Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
  • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/084—Y-type faujasite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/05—Nuclear magnetic resonance [NMR]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y

Definitions

• This invention relates to the production of alkylated aromatic compounds such as, for example, alkyl naphthalenes and substituted alkyl naphthalenes.
• Alkylaromatic fluids have been proposed for use as certain types of functional fluids where good thermal and oxidative properties are required.
• U.S. Patent No. 4,714,794 describes the monoalkylated naphthalenes as having excellent thermal and oxidative stability, low vapor pressure and flash point, good fluidity and high heat transfer capacity and other properties which render them suitable for use as thermal medium oils.
• the use of a mixture of monoalkylated and polyalkylated naphthalenes as a base for synthetic functional fluids is described in U.S. Pat. No. 4,604,491.
• U.S. Pat. Nos. 4,211 ,665 and 4,238,343 describe the use of alkylaromatics as transformer oils.
• the alkylated naphthalenes are usually produced by the alkylation of naphthalene or a substituted naphthalene in the presence of an acidic alkylation catalyst such as a Friedel-Crafts catalyst, for example, an acidic clay as described in U.S. Pat. Nos. 4,714,794 or 4,604,491 , or a Lewis acid such as aluminum trichloride as described in U.S. Pat. Nos. 4,211 ,665 and 4,238,343.
• an acidic alkylation catalyst such as a Friedel-Crafts catalyst
• an acidic clay as described in U.S. Pat. Nos. 4,714,794 or 4,604,491
• a Lewis acid such as aluminum trichloride as described in U.S. Pat. Nos. 4,211 ,665 and 4,238,343.
• zeolites including intermediate pore size zeolites such as ZSM-5 and large pore size zeolites such as zeolite L and ZSM-4 for the alkylation of various monocyclic aromatics such as benzene is disclosed in U.S. Pat. No. 4,301 ,316.
• the preferred alkyl naphthalenes are the mono-substituted naphthalene since they provide the best combination of properties in the finished product. Because the mono-alkylated naphthalenes posses fewer benzylic hydrogens than the corresponding di- substituted or polysubstituted versions, they have better oxidative stability and therefore form better functional fluids and additives.
• the mono-substituted naphthalenes have a kinematic viscosity in the desirable range of about 5-8 cSt (at 100 °C) when working with alkyl substituents of about 14 to about 18 carbon atoms chain length.
• the monoalkylated naphthalenes may be obtained in admixture with more highly alkylated naphthalenes using conventional Friedel-Crafts catalysts such as those mentioned above, or by the use of zeolites such as USY, the selectivity to the desired mono-alkylated naphthalenes is not as high as desired.
• zeolites such as USY
• the patent had examples in which H + , NH + , and Na + were added to USY zeolite by a procedure involving forming a slurry of zeolite and liquid, 1 hour of stirring, decantation, and a repeat of the exchange procedure.
• the present inventors did additional work to see if they could further improve this alkylation process. They wanted to increase the efficiency of the reaction both in terms of conversion and yields.
• an alkylation catalyst comprising a large pore zeolite which has been dealuminated to remove non-framework aluminum by selective ion exchange in acidic conditions, provides unexpectedly superior activity over a corresponding catalyst without the dealumination treatment.
• the catalyst of the invention is effective in alkylation of other compounds containing two aromatic rings including, but not limited to, diphenyl oxide, diphenyl sulfide, diphenyl methane, and biphenyl.
• the present invention provides a process for preparing alkyl substituted aromatic compounds, including long chain alkyl substituted aromatic compounds, which comprises alkylating an aromatic compound with an alkylating agent possessing an alkylating aliphatic group having at least six carbon atoms under alkylation reaction conditions in the presence of an alkylation catalyst comprising a porous crystalline zeolite which has been selectively dealuminated, under acidic conditions, to remove non-framework aluminum.
• the starting materials for the production of the alkylated aromatic compounds include the aromatic compounds themselves.
• aromatic compound is understood by those of ordinary skill in the art to refer to any compound having at least one aromatic ring, such as, for example, benzene, pyridine, naphthalene.
• the aromatic compound may be unsubstituted or substituted with, by way of non-limiting example, halogen, alkyl, alkenyl, nitro, amino, amido, carboxyl, carboxamido, etc.
• Naphthalenes include naphthalene itself as well the substituted naphthalenes which may contain, for example, one or more short chain alkyl groups containing up to about eight carbon atoms, such as methyl, ethyl or propyl.
• Suitable alkyl-substituted naphthalenes include, for example, alpha-methylnaphthalene, dimethylnaphthalene and ethylnaphthalene.
• Naphthalene itself is preferred since the resulting mono-alkylated products have better thermal and oxidative stability than the more highly alkylated materials for the reasons set forth above.
• aromatic chemical compounds containing one or two aromatic rings in the structure can also be alkylated by this process.
• Such compounds include, but are not limited to, alkylbenzenes such as benzene, toluene, xylenes, ethyl benzene, methylethyl benzene, trimethyl benzene, and propyl benzene.
• alkylbenzenes such as benzene, toluene, xylenes, ethyl benzene, methylethyl benzene, trimethyl benzene, and propyl benzene.
• other two-ring aromatic compounds such as, for example, diphenyl oxide, diphenyl sulfide, diphenyl methane, biphenyl, and alkyl-substituted derivative compounds.
• the alkylating agents which are used to alkylate the naphthalene include, but are not limited to, any aliphatic or aromatic organic compound having one or more available alkylating aliphatic groups capable of alkylating the naphthalene.
• the alkylating group itself should have at least about 6 carbon atoms, preferably at least about 8, and still more preferably at least about 12 carbon atoms.
• the alkyl groups on the alkyl-naphthalene preferably have from about 12 to about 30 carbon atoms, with particular preference to about 14 to about 18 carbon atoms.
• a preferred class of alkylating agents are the olefins with the requisite number of carbon atoms, for example, the hexenes, heptenes, octenes, nonenes, decenes, undecenes, dodecenes, tridecenes, tetradecenes, pentadecenes, hexadecenes, heptadecenes, and octadecenes.
• Mixtures of the olefins e.g., mixtures of C 12 -C 20 or C ⁇ 4 -C ⁇ 8 olefins, are also useful.
• Branched alkylating agents especially oligomerized olefins such as, for example, the trimers, tetramers, pentamers, etc., of light olefins including, but not limited to, ethylene, propylene, the butylenes, etc., are also useful.
• alkylating agents which may be used include alcohols (inclusive of monoalcohols, dialcohols, trialcohols, etc.) such as, for example, hexanols, heptanols, octanols, nonanols, decanols, undecanols, and dodecanols; and alkyl halides such as hexyl chlorides, octyl chlorides, dodecyl chlorides; and higher homologs.
• alcohols inclusive of monoalcohols, dialcohols, trialcohols, etc.
• alkyl halides such as hexyl chlorides, octyl chlorides, dodecyl chlorides; and higher homologs.
• the alkylation reaction between the naphthalene and the alkylating agent is carried out in the presence of a zeolite catalyst which contains a cation of certain specified radius.
• the molecular size of the alkylation products will require a relatively large pore size in the zeolite in order for the products to leave the zeolite, indicating the need for a relatively large pore size in the zeolite, which will also tend to reduce diffusion limitations with the long chain alkylating agents.
• the large pore size zeolites are the most useful zeolite catalysts for this purpose although the less highly constrained intermediate pore size zeolites may also be used, as discussed below.
• the large pore size zeolites include, but are not limited to, zeolites such as faujasite, the synthetic faujasites (zeolites X and Y), zeolite L, ZSM-4, ZSM-18, ZSM-20, MCM-68, mordenite, and offretite, which are generally useful for this purpose are characterized by the presence of a 12-membered oxygen ring system in the molecular structure and by the existence of pores with a minimum dimension of at least 7.4 ?, as described by Frilette et al. in J. Catalysis 67, 218-222 (1981 ). See also Chen et al., "Shape-Selective Catalysis in Industrial Applications," (Chemical Industries, Vol.
• the large pore size zeolites may also be characterized by a "Constraint Index" of not more than about 2, in most cases not more than about 1.
• Zeolite beta a zeolite having a structure characterized by twelve-membered pore openings, is included in this class of zeolites although under certain circumstances it has a Constraint Index approaching the upper limit of 2 which is characteristic of this class of zeolites. The method for determining Constraint Index is described in U.S. Patent No. 4,016,218, together with values for typical zeolites and of the significance of the Index in U.S. Patent No. 4,861 ,932, to which reference is made for a description of the test procedure and its interpretation.
• Zeolites whose structure is that of a ten-membered oxygen ring may also be effective catalysts for this alkylation reaction if their structure is not too highly constrained.
• zeolites such as ZSM-12 (Constraint Index 2) may be effective catalysts for this reaction.
• the zeolite identified as MCM- 22 is a useful catalyst for this reaction.
• MCM-22 is described in U.S. patent application Ser. No. 07/254524, filed 6 Oct. 1988, and also in International Patent Application PCT/US88/04251 , to which reference is made for a description of this zeolite.
• zeolites having a Cl up to about 3 will generally be useful catalysts, although the activity may be found to be dependent on the choice of alkylating agent, especially its chain length, a factor which imposes diffusion limitations upon the choice of zeolite.
• MCM-49 and MCM-56 are also useful catalysts according to the present invention.
• a highly useful zeolite for the production of the monoalkylated naphthalenes is ultrastable Y, usually referred to as USY. When this material contains hydrated cations, it catalyses the alkylation in good yields with excellent selectivity.
• Zeolite USY is a material of commerce, available in large quantities as a catalyst for the cracking of petroleum. It is produced by the stabilization of zeolite Y by a procedure of repeated ammonium exchange and controlled steaming. Processes for the production of zeolite USY are described in U.S. Patent Nos.
• Y zeolite ranging from about 0.2 to about 0.4 microns, although materials ranging from about 0.6 to about 1.3 micron, which is more typical of Y zeolite crystals, may also be used.
• the alkylation reaction conditions include a temperature ranging from about 100 °C to about 400 °C and a pressure of from about 0.2 to about 25 atmospheres and a weight hourly space velocity of from about 0.1 to about 10.
• the mole ratio of the alkylatable aromatic to alkylating agent ranges from about 0.1 :1 to about 50:1.
• EXAMPLE 2 Preparation of Dealuminated H + /NH + USY Crystal Sample
• the Na- form USY was made a slurry with deionized (Dl) water to target a 35 wt% solids level.
• a solution of 30 wt% ammonium sulfate was prepared, and then the pH was adjusted to 4.0 using 20 wt% H 2 S0 4 solution.
• the pH 4.0 ammonium sulfate solution was added slowly to the USY slurry (1.3 g of 30% ammonium sulfate solution per 1 g zeolite) while the overall solution pH was adjusted to 4.0.
• the exchanged USY zeolite was filtered and washed with deionized water (10 cc/g zeolite) and then dried in an oven at 120 °C overnight.
• the material was air calcined (5 cc air/g zeolite/min) for 3 hours at 350 °C.
• Table 1 The properties of the final catalyst are shown in Table 1.
• the extent of dealumination can be estimated as follows. For example, if we subject 100 g of Na + -form USY (100% solids basis) to the exchanges in the above examples we can estimate the following yields of Na 2 0 and Al 2 0 3 assuming the Si0 2 content in USY stays constant during the exchange (this assumption is reasonable since Si0 2 does not dissolve in an acidic solution). The following estimates were made using the bulk Si0 2 /AI 2 ⁇ 3 molar ratios determined by elemental analysis and the framework Si0 2 /AI 2 ⁇ 3 molar ratios determined by 29 Si NMR.
• the framework Al content is calculated from SiO 2 /AI 2 O 3 molar ratio determined by 29 Si NMR based on publication by E. Lipmaa, M. Maeigi, A. Samoson, and G. Englehardt, J. Am. Chem. Soc. 103, 4992 (1981).
• the non-framework Al content is an estimate, a difference between the total AI 2 O 3 content and the AI 2 O 3 content corresponding to framework Al.
• Ammonium exchanged USY was slurried and ball milled for 16 hours to produce ⁇ 5 ⁇ average particle size.
• a physical mixture of 40 parts milled USY slurry, 30 parts colloidal silica, and 30 parts kaolin clay was slurried to form a uniform mixture. All components were blended based on parts by weight on a 100% solids basis. Sufficient amount of deionized water was added to form a spray dryable mixture (approximately 32-34 wt% solids). The mixture was spray dried to fine spherical particles
• Catalysts NH 4 + -form USY which was ammonium exchanged at pH 3.5 per procedures described in Example 3, was used for this catalyst preparation.
• the ammonium exchanged USY was slurried and ball milled
• This example shows that the catalyst activity and selectivity can be further varied by varying the H + to NH 4 + ratio of the [H + /NH 4 + ] USY/Silica-Clay catalyst.
• the residual N level was varied from about 0.64 wt% to about 0.02 wt%.
• the catalyst tends to be less active and the selectivity toward monoalkylate reactant increases.
• the high-zeolite, high activity USY containing catalyst has an advantage in commercial practice. After each batch reaction, the catalyst needs to be filtered out and discarded. By lowering the total catalyst charge per batch reaction (from about 5 wt% to about 3-3.7 wt%), the filtration step would take much less time and the catalyst disposal will cost less.
• High Unit Cell Size USY A commercial Na-form USY with a silica-to-alumina ratio of 5.5 and a unit cell size of 24.60 ? was used for this catalyst preparation.
• the Na- form USY was ammonium exchanged at pH 3.5 per procedures described in Example 3.
• the ammonium exchanged USY was slurried and ball milled for 16 hours to produce ⁇ 5 average particle size.
• a physical mixture of 75 parts milled USY slurry, 20 parts colloidal silica, and 5 parts kaolin clay was slurried to form a uniform mixture. All components were blended based on parts by weight on a 100% solids basis.
• EXAMPLE 10 Preparation of Alkyl Diphenyl Sulfides Using H7NH 4 + USY Catalyst
• the H + /NH + USY catalyst from Example 3 was evaluated for alkylation of diphenyl sulfide with a long chain alpha olefin to produce alkylated diphenyl sulfide lube base stock.
• 1-Hexadecene (224 g), diphenyl sulfide (186 g) and the H + /NH 4 + USY catalyst (13.4 g) were added to a reaction flask and heated to 220 °C under a nitrogen
• reaction mass was cooled and the catalyst removed by filtering through a bed of diatomaceous earth filter medium (Celite 545). The filtrate was then heated to 196 °C and
• the alkylated product exhibits favorable VI and pour point suggesting the
• the above catalyst was evaluated for alkylation of diphenyl oxide with a long chain alpha olefin to produce alkylated diphenyl oxide lube base stock.
• Diphenyl oxide (425 g), activated carbon (3.81 g) and the
• the final product contained 97% monoalkylate and 3% dialkylate and had the following physical properties:
• the alkylated product exhibits favorable VI and pour point suggesting the material could be useful as functional fluid or additive for synthetic lube stock.
• the alkylated product exhibits favorable VI and pour point suggesting the material could be useful as functional fluid or additive for synthetic lube stock.
• the present invention may be embodied in other specific forms without departing from its spirit or essential characteristics.
• the described embodiments are to be considered in all respects as illustrative only and not restrictive.
• the scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

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