Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
• • 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
  • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
  • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
  • C07C2/08—Catalytic processes
  • C07C2/26—Catalytic processes with hydrides or organic compounds
  • C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
• • 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
  • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• this invention relates to an improved detergent prepared by dimerizing a C -C predominantly straight chain olefin in the presence of an aluminum alkyl or a dialkyl aluminum halide catalyst, alkylating benzene therewith and sulfonating the resultant alkyl benzene to obtain the final product detergent.
• This invention relates to utilizing a C -C predominantly straight chain alpha olefin stream from steam cracking as the feed to the process and to utilizing mild conditions in alkylation.
• biodegradable detergents having excellent washing properties may be obtained by the process of this invention.
• a C -C predominantly straight chain olefin is dimerized in the presence of an alkyl aluminum catalyst to obtain an olefin predominantly of the following structure.
• R is a predominantly straight chain alkyl group of from 3 to 6, e.g., 4 carbon atoms
• R is a predominantly straight chain alkyl group of from 5 to 8, e.g., 7 carbon atoms
• the extent of the branching of the alkyl groups is such that on the average less than 1.0, preferably less than 0.6 methyl group, in addition to the two terminal methyl groups, are contained in R and R.
• less than 10%, preferably less than 5%, of the branches R and R are higher alkyl groups, e.g., ethyl groups, rather than methyl groups.
• This olefin is then used to alkylate benzene to obtain an alkyl benzene having primarily (e.g., above 75%, preferably greater than 85) the following structure:
• R and R are as above described and wherein again the extent of the branching of the alkyl groups is such that on the average less than 1.0, preferably less than 0.6 methyl groups, in addition to the terminal methyl groups, are contained in R and R.
• the olefin adds very selectively to the benzene through the tertiary carbon atom of the olefin.
• the small amount of other material formed is due mainly to isomerization of the olefin double bond occurring during alkylation and dimerization.
• Suitable feed stocks for use in the present invention process are C -C predominantly straight chain monoolefin streams obtained from commercial processes such as both mild and severe stream cracking. Both the entire C -C stream and selected fractions from this stream, e.g., a C stream, are preferred feed stocks.
• the extent of branching of the olefins in these feed stocks (on other than the ethylenic carbon atoms, i.e., the carbon atoms attached to the double bond) must be on the average less than 0.5, preferably less than 0.3 methyl groups per molecule. By methyl groups per molecule it is intended to include both methyl groups as such and other alkyl group branches.
• those olefins present in the feed stock which contain branches on either of the ethylenic carbon atoms do not react in the dimerization reaction and hence, of course, may be present in the feed wiithout deleterious effect on the dimer product.
• Other olefin containing feed stocks may also be utilized so long as they meet the above described requirement as to the extent of branching permissible. Paraffins and aromatics may be present in these feed stocks since they do not react in the dimerization reaction.
• these feed stocks contain diolefins and acetylenes in a preferred embodiment these materials are removed by known methods such as extraction, hydrogenation, etc., to increase the purity of the dimer product obtained.
• preferred C -C feed stocks are obtained from the low severity steam cracking of wax, petrolatum or a paraffinic gas oil. Temperatures of 10004200 F. and conversions to C minus of 5 to 15 wt. percent are used to produce mainly C -C monoolefins. It should be noted that in a preferred embodiment these olefins are obtained from low conversion steam cracking processes conducted in the vapor phase. The amount of steam utilized is not critical, in general 50 95 mol percent steam based on total feed plus steam being used. The olefins boiling in the C -C range contain above wt. percent, preferably about wt. percent, straight chain olefins. Additionally these olefins are above 80 wt.
• alpha olefins percent alpha olefins. Although non-alpha olefins can be easily isomerized to alpha olefins during dimerization by having an additional catalyst present (as will be described) still some undesirable isomerization is obtained in such a modified dimerization process and therefore predominantly alpha olefin feed stocks are preferred.
• preferred C C feed stocks are obtained by liquid phase thermal cracking a paraffinic feed stock of the type above described at temperatures of 800 F. to 1000 F., and conversions of fresh feed to lighter boiling products of 20 to wt. percent.
• a paraffinic feed stock of the type above described at temperatures of 800 F. to 1000 F., and conversions of fresh feed to lighter boiling products of 20 to wt. percent.
• 40 to 60% of predominantly straight chain olefins are obtained, the remainder, being paraffins and small amounts of diolefins.
• the olefins may be dimerized directly from the parafiins.
• preferred C C feed stocks are obtained from the widely commercially used high conversion steam cracking of gas oils to produce commercially desirable C -C olefins and diolefins as Well as higher boiling materials. Temperatures of about 1250-1500 F., amounts of steam as above described and residence times to obtain conversion to C minus of 20 to 80 wt. percent are used in this process.
• the olefins boiling in the C C range from the high conversion steam cracking process may be treated by extraction to remove aromatics, if desired, or may be used without such a removal of aromatics.
• C -C cuts obtained from the high severity cracking of various gas oils or naphthas contain generally above 20 Wt.
• percent straight chain olefins and certain fractions obtained from paraflinic gas oils may contain as much as 60 Wt. percent straight chain olefins, or even 80 Wt. percent straight chain olefins.
• the amount of benzene present in a C -C cut is, e.g., to 30 wt. percent.
• the benzene present (which boils in the C olefin boiling range) in the feed stream is not remove-d by extraction prior to dimerization since it is advantageous in this reaction, and in the following alkylation it supplies part of the feed benzene required.
• C -C olefinic streams from seam cracking above described are byproducts in the production of other more valuable materials and that these streams are ordinarily used only for their fuel value in gasoline. It is of course also contemplated that particular olefinic streams as above described, after conventional removal of more valuable components, e.g., aromatics, diolefins, etc., may be utilized. These feed streams are extremely inexpensive feed stocks for the present process.
• preferred C -C feed stocks are obtained by an ethylene growth process in the presence of aluminum alkyls.
• ethylene is reacted with an aluminum alkyl, e.g., aluminum triethyl, at temperatures of 160 to 350 F. and pressures of 500 to 5000 p.s.i.a. to obtain C C aluminum trialkyls and these higher aluminum trialkyls are then reacted with an olefin to displace the higher alkyls and thus form C C olefins.
• an aluminum alkyl e.g., aluminum triethyl
• Dimerization is carried out utilizing an aluminum trialkyl or dialkyl aluminum chloride catalyst preferably an aluminum trialkyl catalyst.
• the alkyl groups in these catalysts are C -C alkyl groups.
• the catalyst is used in quantities of from 0.5 to 20 wt. percent, preferably 2 to 10 wt. percent, e.g., 10 Wt. percent, based on the olefin in the feed.
• Preferred catalysts are aluminum trialkyl catalysts prepared from the feed olefins to be dimerized. Such catalysts, of course, do not contaminate the desired dimer product with different dimer materials formed from the catalyst alkyl groups.
• Aluminum trialkyls branched at the beta carbon atoms of the alkyl groups e.g., aluminum triisobutyl. These aluminum trialkyls do not react in the dimerization process and hence also do not contaminate the product.
• An additional different catalyst may be employed if desired, particularly where the feed stock contains in addition to alpha olefins internally double bonded straight chain olefins.
• Suitable additional catalysts are nickel, cobalt, palladium, platinum and the like. Although these catalysts can be supported on inert supports such as alumina, it is preferred to utilize unsupported catalysts.
• the amount of this additional catalyst utilized should be in the range of 0.1 to 10, preferably 0.5 to 5, e.g., 1 wt. percent, based on the aluminum alkyl catalyst.
• an inert solvent such as a C -C acyclic or cyclic paraffin, e.g., normal pentane, hexane, heptane, etc. and isomers of these materials, and cyclopentane, cycloheptane, etc. Chlorobenzene, benzene and toluene may also be used.
• a solvent it is preferred to utilize a feed stock containing the diluent material.
• a preferred diluent is an aromatic hydrocarbon which is to be a coreactant in the next step.
• the dimerization reaction is carried out at temperatures in the range of 80 to 300 C., preferably 110 to 250 C., e.g. 190 C., pressures in the range of atmospheric pressure to 200 atmospheres, e.g., 170 atmospheres, utilizing reaction times in the range of 0.5 to 25 hours, preferably 1 to 20 hours, e.g., 4 hours.
• the reaction is carried out in a liquid phase.
• the dimer is separated, e.g., by distillation, from unreacted olefin and from aluminum alkyl material (and from diluent if a diluent is used).
• the entire mixture after separation of aluminum alkyl material may be supplied to the alkylation step.
• the separated aluminum alkyls are, of course, preferably recycled to the reaction zone for reuse in dimerization.
• Alkylation is carried out utilizing benzene or less preferably toluene, in the presence of a Friedel-Crafts type catalyst at temperatures in the range of 10 to C., e.g. 10 C.
• Preferred catalysts are, for example, AlCl HF, BF and AlBr polyphosphoric acid, H and aluminum chloride hydrocarbon complexes.
• weight ratios of olefin to catalyst are in the range of 30:1 to 10:1, e.g., 20:1.
• an activator such as HCl may be added in an amount of from 15 to 40 wt. percent, e.g., 20 Wt. percent, based on aluminum chloride.
• liquid hydrogen fluoride catalyst In utilizing the liquid hydrogen fluoride catalyst it is preferred to use an acid to hydrocarbon reactants volume ratio of 0.1:1 to 1.021, e.g. 0.3:1 and temperatures in the range of 0 to 15 C., e.g., 10 C.
• concentration of this catalyst may range from to HP by Weight, its water content being maintained very low, e.g., no higher than 1 or 2% by weight, the remainder being dissolved hydrocarbon material.
• the alkylated aromatic fraction is recovered from the alkylation reaction mass and is sulfonated in known manner, e.g., by contact With an excess of concentrated sulfuric acid, oleum, ClSO H, sulfur trioxide, etc.
• the sulfonation may be carried out at temperatures up to 60 C., preferably for oleum 15 C. to 60 C., e.g. 50 C.
• the acid concentration is preferably at least 97%.
• Acid up to 100% concentration and preferably oleum, containing up to, e.g., 20 wt. percent S0 or higher, may be employed.
• volume ratios of sulfuric acid to hydrocarbon may range from 0.8:1 to 1.25:1, a 1:1 ratio being suitable. The larger the ratio, the more inorganic sulfate Will be present in the product following neutralization. In many cases, the inorganic sulfate is a desirable constituent of the finished detergent composition.
• the sulfonation product mixture may be separated by layering to remove part of the excess spent acid before neutralizing or may be neutralized directly.
• the sulfonic acids are thus converted to sulfonic acid salts and the excess sulfuric acid into sulfate.
• the neutralization may be carried out with any base or basic- Example 1 Run 1.-A .3-liter bomb was charged with 500 g. of hexane-1 and :50 g. of Al(nahexyl) wt. percent on olefin) and the bomb was heated at 185190 C. for 17 hours and then cooled. The contents were emptied and distilled. The products consisted of 356 g.
• C olefin which was approximately 82% Type III olefin, 8% Type II (trans) olefin, less than 1% of Type I olefin according to infrared analysis, and the remainder being Type IV olefin.
• This infrared analysis was based on the spectra fractionation. The yield of alkylate was found to be 80 volume percent and was 99% pure C alkylate. It should be noted that tetrapropylene prepared by polymerizing propylene in the presence of phosphoric acid under similar conditions gives only a 72 volume percent yield.
• Run 3 The alkylate prepared as described in Run 2 was sulfonated with 20% oleum at 15 to 60 C. by adding the oleum to the alkylate. The weight ratio of oleum to hydrocarbon was 1.4:1 and the materials were reacted for 45 minutes. Following reaction, the sulfonation product mixture was neutralized to a pH of 7 with aqueous sodium hydroxide to obtain the sodium salts of the sulfonic acids admixed with sulfates produced from excess spent sulfuric acid. The neutralization was carried out at temperatures of about 45 C. utilizing a reaction time of about 15 minutes.
• Example 2 The detergent material prepared as above described was tested for washing properties in dishwashin-g and in cotton laundering tests along with a conventional detergent prepared from tetrapropylene.
• C olefins adjusted to C olefins.
• the non-type III C olefins arise from isomerization of the C Type III olefin, Z-nbutyl-octene-l. It should be noted that in general only Type I and II olefins will not produce the desired alkyl benzene structure on alkylation. Also 92 g. of hexene-l 'was recovered. The remaining product was 86 g. of alkyl aluminum compounds which had a composition corresponding to 90% Al(C and 10% Al(C The alkyl aluminum residue from the distillation can be reused in dimerization. The material balance was 97 Wt.
• Run 2 The C olefin was then used to alkylate benzene and AlCl in the conventional manner to form the dodecylbenzene, consisting essentially of 2-phenyl-2-nbutyl-octane.
• the C olefin as prepared above was used to alkylate benzene in a laboratory glass stirred reactor using a 5:1 volume ratio of benzene to olefin and using 5 wt. percent of aluminum chloride based on olefin as the catalyst.
• Benzene was run into the reaction flask at room temperature and HCl was then supplied to said flask. The glass reactor was then heated to 45-50 C. and /a of the total catalyst was added.
• Olefin addition was begun from a funnel, and when /3 was added in 15 minutes, olefin addition was temporarily discontinued and a further of the catalyst was added. A second /3 of the olefin was then added in another 15 minute period. A final of the catalyst was then added and complete addition of the final A of olefin was made over another 15 minute period.
• the reactor was stirred for an additional 15 minutes (total time 1 hour). The reactor was cooled to room temperature and the contents were transferred to a separatory funnel. The layers were allowed to separate while a hydrocarbon layer was recovered. This layer was then washed with water and dilute carbonate and then finally with water. The hydrocarbon product after excess benzene was stripped off was worked up by As can be seen the experimental detergent is much better in the runs marked with an asterisk, i.e. at low concentrations and in soft water.
• a process for preparing biodegradable alkylbenzene detergents which comprises selecting a C to C predominantly straight chain alpha olefin stream containing on the non-ethylenic carbon atoms, on the average less than 0.5 methyl groups in side chains, dimerizing the predominantly straight chain alpha C to C olefins in the presence of a catalyst consisting essentially of an alumina alkyl at temperatures in the range of to 300 C., pressures in the range of atmospheric pressure to 200 atmospheres and for reaction times in the range of 0.5 to 25 hours, separating olefin dimer from the reaction mixture, reacting benzene with the resultant olefin dimer under active alkylating conditions to produce alkylbenzene at least 75% of which having the structure wherein R is a predominantly straight chain alkyl group of from 3 to 6 carbon atoms, R is a predominantly straight chain alkyl group of from to 8 carbon atoms and the extent of branching of the alkyl groups R and R is such
• a process according to claim 1 wherein the C to C straight chain olefin stream is obtained by steam cracking of a paraffinic gas oil feedstock at temperatures in the range of 1000 to 1200 F. utilizing conversions to C in the range of 5 to 15 wt. percent.
• a process for preparing an al'kylbenzene sulfonate detergent material which comprises dimerizing a stream of C to C predominantly straight chain alpha monoolefins containing on the non-ethylenic carbon atoms, on the average less than 0.5 methyl group in side chains, at temperature in the range of 150 to 200 C., at pressures in the range of atmospheric to 200 atmospheres, utilizing reaction times of 1 to 20 hours, in the presence of 2.0 to 10.0 wt.
• a catalyst consisting essentially of Al(n -hexyl) separating olefin dimers from the reaction mixture, reacting benzene with said olefin dimers at temperatures of 20 to C., in the presence of an aluminum chloride catalyst using ratios of benzene to olefin dimers of about 3:1 to 20:1, sulfonating the resulting alkylated benzene with oleum at temperatures of about 15 to C. and neutralizing the resultant reaction product with a basic aqueous solution at temperatures of about 20 to C. to obtain an alkyl benzene sulfonate.

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• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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Cited By (22)

Citations (13)

• 0
  • BE BE616998D patent/BE616998A/xx unknown
  • BE BE616990D patent/BE616990A/xx unknown
• 1960
  • 1960-09-23 US US57885A patent/US3238249A/en not_active Expired - Lifetime
• 1961
  • 1961-07-27 GB GB27234/61A patent/GB936882A/en not_active Expired

Patent Citations (13)

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