Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
  • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
  • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
  • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/37—Mixtures of compounds all of which are anionic
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the present invention is in the field of processes for making surfactants useful in cleaning products.
• Preferred processes comprise particular combinations of adsorptive separation steps to separate certain hydrocarbons using specific means.
• these means include combinations of two or more particular adsorbent beds and two or more of particular types of rotary valves, as well as specified types of porous adsorbents having pore sizes in excess of those used in conventional linear alkylbenzene manufacture.
• Preferred processes further employ particular alkylation steps having specified internal isomer selectivities, or particular OXO reaction steps.
• the invention is also in the field of products of such processes, including certain modified alkylbenzenes, of modified alkylbenzenesulfonate surfactants, of detergent alcohols and surfactants derivable therefrom, and of consumer cleaning products, especially laundry detergents, containing them.
• Preferred processes herein employ unconventional sequences of adsorptive separation steps to secure certain branched hydrocarbon fractions which are then used in additional process steps as alkylating agents for arenes or for other useful surfactant- making purposes, such as OXO reactions to form particular detergent alcohols, followed by alkoxylation, sulfation or the like.
• such fractions can even be derived from effluents from current linear alkylbenzene manufacture.
• the DETAL® process catalyst or catalysts are believed to lack the moderate acidity and intermediate pore size of alkylation catalysts used in the preferred processes of the present invention.
• Other recent literature describes the use of mordenite as an alkylation catalyst, but no such disclosure makes the combination of specific process steps required by the instant invention.
• they also generally include steps directed to the provision or making of a substantially linear hydrocarbon, not a delinearized one, prior to the alkylation. Possible exceptions are in US 5,026,933 and US 4,990,718.
• This process assertedly involves double urea adduction, for example treating a petroleum fraction once with urea to remove n-alkanes as complexes, and then a second time with excess urea to obtain adducts of mixed n-alkanes and long-chained monomethyl paraffins. While this process may have some limited usefulness and may be included in the overall processes of the invention as most broadly defined, its limitations are considerable. This process, despite dating from 1974, is not known to have been incorporated into any overall process for making surfactants such as the modified alkylbenzenesulfonates described herein.
• OXO alcohols As further described in the Background Art section hereinafter, it is also known how to make various OXO alcohols and to make surfactants therefrom.
• the currently available OXO alcohols have shortcomings, such as in producing surfactants which are less soluble at a given chainlength than might be desired for the increasingly popular low wash temperatures or in relying on relatively expensive processes such as olefin oligomerization, isomerization and disproportionation; or in still having a relatively high content of linear material.
• Cited documents EP 559,510 A and B in particular relate to making high-octane gasolines by recycling streams to an isomerization reactor. Grafted porous materials of EP 559,510 and grafting of zeolites, e.g., by tin alkyls, are useful in the present invention.
• US 5,107,052 likewise relates to improving octane ratings of gasoline and describes separating C4-C6 methyl paraffins using various molecular sieves such as A1PO4-5, SSZ-24, MgAPO-5 and/or MAPSO-5 containing less than 2% water. These sieves are assertedly capable of selectively adsorbing dimethyl paraffins and not adsorbing monomethyl and normal paraffins.
• alkylbenzenesulfonate surfactants has recently been reviewed. See Vol. 56 in “Surfactant Science” series, Marcel Dekker, New York, 1996, including in particular Chapter 2 entitled “Alkylarylsulfonates: History, Manufacture, Analysis and Environmental Properties", pages 39-108 which includes 297 literature references. This work provides access to a great deal of literature describing various processes and process steps such as dehydrogenation, alkylation, alkylbenzene distillation and the like. See also “Detergent Alkylate” in Encyclopedia of Chemical Processing and Design, Eds. Mc.Ketta and Cunningham, Marcel Dekker, N.Y., 1982., especially pages 266-284.
• Adsorption processes such as UOP's Sorbex process and other associated processes are also described in Kirk Othmer's Encyclopedia of Chemical Technology, 4 ⁇ Edition, Vol. 1, see “Adsorption and Liquid Separation", including pages 583-598 and references cited therein. See also publications by UOP Corp., including the “Processing Guide” available from UOP Corp., Des Plaines, Illinois.
• Commercial paraffin isolation and separation processes using molecular sieves include MOLEX® (UOP Inc.), a liquid-phase process, and ISOSIV® (Union Carbide Corp.) as well as ENSORB® (Exxon Corp.) and TSF® or Texaco Selective Finishing process, which are vapor-phase processes.
• FIGs. 1 - 18 are schematic drawings of some processes in accordance with the invention.
• Fig. 8 shows in more detail a configuration of two adsorptive separation units, each individually being of a type as found in the first two adsorptive separation steps of Fig. 1 and Fig. 2. Note that the Fig. 8 interconnections are as shown in Fig. 1., but differ from those shown in Fig. 2.
• Solid lines are used for essential process steps and process streams. Dashed lines identify steps and streams which may not be essential in the processes as most broadly defined but which are present in various preferred process embodiments. Rounded rectangles identify process steps, stages or units. Numbered lines identify feedstocks, intermediate process streams and products.
• SOR identifies an adsorptive separation step.
• 4/5" identifies that the adsorptive separation uses small-pore zeolite, especially Ca zeolite 5A, which is completely conventional in linear alkylbenzene manufacture.
• “5/7” identifies that the adsorptive separation uses a porous material such as SAPO-11 or any equivalent porous material having the ability to adsorb
• nongeminal dimethyl olefins while rejecting geminal dimethyl hydrocarbons, cyclic (five-, six- or higher membered ring) hydrocarbons or higher branched hydrocarbons, whether aromatic or aliphatic.
• the term "geminal dimethyl” as used herein means that there are two methyls attached to an internal carbon atom of a hydrocarbon, as in:
• sorptive stage SOR 4/5 and/or sorptive stage SOR 5/7 herein are of the type used in stage (a) of modified alkylbenzene manufacture or stage (A) of modified primary OXO alcohol manufacture as described hereinafter.
• the large-pore porous materials herein should not adsorb such hydrocarbons.
• the following hydrocarbons should be adsorbed. They are illustrative of what is meant by the term “nongeminal dimethyl" hydrocarbons:
• DEH identifies a step of at least partial dehydrogenation of a stream (partial dehydrogenation being typical in conventional linear alkylbenzene manufacture though complete dehydrogenation can also be used herein), and "ALK” identifies an alkylation step.
• Any step, stage or unit identified by a rounded rectangle can in practice comprise only the essential step or can, more typically, include within it an additional step or steps which may be optional in the invention as most broadly defined, or which may be essential only in a preferred embodiment. Such additional steps not shown include, for example, distillation steps of types commonly practiced in the art.
• Fig. 1 illustrates a process having, in sequence, two adsorptive separations, collectively in accordance with adsorptive separation stage (a) of the invention as defined hereinafter; followed by a dehydrogenation step (step (b) hereinafter); optionally followed by an alkylation step (step (c) hereinafter).
• step (c) is optional in the invention as most broadly defined, it is present in all preferred embodiments which relate to making modified alkylbenzenes in accordance with the invention and, when making modified alkylbenzenesulfonate surfactants, is typically followed by (d) sulfonation, (e) neutralization and (f) mixing to formulate into a consumer cleaning product. Steps (d) though (f) use conventional means and are not explicitly shown in Figs. 1-8.
• a hydrocarbon feed 1 passes to the first adsorptive separation step, for example a step in conformity with US 2,985,589, which uses a bed of 4-5 Angstrom zeolite.
• a linear hydrocarbon stream is discarded as a reject stream 6.
• stream 6 comprising a high proportion of linear hydrocarbons, would pass to DEH while step SOR 5/7 and associated streams would be absent.
• an intermediate branched-enriched hydrocarbon stream is retained 2 and passes to a second adsorptive separation.
• the second adsorptive separation uses a particular type of porous media and produces a branched-enriched stream 3 (product of stage (a) as defined hereinafter) which passes to the dehydrogenation reactor (DEH); as well as a reject stream 7.
• the particular type of porous media is preferably a "large-pore" zeolite, such zeolite herein being characterized by a pore size larger than that of the zeolites used in making linear alkylbenzenes, and very preferably, a pore size of from above about 5 Angstrom to about 7 Angstrom though larger pore materials can be used and their pore sizes can be "tuned down", for example by use of tin alkyls.
• Stream 4 represents dehydrogenated branched- enriched hydrocarbon; stream 8 represents recycled branched paraffins. Also shown is an alkylation step according to the invention which is included in a preferred embodiment of the invention. Output from the alkylation step is a modified alkylbenzene as defined elsewhere herein.
• Fig. 2 is a schematic drawing identifying steps in another embodiment of the present process. While generally similar to the process of Fig. 1, the Fig. 2 process has important differences, especially in that the adsorptive separation steps are reversed with respect to pore sizes in the adsorbent beds.
• Fig. 4 is a schematic drawing identifying an embodiment of the invention which starts with a hydrocarbon feedstock 23 such as branched effluent from a conventional linear alkylbenzene manufacturing process, or from a conventional linear detergent alcohol process. An adsorptive separation step using particular porous media is used to produce a reject stream 27 and a branched-enriched stream 24. The latter is dehydrogenated in the step marked DEH.
• a hydrocarbon feedstock 23 such as branched effluent from a conventional linear alkylbenzene manufacturing process, or from a conventional linear detergent alcohol process.
• An adsorptive separation step using particular porous media is used to produce a reject stream 27 and a branched-enriched stream 24. The latter
• the particular type of porous media is preferably a zeolite having pore size larger than that of the zeolites used in making linear alkylbenzenes, and very preferably has pore size of from above about 5 Angstrom to about 7 Angstrom.
• the dehydrogenated hydrocarbon stream 25 passes to an alkylation step ALK from which passes a modified alkylbenzene product 26.
• An optional recycle stream is identified as 28.
• Fig. 3 is a schematic drawing identifying an embodiment of the invention similar to that of Fig. 4 but using substantially different feedstock and intermediate process stream compositions. For example, Fig.
• C10-C14 paraffin fraction having the intrinsic linear/branched paraffin ratio as received, and from which cyclics, aromatics, gem-dimethyl, ethyl- or higher-than-ethyl branched hydrocarbons are removed as part of the present process.
• Fig. 4 uses as hydrocarbon feed 23 an effluent stream from a linear alkylbenzene manufacturing facility and produces a modified alkylbenzene 26 which is predominantly branched.
• the Fig. 4 process could be built as an "add-on" to a standard linear alkylbenzene manufacturing plant.
• Fig. 4 uses as hydrocarbon feed 23 an effluent stream from a linear alkylbenzene manufacturing facility and produces a modified alkylbenzene 26 which is predominantly branched.
• the Fig. 4 process could be built as an "add-on" to a standard linear alkylbenzene manufacturing plant.
• Fig. 4 uses as hydrocarbon feed 23 an effluent stream from a linear alkylbenzene manufacturing facility and produces a modified alkylbenzene 26 which is predominantly branched.
• the Fig. 4 process could be built as an "add-on" to a standard linear alkylbenzene manufacturing plant.
• Fig. 4 uses as hydrocarbon feed 23 an
• Fig. 3 uses as hydrocarbon feed a mixture of linear and branched paraffins of the kind intrinsically present in, say, a jet/diesel cut derived from kerosene which has not been processed in a linear alkylbenzene manufacturing facility.
• the Fig. 3 process produces a modified alkylbenzene which contains a mixture of methyl-branched (unconventional, in accordance with the invention) and linear (conventional) alkylbenzenes.
• the Fig. 3 process can be built as a "stand-alone" facility requiring no connection to a conventional linear alkylbenzene manufacturing facility.
• Fig. 8 shows in more detail the particular configuration of adsorptive separations which is found in other process illustrations, e.g., in Fig. 1 and Fig. 6.
• Each block represents an adsorptive separation unit.
• a vertical array of adsorptive separation beds AC in the left of each block
• the adsorptive separation is accompanied by distillations in columns RC and EC.
• the streams marked “Feed”, “Extract” and “Raffinate” of the leftmost adsorptive separation correspond with the streams marked "1", "6" and "2" in Fig. 1.
• the raffinate stream of the first adsorptive separation (and not the extract as would be the case in conventional linear alkylbenzene manufacture) becomes the feed for the second adsorptive separation.
• the raffinate of the second adsorptive separation in Fig. 8 corresponds with stream 7 in Fig. 1.
• the extract of the second adsorptive separation in Fig. 8 corresponds with stream 3 in Fig. 1 : this is the stream which in the present process is dehydrogenated and/or alkylated.
• Fig. 8, as noted, also serves to illustrate in more detail individual adsorptive separations herein. Thus, while the connections are not as shown in Figs. 2, 3, 4, 5 and 7, any single adsorptive separation of Figs.
• Fig. 9 illustrates a process for the production of modified primary OXO alcohols using mid-chain methyl- branched internal olefins having carbon numbers suitable for detergent application as intermediates and in which the OXO catalyst largely pre-isomerizes the internal olefin to an alpha-olefin and then hydroformylates predominantly at the terminal carbon atom.
• crude hydrocarbon feed 51 is distilled using distillation column DIST to secure a hydrocarbon feed suitable for the remainder of the process.
• Feed 1 can desirably be a narrow-carbon range paraffin cut.
• a light distillation cut 52 and a heavy distillation cut 53 are also obtained but not further used for making the instant OXO alcohols.
• Hydrocarbon feed 1 is passed through a simulated moving bed sorptive separation system comprising units SOR 4/5 followed by SOR 5/7, each suitably of MOLEX ® type, connected in the order shown.
• the configuration is set such that a linear-enriched stream (an adsorbate) rich in linear paraffin and identified as 6 in Fig. 9 is rejected from unit SOR 4/5.
• An intermediate branched-enriched stream (a raffinate) 2 which is enriched in methyl- branched paraffins, proceeds to unit SOR 5/7.
• Reject stream 7 from SOR 5/7 which contains unwanted cyclics, aromatics, ethyl-branched and higher-branched paraffins is discarded.
• Branched-enriched stream 3 from SOR 5/7 now a purified methyl-branched paraffin stream, proceeds to dehydrogenator DEH, for example of PACOL ® type where up to 20% of it is converted predominantly to the corresponding mono-olefins.
• Branched- enriched stream (olefinic) 4 containing said mono-olefins together with unreacted paraffins and some diolefin impurity, proceeds to SOR O/P, which is a simulated moving- bed adsorptive separation system configured to use OLEX ® or similar approaches for the separation of olefins from paraffins.
• the adsorbent is copper or silver on zeolites X or Y.
• a purified olefinic branched-enriched stream (the adsorbate) 55 now mostly methyl-branched olefins, proceeds to an OXO reactor.
• Recycle stream 8 is predominantly methyl-branched paraffins.
• the OXO reactor is configured for what is termed in the art as a "one-step low-pressure OXO process" using a catalytic metal other than iron, said metal being modified with bulky phosphine ligands (see the references in Background).
• Crude modified primary OXO alcohol, product stream 58 is separated from recyclable material using distillation and other ancilliary means not shown and the clean modified primary OXO alcohol, now freed from recyclable material, emerges as stream 57. See the table hereinafter for more detailed description of the composition of each stream.
• Fig. 10 is similar to Fig.
• Fig. 1 1 is similar to Fig. 10 except that it is simplified in that it uses an olefin/paraffin mixture as feed to the OXO reactor and in that recycle stream 8 is now a large fraction ( > 70%) of the OXO reactor output.
• Fig. 12 is similar to Fig. 10 except that units SOR 4/5 and SOR 5/7 have a reverse configuration.
• Fig. 13 is similar to Fig. 1 1 except that units SOR 4/5 and SOR 5/7 have a reverse configuration.
• Fig. 14 is similar to Fig. 12 except that SOR 4/5 is removed such that a mixture of linear and methyl-branched compounds proceeds through the process.
• the final product is a mixed linear and methyl-branched primary OXO alcohol.
• Fig. 15 is similar to Fig. 13 except that SOR 4/5 is removed such that a mixture of linear and methyl-branched compounds proceeds through the process.
• the final product is a mixed linear and methyl-branched primary OXO alcohol.
• Fig. 16 is similar to Fig. 10 except that the plant is fitted such that the olefinic branched-enriched stream, 55, can be used to make either modified alkylbenzene and/or modified primary OXO alcohols.
• Fig. 17 is similar to Fig. 1 1 except that the plant is fitted such that methyl-branched olefin stream 54 can be used to make either modified alkylbenzene and/or modified primary OXO alcohols.
• Fig. 18 is similar to Fig. 14 except that the plant is fitted such that methyl-branched and linear olefin stream 61 can be used to make product comprising modified alkylbenzene and/or modified primary OXO alcohols along with the corresponding linear counterparts.
• this invention relates to processes for preparing modified alkylbenzenesulfonate surfactants or modified primary OXO alcohols and surfactants derivable therefrom, or even combinations of these different surfactant types.
• the processes start from hydrocarbon feeds defined in more detail elsewhere herein. "Modified” connotes a very particular type of branching.
• modified means that there is methyl branching in positions other than the usual OXO position, while substantially avoiding branching in positions or of types that would adversely affect biodegradation
• modified refers to mid-chain positioned, mono-lower alkyl, especially monomethyl substitution of the OXO alcohol
• the processes comprise (a) a particularly defined adsorptive separation stage and, when making modified alkylbenzenes and/or alkylbenzenesulfonates, (c) an alkylation stage
• the hydrocarbon feed can be an adsorptive separation raffinate or effluent deriving from a linear alkylbenzene manufacturing process or conventional linear detergent alcohol process, though other feeds, such as jet/diesel or olefins can be used
• process embodiments typically and preferably further include (b) a dehydrogenation stage inserted in the sequence between the adsorptive separation and the alkylation and, when a modified alkylbenzene is the desired product, (c) an alkylation stage
• the alkylation stage is preferably followed by (d) sulfonation, (e) neutralization, and (f) formulation into consumer cleaning products by mixing, agglomeration, compaction, spray-drying and the like
• Any stage can have more than one step and include options such as distillation, provided that it includes at least the specified minimum
• stage (a), adsorptive separation comprises at least partially separating the hydrocarbon feed selected from olefinic feeds, paraffinic feeds and mixed olefinic / paraffinic feeds, into at least one branched-enriched stream comprising an increased proportion (e g , in relative terms at least about 50% higher, and in absolute terms, that is in terms of percentage by weight, at least about 10% by weight) of branched acyclic hydrocarbons relative to said hydrocarbon feed and typically, one or more additional streams, for example at least one linear-enriched stream comprising an increased proportion (e g , in relative terms at least about 50% higher, and in absolute terms at least about 10% by weight) of linear acyclic aliphatic hydrocarbons relative to said hydrocarbon feed
• Other streams present in the process can vary in composition Such streams include reject streams, in which cyclic and/or aromatic undesirable components from the feeds are present at levels generally exceeding those of the feed, recycle streams and the like can also be present
• the adsorptive separation part, (a), of the process has one or more steps comprising first, providing the hydrocarbon feed, then at least one step selected from adsorptive separation using porous media (preferred), clathration using a clathrating compound selected from urea, thiourea and alternative clathrating amides, and combinations thereof
• This stage uses simulated moving bed adsorptive separation means known from the art (see in particular US 2,985,589 incorporated herein in its entirety) comprising both of at least one bed holding said porous media or clathrating compound (see, for example Figure 1 of US 2,985,589 and the associated description) and a device, typically a rotary valve of a highly specialized design, for simulating motion of said porous media or clathrating compound countercurrent to a hydrocarbon stream in said bed. (see in particular US 2,985,589 Figure 2).
• the simulated moving-bed adsorptive separation herein is used to obtain an essential branched-enriched stream, that is, the exact opposite of the practice used in linear alkylbenzenesulfonate surfactant manufacture.
• This essential difference is also associated with having a different content of the bed as compared to conventional practice, that is, there is at least one bed containing porous media differing from the 4-5 Angstrom zeolites normally used for linear alkylbenzene manufacture by having larger pore size and reconfiguring the process equipment, notably said bed and said device, so that they connect differently with the associated process steps.
• stage (a) of the instant process (or stage (A), when making modified primary OXO alcohols) suitably comprises use of at least one porous medium selected from the group consisting of porous media having a minimum pore size at least larger than the pore size required for selective adsorption of linear acyclic hydrocarbons, said pore size not exceeding about 20 Angstroms, more preferably not exceeding about 10 Angstroms.
• the present process preferably includes an additional step, (b), of at least partially dehydrogenating said branched-enriched stream.
• Dehydrogenation can be done using known catalysts and conditions.
• the present process preferably comprises (c) reacting a branched-enriched stream prepared by one or both of the preceding steps (adsorptive separation optionally with dehydrogenation provided that the branched -enriched stream ultimately comprises olefin, typically at least about 5%, more typically at least about 15% of olefins, generally 5% to 90% or higher) with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst.
• the preferred alkylation step herein has a low internal isomer selectivity of from 0 to no more than about 40, preferably no more than about 20, and is described and defined more fully elsewhere herein. Such low selectivity alkylations are believed novel in their own right in the context of modified alkylbenzene manufacture.
• said stage (a) means comprise one, two or more of said devices and at least two of said beds, at least one of said beds comprising porous media differentiated relative to the contents of another of said beds by an increased capacity to retain methyl-branched acyclic aliphatic hydrocarbons.
• said step (c) has an internal isomer selectivity of from 0 to no more than about 40, preferably lower as further defined hereinafter.
• said simulated moving bed adsorptive separation means in said stage (a) comprise not one, but two of said devices.
• the number of devices taken in conjunction with their configuration is of especial importance in accomplishing the manufacture of the preferred compositions of the invention and increases specific types of branching in the hydrocarbon streams.
• each comprises a different member of said porous media, each of said beds being controlled by one of said devices, and each of said devices having a minimum of eight ports (as defined in US 2,985,589) for achieving simulated movement of said porous media in said beds.
• Each of said beds is further preferably divided into a vertically positioned array of at least eight sub-beds. (See Figure 1 in US 2,985,589).
• stage (a) uses exclusively porous media, rather than clathrating compounds, in said beds.
• Processes herein when making modified alkylbenzenes can have one or more steps following the alkylation step. Such steps can include the additional step of (d) sulfonating the product of step (c).
• Sulfonation can be followed by the additional step of (e) neutralizing the product of step (d). Such steps can be followed by (f) mixing the product of step (d) or (e) with one or more cleaning product adjunct materials; thereby forming a cleaning product.
• the present invention also encompasses modified alkylbenzene produced by any of the processes herein; as well as modified alkylbenzenesulfonic acid or modified alkylbenzenesulfonate surfactant in any known salt form such as the sodium form, the potassium form, the ammonium form, the substituted ammonium form or the like, produced by any of the processes herein; as well as consumer cleaning products produced by any of the processes herein.
• cleaning product embodiments herein whether they incorporate the modified alkylbenzene sulfonates and/or any of the modified primary OXO alcohol derived surfactants taught herein, include laundry detergents, dishwashing detergents, hard surface cleaners and the like.
• the content of modified surfactants produced by the instant process is from about 0.0001% to about 99.9%), typically from about 1% to about 50%, and the composition further comprises from about 0.1% to about 99.9%, typically from about 1% to about 90%, of cleaning product adjunct materials such as cosurfactants, builders, enzymes, bleaches, bleach promoters, activators or catalysts, and the like.
• the present invention also has alternate embodiments using paraffinic hydrocarbon feeds, in which two adsorptive separations, particularly configured in much the same manner as stage (a) described herein for modified alkylbenzene production, are followed by additional steps other than benzene alkylation step (c), and lead to useful cleaning surfactants.
• Such steps replacing the step (c) alkylation can include at least one step selected from: dehydrogenation, chlorination, sulfoxidation, oxidation to a C8-C20 alcohol and oxidation to a C8-C20 carboxylic acid or salt thereof, optionally followed by one of: glucosamidation, conversion to a nonsaccharide-derived amide surfactant (for example a monoethanolamide surfactant or any such amide not having a glucose moiety), and sulfonation as ester.
• Other alternative embodiments use a hydrocarbon feed comprising 20%) or more of methyl-branched olefins; again, this process has the particularly configured stage (a) adsorptive separations.
• Subsequent steps can include alkylation with benzene or toluene optionally followed by sulfonation; alkylation with phenol followed by at least one of alkoxylation, sulfation, sulfonation or combinations thereof; hydroformylation to alcohol optionally followed at least one of alkoxylation, glycosylation, sulfation, phosphation or combinations thereof; sulfonation; epoxidation; hydrobromination followed by amination and oxidation to amine oxide; and phosphonation.
• the invention also encompasses the surfactants produced by such processes and the cleaning products produced by such processes.
• the present invention moreover includes especially useful embodiments wherein the adsorptive separations of stage (a) comprise at least one separation step using an organometallic-grafted mordenite such as a tin-grafted mordenite.
• the invention also encompasses a method comprising use of a grafted mordenite for manufacturing detergent surfactants and any of the corresponding surfactants and consumer products produced by use of these specific porous media in any of the above-defined processes.
• the present invention has many other important embodiments and ramifications.
• the present invention encompasses a process comprising: (A) a stage of at least partially separating a hydrocarbon feed comprising branched aliphatic hydrocarbons, more particularly, paraffinic hydrocarbons, having from about 8 to about 20 carbon atoms, into at least one branched-enriched stream comprising an increased proportion of branched acyclic hydrocarbons relative to said hydrocarbon feed and optionally, one or more of: - a linear-enriched stream comprising an increased proportion of linear aliphatic hydrocarbons relative to said hydrocarbon feed; and a reject stream comprising cyclic and/or aromatic and/or ethyl- or higher- branched hydrocarbons; wherein said stage (A) comprises: - providing said hydrocarbon feed; and
• stage (A) using simulated moving bed adsorptive separation means comprising both of: at least one bed holding said porous media; and - a device for simulating motion of said porous media countercurrent to a hydrocarbon stream in said bed; followed by further stages (B), (C) and (D) (any of which can have one or more steps) as follows: (B) (i) at least partially dehydrogenating the branched-enriched stream of stage (A) thereby forming an olefinic branched-enriched stream comprising mono-olefin (optionally large proportions, up to 80%> or higher of paraffins may also be present along with impurities such as diolefins and/or aromatic impurities), optionally followed by one or more of (ii) treating said olefinic branched-enriched stream to diminish the content therein of diolefin impurities and (iii) treating said olefinic branched-enriched
• stage (D) reacting said olefinic branched-enriched stream produced in stage (B) or, optionally, as further concentrated in stage (C), with carbon monoxide and hydrogen in the presence of an OXO catalyst, thereby forming a modified primary OXO alcohol.
• stage refers to a collectively identifiable group of one or more process steps.
• A is an adsorptive separation stage, essentially a modified MOLEX ® stage which can be licensed from UOP Corp., here unconventionally configured to enrich (rather than decrease as in normal practice) the branched content of the hydrocarbons. It can optionally include as part of the same stage ancilliary steps such as distillation, addition or removal steps with lower boiling hydrocarbons to wash adsorbent, etc., all as known in the art.
• (B) is a dehydrogenation stage, comprising, at minimum, a dehydrogenation step but often including other optional steps such as those specifically mentioned supra.
• Essential process technology for (B) can be licensed from UOP Corp., for example as the PACOL ® process.
• (C) is essentially a conventional OLEX ® stage, again available from UOP Corp.
• (D) is preferably an OXO stage of the kind referred to in the art as a "one-step low pressure OXO" and is well- known in the art. As with the other stages of this process, stage (D) can be complemented by other optional steps, for example, catalyst removal, etc. Unless otherwise indicated, the convention herein will be to use capitals (A, B, C ...) when referring to stages of the present process embodiments wherein the process includes making a modified primary OXO alcohol.
• the present invention relates to a process for preparing a modified alkylbenzenesulfonate surfactant from a hydrocarbon feedstock.
• feed and/or "feedstock” are used herein to identify any hydrocarbon useful as a starting material in the present process.
• stream is typically used to identify hydrocarbon which has undergone at least one process step.
• the hydrocarbon feed herein in general contains useful proportions of acyclic aliphatic hydrocarbons, whether olefinic or paraffinic, or may include mixtures of such olefins and paraffins.
• the raw feedstock further typically includes varying amounts of cyclic and/or aromatic impurities, as found for example in kerosene, jet/diesel (middle distillate) hydrocarbon cuts.
• the olefins and paraffins generally occur in both branched and linear forms.
• the branched forms in the feedstock can be either undesirable or desirable for the present purposes.
• the present purposes of providing cleaning products differ markedly, for example, from gasoline manufacture in which a high degree of polymethyl-branched hydrocarbons is desirable for increasing octane rating.
• the present invention provides processes for separating particular desired forms of the hydrocarbon feeds for cleaning product purposes, and of incorporating them into surfactants (especially certain modified alkylbenzene sulfonates and/or surfactants based on modified primary OXO alcohols) and into cleaning products and useful surfactant intermediates for such products.
• surfactants especially certain modified alkylbenzene sulfonates and/or surfactants based on modified primary OXO alcohols
• modified as applied in connection with any product of the present process means that the product contains a very particular type of branching and surprisingly departs from the linear structure which is now commonly taught to be preferred and used for cleaning product surfactants.
• modified is further used to differentiate the products herein from conventional highly-branched cleaning surfactant structures, such as those found in tetrapropylene benzene sulfonates, and from all other conventional branched structures such as "two-tailed” or "Guerbet” or aldol-derived branched structures.
• Hydrocarbon feeds herein can in general vary quite widely, but typically include methyl branches such as monomethyl, dimethyl (including gem-dimethyl), trimethyl, polymethyl, ethyl, and higher alkyl branches.
• the hydrocarbon feeds may contain quaternary carbon atoms.
• tolerance for quaternary carbon atoms in the feeds is much superior when the present processes include an alkylation stage as taught hereinafter.
• Preferred feeds herein in embodiments of the invention which have an OXO process stage and do not have an alkylation stage are essentially free from quaternary carbon atoms.
• the desirable components for the present purposes include monomethyl-branched, dimethyl- branched other than gem-dimethyl-branched, and to some extent, especially at carbon contents in excess of about 14, some proportion of trimethyl-branched.
• the hydrocarbon feeds include useful proportions, e.g., 5%-40% or more, of acyclic hydrocarbons having in general from about 9 to about 20 carbon atoms depending on the desired type of cleaning product surfactant or the cleaning product use of the modified surfactant being produced. More preferably, when making modified alkylbenzenes and modified alkylbenzenesulfonates the acyclic aliphatic hydrocarbons of the feedstock comprise from about 10 to about 16, more preferably from about 1 1 to about 14 carbon atoms.
• the present processes comprise a particularly defined adsorptive separation stage and, for the purposes of making modified alkylbenzenes and alkylbenzenesulfonates, an alkylation stage is also essential.
• process embodiments typically and preferably further include a dehydrogenation stage inserted in the sequence between the adsorptive separation and the alkylation, or, when making modified primary OXO alcohols, between the adsorptive separation of type referred to as SOR 4/5 or SOR 5/7 in the Figures, and the OXO process stage.
• the alkylation or OXO stage can be followed by additional steps such as sulfonation, typically followed by neutralization and formulation into consumer cleaning products by mixing, agglomeration, compaction, spray-drying and the like.
• any stage can have more than one step provided that it includes at least the minimum of one step.
• Stage (a), adsorptive separation comprises at least partially separating the hydrocarbon feed selected from olefinic feeds, paraffinic feeds and mixed olefinic / paraffinic feeds into at least one branched-enriched stream comprising an increased proportion (e.g., in relative terms compared to the feed at least about 50%> higher, more preferably at least about 100% higher, typically treble, quadruple or more and in absolute terms, that is in terms of percentage by weight, at least about 10%> by weight, typically at least 20%), more preferably from 30% to about 90% or more) of branched acyclic hydrocarbons (especially the desired types identified supra, particularly methyl-branched paraffins or methyl-branched mono-olefins) relative to said hydrocarbon feed and optionally, one or more of: a linear-enriched stream comprising an increased proportion (e.g., in relative terms at least about 50% higher, more preferably at least about 100% higher, typically treble, quadruple or more and in absolute terms at least about 10% by
• Such streams include reject streams, in which cyclic and/or aromatic undesirable components from the feeds are present at levels generally exceeding those of the feed; recycle streams having compositions depending on the parts of the process they connect, and the like.
• reject streams in which cyclic and/or aromatic undesirable components from the feeds are present at levels generally exceeding those of the feed
• recycle streams having compositions depending on the parts of the process they connect, and the like.
• Known processes such as that of US 5,012,021 or US 4,520,214 both incorporated by reference, can be used herein to convert impurities, such as certain diolefins, back to monoolefins using a selective catalyst.
• the adsorptive separation stage or part of the process used to enrich the content of branched hydrocarbons in the feed has one or more steps comprising at least one step selected from providing a suitable hydrocarbon feed and at least one step selected from adsorptive separation using porous media, clathration using a clathrating compound selected from urea, thiourea and alternative clathrating amides, and combinations thereof.
• At least one step is an adsorptive separation using porous media of the larger-pore type described more fully hereinafter.
• Stage (a) (or stage (A) when making modified primary OXO alcohols) uses simulated moving bed adsorptive separation means well known from the art (see in particular US 2,985,589 incorporated herein in its entirety) comprising both of at least one bed holding said porous media or clathrating compound (see, for example US 2,985,589 Figure 1 and the associated description) and a device for simulating motion of said porous media or clathrating compound countercurrent to a hydrocarbon stream in said bed.
• the simulated moving-bed adsorptive separation herein is used to obtain an essential branched-enriched stream, that is, the exact opposite of the practice used in linear alkylbenzenesulfonate surfactant manufacture.
• This essential difference is also associated with changing the contents of the bed so that it contains porous media differing from the 4-5 Angstrom zeolites normally used for linear alkylbenzene manufacture, and reconfiguring the process equipment, notably said bed and said device, so that they connect differently with the associated process steps. More specifically, these means are configured such that the branched stream is passed on through the process, while any linear-enriched streams, however useful for other purposes, are either rejected from the present process or are present in accompaniment of branched-enriched streams.
• the present process preferably includes an additional stage, (b), or stage (B) when making modified primary OXO alcohols, of at least partially dehydrogenating the product of stage (a).
• Dehydrogenation can be done using any known dehydrogenation catalyst, such as the De- H series from UOP, and are further illustrated hereinafter. Dehydrogenation conditions are similar to those used in current linear alkylbenzenesulfonate manufacture.
• the present process preferably comprises (c) reacting the product of stage (a), or when stage (b) is also present in the foregoing steps, the product of stage (a) followed by stage (b), with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof in the presence of an alkylation catalyst.
• the preferred alkylation step herein has a low internal isomer selectivity of from 0 to about 40, preferably not more than about 20, more preferably not more than about 10, as described and defined more fully elsewhere herein. Such low internal isomer selectivities are believed novel in their own right.
• the alkylation step herein is run in the presence of excess paraffin, which is then recovered and recycled to the dehydrogenator.
• the alkylation step is run in presence of 5 x to 10 x excess of arene. Any combination of such modes is possible.
• the final branched-enriched stream i.e., the product of stage (a)
• this stream can proceed directly to the alkylation step (c), then recovered paraffins can be recycled to a dehydrogenation reactor for at least partial conversion to olefin. See, for example, Figs. 5, 6, 7.
• stage (a) means or, when making modified primary OXO alcohols, stage (A) means
• said stage (a) means comprise one, two or more of said devices (e.g., the aforementioned rotary valves or any equivalent means) and at least two of said beds, at least one of said beds comprising porous media differentiated relative to the contents of another of said beds by an increased capacity to retain methyl-branched acyclic aliphatic hydrocarbons.
• zeolites having pore size at least in excess of sizes used in conventional linear alkylbenzene manufacture and up to about 20 Angstrom, more preferably up to about 10 Angstrom, more preferably still up to about 7 Angstrom, or other porous media such as certain silicoaluminophosphates or Mobil MCM-type materials are suitable herein provided that the pore sizes are as noted.
• porous materials having pore sizes above about 7 Angstrom it is often highly desirable to "tune down" the pore openings, for example by grafting of tin alkyls at the pore openings. See EP 559,510 A incorporated herein by reference in its entirety.
• said step (c) has an internal isomer selectivity of from 0 to no more than about 40, preferably lower, as noted supra and as further defined in detail hereinafter.
• At least one of said beds comprises porous media conventional for the manufacture of linear alkylbenzenes; said beds being connected into said process in a manner consistent with at least partially increasing the proportion of methyl-branched acyclic aliphatic hydrocarbons in streams passing to step (c) of said process, and at least partially decreasing the proportion of linear acyclic aliphatic hydrocarbons passing to step (c) of said process, said linear acyclic aliphatic hydrocarbons being at least partially removed as reject stream in stage (a).
• preferred processes herein operate in a manner contradictory to and inconsistent with conventional practice for making alkylbenzenesulfonate surfactants, which reject branched materials and accept linear materials for further processing. Further, in order to achieve this reversal, it is found necessary to make use of an unconventional interconnection of adsorptive separation operations as already briefly described and as further illustrated in the Figures herein.
• said simulated moving bed adsorptive separation means in said stage (a) (or stage (A) when making modified primary OXO alcohols) comprise not one, but two of said devices, or a single device capable of simulating movement of said porous media in at least two independent beds.
• a single device for example a device as taught in US 2,985,589, will not suffice.
• the number of devices taken in conjunction with their configuration is of especial importance in accomplishing the manufacture of the preferred compositions of the invention.
• an increasing purification of a linear hydrocarbon might be accomplished by two devices and two beds connected in series.
• a highly linear adsorbate of the first stage might proceed to a second stage adsorptive separation process inlet for further purification.
• Such a configuration is outside the present invention on account of its incorrect connection of the stages, which lead to increasing the linearity and purity of a hydrocarbon.
• the present processes involve passing branched streams though the various steps or stages, requiring a connection of the devices which is consistent with the objective This increases specific types of branching in the hydrocarbon streams herein.
• each of said beds comprising a different member of said porous media, each of said beds being controlled by one of said devices, and each of said devices having a minimum of eight ports for achieving simulated movement of said porous media in said beds
• Each of said beds is further preferably divided into a vertically positioned array of at least eight sub- beds.
• stage (a) uses exclusively porous media in said beds.
• said linear-enriched stream is present in stage (a) and stage (a) comprises: (a-i) adsorptive separation of said hydrocarbon feed into said linear-enriched stream and an intermediate branched-enriched stream and rejection of said linear-enriched stream for essential purposes of said process, by means of one of said simulated moving beds, followed by (a-ii) adsorptive separation of said intermediate branched-enriched stream into said branched-enriched stream comprising an increased proportion of branched (more particularly methyl-branched) acyclic aliphatic hydrocarbons relative to said linear-enriched stream, and a reject stream comprising at least an increased proportion of cyclic and/or aromatic hydrocarbons relative to said branched -enriched stream, by means of another of said simulated moving beds
• Said reject stream in said step (a-ii) can further comprise undesired branched hydrocarbons selected from gem-dimethyl branched hydrocarbons, ethyl branched hydrocarbons and higher than ethyl branched hydrocarbons, and wherein the acyclic aliphatic hydrocarbons of said intermediate branched-enriched stream and said branched- enriched stream comprise a reduced proportion of said gem-dimethyl branched hydrocarbons, ethyl branched hydrocarbons and higher than ethyl branched hydrocarbons relative to said hydrocarbon feed
• ethyl branched hydrocarbons are much more acceptable than are gem-dimethyl, cyclic and aromatic components
• a minimum of "increasing proportion", “decreasing proportion", or “enriching" of any component in any step herein corresponds to any increase (enrichment) or decrease in proportion useful for the practically stated purposes of the
• stage (a) comprises: (a-i) adsorptive separation of said hydrocarbon feed into an acyclic aliphatic hydrocarbon-enriched stream comprising linear- and branched (such as the desirable types described supra) acyclic aliphatic hydrocarbons and a first reject stream comprising at least an increased proportion of cyclic and/or aromatic hydrocarbons relative to said hydrocarbon feed, followed by (a-ii) adsorptive separation of said acyclic aliphatic hydrocarbon-enriched stream into said branched-enriched stream and said linear-enriched stream; wherein said adsorptive separations are accomplished using said simulated moving bed adsorptive separation means.
• the "branched-enriched stream” is the final stream of stage or step (a); additional qualifiers such as “intermediate” will otherwise be prefixed on the name to indicate that the stream, though enriched in branched hydrocarbons, requires further treatment before proceeding from the adsorptive separation stages of the instant process to other stages.
• stage (a) the adsorptive separation stage, can freely include other conventional, optional steps, such as distillation, provided that adsorptive separation is conducted.
• current commercial MOLEX® plants will typically further include distillation in this stage and can be useful herein.
• the invention further encompasses a process wherein said first reject stream in said step (a-i) further comprises undesired branched hydrocarbons selected from gem-dimethyl branched hydrocarbons, ethyl branched hydrocarbons and higher than ethyl branched hydrocarbons; and wherein said acyclic aliphatic hydrocarbon-enriched stream and said branched-enriched stream each comprises a reduced proportion of said gem-dimethyl branched hydrocarbons, ethyl branched hydrocarbons and higher than ethyl branched hydrocarbons relative to said hydrocarbon feed.
• stream compositions can be achieved by selecting as said porous media: a member selected from the group consisting of 4-5 Angstrom pore-size zeolites in said step (a-ii) and a member selected from the group consisting of porous media having a pore size at least greater than about the maximum pore size of said step (a-ii) zeolite and at most about 10 Angstrom in said step (a-i).
• stage (a) comprises use of at least one porous medium selected from the group consisting of porous media having a minimum pore size larger than the pore size required for selective adsorption of linear acyclic hydrocarbons, said pore size not exceeding about 20 Angstroms.
• preferred processes herein include those wherein said alkylation step, (c), has an internal isomer selectivity of from 0 to 20; also, a preferred alkylation step, (c) uses an alkylation catalyst consistent with said internal isomer selectivity, and wherein said alkylation catalyst is selected from the group consisting of. at least partially acidic mordenites and at least partially acidic zeolite beta Preferred alkylation catalysts include H-mordenites and H-beta, more preferably H-mordenite, which is at least partially dealuminized.
• the invention also preferably includes the process wherein said hydrocarbon feed comprises at least about 10% methyl-branched paraffins having molecular weight of at least about 128 and no more than about 282; said process having said dehydrogenation step (b) More preferably in such embodiments, said hydrocarbon feed comprises at least about 20% methyl-branched paraffins having molecular weight of at least about 128 and no more than about 226; said process having said dehydrogenation step (b) and having alkylation step (c); and also preferably includes the process wherein said hydrocarbon feed comprises at least about 10% methyl-branched olefins having molecular weight of at least about 126 and no more than about 280. More preferably in such embodiments, the hydrocarbon feed comprises at least about 50% methyl-branched olefins having molecular weight of at least about 126 and no more than about 224; said process having no dehydrogenation step (b)
• the above ranges can be extended somewhat, consistent with going to a total carbon number of up to about C20 or higher. More preferably, the upper-end paraffin molecular weight of 226 supra is extended to about 254, and the upper-end olefin molecular weight of 224 supra is extended to about 252
• the hydrocarbon feed or feedstock herein can be an adsorptive separation raffinate or effluent deriving from a linear alkylbenzene manufacturing process, or from a conventional linear detergent alcohol process.
• Processes herein can have one or more steps following the alkylation step. Such steps can include the additional step of (d) sulfonating the product of step (c). Sulfonation can be followed by the additional step of (e) neutralizing the product of step (d).
• steps can be followed by (f) mixing the product of step (d) or (e) with one or more cleaning product adjunct materials, thereby forming a cleaning product
• the process herein includes highly preferred embodiments having all of the additional steps of (d) sulfonating the modified alkylbenzene product of step (c); (e) neutralizing the modified alkylbenzenesulfonic acid product of step (d); and (f) mixing the modified alkylbenzenesulfonic acid or modified alkylbenzenesulfonate surfactant product of steps (d) or (e) with one or more cleaning product adjunct materials; thereby forming a cleaning product.
• modified alkylbenzene which is the product of said step (c) is blended with a linear alkylbenzene produced by a conventional process.
• modified alkylbenzene sulfonate which is the product of said step (d) is blended with a linear alkylbenzene sulfonate produced by a conventional process.
• a preferred process has a ratio of modified alkylbenzene to linear alkylbenzene of from about 1 : 100 to about 100: 1. When a relatively more linear product is desired, a preferred ratio is from about 10:90 to about 50:50.
• a preferred ratio is from about 90: 10 to about 51 :49.
• the present invention also encompasses modified alkylbenzene produced by any of the processes herein; as well as modified alkylbenzenesulfonic acid or modified alkylbenzenesulfonate surfactant in any known salt form such as the sodium form, the potassium form, the ammonium form, the substituted ammonium form or the like, produced by any of the processes herein; as well as consumer cleaning product produced by any of the processes herein.
• Cleaning product embodiments herein include laundry detergents, dishwashing detergents, hard surface cleaners and the like.
• the content of modified alkylbenzenesulfonate, or content of any surfactant derived from modified primary OXO alcohols, etc., herein and produced by the instant process is from about 0.0001% to about 99.9%, typically from about 1 % to about 50%, and the composition further comprises from about 0. 1 % to about 99.9%, typically from about 1% to about 50%), of cleaning product adjunct materials such as cosurfactants, builders, enzymes, bleaches, bleach promoters, activators or catalysts, and the like.
• Preferred consumer cleaning products produced by these processes suitably comprise from about 1% to about 50% of said modified surfactant and from about 0.0001%) to about 99% of cleaning product adjunct materials selected from enzymes, nonphosphate builders, polymers, activated bleaches, catalyzed bleaches, photobleaches and mixtures thereof.
• cleaning product adjunct materials selected from enzymes, nonphosphate builders, polymers, activated bleaches, catalyzed bleaches, photobleaches and mixtures thereof.
• Alternate Process Embodiments The present invention has alternate embodiments in which two particularly configured adsorptive separations are followed by additional steps which lead to useful cleaning surfactants.
• a process comprising: (I) separating a hydrocarbon feedstock into a branched hydrocarbon-enriched stream comprising, more preferably consisting essentially of, at least about 85% of saturated acyclic aliphatic hydrocarbons having a carbon content of from about C8 to about C20, said branched hydrocarbon-enriched stream comprising at least about 10% of paraffins having methyl branches, said methyl branches being distributed in said paraffins such that any paraffin molecule has from 0 to no more than about 3 of said methyl branches and said branches being positioned within said paraffins to an extent that at least about 90%) of said branches occupy positions other than those forming gem-dimethyl and/or quaternary moieties; wherein said separation is conducted by means including at least two adsorptive separation steps using simulated moving bed adsorptive separation means and at least two porous media having different pore sizes; and (II) converting said branched hydrocarbon enriched stream to a surfactant by further steps including at least two adsorptive separation steps
• a process comprising: (I) separating a hydrocarbon feedstock into a olefinic branched hydrocarbon- enriched stream comprising, preferably consisting essentially of, mixtures of olefinic acyclic aliphatic hydrocarbons having a carbon content of from about C8 to about C20 or mixtures thereof with their saturated analogs, said branched hydrocarbon-enriched stream comprising at least about 10% of the sum of said olefins and their saturated analogs having methyl branches, said methyl branches being distributed in said mixtures such that any of said acyclic aliphatic hydrocarbon molecules has from 0 to no more than about 3 of said methyl branches and said branches being positioned within said acyclic aliphatic hydrocarbon molecules to an extent that at least about 90% of said branches occupy positions other than those forming gem-dimethyl moieties; wherein said separation is conducted by means including at least two adsorptive separation steps using simulated moving bed adsorptive separation
• the invention also encompasses the surfactants produced by such processes and the cleaning products produced by such processes.
• the present invention includes a process for preparing modified alkylbenzenesulfonate surfactants suitable for use in cleaning products such as laundry detergents, hard surface cleaners, dishwashing detergents and the like.
• modified alkylbenzenesulfonate surfactant and “modified alkylbenzene” refer products of the processes herein.
• modified as applied either to the novel alkylbenzenesulfonate surfactants or to the novel alkylbenzenes (MAB) is used to indicate that the product of the present process is compositionally different from that of all alkylbenzenesulfonate surfactants hitherto used in commerce in consumer cleaning compositions.
• the instant compositions differ compositionally from the so-called “ABS” or poorly biodegradable alkylbenzenesulfonates, and from the so-called "LAS” or linear alkylbenzenesulfonate surfactants.
• LAS surfactants are currently commercially available through several processes including those relying on HF-catalyzed or aluminum chloride-catalyzed alkylation of benzene.
• Other commercial LAS surfactants include LAS made by the DETAL® process.
• Preferred alkylbenzenesulfonate surfactants herein made using the preferred low-internal isomer selectivity alkylation step herein are also compositionally different from those made by alkylating linear olefins using fluoridated zeolite catalyst systems, believed also to include fluoridated mordenites. Without being limited by theory, it is believed that the modified alkylbenzenesulfonate surfactants herein are uniquely lightly branched.
• modified alkylbenzenesulfonate products herein differ in physical properties from known alkylbenzenesulfonate surfactants, for example by having improved surfactant efficiency and low tendency to phase-separate internal isomers from solution, especially in presence of water hardness. Feeds and Streams of the Process The term "feed" is used herein to identify a material which has not yet been processed by the present process.
• feed may also be used when a step which is optional in the present process (e.g., adsorptive separation over 5 Angstrom Ca- zeolite) has been applied to such a material, provided that such treatment occurs before the first essential step of the present process.
• a step which is optional in the present process e.g., adsorptive separation over 5 Angstrom Ca- zeolite
• stream is used herein to identify materials which have undergone at least one step of the present process.
• branched-enriched stream herein unless more particularly noted, refers to any processed hydrocarbon fraction containing at least the smaller of the following:
• the branched hydrocarbons referred to can be olefinic, paraffinic or mixed olefin paraffin in any proportion unless otherwise more particularly noted. (Certain preferred processes involving making modified primary OXO alcohols as illustrated in Figures 9 and higher start from paraffinic feeds, though, more generally, variations of these processes can use olefinic feeds).
• the branches are preferably monomethyl branches or isolated (nongeminal) dimethyl branches.
• linear-enriched stream refers to any processed hydrocarbon fraction which contains a higher percentage by weight of normal (n-) acyclic hydrocarbons than does a parent fraction or feed which has not been processed in the present process.
• linear-enriched refers to any processed hydrocarbon fraction containing at least the smaller of the following:
• linear hydrocarbons in relative terms, an increase of at least about 10%, preferably at least 100% (that is, a doubling), more preferably a trebling, quadrupling or more, of linear acyclic C8 to about C20 hydrocarbons, compared to a parent fraction or feed which has not been processed in the present process; or (iv) in absolute terms, at least about 5%, preferably 10% or more, of linear acyclic C8 to about C20 hydrocarbons.
• the linear hydrocarbons can be olefinic, paraffinic or mixed olefin/paraffin in any proportion, unless otherwise more particularly identified.
• Qualifiers such as "intermediate” when used in connection with a branched- enriched stream are used to identify that the branched-enriched stream to which is being referred has not completed passage through the adsorptive separation stage (a) of the present process.
• Other qualifiers such as "olefinic” or “paraffinic” may be used to identify whether the stream contains a preponderance of olefinic or of paraffinic hydrocarbons.
• Feeds and streams in the present process both with respect to embodiments comprising alkylation and with respect to embodiments comprising OXO reaction (or concurrent utilization of both) are further illustrated in the following Table.
• the numbers in the leftmost column refer to the feeds and streams identified in Fi .1 throu h Fi . 18
• hydrocarbon feeds exemplified in the table hereinabove should of course be viewed as illustrative and not limiting of the present invention. Any other suitable hydrocarbon feed may be used.
• suitable hydrocarbon feed may be used.
• crackates of petroleum waxes including crackates of Fischer-Tropsch waxes. These waxes are from lube oil distillate fractions and melt in the relatively low range up to about 72°C, e.g., in the range from about 50°C to about 70°C and contain from about 18 to about 36 carbon atoms.
• Such waxes preferably contain 50% to 90% normal alkanes and 10% to 50% of monomethyl branched alkanes and low levels of various cyclic alkanes.
• Such crackate feeds are especially useful in alternate embodiments of the invention as further described in detail hereinafter, and are described in "Chemical Economics Handbook", published by SRI, Menlo Park, California. See, for example, “Waxes”, S595.5003 L, published 1995. Paraffin waxes are also described in Kirk Othmer's Encyclopedia of Chemical Technology, 3 r . Edition, (1984), Volume 24. See “Waxes” at page 473. Any equivalent alternative hydrocarbon feeds or more preferably shorter-chain equivalents in the C10-C20 range and having appreciable monomethyl-branching in any position on the chain, for example from Fischer-Tropsch synthesis, are also suitable.
• Hydrocarbon feeds herein can contain varying amounts of N,O,S impurity. Certain preferred hydrocarbon feeds, especially if derived from sulfur- and/or nitrogen-containing fractions, are desulfurized and/or freed from nitrogenous matter using conventional desulfurization or "de-NOS' technology. Hydrocarbon feeds herein can be separated before use in the present processes so that the maximum amount of hydrocarbons having specific chainlengths and/or degrees of branching are most effectively utilized to make modified alkylbenzenes and/or modified primary OXO alcohols.
• Adsorptive Separation Step(s) In general, separation techniques in stage (a) or stage (A) of the instant processes rely on adsorption on porous media and/or use of clathrates.
• a landmark patent on adsorptive separation is US 2,985,589 which illustrates devices, adsorbent beds and process conditions of temperature and pressure generally suitable for use herein. '589 does not describe critical modifications, especially pore sizes for specific separations and connection of steps, that are part of the present invention.
• Adsorptive separation steps herein can, in general, be conducted in the vapor phase or the liquid phase, and may or may not employ any of the commercialized process equipment as identified in the background of the invention.
• Porous media used as adsorbents can in general be dried or non-dried. Preferred embodiments include those wherein the adsorbents are dried and contain less than about 2% free moisture.
• Any adsorptive separation step according to the present invention may, or may not use a desorbent or displacing agent.
• any desorption means such as pressure- swing or other means, can be used.
• solvent displacement is a preferred method of desorbing streams from the porous media used herein.
• Suitable desorbents or displacing agents include a lower- molecular weight n-paraffin such as heptane, octane or the like, or a polar desorbent such as ammonia. It should be understood that, irrespective of their presence, such well-known desorbents, being fully conventional, are not explicitly included in identifying any of the streams or their compositions in the processes herein, and can be recycled at will using desorbent recycle steps not explicity shown in Figs. 1-18.
• stage (a) can use a MOLEX® process step of UOP, subject to the difference that the present process must have at least one adsorptive separation using a porous material which has larger pores than the usual 5 Angstrom zeolite as used in linear alkylbenzene manufacture.
• MOLEX® is discussed in the hereinabove-identified Surfactant Science Series Vol. 56, including for example pages 5- 10. Vapor-phase processes such as Union Carbide' s IsoSiv process (see the same reference) are also useful but less preferred.
• Porous media required in stage (a) or stage (A) herein are larger-pore types.
• large-pore is specifically meant porous media having pores large enough to retain mono-methyl-branched linear olefinic or paraffinic hydrocarbons and dimethyl-branched or trimethyl-branched linear olefinic or paraffinic hydrocarbons other than gem-dimethyl hydrocarbons, while being small enough to at least partly exclude gem-dimethyl, ethyl and higher-branched hydrocarbons as well as cyclic (e.g., 5-, 6-membered rings) and aromatic hydrocarbons.
• Such pore sizes large enough to retain appreciable amounts of methyl- branched hydrocarbons are invariably not used in conventional linear alkylbenzene manufacture and in general are far more rarely used in any commercial processes than are the more familiar 4 - 5 Angstrom pore size zeolites.
• the larger-pore porous media are those used in Figs. 1-7 in the adsorptive separation units marked as "SOR 5/7".
• Porous media essential in stage (a) or stage (A) herein accordingly have a minimum pore size larger than the pore size required for selective adsorption of linear acyclic hydrocarbons, i.e., in excess of those used in conventional linear alkylbenzene manufacture, said pore size not exceeding about 20 Angstroms, more preferably not exceeding about 10 Angstroms and very preferably, from above about 5 Angstroms to about 7 Angstroms on average.
• minimum pore size for the so-called "larger-pore” porous materials herein it should be recognized that such materials often have elliptical pores, for example SAPO-1 1 has a pore size of 4.4 by 6.7 Angstrom. (5.55 Angstrom average). See S.
• the convention herein is to look to the average of elliptical dimensions or the larger elliptical dimension - in any event not to the smaller elliptical dimension - when making the size comparison.
• SAPO-1 1 material herein by definition has a pore size larger than a 5 Angstrom, uniform-pore zeolite.
• Porous media having the larger pores essential in stage (a) or stage (A) herein can be either zeolites (aluminosilicates) or non-zeolites.
• Suitable non-zeolites include the silicoaluminophosphates, especially SAPO-11 though other silicoaluminophosphates, e.g., SAPO 31 or 41, can be used if the average pore size is greater than about 5 Angstroms or if elliptical pores are present with at least one elliptical dimension above 5 Angstroms.
• pyrolyzed poly(vinylidene chloride) i.e., pyrolyzed SARAN, for example manufactured according to Netherlands Application NL 71 1 1508 published October 25, 1971.
• SARAN poly(vinylidene chloride)
• SARAN poly(vinylidene chloride)
• the present invention also includes especially useful embodiments wherein the adsorptive separations of stage (a) or stage (A) comprise at least one separation step using an organometallic-grafted mordenite.
• organometallic-grafted mordenite Especially suitable as the "large-pore" porous , media herein are grafted mordenites such as a tin-grafted mordenite.
• the invention encompasses a method comprising use of a grafted mordenite for manufacturing detergent surfactants and any of the corresponding surfactants and consumer products produced by use of these specific porous media in any of the above- defined processes. See EP 559,510 A 9/8/93 incorporated by reference in its entirety.
• grafted mordenites of EP 559,510 which are clearly identifiable from the Examples thereof to be best suited for separations of linear and monomethyl-branched hydrocarbons from gem-dimethyl and polymethyl hydrocarbons.
• Other grafted zeolites useful as the porous media herein include those of US
• the present invention also encompasses a process for making modified alkylbenzenes and/or modified alkylbenzenesulfonates, said process comprising:
• stage (b) at least one stage of alkylating a less branched effluent of stage (a), preferably in an alkylation having internal isomer selectivity of from 0 to 40, and more preferably still, using an at least partially dealuminized, at least partially acidic H-mordenite as catalyst; and (c) at least one stage of sulfonating the product of stage (b) using any conventional sulfonating agent.
• the resulting modified alkylbenzenesulfonic acid can be neutralized and incorporated into cleaning products as taught elsewhere herein.
• stage (a) or stage (A) of the present process there is a preference to use zeolites or other porous media in such a form that they do not actively promote chemical reactions of the feedstock., e.g., cracking, polymerization.
• acidic mordenite is preferably avoided in stage (a) or stage (A). See in contrast alkylation catalysts hereinafter, in which at least partial acid-form is preferred.
• Porous Media (Smaller-pore Types)
• Smaller-pore zeolites optionally useful in stage (a) or stage (A) herein are those used in processes such as those of the adsorptive separation unit identified as "SOR 4/5" in Figs. 1, 2, 5, 6, 9, etc. are those which selectively adsorb linear hydrocarbons and which do not adsorb methyl-branched hydrocarbons appreciably.
• Such porous materials are well-known and include, for example, Calcium Zeolites with 4-5 Angstrom pores. Such materials are further illustrated in US 2,985,589 and are those in current commercial use for manufacture of linear alkylbenzenes.
• Porous Media e.g.. OLEX ® or similar processes
• OLEX ® olefin/paraffin separation step
• Urea clathration can also be used herein in stage (a) for separating n-paraffins from branched paraffins, as is well known in the art. See, for example, Surfactant Science Series, Marcel Dekker, N.Y., 1996, Vol. 56, , pages 9-10 and references therein. See also "Detergent Manufacture Including Zeolite Builders and other New Materials, Ed. Sittig., Noyes Data Corp., 1979, pages 25-30 and especially US 3,506,569 incorporated in its entirety which uses solid urea and no chlorocarbon solvents. More generally but less preferably, processes according to US 3, 162,627 may be used. Dehydrogenation
• dehydrogenation of the olefin or olefin paraffin mixtures in the instant process can be accomplished using any of the well-known dehydrogenation catalyst systems, including those described in the Surfactant Science Series references cited in the background as well as in "Detergent Manufacture Including Zeolite Builders and Other New Materials", Ed. Sittig, Noyes Data Corp., New Jersey, 1979 and other dehydrogenation catalyst systems, for example those commercially available though UOP Corp.
• Dehydrogenation can be conducted in presence of hydrogen gas and commonly a precious metal catalyst (e.g., DeH-5 ®, DeH-7 ® , DeH-9 ® available from UOP) is present though alternatively non-hydrogen, precious-metal free dehydrogenation systems such as a zeolite/air system can be used with no precious metals present.
• a precious metal catalyst e.g., DeH-5 ®, DeH-7 ® , DeH-9 ® available from UOP
• dehydrogenation catalysts useful herein include a catalyst supported on Sn-containing alumina and having Pt: 0.16%, Ir: 0.24%, Sn: 0.50%, and Li: 0.54% as described in US 5,012,027 incorporated by reference.
• This catalyst when contacted with a C9-C14 paraffin mixture (believed to be linear) at 500°C and 0.68 atm. produces olefinic products (38h on stream) with 90.88%) selectivity and 11.02%) conversion and is believed to be very suitable for at least partially dehydrogenating branched-enriched streams of paraffins herein. See also US 4,786,625; EP 320,549 Al 6/21/89; Vora et al., Chem. Age India (1986), 37(6), 415-18; As noted supra, dehydrogenation can be complete or partial, more typically partial.
• this step forms a mixture of olefin (e.g., about 10% though this figure is illustrative and should not be taken as limiting) and the balance unreacted paraffin.
• olefin e.g., about 10% though this figure is illustrative and should not be taken as limiting
• Such mixture is a suitable feed for the alkylation step of the instant process.
• Important embodiments of the present invention further include alkylation, which takes place after delinearization by separative enrichment of lightly branched paraffin and at least partial dehydrogenation of the delinearized olefin or olefin/paraffin mixtures.
• Alkylation is conducted with an aromatic hydrocarbon selected from benzene, toluene and mixtures thereof.
• Preferred embodiments of the present processes require an alkylation step having internal isomer selectivity in the range from 0 to 40, preferably from 0 to 20, more preferably still from 0 to 10.
• the Internal Isomer Selectivity or "IIS" as defined herein is measured for any given alkylation process step by conducting a test alkylation of benzene by 1-dodecene at a molar ratio of 10: 1.
• the alkylation is conducted in the presence of an alkylation catalyst to a conversion of dodecene of at least 90% and formation of monophenyldodecanes of at least 60%.
• Internal isomer selectivity is then determined as:
• IIS 100 * ( 1- amount of terminal phenyldodecanes ) amount of total phenyldodecanes
• amounts are amounts of the products by weight; the amount of terminal phenyldodecanes is the amount of the sum of 2-phenyldodecane and 3- phenyldodecane and the amount of total phenyldodecanes is the amount of the sum of 2-phenyldodecane and 3- phenyldodecane and 4-phenyldodecane and 5- phenyldodecane and 6- phenyldodecane and wherein said amounts are determined by any known analytical technique for alkylbenzenesulfonates such as gas chromatography. See Analytical Chemistry, Nov.
• the specific alkenes used to characterize or test any given alkylation step for suitability are reference materials permitting a comparison of the alkylation step herein with known alkylation steps as used in making linear alkylbenzenes and permitting the practitioner of the invention to decide if a given known alkylation step is, or is not, useful in the context of the series of process steps constituting the present invention.
• the hydrocarbon feedstock for alkylation actually used is of course that which is specified on the basis of the preceding process steps.
• all the current commercial processes for LAS manufacture are excluded from preferred embodiments of the present invention solely on the basis of the IIS for the alkylation step.
• LAS processes based on aluminum chloride, HF and the like all have IIS outside of the range specified for the instant process.
• a few alkylation steps described in the literature but not currently applied in commercial alkylbenzenesulfonate production do have suitable IIS and are useful herein.
• IIS determination The better to assist the practitioner in determining IIS and in deciding whether a given alkylation process step is suitable for the purposes of the present invention, the following are more particular examples of IIS determination.
• test alkylation of benzene by 1-dodecene is conducted at a mole ratio of 10: 1 benzene to 1-dodecene and the alkylation is conducted in the presence of an alkylation catalyst to a conversion of dodecene of at least 90%> and formation of monophenyldodecanes of at least 60%.
• the alkylation test must in general be conducted in a reaction time of less than 200 hours and at a reaction temperature of from about - 15°C to about 500°C, preferably from about 20°C to 500°C. Pressure and catalyst concentration relative to 1-dodecene can vary widely. No solvent other than benzene is used in the test alkylation.
• the process conditions used to determine the IIS for the catalyst or alkylation step in question can be based on the literature. The practitioner will use generally appropriate conditions based on a large body of well-documented data for alkylations. For example, appropriate process conditions to determine if an AICI3 alkylation can be used herein are exemplified by a reaction of 5 mole % AICI3 relative to 1-dodecene at 20-40°C for 0.5-1.0 hour in a batch reactor. Such a test demonstrates that an AICI3 alkylation step is unsuitable for use in the present process. An IIS of about 48 should be obtained. In another example, an appropriate test of alkylation using HF as a catalyst should give an IIS of about 60.
• the low-US alkylation step practiced using H-mordenites herein is capable both of alkylating benzene with the branched-enriched hydrocarbon, but very usefully also of scrambling the position of a methyl branch attached to the hydrocarbon chain.
• alkylation catalysts Accomplishing the required IIS in the alkylation process step is made possible by a tightly controlled selection of alkylation catalysts. Numerous alkylation catalysts are readily determined to be unsuitable. Unsuitable alkylation catalysts include the DETAL® process catalysts, aluminum chloride, HF, HF on zeolites, fluoridated zeolites, non-acidic calcium mordenite, and many others. Indeed no alkylation catalyst currently used for alkylation in the commercial production of detergent linear alkylbenzenesulfonates has yet been found suitable.
• suitable alkylation catalyst herein is selected from shape-selective moderately acidic alkylation catalysts, preferably zeolitic.
• the zeolite in such catalysts for the alkylation step (step (b)) is preferably selected from the group consisting of mordenite, ZSM-4, ZSM-12, ZSM-20, offretite, gmelinite and zeolite beta in at least partially acidic form. More preferably, the zeolite in step (b) (the alkylation step) is substantially in acid form and is contained in a catalyst pellet comprising a conventional binder and further wherein said catalyst pellet comprises at least about 1 %, more preferably at least 5%, more typically from 50% to about 90%, of said zeolite.
• suitable alkylation catalyst is typically at least partially crystalline, more preferably substantially crystalline not including binders or other materials used to form catalyst pellets, aggregates or composites. Moreover the catalyst is typically at least partially acidic. Fully exchanged Ca-form mordenite, for example, is unsuitable whereas H-form mordenite is suitable.
• This catalyst is useful for the alkylation step identified as step (b) in the claims hereinafter: these correspond to Step 7 in Fig. 1.
• the pores characterizing the zeolites useful in the present alkylation process may be substantially circular, such as in cancrinite which has uniform pores of about 6.2 angstroms, or preferably may be somewhat elliptical, such as in mordenite.
• the zeolites used as catalysts in the alkylation step of the present process have a major pore dimension intermediate between that of the large pore zeolites, such as the X and Y zeolites, and the relatively small pore size zeolites ZSM-5 and ZSM-11, and preferably between about 6 A and about 7 A.
• ZSM-5 has been tried and found inoperable in the present invention.
• the pore size dimensions and crystal structures of certain zeolites are specified in ATLAS OF ZEOLITE STRUCTURE TYPES by W. M. Meier and D. H. Olson, published by the Structure Commission of the International Zeolite Association (1978 and more recent editions) and distributed by Polycrystal Book Service, Pittsburgh, Pa.
• the zeolites useful in the alkylation step of the instant process generally have at least 10 percent of the cationic sites thereof occupied by ions other than alkali or alkaline- earth metals.
• Typical but non-limiting replacing ions include ammonium, hydrogen, rare earth, zinc, copper and aluminum. Of this group, particular preference is accorded ammonium, hydrogen, rare earth or combinations thereof.
• the zeolites are converted to the predominantly hydrogen form, generally by replacement of the alkali metal or other ion originally present with hydrogen ion precursors, e.g., ammonium ions, which upon calcination yield the hydrogen form.
• This exchange is conveniently carried out by contact of the zeolite with an ammonium salt solution, e.g., ammonium chloride, utilizing well known ion exchange techniques.
• an ammonium salt solution e.g., ammonium chloride
• the extent of replacement is such as to produce a zeolite material in which at least 50 percent of the cationic sites are occupied by hydrogen ions.
• the zeolites may be subjected to various chemical treatments, including alumina extraction (dealumination) and combination with one or more metal components, particularly the metals of Groups IIB, III, IV, VI, VII and VIII. It is also contemplated that the zeolites may, in some instances, desirably be subjected to thermal treatment, including steaming or calcination in air, hydrogen or an inert gas, e.g. nitrogen or helium.
• thermal treatment including steaming or calcination in air, hydrogen or an inert gas, e.g. nitrogen or helium.
• a suitable modifying treatment entails steaming of the zeolite by contact with an atmosphere containing from about 5 to about 100 percent steam at a temperature of from about 250°C to 1000°C. Steaming may last for a period of between about 0.25 and about 100 hours and may be conducted at pressures ranging from sub-atmospheric to several hundred atmospheres.
• intermediate pore size crystalline zeolites in another material, e.g., a binder or matrix resistant to the temperature and other conditions employed in the process.
• matrix materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica, and/or metal oxides.
• Matrix materials can be in the form of gels including mixtures of silica and metal oxides. The latter may be either naturally occurring or in the form of gels or gelatinous precipitates.
• Naturally occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNamee-Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite.
• Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
• the intermediate pore size zeolites employed herein may be compounded with a porous matrix material, such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, and silica-titania, as well as ternary combinations, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina- magnesia and silica-magnesia-zirconia.
• the matrix may be in the form of a cogel.
• the relative proportions of finely divided zeolite and inorganic oxide gel matrix may vary widely, with the zeolite content ranging from between about 1 to about 99 percent by weight and more usually in the range of about 5 to about 80 percent by weight of the composite.
• a group of zeolites which includes some useful for the alkylation step herein have a silica: alumina ratio of at least 10: 1, preferably at least 20: 1.
• the silica:alumina ratios referred to in this specification are the structural or framework ratios, that is, the ratio for the SiO4 to the A1O4 tetrahedra. This ratio may vary from the silica:alumina ratio determined by various physical and chemical methods. For example, a gross chemical analysis may include aluminum which is present in the form of cations associated with the acidic sites on the zeolite, thereby giving a low silica:alumina ratio.
• thermogravimetric analysis TGA
• a low ammonia titration may be obtained if cationic aluminum prevents exchange of the ammonium ions onto the acidic sites.
• Zeolite beta suitable for use herein (but less preferred than H-mordenite) is disclosed in U.S. Pat. No. 3,308,069 to which reference is made for details of this zeolite and its preparation.
• Such a zeolite in the acid form is also commercially available as Zeocat PB/H from Zeochem.
• Zeocat PB/H from Zeochem.
• the zeolites When the zeolites have been prepared in the presence of organic cations they are catalytically inactive, possibly because the intracrystalline free space is occupied by organic cations from the forming solution. They may be activated by heating in an inert atmosphere at 540°C. for one hour, for example, followed by base exchange with ammonium salts followed by calcination at 540°C. in air.
• the presence of organic cations in the forming solution may not be absolutely essential to the formation of the zeolite; but it does appear to favor the formation of this special type of zeolite.
• Some natural zeolites may sometimes be converted to zeolites of the desired type by various activation procedures and other treatments such as base exchange, steaming, alumina extraction and calcination.
• the zeolites preferably have a crystal framework density, in the dry hydrogen form, not substantially below about 1.6 g.cm -3.
• the dry density for known structures may be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on page 19 of the article on Zeolite Structure by W. M.
• the zeolite When synthesized in the alkali metal form, the zeolite is conveniently converted to the hydrogen form, generally by intermediate formation of the ammonium form as a result of ammonium ion exchange and calcination of the ammonium form to yield the hydrogen form. It has been found that although the hydrogen form of the zeolite catalyzes the reaction successfully, the zeolite may also be partly in the alkali metal form.
• EP 466,558 describes an acidic mordenite type alkylation catalyst also of possible use herein having overall Si/Al atomic ratio of 15-85 (15-60), Na weight content of less than 1000 ppm (preferably less than 250 ppm), having low or zero content of extra- network Al species, and an elementary mesh volume below 2,760 nm3.
• US 5,057,472 useful for preparing alkylation catalysts herein relates to concurrent dealumination and ion-exchange of an acid-stable Na ion-containing zeolite, preferably mordenite effected by contact with a 0.5-3 (preferably 1-2.5) M HNO3 solution containing sufficient NH4NO3 to fully exchange the Na ions for NH4 and H ions.
• the resulting zeolites can have an SiO2:A12O3 ratio of 15-26 (preferably 17-23): 1 and are preferably calcined to at least partially convert the NH4/H form to an H form.
• the catalyst can contain a Group VIII metal (and optionally also an inorganic oxide) together with the calcined zeolite of '472.
• a Group VIII metal and optionally also an inorganic oxide
• Another acidic mordenite catalyst useful for the alkylation step herein is disclosed in US 4,861,935 which relates to a hydrogen form mordenite incorporated with alumina, the composition having a surface area of at least 580 m2 /g
• Other acidic mordenite catalysts useful for the alkylation step herein include those described in US 5,243,116 and US 5,198,595
• Yet another alkylation catalyst useful herein is described in US 5,175,135 which is an acid mordenite zeolite having a silica alumina molar ratio of at least 50: 1, a Symmetry Index of at least 1 0 as determined by X-ray diffraction analysis, and a porosity such that the total pore volume is in the range from about 0 18 cc/g to about
• alkylation catalysts herein include the acidic mordenite catalysts Zeocat FM-8/25H available from Zeochem, CBV 90 A available from Zeolyst International, and LZM-8 available from UOP Chemical Catalysts
• any alkylation catalyst may be used herein provided that the alkylation step meets the internal isomer selectivity requirements identified supra
• any alkylation catalyst may be used herein provided that the alkylation step meets the internal isomer selectivity requirements identified supra Distillation of Modified Alkylbenzenes or Modified Primary OXO Alcohols
• the present process can include distillation of modified alkylbenzenes or modified primary OXO alcohols, for example to remove unreacted starting materials, paraffins, excesses of benzene and the like
• Any conventional distillation apparatus can be used The general practice is similar to that used for distillation of commercial linear alkylbenzenes (LAB) or OXO alcohols Suitable distillation steps are described in the hereinabove-referenced Surfactant Science Series, e g , the review of alkylbenzenesulfonate manufacture Sulfonation / Sulfation and Workup
• sulfonation of the modified alkylbenzenes or sulfation of modified primary OXO alcohols (or their alkoxylates) in the instant process can be accomplished using any of the well-known sulfonation systems, including those described in the hereinabove-referenced volume "Detergent Manufacture Including Zeolite Builders and Other New Materials” as well as in the hereinabove-referenced Surfactant Science Series review of alkylbenzenesulfonate manufacture
• Common sulfonation systems include sulfuric acid, chlorosulfonic acid, oleum, sulfur trioxide and the like Sulfur trioxide/air is especially preferred Details of sulfonation using a suitable air/sulfur trioxide mixture are provided in US 3,427,342, Chemithon Sulfonation processes are further extensively described in "Sulfonation Technology in the Detergent Industry", W.H. de Groot, Kluwer Academic Publishers, Boston, 1991.
• any convenient workup steps may be used in the present process.
• Common practice is to neutralize after sulfonation with any suitable alkali.
• the neutralization step can be conducted using alkali selected from sodium, potassium, ammonium, magnesium and substituted ammonium alkalis and mixtures thereof.
• Potassium can assist solubility
• magnesium can promote soft water performance and substituted ammonium can be helpful for formulating specialty variations of the instant surfactants.
• the invention encompasses any of these derivative forms of the modified alkylbenzenesulfonate surfactants, or of the sulfated modified primary OXO alcohols, or of the alkoxylated, sulfated modified primary OXO alcohols as produced by the present process and their use in consumer product compositions.
• the acid form of the present surfactants can be added directly to acidic cleaning products, or can be mixed with cleaning ingredients and then neutralized. Post-alkylation steps
• the modified alkylbenzene manufacturing process herein includes embodiments having steps that take place subsequent to the alkylation step (c). These steps preferably include (d) sulfonating the product of step (c); and one or more steps selected from (e) neutralizing the product of step (d); and (f) mixing the product of step (d) or (e) with one or more cleaning product adjunct materials; thereby forming a cleaning product. Blended Embodiments
• modified alkylbenzene which is the product of said step (c) is blended with a linear alkylbenzene produced by a conventional process.
• modified alkylbenzene sulfonate which is the product of said step (d) is blended with a linear alkylbenzene produced by a conventional process.
• a preferred process has a ratio of modified alkylbenzene to linear alkylbenzene of from about 10:90 to about 50:50.
• Corresponding blending schemes are of course likewise applicable to modified primary OXO alcohol processes herein.
• any blends can be made of the different types of surfactant, or their precursors, herein.
• the practitioner can freely blend modified alkylbenzene with modified primary OXO alcohol as made herein, alkoxylate the mixture using ethylene oxide, propylene oxide, etc., and then sulfate / sulfonate the resulting mixture.
• modified OXO alcohols can be separated by distillation and various other OXO alcohols including linear OXO alcohol types are known from the art
• the present invention also includes processes of blending any of the modified or branched OXO alcohols attainable herein with any known linear OXO alcohol in any proportion, such as from about 1 : 100 to about 100: 1 by weight branched:linear OXO alcohol, and of converting any of such OXO alcohol blends to surfactants useful for detergents.
• the present invention also encompasses a process for beneficiating an effluent stream from the manufacture of linear alkylbenzenesulfonate surfactants useful in cleaning products, said process comprising (i) at least partially separating an isoparaffin into a normal paraffin enriched stream and an effluent stream having the form of an isoparaffin (especially methyl branched paraffin) enriched stream comprising at least about 10% isoparaffin and having molecular weight of at least about 128 and no more than about 282 wherein said separation comprises at least one step selected from clathration by means of urea and separation by means of sorption and wherein said steps are integral in a process for linear alkylbenzene manufacture; (ii) at least partially further enriching the isoparaffin content of said effluent stream by at least one step selected from urea clathration and adsorptive separation; wherein said step is additional to and follows step (i); and (iii) a step of at least partially dehydrogenating the isopar
• hydrocarbons produced herein can be useful not only in modified alkylbenzenesulfonate surfactants as nonlimitingly illustrated herein but also in modified surfactants other than alkylbenzenesulfonates (such as alkyl sulfates).
• the present invention also encompasses a process for beneficiating a branched paraffinic effluent stream comprising (i) at least partially separating an isoparaffin into a normal paraffin enriched stream and an effluent stream having the form of an isoparaffin enriched stream comprising at least about 10% isoparaffin wherein said separation comprises at least one step selected from clathration by means of urea and separation by means of sorption; (ii) at least partially further enriching the isoparaffin content of said effluent stream by at least one step selected from urea clathration and adsorptive separation; wherein said step is additional to and follows step (i); and (iii) a step of at least partially dehydrogenating the isoparaffin enriched stream of said step (ii).
• the isoparaffin enriched stream may vary from about CIO to about C20 in overall carbon content and the nonlinear fraction of said enriched stream comprises an average of from about one to about two methyl side chains other than terminal methyl side-chains per molecule and further, the nonlinear fraction of said enriched stream preferably comprises less than about 30%, more preferably less than about 10%, more preferably still less than about 1% of molecules having quaternary carbon atoms and less than 50%, preferably less than about 10%, more preferably less than about
• the present invention also has process embodiments involving converting hydrocarbons, via certain sorptive separation selections, into new and useful modified primary OXO alcohols which can be used to make exceptionally soluble sulfates, poly(alkoxy)sulfates, and poly(alkoxylates).
• modified versions of any other surfactant types known in the art to be derivable from OXO alcohols are, of course, included in the present invention.
• a preferred process herein has in stage (A) means comprising one, two or more of said devices and at least two of said beds, at least one of said beds comprising said porous media differentiated relative to the porous media contents of another of said beds by an increased capacity to retain methyl-branched acyclic aliphatic hydrocarbons.
• said stage (D) comprises a one-step OXO stage wherein said OXO catalyst is a phosphine-coordinated transition metal other than iron.
• At least one of said beds comprises porous media conventional for the manufacture of linear alkylbenzenes; said at least one bed having a connection into said process suitable for at least partially increasing the proportion of methyl-branched acyclic aliphatic hydrocarbons in streams passing to said stage (B) of said process, and suitable for at least partially decreasing the proportion of linear acyclic aliphatic hydrocarbons passing to said stage (B) of said process, said linear acyclic aliphatic hydrocarbons being at least partially being removed as the linear-enriched stream in said stage (A).
• said simulated moving bed adsorptive separation means in said stage (A) comprise - one of said device, provided that said device is capable of simulating movement of said porous media in at least two of said at least one bed; or- at least two of said device.
• Fig. 9 wherein unit SOR 4/5 comprises one type of porous media as defined in more detail elsewhere herein, and unit SOR 5/7 comprises another type.
• the "devices" referred to can especially be chosen from special rotary valve devices, as described in detail in various patents identified in the "Background Art” section. See also Fig.
• the present invention accordingly also encompasses a process of the OXO-alcohol producing type wherein said linear-enriched stream is present in said stage (A) and said stage (A) comprises: (A-i) adsorptive separation of said hydrocarbon feed into said linear- enriched stream and an intermediate branched-enriched stream and rejection of said linear- enriched stream by means of one of said simulated moving bed adsorptive separation means; followed by (A-ii) adsorptive separation of said intermediate branched-enriched stream into said branched-enriched stream comprising an increased proportion of branched acyclic aliphatic hydrocarbons relative to said intermediate branched-enriched stream, and said reject stream comprising at least an increased proportion of cyclic and/or aromatic hydrocarbons relative to said branched -enriched stream, by means of another of said simulated moving bed adsorptive separation means.
• all of said beds comprises porous media not conventional for the manufacture of linear alkylbenzenes (for example a SAPO-11 containing unit SOR 5/7 or other equivalent molecular sieve of a pore size larger than is used in making linear alkylbenzenes) said porous media having pore sizes suitable for, and being connected into said process, in a manner consistent with at least partially increasing the proportion of methyl-branched plus linear acyclic aliphatic hydrocarbons in streams passing to said step (B) of said process, and at least partially decreasing the proportion of cyclic, aromatic and/or ethyl-branched or higher, aliphatic hydrocarbons passing to said step (B) of said process, said hydrocarbons other than said linear- and methyl-branched hydrocarbons being at least partially being removed as a reject stream in said stage (A).
• porous media not conventional for the manufacture of linear alkylbenzenes (for example a SAPO-11 containing unit SOR 5/7 or other equivalent molecular sieve of a
• said hydrocarbon feed comprises at least about 10% methyl-branched paraffins having molecular weight of at least about 128 and no more than about 282. See the tables elsewhere herein for additional description of suitable feeds.
• Crude feed materials in the OXO-alcohol processes herein are desirably distilled before use.
• the hydrocarbon feed (as it proceeds from such a distillation unit into the remainder of the process) comprises a narrow cut of not more than about three carbon atoms (preferably not more than about two carbon atoms) in the range C I O to C17.
• Such cuts can be single carbon cuts, two- carbon cuts, three-carbon cuts, or cuts comprising a nonexact range of carbon numbers, such as a one-and-one-half carbon cut.
• Suitable cuts are further illustrated by a C11-C13 cut, a C14-C15 cut, and a C 15-C17 cut, though it is not intended to exclude other cuts such as a C 16.5 cut.
• Such cuts designated by nonintegral carbon numbers can be generated by any means, such as blending shorter and longer single carbon number fractions.
• a C16.5 cut can be made by blending C 16 and C17 or by blending C14 and C17, etc.
• Preferred cuts have narrower "spread" of carbon numbers in a blend.
• the distillation could be performed directly on the olefinic branced enriched stream just before the oxo reaction on the olefinic branced enriched stream to produce the desired cut.
• said hydrocarbon feedstock is an adsorptive separation raffinate deriving from a linear alkylbenzene manufacturing process or from a conventional linear detergent alcohol process.
• the present invention opens up all manner of new possibilities for combining linear alkylbenzene manufacturing and/or conventional linear detergent alcohol process and OXO alcohol manufacturing in a manner not hitherto accomplished. This results in better utilization of the feeds.
• new alkylbenzenes and OXO alcohols are accessible. These can be made on their own, or can be made in any permutation with conventional linear alkylbenzenes and/or OXO alcohols by configuring the plant appropriately using the steps taught herein.
• the modified primary OXO alcohol can of course be converted in the same plant or at a remote facility to another useful derivative.
• the present process can have the additional stage or stages in sequence selected from: (E) sulfating and neutralizing the product of said stage (D);(F) alkoxylating the product of said stage (D); and (G) alkoxylating, sulfating and neutralizing the product of said stage (D).
• surfactant derivatives of the above kinds can readily be incorporated into all manner of cleaning compositions.
• the present process can have the additional step of (H) mixing the product of the preceding stages with one or more cleaning product adjunct materials; thereby forming a cleaning product.
• the invention encompasses any consumer cleaning product produced by the above-described processes that include the specific OXO alcohol manufacture shown herein, followed by a stage comprising admixing at least one cleaning product adjunct ingredient.
• the processes herein include those in which prior to said OXO stage, (D), the product of said stage (B) or (C) is blended with a conventional detergent olefin; or wherein the product of any of said stages (E), (F) or (G) are blended with a conventional detersive surfactant.
• one such nonlimiting process according to the invention further comprising at least one stage of reacting the product of stage (A) with an aromatic hydrocarbon selected from the group consisting of benzene, toluene and mixtures thereof in the presence of an alkylation catalyst; for making modified (crystallinity-disrupted) alkylbenzenes, said alkylation catalyst has an internal isomer selectivity of from 0 to 40.
• Ramifications include providing means are provided to route the product of stage (C) to stage (D), to said alkylation step, or to both of said stages in parallel.
• the invention also encompasses a detergent or cleaning composition
• a detersive surfactant selected from alkyl sulfates, alkylpoly(alkoxy)sulfates, alkylpoly(alkoxylates) and mixtures thereof, said surfactant incorporating (preferably in an amount of up to one
• Cleaning product embodiments of the present invention include laundry detergents, dishwashing detergents, hard surface cleaners and the like.
• the content of modified alkylbenzenesulfonate or surfactant derived from modified primary OXO alcohol produced by the instant process is from about 0.1% to about 99.9%, typically from about 1% to about 50%, and the composition further comprises from about 0.1%) to about 99.9%, typically from about 1 % to about 50%, of cleaning product adjunct materials such as cosurfactants, builders, enzymes, bleaches, bleach promoters, activators or catalysts, and the like.
• the present invention also encompasses a cleaning product formed by the instant process comprising: (a) from about 0.1% to about 99.8%, more typically up to about 50%, of modified alkylbenzenesulfonate surfactant or modified primary OXO alcohol derived surfactant such as modified alkyl sulfate, modified poly(alkoxy)sulfate etc., as prepared herein and (b) from about 0.00001%), more typically at least about 1%, to about 99.9% of one or more of said cleaning product adjunct materials.
• Adjunct materials can vary widely and accordingly can be used at widely ranging levels.
• detersive enzymes such as proteases, amylases, cellulases, lipases and the like as well as bleach catalysts including the macrocyclic types having manganese or similar transition metals all useful in laundry and cleaning products can be used herein at very low, or less commonly, higher levels.
• bleaches especially the oxygen bleach types including activated and catalyzed forms with such bleach activators as nonanoyloxybenzenesulfonate and/or tetraacetylethylenediamine and/or any of its derivatives or derivatives of phthaloylimidoperoxycaproic acid or other imido- or amido- substituted bleach activators including the lactam types, or more generally any mixture of hydrophilic and/or hydrophobic bleach activators (especially acyl derivatives including those of the C6-C16 substituted oxybenzenesulfonates); preformed peracids related to or based on any of the hereinbefore mentioned bleach activators, builders including the insoluble types such as zeolites including zeolites A, P and the so-called maximum aluminum P as well as the soluble types such as the phosphates and polyphosphates, any of the hydrous, water-soluble or water-insoluble silicates, 2,2'-oxydisuccin.
• bleach activators especially the
• any of the anhydrous, hydrous, water-based or solvent-borne cleaning products are readily accessible as granules, tablets, powders, flakes, gels, extrudates, pouched or encapsulated forms or the like.
• the present invention also includes the various cleaning products made possible or formed by any of the processes described. These may be used in discrete dosage forms, used by hand or by machine, or may be continuously dosed into all suitable cleaning appliances or delivery devices.
• the surfactant compositions prepared by the processes of the present invention can be used in a wide range of consumer cleaning product compositions including powders, granules, gels, pastes, tablets, pouches, bars, types delivered in dual-compartment containers, spray or foam detergents and other homogeneous or multiphasic consumer cleaning product forms.
• They can be used or applied by hand and/or can be applied in unitary or freely alterable dosage, or by automatic dispensing means, or are useful in appliances such as washing- machines or dishwashers or can be used in institutional cleaning contexts, including for example, for personal cleansing in public facilities, for bottle washing, for surgical instrument cleaning or for cleaning electronic components
• They can have a wide range of pH, for example from about 2 to about 12 or higher, and they can have a wide range of alkalinity reserve which can include very high alkalinity reserves as in uses such as drain unblocking in which tens of grains of NaOH equivalent can be present per 100 grams of formulation, ranging through the 1-10 grams of NaOH equivalent and the mild or low- alkalinity ranges of liquid hand cleaners, down to the acid side such as in acidic hard- surface cleaners Both high-foaming and low-foaming detergent types are encompassed.
• Heavy Duty Liquid Detergents these compositions include both the so- called “structured” or multi-phase (see for example US 4,452,717; US 4,526,709; US 4,530,780, US 4,618,446, US 4,793,943, US 4,659,497, US 4,871 ,467, US 4,891, 147; US 5,006,273, US 5,021 , 195, US 5, 147,576, US 5, 160,655) and "non-structured” or isotropic liquid types and can in general be aqueous or nonaqueous (see, for example EP 738,778 A; WO 97/00937 A; WO 97/00936 A; EP 752,466 A; DE 19623623 A; WO 96/10073 A; WO 96/10072 A; US 4,647,393; US 4,648,983; US 4,655,954; US 4,661,280; EP 225,654; US 4,690,771
• Heavy Duty Granular Detergents these compositions include both the so- called “compact” or agglomerated or otherwise non-spray-dried, as well as the so-called “fluffy” or spray-dried types. Included are both phosphated and nonphosphated types.
• Such detergents can include the more common anionic-surfactant based types or can be the so-called "high-nonionic surfactant” types in which commonly the nonionic surfactant is held in or on an absorbent such as zeolites or other porous inorganic salts.
• Softergents include the various granular or liquid (see for example EP 753,569 A; US 4, 140,641 ; US 4,639,321 ; US 4,751,008; EP 315,126; US 4,844,821 ; US 4,844,824; US 4,873,001 ; US 4,91 1 ,852; US 5,017,296; EP 422,787) softening-through-the wash types of product and in general can have organic (e.g., quaternary) or inorganic (e.g., clay) softeners.
• organic e.g., quaternary
• inorganic e.g., clay
• Hard Surface Cleaners these compositions include all-purpose cleaners such as cream cleansers and liquid all-purpose cleaners; spray all-purpose cleaners including glass and tile cleaners and bleach spray cleaners; and bathroom cleaners including mildew-removing, bleach-containing, antimicrobial, acidic, neutral and basic types. See, for example EP 743,280 A; EP 743,279 A. Acidic cleaners include those of WO 96/34938 A.
• Bar Soaps and/or Laundry Bars include personal cleansing bars as well as so-called laundry bars (see, for example WO 96/35772 A); including both the syndet and soap-based types and types with softener (see US 5,500, 137 or WO 96/01889 A); such compositions can include those made by common soap-making techniques such as plodding and/or more unconventional techniques such as casting, absorption of surfactant into a porous support, or the like.
• Other bar soaps see for example BR 9502668; WO 96/04361 A; WO 96/04360 A; US 5,540,852
• Other handwash detergents include those such as are described in GB 2,292, 155 A and WO 96/01306 A.
• Shampoos and Conditioners S&CV (see, for example WO 96/37594 A; WO
• compositions in general include both simple shampoos and the so-called "two-in-one" or "with conditioner” types.
• Liquid Soaps these compositions include both the so-called “antibacterial” and conventional types, as well as those with or without skin conditioners and include types suitable for use in pump dispensers, and by other means such as wall-held devices used institutionally.
• SPCV Special Purpose Cleaners
• bleach pretreatment products for laundry see EP 751,210 A
• fabric care pretreatment products see for example EP 752,469 A
• liquid fine fabric detergent types, especially the high-foaming variety rinse-aids for dishwashing
• liquid bleaches including both chlorine type and oxygen bleach type, and disinfecting agents, mouthwashes, denture cleaners see, for example WO 96/19563 A; WO 96/19562 A
• car or carpet cleaners or shampoos see, for example EP 751,213 A; WO 96/15308 A
• hair rinses, shower gels, foam baths and personal care cleaners see, for example WO 96/37595 A; WO 96/37592 A; WO 96/37591 A; WO 96/37589 A; WO
• Process Integration can be integrated with current LAB manufacturing processes or with conventional linear detergent alcohol process in any convenient manner.
• conventional erected plant can be switched to produce the modified alkylbenzenes and/or modified primary OXO alcohols in their entirety
• plant for the manufacture of the instant modified alkylbenzenes and/or modified primary OXO alcohols may be erected as an addon or complement to an existing LAB facility, or as a stand-alone Both batch and continuous operation of the present process are envisaged
• the present invention encompasses steps of making vinylidene olefin and from the vinylidene olefin, modified alkylbenzene or alkyltoluene and/or modified primary OXO alcohol using the steps described in detail hereinabove
• the modified alkylbenzene or alkyltoluene is blended at a ratio of from about 1 100 to 100 1, more typically from about 1 10 to about 10 1, for example about 1 5, into a conventional linear alkylbenzene, for example a C 1 1 8 average alkylbenzene or any alkylbenzene produced by the DETAL® process
• the blend is then sulfonated, neutralized and incorporated into consumer cleaning product compositions Parallel process stages or alternate process stages lead to modified primary OXO alcohol
• the present invention should not be considered limited by the specifics of its illustration in the specification including the examples given for illustration hereinafter. Most generally, the present invention should be taken to encompass any consumer cleaning composition comprising any surfactant product of any type wherein the hydrophobe of the surfactant has been modified by an approach using the essential teachings of the instant process.
• the present teachings especially with respect to the delinearization approach, are believed to be reapplicable, for example, to the manufacture of modified alkyl sulfates and other surfactants
• This feed contains paraffinic branched and linear hydrocarbons, wherein the linear hydrocarbons are of suitable chainlength for LAB manufacture and wherein the branched hydrocarbons include at least about 10% of methyl branched paraffins, along with cyclic hydrocarbons, aromatics and other impurities
• This stream is passed continuously to two adsorptive separation units, connected as shown in Fig 8 and Fig 1 wherein unit ACl of detail Fig 8 is loaded with 5 Angstrom Ca zeolite as used in conventional linear alkylbenzene manufacture and unit AC2 of detail Fig. 8 is loaded with the silicoaluminophosphate SAPO-1 1.
• the units ACl and AC2 along with the associated rotary valve devices, raffinate columns and extract columns (RC and EC) and condensers (shown as unlabelled horizontal tanks in Fig. 8.) and other means shown, though connected in unique manner, are of construction generally in accordance with units licensable and commercially available through UOP Corp. (MOLEX® units).
• the adsorbate (extract) from the Ca zeolite adsorptive unit AC l is rejected and the raffinate is passed continuously to the second adsorptive separation unit AC2 containing the SAPO- 11.
• the branched-enriched stream taken from unit AC2 as adsorbate or extract is passed to a standard commercial LAB process dehydrogenation unit provided by UOP Corp.
• the above procedure can be repeated except with discharge on reaching a conversion (based on olefin) to the desired modified alkylbenzene of at least about 80%.
• a recycle of paraffins is obtained by distillation at the back-end of the alkylation unit and the recycle is passed back to the dehydrogenator.
• the process to this point includes the steps and streams of Fig. 1.
• the modified alkylbenzene can be further purified by additional conventional distillation (such distillative steps are not shown in Fig. 1).
• the distilled modified alkylbenzene mixture is sulfonated batchwise or continuously, at a remote facility if desired, using sulfur trioxide as sulfonating agent.
• a suitable feedstock is obtained in the form of effluent or raffinate from an LAB plant, specifically the MOLEX ® process unit of such a plant.
• This raffinate contains a high proportion of branched paraffinic hydrocarbons along with undesirable cyclic hydrocarbons, aromatics and other impurities.
• This raffinate is passed continuously to an adsorptive separation unit constructed conventionally, e.g., after the manner of a MOLEX® unit, but having a charge of SAPO- 1 1 .
• This unit operates under conditions generally similar to the MOLEX® unit as used in linear alkylbenzene manufacture and resembles the unit AC2 described in Example 1.
• the raffinate or effluent from the SAPO- 11 adsorptive unit is rejected and the adsorbate or extract now meeting the invention definition of a branched-enriched stream is passed continuously to a standard commercial LAB process dehydrogenation unit provided by UOP Corp. (PACOL® process) charged with a standard LAB dehydrogenation catalyst (e.g., DeH 7 ®) proprietary to UOP Corp.
• LAB dehydrogenation catalyst e.g., DeH 7 ®
• the hydrocarbons are passed continuously to an alkylation unit which is otherwise conventional but is charged with H-mordenite (ZEOCAT ® FM 8/25 H) where alkylation proceeds continuously at a temperature of about 200°C with discharge on reaching an alkylating agent conversion of at least about 90%.
• the modified alkylbenzene mixture is purified by conventional distillation and branched paraffins are recycled to the dehydrogenation unit. Steps in the process to this point follow Fig. 4.
• the distilled modified alkylbenzene mixture produced in process to this point is sulfonated batchwise or continuously, at a remote facility if desired, using sulfur trioxide as sulfonating agent. Details of sulfonation using a suitable air/sulfur trioxide mixture are provided in US 3,427,342, Chemithon.
• the modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to give modified alkylbenzene sulfonate, sodium salt mixture.
• EXAMPLE 3 Modified alkylbenzenesulfonate prepared via hydrocarbon feed sourced from MOLEX ® effluent, separation over pyrolyzed poly(vinylidene chloride), dehydrogenation using standard UOP method, alkylation over H-ZSM-12, sulfonation using sulfur trioxide/air and neutralization
• a suitable feedstock is obtained in the form of raffinate from an LAB plant, specifically the MOLEX® process unit of such a plant. This raffinate contains branched paraffinic hydrocarbons along with cyclic hydrocarbons, aromatics and other undesired impurities.
• This raffinate is passed continuously to an adsorptive separation unit of conventional construction, e.g., MOLEX® type, not conventionally being incorporated in LAB plant design and hereinafter termed the "SARAN ® unit” having a charge of pyrolyzed poly(vinylidene chloride), sieve diameter >5 Angstrom, manufactured according to Netherlands Application NL 71 1 1508 published October 25, 1971.
• SARAN ® unit having a charge of pyrolyzed poly(vinylidene chloride), sieve diameter >5 Angstrom, manufactured according to Netherlands Application NL 71 1 1508 published October 25, 1971.
• the "SARAN unit” operates under conditions similar to the MOLEX® unit.
• the raffinate from the "SARAN unit” is rejected and the adsorbate is passed continuously to a standard commercial LAB process dehydrogenation unit provided by UOP Corp.
• the modified alkylbenzene mixture produced in the preceding step is distilled and sulfonated batchwise or continuously using sulfur trioxide as sulfonating agent. Details of sulfonation using a suitable air/sulfur trioxide mixture are provided in US 3,427,342, Chemithon.
• the modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to give modified alkylbenzene sulfonate, sodium salt mixture.
• EXAMPLE 4 Modified alkylbenzenesulfonate prepared via hydrocarbon feed from urea clathration, separation over SAPO-1 1, dehydrogenation using Pt catalyst, alkylation over acidic zeolite beta, sulfonation using sulfur trioxide/air and neutralization
• a suitable feedstock is obtained from kerosene by urea clathration which is used to remove a fraction rich in the more commercially valuable linear hydrocarbons. See US 3,506,569.
• the low-grade branched effluent from the urea clathration stage is a suitable hydrocarbon feed for the present process.
• SAPO-1 1 is stripped of any activator solvent such as methanol, if present, and is passed continuously to an adsorptive separation unit constructed in any conventional manner, for example after the fashion of MOLEX® process units, but differently charged, having a charge of SAPO-1 1
• the SAPO-11 unit operates under conditions similar to a standard MOLEX® process unit.
• the raffinate from the SAPO-1 1 unit is rejected and the adsorbate is passed continuously to a standard commercial LAB process dehydrogenation unit provided by UOP Corp. (PACOL® process) charged with a nonproprietary Platinum dehydrogenation catalyst.
• the hydrocarbons are passed continuously to an alkylation unit which is otherwise conventional but is charged with Zeocat PB/H* where alkylation proceeds continuously at a temperature of about 200°C with discharge on reaching a conversion of the input hydrocarbon of at least about 90%.
• the modified alkylbenzene mixture produced in the preceding step is sulfonated batchwise or continuously using sulfur trioxide as sulfonating agent. Details of sulfonation using a suitable air/sulfur trioxide mixture are provided in US 3,427,342, Chemithon.
• the modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to give modified alkylbenzene sulfonate, sodium salt mixture.
• EXAMPLE 5 Modified alkylbenzenesulfonate prepared via hydrocarbon feed from kerosene cut from a high paraffinic petroleum source, separation over grafted nonacidic zeolite, dehydrogenation using DeH 9 ® catalyst, alkylation over H-mordenite, sulfonation using chlorosulfonic acid, and neutralization
• a jet/kerosene cut is taken from a low-viscosity crude, e.g., Brent light. This is passed continuously to an adsorptive separation unit constructed in any conventional manner, for example after the fashion of MOLEX® process units, but differently charged, having a charge of grafted zeolite prepared in accordance with US 5,326,928. The unit operates under conditions similar to a conventionally charged MOLEX® unit. The raffinate from this unit is rejected and the adsorbate is passed continuously to a standard commercial
• LAB process dehydrogenation unit provided by UOP Corp. (PACOL® process) charged with a standard LAB dehydrogenation catalyst DeH 9 ® proprietary to UOP Corp.
• the hydrocarbons are passed continuously to an alkylation unit which is otherwise conventional but is charged with H-mordenite (ZEOCAT FM 8/25 H) where alkylation proceeds continuously at a temperature of about 200°C with discharge on reaching a conversion of the input hydrocarbon of at least about 90%.
• the modified alkylbenzene mixture produced in the preceding step is sulfonated batchwise or continuously using sulfur trioxide as sulfonating agent. Details of sulfonation using a suitable air/sulfur trioxide mixture are provided in US
• modified alkylbenzenesulfonic acid product of the preceding step is neutralized with sodium hydroxide to give modified alkylbenzene sulfonate, sodium salt mixture.
• amylase is selected from: Fungamyl®;
• Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
• Brightener 1 Disodium 4.4'-bis(2-sulphostyryl)biphenyl
• Brightener 2 Disodium 4.4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate
• Cellulase Cellulolytic enzyme 1000 CEVU/g, NOVO, Carezyme®
• Citrate Trisodium citrate dihydrate 86.4%.425 ⁇ m - 850 ⁇ m
• CxyAS Alkyl sulfate, Na salt or olhcr salt if specified having an average total carbon range of alkyl moiety from 10+x to 10+y CxyEz
• Diamine Alkyl diamine e.g., 1,3 propancdiamine, Dytck EP, Dytek A,
• Blend of SE-76 dimethicone gum (G.E
• Endolase Endoglucanase activity 3000 CEVU/g, NOVO EtOH Ethanol
• Lipase Lipolytic enzyme , lOOkLU/g, NOVO, Lipolase ⁇ .
• the lipase is selected from: Amano-P; Ml Lipase®; Lipomax®;
• Humicola lanuginosa as described in US Serial No. 08/341,826; and the Humicola lanuginosa strain DSM 4106.
• Bcyclam 5,12-di ⁇ nethyl-l,5,8,12-tetraaza-b ⁇ cyclo[6.6.2]hexadecane or a comparable bridged tetra-aza macrocycle
• Protease Proteolytic enzyme 4KNPU/g, NOVO, Savinase®®.
• the protease is selected from: Maxatase®; Maxacal®; Maxapem 15®; subtilisin BPN and BPN'; Protease B; Protease A; Protease D; Primase®; Durazym®; Opticlean®;and Optimase®; and Alcalase ®-
• Silicate Sodium Silicate, amorphous (Si0 2 :Na 2 0; 2.0 ratio) Silicone antifoam Polydimethylsiloxane foam controller + siloxane-oxyalkylene copolymer as dispersing agent; ratio of foam controlle ⁇ dispersing agent 10: 1 to 100: 1 ; or, combination of filmed silica and high viscosity polydimethylsiloxane (optionally chemically modified)
• Solvent nonaqueous solvent e.g., hcxylene glycol, see also propylene glycol
• Zeolite A Hydrated Sodium Aluminosilicate. Na ⁇ (A 10 2 SiO 2 ) ⁇ 2 .
• Typical ingredients often referred to as “minors” can include perfumes, dyes, pH trims etc.
• the following example is illustrative of the present invention, but is not meant to limit or otherwise define its scope. All parts, percentages and ratios used are expressed as percent weight unless otherwise noted.
• the following laundry detergent compositions A to F are prepared in accordance with the invention:
• EXAMPLE 9 In the present Example, a branched-enriched hydrocarbon stream is made and it is dehydrogenated, subjected to hydroformylation to make a modified primary OXO alcohol, ethoxylated and sulfated A suitable crude hydrocarbon feed is obtained in the form of a jet/diesel or kerosene distillation cut.
• This feed is low in sulfur, nitrogen and aromatics (to the extent that these are known to have some adverse effect on lifetime of MOLEX ® and OLEX ® adsorbent beds) and contains paraffinic branched and linear hydrocarbons, wherein the linear hydrocarbons are of suitable chainlength for detergent manufacture and wherein the branched hydrocarbons include at least about 10% of methyl branched paraffins; along with cyclic hydrocarbons, aromatics and other impurities.
• the crude hydrocarbon feed is distilled to obtain a two-carbon cut at about C14 - C15. This forms a suitable hydrocarbon feed for the rest of the process. See Fig. 10, stream 1.
• the distilled hydrocarbon feed is passed continuously to two adsorptive separation units, connected as shown in Fig. 10 wherein unit SOR 4/5 is loaded with 5 Angstrom Ca zeolite as used in conventional linear alkylbenzene manufacture, and unit SOR 5/7 is loaded with the silicoaluminophosphate SAPO-1 1.
• the general construction of the units SOR 4/5 and SOR 5/7 and ancilliary equipment not shown in Fig. 10 is in accordance with units licensable and commercially available through UOP Corp. (MOLEX® units).
• the linear-enriched stream (stream 6 in Fig. 10, rich in linear hydrocarbon) from the Ca zeolite MOLEX ® unit SOR 4/5 is rejected and the intermediate branched-enriched stream (stream 2 in Fig. 10, enriched in branched hydrocarbon) is passed continuously to the second adsorptive separation unit SOR 5/7 containing the SAPO-1 1.
• the branched- enriched stream taken from unit SOR 5/7 as adsorbate or extract (stream 3 in Fig. 10, more branched hydrocarbon) is passed to a standard commercial LAB process dehydrogenation unit (DEH in Fig. 10) provided by UOP Corp.
• OXO proceeds continuously with discharge on reaching a selectivity to the modified primary OXO alcohol of at least about 90%o, and essentially all the olefin of the input stream has reacted
• a small amount of reduction also occurs to form paraffin
• the paraffins are separated by distillation and can be recycled to the dehydrogenator
• the process to this point includes the steps and streams of Fig. 10
• the modified primary OXO alcohol (stream 57 in Fig 10) is ethoxylated to an average of one mole of ethylene oxide content Alternatively ethoxylation, propoxylation etc.
• alkyl chain length of the hydrocarbon can be varied so as to produce the desired chainlength modified OXO alcohol derived surfactants as used in the formulation Examples
• the modified OXO alcohol can be sulfated without any prior alkoxylation EXAMPLE 10
• bleach-containing nonaqueous liquid laundry detergent is prepared having the composition as set forth in the following Table
• Brightener 1 0.4 0-0.6
• the resulting composition is an anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations.
• liquid detergent compositions (A-D) are found to be very efficient in the removal of a wide range of stains and soils from fabrics under various usage conditions
• EXAMPLE 12 The following compositions (E to J) are heavy duty liquid laundry detergent com ositions accordin to the resent invention
• EXAMPLE 13 Aqueous based heavy duty liquid laundry detergent compositions K to O which comprise the mid-chain branched surfactants of the resent invention are resented below.
• EXAMPLE 14 The following aqueous liquid laundry detergent compositions P to T are prepared in accord with the invention:
• EXAMPLE 18 The following high density detergent formulations U to X, according to the present invention, are prepared
• hydrocarbon feeds as already illustrated herein.
• Alternate hydrocarbon feeds that can be used in this process include mixtures of specific types of paraffins and/or mono-olefins. These hydrocarbon mixtures can be selected from:
• More highly preferred paraffins have only H, methyl, ethyl, propyl or butyl in R, Rl, and R ⁇ , more preferably only H and methyl, provided R, ⁇ and R ⁇ include at least one alkyl moiety, and methyl, when present, is preferably internal, that is, removed as much as possible from the 1-, 2- and preferably even 3- carbon positions in the longest countable chain
• hydrocarbons herein also encompass
• a mixtures of mono-olefins are related to the paraffins of A above, in that any of the suitable mono-olefins can be made by dehydrogenating any of the paraffins of A above (In practice, one can first isolate suitable olefins, then hydrogenate them to the paraffins)
• the preferred olefins are mono-olefins, though in general, up to about 10% by weight of the olefinic hydrocarbon can be diolefins, after dehydrogenation of suitable paraffins
• the olefins herein can vary widely in structure, for example, possible mono-olefins are
• hydrocarbons herein also encompass
• hydrocarbon mixtures herein can be in any possible combination, and can, for example, be a result of combining compositions containing only paraffins, only olefins, or paraffin/olefin mixtures in any proportion
• the mixtures can be derived "inherently" as a consequence of the hydrocarbon coming from a natural, e g , geologically sourced petroleum raw material (e.g., light crude or kerosene or jet/diesel fuels distilled therefrom), typically with some treatment of such material (for example by fractionation, selective sorption, distillation, clathration etc.) to isolate preferred hydrocarbon mixtures.
• the mixtures can be made up by progressively mixing more complex mixtures from a series of compositionally simple hydrocarbons.
• the present hydrocarbon mixtures can also derive from any synthetic transformation known in petroleum chemistry, for example cracking, hydrocracking, hydroisomerisation, hydrogenation, dimerization, dehydrogenation, isomerization, disproportionation, and the like.
• equivalent compositions can more painstakingly be built up by means of known organic synthetic schemes, for example those involving Grignard reactions. Catalytic isomerizations on zeolites and modified zeolites can be particularly useful.
• Hydrocarbon mixtures useful herein can further include:
• hydrocarbons herein also encompass:
• One group of preferred paraffins have the formula selected from:
• the present hydrocarbon compositions can accommodate varying amounts of impurities (say up to about 20%, preferably below about 1 %), such as impurities in which one or more ether or alcohol oxygen atoms are present or interrupt the carbon chain(so called “oxygenated” impurities); or impurities in which moieties such as aryl, arylalkyl or alkaryl are attached to the carbon chain as the branches, or impurities in which quaternary carbon atoms are present, or diolefins, or impurities in which nonhydrogen moieties are attached to adjacent carbon atoms.
• impurities are of course not desired. It is especially preferred to limit any impurities known to adversely affect biodegradation or to produce malodors.
• Preferred paraffins and/or olefins herein may contain varying amounts of nonalkylbenzene aromatic, cycloalkyl and alkyl cycloalkyl impurities, though these are more desirably removed, for example by known sorption steps.
• Preferred paraffins and/or olefins herein can contain some sulfur and/or nitrogen, but these can produce objectionable odors and for this or other reasons are preferably removed by any of the desulfurization and/or nitrogen removal techniques well known in the petroleum industry.
• Preferred olefins are closely related to the paraffins above: they have structures formed by dehydrogenating any of the paraffins in any accessible position to form the corresponding mono-olefin.
• Especially preferred olefins are monomethyl-branched and dimethyl-branched, particularly monomethyl-branched. It should be understood and appreciated that the underlying concept being taught for how to select preferred paraffins and olefins for best results herein involves several features including:
• hydrophobes for highly soluble hardness resistant , cold water tolerant "modified" surfactants including the alkylbenzenes and oxo alcohols.
• these hydrocarbon mixtures can be broadly used in the production of modified surfactants. They can be used to prepare the modified alkyl sulfates, alkyl alkoxylates, alkylalkoxy sulfates or alkylaryl sulfonates, such as alkylbenzene sulfonates.
• the alkyl sulfates, alkyl alkoxylates, alkylalkoxy sulfates are prepared by first converting the hydrocarbon mixtures in to the corresponding alcohol and then optionally sulfating and/or alkoxylating the alcohol.
• the alcohol can be formed by any conventional means, such as by the oxo process. And similarly the sulfation and/or alkoxylation can be by conventional means.
• the alkylbenzene sulfonates are formed by alkylating benzene with the olefinic containing hydrocarbon mixtures and then sulfonating the resulting alkylbenzene.
• the alkyl benzene sulfonates formed are the so-called "modified alkyl benzene sulfonate".

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Analytical Chemistry (AREA)
• Water Supply & Treatment (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Detergent Compositions (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=22271511

Family Applications (1)

Country Status (14)

Families Citing this family (15)

Family Cites Families (7)

• 1999
  • 1999-09-01 EP EP99946725A patent/EP1109764A1/en not_active Withdrawn
  • 1999-09-01 KR KR10-2004-7006602A patent/KR20040053247A/ko not_active Application Discontinuation
  • 1999-09-01 TR TR2001/00644T patent/TR200100644T2/ unknown
  • 1999-09-01 JP JP2000567488A patent/JP2002523480A/ja not_active Withdrawn
  • 1999-09-01 CZ CZ2001715A patent/CZ2001715A3/cs unknown
  • 1999-09-01 HU HU0103529A patent/HUP0103529A3/hu unknown
  • 1999-09-01 KR KR10-2004-7006611A patent/KR20040053249A/ko not_active Application Discontinuation
  • 1999-09-01 KR KR1020017002767A patent/KR20010087304A/ko not_active Application Discontinuation
  • 1999-09-01 AU AU59070/99A patent/AU763208B2/en not_active Ceased
  • 1999-09-01 BR BR9913663-5A patent/BR9913663A/pt not_active IP Right Cessation
  • 1999-09-01 ID IDW20010525A patent/ID28647A/id unknown
  • 1999-09-01 CN CN99812993A patent/CN1325372A/zh active Pending
  • 1999-09-01 CA CA002341224A patent/CA2341224A1/en not_active Abandoned
  • 1999-09-01 WO PCT/US1999/020124 patent/WO2000012451A1/en not_active Application Discontinuation
  • 1999-09-02 MA MA25752A patent/MA24994A1/fr unknown
  • 1999-09-02 EG EG109699A patent/EG22509A/xx active

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events