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WO2003096807A1 - Preparations pour l'agriculture contenant des tensio-actifs ameliores - Google Patents

Preparations pour l'agriculture contenant des tensio-actifs ameliores Download PDF

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Publication number
WO2003096807A1
WO2003096807A1 PCT/US2002/015278 US0215278W WO03096807A1 WO 2003096807 A1 WO2003096807 A1 WO 2003096807A1 US 0215278 W US0215278 W US 0215278W WO 03096807 A1 WO03096807 A1 WO 03096807A1
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WIPO (PCT)
Prior art keywords
composition according
ofthe
surfactant component
group
emulsifiable concentrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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PCT/US2002/015278
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English (en)
Inventor
Curtis M. Elsik
Howard M. Stridde
George A. Smith
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Huntsman Specialty Chemicals Corp
Huntsman Petrochemical LLC
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Huntsman Specialty Chemicals Corp
Huntsman Petrochemical LLC
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Priority to PCT/US2002/015278 priority Critical patent/WO2003096807A1/fr
Priority to AU2002316112A priority patent/AU2002316112A1/en
Publication of WO2003096807A1 publication Critical patent/WO2003096807A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • This invention relates generally to agricultural formulations having enhanced
  • the invention relates more particularly to
  • an aromatic material such as benzene,
  • toluene, ethylbenzene, or naphthalene may be alkylated and sulfonated to provide a
  • surfactant useful in agricultural formulations according to the invention.
  • Saponification is essentially a process
  • aqueous alkali metal hydroxide is mixed with an ester (such as an animal fat or
  • carboxylic acid(s) include as part of their molecular structure a hydrophilic portion, i.e.,
  • hydrophobic portion as part of their molecular structure, which is typically a
  • hydrocarbon-based portion containing between about 12 and 22 carbon atoms per
  • salts are commonly referred to by those skilled in the art as “salts of fatty acids”, and by laypersons as “soap”.
  • Aqueous solutions of salts of fatty acids are well-
  • chain ofthe alkyl substituent on the ring structure is selected to provide a high level of
  • substituent may typically contain 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,
  • alkylbenzene isomer being produced in each such case. Sulfonation of such a variety of
  • the sulfonates ofthe 2-phenyl alkyl isomers are highly desirable materials, as
  • phenyl alkyl materials have superior surfactancy when compared with the sulfonation
  • alkylbenzenes results from such alkylation, depending upon the process conditions.
  • alkyltoluenes which are linear alkylbenzenes as structurally defined above
  • isomer content possess unique physical properties making them particularly useful as
  • the present invention is in one
  • surfactant range having an enhanced 2-phenyl isomer content having an enhanced 2-phenyl isomer content; or 2) a surfactant
  • alkylbenzenes and alkyltoluenes result.
  • alkylating with a mixture of mono- olefins in the surfactant range a mixture of alkyltoluenes and alkylbenzenes results,
  • phenyl alkylbenzene 4-toluyl alkyltoluene, 5-phenyl alkylbenzene, 5-toluyl alkyltoluene,
  • 6-phenyl alkylbenzene 6-toluyl alkyltoluene, etc.
  • alkylbenzenes or "LAB's” interchangeably with their sulfonates.
  • alkyltoluenes may be referred to as "LAT's”.
  • isomer in such reactions as known in the prior art is low, generally being about 30% or less.
  • benzene is a toxic material which requires
  • aqueous solution is its solubility.
  • Formulations generally need to have a high degree of
  • Surfactant molecules generally comprise a hydrophobic
  • the surfactant becomes less soluble in water.
  • the surfactant becomes more water soluble as
  • the hydrophilic group becomes more water soluble.
  • linear alkylbenzene sulfonate and linear
  • alkyltoluene sulfonate surfactants are provided, wherein the aromatic nucleus is appended to
  • the surfactant range olefin may
  • the surfactant range alkyl group on the ring are themselves ortho, para directors.
  • the present invention provides a method and catalyst for LAB (linear
  • phenyl alkylbenzenes and/or 2-toluyl alkyltoluenes may be readily produced having 2-
  • the present invention provides agriculturally-useful compositions
  • the aromatic nucleus may comprise any number of carbon atoms in the surfactant
  • alkyltoluene or alkylbenzene isomers present have the aromatic group attached to the
  • alkylbenzene isomers present have the aromatic group attached to the hydrocarbon group in the 2 position ofthe hydrocarbon group.
  • the invention has an enhanced 2-isomer content, and such surfactant components
  • the invention further provides pesticide compositions and formulations which are
  • a surfactant component that includes either: a) an alkyltoluene sulfonate
  • isomers comprise any percentage between 40.0% and 80.0%, including every hundredth
  • alkyltoluene sulfonate component or b) an alkylbenzene sulfonate comprising 2-phenyl
  • alkylbenzene sulfonates in which 2-phenyl alkylbenzene sulfonate isomers comprise any
  • invention provides pesticide compositions and formulations which are formed using a
  • surfactant component that comprises one, or a mixture of, the following: 1) a first
  • surfactant component which comprises: a) a first alkyltoluene sulfonate component
  • isomers comprise any percentage between 40.0% and 80.0%, including every hundredth
  • alkyltoluene sulfonate component or b) a first alkylbenzene sulfonate component comprising 2-phenyl alkylbenzene sulfonates in which 2-phenyl alkylbenzene sulfonate
  • isomers comprise any percentage between 40.0% and 80.0%, including every hundredth
  • alkylbenzene sulfonate component or c) any combination of a) and b); and 2) a second
  • surfactant component which may comprise: a) alkylbenzene sulfonates in which isomers
  • alkyl group's 2 position comprise at least 60 % of all alkylbenzene
  • alkyl group's 2 position comprise at least 80 % of all alkylbenzene sulfonate isomers
  • toluene nucleus attached to a linear alkyl group at a position other than the alkyl group's 2
  • lower activity isomers (those isomers other
  • the second surfactant component may be any suitable surfactant component.
  • the second surfactant component may be any suitable surfactant component.
  • the second surfactant component may be any surfactant component.
  • the second surfactant component may be any surfactant component.
  • the second surfactant component may be any surfactant component.
  • the second surfactant component may be any surfactant component.
  • agricultural formulation according to the invention may contain sulfonated 2-phenyl
  • alkyltoluenes in an amount of at least 30.00 % by weight based upon the total weight of
  • alkyltoluene the sulfonated alkyltoluene component.
  • alkyltoluene an alkyltoluene
  • sulfonate surfactant component may contain sulfonated 2-phenyl alkyltoluenes in an
  • alkyltoluene component in yet another form ofthe invention, an alkyltoluene sulfonate
  • surfactant component may contain sulfonated 2-phenyl alkyltoluenes in an amount of at
  • an alkyltoluene sulfonate surfactant in yet another form ofthe invention, an alkyltoluene sulfonate surfactant
  • component may contain sulfonated 2-phenyl alkyltoluenes in an amount of at least 60.00 % by weight based upon the total weight ofthe sulfonated alkyltoluene component.
  • an alkyltoluene sulfonate surfactant component may
  • an alkyltoluene sulfonate surfactant component may
  • detergents a mixture of sulfonated alkylbenzenes and sulfonated alkyltoluenes useful as
  • alkyltoluenes are useful as components in forming agricultural compositions useful in a
  • an existing facility may be
  • a slip in one embodiment, can instead produce high 2-isomer at its discretion.
  • a slip in one embodiment, can instead produce high 2-isomer at its discretion.
  • stream of reactant is drawn and sent to one or more reactors containing fluorine-containing
  • the invention in one broad respect, is directed at agriculturally useful formulations
  • formulations comprise an alkyltoluene and/or
  • alkylbenzene sulfonate component having a much higher 2-position isomer content than
  • the invention in another broad respect is a process useful for the production of
  • mono-alkyltoluene or mono-alkylbenzene comprising: contacting toluene (or benzene)
  • this invention is a process for the production of linear
  • alkyltoluene (or alkylbenzene), comprising: a) contacting toluene (or benzene) and an
  • toluene or benzene
  • an olefin having about 8 to about 30 carbons in the presence of a
  • alkyltoluene (or alkylbenzene) stream as well as the mono-sulfonation product made
  • this invention is a process useful for the production of
  • linear aromatic alkylate comprising: combining a product from a conventional linear
  • alkylbenzene alkylation reactor with a product from a linear alkyltoluene alkylation
  • this invention is a process for the production of linear
  • alkyltoluene (or alkylbenzene), comprising: a) dehydrogenating a paraffin to form an
  • linear alkylbenzene alkylation catalyst under conditions effective to react the toluene (or
  • Such process may optionally include the steps of: g) distilling the toluene-free (or
  • this invention is a process useful for the production of
  • monoalkyltoluene (or monoalkylbenzene) comprising: introducing a feed comprising
  • toluene or benzene refluxes to further contact the fluorine-containing mordenite.
  • this invention relates to mordenite useful for alkylating
  • toluene or benzene
  • olefin having a silica to alumina molar ratio of about 10:1 to about 100: 1 ; wherein the mordenite has been treated with an aqueous hydrogen fluoride solution
  • mordenite contains from about 0.1 to about 4 percent fluorine by weight.
  • the invention relates to a chemical mixture that contains
  • linear alkyltoluenes or linear alkylbenzenes produced using the process(es) and/or
  • the invention comprises formulations for finished
  • sulfonated alkylbenzene-type detergents be they linear or branched. This is true whether all
  • phenylalkyl concentration (any percentage between 30.00% and 80.00%, including every
  • the invention is a method useful for the preparation of
  • fluorine-containing mordenite comprising contacting a mordenite having a silica to alumina
  • FIGS. 1 and 2 has the advantage that rising toluene (or benzene) from the
  • this invention advantageously produces only low amounts of dialkylate, which is
  • the invention provides solid salts of alkyltoluene and alkylbenzene
  • sulfonates which solid salts may contain various cations necessary for charge balance.
  • the invention provides finished pesticide compositions useful for
  • compositions may include
  • Pesticide formulations according to one preferred embodiment
  • form ofthe invention are formed from components comprising: a) an alkylbenzene
  • sulfonate surfactant component present in any amount between 2.00 % and 10.00 % by
  • n is equal to any integer between 4 and 26; wherein any one, but only one, of R
  • R 2 , R 3 , R 4 and R 5 is selected from the group consisting of: a sulfonic acid group or a
  • R 5 may be optionally replaced by a hydrocarbyl group selected from the group
  • composition further includes an
  • agricultural adjuvant present in an amount of between 0.10 % and 5.00 % by weight
  • composition in another preferred form ofthe invention such a composition further comprises
  • such a composition further includes a water
  • the mordenite catalyst ofthe present invention is useful as a catalyst in the
  • LAT is useful as starting material to produce sulfonated LAT, which itself is
  • hydrocarbyl substituents or groups are predominantly hydrocarbon character. Examples of hydrocarbyl substituents or groups
  • hydrocarbon substituents that is, aliphatic (e.g., alkyl or alkenyl), alicyclic
  • the predominantly hydrocarbon substituent e.g., halo (especially chloro and fluoro)
  • heteroatoms include sulfur, oxygen, nitrogen, and
  • Meq/g means milliequivalents of titratable acid per gram of catalyst, which is a
  • Acidity is generally determined by titration
  • olefin conversion is about 95 percent or more in the practice of this
  • selectivity to the 2-phenyl isomer is about 70 % or more in the practice
  • “Surfactant range” refers to an alkyl group or an olefin (as warranted by the context)
  • a surfactant range alkyl
  • alkylbenzene or alkyltoluene is part of an alkylbenzene or alkyltoluene, (whether the alkylbenzene or alkyltoluene is
  • sulfonated or not means a hydrocarbyl moiety comprising any number of carbon atoms
  • Branched alkyl when referring to a surfactant range olefin or alkyl group that is
  • sulfonated or not means a hydrocarbyl moiety comprising between 8 and 28 carbon atoms
  • said straight chain have a hydrogen atom and an alkyl group other than a methyl group
  • Branched alkylbenzene means a molecular species which comprises a branched
  • Branched alkyltoluene means a molecular species which comprises a branched
  • Branched alkylbenzene sulfonate means a water-soluble salt of a branched
  • alkylbenzene that has been sulfonated. Also referred to as "BAS"
  • Branched alkyltoluene sulfonate means a water-soluble salt of a branched
  • 2-phenyl alkylbenzene means a material whose structure comprises a benzene
  • alkyl group comprises any alkyl group attached to it, wherein the alkyl group comprises any
  • benzene ring is attached the alkyl group at a carbon atom that is adjacent to a terminal
  • benzene ring has a methyl group and another alkyl group attached to it in a 2-phenyl alkylbenzene.
  • 2-toluyl alkyltoluene means a material whose structure comprises a benzene ring
  • molecule is attached the alkyl group at a carbon atom that is adjacent to a terminal carbon
  • ring ofthe toluene has a methyl group and another alkyl group attached to it in a 2-toluyl
  • Sulfonated 2-phenyl alkylbenzenes means 2-phenyl alkylbenzenes as defined
  • Sulfonated 2-toluyl alkyltoluenes means 2-toluyl alkyltoluenes as defined above
  • LAB linear alkylbenzene
  • LAT linear alkyltoluene
  • toluene molecule having appended to its aromatic ring any carbon atom of an alkyl chain in
  • the surfactant range, whether straight-chain or branched.
  • LAB sulfonate means an LAB which comprises a sulfonate group appended to the
  • LAT sulfonate means an LAT which comprises a sulfonate group appended to the
  • 2-phenyl isomer means 2-phenyl alkylbenzenes or sulfonates thereof, as
  • 2-toluyl isomer means 2-toluyl alkylbenzenes or sulfonates thereof, as warranted
  • linear 2-phenyl alkylbenzenes linear 2- toluyl alkyltoluenes
  • sulfonates linear 2-phenyl alkylbenzenes, linear 2- toluyl alkyltoluenes, and sulfonates
  • aromatic nucleus means a material whose chemical structure includes a benzene
  • aromatic feedstock means an aromatic compound from which an aromatic
  • alkylate is derived via an alkylation reaction, and includes without limitation benzene,
  • aromatic alkylate means a material whose chemical structure includes an
  • hydrocarbyl group is an alkyl group having any number of carbon atoms in
  • the surfactant range, whether linear, branched, saturated or un-saturated.
  • aromatic alkylate means an aromatic alkylate which further includes
  • FIG. 1 shows a representation of a first continuous reactive distillation column employed in
  • FIG. 2 shows a representation of a second continuous reactive distillation column employed
  • FIG. 3 shows a representative process scheme for one embodiment of this invention
  • reactor may be adjusted to vary the 2-phenyl isomer LAB or LAT content ofthe effluent
  • FIG. 4 shows another representative process scheme for one embodiment of this invention
  • slip stream of reactant to the conventional reactor is sent to one or both of a pair of
  • FIG. 5 shows the turbidity of aqueous solutions containing conventional alkylbenzene
  • FIG. 6 shows the turbidity of aqueous solutions containing alkylbenzene surfactant having a
  • 2-phenyl isomer content of about 80% as a function of differing water hardness in parts per
  • FIG. 7 shows the turbidity of 0.10 % aqueous solutions of both conventional LAS sulfonate
  • FIG. 8 shows turbidity of 0.10 % aqueous solutions having a constant water hardness of
  • isomer content ofthe alkylbenzene sulfonates and the alkyltoluene sulfonates is greater than
  • FIG. 9 shows turbidity of 0.10% aqueous solutions of LAS having a 2-isomer content
  • FIG. 10 shows the performance of conventional LAB and LAB according to the present
  • FIG. 11 shows the efficiency of emulsifiable concentrate branched alkylbenzene level
  • FIG. 12 shows sedimentation observed as a function of water hardness and 2-isomer
  • FIG. 13 shows spontaneity observed as a function of water hardness and 2-isomer content
  • FIG. 14 shows the emulsion performance as a function of water hardness and 2-isomer
  • the catalysts used to prepare aromatic alkylates according to this invention are:
  • silica-alumina molar ratio of from about 10:1 to about
  • the starting mordenite has a silica/alumina molar ratio of from about
  • the aqueous solution used to treat the mordenite may contain a range of HF
  • the HF concentration is a minimum of about 0.1 percent by
  • the HF concentration on the upper end is about 10 percent by weight or less.
  • the aqueous HF solution may be prepared by diluting commercially available 48%
  • HF solutions to the desired concentration.
  • HF can be sparged into water to
  • the treatment is carried out by adding mordenite powder or pellets to a
  • This time may vary depending on factors such as HF concentration, amount
  • mordenite can be recovered by filtration,
  • fluoride-treated mordenite would be calcined in air prior to use in alkylation
  • the preferred calcination temperature would be in the range from about 400 ° C to
  • hydrogen fluoride include ammonium fluoride, fluorided silicon compounds and fluorided
  • the HF -treated mordenite of this invention generally has about 0.1 percent by
  • the weight or more of fluorine based on the total weight ofthe mordenite.
  • the weight or more of fluorine based on the total weight ofthe mordenite.
  • fluorine-containing mordenite contains about 4 percent by weight or less fluorine.
  • fluorine-containing mordenite most typically contains about 1 percent by weight of fluorine.
  • mordenite can be used in the practice of this invention as a powder, in pellet
  • mordenite can be formed into pellets or extrudates using binders well known to those of skill in the art, such as alumina, silica or
  • an aromatic nucleus such as benzene or toluene is
  • the reactants are water and alcohol free.
  • the olefin be mono-unsaturated. It is most preferred that the olefin be an
  • alpha-olefin containing a terminal ethylenic unit although internal olefins are suitable for
  • Olefins in the 10 to 14 carbon number range are typically available from the
  • C 10 to C 14 mixture typically comprises a mixture which is predominantly
  • paraffins and has an olefin content of about 5 to 20%, and is readily available. Often, the
  • olefin content of such an olefin-paraffin mixture may be 8 to 10 weight %.
  • compound-to-olefin molar ratio range of about 1:1 to 100:1 flows from feed pump 10 to
  • feed inlet 14 via line 12.
  • the feed mixture falls to packed mordenite catalyst bed 32 where
  • aromatic compound and olefin can be introduced separately into
  • the bed with mixing occurring in the bed or the reactants can be mixed via an in-line mixer
  • FIG. 1 for laboratory scale may be made of two lengths of 1.1 inch internal diameter tubing
  • thermocouple 38 which monitors
  • olefin and/or olefin also pass through standard packing 36 (e.g., 7.5 inches of goodloe packing).
  • the rising vapors heat thermocouple 30 which connects to bottoms temperature controller
  • the system may be flushed with nitrogen which enters via line 54
  • the water trap 24 may not be
  • Condenser 21 is cooled via coolant such as water
  • the bottoms aromatic alkylate product may be removed from the system via line 47, using
  • valve 44 is opened.
  • dip tube 46 which is optional, is employed to slightly increase the
  • a pressure generator 56 may be optionally employed to raise the pressure
  • control mechanisms for heat shutoff 50 and pump shutoff 52 are depicted
  • control mechanisms are optional and may be included so that the catalyst bed does
  • Line 60 connects pump shutoff 52 to
  • the temperature in the catalyst bed may vary depending on reactants, rate of introduction
  • the bed is maintained at the
  • temperature ofthe catalyst bed is above about 100°C, and most preferably in the case of
  • toluene is about 110° to 130°C or more in order to have reasonable reaction rates, and about
  • the catalyst by coke build-up.
  • the temperature is in the range from about 120°C
  • the process may be operated at a variety of pressures during the
  • the process is operated using a system as depicted in FIGS. 1 and 2, the reboiler temperature
  • composition ofthe reboiler will vary over time, but is
  • LHSV liquid hourly space velocity
  • mole ratio of toluene to olefin introduced into the catalyst bed is generally from about 1:1 to
  • ratios of from about 2: 1 to about 20: 1 which can suitably be employed in the practice of
  • olefin-paraffin mixture comprising 5% to 20% olefin content.
  • Said olefin-paraffin mixtures are normally generated commercially through
  • FIG. 2 Another continuous reactive distillation apparatus is depicted in FIG. 2.
  • FIG. 2 Another continuous reactive distillation apparatus is depicted in FIG. 2.
  • the feed mixture enters the reactor via feed inlet 114.
  • the feed mixture falls through the
  • thermowell 133 monitors the
  • the catalyst bed 132 may be optionally heated
  • electric heater 140 heats the contents of reboiler 142 such that heated vapors of aromatic
  • the bottoms aromatic alkylate product may be removed from reboiler 142 by
  • thermocouples 138, 130, and 165 Temperature in the system is monitored via thermocouples 138, 130, and 165.
  • the system includes pressure release valve 166.
  • a nitrogen blanket over the system is
  • Level control activator 150 is maintained by introduction of nitrogen gas via inlet line 154.
  • bottoms level control valve 151 activates bottoms level control valve 151 to open when the liquids level in the reboiler rises
  • Line 160 connects level control activator 150 to the
  • FIG. 1 and FIG. 2 show single catalyst bed systems
  • process may be run in batch mode, or in other continuous processes
  • alkylate especially 2-isomer aromatic alkylate, may incrementally decrease. If desired, the
  • product ofthe alkylation using HF -treated mordenite may be sent to a second, finishing
  • Such a catalyst may
  • Branched alkyltoluene or branched alkylbenzene sulfonates may be introduced
  • nucleus may be replaced by branched olefin(s), to provide an alkyltoluene or
  • alkylbenzene mixture for sulfonation in which the alkyltoluene or alkylbenzene contains a
  • alkyltoluene sulfonates in a finished formulation according to the invention is when
  • branched alkyltoluenes or alkylbenzenes are used as a blending component in the
  • branched isomers comprise
  • alkyltoluene) sulfonate isomers present in a given formulation according to the invention.
  • branched isomers comprise any amount less
  • isomers comprise any amount less than 2.00% ofthe total alkylaromatic sulfonate isomers
  • the fluorine-containing mordenite of this invention generally produces aromatic
  • alkylates having high 2-isomer content such as higher than about 70%.
  • 2-isomer content such as higher than about 70%.
  • Aluminum chloride in contrast, produces about 26-28 percent ofthe 2-phenyl isomer.
  • LAB alkylation catalysts such as HF and aluminum chloride alkylation catalysts. This may be affected by withdrawing a
  • the catalyst of this invention can typically produce a 2-phenyl isomer
  • mixture may thus be engineered to contain any desired 2-phenyl isomer content in the range
  • the levels of 2-phenyl isomer may be adjusted by the amount of reactants
  • the conventional LAB catalysts used most frequently are HF alkylation reactors
  • alkylation catalysts include various aluminum chloride alkylation catalysts.
  • Other alkylation catalysts include various aluminum chloride alkylation catalysts.
  • Other alkylation catalysts include various aluminum chloride alkylation catalysts.
  • zeolites zeolites, alumina-silica, and various clays.
  • FIG. 3 depicts a representative, non-limiting scheme for practice of this invention
  • apparatus 210 is then pumped into a conventional alkylation reactor 230 containing
  • paraffin feed may of course be supplied from any provider, as the source of
  • paraffin dehydrogenated paraffin (olefin) is not critical to the practice of this invention.
  • Aromatic is not critical to the practice of this invention.
  • alkylate product from alkylation unit 230 may thereafter be purified by a series of
  • alkylation effluent is delivered to a aromatics column 240 (whose
  • the alkylation product may be sent
  • Aromatic feedstock is then recycled to the alkylation reactor 230.
  • alkylate product (having been stripped of aromatic feedstock) from the aromatics column
  • Paraffin-free crude aromatic alkylate from the paraffin column 250 is
  • Heavies e.g., dialkylates and olefin derivatives
  • feedstock/dehydrogenated paraffin feed is taken from line 214 and pumped through
  • mordenite reactor 220 may be
  • effluent from reactor 220 may, in the
  • columns 240, 250, and 260 may be maintained at conditions (e.g., pressure and
  • FIG. 4 depicts an alternative configuration to that shown in FIG. 3.
  • FIG. 4
  • one ofthe mordenite reactors may be in operation while
  • the other reactor is down for catalyst regeneration.
  • olefin olefin
  • feed dehydrogenated paraffin
  • aromatic feedstock is supplied via line 301, with aromatic feedstock being
  • the admixed reactants may flow to standard alkylation reactor 330
  • mixed feed stream being withdrawn may be varied depending on the desired level of 2-
  • containing mordenite 320, 321 may be fed to the first alkylation reactor 330, particularly
  • the slip stream reactants may optionally be sent to dewatering unit 317 by
  • water is distilled from the reactants in dewatering tower 310. Rising vapor exits via
  • dewatering tower 310 Dewatered reactants may be removed via line 316 and conveyed
  • heat exchanger 315 may serve as a reboiler.
  • one ofthe catalyst beds may be regenerated, as by calcination for example,
  • regeneration heater 350 which may be connected to the reactor of choice
  • reactors 320 and 321 may optionally be run simultaneously.
  • the reactors 320 and 321 may be loaded
  • a plugged flow arrangement is used.
  • the amount of catalyst employed may
  • mordenite reactors 320 or 321 may be fed to a second conventional reactor 340, or
  • the alkylation reactor is advanced to a purification section.
  • the second alkylation reactor is advanced to a purification section.
  • FIG. 2 The apparatus depicted in FIG. 2 was used for example 5.
  • example 2 illustrates LAB production from paraffin
  • Example 5 illustrates LAB
  • This example illustrates the preparation of a hydrogen fluoride-modified mordenite.
  • the example illustrates the preparation of a hydrogen fluoride-modified mordenite.
  • Alkylation was conducted by first charging 500 ml of a benzene/paraffin
  • dehydrogenate mix (10:1 molar ratio, benzene/C 10 -C 14 olefin) to the reboiler and 250 cc of
  • paraffin dehydrogenate mix in a 10:1 molar ratio of benzene/C 10 -C 14 olefin.
  • the recovered mordenite showed by analysis: Acidity: 0.29 meq/g; H 2 O: 2.1%
  • This example also illustrates the preparation of linear alkylbenzene from paraffin
  • reboiler temperature was typically in the range of 122- 188° C, the column head temperature
  • This example also illustrates the preparation of linear alkylbenzenes from paraffin
  • reaction zone was charged 500 cc of HF-treated mordenite of Example B.
  • Example B was charged to the column.
  • the liquid feed comprised benzene plus C, 0 -C 14 paraffin dehydrogenate mix in a 10:1 molar ratio of benzene/C 10 -C 14 olefin.
  • the LHSV varied from 0.2 to 0.4 hr "1 .
  • Alkylation was conducted over a range of column and reboiler temperatures and a
  • C 12 -Linear alkyltoluene is prepared by using mordenite, CBV20A, a
  • cloudy toluene is collected into the trap and is removed from the trap to make the reaction
  • ClO-linear alkyltoluene is prepared by using mordenite, CBV20A, catalyst
  • reaction apparatus is the same as the one used in Example 10
  • Linear light alkyltoluene (LLAT) is prepared by using mordenite CBV20A
  • the reactor setup is the same as for Example 10 above. About 50 grams of
  • toluene azeotrope is removed to make the reaction completely anhydrous.
  • About 600 grams of a hydrocarbon mix containing about 10% olefins and 90 % paraffins is added
  • reaction mixture is cooled, filtered, and the excess toluene is removed to obtain a crude
  • alkylates have a high 2-isomer content. This in turn means that for the first time there are
  • surfactants may be used in formulating agriculturally valuable pesticide materials.
  • active material means any chemical substance that: 1) when applied to a given foliage

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention porte sur des compositions détergentes utilisant comme tensio-actifs des alkyltoluènes sulfonés et présentant une plus haute teneur en isomères de 2-phényl alkyltoluènes sulfonés que les tensio-actifs d'alkyltoluènes sulfonés antérieurs. Les compositions de nettoyage de l'invention sont plus efficaces que leurs contreparties antérieures à plus faible teneur en isomères de 2-phényl alkyltoluènes sulfonés, en raison de leur meilleure tolérance aux minéraux responsables de la dureté de l'eau normalement associés à la précipitation des agents détergeants actifs. L'invention porte également sur des sulfonates solides d'alkyltoluènes et sur des lessives les contenant. Les alkyltoluènes de l'invention peuvent être combinés à des tensio-actifs d'alkylbenzène de manière à former des mélanges détergents présentant une tolérance accrue aux eaux dures, une température de Krafft plus basse, et une efficacité supérieure à celle des produits antérieurs.
PCT/US2002/015278 2002-05-14 2002-05-14 Preparations pour l'agriculture contenant des tensio-actifs ameliores Ceased WO2003096807A1 (fr)

Priority Applications (2)

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PCT/US2002/015278 WO2003096807A1 (fr) 2002-05-14 2002-05-14 Preparations pour l'agriculture contenant des tensio-actifs ameliores
AU2002316112A AU2002316112A1 (en) 2002-05-14 2002-05-14 Agricultural formulations containing enhanced surfactants

Applications Claiming Priority (1)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012145177A1 (fr) * 2011-04-20 2012-10-26 Huntsman Petrochemical Llc Agents de réduction de la dérivé de produits pulvérisés comprenant des agents tensioactifs à valeur d'équilibre hydrophile-lipophile basse
WO2014059125A1 (fr) * 2012-10-12 2014-04-17 Dow Agrosciences Llc Tensioactifs à base de sulfonate d'alkylbenzène pour réduire la dérive d'une pulvérisation herbicide
US10021901B2 (en) 2011-11-30 2018-07-17 Anitox Corporation Antimicrobial mixture of aldehydes, organic acids and fatty acid esters
US10785975B2 (en) 2009-08-06 2020-09-29 Anitox Corporation Water and feed antimicrobial preservative

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5565409A (en) * 1993-04-02 1996-10-15 Monsanto Company Liquid concentrated herbicidal microemulsion compositions comprising glyphosate and either oxyfluorfen or acifluorfen
US5683958A (en) * 1990-08-09 1997-11-04 Monsanto Company Surfactants mixtures

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5683958A (en) * 1990-08-09 1997-11-04 Monsanto Company Surfactants mixtures
US5565409A (en) * 1993-04-02 1996-10-15 Monsanto Company Liquid concentrated herbicidal microemulsion compositions comprising glyphosate and either oxyfluorfen or acifluorfen

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10785975B2 (en) 2009-08-06 2020-09-29 Anitox Corporation Water and feed antimicrobial preservative
WO2012145177A1 (fr) * 2011-04-20 2012-10-26 Huntsman Petrochemical Llc Agents de réduction de la dérivé de produits pulvérisés comprenant des agents tensioactifs à valeur d'équilibre hydrophile-lipophile basse
US10123532B2 (en) 2011-04-20 2018-11-13 Huntsman Petrochemical Llc Spray drift reduction agents comprising low hydrophilic-lipophilic balance surfactants
US10021901B2 (en) 2011-11-30 2018-07-17 Anitox Corporation Antimicrobial mixture of aldehydes, organic acids and fatty acid esters
WO2014059125A1 (fr) * 2012-10-12 2014-04-17 Dow Agrosciences Llc Tensioactifs à base de sulfonate d'alkylbenzène pour réduire la dérive d'une pulvérisation herbicide

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