US3328460A - Process for sulfonation of organic compounds - Google Patents

Process for sulfonation of organic compounds Download PDF

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Publication number
US3328460A
US3328460A US342485A US34248564A US3328460A US 3328460 A US3328460 A US 3328460A US 342485 A US342485 A US 342485A US 34248564 A US34248564 A US 34248564A US 3328460 A US3328460 A US 3328460A
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sulfur trioxide
organic liquid
gas
liquid
organic
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US342485A
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Mey John E Vander
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Allied Corp
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Allied Chemical Corp
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Priority to US342485A priority Critical patent/US3328460A/en
Application filed by Allied Chemical Corp filed Critical Allied Chemical Corp
Priority to GB4919/65A priority patent/GB1029029A/en
Priority to DK58465AA priority patent/DK129280B/da
Priority to DE1518465A priority patent/DE1518465C3/de
Priority to ES308998D priority patent/ES308998A1/es
Priority to BE659278A priority patent/BE659278A/xx
Priority to ES0308998A priority patent/ES308998A3/es
Priority to NL656501442A priority patent/NL146135B/xx
Priority to IL22916A priority patent/IL22916A/xx
Priority to FR4439A priority patent/FR1439060A/fr
Priority to US656609A priority patent/US3501276A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/02—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor of the thin-film type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/247—Suited for forming thin films
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B45/00—Formation or introduction of functional groups containing sulfur
    • C07B45/02—Formation or introduction of functional groups containing sulfur of sulfo or sulfonyldioxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof

Definitions

  • FIGS. 1 A first figure.
  • alkyl aromatic sulfonates have received considerable attention principally for their use as synthetic detergents.
  • certain higher alkyl substituted mononuclear aromatic monosulfonates in which the alkyl groups are predominantly in the range containing from 8 to 20 carbon atoms, many of the more useful alkylates predominating in compounds containing 12 to 14 carbon -atoms in the alkyl side chain.
  • These compounds are normally prepared by Sulfonation of alkylated mononuclear aromatic compounds commonly referred to ⁇ as detergent alkylates, among which are the so-called dodecyl benzenes and tridecyl benzenes.
  • the alkyl groups may -be of mixed configuration and the products may contain minor proportions of higher and lower alkyl groups mainly in the C11 to C14 range.
  • detergent valkylates are commercial products known by various trade names.
  • the commercial dodecyl benzenes and tn'decylbenzenes of this character usually boil within the range between about 530 F. and about 630 F.; the dodecyl benzenes usually boiling predominantly between about 550 F. and about 575 F.; the tridecylbenzenes usually boiling predominantly between about 550 F. and about 600 F.
  • a method has been proposed to prepare high active materials which involves subjecting the composite material to solvent extraction whereby separation of the sodium sulfate and other inorganic salts is effected by dissolving the active detergent material in the solvent.
  • Thisprocedure is costly since the sodium sulfate is discarded and there is considerable loss of solvent in the process.
  • It has been suggested to produce a high active product by direct reaction of sulfur trioxide with the detergent alkylate. Although this procedure is elfective for producing high active products, the reaction with sulfur tri.- oxide is highly exothermic and the product is often olf color. In addition, decomposition of the ⁇ organic compound occurs contributing to alkylate losses. For many commercial purposes the off-color product produced -is not desirable.
  • the synthetic detergent to be commercially ac- Patented June 27, 1967 ceptable must for most purposes possess a light color generally about Klett or less (based on a 10% active solution) and contain not more than 5% preferably less than 2% oil (based on 100% active).
  • Various methods have heretofore been proposed to avoid these objectionable effects resulting from the Sulfonation process.
  • sulfur trioxide was dissolved in an inert solvent and thereafter the reaction was carried out in the diluent medium. This procedure is complicated and expensive since it was found that the solvents utilized were costly to recover and entailed losses.
  • U.S. Patent 2,923,728 suggests reaction of sulfur trioxide in diluting gas in a circular tube with organic compounds propelled linto and through the system by gas.
  • An object of the present invention is to provide ya continuous, eliicient, and economical process for the reaction of sulfur trioxide with organic compounds. Another object is to significantly reduce formation of color bodies which normally occur during the Sulfonation of organic compounds. Another object is to provide an apparatus for reacting organic compounds continuously with sulfur trioxide. A further object is to provide a new organic feed injection design wherein the organic liquid is injected into the reaction chamber circumferentially and in contacting relation to the inert gas sulfur trioxide mixture, avoidingv formation of color bodies at the point of contact.
  • an apparatus and process for sulfonating and sulfating an organic liquid by reacting the same with :the sulfur trioxide constituent of a gas mixture of inert gas and gaseous sulfur trioxide comprising in combination a vertically disposed elongated enclosed reaction chamber, a separating chamber associated with 'the lower end thereof for separately discharging gas and liquid therefrom, means providing a slot in the upper portion of the reaction chamber Wall extending entirely around the periphery thereof, means for cooling said wall extending entirely around the periphery thereof from and below said slot, means for supplying organic liquid through said slot at velocity suliiciently low that all of the Iorganic liquid forms a smooth, thin film extending entirely around the periphery, of said wall and descending downwardly in quiescent How while adhering thereto, and an inlet for a' gaseous mixture of inert gas and sulfur trioxide arranged and adapted to discharge a stream of the same downwardly through
  • the thickness of the film of organic liquid undergoing resulting Sulfonation or sulfation is of the order of .002 to .030 inch, preferably .005 to .015 inch.
  • the means for supplying organic liquid preferably comprises an yorganic liquid supply chamber for the same disposed above the slot and an organic supply inlet to the organic liquid chamber which together is adapted to provide the liquid preferably through metering orifices to the slot at predetermined head uniform throughout slot length and through a laterally extending peripheral channel terminating in the slot.
  • two smooth quiescent flowing films of organic liquid are provided and ⁇ are contacted while adhering to cooled wall surfaces with sulfur trioxide-air gas mixture passed downwardly between them.
  • peripheral slots are provided in inner and outer concentric walls defining the reaction chamber, each wall being water jackerted or otherwise suitably exposed to cooling iiuid.
  • Supply organic liquid is connected to each of the slots.
  • the process of the invention comprises providing a stream of organic liquid extending around the entire pevriphery of the reaction zone, flowing the stream laterally the periphery of the zone and descending in quiescent flow v along the walls thereof, continuously flowing a gaseous stream ofsulfur trioxide and inert gas diluent downwardly through the zone in contact with the lm, maintaining the contact until reaction between the sulfur trioxide and organic liquid is substantially complete, and cooling the said film through substantially the entire extent of said contact.
  • the new process is applicable to the sulfation or sulfonation whichterms will hereafter be used interchangeably to connote reaction of sulfur trioxide with an organic compound of any of the materials known in the rart to bev directly sulfatable or :sulfonatable by reaction with sulfur trioxide.
  • compounds suitable lfor sulfation by sulfur trioxide are fatty alcohols.
  • compounds suitable for sulfonation are olenic compounds, e.g., aliphatic olens containing one or more double bonds, such as tetradecene, hexadecene, etc., aromatic hydrocarbons ⁇ such as those containing a benzene, anth-racene, or like structure and alkylated aromatic hydrocarbons such as toluene, ethylbenzene, dodecyl benzene, etc.
  • alkyl aromatic sulfonic acids which when neutralized with a suitable basic reagent such as an alkali metal hydroxide, an amine or an alkanol amine form highly effective detergent compounds.
  • a suitable basic reagent such as an alkali metal hydroxide, an amine or an alkanol amine form highly effective detergent compounds.
  • the process of the present invention will be preferably applied to those alkylated, .aromatic compounds in which the alkyl group or groups contain a total of from 8 to 22 carbon atoms and in particular, 12 to 14 carbon atoms.
  • the organic compound is a solid at lroom temperature, it may be converted to liquid form by any -known procedure such as, for example, by preheating the compound.
  • the sulfur trioxide used as the active ingredient may be obtained from any suitable source, For example, it may .be vaporized from stabilized liquid sulfur trioxide and mixed with air, nitrogen or other inert gas by ⁇ any suitable known means as, for example, by merging sepa- ⁇ rate streams of sulfur trioxide and diluent inert gas.
  • the sulfur trioxide may be obtained from oleum or may be in the form of the well-known converter gas from the contact sulfuric acid process such converter gas being usually an air-sulfur trioxide mixture containing between 6% and about 15% sulfur trioxide.
  • the inert carrier gas in which.
  • the vaporized sulfur trioxide is ysuspended is one which does not react with the sulfonating agent or the sulfonatable organic compound at the specified sulfonation conditions.
  • gases include air, carbon dioxide, carbon monoxide, sulfur dioxide, and nitrogen. Air is preferred because of its availability, low cost and because of the excellent results obtained.
  • FIGURE 1 is a side elevationof a preferred embodiment of the assembled apparatus showing the yfeed injector and reactor section, additional -reactor sections and also lshowing the separator section for separating the sulfated or sulfonated organic compound from spent gas.
  • FIGURE 2 is a view in sectionV of the feed injector section and part of the top reactor section with apparatus broken away from a better understanding.
  • FIGURE 3 is a view similar to FIGURE 2 showing the separator ⁇ section.
  • FIGURE 4 is a section taken along line 4--4 of FIG- URE 2.
  • FIGURE 5 is a front elevation of another embodiment of the. invention.
  • FIGURE 6 is a view in section taken along line 66 of FIGURE 5.
  • FIGURE 7 is a broken away view of the separator section of the4 apparatus generally taken along the line 7;7 of FIGURE 5.
  • FIGURE 8 is a side view in section of the ⁇ apparatus shown in FIGURE 7.
  • FIGURE 9 is a view taken alongy line l9-9 of FIG- URE 5.
  • the reactor designated generally by reference numeral 1 comprises three main sections, a feed injector section 2, a plurality of reactor sections 3, and a separator section 4.
  • the reactor section 3 comprises a vertically disposed, vertically elongated casing 5, including an inner reaction wall 6 and an outer reaction wall 7 concentrically disposed within the casing 5 and adapted to form an annular reaction chamber 8 in the space provided between the inner and outer reaction walls.
  • the reaction between the sulfonatable organic liquid and the sulfur trioxide takes place on the surfaces of the inner and outer reaction walls in the reaction chamber and it is highly important that adequate Cooling of these walls and the reaction chamber take place during the reaction.
  • cooling jackets 9 and 11 respectively vwhich extend around the inner and outer walls of the reaction chamber.
  • cooling jackets are provided with inlet and outlet ports, not shown, which admit and discharge a cooling medium such as water, the cooling medium being circulated through the cooling jackets at a temperatureand rate such that the temperature inside thel reaction Zone is maintained within the range of about 0 to 150 C. during the reaction.
  • a cooling medium such as water
  • a flange assembly 12 having an inner component 13and an outer component 14, the outer component extending outwardly away from the casing as shown in FIGURE 2. Both the inner and outer components ofthe flange assembly 12 are arranged and adapted so as to form the upper part of the reaction chamber 8 between the outer end of the inner component 13 and the adjacent inner end of the outer component 14.
  • the feed injection section 15 includes inner and outer vertically disposed organic liquid feed chambers 16 and 17 concentrically arranged so as to provide a gas inlet passage 18 between the adjacent vertical walls 19 and 21 of the organic feed.
  • feed injector section 15 The upper half of feed injector section 15, the organic liquid'feed chambers 16'and 17, and the reactor section 10, are all secured together by means of threaded bolt 34 and bolts 35, which pass through openings in flanges 12, 24, ⁇ and 25 and through extension 36 disposed at the lower end of gas inlet conduit 31'.
  • the mixture of inert gas and S03 is introduced intov the apparatus through opening 37 of gas inlet conduit 31, which is associated in gas tight relationship withy the upperk end of gas inletpassage 18.
  • the sulfonatable organic liquid entering the organic chambers 16 and 17 through oil inlet pipes 22 and 23 is discharged from the chambers. 16 and 17 through orifices 38 which are spaced along the inner and outer ends of fiange 24 and enter channels 6i) peripherally disposed around slots 39 which are located at the inner and outer peripheries of flange components 13 and 14 respectively terminating at their outer ends at the top of reaction chamber 8.
  • the vertical height of each slot can be adjusted by means of shims 41 in recesses 42 which are disposed in concentric relation circumferentially around components 13 and 14 of fiange 24.
  • These shims also serve as a seal in that they contain the organic liquid in channels 60x It is understood that the peripheral channels 60 Ibehind the slot may be of the same or different height as slots 39. It is convenient for the fabrication and designthat such channels be of the same height as slots 39 as is indicated in the drawings.
  • the organic liquid, entering the reaction chamber 8 through slots 39, is immediately contacted with the inert gas-S03 gas mixture which enters the reaction zone from gas passage 18 and the sulfonation of the organic liquid takes place immediately at the point of contact and as it continues its path along the reactor walls 6 and 7.
  • separator 43 Situated at the bottom of the reactor section 3 and attached thereto as shown in FIGURE 1 is separator 43 which separates the spent gas from the sulfated or sulfonated compound.
  • the separator prevents the spent gas from entraining droplets of the liquid product.
  • the design of the separator enables the gas to separate from the organic liquid without breaking through it. This is accomplished by enlarging the cross-sectional area in such a way that the moving organic liquid film is gradually moved out of the path of the spent gas stream producing an increase in the liquid product yield, a cleaner gas stream ready for recycle, and a lighter product.
  • the separator 43 comprises a cylindrical housing 44 enclosing a pair of inner and outer walls 45 and 46 respectively providing a gas escape conduit 47. Extending perpendicularly from the housing 44 it gas outlet conduit 43 which communicates with gas escape conduit 47.
  • discharge port Si Situated near the lower end of the housing 44 on the side opposite gas outlet conduit 48 is discharge port Si) which discharges the sulfonated organic compound from the separator.
  • discharge port Si Situated near the lower end of the housing 44 on the side opposite gas outlet conduit 48 is discharge port Si) which discharges the sulfonated organic compound from the separator.
  • the flow of the sulfonated organic compound is directed along the wall of the housing 43 and the inner wall S1 and follows a path to the discharge port 50.
  • withdrawal conduit 52 At the bottom of the housing is withdrawal conduit 52 which is adapted to remove any entrapped organic compound.
  • the sulfonatable organic charge which is preferably dodecyl benzene is fed under pressure into organic liquid supply chambers 16 and 17 through oil inlet pipes 22 and 23 respectively.
  • the pressure and rate of feed of the organic liquid should be such that the liquid present in the chamber is sufficient to maintain channels 60 in liquid ooded condition throughout the operation and to cause the organic liquid to dischargev out of the slots onto the reactor walls 6 and 7 at a velocity not in excess of 30 inches per second preferably about 4 to 2O inches per second and differential pressure of about to lbs., preferably substantially zero, i.e., the difference between the pressure at which the organic liquid enters the reaction chamber 8 and the pressure in the reaction chamber is about 0 to 5 lbs. preferably substantially Zero.
  • the liquid dodecyl benzene passes from organic liquid chambers 16 and 17 into channels 60 through orifices 38.
  • Slots 39 may conveniently have a thickness or height of about .002 to .030 inch preferably .005 to .015 inch. This can be regulated by tightening or loosening the bolts 34 and 35.
  • T'he inert gas which is preferably air and the gaseous sulfur trioxide which may vary from about 2 to preferably about 5 to 10% sulfur trioxide by volume is introduced into gas inlet conduit 31 through opening 37 to give a gas velocity in the reaction chamber 8 of from about 40 to 300 feet per second, preferably 75 to 150 feet per second.
  • the air-sulfur trioxide mixture passes through gas inlet conduit 31 and into gas passage 18 in a contacting relation with the organic liquid film leaving slots 39. Because of the organic liquid Velocity and the pressure difference at which the organic liquid leaves the slots 39 and the pressure in the reaction chamber 8 being substantially zero, the organic liquid discharges out of the slots 39 and immediately turns downward on the reactor walls 6 and 7 without breaking contact or interfering "with satisfactory sulfonation. Uneven contact of the organic film with the sulfur trioxide gas mixture tends to promote localized overheating and color bodies form by reason of contact with the stream of sulfur trioxide inert gas. That contact is absolutely uniform throughout the length of the reaction chamber.
  • the cooling of the organic liquid takes place immediately after contacting the air-sulfur trioxide gas mixture and the cooling is continued while a substantial portion of the reaction is taking place.
  • the organic liquid is also cooled prior to discharge into the reaction chamber by the action of the circulating cooling medium in contact with the lower portions'of ange 12.
  • the cooling medium is preferably water which enters cooling jackets 9 and 11 through inlet and outlet ports, not shown. The temperature of the water which circulates through the cooling jackets 9 and 11 maintains the temperature of the reaction which under most conditions is at room temperature. If desired, and depending upon the organic liquid to be sulfonated, additional reactor sections may be added.
  • These additional reactor sections 3 increase the reaction time by increasing the path of the organic liquid. This is particularly advantageous in those reactions where longer contact with air-sulfur trioxide is necessary to produce sufficient sulfonation.
  • Each reactor section is provided with its own cooling means similar to the cooling means of the lirst reactor section. Thus, the temperature in each reaction zone may be controlled independently, and if desired, the temperature in subsequent stages may be increased for greater activity resulting in substantially complete sulfonation of the organic compound.
  • the additional reactor sections are not provided with the particular flange assembly of the top reactor section which includes provision for the particular type of feed injection necessary for the present invention.
  • the sulfonated liquid together with the spent gas then passes into separator 43 where the path of the organic compound is defined by the shape of the walls 48a and 49.
  • the sulfonated organic compound continues to fiow along the upper walls 48a and 49 of the separator away from the path of the spent gas, discharging from the separator 43 through discharge port 50.
  • the spent gas containing trace amounts of the organic compound enters the separator 43 through opening 53 and is caused to follow the path of gas escape conduit 47, where it is discharged through gas voutlet conduit 48 and, if desired, recycled for pickup of additional sulfur trioxide.
  • the apparatus features the new horizontal flange injection design as employed with a slot-type reactor.
  • the reactor designated generally by numeral 54 comprises three main sections, a feed and reactor section 55, a plurality of reactor sections 56 and a separator section 57. These sections are suitably detachably secured together as by bolted flanges 58a.
  • the apparatus is provided with a vertically disposed, vertically elongated casing 56a including vertically spaced apart planar side walls 57 of substantial Width.
  • the width of the parallel side Walls 57 may vary over a wide range depending on the desired ycommercial output.v
  • the width is normally from about two inches to l as much as 100 inches.
  • These walls are associated at their adjacent vertical edges 58 so as to form vertically elongated reaction chamber 59 as shown in FIGURES 6 and 9 of substantial rectangular slot-like cross section.
  • the distance between the Walls ⁇ of reaction chamber is such that the inert gas-sulfur trioxide mixture is emitted in the form of a sheet-like stream.
  • Communicating with the reaction chamber 59 is gas inlet passage 61 through which the inert ⁇ gas-sulfur trioxide gas mixture passes after it leaves gas inlet nozzle 61a.
  • liquid organic chamber 62 Surrounding the gas inlet passage 61- is liquid organic chamber 62 in which the organic liquid iscontained after entering through oil inlet pipe 63.
  • a flange 64 Disposed at the bottom of the organic liquid chamber 62 is a flange 64.
  • This ange is rigidly associated with the bottom of the organic liquid chambers and has spaced holes 65 in the ange for discharging the organic liquid into channel 66a thence into slot 66 situated lat the top of reaction chamber 59.
  • the slot is formed by the space provided between flanges ⁇ 64 and 67, the latter being rigidly secured to the upper part of the cooling jacket 68 and being attached to flange 64 by means of bolts 60a.
  • the space between the flanges is provided by means of shims 70 disposed in recesses 80 which surround the gas inlet passage I61.
  • cooling jacket 68 which surrounds casing 56 and is of similar coniigurati-on therewith.
  • Jacket 68 is provided with inlet port 69 as seen in FIGURE 9, which receives a cooling medium for circulation through the jacket 68 and the Icooling medium is discharged through outlet port 71.
  • gas injection nozzle 61a which receives the inert gas-sulfur trioxide mixture from an outside source.
  • the gas injection nozzle has an upper portion of larger cross-sectional area than the lower portion.
  • a flange 30 which is adapted to engageflange 40 disposed at the upper end of the organic chambenThese flanges secure the gas injection nozzle t the top of the organic liquid chambers by means of bolts or other securing members.
  • the separator is designed to prevent spent gas from entrainin-g droplets of the liquid product and the design of the separator enables the gas to separate from the organic liquid without breaking through it.
  • theV separator comprises a vertically disposed gas escape tube 73 Which has an upper portion 74 of larger cross-sectional area than the base of the escape tube.
  • a housing 75 has an upper portion of outwardly flaring walls 76 which extend into cylindrical base 78 the outer walls surrounding at their lower porti-on, the upper portion of escape tube 73.
  • outlet conduit 79 Situated at the bottom of the cylindrical base 78, extending from the lower portion of tube 73 is outlet conduit 79 which dischargesthe spent gas mixture.
  • withdrawal conduit 81 At the bottom of cylindrical base is withdrawal conduit 81 which is adapted to removeorganic compound.
  • the organic liquid may be continuously removed as desired through withdrawal conduit 81.
  • the operation of this embodiment of the invention is similar to the operation of the preferred embodiment.
  • the sulfatable organic Icharge is fed under pressure into liquid supply chamber 62 through oil inlet nozzle 63.
  • the pressure and rate of feed of the organic liquid in the liquid supply chamber 62 should be such as to maintain channel 66a in liquid flooded condition throughout the operation.
  • Slot 66 may have the same height as in the first embodiment that is, about .002 to .030 inch preferably .005 to .015 inch.
  • the organic liquid lm thickness, the inert gas-sulfur vtrioxide, and organic velocities are substantially the same as in the first embodiment of this invention.
  • the procedure for cooling of the organic liquid and the temperatures employed are substan tially the same as in the first embodiment and, if desired, additional reactor sections may be added to the apparatus.
  • the sulfonated liquid and spent gas leaving the last reactor section enters the separator 72 where the path of the organic liquid is dened by the shape of the walls 76. Referring Ito FIGURES 7 and 8, the sulfonated organic compound continues to ow along the upper walls 76 away form the path yof the spent gas discharging-from the separator through discharge port 81.
  • the spent gas, containing trace amounts ofthe organic compound enters the separator 72 through opening 82 and is caused to follow the path of escape tube 73 where it is discharged through gas outlet conduit 79 and, if desired, recycled for pickup of additional sulfur trioxide.
  • Example 1 The preferred apparatus of the present invention was employed and measured approximately 20 feet in length.
  • the apparatus consisted of a feed andV reactor section of 6 vfeet in length and 2 additional reactor sections eachv second and at a differential pressure of about 1 lb. Cool-v ing water was circulated through the water jackets, at about 57 F. and the temperature of the S03 mixture was about F. The operating air pressure was 18.5 p.s.i.g.
  • the product was obtained from the separator. at 87 lbs. per hour for about 99% conversion based on the dodecyl benzene.
  • An analysis of the neutralized product showed a color of 30 based on a 10% solution of the neutralized acid and contained one percent unreacted ma-v terial based on active.
  • Example Z Utilizing the apparatus of Example l, the procedure was repeated except that the sulfur trioxide vaporized at the rate of 35.9 pounds per hour was mixed with 3840' cubic feet per hour of recycled rair and reacted with pounds per hour of dodecyl benzene.
  • the velocity of the dodecyl benzene entering the reaction chamber through the slots was 13 inches per second and entered at a differential pressure of about 1 lb.
  • the operating air pressure was 18.2 p.s.i.g. Cooling water was circulated through the water jackets at about 56 F. and the temperature of the air-S03 mixture was about 85"v F.
  • a ten percent solution of the neutralized acid containing 0.6% unreacted material based on 100% active gave a Klett reading of 50.
  • Example 3 Utilizing the apparatus of Example 1, the procedure was repeated except that the sulfur trioxide vaporized at the rate of 22.3 pounds per hour was mixed with 2406 cubic feet per hour of recycled air and reactedwith 65 pounds per hour of dodecyl benzene.
  • the velocity-of the dodecyl benzene entering the reaction chamber through the slots was 8 inches per second and entered at a differential pressure of about 1 lb.
  • the operating air pressure was 18.5 p.s.i.g. Cooling water was circulated through the water jackets at about 57 F. and the temperature of the air-S03 mixture was about 85 F.
  • a ten percent solution of the neutralized acid containing 0.7% unreacted material based on 100% active gave a Klett reading of 50.
  • Example 4 the reaction chamber was in the form of a round tube and the reactor measured approximately 19 feet inA length.
  • the apparatus consisted of a feed and reactor section of 5 feet in length and 2 additional reactor sections each measuring 6 feet in length.
  • the separator which was attached to the reactor section was 2 feet in length.
  • Into the feed and reactor section was introduced a mixture of 11.8 pounds per hour of sulfur trioxide diluted with 1200 c.f.h. of recycled air.
  • the air sulfur trioxide was then contacted with dodecyl benzene fed to the reactor at a rate of about 33.3 pounds per hour.
  • the dodecyl benzene entered the reaction chamber at a velocity of about 6 inches per second and at a differential pressure of about l lb.
  • Cooling Water was circulated through the water jackets at about 44 F. and the temperature of the air-S03 mixture was about 82 F.
  • the operating air pressure was 9.6 p.s.i.g. 'I'he product was obtained from the separator at 45 lbs. per hour for about 99.1% conversion based on the dodecyl benzene.
  • An analysis of the neutralized product showed a color of 30 based on a 10% solution of the neutralized acid and contained 0.9% unreacted material based on 100% active.
  • Example 5 A reactor having a slot-like reaction chamber was employed for this example.
  • the lwidth of the casing was six inches, the thickness of the casing was 1%; inch and the total length, excluding the separator, was 22 feet.
  • the reactor consisted of a feed and reactor section of 2 feet in length, and three additional reactor sections 4, 8 and 8 feet in length.
  • the separator which was attached to the reactor section was 3 feet in length.
  • Into the feed and reactor section Was introduced a mixture of 120 pounds per hour of sulfur trioxide diluted with 12,900 c.f.h. air. The air-sulfur trioxide was then contacted with dodecyl benzene fed to the reactor at a rate of about 360 pounds per hour.
  • the dodecyl benzene entered the reaction chamber at a velocity ⁇ of about inches per second and at a dilerential pressure of about 3 lbs. Cooling water Iwas circulated through the water jacket at about 52 F. and the temperature of the S03 mixture was about 90 F. The product was obtained from separator at 479 lbs. per hour for about 99.4% conversion based on the dodecyl benzene. An analysis of the neutralized product showed a color of 48 based on a 10% solution of the neutralized acid and contained 0.6% unreacted material based on 100% active.
  • Example 6 Utilizing the apparatus of Example 5, the procedure was repeated except that the sulfur trioxide vaporized at the rate of 91 pounds per hour was mixed with 10,200 c.f.h. of recycled air and reacted with 272 pounds per hour of dodecyl benzene.
  • the velocity of the dodecyl benzene entering the reaction chamber through the slots was 11 inches per second and entered at a dilerential pressure of about 1 lb.
  • Cooling water was circulated through the water jacket at about 90 F. and the ternperature of the air-S03 gas mixture was 110 F.
  • a ten percent solution of the neutralized acid containing 1.0% nnreacted material based on 100% active gave a Klett reading of 48.
  • the process and apparatus of the present invention now makes it economically feasible to' produce detergent products on a commercial production basis.
  • the concentric tube-type reactor described herein is intended to be used in those cases where huge quantities of sulfonated products are desired: -for example, six million pounds or over where as the slot-type reactor may be employed for quan. tities up to about three million pounds per year capacity.
  • the color of the iinished product is substantially White which is particularly significant in those cases where only a light color detergent product is thought to be desirable because of the association of whiteness with cleanliness.
  • the apparatus of the present invention is particularly economically attractive because of the elimination of moving parts which reduce the chance of breakdown to the very minimum.
  • a process for sulfonating a sulfonatable organic liquid selected from the group consisting of saturated alcohols, phenols, oleiinic compounds, and monocyclic and polycyclic aromatic hydrocarbons by reacting the same in a stationary reaction zone with the sulfur trioxide constituent of a gas mixture of inert gas and gaseous sulfur trioxide which comprises forming a 0.005 to 0.015 inch deep layer of said organic liquid surrounding the entire periphery of the reaction zone, flowing the layer laterally into the reaction zone around its entire periphery at velocity of about 4 to 20 inches per second, -as admitted into the reaction zone, to form a smooth lm of the liquid extending entirely around the periphery of the zone and descending in quiescent flow along the Walls thereof, continuously flowing a gaseous stream of sulfur trioxide and inert gas diluent downwardly through the zone in contact with the ilm, maintaining the contact until reaction between the sulfur trioxide and organic liquid is substantially complete, cooling the said film through
  • a process for sulfonating a sulfonata'ble organic compound selected from the group consisting of saturated alcohols, phenols, olenic compounds and monocyclic and polycyclic aromatic hydrocarbons by reactingy the same in a stationary reaction zone with the sulfurtrioxideV constituent of a gas mixture of inert gasy and gaseoussulfur trioxide which comprises forming a 0.005 to 0.015 inch deep layer of said organic liquid surrounding the entire periphery of the: reaction zone, flowing the layer laterally into the reaction zone around its entire peripheryy at velocity of about 4 to 20 inches per second, as admitted into the reactionI zone, to form a smooth lm of the liquid extending entirely around the periphery of the zone and descending in quiescent flow along the walls thereof, continuously owing a gaseous stream'of sulfurv trioxide and inert gas diluent downwardly through the zone in contact with the film, .maintaining the contact 15 until yreaction between the sulfur

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
US342485A 1964-02-04 1964-02-04 Process for sulfonation of organic compounds Expired - Lifetime US3328460A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US342485A US3328460A (en) 1964-02-04 1964-02-04 Process for sulfonation of organic compounds
IL22916A IL22916A (en) 1964-02-04 1965-02-04 Sulphonation of organic compounds
DE1518465A DE1518465C3 (de) 1964-02-04 1965-02-04 Verfahren und Vorrichtung zum Sulfomeren oder Sulfatleren organi scher Verbindungen
ES308998D ES308998A1 (es) 1964-02-04 1965-02-04 Procedimiento y aparato de sulfonacion de compuestos organicos.
BE659278A BE659278A (US20110009641A1-20110113-C00116.png) 1964-02-04 1965-02-04
ES0308998A ES308998A3 (es) 1964-02-04 1965-02-04 Un dispositivo refrigerador de evaporaciën
GB4919/65A GB1029029A (en) 1964-02-04 1965-02-04 Process and apparatus for sulphonation of organic compounds
DK58465AA DK129280B (da) 1964-02-04 1965-02-04 Fremgangsmåde til sulfonering eller sulfatering af en organisk forbindelse samt apparat til anvendelse ved fremgangsmåden.
FR4439A FR1439060A (fr) 1964-02-04 1965-02-04 Procédé et appareil pour la sulfonation de composés organiques au moyen du trioxyde de soufre
NL656501442A NL146135B (nl) 1964-02-04 1965-02-04 Werkwijze voor het sulfoneren van een organische verbinding en inrichting voor het uitvoeren daarvan.
US656609A US3501276A (en) 1964-02-04 1967-04-12 Apparatus for sulfonation of organic compounds

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US342485A US3328460A (en) 1964-02-04 1964-02-04 Process for sulfonation of organic compounds

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BE (1) BE659278A (US20110009641A1-20110113-C00116.png)
DE (1) DE1518465C3 (US20110009641A1-20110113-C00116.png)
DK (1) DK129280B (US20110009641A1-20110113-C00116.png)
ES (2) ES308998A1 (US20110009641A1-20110113-C00116.png)
FR (1) FR1439060A (US20110009641A1-20110113-C00116.png)
GB (1) GB1029029A (US20110009641A1-20110113-C00116.png)
IL (1) IL22916A (US20110009641A1-20110113-C00116.png)
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3482947A (en) * 1966-07-14 1969-12-09 Procter & Gamble Feed device for a film reactor
US3492343A (en) * 1966-04-26 1970-01-27 Lever Brothers Ltd Sulphonates
US3531518A (en) * 1966-07-14 1970-09-29 Procter & Gamble Process for the reaction of alpha-olefins and gaseous sulfur trioxide
US3538684A (en) * 1966-05-06 1970-11-10 Allied Chem Liquid/gas separation process and apparatus
DE2107968A1 (de) * 1970-02-23 1971-10-28 Costruzioni Meccaniche G. Mazzoni S.P.A., Busto Arsizio, Varese (Italien) Verfahren zum Sulfurieren und Sulfatieren organischer Verbindungen mit Schwefeltrioxyd und Vorrichtung zur Durchführung dieses Verfahrens
US3758608A (en) * 1971-08-26 1973-09-11 Texaco Inc Process for acid treating of olefins
DE2423959A1 (de) * 1973-05-17 1974-12-05 Jefferson Chem Co Inc Verfahren zur herstellung von olefinsulfonaten
US3969375A (en) * 1973-11-29 1976-07-13 Lion Fat & Oil Co., Ltd. Method of manufacturing salt of α-sulfofatty acid ester
US4036596A (en) * 1975-06-30 1977-07-19 Lion Fat & Oil Co., Ltd. Apparatus for continuous sulfonation
US4390475A (en) * 1979-07-06 1983-06-28 Lion Corporation Thin film type sulfonation process of alkylbenzene
US5196574A (en) * 1991-12-23 1993-03-23 Uop Detergent alkylation process using a fluorided silica-alumina
US5587500A (en) * 1993-09-17 1996-12-24 The Chemithon Corporation Sulfonation of fatty acid esters
US5922903A (en) * 1997-11-10 1999-07-13 Uop Llc Falling film reactor with corrugated plates
US20080139840A1 (en) * 2006-11-03 2008-06-12 Matthew Thomas Anderson Process for preparing alkyl aryl sulphonic acids and alkyl aryl sulphonates

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5218682B2 (US20110009641A1-20110113-C00116.png) * 1972-04-15 1977-05-24
US4072470A (en) * 1976-03-31 1978-02-07 Kao Soap Co., Ltd. Gas feeder for sulfonation apparatus

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2088027A (en) * 1934-05-09 1937-07-27 Union Carbide & Carbon Corp Alcohol sulphation process
US2923728A (en) * 1957-11-19 1960-02-02 Du Pont Process of reacting organic compounds with sulfur trioxide

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US2747794A (en) * 1956-05-29 Zero printing control mechanism
US3169142A (en) * 1960-05-25 1965-02-09 Stepan Chemical Co Method for sulfonation and sulfation of organic compounds
AT243951B (de) * 1963-09-19 1965-12-10 Goldschmidt Ag Th Lösungsmittelhaltige Aluminiumfarbe auf Emulsionsbasis sowie Verfahren zu deren Herstellung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2088027A (en) * 1934-05-09 1937-07-27 Union Carbide & Carbon Corp Alcohol sulphation process
US2923728A (en) * 1957-11-19 1960-02-02 Du Pont Process of reacting organic compounds with sulfur trioxide

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3492343A (en) * 1966-04-26 1970-01-27 Lever Brothers Ltd Sulphonates
US3538684A (en) * 1966-05-06 1970-11-10 Allied Chem Liquid/gas separation process and apparatus
US3482947A (en) * 1966-07-14 1969-12-09 Procter & Gamble Feed device for a film reactor
US3531518A (en) * 1966-07-14 1970-09-29 Procter & Gamble Process for the reaction of alpha-olefins and gaseous sulfur trioxide
DE2107968A1 (de) * 1970-02-23 1971-10-28 Costruzioni Meccaniche G. Mazzoni S.P.A., Busto Arsizio, Varese (Italien) Verfahren zum Sulfurieren und Sulfatieren organischer Verbindungen mit Schwefeltrioxyd und Vorrichtung zur Durchführung dieses Verfahrens
US3758608A (en) * 1971-08-26 1973-09-11 Texaco Inc Process for acid treating of olefins
DE2423959A1 (de) * 1973-05-17 1974-12-05 Jefferson Chem Co Inc Verfahren zur herstellung von olefinsulfonaten
US4059620A (en) * 1973-05-17 1977-11-22 Texaco Development Corporation Process for preparing olefin sulfonates
US3969375A (en) * 1973-11-29 1976-07-13 Lion Fat & Oil Co., Ltd. Method of manufacturing salt of α-sulfofatty acid ester
US4036596A (en) * 1975-06-30 1977-07-19 Lion Fat & Oil Co., Ltd. Apparatus for continuous sulfonation
US4390475A (en) * 1979-07-06 1983-06-28 Lion Corporation Thin film type sulfonation process of alkylbenzene
US5196574A (en) * 1991-12-23 1993-03-23 Uop Detergent alkylation process using a fluorided silica-alumina
US5587500A (en) * 1993-09-17 1996-12-24 The Chemithon Corporation Sulfonation of fatty acid esters
US5922903A (en) * 1997-11-10 1999-07-13 Uop Llc Falling film reactor with corrugated plates
US6596244B1 (en) 1997-11-10 2003-07-22 Uop Llc Falling film reactor with corrugated plates
US20080139840A1 (en) * 2006-11-03 2008-06-12 Matthew Thomas Anderson Process for preparing alkyl aryl sulphonic acids and alkyl aryl sulphonates
WO2008053037A3 (en) * 2006-11-03 2008-06-26 Shell Int Research Process for preparing alkyl aryl sulphonic acids and alkyl aryl sulphonates
JP2010508329A (ja) * 2006-11-03 2010-03-18 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー アルキルアリールスルホン酸およびアルキルアリールスルホネートを調製するための方法
AU2007316075B2 (en) * 2006-11-03 2011-07-14 Shell Internationale Research Maatschappij B.V. Process for preparing alkyl aryl sulphonic acids and alkyl aryl sulphonates
RU2462453C2 (ru) * 2006-11-03 2012-09-27 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ получения алкиларилсульфоновых кислот и алкиларилсульфонатов

Also Published As

Publication number Publication date
BE659278A (US20110009641A1-20110113-C00116.png) 1965-08-04
IL22916A (en) 1968-04-25
DE1518465C3 (de) 1973-11-22
DE1518465A1 (de) 1972-05-04
DK129280C (US20110009641A1-20110113-C00116.png) 1975-02-10
DK129280B (da) 1974-09-23
US3501276A (en) 1970-03-17
DE1518465B2 (de) 1973-04-26
GB1029029A (en) 1966-05-11
FR1439060A (fr) 1966-05-20
NL6501442A (US20110009641A1-20110113-C00116.png) 1965-08-05
ES308998A3 (es) 1965-05-16
ES308998A1 (es) 1965-07-01
NL146135B (nl) 1975-06-16

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