US20120271076A1 - Iridium-Containing Catalysts, Their Production and Use - Google Patents

Iridium-Containing Catalysts, Their Production and Use Download PDF

Info

Publication number
US20120271076A1
US20120271076A1 US13/512,620 US201013512620A US2012271076A1 US 20120271076 A1 US20120271076 A1 US 20120271076A1 US 201013512620 A US201013512620 A US 201013512620A US 2012271076 A1 US2012271076 A1 US 2012271076A1
Authority
US
United States
Prior art keywords
support
organic
catalyst
iridium complex
temperature
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.)
Abandoned
Application number
US13/512,620
Other languages
English (en)
Inventor
Stuart L. Soled
Sabato Miseo
Joseph E. Baumgartner
Christine E. Kliewer
Jane C. Cheng
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Chemical Patents Inc
Original Assignee
ExxonMobil Chemical Patents Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Priority to US13/512,620 priority Critical patent/US20120271076A1/en
Assigned to EXXONMOBIL CHEMICAL PATENTS INC. reassignment EXXONMOBIL CHEMICAL PATENTS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MISEO, SABATO, CHENG, JANE C., SOLED, STUART L., BAUMGARTNER, JOSEPH E., KLIEWER, CHRISTINE E.
Publication of US20120271076A1 publication Critical patent/US20120271076A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/468—Iridium
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/31—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C07C2531/08—Ion-exchange resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention relates to iridium-containing catalysts, their production and use.
  • Iridium like other elements of Group VIII of the Periodic Table, is known to be active for hydrogenation/dehydrogenation reactions and, in particular, for the carbon-carbon bond scission reactions involved in ring opening of cyclic hydrocarbons.
  • U.S. Pat. No. 7,579,511 lists iridium as one suitable Group VIII metal for catalyzing the ring opening conversion of methylcyclopentane produced as a by-product of the hydroalkylation of benzene to cyclohexylbenzene.
  • any commercial application of iridium as a catalyst requires that utilization of the iridium is maximized, or in other words that the iridium is effectively and uniformly dispersed on its catalytic support in a thermally stable manner.
  • few studies have focused on producing highly dispersed, stable supported iridium catalysts, particularly on non-acidic supports such as silica.
  • US Published Patent Application No. 2006/0166809 discloses a process for the manufacture of a catalyst comprising a catalytically active metal dispersed on a support, which process comprises a) treating a porous support with a compound or salt of the metal and a organic compound selected from (i) amino acids and (ii) compounds containing both an amino group and an alcohol group, to form the organic metal complex on the support; b) partially decomposing the organic metal complex on the support to the extent that the partially decomposed product (I) retains between 10 and 95% by weight of the dry weight attributed to the organic complex prior to partial decomposition, and (II) exhibits one or more infra-red absorption bands between 2100-2200 cm ⁇ 1 that are not present in the organic complex before partial decomposition; and converting the partially decomposed organic metal complex into catalytically active metal.
  • iridium as one of about forty suitable catalytically active metals
  • the Examples focus on the production of ruthenium catalysts via reaction of a nitrate salt.
  • no nitrate salt is available with iridium.
  • a silica-supported iridium catalyst with excellent dispersion and nanoscale homogeneity can be prepared by modifying the partial decomposition process described in the '809 application.
  • the resultant iridium catalyst exhibits higher hydrogen chemisorption uptakes and activity for carbon-carbon bond hydrogenolysis than conventional iridium catalysts.
  • the invention resides in a process for producing a catalyst composition comprising an iridium component dispersed on a support, the process comprising:
  • the partially decomposed product retains between 10 and 95% by weight of the dry weight attributed to the organic complex prior to partial decomposition.
  • the partially decomposed product exhibits one or more infra-red absorption bands between 2100-2200 cm ⁇ 1 that are not present in the organic complex before partial decomposition.
  • the organic compound comprises an aliphatic amine containing one or more hydroxyl groups, such as a mono-, di-, or tri-, substituted aliphatic hydroxyalkylamine, especially triethanolamine.
  • the organic compound comprises an amino acid, such as arginine.
  • heating step (b) comprises heating the treated support to a temperature of about 375° C. to about 425° C.
  • the reducing atmosphere in heating step (c) is selected from a source of hydrogen, a source of CO, and mixtures thereof.
  • the invention resides in a silica-supported iridium catalyst composition produced by the process described herein and in the use of the resultant catalyst composition in converting a cyclic aliphatic hydrocarbon to an acyclic alkane and/or alkene.
  • FIG. 1 is a graph of the DTA-TGA (Differential Thermal Analysis and Thermal Gravimetry Analysis) for the dried 1 wt % Ir (arginine)/SiO 2 catalyst precursor of Example 2 when heated in air according to Example 3.
  • DTA-TGA Differential Thermal Analysis
  • FIG. 2 is a graph of percentage weight change against temperature and a DTA spectrum for the dried and calcined (at 400° C.) 1 wt % Ir(arginine)/SiO 2 catalyst precursor of Example 2 when heated in air according to Example 4.
  • FIG. 3 is a graph of temperature and percentage weight change against time on stream for the dried and calcined (at 400° C.) 1 wt % Ir(arginine)/SiO 2 catalyst precursor of Example 2 when reduced in 100% H 2 according to Example 5.
  • FIG. 4 is a graph of percentage weight change against temperature and a DTA spectrum for the dried 1 wt % Ir/SiO 2 catalyst precursor of Example 1 when heated in air according to Example 5.
  • This invention relates to a process for producing a silica-supported iridium catalyst with improved dispersion of the iridium component and to use of the resultant catalyst in converting a cyclic aliphatic hydrocarbon, especially methylcyclopentane, to an acyclic alkane and/or alkene.
  • the catalyst shows particular utility in reducing the level of methylcyclopentane that is inevitably produced during the hydroalkylation of benzene to cyclohexylbenzene.
  • the present process involves initially treating a silica-containing support with an iridium compound and a organic compound comprising an amino group to form an organic iridium complex on the support.
  • the silica-containing support employed in the present process may be an amorphous material, such as a silica gel, or a crystalline material, such as a microporous silicate or aluminosilicate zeolite.
  • the support can be a mesoporous silicate, such as MCM-41, MCM-48, and MCM-50.
  • the support is treated, normally by impregnation, with a liquid composition comprising an iridium compound, normally chloroiridic acid, and at least one organic compound comprising an amino group wherein the organic compound may be selected from an amino acid or an amino alcohol or mixtures thereof.
  • a liquid composition comprising an iridium compound, normally chloroiridic acid, and at least one organic compound comprising an amino group wherein the organic compound may be selected from an amino acid or an amino alcohol or mixtures thereof.
  • the organic compound may be dispersed or dissolved in a liquid carrier, such as water.
  • suitable amino alcohols include aliphatic hydroxyalkylamines, such as methanolamine, di-methanolamine, tri-methanolamine, ethanolamine, di-ethanolamine, tri-ethanolamine, butanolamine, di-butanolamine, tri-butanolamine, propanolamine, di-propanolamine, dimethylethanolamine, di-isopropylethanolamine, methyldiethanolamine, dimethylamino-2-propanol and tri-propanolamine.
  • aliphatic hydroxyalkylamines such as methanolamine, di-methanolamine, tri-methanolamine, ethanolamine, di-ethanolamine, tri-ethanolamine, butanolamine, di-butanolamine, tri-butanolamine, propanolamine, di-propanolamine, dimethylethanolamine, di-isopropylethanolamine, methyldiethanolamine, dimethylamino-2-propanol and tri-propanolamine.
  • amino acids examples include alanine, arginine, asparagines, aspartic acid, cysteine, cystine, 3,5-dibromotyrosine, 3,5, diiodotyrosine, glutamic acid, glutamine, glycine, histidine, hydroxylysine, hydroxyproline, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, thyroxine, tryptophane, tyrosine and valine, with arginine being preferred.
  • Treatment of the support with the iridium compound and the organic compound forms an organic iridium complex on the support.
  • the treated support is then heated in an oxidizing atmosphere, such as air, at a temperature of about 325° C. to about 450° C., such as about 375° C. to about 425° C., to partially, but not completely, decompose the organic metal complex on the support.
  • the heating is typically conducted for a period of about 1 hour to about 4 hours such that the partially decomposed product retains between 10 and 95% by weight of the dry weight attributed to the organic complex prior to partial decomposition.
  • the partially decomposed product typically exhibits one or more infra-red absorption bands between 2100-2200 cm ⁇ 1 that are not present in the organic complex before partial decomposition.
  • the treated support is heated in an reducing atmosphere at a temperature of about 350° C. to about 500° C., such as about 400° C. to about 450° C., to convert the partially decomposed organic metal complex into finely dispersed iridium particles on the silica support.
  • a reducing atmosphere comprise a source of hydrogen, a source of CO, and mixtures thereof.
  • the resultant catalyst is found to be effective in the ring-opening conversion of cyclic aliphatic hydrocarbons, especially methylcyclopentane, to acyclic alkanes and/or alkenes.
  • This reaction is important since, for example, methylcyclopentane is a significant by-product in the hydroalkylation of benzene to cyclohexylbenzene, such as described in U.S. Pat. No. 7,579,511 incorporated herein by reference.
  • methylcyclopentane has a similar boiling point to benzene, it cannot be readily removed from the unreacted benzene by distillation and so, without removal, will tend to build up in the benzene recycle stream.
  • Suitable conditions for such a ring opening reaction comprise a temperature between about 250° C. and about 400° C. and a pressure between about 100 and about 1000 kPa.
  • Also described herein is a process for dehydrogenating and ring opening a hydrocarbon stream comprising at least one non-aromatic six-membered ring compound and at least one non-aromatic five-membered ring compound and optionally comprising at least one aromatic compound, such as benzene.
  • the process comprises producing a first reaction product comprising the step of contacting at least a portion of the hydrocarbon stream with a first catalyst under conditions effective to convert at least a portion of the at least one five-membered ring compound to at least one paraffin and producing a second reaction product comprising the step of contacting at least a portion of the at least one six-membered ring compound with a second catalyst under conditions effective to convert at least a portion of the at least one six-membered ring compound to at least one aromatic compound such as benzene.
  • the hydrocarbon stream comprises at least 10 wt % benzene, at least 20 wt % benzene, at least 30 wt % benzene, at least 40 wt % benzene, at least 50 wt % benzene, at least 60 wt % benzene, at least 70 wt % benzene, and at least 80 wt % benzene.
  • the hydrocarbon stream comprises at least 1 wt % cyclohexane, at least 5 wt % cyclohexane, at least 10 wt % cyclohexane, and at least 20 wt % cyclohexane.
  • the hydrocarbon stream comprises at least 0.05 wt % methylcyclopentane, at least 0.5 wt % methylcyclopentane, and 5 wt % methylcyclopentane.
  • the first catalyst employed in this process comprises an iridium-containing catalyst comprising an iridium component dispersed on a support wherein the iridium catalyst is prepared by the method described herein.
  • the second catalyst employed in the present process comprises at least one metal component and at least one support.
  • metal component is used herein to include elemental metal and a metal compound that may not be purely the elemental metal, but could, for example, be at least partly in another form, such as an oxide, hydride or sulfide form.
  • the weight % (wt %) of the metal component is herein defined as being measured as the metal present based on the total weight of the catalyst composition irrespective of the form in which the metal component is present.
  • Suitable metal components for use in the second catalyst comprise metals from Groups 6 to 10 of the Periodic Table of the Elements, especially platinum, palladium, ruthenium, nickel, zinc, tin, cobalt and mixtures thereof.
  • the numbering scheme for the Periodic Table Groups is as disclosed in Chemical and Engineering News, 63(5), p. 27 (1985).
  • the second catalyst employed herein has an alpha value less than 10, less than 5, and from about 0 to about 3.
  • the alpha value is a measure of the acidic functionality of the catalyst and is described together with details of its measurement in U.S. Pat. No. 4,106,218 and in J. Catalysis, Vol. VI, pp. 278-287 (1966) and reference is made to these for such details.
  • Higher alpha values correspond with a more active cracking catalyst.
  • the alpha value of the catalyst can be adjusted by methods known in the art, for example by steaming.
  • the alpha value for the second catalyst is less than about 10 or less than about 5.
  • the alpha value lower limit may be about 0, about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about 4, and about 5; and the upper alpha value limit may be about 10, about 9, about 8, about 7, about 6, about 5, about 4, about 3 and about 2 with ranges from any lower limit to any upper limit being contemplated.
  • the support employed in the second catalyst is selected from the group consisting of silica, alumina, a silicate, an molecular sieve, zirconia, carbon, and carbon nanotubes, and preferably comprises silica.
  • the molecular sieve may be selected from aluminosilicate, an aluminophosphate, a silicoaluminophosphate, or a combination thereof.
  • Impurities which can be present in the catalyst support e.g., silica
  • Impurities which can be present in the catalyst support are, for example, sodium salts such as sodium silicate which can be present from anywhere from 0.01 to 2 wt %.
  • the second catalyst comprises a silica support having pore volumes and median pore diameters determined by the method of mercury intrusion porosimetry described by ASTM Standard Test D4284.
  • the silica support may have surface areas as measured by ASTM D3663.
  • the pore volumes are in the range of from about 0.2 cc/gram to about 3.0 cc/gram.
  • the median pore diameters are in the range from about 10 angstroms to about 2000 angstroms or from 20 angstroms to 500 angstroms; and the surface areas (m2/gram) are in the range from 10 to 1000 m2/gram or from 20 to 500 m2/gram.
  • the support may or may not comprise a binder.
  • the second catalyst comprises at least two metal components: (i) a metal promoter, and (ii) a dehydrogenation metal.
  • the metal promoter comprises at least one metal component selected from Group 1 and Group 2 of the Periodic Table of Elements, such that the metal promoter may comprise any combination or mixture of metal components selected from Groups 1 and 2 of the Periodic Table of Elements.
  • the metal promoter is present in an amount of at least 0.1 wt %, at least 0.2 wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least 0.6 wt %, at least 0.7 wt %, at least 0.8 wt %, at least 0.9 wt %, and at least 1.0 wt %.
  • the metal promoter comprises at least one metal component selected from Group 1 of the Periodic Table of Elements, such as potassium, cesium and rubidium; preferably potassium and potassium compounds.
  • the metal promoter comprises at least one metal component selected from Group 1 of the Periodic Table of Elements.
  • the metal promoter comprises at least one metal component selected from Group 2 of the Periodic Table of Elements such as beryllium, calcium, magnesium, strontium, barium and radium; preferably calcium and magnesium.
  • the metal promoter is present in an amount between about 0.1 and about 5 wt % of the catalyst or between about 0.2 and about 4 wt % of the catalyst or between about 0.3 and about 3 wt % of the catalyst.
  • the second catalyst comprises a dehydrogenation component comprising at least one metal component selected from Groups 6 to 10 of the Periodic Table of Elements, such as platinum and palladium such that the dehydrogenation component may comprise any combination or mixture of metal components selected from Groups 6 to 10 of the Periodic Table of Elements.
  • the dehydrogenation component comprises at least one metal component selected from Group 10 of the Periodic Table of Elements.
  • the dehydrogenation component is present in an amount between about 0.1 and about 10 wt % of the catalyst such as between about 0.1 and about 5 wt % of the catalyst or between about 0.2 and about 4 wt % of the catalyst or between about 0.3 and about 3 wt % of the catalyst.
  • the metal promoter is present in an amount of at least 0.1 wt %, at least 0.2 wt %, at least 0.3 wt %, at least 0.4 wt %, at least 0.5 wt %, at least 0.6 wt %, at least 0.7 wt %, at least 0.8 wt %, at least 0.9 wt %, and at least 1.0 wt %.
  • the second catalyst is produced by initially treating the support, such as by impregnation, with a solution of the metal promoter, such as an aqueous solution of potassium carbonate. After drying, the treated support is calcined, normally in an oxygen-containing atmosphere, such as air, at a temperature of about 100° C. to about 700° C. for a time of about 0.5 to about 50 hours. The calcined support is then treated, again typically by impregnation, with a solution of the dehydrogenation component or a precursor thereof.
  • a solution of the metal promoter such as an aqueous solution of potassium carbonate.
  • the dehydrogenation component may be impregnated into the support with the aid of at least one organic dispersant.
  • the organic dispersant may help to increase the metal dispersion of the metal promoter.
  • the at least one organic dispersant may be used to increase the metal dispersion of the dehydrogenation component with or without the impregnation of the metal promoter into the support.
  • the at least one organic dispersant is selected from an amino alcohol and an amino acid, such as arginine. Generally, the organic dispersant is present in an amount between about 1 and about 20 wt % of the solution.
  • the support After treatment with the dehydrogenation component, the support is again dried and calcined, normally in an oxygen-containing atmosphere, such as air, at a temperature of about 100° C. to about 600° C. for a time of about 0.5 to about 50 hours.
  • an oxygen-containing atmosphere such as air
  • the dehydrogenation catalyst is produced by initially treating the support, such as by impregnation, with a solution containing both the metal promoter and the dehydrogenation component or a precursor thereof, optionally together with at least one organic dispersant selected from an amino alcohol and an amino acid, such as arginine.
  • a single calcination procedure normally in an oxygen-containing atmosphere, such as air, at a temperature of about 100° C. to about 700° C. for a time of about 0.5 to about 50 hours, is used to produce the finished catalyst.
  • the first reaction product will be produced in a first reaction zone comprising the first catalyst and the second reaction product will be produced in a second reaction zone comprising the second catalyst.
  • the different reaction zones may be contained within the same reactor vessel such as a stacked bed configuration.
  • the first and second catalyst may be contained in separate reactor vessels.
  • the first reaction zone is generally operated at a temperature between about 200° C. and about 750° C., such as between about 300° C. and about 500° C., a pressure between about 100 and about 7,000 kPaa, such as between about 300 and about 3000 kPaa, a weight hourly space velocity (WHSV) between about 0.2 and about 50 hr ⁇ 1 , such as between about 1 and about 20 hr ⁇ 1 and a hydrogen to hydrocarbon feed molar ratio between about 0.1 and about 20, such as between about 1 and about 5.
  • WHSV weight hourly space velocity
  • the first reaction zone It is preferable to operate the first reaction zone at a temperature between about 100° C. and about 400° C., a pressure between about 100 and about 7,000 kPaa, and a hydrogen to hydrocarbon molar ratio between about 0.1 to about 10.
  • the temperature of the first reaction zone is from about 300° C. to about 750° C.; from about 350° C. to about 650° C.; from about 400° C. to about 550° C., from about 450° C. to about 550° C., and from about 400° C. to about 500° C.
  • the temperature lower limit may be about 350° C., about 400° C., about 430° C., about 440° C., about 450° C., about 460° C., about 470° C., about 480° C., and about 490° C.; and the upper limit temperature may be about 500° C., about 510° C., about 520° C., about 530° C., about 540° C., about 550° C., about 600° C., about 650° C., about 700° C., and about 750° C. with ranges from any lower limit to any upper limit being contemplated.
  • the temperature lower limit may be about 500° C., about 510° C., about 520° C., about 530° C., about 540° C., and about 550° C.; and the upper limit temperature may be about 560° C., about 570° C., about 580° C., about 590° C., about 600° C., about 650° C., about 700° C., and about 750° C. with ranges from any lower limit to any upper limit being contemplated.
  • the pressure of the first reaction zone is from 0 to about 300 psig (0 to 2068 kPag), 50 to 300 psig (345 to 2068 kPag), from 60 to 300 psig (414 to 2068 kPag), from 70 to 300 psig (482 to 2068 kPag), from 80 to 300 psig (552 to 2068 kPag), from 90 to 300 psig (621 to 2068 kPag), and from 100 to 300 psig (689 to 2068 kPag).
  • the temperature lower limit may be 50 psig (345 kPag), 60 psig (414 kPag), 70 psig (482 kPag), 80 psig (552 kPag), 90 psig (621 kPa), and 100 psig (689 kPag); and the upper limit temperature may be 125 psig (862 kPag), 150 psig (1034 kPag), 175 psig (1207 kPag), 200 psig (1379 kPag), 250 psig (1724 kPag), 300 psig (2068 kPag), 400 psig (2758 kPag), and 500 psig (3447 kPag) with ranges from any lower limit to any upper limit being contemplated.
  • the temperature lower limit may be 150 psig (1034 kPag), 160 psig (1103 kPag), 170 psig (1172 kPag), 180 psig (1241 kPag), 190 psig (1310 kPag), and 200 psig (1379 kPag); and the upper limit temperature may be 250 psig (1724 kPag), 300 psig (2068 kPag), 400 psig (2758 kPag), and 500 psig (3447 kPag) with ranges from any lower limit to any upper limit being contemplated.
  • the second reaction zone may be operated at about the same conditions as the first reaction zone but preferably is operated at a temperature between about 250° C. and about 650° C., a pressure between about 100 and about 7,000 kPaa, and a hydrogen to hydrocarbon molar ratio between about 0.1 to about 10. This is generally true when stacked bed process is utilized; however, the operating conditions can fluctuate between the first and second beds regardless of the configuration. In the separate reactor embodiment, the conditions will be within the same range of the first reaction zone, but may be different from the first reaction zone conditions.
  • the present process can be used with any hydrocarbon stream comprising at least one non-aromatic six-membered ring compound and at least one non-aromatic five-membered ring compound
  • the process has particular application as part of an integrated process for the conversion of benzene to phenol.
  • the benzene is initially converted to cyclohexylbenzene by any conventional technique, including alkylation of benzene with cyclohexene in the presence of an acid catalyst, such as zeolite beta or an MCM-22 family molecular sieve, or by oxidative coupling of benzene to biphenyl followed by hydrogenation of the biphenyl.
  • an acid catalyst such as zeolite beta or an MCM-22 family molecular sieve
  • the cyclohexylbenzene is generally produced by contacting the benzene with hydrogen under hydroalkylation conditions in the presence of a hydroalkylation catalyst whereby the benzene undergoes the following reaction (1) to produce cyclohexylbenzene (CHB):
  • the hydroalkylation reaction can be conducted in a wide range of reactor configurations including fixed bed, slurry reactors, and/or catalytic distillation towers. In addition, the hydroalkylation reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in which at least the hydrogen is introduced to the reaction in stages.
  • Suitable reaction temperatures are between about 100° C. and about 400° C., such as between about 125° C. and about 250° C., while suitable reaction pressures are between about 100 and about 7,000 kPa, such as between about 500 and about 5,000 kPa.
  • Suitable values for the molar ratio of hydrogen to benzene are between about 0.15:1 and about 15:1, such as between about 0.4:1 and about 4:1 for example between about 0.4 and about 0.9:1.
  • the catalyst employed in the hydroalkylation reaction is generally a bifunctional catalyst comprising a molecular sieve of the MCM-22 family and a hydrogenation metal.
  • MCM-22 family material (or “material of the MCM-22 family” or “molecular sieve of the MCM-22 family”), as used herein, includes one or more of:
  • molecular sieves made from a common first degree crystalline building block unit cell, which unit cell has the MWW framework topology.
  • a unit cell is a spatial arrangement of atoms which if tiled in three-dimensional space describes the crystal structure. Such crystal structures are discussed in the “Atlas of Zeolite Framework Types”, Fifth edition, 2001, the entire content of which is incorporated as reference);
  • molecular sieves made from a common second degree building block, being a 2-dimensional tiling of such MWW framework topology unit cells, forming a monolayer of one unit cell thickness, preferably one c-unit cell thickness;
  • molecular sieves made from common second degree building blocks, being layers of one or more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness.
  • the stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof;
  • molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.
  • Molecular sieves of MCM-22 family generally have an X-ray diffraction pattern including d-spacing maxima at 12.4 ⁇ 0.25, 6.9 ⁇ 0.15, 3.57 ⁇ 0.07 and 3.42 ⁇ 0.07 Angstrom.
  • the X-ray diffraction data used to characterize the material (b) are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system.
  • Molecular sieves of MCM-22 family include MCM-22 (described in U.S. Pat. No. 4,954,325); PSH-3 (described in U.S. Pat. No. 4,439,409); SSZ-25 (described in U.S. Pat. No.
  • the molecular sieve is selected from (a) MCM-49, (b) MCM-56 and (c) isotypes of MCM-49 and MCM-56, such as ITQ-2.
  • any known hydrogenation metal can be employed in the hydroalkylation catalyst, although suitable metals include palladium, ruthenium, nickel, zinc, tin, and cobalt, with palladium being particularly advantageous.
  • the amount of hydrogenation metal present in the catalyst is between about 0.05 and about 10 wt %, such as between about 0.1 and about 5 wt %, of the catalyst.
  • the amount of hydrogenation metal present is such that the molar ratio of the aluminum in the molecular sieve to the hydrogenation metal is from about 1.5 to about 1500, for example, from about 75 to about 750, such as from about 100 to about 300.
  • the hydrogenation metal may be directly supported on the MCM-22 family molecular sieve by, for example, impregnation or ion exchange.
  • at least 50 wt %, for example, at least 75 wt %, and generally substantially all of the hydrogenation metal is supported on an inorganic oxide separate from but composited with the molecular sieve.
  • the activity of the catalyst and its selectivity to cyclohexylbenzene and dicyclohexylbenzene are increased as compared with an equivalent catalyst in which the hydrogenation metal is supported on the molecular sieve.
  • the inorganic oxide employed in such a composite hydroalkylation catalyst is not narrowly defined provided it is stable and inert under the conditions of the hydroalkylation reaction.
  • Suitable inorganic oxides include oxides of Groups 2, 4, 13 and 14 of the Periodic Table of Elements, such as alumina, titania, and/or zirconia. As used herein, the numbering scheme for the Periodic Table Groups is as disclosed in Chemical and Engineering News, 63(5), p. 27 (1985).
  • the hydrogenation metal is deposited on the inorganic oxide, conveniently by impregnation, before the metal-containing inorganic oxide is composited with the molecular sieve.
  • the catalyst composite is produced by co-pelletization, in which a mixture of the molecular sieve and the metal-containing inorganic oxide are formed into pellets at high pressure (generally about 350 to about 350,000 kPa), or by co-extrusion, in which a slurry of the molecular sieve and the metal-containing inorganic oxide, optionally together with a separate binder, are forced through a die. If necessary, additional hydrogenation metal can subsequently be deposited on the resultant catalyst composite.
  • Suitable binder materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Naturally occurring clays which can be used as a binder include those of the montmorillonite and kaolin families, which families include the subbentonites 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.
  • Suitable metal oxide binders include silica, alumina, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • the hydroalkylation step is highly selective towards cyclohexylbenzene
  • the effluent from the hydroalkylation reaction will normally contain unreacted benzene feed, some dialkylated products, and other by-products, particularly cyclohexane, and methylcyclopentane.
  • typical selectivities to cyclohexane and methylcyclopentane in the hydroalkylation reaction are 1-25 wt % and 0.1-2 wt % respectively.
  • the hydroalkylation reaction effluent is therefore fed to a separation system normally comprising at least two distillation towers.
  • This C 6 -rich stream is then subjected to the dehydrogenation process described above such that at least a portion of the cyclohexane in the stream is converted to benzene and at least a portion of the methylcyclopentane is converted to linear and/or branched paraffins, such as 2-methylpentane, 3-methylpentane, n-hexane, and other hydrocarbon components such as isohexane, C 5 aliphatics, and C 1 to C 4 aliphatics.
  • linear and/or branched paraffins such as 2-methylpentane, 3-methylpentane, n-hexane, and other hydrocarbon components such as isohexane, C 5 aliphatics, and C 1 to C 4 aliphatics.
  • the dehydrogenation product stream is then fed to a further separation system, typically a further distillation tower, to divide the dehydrogenation product stream into a C 6 recycle stream and a paraffin-rich stream comprising 2-methylpentane, 3-methylpentane, and other C 1 to C 6 paraffins.
  • the C 6 recycle stream can then be recycled to the hydroalkylation step, while the paraffinic stream can be used as a fuel for the process.
  • the remainder of hydroalkylation reaction effluent is fed a second distillation tower to separate the monocyclohexylbenzene product from any dicyclohexylbenzene and other heavies.
  • a second distillation tower to separate the monocyclohexylbenzene product from any dicyclohexylbenzene and other heavies.
  • Transalkylation with additional benzene is typically effected in a transalkylation reactor, separate from the hydroalkylation reactor, over a suitable transalkylation catalyst, including large pore molecular sieves such as a molecular sieve of the MCM-22 family, zeolite beta, MCM-68 (see U.S. Pat. No. 6,014,018), zeolite Y, zeolite USY, and mordenite.
  • a large pore molecular sieve has an average pore size in excess of 7 ⁇ in some embodiments or from 7 ⁇ to 12 ⁇ in other embodiments.
  • the transalkylation reaction is typically conducted under at least partial liquid phase conditions, which suitably include a temperature of about 100 to about 300° C., a pressure of about 800 to about 3500 kPa, a weight hourly space velocity of about 1 to about 10 hr ⁇ 1 on total feed, and a benzene/dicyclohexylbenzene weight ratio about of 1:1 to about 5:1.
  • the transalkylation reaction effluent can then be returned to the second distillation tower to recover the additional monocyclohexylbenzene product produced in the transalkylation reaction.
  • the cyclohexylbenzene is converted into phenol by a process similar to the Hock process.
  • the cyclohexylbenzene is initially oxidized to the corresponding hydroperoxide. This is accomplished by introducing an oxygen-containing gas, such as air, into a liquid phase containing the cyclohexylbenzene.
  • an oxygen-containing gas such as air
  • atmospheric air oxidation of cyclohexylbenzene in the absence of a catalyst is very slow and hence the oxidation is normally conducted in the presence of a catalyst.
  • Suitable catalysts for the cyclohexylbenzene oxidation step are the N-hydroxy substituted cyclic imides described in U.S. Pat. No. 6,720,462 and incorporated herein by reference, such as N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, tetrabromo-N-hydroxyphthalimide, tetrachloro-N-hydroxyphthalimide, N-hydroxyhetimide, N-hydroxyhimimide, N-hydroxytrimellitimide, N-hydroxybenzene-1,2,4-tricarboximide, N,N′-dihydroxy(pyromellitic diimide), N,N′-dihydroxy(benzophenone-3,3′,4,4′-tetracarboxylic diimide), N-hydroxymaleimide, pyridine-2,3-dicarboximide, N-hydroxysuccinimide, N-hydroxy(tartaric imide), N-hydroxy-5-n
  • the N-hydroxy substituted cyclic imide or the N,N′,N′′-trihydroxyisocyanuric acid is employed in an amount between 0.0001 wt % to 15 wt %, such as between 0.001 to 5 wt %, of the cyclohexylbenzene.
  • Suitable conditions for the oxidation step include a temperature between about 70° C. and about 200° C., such as about 90° C. to about 130° C., and a pressure of about 50 to 10,000 kPa.
  • Any oxygen-containing gas, preferably air, can be used as the oxidizing medium.
  • the reaction can take place in batch reactors or continuous flow reactors.
  • a basic buffering agent may be added to react with acidic by-products that may form during the oxidation.
  • an aqueous phase may be introduced, which can help dissolve basic compounds, such as sodium carbonate.
  • the final reactive step in the conversion of the cyclohexylbenzene into phenol and cyclohexanone involves cleavage of the cyclohexylbenzene hydroperoxide, which is conveniently effected by contacting the hydroperoxide with a catalyst in the liquid phase at a temperature of about 20° C. to about 150° C., such as about 40° C. to about 120° C., a pressure of about 50 to about 2,500 kPa, such as about 100 to about 1000 kPa.
  • the cyclohexylbenzene hydroperoxide is preferably diluted in an organic solvent inert to the cleavage reaction, such as methyl ethyl ketone, cyclohexanone, phenol or cyclohexylbenzene, to assist in heat removal.
  • the cleavage reaction is conveniently conducted in a catalytic distillation unit.
  • the catalyst employed in the cleavage step can be a homogeneous catalyst or a heterogeneous catalyst.
  • Suitable homogeneous cleavage catalysts include sulfuric acid, perchloric acid, phosphoric acid, hydrochloric acid and p-toluenesulfonic acid. Ferric chloride, boron trifluoride, sulfur dioxide and sulfur trioxide are also effective homogeneous cleavage catalysts.
  • the preferred homogeneous cleavage catalyst is sulfuric acid, with preferred concentrations in the range of 0.05 to 0.5 wt %.
  • a neutralization step preferably follows the cleavage step. Such a neutralization step typically involves contact with a basic component, with subsequent decanting of a salt-enriched aqueous phase.
  • a suitable heterogeneous catalyst for use in the cleavage of cyclohexylbenzene hydroperoxide includes a smectite clay, such as an acidic montmorillonite silica-alumina clay, as described in U.S. Pat. No. 4,870,217, the entire disclosure of which is incorporated herein by reference.
  • the effluent from the cleavage reaction comprises phenol and cyclohexanone in substantially equimolar amounts and, depending on demand, the cyclohexanone can be sold or can be dehydrogenated into additional phenol. Any suitable dehydrogenation catalyst for the dehydrogenation of cyclohexanone can be used in this reaction.
  • the cyclohexanone dehydrogenation catalyst is selected from the catalyst compositions described as being useful for the second catalyst in the first conversion step of this invention.
  • Suitable conditions for the dehydrogenation step comprise a temperature of about 250° C. to about 700° C. and a pressure of about 0.01 atm to about 20 atm (1 kPa to 2000 kPa), such as a temperature of about 300° C. to about 450° C. and a pressure of about 1 atm to about 10 atm (100 kPa to 1000 kPa).
  • a stream is described as being “rich” in a specified species, it is meant that the specified species in that stream is enriched relative to other species in the same stream or composition on a weight percentage basis.
  • a cyclohexylbenzene-rich stream will have a cyclohexylbenzene wt % greater than any other species or component in that same stream.
  • a “C 6 ” species generally means any species containing 6 carbon atoms.
  • DTA spectra were obtained using approximately 150 mg of catalyst loaded into a Mettler TGA 851 thermal balance.
  • the catalysts were treated under flowing air (50 cc/min) at one atmosphere total pressure.
  • the samples were heated at 4° C./min from room temperature to the final temperature. Heat effects were measured by an integrated thermopile to assess the relative strength of the endothermic and exothermic events.
  • An arginine-containing catalyst was prepared by dissolving 1.09 g of a chloroiridic acid stock solution of 18.5 wt % Ir content along with 1.465 g of arginine into water to a total volume of 22 cc.
  • the resultant solution had an arginine to Ir mole ratio of 8:1 and was impregnated by incipient wetness onto 20 grams of Davison 646 silica support. After impregnation, the sample was dried overnight at 100° C. to give an arginine-containing 1 wt % Ir/SiO 2 catalyst. A portion of the dried catalyst was then calcined for 4 hours at 400° C. and another portion calcined for 4 hours at 500° C. A ramp rate of 2° C./minute was used to reach the desired calcination temperature.
  • Example 2 A portion of the dried arginine-containing 1 wt % Ir/SiO 2 sample of Example 2 was heated in air to 600° C. at 4° C./min.
  • the DTA-TGA (Differential Thermal Analysis and Thermal Gravimetry Analysis) plot is shown in FIG. 1 .
  • Several weak exotherms are shown at temperatures lower than 400° C. and then a very sharp and strong exotherm at about 475° C.
  • Example 2 A portion of the arginine-containing 1 wt % Ir/SiO 2 sample of Example 2 that had been calcined at 400° C. was heated in air to 600° C. at 4° C./min.
  • the DTA-TGA plot is shown in FIG. 2 , which shows a single strong exotherm still exists indicating that the complex formed after partial decomposition of the impregnate is intact after the 400° C. calcination.
  • the reduction profile is given in FIG. 3 and shows that reduction starts near 350° C. and requires temperatures of 400-450° C. to fully reduce the sample.
  • Example 1 A portion of the dried 1 wt % Ir/SiO 2 sample of Example 1 was heated in air to 600° C. at 4° C./min.
  • the TG/DTA plot is given in FIG. 4 and shows the (endothermic) water loss at low temperature and then the decomposition of the chloroiridate complex at temperatures above 420° C. (with a very weak exotherm) to form iridium oxide.
  • Table 1 show that the hydrogen chemisorption values are relatively low and do not substantially change with calcinations at 100° C. or 350° C. As seen in FIG. 4 , after the chloroiridate complex decomposes to form IrO 2 at temperatures of about 450° C., the hydrogen chemisorption number (post 500° C. calcination) is very low. Table 1 also shows that reduction of the Example 1 samples occurs between 325 and 400° C.
  • Table 2 shows that there after the 400° C. calcinations of the arginine-containing complex of Example 2, a reduction temperature of 400° C. is required to reduce the complex and obtain metal sites.
  • the high hydrogen chemisorption values after 400 and 450° C. reduction greatly exceed those obtained with the arginine-free samples of Example 1.
  • the complex After 500° C. calcination, the complex fully oxidizes and the iridium oxide that forms is mobile and on reduction forms large particles (low dispersion values).
  • a 1 wt % Ru(arginine)/SiO 2 catalyst was prepared in an analogous way to the 1 wt % Ir(arginine)/SiO 2 catalyst of Example 2.
  • To 13.46 g of an aqueous ruthenium nitrosyl nitrate solution containing 1.5 wt % Ru were added 2.78 g arginine (arginine/Ru molar ratio of 8:1) and enough water to bring the total volume to 22 cc.
  • the solution was impregnated by incipient wetness onto 20 grams of Davison 646 silica, and dried overnight at 100° C. One portion of the catalyst was heated in air at 4° C./min to 300° C.
  • TEA-containing catalyst was prepared by dissolving 1.09 g of a chloroiridic acid stock solution of 18.5 % Ir content along with 1.26 g of TEA into water to a total volume of 22 cc. This was impregnated by incipient wetness onto 20 g of Davison 646, and then dried overnight at 100° C. A portion of this catalyst was calcined at 400° C. for 4 hours using a ramp rate of 2° C./minute to reach the desired calcination temperature. The hydrogen chemisorption values were measured and are shown in Table 4.
  • Each catalyst was sized to 14-30 mesh particles and 0.5 to 2.0 g of the sized catalyst was diluted with 40-60 mesh quartz chips to 3 cc.
  • the catalyst/quartz chips mixture was thoroughly mixed and loaded into an isothermal, down-flow, 3 ⁇ 8 inch (0.95 cm) outside diameter, fixed-bed reactor operated in a down-flow mode.
  • the reactor was pressurized to 100 psig (791 kPa) with hydrogen flow set at 200 cc/min.
  • the reactor was ramped up to 425° C. at 2° C./min. Once reaching 425° C., the temperature was held constant for 1 hour.
  • the reactor was then cooled down to at 5° C./min until a stable temperature of 260° C. was achieved.
  • the pressure of the reactor was increased to 350 psig (2514 kPa).
  • the hydrogen flow was reduced to 96 cc/min, and methylcyclopentane was introduced by a liquid feed pump at 5.34 cc/hr.
  • H 2 /MCP molar ratio was 5:1.
  • Total product analysis (except hydrogen content) was determined every 2 hours starting at 0.5 hour on stream with an HP-5890 GC.
  • the GC was equipped with a 60 meter DB-1 column (0.25 mm internal diameter and 1 mm film thickness) and flame ionization detector.
  • the GC temperature program was: ⁇ 20° C., 2 min, 8° C./min to 250° C., and hold for 30 min.
  • MCP conversion was measured after 0.5 hour on stream and 3 days on stream and are denoted as fresh and stabilized activities respectively. Conversion was all kept below 98%.
  • First order kinetics were used to calculate a rate constant (k) for each sample, with k i indicating the initial value at 0.5 hour on stream and k s the value at 3 days on stream.
  • k rate constant
  • FIG. 5 shows that the initial activity for methylcyclopentane ring opening is a function of the number of metal sites at the particle surface as measured by hydrogen chemisorption (i.e., the dispersion x the metal loading).
  • the 1 wt % Ir(arginine)/SiO 2 catalyst of Example 2 that had been calcined at 400° C. exhibited the highest ring opening activity.
  • FIG. 6 shows the activity data after the catalysts have been on stream for 3 days. During this time there is significant deactivation. This activity is plotted as a function of the hydrogen chemisorption of the fresh catalysts.
  • this invention relates to:
  • a process for producing a catalyst composition comprising an iridium component dispersed on a support, the process comprising:
  • the at least one organic compound is selected from an (i) amino acids and (ii) compounds comprising an amino group and an alcohol group.
  • the partially decomposed organic iridium complex retains between 10 and 95% by weight of the dry weight attributed to the organic iridium complex prior to partial decomposition.
  • the partially decomposed organic iridium complex exhibits one or more infra-red absorption bands between 2100-2200 cm ⁇ 1 that are not present in the organic complex before partial decomposition.
  • the organic compound comprises an aliphatic amine containing one or more hydroxyl groups. 6.
  • the organic compound comprises a hydroxyalkylamine.
  • the hydroxyalkylamine comprises one or more of: methanolamine, di-methanolamine, tri-methanolamine, ethanolamine, di-ethanolamine, tri-ethanolamine, butanolamine, di-butanolamine, tri-butanolamine, propanolamine, di-propanolamine, dimethylethanolamine, di-isopropylethanolamine, methyldiethanolamine, dimethylamino-2-propanol and tri-propanolamine 8.
  • the process of embodiment 1, wherein the organic compound comprises tri-ethanolamine.
  • the organic compound comprises an amino acid. 10.
  • the process of embodiment 1, wherein the amino acid comprises arginine.
  • heating step (b) comprises heating the treated support to a temperature of about 375° C. to about 425° C.
  • a catalyst composition produced by the process of embodiment 1. 13 A method for converting a cyclic aliphatic hydrocarbon to acyclic alkane or alkene comprising contacting the cyclic aliphatic hydrocarbon under ring-opening conditions with a catalyst wherein the catalyst is produced by a method comprising:
  • the at least one organic compound is selected from an (i) amino acids; and (ii) compounds comprising an amino group and an alcohol group.
  • the partially decomposed organic iridium complex retains between 10 and 95% by weight of the dry weight attributed to the organic iridium complex prior to partial decomposition.
  • the cyclic aliphatic hydrocarbon is methylcyclopentane.
  • the partially decomposed organic iridium complex exhibits one or more infra-red absorption bands between 2100-2200 cm ⁇ 1 that are not present in the organic complex before partial decomposition. 18.
  • the organic compound comprises an aliphatic amine containing one or more hydroxyl groups. 19. The process of embodiment 13, wherein the organic compound comprises a substituted aliphatic hydroxyalkylamine. 20. The process of embodiment 13, wherein the hydroxyalkylamine comprises one or more of: methanolamine, di-methanolamine, tri-methanolamine, ethanolamine, di-ethanolamine, tri-ethanolamine, butanolamine, di-butanolamine, tri-butanolamine, propanolamine, di-propanolamine, dimethylethanolamine, di-isopropylethanolamine, methyldiethanolamine, dimethylamino-2-propanol and tri-propanolamine. 21.
  • step (v) separating at least a portion of the second reaction product stream produced in producing step (iv) into a benzene recycle stream and a paraffins-rich stream comprising 2-methylpentane and 3-methylpentane;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
US13/512,620 2010-02-05 2010-12-17 Iridium-Containing Catalysts, Their Production and Use Abandoned US20120271076A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/512,620 US20120271076A1 (en) 2010-02-05 2010-12-17 Iridium-Containing Catalysts, Their Production and Use

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US30179910P 2010-02-05 2010-02-05
US30179410P 2010-02-05 2010-02-05
US33478410P 2010-05-14 2010-05-14
US13/512,620 US20120271076A1 (en) 2010-02-05 2010-12-17 Iridium-Containing Catalysts, Their Production and Use
PCT/US2010/061027 WO2011096996A1 (en) 2010-02-05 2010-12-17 Iridium-containing catalysts, their production and use

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/061027 A-371-Of-International WO2011096996A1 (en) 2010-02-05 2010-12-17 Iridium-containing catalysts, their production and use

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/336,312 Division US9382171B2 (en) 2010-02-05 2014-07-21 Iridium-containing catalysts, their production and use

Publications (1)

Publication Number Publication Date
US20120271076A1 true US20120271076A1 (en) 2012-10-25

Family

ID=43846782

Family Applications (2)

Application Number Title Priority Date Filing Date
US13/512,620 Abandoned US20120271076A1 (en) 2010-02-05 2010-12-17 Iridium-Containing Catalysts, Their Production and Use
US14/336,312 Active US9382171B2 (en) 2010-02-05 2014-07-21 Iridium-containing catalysts, their production and use

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/336,312 Active US9382171B2 (en) 2010-02-05 2014-07-21 Iridium-containing catalysts, their production and use

Country Status (3)

Country Link
US (2) US20120271076A1 (zh)
CN (1) CN102711988B (zh)
WO (1) WO2011096996A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160193591A1 (en) * 2013-10-18 2016-07-07 Exxonmobile Chemical Patents Inc. Hydrogenation Catalyst, Its Method of Preparation and Use

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9580368B2 (en) 2010-12-17 2017-02-28 Exxonmobil Chemical Patents Inc. Dehydrogenation process
CN106902862A (zh) * 2017-03-01 2017-06-30 武汉凯迪工程技术研究总院有限公司 选择性加氢催化剂和制备方法及其生成2‑甲基烯丙醇的催化评价方法
US20230021410A1 (en) * 2019-12-19 2023-01-26 Exxonmobil Chemical Patents Inc. Alkyl-Demethylation Processes and Catalyst Compositions Therefor

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020038068A1 (en) * 2000-07-21 2002-03-28 Baird William C. Naphthene ring opening over a ring opening catalyst combination
US20060166809A1 (en) * 2002-11-20 2006-07-27 Andrzej Malek Methods for preparing catalysts
US7605107B2 (en) * 2005-09-29 2009-10-20 Exxonmobil Research And Engineering Company Method of preparing a supported hydrotreating catalyst

Family Cites Families (62)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB514587A (en) 1938-06-01 1939-11-13 Distillers Co Yeast Ltd Improvements in or relating to the catalytic dehydrogenation of isopropyl benzene
US3194843A (en) 1961-04-11 1965-07-13 Halcon International Inc Reactivation of catalyst in production of a phenol
US3358044A (en) 1961-08-25 1967-12-12 Halcon International Inc Method for preparing phenol-type compounds employing an improved catalyst
US3308069A (en) 1964-05-01 1967-03-07 Mobil Oil Corp Catalytic composition of a crystalline zeolite
USRE28341E (en) 1964-05-01 1975-02-18 Marshall dann
FR1499878A (fr) 1965-12-08 1967-11-03 Inst Francais Du Petrole Procédé de fabrication de phénol par déshydrogénation catalytique de cyclohexanol, de cyclohexanone ou de leurs mélanges
US3442958A (en) 1966-06-23 1969-05-06 Halcon International Inc Purification of phenol
FR1549174A (zh) 1967-01-04 1968-12-13
US3580970A (en) 1967-11-22 1971-05-25 Gulf Research Development Co Dehydrogenation of cycloaliphatic ketones and alcohols
US3534116A (en) 1968-10-11 1970-10-13 Exxon Research Engineering Co Slurry adduction process
US3519575A (en) 1968-11-25 1970-07-07 Gulf Research Development Co Method of preparing an iron group metal-tin catalyst
FR2080099A5 (zh) * 1970-02-23 1971-11-12 Inst Francais Du Petrole
US3856661A (en) 1970-02-23 1974-12-24 Inst Francais Du Petrole Reforming using homogeneous platinum-iridium catalyst
US3691102A (en) 1970-05-11 1972-09-12 Gulf Research Development Co Group viii metal-tin catalyst and method of making same
US3843560A (en) 1972-02-01 1974-10-22 Universal Oil Prod Co Multicomponent dehydrogenation catalyst containing platinum,iridium,alkali or alkaline earth metal oxide,and sulfur
US3962362A (en) 1975-03-31 1976-06-08 Texaco Development Corporation Method for preparing polyphenyls
US4106218A (en) 1975-06-25 1978-08-15 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Simulator method and apparatus for practicing the mating of an observer-controlled object with a target
US4070413A (en) 1976-10-28 1978-01-24 Uop Inc. Dehydrogenation of saturated hydrocarbons
US4206082A (en) 1976-11-08 1980-06-03 Phillips Petroleum Company Hydroalkylation process and a composition and process for producing said composition
US4147726A (en) 1976-11-08 1979-04-03 Phillips Petroleum Company Acid-catalyzed hydrolysis of organic hydroperoxide employing a polar solvent and phenol as reaction medium
US4122125A (en) 1976-11-08 1978-10-24 Phillips Petroleum Company Hydroalkylation using multimetallic zeolite catalyst
US4094918A (en) 1977-02-10 1978-06-13 Phillips Petroleum Company Hydroalkylation process using multi-metallic zeolite catalyst
US4177165A (en) 1977-02-10 1979-12-04 Phillips Petroleum Company Hydroalkylation composition and process for producing said composition
US4417076A (en) 1979-12-27 1983-11-22 Rozovsky Alexandr Y Catalyst and process for dehydrogenation of oxygen-containing derivatives of the cyclohexane series into corresponding cyclic ketones and/or phenols
US4418237A (en) 1981-03-30 1983-11-29 Uop Inc. Dehydrogenation of dehydrogenatable hydrocarbons
DE3117135A1 (de) 1981-04-30 1982-11-18 Bayer Ag, 5090 Leverkusen Kristallines alumosilicat, verfahren zu dessen herstellung sowie dessen verwendung zur katalytischen umwandlung von methanol und/oder dimethylether in kohlenwasserstoffe
JPS5867636A (ja) 1981-10-16 1983-04-22 Mitsubishi Chem Ind Ltd 多価フエノ−ルの製造方法
US4501926A (en) 1982-05-18 1985-02-26 Mobil Oil Corporation Catalytic dewaxing process with zeolite beta
US4826667A (en) 1986-01-29 1989-05-02 Chevron Research Company Zeolite SSZ-25
US4954325A (en) 1986-07-29 1990-09-04 Mobil Oil Corp. Composition of synthetic porous crystalline material, its synthesis and use
IT1205681B (it) 1987-05-26 1989-03-31 Eniricerche Spa Materiale sintetico cristallino poroso contenente ossidi di silicio e boro
JPH01146837A (ja) 1987-12-03 1989-06-08 Mitsui Petrochem Ind Ltd シクロヘキセノンの脱水素方法
US4891458A (en) 1987-12-17 1990-01-02 Innes Robert A Liquid phase alkylation or transalkylation process using zeolite beta
US4788371A (en) 1987-12-30 1988-11-29 Uop Inc. Catalytic oxidative steam dehydrogenation process
DE68900118D1 (de) 1988-02-11 1991-07-25 Fina Research Verfahren zur herstellung von platingruppenmetallen enthaltenden katalysatoren und deren verwendungen.
JPH01226840A (ja) 1988-03-07 1989-09-11 Mitsui Petrochem Ind Ltd フェノール類および／またはシクロヘキサノン類の製造方法
GB8809214D0 (en) 1988-04-19 1988-05-25 Exxon Chemical Patents Inc Reductive alkylation process
US4870217A (en) 1988-10-24 1989-09-26 Texaco Chemical Company Method for production of phenol/acetone from cumene hydroperoxide
GB8924410D0 (en) 1989-10-30 1989-12-20 Exxon Chemical Patents Inc Zeolite l
US5250277A (en) 1991-01-11 1993-10-05 Mobil Oil Corp. Crystalline oxide material
US5256348A (en) 1991-06-13 1993-10-26 Waller Michael V Tire shaping pressure control system and method
US5236575A (en) 1991-06-19 1993-08-17 Mobil Oil Corp. Synthetic porous crystalline mcm-49, its synthesis and use
US5362697A (en) 1993-04-26 1994-11-08 Mobil Oil Corp. Synthetic layered MCM-56, its synthesis and use
US5811624A (en) 1995-09-05 1998-09-22 Exxon Research And Engineering Company Selective opening of five and six membered rings
ES2124154B1 (es) 1995-11-08 1999-12-01 Univ Politecnica De Valencia C Metodo de preparaciion y propiedades cataliticas de un solido microporoso con alta superficie externa.
ES2105982B1 (es) 1995-11-23 1998-07-01 Consejo Superior Investigacion Zeolita itq-1
US5906729A (en) 1997-12-08 1999-05-25 Mobil Oil Corporation Process scheme for processing sour feed in isomerization dewaxing
TW382146B (en) 1998-06-19 2000-02-11 United Microeletronics Corp Semiconductor step-down voltage device having low power consumption
US6037513A (en) 1998-07-09 2000-03-14 Mobil Oil Corporation Hydroalkylation of aromatic hydrocarbons
WO2000067902A1 (en) 1999-05-07 2000-11-16 Dsm N.V. Stable catalysts and processes for making and using the same
EP1050339A1 (en) 1999-05-07 2000-11-08 Dsm N.V. Stable catalysts and processes for making and using the same
US6489529B1 (en) 2000-01-24 2002-12-03 Exxonmobil Oil Corporation Production of monocycloalkyl aromatic compounds
DE10015874A1 (de) 2000-03-30 2001-10-11 Creavis Tech & Innovation Gmbh Verfahren zur Herstellung von aromatischen Alkoholen insbesondere Phenol
EP1288188A1 (en) 2001-08-28 2003-03-05 Avantium International B.V. Supported catalyst composition, processes for the preparation thereof and use of the supported catalyst composition
US6756030B1 (en) 2003-03-21 2004-06-29 Uop Llc Crystalline aluminosilicate zeolitic composition: UZM-8
DE10333755A1 (de) 2003-07-24 2005-03-31 Basf Ag Verfahren zur Dehydrierung von Carbonylverbindungen
US7538066B2 (en) 2005-09-29 2009-05-26 Exxonmobil Research And Engineering Company Method of preparing a hydrotreating catalyst on a support containing a rare earth metal
JP4907210B2 (ja) 2006-03-30 2012-03-28 千代田化工建設株式会社 水素の貯蔵輸送システム
US7563358B2 (en) 2006-08-24 2009-07-21 Exxonmobil Chemical Patents Inc. Process for the production of benzene, toluene, and xylenes
US20100075842A1 (en) 2006-11-29 2010-03-25 Hyun-Sik Han Potassium oxide-incorporated alumina catalysts with enhanced storage capacities of nitrogen oxide and a producing method therefor
JP5444327B2 (ja) 2008-04-25 2014-03-19 エクソンモービル・ケミカル・パテンツ・インク フェノール及び／又はシクロヘキサノンの製造方法
US7579511B1 (en) 2008-10-10 2009-08-25 Exxonmobil Research And Engineering Company Process for making cyclohexylbenzene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020038068A1 (en) * 2000-07-21 2002-03-28 Baird William C. Naphthene ring opening over a ring opening catalyst combination
US20060166809A1 (en) * 2002-11-20 2006-07-27 Andrzej Malek Methods for preparing catalysts
US7605107B2 (en) * 2005-09-29 2009-10-20 Exxonmobil Research And Engineering Company Method of preparing a supported hydrotreating catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160193591A1 (en) * 2013-10-18 2016-07-07 Exxonmobile Chemical Patents Inc. Hydrogenation Catalyst, Its Method of Preparation and Use
US9861960B2 (en) * 2013-10-18 2018-01-09 Exxonmobil Chemical Patents Inc. Hydrogenation catalyst, its method of preparation and use

Also Published As

Publication number Publication date
WO2011096996A1 (en) 2011-08-11
CN102711988B (zh) 2015-11-25
US9382171B2 (en) 2016-07-05
US20140330058A1 (en) 2014-11-06
CN102711988A (zh) 2012-10-03

Similar Documents

Publication Publication Date Title
US9580368B2 (en) Dehydrogenation process
US8884088B2 (en) Dehydrogenation process
JP6014943B2 (ja) 脱水素触媒及び方法
US20120271078A1 (en) Dehydrogenation Process
US9364823B2 (en) Activation and use of hydroalkylation catalysts
US20120302799A1 (en) Dehydrogenation Catalyst And Process
US20140187821A1 (en) Process for Producing Cycloalkylaromatic Compounds
US8969639B2 (en) Dehydrogenation process
US9382171B2 (en) Iridium-containing catalysts, their production and use
US9545622B2 (en) Activation and use of hydroalkylation catalysts
US9090528B2 (en) Hydroalkylation process
US8884075B2 (en) Process for producing phenol
US8802907B2 (en) Dehydrogenation process
KR101745220B1 (ko) 탈수소화 방법
US9029611B2 (en) Dehydrogenation of cyclohexanone to produce phenol
US9469580B2 (en) Dehydrogenation process
US20190176131A1 (en) Methods of Making Supported Mixed Metal Dehydrogenation Catalysts
US11213804B2 (en) Dehydrogenation catalysts and methods of making and using the same
JP5861795B2 (ja) 脱水素化法
US9382172B2 (en) Process of producing cyclohexylbenzene

Legal Events

Date Code Title Description
AS Assignment

Owner name: EXXONMOBIL CHEMICAL PATENTS INC., TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SOLED, STUART L.;MISEO, SABATO;BAUMGARTNER, JOSEPH E.;AND OTHERS;SIGNING DATES FROM 20120613 TO 20120618;REEL/FRAME:028534/0040

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION