Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/02—Monocyclic hydrocarbons
  • C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
• • 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
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
  • C07C2/68—Catalytic processes with halides
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S585/00—Chemistry of hydrocarbon compounds
  • Y10S585/8995—Catalyst and recycle considerations
  • Y10S585/901—Catalyst and recycle considerations with recycle, rehabilitation, or preservation of solvent, diluent, or mass action agent

Definitions

• An n-alkyl benzene detergent alkylate composition having a desirably high content of internally substituted phenyl alkanes is produced by alkylating benzene with a partially chlorinated detergent-range n-paraffin or mixture thereof in the presence of a recycle stream recovered as a fraction from a previous alkylation run, said fraction being rich in the external phenyl alkane isomers of the highest molecular weight alkyl benzenes present in the run from whence obtained.
• This invention relates to a process for the preparation of detergent alkylate and more particularly concerns the production of an isomeric mixture of detergent grade monophenyl-n-alkane wherein the presence of internal isomers predominates.
• a method is provided for alkylating benzene with an n-alkyl halide or straight-chain olefin in the presence of a recycle product stream having a rich content of the external isomers of a detergent grade monophenyl n-alkane whereby said isomer content equilibrates to an isomeric distribution corresponding to that obtained in the underlying alkylation reaction.
• the present invention is directed to the process for preparing alkyl benzenes wherein the alkyl substituents are derived from a detergent grade linear paraffin or mixture thereof. Such paraffins vary in carbon atom length from about -15.
• Two related ways are currently favored by the industry for producing n-alkyl benzenes. Each of these process schemes initially contemplates partially chlorinating a detergent grade parafiin or mixture thereof to yield a chlorinated product having a high selectivity to monochlorides.
• the partially chlorinated product itself can be used to alkylate benzene in accordance with the Friedel- Crafts reaction or alternately, the product can be dehydrochlorinated to yield an olefinic alkylating agent.
• the resulting alkylate is an isomeric alkyl benzene ice mixture having an equilibrium distribution of all possible secondary isomers.
• the various isomers of a given species of alkyl benzene provide surfactants having diiferent detergency properties.
• detergency properties not only refers to the actual detersive ability of the surfactant but also contemplates other related properties of importance such as foam stability, wetting power and the like.
• the detergency properties of any given species of alkyl benzene improves as the phenyl attachment moves toward the center of the alkane chain.
• the differences noted are of such magnitude that the sulfonate salts of the external secondary isomers of a detergent grade n-alkyl benzene are regarded to be comparatively inferior detergents.
• isomerization catalyst poisoners are generated in the type of alkylation reaction environment with which this invention is concerned and moreover, that these poisoners are prone to become entrained in the fraction recovered for purpose of recycle. While we have been unable to characterize completely these impurities, it appears that they are some type of condensed or fused ring aromatic compounds. It further was noted that these compounds are such potent inhibitors that amounts thereof even in the order of 1% or even lower will effectively inhibit the isomerization of the external isomers present in the recycle fraction under the conditions normally experienced in the alkylation operation.
• the alkylating agent contemplated is either a partially chlorinated paraffin or mixture thereof or an olefinic material derived therefrom.
• the amount of dichlorides formed will vary proportionally to the level of chlorination observed. For example, at a 10% mole level of chlorination about 95% of the total chlorides produced will be monochlorides and at a 40% mole level the monochloride content decreases to about 80% of the amount of chlorides formed.
• benzene When benzene is alkylated with these partially chlorinated products, part of the dichlorides react with benzene to form alicyclic compounds.
• the alicyclic compounds produced are believed to be composed predominately of alkyl substituted 1,2,3,4-tetrahydronaphthalanes although there is some evidence that a very minor amount of indanes and other related compounds are produced.
• the alicyclic type alkylate boils very close to the alkyl benzenes having a corresponding carbon atom content. Consequently, in order to recover a satisfactory amount of the external isomers in a fraction designed to be employed as a recycle stream, it is necessary to include a substantial amount of the corresponding alicyclic alkylate present in the alkylation reaction mixture.
• This isomerization test is desirably conducted in a medium of benzene in order to obviate any disproportionation of the alkyl benzenes.
• Suitable amounts of benzene range from about 1 to parts per part of the overhead.
• the testing procedure described indicates that the accumulated fraction rich in external isomers will effectively isomerize when recycled to a conventional alkylation operation.
• many modifications of this test will sufiice and possibly other procedures such as, for example, UV analysis, can be devised to provide the same information.
• the proper cut point will be maintained at a given predetermined distillation temperature.
• Suitable fractions rich in external isomers obtained as described above can be recycled to a reaction mixture undergoing alkylation in whole or in part.
• same can be isomerized by treatment with AlCl and thereupon the internal isomers resulting from a direct isomerization procedure of this type can be recovered by distillation.
• a suitable amount of AlCl for effecting direct isomerization is from about 2 to 10% based on the weight of the total fraction subjected to treatment. Satisfactory isomerization temperatures range from about 40 to C. As indicated above, it is preferred to carry out the isomerization reaction in the presence of from about 1 to 25 parts benzene.
• Partially chlorinated products suitable for use in the alkylation process to which this invention is directed can be obtained by reacting between about 0.1 and 0.4 mole of chlorine per mole of paraffin. Within this range satisfactory selectivities to monochloride formation can be .realized. Conventional methods for effecting the chlorination reaction can be observed, i.e., either liquid or vapor phase chlorination is applicable. The reaction can be either catalytically or thermally induced. The whole of the partially chlorinated product or dehydrohalogenated derivative thereof is customarily charged to the alkylation reaction sphere as it is too difiicult to separate the converted parafiins from the unreacted parafiins.
• a catalyst is required to effect the reaction between alkyl chlorides or olefins and an alkylatable compound, here specifically benzene.
• alkyl chlorides or olefins and an alkylatable compound, here specifically benzene.
• a variety of Friedel-Crafts catalysts are applicable. An enumeration of such catalysts include aluminum chloride, iron chloride, zinc chloride, titanium chloride, hydrofluoric acid, boron trifiuoride, and the like.
• the preferred catalyst is aluminum chloride.
• AlCl As the alkylation catalyst. Amounts of the aluminum chloride that can be used range from between about 1 and 10% based upon the amount of alkyl chlorides present in the reaction mixture.
• An especially preferred catalyst system consists of aluminum chloride in admixture with catalyst sludge obtained from a previous alkylation run employing said aluminum salt as the catalyst. This affords use of substantially less aluminum chloride than is ordinarily needed to effect a given rate for th alkylation reaction.
• the alkylating agent is an alkyl chloride
• another advantage of using sludge is that aluminum powder can be incorporated in the sludge and such a mixture under the conditions of reaction encountered will provide for the in situ formation of aluminum chloride enriched sludge.
• the alkylation temperature can be varied over wide limits ranging from about room temperature to 80 C. A preferred range is in the order from about 40-80 C.
• the ratio of benzene to alkyl chlorides or olefins present in the reaction mixture can also be varied over wide limits. Applicable ratios are from about 1 to 20 moles benzene to 1 mole of alkyl chloride or olefin. On the aftersaid basis, a preferred range of benzene to alkyl chloride or olefin is from about 5:1 to 10:1, respectively.
• the alkylation reaction can be carried out in a continuous or batch manner. In either type of operation, an effective reaction time is from about 15 to minutes. The precise time needed for effecting substantially complete alkylation is dependent upon a number of factors, including the amount of catalyst used, ratio of benzene to alkylating agent, temperature, etc. The course of the reaction can be readily followed by analyzing for organic chloride.
• alkylation runs No. 1 and No. 2 were conducted using as the alkylating agent a partially chlorinated n-dodecane and a partially chlorinated mixture of C -C linear paraffins, respectively.
• Each partially chlorinated product contained about 4% combined chlorine representing about a 20% level (mole) of chlorination.
• the alkylation reaction was carried out at 65 C.
• the reaction mixtures were stripped of unreacted benzene and parafiins. Thereupon, the alkylate product of each run was fractionated to yield various cuts or fractions selected to show approximately where the isomerization inhibitors occur in the product in terms of its boiling point characteristics. A portion of each cut collected was combined with an equal part of pure 2-phenyl isomer and the mixtures were then isomerized; whereupon, the extent of isomerization of the added Z-phenyl isomer was noted. In order to simplify analysis, a pure Z-phenyl tetradecane sample was employed in testing the various fractions comprising run No. 1 whereas pure 2-phenyl dodecane was used in testing the selected fractions of run No. 2.
• the Z-phenyl isomer content of the total alkylate (fractions 3 and 4 combined) was 30.6% when normalized on a monoalkylbenzene basis.
• a second alkylation run was conducted in which the 2- phenyl isomer rich fraction 4 was employed as a recycle stream.
• an alkylation reaction vessel such as described above were charged 5352 parts of chlorinated tetradecane (4.95% chlorine), 5800 parts benzene, 86 parts aluminum chloride, and 396 parts of fraction 4.
• the alkylation conditions employed here corresponded essentially to those described above in connection with the previous run.
• EXAMPLE III This example serves to illustrate the improved detersive properties exhibited by detergent compositions derived from monophenyl alkane mixtures which can be economically obtained in the practice of this invention.
• a process for the preparation of detergent alkylate which comprises alkylating an excess of benzene with a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a hydrocarbon selected from the group consisting of C -C linear paraffins and mixtures thereof at a temperature from about C. to 80 C.
• a process for the preparation of detergent alkylate which comprises reacting an excess of benzene at a temperature from about 20 to 80 C. with an alkylating agent obtained by dehydrohalogenating a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a hydrocarbon selected from the group consisting of C C linear paraffins and mixtures thereof in the presence of from about 110% AlCl based on the olefin content of the dehydrohalogenated derivative and in the presence of the hercin below-defined recycle stream, distilling the alkylation reaction mixture to recover successively a detergent alkylate fraction consisting of a mixture of secondary monophenyl alkane isomers containing a substantially reduced amount of the external secondary isomers of the highest molecular weight phenyl alkane present in the alkylation reaction mixture and a higher boiling second fraction constituting said recycle stream consisting of a mixture of said external isomers and corresponding alicyclic alkylate but containing not in excess of that amount of
• a process for the preparation of detergent alkylate which comprises alkylating an excess of benzene with a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a linear parafi'in having a carbon atom length of from 1015 at a temperature from about 40 to 80 C.
• a process for the preparation of detergent alkylate which comprises reacting an excess of benzene at a temperature of from about 40 to C. with an alkylating agent obtained by dehydrohalogenating a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a linear parafiin having a carbon atom length of from 10-15 in the presence of from about 1-10% AlCl based on the olefin content of the dehydrohalogenated derivative and in the presence of the hereinbelowdefined recycle stream, distilling the alkylation reaction mixture to recover successively a detergent alkylate fraction consisting of a mixture of the secondary isomers of the monophenyl alkane and containing a substantially reduced amount of the external isomers thereof present in the alkylation reaction mixture and a higher boiling second fraction constituting said recycle stream consisting of a mixture of said external isomers and not in excess of about 70% of the alicyclic alkylate present in the alkylation reaction mixture.
• a process for the preparation of internal secondary isomers of a monophenyl alkane which comprises alkylating an excess of benzene with a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a linear paraffin having a carbon atom length of from 10-15 at a temperature from about 40 to 80 C.
• a process for the preparation of detergent alkylate which comprises alkylating an excess of benzene with a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a C -C linear paraflin at a temperature from about 40 to 80 C.
• a process for the preparation of detergent alkylate which comprises alkylating an excess of benzene with a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a C -C linear paraffin at a temperature from about 40 to 80 C.
• a process for the preparation of internal secondary isomers of a monophenyl alkane which comprises alkylating an excess of benzene with a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a C -C linear paraffin at a temperature from about 40 to 80 C.
• a process for the preparation of detergent alkylate which comprises alkyl'ating an excess of benzene With a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a C C linear parafiin at a temperature from about 40 to 80 C.
• a process for the preparation of detergent alkylate which comprises alkylating an excess of benzene with a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a C C linear parafiin at a temperature from about 40 to 80 C.
• a process for the preparation of internal secondary isomers of a monophenyl alkane which comprises alkylating an excess of benzene with a chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a C -C linear paraffin at a temperature from about 40 to C.
• a process for the preparation of detergent alkylate which comprises alkylating an excess of benzene with the chlorination product of from about 0.1 to 0.4 mole of chlorine and a mole of a mixture of at least two but not in excess of four adjacent members of homologous series of C -C linear paratfins at a temperature of from about 40 to 80 C.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Detergent Compositions (AREA)

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Cited By (3)

Citations (2)

• 1965
  • 1965-02-17 US US433512A patent/US3391210A/en not_active Expired - Lifetime
• 1966
  • 1966-02-03 NL NL6601373A patent/NL6601373A/xx unknown
  • 1966-02-10 FR FR49137A patent/FR1467786A/fr not_active Expired
  • 1966-02-15 GB GB6652/66A patent/GB1142604A/en not_active Expired
  • 1966-02-16 DE DE19661568251 patent/DE1568251A1/de active Pending
• 1967
  • 1967-01-03 BE BE692152D patent/BE692152A/fr unknown

Patent Citations (2)

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