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WO1997014676A1 - Procede ameliore de preparation de sulfonates d'alkylbenzene lineaires - Google Patents

Procede ameliore de preparation de sulfonates d'alkylbenzene lineaires Download PDF

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Publication number
WO1997014676A1
WO1997014676A1 PCT/US1996/016648 US9616648W WO9714676A1 WO 1997014676 A1 WO1997014676 A1 WO 1997014676A1 US 9616648 W US9616648 W US 9616648W WO 9714676 A1 WO9714676 A1 WO 9714676A1
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Prior art keywords
linear alkylbenzene
sulfonic acid
product
mixture
process according
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PCT/US1996/016648
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English (en)
Inventor
Paul S. Tully
Marshall J. Nepras
Randal J. Bernhardt
James A. Hartlage
William R. Mohring
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Stepan Company
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Publication of WO1997014676A1 publication Critical patent/WO1997014676A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification
    • 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

Definitions

  • the present invention relates to linear alkylbenzene sulfonic acid compositions and methods for preparing such compositions having low color. It also relates to neutralized linear alkylbenzene sulfonic acid compositions, i.e., linear alkylbenzene sulfonates and methods for preparing such compositions having low color.
  • wnerei ⁇ R is typically C]_-22 linear cr brancne ⁇ aikyi.
  • the linear alkylbenzene sulfonic acid is subsequently optionally bleached and/or neutralized.
  • branched alkylbenzenes also known as 2-phenyl isomers
  • dialkylbenzenes diphenylalkanes
  • alkyl indanes alkyl tetralines
  • alkylated poly-aromatics such as naphthalene and anthracene derivatives.
  • trace amounts of organochlorides and aluminum trichloride catalyst residues may be present .
  • Modern methods for preparing the starting linear alkylbenzene typically involve a Friedel-Crafts alkylation of benzene with an olefin or n-paraffin in the presence of a suitable catalyst; modern methods omit the usage of chloroparaffins .
  • Conventional sulfonation processes involve reaction of the linear alkylbenzene with a sulfatmg agent, e.g., SO3, SO2-SO3, oleum, or H2SO4, etc., to produce the desired sulfonic acid.
  • a sulfatmg agent e.g., SO3, SO2-SO3, oleum, or H2SO4, etc.
  • sulfonation of a linear alkylbenzene starting material derived from benzene and chloroparaffins with such an amount of sulfonating agent typically yields linear alkylbenzene sulfonic acids products having high, unsuitable amounts of color, as compared to sulfonation of a linear alkylbenzene starting material derived from benzene and n-paraffins or olefins.
  • a typical molar ratio of sulfonating agent to linear alkylbenzene is from about 1.00:1.00 to about 1.04:1.00.
  • a more preferred range of sulfonating agent to linear alkylbenzene is from about 1.01:1.00 to 1.02:1.00.
  • a slight excess of sulfonating agent is generally believed to be necessary to drive the reaction to completion, i.e. to obtain a high level of conversion of linear alkylbenzene to linear alkylbenzene sulfonic acid.
  • Conventional methods for maximizing the conversion of linear alkylbenzene to linear alkylbenzene sulfonic acid typically include: (1) increasing the molar ratio of sulfonating agent to linear alkylbenzene, ⁇ 2 ⁇ providing an aging step for the sulfonic acid product after tne sulfonation reaction has taxen place.
  • Aging of linear alkylbenzene sulfonic acid typically involves heating the acid to a temperature of about 40-60°C for a period of time of about 2-20 minutes. As the aging process at any elevated temperature for any reasonable period of time is employed, tne color of the sulfonic acid product increases.
  • the invention provides processes for preparing linear alkylbenzene sulfonic ac ⁇ s.
  • T e retr.co comprises treating ⁇ linear alr-.ylcer.:er.'- ⁇ _t:. _ z___. : ::._: ir.d agent to yield a sulfonation product.
  • the -.near ai.-.y.cer.zer.e utilized is produced by a reaction cetweer. o.efir. or paraffin and Denzene.
  • the resulting linear alkylbenzene sulfonic acid is contacted with a protic reagent ano hydrogen peroxide.
  • the contacting is typically for a time and temperature sufficient to produce a linear alkylbenzene sulfonic acid having a greatly reduced color.
  • Sulfonation products prepared according the inventive method typically have Klett colors less than 15. In certain embodiments of the inventive method, the sulfonation products have Klett colors less than about 2.
  • the invention further provides sulfonation products that are neutralized to provide a salt of the sulfonic acid (i.e. a sulfonate) .
  • the invention also encompasses a process for reducing the Klett color in a linear alkylbenzene sulfonic acid product that has previously been treated with a protic reagent and hydrogen peroxide, the process comprising contacting a sulfonic acid product with a neutralizing agent.
  • the invention encompasses a process for reducing the Klett color in a linear alkylbenzene sulfonate product that has previously been treated with a protic reagent, hydrogen peroxide, and a neutralizing agent, the process comprising contacting a sulfonate product with a reducing a ⁇ ent, such as sodium hypochlorite, to produce a sulfonate with a additional unexpected amount cf Klett color reduction.
  • a reducing a ⁇ ent such as sodium hypochlorite
  • the invention furtner provides sulfonic acid compositions comprising from aoout 55 percent to
  • the invention further provides linear alkylbenzene sulfonic acid compositions comprising from about 85 percent to 99 percent by weight linear alkylbenzene sulfonic acid and about 0.5 percent to 15 percent by weight water and preferably about 0.01 to about 0.5 percent by weight un-reacted linear alkylbenzene.
  • the invention further provides linear alkylbenzene sulfonic acid compositions comprising from about 85 percent to 99 percent by weight linear alkylbenzene sulfonic acid and about 0.5 percent to 15 percent by weight water and preferably about 0.01 to about 0.2 percent by weight un-reacted linear alkylbenzene.
  • the invention further provides linear alkylbenzene sulfonic acid compositions prepared by rapid sulfonation conditions.
  • irrigation rates above 45 are considered rapid to one skilled in the art. Standard irrigation rates from about 30 to 45 are common for continuous falling film sulfonation. The standard definition of irrigation rate "I.R.” V for falling
  • compositions sulfonated under rapid conditions comprise from about 85 percent to 99 percent by weight linear alkylbenzene sulfonic acid and about 0.5 percent to 15 percent by weight water and preferably about 0.01 to about 0.5 percent by weight un-reacted linear alkylbenzene.
  • the invention further provides linear alkylbenzene sulfonic acid compositions prepared by rapid sulfonation conditions. These compositions comprise from about 85 percent to 99 percent by weight linear alkylbenzene sulfonic acid and about 0.5 percent to 15 percent by weight water and preferably about 0.01 to about 0.2 percent by weight un-reacted linear alkylbenzene.
  • linear alkylbenzene means an alkylbenzene having a straight or branched chain alkyl group of from about 8 to 22 carbon atoms.
  • Linear alkylbenzene sulfonic acid or sulfonate means an alkylbenzene sulfonic acid or sulfonate having a straight or branched chain alkyl group of from about 8 to 22 carbon atoms.
  • Klett color is defined by the equation (1000) (D)/2, where
  • D is the optical density of the material Deing measured at a given concentration.
  • the Klett color of the sulfonic acids and sulfonates described herein are measured at a 5 weignt percent concentration in water.
  • the present invention provides methods for preparing linear alkylbenzene sulfonic acid and salts of these acids. Surprisingly, the methods result in linear alkylbenzene sulfonic acid and salt products having substantially reduce ⁇ amounts of color and/cr substantially reduced cr non-existent amounts of un-reacted i.e. un-sulfonated ⁇ ..near alkvlbenzene.
  • the present invention also provides metnoos for preoarin ⁇ sue. .inear alkylbenzene sulfonic aci ⁇ s and sulfonates at greatly increased rates.
  • the present invention encompasses processes for preparing linear alkylbenzene sulfonic acids (I) and linear alkylbenzene sulfonates (II) of the formulas
  • R represents branched or straight chain alkyl having i-22 carbon atoms
  • M represents an alkali metal, ammonium, or organic ammonium cation, or mixtures thereof.
  • dark colored acid is defined as material having a Klett color of greater than 30; light colored material is defined as having a Klett colcr of from about 10 to about 30; and very
  • R represents branched or straight chain alkyl having 8-22 carbon atoms.
  • the starting linear alkylbenzene for use in this invention is preferably derived from the reaction of benzene and n- paraffins and/or olefins in the presence of a Friedel Crafts alkylation catalyst, such as hydrogen fluoride or aluminum chloride.
  • sulfonation of linear alkylbenzene starting material with a sulfonating agent is accomplished by treating the linear alkylbenzene starting material with a sulfonating agent.
  • the sulfonating agent may be liquid or gaseous.
  • the starting linear alkylbenzene is m the liquid pnase.
  • the treatment step typically occurs at a temperature from about 0°C to about 90°C and somewhat more preferably from about 25°C to about 50°C.
  • sulfonating agents are suitac., ::r use .r. tne invention.
  • Sulfur trioxide (SO3) is a preferred sulfonating agent because of its vigorous reactivity. Sulfur trioxide also produces less byproducts than other sulfonating agents.
  • a linear alkylbenzene sulfonic acid which is essentially free of un-reacted, i.e. un-sulfonated linear alkylbenzene, can be produced by employing a molar ratio of sulfonating agent to linear alkylbenzene of greater than about 1.04:1.00, in combination with an aging step at an elevated temperature.
  • linear alkylbenzene sulfonic acid which is essentially free of un-reacted linear alkylbenzene can be produced by employing a molar ratio of sulfonating agent to linear alkylbenzene of about 1.1:1.0 without the need of an aging step.
  • a sulfonation reaction is relatively fast and quite exothermic. Accordingly, care must be taken to avoid over-sulfonation in localized areas (i.e. charring) to adequately control the exotherm and to insure good contact between the reactants.
  • Suitable methods of treating the linear alkylbenzene starting material with a sulfonating reagent include continuous agitation (batch sulfonation) methods, or oy contacting a gas stream containing the sulfonating agent against a moving surface film (continuous falling film sulfonation) of linear alkylbenzene under turbulent conditions wnereby the various molecules are vigcrous v stirred or intermixed within the reaction mass.
  • Both cater and continuous -netnoos of sulfonation require that the exterior walls c: tne reaction vessel be cooled, for example, with a heat-exchange medium, providing a heat sink for the exothermic reaction conditions.
  • sulfonating agent for example, SO3 in air
  • SO3 is normally introduced in a pressurized gas stream as a gas in a gas (i.e., SO2, air, nitrogen or other relatively inert gas) in a so-called falling film reactor.
  • SO2 is normally introduced in a pressurized gas stream as a gas in a gas (i.e., SO2, air, nitrogen or other relatively inert gas) in a so-called falling film reactor.
  • a so-called wiped film reactor may be utilized so that a relatively thin film of linear alkylbenzene is contacted by the gas stream, mechanically wiped from the reactor walls at the area of contact and re-oeposited downstream on freshly cooled reactor walls.
  • tne color quality and composition of the linear alkylbenzene sulfonic acid product is effected by the rate of sulfonation and the control of the resulting exotherm, i.e. the efficiency of the heat sink provided. Irrigation rates from aoout 30 to 45 are common.
  • irrigation rates aoove 4 are emclcveo, tne color quality of tne linear alkylbenzene _ulfor. ⁇ o _c ⁇ c crc ⁇ uct normally is degraded, as it is very ciffic-.t to crevice tne necessary heat sink to counter act the increase ir. exotnerr of tne reaction at such high irrigation rates. Sulfonation at high irrigation rates is not typically practiced since such irrigation rates produce linear alkylbenzene sulfonic acid with unacceptable color.
  • linear alkylbenzene sulfonic acids can be produced by employing irrigation rates of 45-100; irrigation rates of greater than 100 are also possible.
  • linear alkylbenzene sulfonic acid which is essentially free of un-reacted, i.e., un-sulfonated linear alkylbenzene
  • a linear alkylbenzene sulfonic acid which is essentially free of un-reacted, i.e., un-sulfonated linear alkylbenzene
  • a molar ratio of sulfonating agent to linear alkylbenzene of greater than 1.04:1.00
  • a solvent may optionally oe present during the treating step to both reduce the viscosity of the reaction mixture and to function as another heat sink for the reaction.
  • preferred solvents are sulfur dioxide, ⁇ ioxane, dimethyl formami ⁇ e, C_j to C20 hydrocarbons, nitroparaffins, acetomtriie, chlcroalkyls, carDoxylic acids, straight or crancned a ..ary. s-_.fonate compounds, naving 1 to 16 a ⁇ y.
  • tne ::_ve may reduce tne viscosity of the reactants/reaction products ana are liquid under reaction conditions.
  • Some solvents sucn as, for example, sulfur dioxide may be gaseous even at relatively low temperature so that super-atmospheric pressure may be required to maintain such solvents in liquid form. Generally pressures of up to about 100 p.s.i. or more are utilized.
  • the amount of solvent may be present from about 0.01 percent to about 1000 percent by weight, based on the weight of the linear alkylbenzene, and somewhat more preferably, the amount of solvent may be present from about 10 percent to about 1000 percent by weight, on the same basis.
  • a presently preferred solvent is sulfur dioxide, because it complexes with sulfonating agents, particularly SO3.
  • the treating step may occur in the presence of a sulfonatable agent capaole of reacting and/or complexmg with any free and/or complexed SO3.
  • these sulfonatable agents likewise may function as aids in controlling the viscosity of the reactants/reaction products, and as heat sinks for the exotherm of the sulfonatior reaction.
  • the sulfonation agents aiso tend to minimize .ocalizeo over- s_-ifonation e: the .
  • sulfonatac.- a ⁇ ents cacao.e cr reaction and/or complexmg with any free and/or compiexeo sulfonating agents are linear or branched alkylaryl compounds, toluene, cumene, xylene, olefins, unsaturated esters, ammonia, organic ammonia derivatives, water and mixtures thereof.
  • the amount of sulfonatable agent present (if any) during the treating step may range from about 0.01 percent to about 1000 percent by weight, based on the weight of the sulfonating agent utilized. In preferred embodiments, the amount of sulfonatable agent present during the treating step may range from about 10 percent to about 100 percent by weight, on the same basis.
  • both a sulfonatable agent capable of reacting and/or complexmg with any free and/or complexed sulfonating agent, as well as the earlier described solvents may be present in equal or different amounts during the treating of linear alkylbenzene with a sulfonating agent, the aging step, the bleaching step and the neutralization step.
  • matrix sulfonation may also be utilized. Matrix sulfonation involves pre-mix g of linear alkylbenzene and a sulfonatable agent moderator prior to treating with the sulfonating agent and subsequently allowing the sulfonation to occur.
  • sulfonatable agent moderators include, but are not _imited to, pyridine, dimethyl ormamide, and trimet.nyiamine. Such a method moderates the attac-. of tne sulfonation agent en tne reeostoc. oorco-e ⁇ to, "inir.zes loca.izeo over-sulfonation cr tne ..near J.- ..cenzene, ano minimizes tne production cf un ⁇ esire ⁇ c_.crc ⁇ _::s and ceicr oodies.
  • loop sulfonation may be practiced.
  • the treating step is repeated a number of times, either in a continuous loop-type re-circulating system or in batch re- sulfonation whereby additional sulfonating agent is added to an initially sulfonated intermediate reaction product.
  • additional sulfonating agent is added to an initially sulfonated intermediate reaction product.
  • the reaction is conducted under sulfonation conditions, especially as described above.
  • linear alkylbenzene sulfonic acids are stabilized with water.
  • the amount of water used is typically about 0.5 to 1.0 percent by weight, based on the weight of the linear alkylbenzene sulfonic acid.
  • the water breaks up undesirable linear alkylbenzene sulfonic anhydrides which may be formed during the sulfonation step.
  • the resulting dark colored linear alkylbenzene sulfonic acid is contacted with a protic reagent and an oxidizing agent, i.e. hydrogen peroxide, where the contacting is performed at a sufficient temperature ano for a sufficient time to produce a linear alkylbenzene sulfonic acid product r.avi e _. reduced color.
  • Tne cleacr.m ⁇ step may ce conducted eitner oefore or after the water staeilizaticr. step. In certain emoooiments of the invention, the .
  • near alkylbenzene sulfonic acid may be treated with an cxi ⁇ izmg a ⁇ ent and a protic reagent in a batch mode, a continuous mo ⁇ e or a combination thereof.
  • the linear alkylbenzene sulfonic acid may be treated with a premix of an oxidizing agent and a protic reagent in a batch mode, a continuous mode or a combination thereof.
  • protic reagents suitable for use in the bleaching step of the invention include, but are not limited to, water, alcohols of the formula R(OCH2CH2) n 0H where to
  • the linear alkylbenzene sulfonic acid is treated with protic reagent in a range of 0.50 percent to about 15.0 percent by weight, based on the weight of the linear alkylbenzene sulfonic acid. Somewhat more preferably, the amount of protic reagent used is 4 percent to 10 percent by weight, on the same basis.
  • the most preferred oxidizing agent is hydrogen peroxide, which may be supplied in various forms and concentrations. The form of choice is an aqueous solution, with a concentration in the range of 0.10 percent to 70 percent, based on the total weight of the solution.
  • a more preferred concentration is in the range of 30 percent to 50 percent, on the same basis.
  • the linear alkylbenzene sulfonic acid is treated with hydrogen peroxide m a range of 0.10 percent to aoout 5.0 percent oy weight, cased on the wei ⁇ r.t of tne linear alkyioenzene sulfonic acid.
  • the amount cf ydrogen peroxide used is aoout C.5 percent to 2.C percent by weight, on the same basis.
  • the linear alkylbenzene sulfonic acid and protic reagent are contacted at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homogeneous mixture with agitation.
  • the linear alkylbenzene sulfonic acid and protic reagent are contacted at a temperature of about 25°C to about 50°C, for a time sufficient to produce a homogeneous mixture.
  • the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homogeneous mixture.
  • the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses a Klett color of about 8.
  • the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture with agitation; said mixture posses a Klett color of less than about 2.
  • the linear alkylbenzene sulfonic acid and a protic reagent/hydrogen peroxide pre- mixture solution are contacted at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homo ⁇ eneous mixture with agitation.
  • the linear alkylbenzene sulfonic acid and erotic reagent/hydrogen peroxide mixture are contacted at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses a Klett color of less than about 8.
  • the linear alkylbenzene sulfonic acid and protic reagent/hydrogen peroxide mixture are contacted at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses Klett a color of less than about 2.
  • the linear alkylbenzene sulfonic acid and protic reagent are contacted at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homogeneous mixture.
  • the linear alkylbenzene sulfonic acid and protic reagent are contacted at a temperature of about 25°C to about 50°C, for a time sufficient to produce a homogeneous mixture.
  • the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homogeneous mixture.
  • the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses a Klett color of less than 8.
  • the linear alkylbenzene sulfonic acid/protic reagent mixture is contacted with r.y ⁇ ro ⁇ er. peroxide at a temperature cf aDout __5°C to aoout 60°C, for a time sufficient tc produce a nomogenecus mixture; said mixture posses a Klett color cf less than aoout
  • the linear alkylbenzene sulfonic acid and protic reagent/hydrogen peroxide pre-mixed solution are contacted at a temperature of about 0°C to about 80°C, for a time sufficient to produce a homogeneous mixture.
  • the linear alkylbenzene sulfonic acid and protic reagent/hydrogen peroxide pre-mixed solution are contacted at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous.
  • the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses a Klett color of less than 8.
  • the linear alkylbenzene sulfonic acid/protic reagent mixture is then contacted with hydrogen peroxide at a temperature of about 25°C to about 60°C, for a time sufficient to produce a homogeneous mixture; said mixture posses a Klett color of less than about 2.
  • the bleaching step of the invention has been found to significantly reduce the color of the starting linear alkylbenzene sulfonic acids to a Klett of less than about 15, independent of the mode of sulfonation, the starting color of sulfonic acid, the irrigation rate at which the sulfonic acid was produced (continuous falling film mode) , or the presence or acsence of un-sulfonated linear al yloenzene.
  • the lignt colored linear ai.:yloenzer.e suifen.c acids produced by tne invention may be further converted to linear alkylbenzene sulfonates by a neutralization procedure.
  • This neutralization procedure may take place immediately after the above described bleaching step(s) or at a later time. It has been discovered that neutralization of the bleached linear alkylbenzene sulfonic acid mixture to a pH of about 6.0 or greater affords an additional color reducing effect to the final linear alkylbenzene sulfonate material, as compared to un-bleached linear alkylbenzene sulfonic acid.
  • the color reduction is typically about 5 to 20 Klett units. Without being bound by any particular theory, it is believed that this effect is an in situ activation of residual hydrogen peroxide.
  • the above described neutralization can be effected utilizing a solution of base have a cation selected for the group consisting of alkali metals, ammonium cations, organic ammonium cations, and mixtures thereof.
  • the neutralizing agent is selected from, but not limited to, the group consisting of NaOH, MgO, Mg(OH) 2 , KOH, Ca(OH) 2 , t ⁇ ethanolamme, diethanolam e, ammonia, isopropylamine, and mixtures thereof.
  • Linear alkylbenzene sulfonic acid is prepared using standard sulfonation techniques by contacting linear alkylbenzene (LAB) produced by the reaction of an olefm and benzene, with one of the following: Gaseous S ⁇ 3/a ⁇ r, SO2/SO3,
  • the LAS acid is then stabilized by the addition of about 0.5 wt. % water.
  • the color of the crude sulfonic acid is deep red, with a Klett of about 40.
  • the first step of the bleaching process involves combining lOOg of LAS with aDout 6 g of water (6 wt . " ) at room temperature (23°C) with mixing, which produces a 20°C exotherm.
  • the temperature of the LAS/H2O slurry is ad]uste ⁇ to about 23°C and about 4g of H2O2 in tne form of a 50- active aqueous solution (4 w . r ) is added; this additie*" results .r ⁇ 5°C exctr.er ⁇ .
  • Linear alkylbenzene sulfonic acid is prepared using standard sulfonation techniques by contacting linear alkylbenzene (LAB) produced by the reaction of an olefm and benzene, with one of the following: Gaseous S ⁇ 3/a ⁇ r, SO2/SO3,
  • the first step of the bleaching process involves combining lOOg of LAS with about 6 g of water (6 wt . %) at room temperature (23°C) with mixing, which produces a 20°C exotherm.
  • the temperature of the LAS/H2O slurry is adjusted to about 38°C ano about 4g of H2O2 m the form of a 501 active aqueous solution (4 wt . %) is added; this addition results in a 5°C exotherm.
  • the H2O/H2O2 treated LAS is allowed to bleacn approximately 45 minutes at a temperature of about 38 C. After this period of time the sulfonic acid solution had a Klett of about 2.
  • Approximately lOOg of LAS produced from tne aoove reaction is heated to about 40 C C for about 20 minutes i.e., aged) to drive the reaction to completion.
  • the LAS acid is then stabilized by the addition of about 0.5 wt . % water.
  • the color of the crude sulfonic acid is deep red, with a Klett of about 40.
  • the first step of the bleaching process involves combining lOOg of LAS with about 6 g of methyl alcohol (6 wt . °- ) at room temperature (23°C) with mixing, which produces a 15°C exotherm.
  • the temperature of the LAS/H2O slurry is adjusted to about 38°C and about 4g of H2O2 in the form of a 50% active aqueous solution (4 wt. %) is added; this addition results in a 5°C exotherm.
  • the methyl alcohol/H2 ⁇ 2 treated LAS is allowed to bleach approximately 45 minutes at a temperature of about 38 C. After this period of time the sulfonic acid solution had a Klett of about 2.
  • Linear alkylbenzene sulfonic acid is prepared using standard sulfonation techniques by contacting linear alkylbenzene (LAB) produced by the reaction of an olefm and benzene, with one of the following: Gaseous S ⁇ 3/a ⁇ r, SO2/SO3,
  • LAS tnen stacil zeo by the addition of aoout C.5 w . water.
  • the color of the crude sulfonic acid is deep red, with a Klett of aoout 50.
  • the first step of tne bleaching process involves con_c ⁇ r. ⁇ ng lOOg cf LAS with about 6 g of water (6 wt . %) at room temperature (23°C) with mixing, which produces a 20°C exotherm.
  • the temperature of the LAS/H2O slurry is adiusted to about 38°C and about 2g of H2O2 in the form of a 50% active aqueous solution (2 w . %) is added; this addition results a 5°C exotherm.
  • the H2O/H2O2 treated LAS is allowed to bleach approximately 45 minutes at a temperature of about 38 C. After this period of time the sulfonic acid solution had a Klett of about 24.
  • Neutralization of the sulfonic acid solution is carried out at room temperature (23°C) by sequentially charging a vessel equipped with stirring means with: (1) a sufficient amount of H2O/H2O2 treated LAS and water to prepare a slurry containing 35% by weight of neutralized LAS and (2) a sufficient amount of caustic (NaOH) to neutralize about 75% of the acid in the slurry.
  • the remaining caustic is then added slowly and the pH adjusted to approximately 8.5. This method of neutralization avoids foaming due to hydrogen peroxide destruction.
  • Linear alkylbenzene sulfonic acid (LAS) s prepared using standard sulfonation techniques by centactm ⁇ linear al K . -oenzene LAB) produced ⁇ y tne reaction _r .:. .er.r ana cenzene, with one of tne following: Gaseous 21./ air, 223 ⁇ C3, J 2SC-4 or oieum.
  • Approximately lOOg or LAS cro ⁇ ucec rrcr tne acove reaction is heated to aoout 40°C for about 20 minutes
  • the LAS acid is then stabilized by the addition of about 0.5 wt. % water.
  • the color of the crude sulfonic acid is deep red, with a Klett of about 55.
  • the first step of the bleaching process involves combining lOOg of LAS with about 6 g of water (6 wt. %) at room temperature (23°C) with mixing, which produces a 20°C exotherm.
  • the temperature of the LAS/H2O slurry is adjusted to about 40°C and about lg of H2O2 in the form of a 50% active aqueous solution (1 wt . %) is added; this addition results in a 5°C exotherm.
  • the H2O/H2O2 treated LAS is allowed to bleach
  • Linear alkylbenzene sulfonic acid is prepared using standard sulfonation techniques at greatly increased irrigation rates by contacting linear alkylbenzene (LAB) produced by the reaction of an olefin and benzene with gaseous SO3 and air in a falling film reactor.
  • the irrigation rate used is 76.
  • the LAS product produced from the above reaction rates requires no digestion/aging.
  • the resulting LAS acid is stabilized with 0.5 wt . " ; water.
  • the color cf the crude sulfonic acid is black in appearance, with a Klett of acout 85.
  • the first step cr tne _: leaching process involves combining lOOg of LAS with aoout 5 g of water 5 wt . ' • at a temperature of aoout 35°C with mixing, wnicn produces a 18°C exotherm.
  • the temperature of the LAS/H2O slurry is adjusted to about 35°C and about lg of H2O2 in the form of a 50% active aqueous solution
  • Linear alkylbenzene sulfonic acid is prepared using standard sulfonation techniques at greatly increased irrigation rates by contacting linear alkylbenzene (LAB) produced by the reaction of an olefm and benzene with gaseous SO3 and air in a falling film reactor.
  • the irrigation rate used is 76.
  • the ratio of LAB:S ⁇ 3 is about 1:1.09.
  • the LAS product produced from the above reaction rates requires no digestion/aging.
  • the resulting LAS acid is stabilized with 0.5 wt . % water.
  • the color of the crude sulfonic acid is black in appearance, with a
  • the first step of the bleaching process involves combining lOOg of LAS with about 6 g of water (6 wt . %) at a temperature of about 35°C with mixing, whicn produces a 20°C exotherm.
  • the temperature of the LAS/H2O slurry is adjusted to about 35°C and about 2g of H2O2 the form cf a 50- active aqueous solution
  • Tne H2O H2O2 treated LAS is alioweo to cleac ⁇ approximately 20 c rrinutes at a temperature cf aoout 35 Z . After this pence cf time the sulfonic acid solution has a Klett of acout 24.
  • Linear alkylbenzene sulfonic acid is prepared using standard sulfonation techniques at greatly increased irrigation rates by contacting linear alkylbenzene (LAB) produced by the reaction of an olefin and benzene with gaseous SO3 and air in a falling film reactor.
  • the irrigation rate used is 76.
  • the ratio of LAB:S03 is about 1:1.09.
  • the LAS product produced from the above reaction rates requires no digestion/aging.
  • the resulting LAS acid is stabilized with 0.5 wt. % water.
  • the color of the crude sulfonic acid is black in appearance, with a Klett of about 109.
  • the iHNMR and GC-MS analysis indicates that the product contains no detectable residual LAB.
  • the first step of the bleaching process involves combining lOOg of LAS with about 6 g of water (6 wt . %) at a temperature of about 38°C with mixing, which produces a 20°C exotherm.
  • the temperature of the LAS/H2O slurry is adjusted to aoout 35°C and about 2g of H2O2 in the form of a 50% active aqueous solution
  • the H2O/H2O2 treated LAS is allowed to bleacn approximately 2C minutes at a temperature of about 35 C. After this period of time the sulfonic acid solution has a Klett of about 24.
  • Neutralization of the sulfonic acid solution is carried out at room temperature ⁇ 23°C) by sequential,y cnargmc a vessel equipped with stirring means _ ⁇ :h: 1 a sufficient amount of H2O H2O2 treated LAS ano ..attr * r rec.re _ s._rr_ containing 35% by weight of neutra..zee LAS a.na 2 a sufficient amount of caustic (NaOH to ne._tra. ze acc_- " or the acid n the slurry.
  • the remaining caustic is then added slowly and the pH adjusted to approximately 8.5. This method of neutralization avoids foaming due to hydrogen peroxide destruction.
  • Linear alkylbenzene sulfonic acid is prepared using standard sulfonation techniques by contacting linear alkylbenzene (LAB) produced by the reaction of an olefin and benzene, with one of the following: Gaseous S03/air, SO2/SO3, H2SO4 or oleum. Approximately lOOg of LAS produced from the above reaction is heated to about 40°C for about 20 minutes
  • the LAS acid is then stabilized by the addition of about 0.5 wt. % water.
  • the color of the crude sulfonic acid is light red, with a Klett of about 21.
  • the first step of the bleaching process involves combining lOOg of LAS with about 5 g of water (5 wt . %) at a temperature of about 37°C with mixing, which produces a 20°C exotherm.
  • the temperature of the LAS/H2O slurry is adjusted to about 37°C and about 0.2g of H2O2 m the form of a 50% active aqueous solution
  • Neutralization of the sulfonic acid solution is carrie ⁇ out at room temperature (23°C) by sequentially cnarging a vessel equipped with stirring means with: (1) a sufficient amount of H2O/H2O2 treated LAS and water to prepare a slurry containing 41% by weight of neutralized LAS and (2) a sufficient amount of caustic (NaOH) to neutralize about 75% of the acid in the slurry.
  • the remaining caustic is then added slowly and the pH adjusted to approximately 11.0.
  • the neutralized product is treated with 400 ppm active NaOCl, and heated to 65°C for 2.5 hours.
  • the color of the resulting material has a Klett of about 5.
  • Linear alkylbenzene sulfonic acid is prepared using standard sulfonation techniques by contacting linear alkylbenzene (LAB) produced by the reaction of a chloroparaffin and benzene, with one of the following: Gaseous S ⁇ 3/a ⁇ r,
  • the first step cf the bleacninc process inv-.ves "errr nir.e lOOg cf LAS with aDout 6 g of water 1 ..t . _: roerr temperature (23°C) with mixing, whicn produces _ 2C C 2 exotr.err.
  • Tne temperature of the LAS/H2O slurry is adjusted to aoout 23°C and aoout 4g of H2O2 in the form of a 50% active aqueous solution (4 wt . %) is added; this addition results in a 5°C exotherm.
  • the H2O/H2O2 treated LAS is allowed to bleach approximately 4 hours at room temperature (23°C) . After this period of time the sulfonic acid solution had a Klett of about 64. Extended bleaching times up to 48 hours produced no further lowering of the sulfonic acid color.

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

Abstract

La présente invention concerne des procédés de préparation d'acides sulfoniques d'alkylbenzène linéaires et de leurs sels correspondants. Ces procédés comprennent: (a) le traitement d'un alkylbenzène avec un agent de sulfonation, l'alkylbenzène linéaire étant produit par une réaction entre une oléfine et le benzène, et (b) la mise en contact du produit de sulfonation de (a) avec un mélange d'un réactif protique et de peroxyde d'hydrogène, ce qui donne un mélange d'acide sulfonique et de peroxyde.
PCT/US1996/016648 1995-10-20 1996-10-17 Procede ameliore de preparation de sulfonates d'alkylbenzene lineaires WO1997014676A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999025804A1 (fr) * 1997-11-18 1999-05-27 The Procter & Gamble Company Procede de preparation a faible ph de pates de tensioactifs aussi claires que de l'eau
WO2000040551A1 (fr) * 1999-01-06 2000-07-13 The Procter & Gamble Company Procede de fabrication d'un tensioactif a base d'alkyl-benzene sulfonate lineaire et compositions de nettoyage contenant ces compositions
RU2221778C2 (ru) * 1997-08-06 2004-01-20 Зингента Партисипейшнс N-сульфонилглициналкинилоксифенэтиламидные производные, обладающие бактерицидной активностью
RU2795626C1 (ru) * 2022-10-07 2023-05-05 Федеральное государственное автономное образовательное учреждение высшего образования "Белгородский государственный национальный исследовательский университет" (НИУ "БелГУ") Способ получения основы синтетических моющих средств

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806055A (en) * 1955-03-14 1957-09-10 Continental Oil Co Purification of alkaryl sulfonates
US2827484A (en) * 1956-02-17 1958-03-18 Allied Chem & Dye Corp Sulfonic acid bleaching process
US2858276A (en) * 1956-09-21 1958-10-28 Monsanto Chemicals Method of bleaching alkyl aryl sulfonic acids
US2880235A (en) * 1957-09-23 1959-03-31 Monsanto Chemicals Color stabilization of alkylarenesulfonic acids
GB1011435A (en) * 1963-04-06 1965-12-01 Sicedison Spa Stabilization of alkylaromatic sulphonic acids
US3997575A (en) * 1973-11-12 1976-12-14 Lion Fat & Oil Co., Ltd. Bleaching method for sulfonic acid
GB2055807A (en) * 1979-07-06 1981-03-11 Lion Corp Thin film type sulphonation process of alkylbenzene

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2806055A (en) * 1955-03-14 1957-09-10 Continental Oil Co Purification of alkaryl sulfonates
US2827484A (en) * 1956-02-17 1958-03-18 Allied Chem & Dye Corp Sulfonic acid bleaching process
US2858276A (en) * 1956-09-21 1958-10-28 Monsanto Chemicals Method of bleaching alkyl aryl sulfonic acids
US2880235A (en) * 1957-09-23 1959-03-31 Monsanto Chemicals Color stabilization of alkylarenesulfonic acids
GB1011435A (en) * 1963-04-06 1965-12-01 Sicedison Spa Stabilization of alkylaromatic sulphonic acids
US3997575A (en) * 1973-11-12 1976-12-14 Lion Fat & Oil Co., Ltd. Bleaching method for sulfonic acid
GB2055807A (en) * 1979-07-06 1981-03-11 Lion Corp Thin film type sulphonation process of alkylbenzene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2221778C2 (ru) * 1997-08-06 2004-01-20 Зингента Партисипейшнс N-сульфонилглициналкинилоксифенэтиламидные производные, обладающие бактерицидной активностью
WO1999025804A1 (fr) * 1997-11-18 1999-05-27 The Procter & Gamble Company Procede de preparation a faible ph de pates de tensioactifs aussi claires que de l'eau
WO2000040551A1 (fr) * 1999-01-06 2000-07-13 The Procter & Gamble Company Procede de fabrication d'un tensioactif a base d'alkyl-benzene sulfonate lineaire et compositions de nettoyage contenant ces compositions
RU2795626C1 (ru) * 2022-10-07 2023-05-05 Федеральное государственное автономное образовательное учреждение высшего образования "Белгородский государственный национальный исследовательский университет" (НИУ "БелГУ") Способ получения основы синтетических моющих средств

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