonic acid products in commercial practice of SO 3 sulfonation represents a compromise between achieving high conversion of feedstock, sulfone generation, and color development.
  • Typical finished products are comprised of about 95-98% of sulfonic acid, about 0.9-2% of total free oil including sulfone, and about 0.5-1.2% of sulfone.
  • anionic surfactants such as alkylaryl sulfonates
  • cleaning products such as heavy duty liquid laundry detergents and light duty liquid dish washing detergents
  • a low cost and desirable approach for increasing viscosity, especially in low actives formulations, is by the addition of salts such as magnesium sulfate or sodium chloride.
  • salts such as magnesium sulfate or sodium chloride.
  • free oils, including sulfones can have a substantial negative impact on the ability to increase formulation viscosity through the addition of salts.
  • Alkylaryl sulfonates that are manufactured by sulfonation processes utilizing oleum can be produced with low free oil and very low sulfone levels as compared to continuous processing with gaseous SO 3 . These sulfonates can demonstrate acceptable viscosity increase in economy detergent formulations by the addition of salts, whereas sulfonates produced by commercial SO 3 sulfonation methods may not demonstrate acceptable viscosity building properties.
  • the use of oleum processing to produce alkylaryl sulfonates requires equipment specific to the process and can generate considerable amounts of sulfuric acid by-product that must either be disposed of or recycled back to the oleum supplier. It would be desirable to identify process methods that could enable the production of high viscosity- building alkylaryl sulfonates on standard commercial SO 3 processing equipment.
  • inhibitors such as sodium sulfate are insoluble in typical alkylaromatic feedstocks suitable for continuous SO 3 sulfonation, thereby rendering viable processing and needed contact time with conventional equipment difficult or unfeasible.
  • inhibitors such as acetone are highly volatile in the context of continuous SO 3 sulfonation conditions, resulting in the high potential for excessive "pluming,” loss of the inhibitor from the reaction liquid, and possible safety concerns.
  • the present technology provides in general, one or more methods for preparing alkylaryl sulfonic acid compositions (e.g., alkylaryl sulfonates) by gaseous SO 3 sulfonation that result in the compositions having reduced total free oils and sulfones compared to such compositions prepared by conventional and known processes.
  • alkylaryl sulfonic acid compositions e.g., alkylaryl sulfonates
  • neutralized salts of sulfonated products of alkyl aromatic feedstock are used as sulfone inhibitors in the SO 3 sulfonation of the alkylaromatic compounds.
  • the present technology provides a method for preparing alkylaryl sulfonates by gaseous SO 3 sulfonation and with reduced total free oils and sulfones comprising the steps of:
  • step (d) comprises dissolving about 0.01 to about 50 percent by weight of the sulfonate salt or mixture of sulfonate salt and un-neutralized sulfonic acid in the alkylaromatic feedstock to obtain a modified feedstock.
  • the present technology provides a method for preparing alkylaryl sulfonate by gaseous SO 3 sulfonation having reduced total free oils and sulfones comprising the steps of:
  • step (c) comprises dissolving about 0.01 % to about 50% by weight of the at least one alkylaryl sulfonic acid in the alkylaromatic feedstock.
  • the present technology provides a method for preparing alkylaryl sulfonate by gaseous SO 3 sulfonation and with reduced total free oils and sulfones comprising the steps of:
  • the present technology provides a method for preparing alkylaryl sulfonic acid compositions, e.g., alkylaryl sulfonates, by gaseous SO 3 sulfonation and with reduced total free oils and sulfones which comprises the additional step of digesting the mixture of sulfonated reaction product for about 0.5 to about 90 minutes at a temperature of about 25 Q C to about 80 Q C in order to promote the conversion of sulfonic anhydrides and unreacted alkylaromatic compounds to sulfonic acid.
  • the described method for preparing alkylaryl sulfonic acid compositions by gaseous SO 3 sulfonation and with reduced total free oils and sulfones comprises the additional step of treating the digested sulfonated reaction product with about 0.02% to about 2% (wt/wt) of water in order to hydrolyze remaining sulfonic anhydrides and to stabilize the product against color degradation.
  • the alkylaryl sulfonates of the present technology are prepared by sulfonating alkylaromatic compounds by utilizing sulfur trioxide (SO 3 ) as the sulfonation agent.
  • SO 3 sulfur trioxide
  • An important aspect of the presently described technology for sulfonating alkyl aromatic feedstocks in the presence of neutralized sulfonates is the solubility of the neutralized sulfonates in the feedstock.
  • the methods of the present technology utilize mixtures of alkylaromatic feedstocks and sulfonate salts that have low viscosity, are homogeneous and are suitable for processing on commercial continuous SO 3 sulfonation equipment, for example falling film reactors, with little or no modification to said equipment.
  • the sulfone inhibitor is comprised of a partially neutralized alkylaryl sulfonic acid, i.e., a mixture of sulfonic acid and sulfonate salts.
  • the sulfone inhibitor is prepared by partially or fully neutralizing an alkylaryl sulfonic acid with a base and then dissolving the obtained product into an alkylaromatic feedstock prior to sulfonation of the feedstock.
  • the sulfone inhibitor is prepared in situ in an alkylaromatic feedstock prior to sulfonation of the feedstock by dissolving an alkylaryl sulfonic acid in the feedstock and partially or fully neutralizing the acid by addition of a base.
  • the sulfone inhibitor may not be fully soluble in the alkylaromatic feedstock but is sufficiently well dispersed so as to afford the desired sulfone inhibition and ability to be processed on standard continuous SO 3 sulfonation equipment.
  • the sulfone inhibitor may be prepared by partially or fully neutralizing an alkylaryl sulfonic acid with a base and then sufficiently dispersing this obtained product into an alkylaromatic feedstock prior to sulfonation of the feedstock.
  • the present technology provides a method for preparing alkylaryl sulfonate by gaseous SO 3 sulfonation and with reduced total free oils and sulfones.
  • the method includes providing at least one alkylaromatic feedstock and partially sulfonating the feedstock to a conversion of about 0.01 % to about 50% percent of at least one sulfonic acid component.
  • the method further includes at least partially neutralizing the sulfonic acid components of the partially sulfonated feedstock with at least one base to obtain at least one modified feedstock and sulfonating the modified feedstock with gaseous SO 3 to afford a sulfonated reaction product.
  • the present technology provides a method for preparing alkylaryl sulfonic acid compositions by gaseous SO 3 sulfonation and with reduced total free oils and sulfones.
  • the method comprises the steps of providing at least one alkylaryl sulfonic acid and at least partially neutralizing the at least one sulfonic acid with a base to obtain a sulfonate salt or a mixture of sulfonate salt and un-neutralized sulfonic acid.
  • the method further includes the step of providing an alkylaromatic feedstock and dissolving about 0.01 % to about 50% by weight, alternatively about 0.1 % to about 50%, alternatively about 0.5% to about 30%, alternatively about 1 % to about 20% of the sulfonate salt or mixture of sulfonate salt and un-neutralized sulfonic acid in the alkylaromatic feedstock to obtain a modified feedstock.
  • the sulfonate salt or mixture of sulfonate salt and un-neutralized sulfonic acid dissolved can be about 0.01 % to about 40% by weight, alternatively about 0.01 % to about 30%, alternatively about 0.01 % to about 20%, alternatively about 0.01 % to about 10%, alternatively about 0.01 % to about 5%, alternatively 0.1 % to about 40% by weight, alternatively about 0.1 % to about 30%, alternatively about 0.1 % to about 20%, alternatively about 0.1 % to about 10%, alternatively about 0.1 % to about 5%, alternatively about 0.5% to about 50%, alternatively about 0.5% to about 40% by weight, alternatively about 0.5% to about 30%, alternatively about 0.5% to about 20%, alternatively about 0.5% to about 10%, alternatively about 0.5% to about 5 %m alternatively about 1 % to about 50%, alternatively about 1 % to about 40% by weight, alternatively about 1 % to about 30%, alternatively about 1 % to about 25%, alternatively about 1 %m
  • the method of the present technology comprises the steps of providing at least one alkylaryl sulfonic acid and an alkylaromatic feedstock; dissolving about 0.01 % to about 50% by weight, alternatively about 0.1 % to about 50%, alternatively about 0.5% to about 30%, alternatively about 1 % to about 20%, of the at least one alkylaryl sulfonic acid in the alky I aromatic feedstock; and at least partially neutralizing the sulfonic acid with a base to obtain a modified feedstock.
  • the alkylaryl sulfonic acid can be 0.01 % to about 40% by weight, alternatively about 0.01 % to about 30%, alternatively about 0.01 % to about 20%, alternatively about 0.01 % to about 10%, alternatively about 0.01 % to about 5%, alternatively 0.1 % to about 40% by weight, alternatively about 0.1 % to about 30%, alternatively about 0.1 % to about 20%, alternatively about 0.1 % to about 10%, alternatively about 0.1 % to about 5%, alternatively about 0.5% to about 50%, alternatively about 0.5% to about 40% by weight, alternatively about 0.5% to about 30%, alternatively about 0.5% to about 20%, alternatively about 0.5% to about 10%, alternatively about 0.5% to about 5 %m alternatively about 1 % to about 50%, alternatively about 1 % to about 40% by weight, alternatively about 1 % to about 30%, alternatively about 1 % to about 25%, alternatively about 1 % to about 20%, alternatively about 1 % to about 10%, alternatively about 1 % to about 1
  • the method of the present technology comprises steps of providing an alkylaromatic feedstock and partially sulfonating the feedstock to a conversion of about 0.01 % to about 50% by weight, alternatively about 0.1 % to about 50%, alternatively about 0.5% to about 30%, alternatively about 1 % to about 20% of the at least one sulfonic acid component to obtain a partially sulfonated feedstock.
  • the at least one sulfonic acid is converted at 0.01 % to about 40% by weight, alternatively about 0.01 % to about 30%, alternatively about 0.01 % to about 20%, alternatively about 0.01 % to about 10%, alternatively about 0.01 % to about 5%, alternatively 0.1 % to about 40% by weight, alternatively about 0.1 % to about 30%, alternatively about 0.1 % to about 20%, alternatively about 0.1 % to about 10%, alternatively about 0.1 % to about 5%, alternatively about 0.5% to about 50%, alternatively about 0.5% to about 40% by weight, alternatively about 0.5% to about 30%, alternatively about 0.5% to about 20%, alternatively about 0.5% to about 10%, alternatively about 0.5% to about 5 %m alternatively about 1 % to about 50%, alternatively about 1 % to about 40% by weight, alternatively about 1 % to about 30%, alternatively about 1 % to about 25%, alternatively about 1 % to about 20%, alternatively about 1 % to about 10%, alternatively about 1 % to about 1
  • the method further includes the steps of at least partially neutralizing the sulfonic acid components of the partially sulfonated feedstock with a base to obtain a modified feedstock; and sulfonating the modified feedstock with gaseous SO 3 to afford a sulfonated reaction product.
  • Alkylaromatic feedstock Alkylaromatic feedstocks that are suitable for conversion to sulfonic acid-based components by sulfonation with gaseous SO 3 may be used and are considered within the spirit and scope of the presently described technology and appended claims.
  • alkylbenzene feedstock that may be used to produce alkylbenzene sulfonate compounds which are known in the art can be used in the practice of the present technology.
  • Alkylbenzene sulfonate compounds having varying molecular weights, alkyl chain length and alkyl chain phenyl location combinations may also be employed. Examples of such compounds may be found in, for example, U.S. Pat. No. 6,617,303; U.S. Pat.
  • Some preferred alkylaromatic feedstocks are mixtures comprised of compounds of the general structure:
  • R and R' are linear or branch saturated alkyl of about 1 to about 21 carbons
  • R" is H or CH 3
  • the total number of carbons in R+R'+R" is from about 8 to about 22.
  • These preferred feedstocks may further comprise minor amounts of diphenyl alkanes, tetralins, indanes, naphthalenes, and/or dialkylbenzenes as well as derivatives thereof.
  • Alkylaryl sulfonic acid Alkylaryl sulfonic acids that may be obtained from the sulfonation of any of the indicated alkylaromatic feedstocks may be used within the scope of this invention. These alkylaryl sulfonic acids encompass both the sulfonic acids that may be partially or fully neutralized for the purposes of modifying alkylaromatic feedstock for subsequent sulfonation and the sulfonic acid products that result from this subsequent sulfonation. Some preferred alkylaryl sulfonic acids are mixtures comprised of compounds of the general structure:
  • R and R' are linear or branch saturated alkyl of about 1 to about 21 carbons, R" is H or CH 3 , and the total number of carbons in R+R'+R" is from about 8 to about 22.
  • the alkylaryl sulfonic acid that is to be partially or fully neutralized for the purposes of producing modified feedstock may be prepared by the reaction alkylaromatic feedstocks with sulfonation reagents including but not limited to SO 3 , oleum, H 2 SO 4 , and chlorosulfonic acid.
  • the alkylaryl sulfonic acid is produced by falling film sulfonation of alkylaromatic feedstock with SO 3 .
  • the molar ratio of SO 3 to alkylaromatic feedstock may be from about 0.001 to about 1.10, alternatively from about 0.01 to about 1.05, alternatively from about 0.1 to about 1.05, alternatively from about 0.2 to about 1.05, and can be any numerical value in between these values and can be, for example, in additional increments of, for example, 0.001 , 0.002, 0.0025, 0.005, 0.0075, 0.01 , 0.02, 0.025, 0.05, 0.075, 0.1 , 0.2, 0.25, 0.3, 0.4, 0.5, and multiplied factors thereof, (e.g. x1 , x2, x10, x100, etc).
  • thermal aging of the alkylaryl sulfonic acid that is to be partially or fully neutralized for the purposes of producing modified feedstock can be conducted for the purpose of reducing the amount of incidental H 2 SO 4 (sulfuric acid) present in the sulfonic acid.
  • This thermal aging may be conducted at a temperature of from about 20 Q C to about 100 Q C for a time period of from about 1 minute to 24 hours or more.
  • H 2 SO 4 sulfuric acid
  • H 2 SO 4 reaction with a base is believed to result in insoluble components (e.g., metal hydrogen sulfate salt) that can interfere with material handling and falling film sulfonation of modified feedstock, thereby necessitating filtration, decantation, or another means of removal of insoluble components from the modified feedstock.
  • insoluble components e.g., metal hydrogen sulfate salt
  • H 2 SO 4 is believed to potentially retard the solid-liquid reaction of sulfonic acid with a base under some conditions.
  • the alkylaryl sulfonic acid that is to be partially or fully neutralized for the purposes of producing modified feedstock comprises less than about 0.75% H 2 SO 4 .
  • Thermal aging of partially sulfonated linear alkylbenzene is believed to result in gradual consumption of H 2 SO 4 in the acid to the point that it is no longer detected by titration.
  • Such aged acid reacts completely with solid bases such as sodium carbonate and produces modified feedstocks that are free of particulate salts.
  • the alkylaryl sulfonic acid that is to be partially or fully neutralized for the purposes of producing modified feedstock may be a sulfonic acid that comprises in excess of about 0.75% by weight of H 2 SO 4 .
  • the subsequently obtained partially or fully neutralized sulfonic acid, or alternatively the further subsequently obtained modified feedstock may be filtered, decanted, or processed by other means to remove insoluble components so as to improve the handling and falling film sulfonation processing of the modified feedstock.
  • Base Any Bronstedt or Lewis base that can be reacted with alkylaryl sulfonic acid to produce a partially or fully neutralized alkylaryl sulfonic acid can be used to prepare one or more modified feedstocks of the present technology, provided that the obtained sulfonate salt is soluble in the alkylaromatic feedstock to a degree sufficient to enable, with or without prior removal of insoluble components, sulfonation of the modified feedstock on commercial continuous SO 3 sulfonation equipment such as a falling film reactor.
  • the obtained sulfonate salt should exhibit about greater than about 0.01 % solubility (wt/wt), alternative greater than about 0.1 % solubility (wt/wt), alternatively greater than about 0.5% solubility (wt/wt), alternatively greater than about 1 % solubility (wt/wt), and can be any value in additional increments of, for example, 0.1 , 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9 or 1.0 % and multiplied factors thereof, (e.g. x1 , x2, x10, x100, etc).
  • the base that is used to partially or fully neutralize alkylaryl sulfonic acid for the purposes of producing one or more modified feedstocks is a member of the group consisting of alkali metal, alkaline earth metal, and ammonium or substituted ammonium salts of hydroxide anion, oxide anion, carbonate anion, and hydrogen carbonate anion, including mixtures thereof; ammonia, and substituted amines.
  • Alkali metals include, but are not limited to, lithium, sodium, potassium, cesium and mixtures thereof.
  • Alkali earth metals include, but are not limited to magnesium, calcium, strontium, barium, and mixtures thereof.
  • Substituted ammonium cations include, but are not limited to, monoethanol ammonium, diethanol ammonium, triethanol ammonium, and mixtures thereof.
  • Substituted amines include, but are not limited to, monoethanolamine, diethanolamine, and triethanolamine.
  • the base is a member of the group containing of sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium carbonate, potassium hydrogen carbonate, potassium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, and ammonia.
  • the base is substantially free of water.
  • an aqueous base may be used provided that water is removed from the modified feedstock prior to sulfonation to a sulfonated reaction product.
  • Degree of alkylaryl sulfonic acid neutralization The molar degree of neutralization of the alkylaryl sulfonic acid that is used to produce one or more modified feedstocks of the present technology may be in the range of about 1 % to about 100 %, alternatively between 1 % and 80%, alternatively between 1 % and about 75%, alternatively between about 1 % and about 50%, alternatively from about 5 % to about 100 %, alternatively between about 10% and 100%, alternatively between about 20% and about 100%, alternatively from about 25 % to about 100 %, alternatively between about 30% and about 100%, alternatively between about 40% and about 100%, alternatively between about 50% and about 100%, alternatively between about 25% and about 80%, and can be any percentages in between these values and can be, for example, in additional increments of, for example, 0.1 , 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1.0, 2.0%, or 2.5 % and multipli
  • the degree of neutralization is less than that which causes substantial insolubility of the alkylalkyl sulfonic acid salt or other salts in the modified feedstock.
  • the degree of neutralization is preferable to limit the degree of neutralization to a level less than that which, upon neutralization, results in excessive viscosity that renders handling of the material difficult and impractical, for example, viscosity in excess of about 10,000 centipoise, alternatively in excess of about 2000 centipoise, alternatively in excess of about 1 ,000 centipoise, alternatively in excess of about 500 centipoise and can be in additional increments of, for example, 0.1 , 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1.0, 2.0, 5.0, 7.5, 10, 20, 25, 30, 40, 50 centipoise and multiplied factors thereof, (e.g. x1 , x2, x10, x100, etc).
  • Amount of partially or fully neutralized alkylaryl sulfonic acid in alkylaromatic feedstock can be any amount that can enable the desired amount of sulfone inhibition during the sulfonation of the modified feedstock, provided that the modified feedstock, prepared either with or without a step to remove insoluble components, is sufficiently free of solid particulate matter greater than about 50 micrometers in diameter, has a low in viscosity, preferably from about 0.5 centipoise to about 400 centipoise, alternatively from about 1 centipoise to about 200 centipoise, alternatively from about 1 centipoise to about 50 centipoise, and can be in additional increments of, for example, 0.1 , 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9
  • This amount may be from about 0.01 % to about 50% of the total weight of the modified feedstock, alternatively from about 0.01 % to about 30%, alternatively from about 0.01 % to about 20%, alternatively from about 0.01 % to about 10%, alternatively from about 0.01 % to about 5%, alternatively from about 0.1 % to about 50%, alternatively from about 0.1 % to about 40%, alternatively from about 0.1 % to about 30%, alternatively from about 0.1 % to about 20%, alternatively from about 0.1 % to about 10%, alternatively from about 0.1 % to about 5%, alternatively from about 0.5% to about 50%, alternatively from about 0.5% to about 40%, alternatively from about 0.5% to about 30%, alternatively from about 0.5% to about 20%, alternatively from about 0.5% to about 10%, alternatively from about 0.5% to about 5%, alternatively from about 1 % to about 50%
  • alkylaryl Sulfonic Acid Neutralization Reaction Conditions and Preparation of Modified Feedstock The neutralization of alkylaryl sulfonic acid for the purposes of producing one or more modified feedstocks of the present technology can be conducted in-situ (i.e., within the bulk of the alkylaromatic feedstock that is to be modified), or in a separate step.
  • heating of the neutralization reaction mixture from about ambient (about 25 " C) to about 150 ° C, alternatively from about 50 ° C to about 100 ° C for reaction times from less than about 1 minute to more than about 24 hours or more, alternatively from less than 1 minute to about 10 hours or more, alternatively from about 15 minutes to about 4 hours, alternatively from about 5 seconds to about 1 minute may be used and can be in additional increments of, for example, 0.1 , 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1.0, 2.0, 5.0, 7.5, 10, 20, 25, 30, 40, 50 minutes and multiplied factors thereof, (e.g.
  • the alkylaromatic sulfonic acid and base may be added sequentially in any order or alternatively these components may be added concurrently.
  • the neutralization is conducted as a separate step, the partially or fully neutralized alkylaryl sulfonic acid intermediate may be blended with alkylaromatic feedstock in advance or immediately prior to sulfonation of the modified feedstock.
  • the modified feedstock preferably is homogeneous and can be obtained as such through selection of the degree of sulfonation and neutralization of the alkylaryl sulfonic acid, the amount of partially or fully neutralized alkylaryl sulfonic acid that is used, and/or the selection of cation that is used.
  • one or more homogeneous modified feedstocks of the present technology may be obtained by filtration or decantation of the modified feedstock to remove insoluble material such as inorganic sulfate salts or unreacted solid base. Water may be produced in the neutralization of alkylaryl sulfonic acid with base, the amount being dependent on the base that is used.
  • the reactions of metal carbonates with sulfonic acid can, for example, produce about 0.5 moles of water per mole of sulfonic acid that is neutralized.
  • the reaction of metal or ammonium hydroxides with sulfonic acid can produce, for example, about 1.0 moles of water per mole of sulfonic acid that is neutralized.
  • the reaction of ammonia with sulfonic acid produces no water.
  • the amount of water that is present in the modified feedstock preferably should be less than the solubility limit of the water in the modified feedstock. Furthermore, the amount of water should be preferably less than that which will negatively impact the subsequent continuous sulfonation of the modified feedstock.
  • the amount of water that is present in the modified feedstock is less than about 1 percent (wt/wt), alternatively less than about 0.5 percent, alternatively less than about 0.1 percent.
  • excess water may be removed from the modified feedstock by any suitable means.
  • One such means for example, may be the heating of the modified feedstock under vacuum.
  • Modified Feedstock Sulfonation The modified feedstock is sulfonated by any means of continuous gaseous SO 3 sulfonation to produce a sulfonated reaction product, for example, falling film reaction equipment.
  • the amount of SO 3 that is contacted with the modified feedstock is affected by the amount of sulfonatable alkylaromatic compounds present in the modified feedstock.
  • the molar ratio of SO 3 to sulfonatable alkylaromatic compounds is from about 0.9 to about 1.2, alternatively about 0.98 to about 1.10, alternatively from about 1.00 to about 1.07, alternatively from about 1.00 to about 1.05 and can be in additional increments of, for example, 0.01 , 0.02, 0.05, 0.1 , 0.2, 0.25, 0.3.
  • the amount of SO 3 that is used is optimized so as to maximize the conversion of sulfonatable alkyl aromatic compounds while not significantly increasing the generation of by-product sulfones.
  • Acid aging The sulfonated reaction product produced from continuous SO 3 sulfonation of modified feedstock may be subjected to an acid aging step for the purposes of improving the conversion of alkylaromatic compounds to sulfonic acid.
  • This aging can be conducted by digesting the mixture of sulfonated reaction product for about 0.5 to about 90 minutes, alternatively for about 1 minute to about 60 minutes, at temperatures of about 25 ° C to about 80 ° C, alternatively of about 30 ° C to about 60 ° C and can be in additional increments of, for example, 0.1 , 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1.0, 2.0, 5.0 ° C and multiplied factors thereof, (e.g. x1 , x2, x10, x100, etc).
  • the digestion can be conducted, for example, in a continuous or batch process.
  • Acid product stabilization The aged sulfonated reaction product may be treated with water in order to hydrolyze remaining sulfonic anhydrides and to stabilize the product against color degradation.
  • the amount of water that can be used is from about 0.02% to about 2% (wt/wt) relative to the total mass, alternatively from about 0.2% to about 1 %.
  • the incorporation of neutralized alkylaryl sulfonates into alkylaromatic feedstock enables the sulfonation of the feedstock to very high degrees of conversion while inhibiting sulfone generation.
  • the molar conversion of alkylaromatic components in the feedstock to sulfonated products is greater than about 99%, alternatively greater than about 99.5%.
  • the resulting sulfonated products are low in free oil as measured by, for example, petroleum ether extraction of neutralized solutions of product in aqueous alcohol.
  • the sulfonated products comprise less than about 1.5 percent (wt/wt) of free oil, alternatively less than about 1.2 percent (wt/wt) of free oil, alternatively less than about 1 percent (wt/wt) of free oil, alternatively less than about 0.8 percent (wt/wt) of free oil.
  • the free oils of sulfonated alkylaromatic feedstocks are typically comprised of mixtures of unsulfonated alkyl aromatics and sulfones.
  • the sulfonated products comprise less than about 0.8 percent (wt/wt) of sulfones, alternatively less than about 0.6 percent (wt/wt) of sulfones, alternatively less than about 0.5 percent (wt/wt) of sulfones, alternatively less than about 0.4 percent (wt/wt) of sulfones.
  • the low free oil products that can be obtained by the presently described technology exhibit substantially improved viscosity building properties for the purposes of formulating detergents, cleaning products and the like.
  • the sulfonated reaction products of the present technology can have utility in any known application of linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, or any other sulfonated alkylaromatics, where the reduction of sulfones and unreacted alkylaromatics is of potential benefit.
  • Such benefits can include increased or reduced formulation viscosity, improved formulation stability, improved compatibility or solubility in formulation or in end-use application, and improved properties or performance attributes such as foaming, wetting, or detergency.
  • these benefits may be uniquely accessible through this technology if low H 2 SO 4 levels, not obtainable through oleum- based sulfonation methods, are important to realizing the benefits.
  • these partially or fully neutralized alkylaryl sulfonic acids might reduce the rate of color generation that occurs upon acid aging so that more extensive aging may be feasible, enabling still further reductions in sulfones and unreacted alkylaromatics.
  • alkylaryl sulfonate compositions that are not obtained from either continuous gaseous SO 3 sulfonation or oleum sulfonation of alkylaromatic feedstock.
  • the alkylaryl sulfonate compositions are comprised of, for example, sulfonic acid, sulfuric acid, unsulfonatable organics such as paraffins, and sulfones, wherein a portion of the sulfonic acid and/or sulfuric acid is neutralized as a salt.
  • the alkylaryl sulfonate compositions may further comprise unreacted alkylaromatic feedstock.
  • the alkylaryl sulfonate compositions comprise about 3% or less of sulfuric acid, alternatively 2% or less; less than about 0.8% sulfone, more preferably less than about 0.6% sulfone, alternatively less than about 0.5% sulfone, alternatively less than about 0.4% sulfone; and low amounts of total free oil, preferably less than 1.5%, alternatively less than about 1.2%, alternatively less than 1.0%, alternatively less than 0.8% total free oil and include percentages that can be in additional increments of, for example, 0.1 , 0.2, 0.25, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, or 1.0, % and multiplied factors thereof, (e.g. x1 , x2, x10, x100, etc). .
  • alkylaryl sulfonic acid via sulfonation of linear alkylbenzene with SO 3 can be represented by the following formula:
  • Sulfonation of linear alkylbenzenes is typically accompanied by the formation of sulfonic anhydrides, which can be represented by the following overall net reaction:
  • Samples 1 -4 demonstrate the preparation of partially sulfonated, partially neutralized linear alkylbenzene compositions. These compositions can be subsequently dissolved in alkylaromatic feedstocks to prepare modified feedstocks that are suitable for sulfonation with SO 3 to create alkylaryl sulfonated products.
  • a detergent-grade linear alkylbenzene feedstock available commercially from Deten Quimica S. A. as Deten LAB 240, was used in this example.
  • the mole equivalent weight of the feedstock for the purposes of sulfonation was 240.
  • the feedstock was comprised of about 95% linear alkylbenzenes; about 5% other sulfonatable aromatics including dialkyltetralins, dialkylbenzenes, and diphenylalkanes; and less than about 0.1 % unsulfonatable paraffins.
  • the average alkyl chain length of the feedstock was about Cn 5 , and the 2-phenyl isomer content of the feedstock was about 15%.
  • the feedstock was sulfonated in a batch reactor as follows. To an addition funnel was dispensed 58.8 grams (0.734 mole) of liquid SO 3 (stabilized, Aldrich Chemical Company). The addition funnel was then attached to a flash pot comprised of a three neck round bottom flask equipped with a magnetic stir bar, an N 2 inlet stream, and a gas outlet line. The flash pot was maintained at about 120-160 Q C by use of a heating mantel. Infrared heat lamps were used to prevent the SO 3 from freezing in or on the tip of the addition funnel.
  • liquid SO 3 stabilized, Aldrich Chemical Company
  • the gas outlet line of the flash pot was attached to a 25 Q C water-jacketed glass reactor that was designed to deliver the gas from the flash pot to a liquid feedstock via multiple small pin-holes in the bottom of the reactor.
  • the N 2 flow rate through the reactor was adjusted to about 5 liters per minute and then 213.4 gram (0.889 moles) of linear alkylbenzene feedstock was then added to the water-jacketed reactor.
  • the liquid SO 3 was placed slowly into the flash pot so as to maintain the reaction temperature in the reaction vessel below about 55 Q C.
  • the total SO 3 addition time was about 30 minutes. An orange sulfonic acid product was obtained, which was stored at ambient temperature.
  • Samples 5-7 demonstrate the preparation of modified feedstocks by dissolution of partially neutralized, partially sulfonated linear alkylbenzenes into linear alkylbenzene feedstock.
  • Sample 8 demonstrates the preparation of a modified feedstock by the in-situ reaction of partially sulfonated linear alkylbenzene and sodium carbonate in linear alkyl benzene feedstock.
  • Sample 9 and Comparative Sample A demonstrate the reduction of sulfone generation during the sulfonation of the modified feedstock produced in Example 3 (Sample 8) as compared to the sulfonation of unmodified Deten LAB 240 linear alkylbenzene.
  • feedstock was sulfonated at 30-40 Q C with about 1.03 molar equivalents of gaseous SO 3 relative to alkylbenzene in the feedstock using a sulfonation method comparable to that described in Example 1.
  • SO 3 gaseous SO 3
  • about 1 milliliter aliquots of reaction mixture were pulled from the reactor. These aliquots were digested at 50 Q C for 30 minutes and were then analyzed by 1 H NMR (acetone-d6, RT).
  • the molar conversions of linear alkylbenzene to sulfonated products were calculated from integration data for unreacted linear alkylbenzene (NMR chemical shift of 7.35 to 7.0 parts per million (ppm)) relative to total aromatic protons (about 8.0 ppm to 6.9 ppm).
  • the molar conversion of linear alkylbenzene to sulfone was estimated as follows. About 0.5- 0.8 grams of acid sample, 20 milliliter of deionized water, 20 milliliter of ethanol, and 40 milliliter of petroleum ether were added to a flask.
  • the signals for the other one-half of protons were observed to overlap with proton signals for linear alkylbenzene; the relative molar amount of linear alkylbenzene in the extract was determined by subtracting out the integration values for the resolved sulfone and sulfonic anhydride signals.
  • the relative mole fraction of sulfone to linear alkylbenzene in the extract in combination with the estimated molar conversion of linear alkylbenzene to sulfonated product, enabled a calculation of the molar conversion of linear alkylbenzene to sulfone.
  • Samples 10-13 and Comparative Sample B demonstrate the preparation of alkylaryl sulfonate compositions by falling film sulfonation of a modified feedstock that was prepared from Deten LAB 240 linear alkylbenzene, and demonstrates the reduced levels of sulfones in the obtained products relative to sulfonic acid produced by commercial falling film sulfonation of un-modified feedstock.
  • Modified Feedstock was sulfonated at several mole ratios of SO 3 to linear alkylbenzene on a single-tube falling film reactor at an acid production rate of about 85 lbs per hour.
  • Modified feedstock was pumped from the 170 gallon stirred vessel and through a 30 micron filter prior to metering into the falling film reactor. Crude sulfonation product exiting the falling film reactor was digested in a continuous flow reactor. The residence time of the acid in the flow reactor was about 27 minutes and the outlet temperature was about 49 Q C.
  • Acid collected from the flow reactor was treated with 0.6 % water (wt/wt acid) in order to hydrolyze sulfonic anhydrides and to stabilize the product.
  • the obtained sulfonate compositions were analyzed for free oil by petroleum ether extractions of approximately 10 gram samples that were dissolved in 50/50 (vol/vol) water/ethanol and neutralized to phenolphthalein endpoint with sodium hydroxide. Following recovery of the extracted oils by rotary evaporation, the mass of free oil obtained allowed for a calculation of free oil as a weight percentage of the sulfonic acid product.
  • the sulfone content of the sulfonate compositions was determined by 1 H NMR spectroscopy (CDCI 3 solvent, RT) of the obtained free oils, using isopropyl myristate as an internal standard, and calculating the mass of sulfone based on molar integration of sulfone 1 H signals at 7.84 ppm relative to molar integration of isopropyl myristate 1 H signal at about 5.0 ppm.
  • Table 4 summarizes Samples 1 1 -13 and compares the results of these Samples to the analysis results for alkylbenzene sulfonic acid produced from un-modified Deten LAB 240 linear alkylbenzene on a commercial falling film reactor of comparable design to the pilot plant reactor (Comparative Sample B). From the data in Table 4, it is concluded that falling film sulfonation of the modified feedstock affords a sulfonated alkylbenzene composition with reduced sulfones at high conversions of linear alkylbenzene as compared to optimized commercial conversion of un-modified feedstock by falling film sulfonation.
  • Sample 14 and Comparative Sample C demonstrate the improved ability to build viscosity in water by the addition of MgSO 4 for sodium linear alkylbenzene sulfonate prepared from the sulfonic acid product obtained in Example 5 (Sample 13), as compared to sodium sulfonate prepared from Comparative Sample B.
  • Sodium sulfonate stock solutions of pH 7 were prepared by neutralization of sulfonic acid in water by the addition of 50% aqueous NaOH. These stock solutions were used to prepare diluted solutions containing 6.0 wt% sulfonate actives (sodium sulfonate equivalent weight of 342 grams/mole) and varying amounts of MgSO 4 . The viscosities of these solutions were measured at 25 Q C on a TA Instruments AR2000 rheometer using concentric cylinders geometry at 10 sec "1 shear rate; results are summarized in Table 5.
  • the data indicate that at equivalent actives concentration, the sodium alkylbenzene sulfonate produced from modified feedstock builds higher viscosity by the addition of MgSO 4 than can be achieved with sulfonate produced by falling film sulfonation from unmodified feedstock.
  • Samples 15-20 demonstrate the effect of sulfuric acid in alkylaromatic sulfonic acid on the reaction of the sulfonic acid with solid sodium carbonate.
  • Partially sulfonated linear alkylbenzene was produced via falling film sulfonation at a ratio of 0.80 mole of SO 3 per mole of linear alkylbenzene as described in Example 5.
  • Acid collected directly off of the sulfonation equipment, which contained about 0.65 percent (wt/wt) H 2 SO 4 was stored in a closed glass jar and allowed to stand at room temperature for two days.
  • Sample 21 demonstrates the utility of ammonia gas in the preparation of partially neutralized, partially sulfonated linear alkylbenzene.
  • Partially sulfonated linear alkylbenzene was produced via falling film sulfonation at a ratio of 0.80 mole of SO 3 per mole of linear alkylbenzene as described in Example 1.
  • Sample 22 demonstrates the sulfonation of a modified feedstock produced from Deten LAB 240 and the product of Example 8 (Sample 21 ).
  • a modified feedstock was prepared by dissolving Sample 21 into Deten LAB 240 at a 1 :9 ratio (wt/wt). This feedstock was then batch sulfonated as described in Example 4. At 98.7 mole percent conversion of LAB, the conversion of LAB to sulfone was found to be 0.25 mole percent.
  • Samples 23 and 24 demonstrate the preparation of modified feedstocks from Deten LAB 240 and a partially neutralized product that was derived from commercial alkylbenzene sulfonic acid.
  • Example 23 Dissolution of the filtered liquid into Deten LAB 240 at a 1 :9 ratio afforded a modified feedstock (Sample 23). Another portion of the partially neutralized product was allowed to stand at ambient temperature for 24 hours to afford a sample wherein the particulate material had fully settled to the bottom of the container. A clear liquid was decanted from this sample and this liquid was dissolved into Deten LAB 240 at a 1 :19 ratio to afford a second modified feedstock (Sample 24).
  • Samples 25-27 demonstrate the sulfonation of Deten LAB 240 linear alkylbenzene feedstock modified with varying amounts of partially neutralized, partially sulfonated linear alkylbenzene.
  • modified feedstocks were prepared by dissolving a partially neutralized, partially sulfonated linear alkylbenzene composition that was comparable to Sample 2 of Example 1 , referenced as "sulfone inhibitor", into Deten LAB 240 linear alkylbenzene.
  • the modified feedstocks were batch sulfonated and the sulfonic acid products were analyzed as described in Example 4. Sample analysis results are summarized in Table 7. These results indicate that relative to Comparative Sample A of Example 4, even low levels of partially neutralized, partially sulfonated linear alkybenzene are effective in reducing the amount of sulfone generated during the sulfonation of LAB.

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Abstract

La présente invention concerne des procédés de préparation de sulfonates d’alkylaryle par sulfonation au SO3 gazeux qui permettent de réduire la totalité des huiles et sulfones libres des produits en utilisant des sels neutralisés de produits sulfonés de charges alkylaromatiques comme inhibiteurs de sulfone dans la sulfonation au SO3 de composés alkylaromatiques. Ces procédés utilisent des mélanges de charges alkylaromatiques et de sels de sulfonate qui présentent une faible viscosité, qui sont homogènes et qui conviennent pour un traitement dans un équipement commercial de sulfonation au SO3 continu, par exemple des réacteurs à film tombant, avec peu ou pas de modification dudit équipement. Dans certains modes de réalisation préférés des procédés de l’invention, l’inhibiteur de sulfone se compose d'un acide alkylarylsulfonique partiellement neutralisé, c.-à-d. d'un mélange d'acide sulfonique et de sels de sulfonate. Dans un autre mode de réalisation, l’inhibiteur de sulfone est préparé en neutralisant partiellement ou totalement un acide alkylarylsulfonique avec une base puis en dissolvant et/ou en homogénéisant le produit obtenu en une charge alkylaromatique avant sulfonation de la charge.
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CN109627195A (zh) * 2018-05-18 2019-04-16 南京科技职业学院 一种利用微反应器制备重烷基苯磺酸盐的方法
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CN107827788A (zh) * 2017-11-21 2018-03-23 赞宇科技集团股份有限公司 一种高品质烷基苯磺酸的生产工艺
CN109627195A (zh) * 2018-05-18 2019-04-16 南京科技职业学院 一种利用微反应器制备重烷基苯磺酸盐的方法
CN113454072A (zh) * 2021-05-28 2021-09-28 安徽金禾实业股份有限公司 乙酰磺胺酸钾的制备方法
CN113454072B (zh) * 2021-05-28 2022-11-25 安徽金禾实业股份有限公司 乙酰磺胺酸钾的制备方法

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