US3326971A - Process of preparing alkyl aryl sulfonates having improved water solubility and foam properties - Google Patents

Process of preparing alkyl aryl sulfonates having improved water solubility and foam properties Download PDF

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US3326971A
US3326971A US394306A US39430664A US3326971A US 3326971 A US3326971 A US 3326971A US 394306 A US394306 A US 394306A US 39430664 A US39430664 A US 39430664A US 3326971 A US3326971 A US 3326971A
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monoalkylbenzene
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William K Griesinger
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Atlantic Richfield Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
    • C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
    • C07C309/31—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups by alkyl groups containing at least three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/125—Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium
    • C07C2527/126—Aluminium chloride

Definitions

  • This invention relates to a method for controlling the solubility properties and foaming properties of alkyl aryl sulfonate detergents and, more particularly, it relates .to a method for preparing liquid alkyl aryl sulfonates of high solids content and solid alkyl aryl sulfonates of improved foaming properties wherein the alkyl groups of such sulfonates are derived from straight chain parafiim'c hydrocarbons.
  • alkyl aryl sulfonate detergents have been faced with a problem of the Modegradability of such detergents.
  • the method most widely employed for manufactur ng alkyl aryl sulfonate detergents involves polymerizing propylene to the trimer, tetramer or pentamer, alkylating benzene with the resulting propylene polymer, sulfonating the alkylated benzene and neutralizing the alkylbenzene sulfonic acids to produce the finished detergent.
  • alkyl groups of such alkyl aryl sulfonates are highly branched and are highly resistant to biodegradation thus causing problems of contamination in streams and rivers, underground water supplies and in sewage disposal plants. It has been found, however, that if the alkyl group of the alkyl aryl sulfonate is straight chain, the biodegradability of the alkyl aryl sulfonate is greatly increased and the compound is termed bio-soft or biodegradable.
  • One method of preparing alkyl aryl sulfonates wherein the alkyl group is straight chain involves monochlorinating straight chain paraffinic hydrocarbons having the desired number of carbon atoms in the molecule, monoalkylating benzene with the resulting straight chain alkyl chlorides in the presence of .an aluminum chloride catalyst and sulfonating the monoalkylated benzenes. In carrying out this series of reactions all of the possible isomers of the monoalkylbenzenes are produced.
  • the alkylbenzene is designated as the 2-phenyl isomer
  • the compound when the alkyl group is attached through the third carbon atom, the compound is termed the B-phenyl isomer and so on.
  • the most common isomer is the 2-phenyl isomer.
  • the isomers after sulfona-tion and neutralization produce sulfonates having different water solubility and foaming properties. A method now has been found which permits the control of the solubility properties and of the foaming properties in the finished detergent product.
  • straight chain par- .afiin hydrocarbons having from 10 to 14 carbon atoms in the molecule are fractionated to produce a light fraction consisting essentially of the C and C straight chain paraflins, an intermediate fraction consisting essentially of the C straight chain paraffin and a heavy fraction consisting essentially of the C and C straight chain paraflins.
  • Each of these straight chain paraffin fractions are separately monochlorinated to produce respectively straight chain C and C alkyl chlorides, straight chain C alkyl chlorides and straight chain C and C alkyl chlorides.
  • Each of these alkyl chloride fractions thus produced are separately reacted with benzene in the presence of an aluminum chloride catalyst to produce the corresponding monoalkylated benzene fractions, i.e. those having alkyl groups containing, respectively, 10 to 11 carbon atoms, 12 carbon atoms, and 13 to 14 carbon atoms.
  • each alkylbenzene fraction consists of all the possible isomers, for example, a small portion of each alkylbenzene fraction consists of compounds wherein the alkyl group is attached to the benzene ring through a terminal carbon atom on the alkyl chain.
  • a much larger fraction of each alkylbenzene fraction is com-posed of compounds wherein the alkyl group is attached to the benzene ring through the second carbon atom on the alkyl chain.
  • the higher boiling bottoms fraction is high in the 2-phenyl isomer, i.e. it contains a larger proportion of the 2-phenyl isomer than is obtained by the normal distribution during alkylation.
  • the lower boiling overhead fraction contains a lower proportion of the 2-phenyl isomer than is obtained by the normal distribution of isomers during alkylation.
  • the products thus produced are monoalkylbenzene sulfonates containing from 10 to 12 carbon atoms in the alkyl group and characterized by having an improved solubility in water and a monoalkylbenzene 'sulfonate having from 12 to 14 carbon atoms in the alkyl group characterized by having improved foam properties.
  • the monochlorination step may be carried out in a continuous reactor at a temperature in the range from 250 F. to 350 F. at a chlorine pressure of from 5 to 30 p.s.i.g.
  • the mole ratio of paraffin to chlorine is in the range of from .7:1 to :1 in order to obtain the alkyl rnonochlorides with the substantial exclusion of the alkyl dichlorides and alkyl polychlorides.
  • the alkylation step is carried out utilizing a conven tional aluminum chloride catalyst.
  • the makeup aluminum chloride ranges from 0.05 to 5 parts by weight of aluminum chloride per part by weight of alkylbenzene produced.
  • the alkylation temperature may range between 100 F. and 250 F., preferably between 180 F. and 220 F., at a pressure of from 5 to 50 p.s.i.g A minimum ratio of 5 volumes of benzene to 1 volume of alkyl chloride is utilized.
  • the boiling range of the monoalkylbenzene where in the alkyl group contains from 10 to 11 carbon atoms is in the range of from 520 F. to 570 F. at 760 mm. Hg pressure.
  • the boiling range of the monoalkylbenzene fraction wherein the alkyl group contains 12 carbon atoms ranges from 570 F. to 600 F. at 760 mm. and the boiling range of the monoalkylated benzene fraction wherein the alkyl group contains from 13 to 14 carbon atoms ranges from about 590 F. to 650 F. at 760 mm.
  • the 2-phenyl isomer content of the alkylbenzene fraction wherein the alkyl group contains from 12 to 14 carbon atoms is further decreased by fractionating the alkylbenzene fraction having 13 to 14 carbon atoms in the alkyl group to obtain an overhead fraction and leaving the 2-phenyl C alkylbenzene isomer as a bottoms.
  • the above-mentioned C alkylbenzene fraction low in the 2- phenyl isomer is then added to the C C alkylbenzene overhead fraction to give a monoalkylbenzene fraction having 12 to 14 carbon atoms in the alkyl group and a markedly reduced 2-phenyl isomer content.
  • alkylbenzene fractions are sulfonated and neutralized by conventional means.
  • a preferred embodiment is described in the following example.
  • Example 1 A typical straight chain paraffin hydrocarbon fraction such as that obtained from a molecular sieve process containing 10 to 14 carbon atoms in the molecule is utilized as the charge stock. In 100 pounds of this feed the 10- carbon atom paraffin amounts to 17 pounds, the 11 carbon atom, 12-carbon atom and 13-carbon atom paraffins amount to 22 pounds each and the C atom paraffin amounts to 17 pounds. In fractionating 100 pounds of this charge there is produced 39 pounds of the C -C fraction which contains 17 pounds of the C paraffin, 21
  • the C fraction amounts to 22 pounds and is composed of approximately 1 pound of the C paraflin hydrocarbon, 20 pounds of the C paraffin hydrocarbon and 1 pound of the C paraffin hydrocarbon.
  • the (I -C straight chain paraffin hydrocarbon fraction amounts to 39 pounds and is composed of about 1 pound of the C paraffin hydrocarbon, 21 pounds of the C paraffin hydrocarbon and 17 pounds of the C paraifin hydrocarbon. Each of the three fractions is separately monochlorinated.
  • the 39 pounds of the C -C fraction are passed into a continuous chlorination reactor together with 270 pounds of recycle C C parafiins.
  • the parafiin hydrocarbons are contacted with 25 pounds of chlorine at a temperature from 250 F. to 300 F. and the alkyl rnonochlorides together with unreacted paraffin, after separation of the HCl produced, are passed into the alkylation reactor.
  • the effluent from the chlorinator is contacted in the alkylation reactor with 260 pounds of benzene which is composed of 25.7 pounds of fresh benzene and 234.3 pounds of recycle benzene.
  • the alkylation is carried out at 210 F. in the presence of aluminum chloride catalyst.
  • the HCl is removed during the alkylation and following the alkylation step the aluminum chloride sludge is separated.
  • the reaction mixture is thereafter neutralized with sodium hydroxide and the benzene is fractionated from the alkylate and recycled to the alkylation step as has been described.
  • the unreacted paraffins thereafter are fractionated from the alkylated benzenes and recycled to the chlorinator.
  • the 22 pounds of the C straight chain paraffin hydrocarbon fraction are passed into the continuous chlorination reactor together with 153 pounds of recycle C paraffins.
  • the parafiin hydrocarbons are contacted with 12.3 pounds of chlorine at a temperature of 250 F. to 300 F. and the alkyl monochlorides together with unreacted paraffins, after separation of the HCl produced, are passed into the alkylation reactor.
  • the alkyl rnonochlorides and paraffins from the chlorinator are contacted in the alkylation reactor with 147 pounds of benzene which is composed of 12.6 pounds of fresh benzene and 134.4 pounds of recycle benzene.
  • the alkylation is carried out at 210 F. in the presence of aluminum chloride.
  • the HCl is removed during the alkylation and following the alkylation step the aluminum chloride sludge is separated.
  • the reaction mixture is thereafter neutralized with sodium hydroxide and the benzene is fractionated from the alkylate and recycled to the alkylation step as described.
  • the unreacted paraffins are thereafter fractionated from the alkylated benzenes and recycled to the chlorinator.
  • the combined fractions are fractionated to obtain an overhead fraction boiling above 600 F. amounting to 67.9 pounds of monoalkylated benzenes having from to 12 carbon atoms in the alkyl group and containing a total of 41 weight percent 2- phenyl isomer.
  • the normal 2-phenyl isomer content of such a fraction is of the order of 34 weight percent.
  • the bottoms fraction amounting to 11.3 pounds contains the undesired high boiling, heavy materials such as the dialkylbenzenes, diphenyl alkanes, indans and the like wherein the alkyl groups attached to the benzene ring have from 10 to 12 carbon atoms.
  • the 39 pounds of the Chg-C14 straight chain paraflin fraction are passed into the continuous chlorination reactor together with 270 pounds of recycle C C straight chain paraflins.
  • the paraflin hydrocarbons are contacted with 19.5 pounds of chlorine at a temperature of from 250 F. to 300 F. and the alkyl monochlorides together with unreacted parafiins, after separation of the HCl produced, are passed into the alkylation reactor.
  • the alkyl monochlorides and the unreacted straight chain parafiins from the chlorinator are contacted in the alkylation reactor with 245 pounds of benzene which is composed of 20 pounds of fresh benzene and 225 pounds of recycle benzene.
  • the alkylation is carried out at 210 F. in the presence of aluminum chloride.
  • the I-ICl is removed during the alkylation and following the alkylation step the aluminum chloride sludge is separated.
  • the reaction mixture is thereafter neutralized with sodium hydroxide and the benzene is fractionated from the alkylate and recycled to the alkylation step as has been described.
  • the unreacted parafl'ins are thereafter fractionated from the alkylated benzenes and are recycled to the chlorinator.
  • the 44.9 pounds of the monoalkylated benzenes having 13 to 14 carbon atoms in the alkyl group contains 21 percent of the 2-phenyl isomer and when this fraction is combined with the alkylated benzene fraction having 12 carbon atoms in the alkyl group, i.e. the fraction amounting to 17.5 pounds and having 8 percent 2-phenyl isomer which is prepared as described above, there is produced a combined fraction consisting of monoalkylated benzenes having from 12 to 14 carbon atoms in the alkyl group and containing a total of 17.5 weight percent of the 2-phenyl isomer.
  • the normal 2-phenyl isomer content of such a fraction is of the order of 30 weight percent.
  • the monoalkylated benzene fraction wherein the alkyl group has from 10 to 12 carbon atoms and the fraction contains 41 weight percent of the 2-phenyl isomer is separately sulfonated and neutralized as is the monoalkylated benzene fraction wherein the alkyl group has from 12 to 14 carbon atoms and the fraction contains 17.5 weight percent of the 2-phenyl isomer.
  • the sulfonation and neutralization steps they are described on the basis of a charge of 100 pounds of monoalkylated benzene. There is charged to the stirred sulfonation reactor 100 pounds of the monoalkylated benzene together with 105 pounds of 20 percent oleum.
  • the reaction is carried out for 1.5 hours at a temperature of 120 F.
  • the sulfonation mixture is then passed into a cooled vessel wherein 10.5 pounds of water are added and the temperature is maintained at about 135 F. Thereafter the mixture is passed into a centrifuge where spent acid is removed and the sulfonic acid layer is passed into a third vessel to which 552 pounds of water containing 16 pounds of sodium hydroxide are added.
  • the neutralized sulfonates are removed from this vessel and amount to 138 pounds of sodium sulfonate and 552 pounds of water, i.e. approximately a 20 percent solution of solids, This solution may be concentrated to produce either spray dried material or liquid concentrate. In producing either forms of the finished sulfonate it may be desirable to produce a more concentrated original solution and therefore less water may be employed in the neutralization step.
  • Example [I] In order to demonstrate the advantage of increasing the 2-phenyl isomer content, several solubility experiments were carried out on sodium alkylbenzene sulfonates wherein the alkyl group contained an average of 11.5 carbon atoms.
  • the 2-phenyl isomer content of the alkylated benzenes which were utilized to produce the sulfonates was estimated to range between 15 and 20 percent and the finished sodium alkylbenzene sulfonate had a solubility of 23 grams per m1. of water.
  • Example III In order to study the effect of the 2-phenyl isomer content on performance, a sodium alkylbenzene sulfonate having from 12 to 14 carbon atoms in the alkyl group and having about a 20 weight percent 2-phenyl isomer content was compared with a sodium alkylbenzene sulfonate having from 12 to 14 carbon atoms in the alkyl group and having a Z-phenyl isomer content of about 39 weight percent. These sulfonates were admixed in a standard heavy duty formulation, i.e. 20 percent sulfonate, 40* percent sodium tripolyphosphate, 3 percent sodium silicate and 33 percent sodium sulfate.
  • the sulfonate having the low 2-phenyl isomer content was found to give superior foam heights, both in the standard Launderometer tests and dishwashing tests, thus demonstrating that improved foam can be obtained by decreasing the 2-phenyl isomer content of the sulfonate.
  • the method of producing an alkylbenzene sulfonate of improved water solubility having from 10 to 12 carbon atoms in the alkyl group and an alkylbenzene sulfonate of improved foam properties having from 12 to 14 carbon atoms in the alkyl group which comprises (1) separately monochlorinating a straight chain C C paraffinic hydrocarbon fraction to produce the straight chain C -C alkyl monochlorides, a straight chain C parafiin to produce the straight chain C alkyl monochlorides. and a straight chain C C paraffinic hydrocarbon fraction to produce the straight chain C C alkyl monochlorides,
  • the method of producing an alkylbenzene sulfonate of improved Water solubility having from 10 to 12 carbon atoms in the alkyl group and an alkylbenzene sulfonate of improved foam properties having from 12 to 14 carbon atoms in the alkyl group which comprises 1) separately monochlorinating a straight chain C C paraffmic hydrocarbon fraction to produce the straight chain C C alkyl monochlorides, a straight chain C paraflin to produce the straight chain C alkyl monochlorides, and a straight chain C C parafiinic hydrocarbon fraction to produce the straight chain C 43 alkyl monochlorides,

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Description

United States Patent PROCESS OF PREPARING ALKYL ARYL SULFU- NATES HAVING IMPROVED WATER SOLUBEL- ITY AND FOAM PROPERTIES William K. Griesinger, Haverford, Pa, assignor to The Atlantic Refining Company, Philadelphia, Pa, 21 corporation of Pennsylvania No Drawing. Filed Sept. 3, 1964, Ser. No. 394,306
2 Claims. (Cl. 260505) This invention relates to a method for controlling the solubility properties and foaming properties of alkyl aryl sulfonate detergents and, more particularly, it relates .to a method for preparing liquid alkyl aryl sulfonates of high solids content and solid alkyl aryl sulfonates of improved foaming properties wherein the alkyl groups of such sulfonates are derived from straight chain parafiim'c hydrocarbons.
In recent years manufacturers of alkyl aryl sulfonate detergents have been faced with a problem of the Modegradability of such detergents. The method most widely employed for manufactur ng alkyl aryl sulfonate detergents involves polymerizing propylene to the trimer, tetramer or pentamer, alkylating benzene with the resulting propylene polymer, sulfonating the alkylated benzene and neutralizing the alkylbenzene sulfonic acids to produce the finished detergent. The alkyl groups of such alkyl aryl sulfonates are highly branched and are highly resistant to biodegradation thus causing problems of contamination in streams and rivers, underground water supplies and in sewage disposal plants. It has been found, however, that if the alkyl group of the alkyl aryl sulfonate is straight chain, the biodegradability of the alkyl aryl sulfonate is greatly increased and the compound is termed bio-soft or biodegradable.
One method of preparing alkyl aryl sulfonates wherein the alkyl group is straight chain involves monochlorinating straight chain paraffinic hydrocarbons having the desired number of carbon atoms in the molecule, monoalkylating benzene with the resulting straight chain alkyl chlorides in the presence of .an aluminum chloride catalyst and sulfonating the monoalkylated benzenes. In carrying out this series of reactions all of the possible isomers of the monoalkylbenzenes are produced. Thus there will be a very small percentage of the monoalkylbenzenes wherein the alkyl group is attached to the benzene ring through a terminal carbon of the alkyl chain, a much greater percentage of the monoalkylbenzenes will have the alkyl group attached to the benzene ring through the second carbon atom on the alkyl chain and lesser percentages of the monoalkylbenzenes will have the alkyl group attached to the benzene ring through the other carbon atoms along the chain. For convenience when the alkyl group is attached to the 'benzene ring through the second carbon atom on the alkyl chain, the alkylbenzene is designated as the 2-phenyl isomer, when the alkyl group is attached through the third carbon atom, the compound is termed the B-phenyl isomer and so on. Thus, the most common isomer is the 2-phenyl isomer. The isomers, however, after sulfona-tion and neutralization produce sulfonates having different water solubility and foaming properties. A method now has been found which permits the control of the solubility properties and of the foaming properties in the finished detergent product.
It is an object of this invention to provide a method for controlling the solubility pro erties and the foaming properties of biodegradable alkyl aryl sulfonate detergents.
It is another object of this invention to provide a method for preparing liquid biodegradable alkyl aryl sulfonated detergents having a high solids content.
It is another object of this invention to provide a 3,326,971 Patented June 20, 1967 method for preparing solid biodegradable alkyl aryl sulf-onated detergents having superior foaming properties.
Other objects of this invention will be apparent from the description and claims that follow.
In accordance with this invention straight chain par- .afiin hydrocarbons having from 10 to 14 carbon atoms in the molecule are fractionated to produce a light fraction consisting essentially of the C and C straight chain paraflins, an intermediate fraction consisting essentially of the C straight chain paraffin and a heavy fraction consisting essentially of the C and C straight chain paraflins. Each of these straight chain paraffin fractions are separately monochlorinated to produce respectively straight chain C and C alkyl chlorides, straight chain C alkyl chlorides and straight chain C and C alkyl chlorides. Each of these alkyl chloride fractions thus produced are separately reacted with benzene in the presence of an aluminum chloride catalyst to produce the corresponding monoalkylated benzene fractions, i.e. those having alkyl groups containing, respectively, 10 to 11 carbon atoms, 12 carbon atoms, and 13 to 14 carbon atoms.
The monoalkylated benzenes are produced from alkyl monochlorides which are both primary alkyl chlorides and secondary alkyl chlorides, i.e. wherein the chlorine atom is attached to the terminal carbon atom and the various carbon atoms along the chain. Thus, each alkylbenzene fraction consists of all the possible isomers, for example, a small portion of each alkylbenzene fraction consists of compounds wherein the alkyl group is attached to the benzene ring through a terminal carbon atom on the alkyl chain. A much larger fraction of each alkylbenzene fraction is com-posed of compounds wherein the alkyl group is attached to the benzene ring through the second carbon atom on the alkyl chain. For convenience these isomers are termed the Z-phenyl isomers. Smaller proportions of the alkylbenzene fraction are composed of compounds wherein the alkyl group is attached to the benzene ring through the third, the fourth, the fifth, etc. carbon atoms on the alkyl chain and these isomers are termed respectively the 3-pheny1, the 4-phenyl, the 5- phenyl etc. isomers.
The various individual isomers after sulfonation and neutralization produce compounds which have different solubilities in water and different foam properties, however, when in admixture with each other these isomeric compounds produce somewhat unexpected results. In has been found that a detergent containing a decreased proportion of the 2-phenyl isomer over that which is produced by the normal distribution during the alkylation reaction has improved foam properties. However, if an alkylbenzene fraction higher in the Z-phenyl isomer over that obtained in the normal distribution (after sulfonation and neutralization) is admixed with lower molecular the alkyl group into a low boiling overhead fraction and a higher boiling bottoms fraction. The higher boiling bottoms fraction is high in the 2-phenyl isomer, i.e. it contains a larger proportion of the 2-phenyl isomer than is obtained by the normal distribution during alkylation. The lower boiling overhead fraction contains a lower proportion of the 2-phenyl isomer than is obtained by the normal distribution of isomers during alkylation. The
high boiling bottoms fraction is added to the alkylbenzene fraction wherein the alkyl group contains from 10 to 11 carbon atoms and the low boiling overhead fraction is added to the alkylbenzene fraction wherein the alkyl group contains from 13 to 14 carbon atoms. The resulting monoalkylated benzene fractions, i.e. the lower molecular weight fraction wherein the alkyl group now has from 10 to 12 carbon atoms and is characterized by having a high 2-phenyl isomer concentration as compared with the normal 2-phenyl isomer concentration and the higher molecular weight alkylbenzene fraction wherein the alkyl group has from 12 to 14 carbon atoms and is characterized by having a Z-phenyl isomer concentration lower than that obtained in the normal distribution of isomers, are separately sulfonated by conventional means and the resulting sulfonic acids are neutralized, preferably to produce the sodium salts. The products thus produced are monoalkylbenzene sulfonates containing from 10 to 12 carbon atoms in the alkyl group and characterized by having an improved solubility in water and a monoalkylbenzene 'sulfonate having from 12 to 14 carbon atoms in the alkyl group characterized by having improved foam properties.
' The monochlorination step may be carried out in a continuous reactor at a temperature in the range from 250 F. to 350 F. at a chlorine pressure of from 5 to 30 p.s.i.g. The mole ratio of paraffin to chlorine is in the range of from .7:1 to :1 in order to obtain the alkyl rnonochlorides with the substantial exclusion of the alkyl dichlorides and alkyl polychlorides.
The alkylation step is carried out utilizing a conven tional aluminum chloride catalyst. The makeup aluminum chloride ranges from 0.05 to 5 parts by weight of aluminum chloride per part by weight of alkylbenzene produced. The alkylation temperature may range between 100 F. and 250 F., preferably between 180 F. and 220 F., at a pressure of from 5 to 50 p.s.i.g A minimum ratio of 5 volumes of benzene to 1 volume of alkyl chloride is utilized. The boiling range of the monoalkylbenzene where in the alkyl group contains from 10 to 11 carbon atoms is in the range of from 520 F. to 570 F. at 760 mm. Hg pressure. The boiling range of the monoalkylbenzene fraction wherein the alkyl group contains 12 carbon atoms ranges from 570 F. to 600 F. at 760 mm. and the boiling range of the monoalkylated benzene fraction wherein the alkyl group contains from 13 to 14 carbon atoms ranges from about 590 F. to 650 F. at 760 mm.
In a particularly preferred embodiment of the invention the 2-phenyl isomer content of the alkylbenzene fraction wherein the alkyl group contains from 12 to 14 carbon atoms is further decreased by fractionating the alkylbenzene fraction having 13 to 14 carbon atoms in the alkyl group to obtain an overhead fraction and leaving the 2-phenyl C alkylbenzene isomer as a bottoms. The above-mentioned C alkylbenzene fraction low in the 2- phenyl isomer is then added to the C C alkylbenzene overhead fraction to give a monoalkylbenzene fraction having 12 to 14 carbon atoms in the alkyl group and a markedly reduced 2-phenyl isomer content.
The alkylbenzene fractions are sulfonated and neutralized by conventional means. A preferred embodiment is described in the following example.
Example 1 A typical straight chain paraffin hydrocarbon fraction such as that obtained from a molecular sieve process containing 10 to 14 carbon atoms in the molecule is utilized as the charge stock. In 100 pounds of this feed the 10- carbon atom paraffin amounts to 17 pounds, the 11 carbon atom, 12-carbon atom and 13-carbon atom paraffins amount to 22 pounds each and the C atom paraffin amounts to 17 pounds. In fractionating 100 pounds of this charge there is produced 39 pounds of the C -C fraction which contains 17 pounds of the C paraffin, 21
pounds of the C paraffin and approximately 1 pound of the C paraffin because of the imperfect fractionation. The C fraction amounts to 22 pounds and is composed of approximately 1 pound of the C paraflin hydrocarbon, 20 pounds of the C paraffin hydrocarbon and 1 pound of the C paraffin hydrocarbon. The (I -C straight chain paraffin hydrocarbon fraction amounts to 39 pounds and is composed of about 1 pound of the C paraffin hydrocarbon, 21 pounds of the C paraffin hydrocarbon and 17 pounds of the C paraifin hydrocarbon. Each of the three fractions is separately monochlorinated.
The 39 pounds of the C -C fraction are passed into a continuous chlorination reactor together with 270 pounds of recycle C C parafiins. In the chlorination reactor the parafiin hydrocarbons are contacted with 25 pounds of chlorine at a temperature from 250 F. to 300 F. and the alkyl rnonochlorides together with unreacted paraffin, after separation of the HCl produced, are passed into the alkylation reactor.
The effluent from the chlorinator is contacted in the alkylation reactor with 260 pounds of benzene which is composed of 25.7 pounds of fresh benzene and 234.3 pounds of recycle benzene. The alkylation is carried out at 210 F. in the presence of aluminum chloride catalyst. The HCl is removed during the alkylation and following the alkylation step the aluminum chloride sludge is separated. The reaction mixture is thereafter neutralized with sodium hydroxide and the benzene is fractionated from the alkylate and recycled to the alkylation step as has been described. The unreacted paraffins thereafter are fractionated from the alkylated benzenes and recycled to the chlorinator. There is produced 63 pounds of crude alkylated benzenes based on the original paraffin charge which are further fractionated as will be described.
The 22 pounds of the C straight chain paraffin hydrocarbon fraction are passed into the continuous chlorination reactor together with 153 pounds of recycle C paraffins. In the chlorination reactor the parafiin hydrocarbons are contacted with 12.3 pounds of chlorine at a temperature of 250 F. to 300 F. and the alkyl monochlorides together with unreacted paraffins, after separation of the HCl produced, are passed into the alkylation reactor. The alkyl rnonochlorides and paraffins from the chlorinator are contacted in the alkylation reactor with 147 pounds of benzene which is composed of 12.6 pounds of fresh benzene and 134.4 pounds of recycle benzene. The alkylation is carried out at 210 F. in the presence of aluminum chloride. The HCl is removed during the alkylation and following the alkylation step the aluminum chloride sludge is separated. The reaction mixture is thereafter neutralized with sodium hydroxide and the benzene is fractionated from the alkylate and recycled to the alkylation step as described. The unreacted paraffins are thereafter fractionated from the alkylated benzenes and recycled to the chlorinator. These is produced 33.7 pounds of crude alkylated benzenes based on the original paraffin charge which is fractionated to produce an overhead cut boiling between about 570 F. and 590 F. amounting percent of the 2-phenyl isomer. The bottoms fraction boil- 1 ing above 590 F. is composed of 12.3 pounds of monoalkylated benzenes having 12 carbon atoms in the alkyl group boiling between 590 F. and 600 F. of which 64 weight percent is the Z-phenyl isomer, and 3.9 pounds of a fraction boiling above 600 R, which fraction is composed of dialkylbenzenes, diphenyl alkanes, indan's, and the like wherein the alkyl group attached to the benzene ring have 12 carbon atoms. This bottoms fraction, however, is not fractionated at this point, but is added to the 63 pounds of alkylated benzenes from the previous step wherein the alkyl group of the alkylated benzenes contain from 10 to 11 carbon atoms. The combined fractions are fractionated to obtain an overhead fraction boiling above 600 F. amounting to 67.9 pounds of monoalkylated benzenes having from to 12 carbon atoms in the alkyl group and containing a total of 41 weight percent 2- phenyl isomer. The normal 2-phenyl isomer content of such a fraction is of the order of 34 weight percent. The bottoms fraction amounting to 11.3 pounds contains the undesired high boiling, heavy materials such as the dialkylbenzenes, diphenyl alkanes, indans and the like wherein the alkyl groups attached to the benzene ring have from 10 to 12 carbon atoms.
The 39 pounds of the Chg-C14 straight chain paraflin fraction are passed into the continuous chlorination reactor together with 270 pounds of recycle C C straight chain paraflins. In the chlorination reactor the paraflin hydrocarbons are contacted with 19.5 pounds of chlorine at a temperature of from 250 F. to 300 F. and the alkyl monochlorides together with unreacted parafiins, after separation of the HCl produced, are passed into the alkylation reactor.
The alkyl monochlorides and the unreacted straight chain parafiins from the chlorinator are contacted in the alkylation reactor with 245 pounds of benzene which is composed of 20 pounds of fresh benzene and 225 pounds of recycle benzene. The alkylation is carried out at 210 F. in the presence of aluminum chloride. The I-ICl is removed during the alkylation and following the alkylation step the aluminum chloride sludge is separated. The reaction mixture is thereafter neutralized with sodium hydroxide and the benzene is fractionated from the alkylate and recycled to the alkylation step as has been described. The unreacted parafl'ins are thereafter fractionated from the alkylated benzenes and are recycled to the chlorinator. There is produced 57.5 pounds of crude alkylated benzenes based on the original parafiin charge which are further fractionated to produce 44.9 pounds of monoalkylated benzenes having from 13 to 14 carbon atoms in the alkyl group and 12.6 pounds of high boiling material consisting of dialkylbenzenes, diphenyl alkanes, indans wherein the alkyl groups attached to the benzene ring have from 13 to 14 carbon atoms and the 2-phenyl isomer of the alkylated benzene having 14 carbon atoms in the alkyl group. The 44.9 pounds of the monoalkylated benzenes having 13 to 14 carbon atoms in the alkyl group contains 21 percent of the 2-phenyl isomer and when this fraction is combined with the alkylated benzene fraction having 12 carbon atoms in the alkyl group, i.e. the fraction amounting to 17.5 pounds and having 8 percent 2-phenyl isomer which is prepared as described above, there is produced a combined fraction consisting of monoalkylated benzenes having from 12 to 14 carbon atoms in the alkyl group and containing a total of 17.5 weight percent of the 2-phenyl isomer. The normal 2-phenyl isomer content of such a fraction is of the order of 30 weight percent.
The monoalkylated benzene fraction wherein the alkyl group has from 10 to 12 carbon atoms and the fraction contains 41 weight percent of the 2-phenyl isomer is separately sulfonated and neutralized as is the monoalkylated benzene fraction wherein the alkyl group has from 12 to 14 carbon atoms and the fraction contains 17.5 weight percent of the 2-phenyl isomer. In order to simplify the description of the sulfonation and neutralization steps, they are described on the basis of a charge of 100 pounds of monoalkylated benzene. There is charged to the stirred sulfonation reactor 100 pounds of the monoalkylated benzene together with 105 pounds of 20 percent oleum. The reaction is carried out for 1.5 hours at a temperature of 120 F. The sulfonation mixture is then passed into a cooled vessel wherein 10.5 pounds of water are added and the temperature is maintained at about 135 F. Thereafter the mixture is passed into a centrifuge where spent acid is removed and the sulfonic acid layer is passed into a third vessel to which 552 pounds of water containing 16 pounds of sodium hydroxide are added. The neutralized sulfonates are removed from this vessel and amount to 138 pounds of sodium sulfonate and 552 pounds of water, i.e. approximately a 20 percent solution of solids, This solution may be concentrated to produce either spray dried material or liquid concentrate. In producing either forms of the finished sulfonate it may be desirable to produce a more concentrated original solution and therefore less water may be employed in the neutralization step.
It will be understood that other bases may be utilized for neutralization to produce other salts, for example, the potassium, ammonium, triethanolammonium and like salts.
Example [I In order to demonstrate the advantage of increasing the 2-phenyl isomer content, several solubility experiments were carried out on sodium alkylbenzene sulfonates wherein the alkyl group contained an average of 11.5 carbon atoms. In the first experiment the 2-phenyl isomer content of the alkylated benzenes which were utilized to produce the sulfonates was estimated to range between 15 and 20 percent and the finished sodium alkylbenzene sulfonate had a solubility of 23 grams per m1. of water.
In the second experiment the 2-phenyl isomer content was 34 percent and the solubility of the sodium alkylbenzene sulfonate produced therefrom was 34 grams per 100 ml. of water.
In the third experiment the Z-phenyl isomer content was approximately 40 percent and the solubility was about 38 grams per 100 ml. of water.
These experiments demonstrate the advantage of increasing the 2-phenyl isomer content of the alkylbenzene sulfonate above the normal isomer content which, for this molecular weight, is about 34 weight percent. This is particularly surprising since the 2-phenyl isomer alone gives sulfonates which are the least soluble of the various isomers.
Example III In order to study the effect of the 2-phenyl isomer content on performance, a sodium alkylbenzene sulfonate having from 12 to 14 carbon atoms in the alkyl group and having about a 20 weight percent 2-phenyl isomer content was compared with a sodium alkylbenzene sulfonate having from 12 to 14 carbon atoms in the alkyl group and having a Z-phenyl isomer content of about 39 weight percent. These sulfonates were admixed in a standard heavy duty formulation, i.e. 20 percent sulfonate, 40* percent sodium tripolyphosphate, 3 percent sodium silicate and 33 percent sodium sulfate. The sulfonate having the low 2-phenyl isomer content was found to give superior foam heights, both in the standard Launderometer tests and dishwashing tests, thus demonstrating that improved foam can be obtained by decreasing the 2-phenyl isomer content of the sulfonate.
I claim:
1. The method of producing an alkylbenzene sulfonate of improved water solubility having from 10 to 12 carbon atoms in the alkyl group and an alkylbenzene sulfonate of improved foam properties having from 12 to 14 carbon atoms in the alkyl group which comprises (1) separately monochlorinating a straight chain C C paraffinic hydrocarbon fraction to produce the straight chain C -C alkyl monochlorides, a straight chain C parafiin to produce the straight chain C alkyl monochlorides. and a straight chain C C paraffinic hydrocarbon fraction to produce the straight chain C C alkyl monochlorides,
(2) alkylating benzene employing an aluminum chloride catalyst with each of the separate alkyl monochloride fractions produced in (1) to produce, respectively, a monoalkylbenzene fraction having from 10' to 11 carbon atoms in the alkyl group, a monoalkylbenzene fraction having 12 carbon atoms in the alkyl group and a monoalkylbenzene fraction having from 13 to 14 carbon atoms in the alkyl group,
(3) fractionating the monoalkylbenzene fraction having 12 carbon atoms in the alkyl group produced in (2) to produce a lower boiling overhead fraction characterized by having a low 2-phenyl monoalkylbenzene isomer content and a higher boiling bottoms fraction characterized by having a high 2-phenyl monoalkylbenzene isomer content,
(4) adding said bottoms fraction from (3) to said monoalkylbenzene fraction having from 10 to 11 carbon atoms in the alkyl group from (2) to produce a monoalkylbenzene fraction having from 10 to 12 carbon atoms in the alkyl group and characterized by having an increased 2-pheny1 monoalkylbenzene isomer content,
(5) adding said overhead fraction from (3) to said monoalkylbenzene fraction having from 13 to 14 carbon atoms in the alkyl group from (2) to produce a monoalkylbenzene fraction having from 12 to 14 carbon atoms in the alkyl group and characterized by having a decreased 2-ph-enyl monoalkylbenzene isomer content,
(6) separately sulfonating the monoalkylbenzene fractions to produce the corresponding sulfonic acid fractions, and
(7) neutralizing the sulfonic acid fractions to produce a monoalkylbenzene sulfonate having from 10 to 12 carbon atoms in the alkyl group and characterized by having increased water solubility and a monoalkylbenzene sulfonate having from 12 to 14 carbon atoms in the alkyl group and characterized by having improved foam properties. a
2. The method of producing an alkylbenzene sulfonate of improved Water solubility having from 10 to 12 carbon atoms in the alkyl group and an alkylbenzene sulfonate of improved foam properties having from 12 to 14 carbon atoms in the alkyl group which comprises 1) separately monochlorinating a straight chain C C paraffmic hydrocarbon fraction to produce the straight chain C C alkyl monochlorides, a straight chain C paraflin to produce the straight chain C alkyl monochlorides, and a straight chain C C parafiinic hydrocarbon fraction to produce the straight chain C 43 alkyl monochlorides,
(2) alkylating benzene employing an aluminum chloride catalyst With each of the separate alkyl monochloride fractions produced in (1) to produce, respectively, a monoalkylbenzene fraction having from 10 to 11 carbon atoms in the alkyl group together with higher boiling compounds, a monoalkylbenzene fraction having 12 carbon atoms in the alkyl group together With higher boiling compounds and a monoalkylbenzene fraction having from 13 to 14 carbon atoms in the alkyl group together with higher boiling compounds,
(3) fractionating the alkylbenzene fraction having 12 carbon atoms in the alkyl group produced in (2) to produce a lower boiling overhead fraction character,- ized by having a low 2-phenyl monoalkylbenzene content and a higher boiling bottoms fraction characterized by having a high 2-phenyl rnonoalkylbenzene isomer content and containing said higher boiling compounds,
(4) addingv said bottoms fraction from (3) to said rnonoalkylbenzene fraction having from 10 to 11 carbon atoms in the alkyl group together with said higher boiling compounds from (2) and fractionating said mixture to produce a monoalkyl'benzene fraction having from 10 to 12 carbon atoms in the alkyl group and characterized by having an increased 2-pheny1 monoalkylbenzene content and a bottoms fraction consisting of said higher boiling compounds,
(5) fractionating said monoalkylbenzene fraction having from 13 to 14 carbon atoms in the alkyl group together With higher boiling compounds from (2) to produce an overhead fraction consisting of a monoalkylbenzene fraction having from 13 to 14 carbon atoms in the alkyl group and a bottoms fraction consisting of said higher boiling compounds together With the 2-phenyl isomer of the alkyl'oenzene having 14 carbon atoms in the alkyl group.
(6) adding said overhead fraction from (3) to said overhead fraction from (5) to produce a monoalkylbenzene fraction having from 12 to 14 carbon atoms in the alkyl group and characterized by having a decreased 2-phenyl monoalkylbenzene isomer content,
(7) separately sulfonating the monoalkylbenzene fractions to produce the corresponding sulfonic acid frac tions, and
(8) neutralizing the sulfonic acid fractions to produce a monoalkylbenzene sulfonate having from 10 to 12 carbon atoms in the alkyl group and characterized by having an increased Water solubility and a monoalkylbenzene sulfonate having from 12 to 14 carbon atoms in the alkyl group and characterized by having improved foam properties.
References Cited UNITED STATES PATENTS 2,220,099 11/ 194-0 Guenther et al 260505 3,248,413 4/1966 McEwan et al. 260671 LORRAINE A. WEINBERGER, Primary Examiner.
MARY B. WEBSTER, Assistant Examiner.

Claims (1)

1. THE METHOD OF PRODUCING AN ALKYLBENZENE SULFONATE OF IMPROVED WATER SOLUBILITY HAVING FROM 10 TO 12 CARBON ATOMS IN THE ALKYL GROUP AND AN ALKYLBENZENE SULFONATE OF IMPROVED FOAM PROPERTIES HAVING FROM 12 TO 14 CARBON ATOMS IN THE ALKYL GROUP WHICH COMPRISES (1) SEPARATELY MONOCHLORINATING A STRAIGHT CHAIN C10C11 PARAFFINIC HYDROCARBON FRACTION TO PRODUCE THE STRAIGHT CHAIN C10-C11 ALKYL MONOCHLORIDES, A STRAIGHT CHAIN C12 PARAFFIN TO PRODUCE THE STRAIGHT CHAIN C12 ALKYL MONOCHLORIDES, AND A STRAIGHT CHAIN C13-C14 PARAFFINIC HYDROCARBON FRACTION TO PRODUCE THE STRAIGHT CHAIN C13-C14 ALKYL MONOCHLORIDES, (2) ALKYLATING BENZENE EMPLOYING AN ALUMINUM CHLORIDE CATAYST WITH EACH OF THE SEPARATE ALKYL MONOCHLORIDE FRACTIONS PRODUCED IN (1) TO PRODUCE, RESPECTIVELY, A MONOALKYLBENZENE FRACTION HAVING FROM 10 TO 11 CARBON ATOMS IN THE ALKYL GROUP, A MONOALKYLBENZENE FRACTION HAVING 12 CARBON ATOMS IN THE ALKYL GROUP AND A MONOALKYLBENZENE FRACTION HAVING FROM 13 TO 14 CARBON ATOMS IN THE ALKYL GROUP, (3) FRACTIONATING THE MONOALKYLBENZENE FRACTION HAVING 12 CARBON ATOMS IN THE ALKYL GROUP PRODUCED IN (2) TO PRODUCE A LOWER BOILING OVERHEAD FRACTION CHARACTERIZED BY HAVING A LOW 2-PHENYL MONOALKYLBENZENE ISOMER CONTENT AND A HIGHER BOILING BOTTOMS FRACTION CHARACTERIZED BY HAVING A HIGH 2-PHENYL MONOALKYLBENZENE ISOMER CONTENT, (4) ADDING SAID BOTTOMS FRACTION FROM (3) TO SAID MONALKYLBENZENE FRACTION HAVING FROM 10 TO 11 CARBON ATOMS IN THE ALKYL GROUP FROM (2) TO PRODUCE A MONOALKYLBENZENE FRACTION HAVING FROM 10 TO 12 CARBON ATOMS IN THE ALKYL GROUP AND CHARACTERIZED BY HAVING AN INCREASED 2-PHENYL MONOALKYLBENZENE ISOMER CONTENT, (5) ADDING SAID OVERHEAD FRACTION FROM (3) TO SAID MONOALKYLBENZENE FRACTION HAVING FROM 13 TO 14 CARBON ATOMS IN THE ALKYL GROUP FROM (2) TO PRODUCE A MONOALKYLBENZENE FRACTION HAVING FROM 12 TO 14 CARBON ATOMS IN THE ALKYL GROUP AND CHARACTERIZED BY HAVING A DECREASED 2-PHENYL MONOALKYLBENZENE ISOMER CONTENT, (6) SEPARATELY SULFONATING THE MONOALKYLBENZENE FRACTIONS TO PRODUCE THE CORRESPONDING SULFONIC ACID FRACTIONS, AND (7) NEUTRALIZING THE SULFONIC ACID FRACTIONS TO PRODUCE A MONOALKYLBENZENE SULFONATE HAVING FROM 10 TO 12 CARBON ATOMS IN THE ALKYL GROUP AND CHARACTERIZED BY HAVING INCREASED WATER SOLUBILITY AND A MONOALKYLBENZENE SULFONATE HAVING FROM 12 TO 14 CARBON ATOMS IN THE ALKYL GROUP AND CHARACTERIZED BY HAVING IMPROVED FOAM PROPERTIES.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3478113A (en) * 1965-09-07 1969-11-11 Bray Oil Co Hydrocarbon hydraulic oil
WO2018083140A1 (en) * 2016-11-07 2018-05-11 Shell Internationale Research Maatschappij B.V. Normal paraffin composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) * 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US3248413A (en) * 1962-06-28 1966-04-26 Procter & Gamble Process of reacting organic compounds with sulfur trioxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2220099A (en) * 1934-01-10 1940-11-05 Gen Aniline & Flim Corp Sulphonic acids
US3248413A (en) * 1962-06-28 1966-04-26 Procter & Gamble Process of reacting organic compounds with sulfur trioxide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3478113A (en) * 1965-09-07 1969-11-11 Bray Oil Co Hydrocarbon hydraulic oil
WO2018083140A1 (en) * 2016-11-07 2018-05-11 Shell Internationale Research Maatschappij B.V. Normal paraffin composition

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