EP0000432B1 - A process for effecting catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon compounds - Google Patents

A process for effecting catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon compounds Download PDF

Info

Publication number
EP0000432B1
EP0000432B1 EP78300119A EP78300119A EP0000432B1 EP 0000432 B1 EP0000432 B1 EP 0000432B1 EP 78300119 A EP78300119 A EP 78300119A EP 78300119 A EP78300119 A EP 78300119A EP 0000432 B1 EP0000432 B1 EP 0000432B1
Authority
EP
European Patent Office
Prior art keywords
zeolite
zsm
feedstock
catalyst
process according
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.)
Expired
Application number
EP78300119A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0000432A1 (en
Inventor
Fritz Arthur Smith
Albert B. Schwartz
Lloyd Lee Breckenridge
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 Oil Corp
Original Assignee
Mobil Oil Corp
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 Mobil Oil Corp filed Critical Mobil Oil Corp
Publication of EP0000432A1 publication Critical patent/EP0000432A1/en
Application granted granted Critical
Publication of EP0000432B1 publication Critical patent/EP0000432B1/en
Expired legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
    • C07C5/2732—Catalytic processes
    • C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • the present invention relates to a process for the vapour-phase catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon feedstock.
  • U.S. Patent 3,856,872 A recently developed and widely adopted catalyst for use in such processes is taught by U.S. Patent 3,856,872 to be of the ZSM-5 type of zeolite, whereby the process operates at high space velocities. Further, a process utilizing ZSM-5 type zeolites in acid form for vapor-phase conversion of a feedstock containing mixed C ⁇ aromatics in the absence of added hydrogen is taught by U.S. Patent 3,856,873.
  • the catalyst has increased acid activity, there can be a loss of xylene, the primary isomerization product, presumably due in part to disproportionation of xylenes and/or transalkylation of xylenes with any ethylbenzene which may be present in the reaction system.
  • Patent 3,293,314 is a solid acidic mixed metal-oxide catalyst, e.g., a silica-alumina mixture, having equilibration (tending to produce equilibrium products) and coke forming activities.
  • equilibration ending to produce equilibrium products
  • coke forming activities Unfortunately, such catalyst materials lose their ability to maintain their equilibration tendency and, therefore, there is a decrease in desirable isomeric products as the catalysts age.
  • Our DTOS 2,558,035 discloses catalytic conversion of alkyl aromatic hydrocarbons in the presence of zeolitic catalysts.
  • the conversion alternates between catalytic disproportionation of toluene and non-catalytic (i.e. thermal) dealkylation of toluene in the same reactor.
  • the change from the catalytic to the non-catalytic conversion is effected by eliminating the acid activity of the catalyst by contacting it with a nitrogenous poison such as ammonia or an amine, and raising the temperature.
  • a process for effecting catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon compounds of from 8 to 10 carbon atoms contained in a feedstock also containing ethylbenzene comprises contacting said feedstock in the vapor phase in a reactor with a catalyst comprising a crystalline aluminosilicate zeolite having a constraint index within the range of 1 to 12, said zeolite containing hydrogen and/or Group VIII metal cations at a temperature of 316°C to 482°C (600°F to 900°F), a pressure of 101.3 kPa to 3548.7 kPa (0 psig to 500 psig), a hydrogen/hydrocarbon mole ratio of 0 to 10 and a weight hourly space velocity of 0.1 to 200, said catalyst having been contacted, in the reactor with one or more basic nitrogen compounds, the resulting ratio of nitrogen atoms/aluminum atoms in the zeolite being from 0.01 to
  • the process of the present invention wherein the catalyst has been contacted with one or more basic nitrogen-containing compounds, exhibits substantially reduced xylene loss.
  • This reduction in xylene loss for isomerization of xylenes is an unexpected and significant benefit, and indicates that, whatever the monocyclic methyl-substituted aromatic hydrocarbon feedstock may be, substantial reduction in primary product losses will be effected and selectivity to desired product isomer will be enhanced.
  • the preferred zeolites for use in the process are zeolites ZSM-5, ZSM-11, ZSM-12, ZSM-35 and ZSM-38: they usually constitute from 10 to 90 weight percent of a composite with a binder therefor, such as alumina.
  • the preferred Group VIII metal cations are nickel, iron and/or cobalt.
  • the process is particularly applicable to the isomerisation of a feedstock which contains xylenes.
  • the basic nitrogen containing compounds which are employed are ammonia, alkylamines of from 1 to 40 carbon atoms, alkylenediamines of from 2 to 40 carbon atoms, aromatic amines of from 6 to 40 carbon atoms e.g. aniline, and heterocyclic nitrogen compounds such as pyridine and pyrrolidine.
  • Their contact with the catalyst may be effected by periodic or continuous addition to the feedstock.
  • Preferred zeolites for use in the present invention are those with a SiO 2/ A' 2 0 1 mole ratio of at least 12. Many are very well known. Zeolite ZSM-5, for instance, is described in U.S. Specification 3,702,886. Zeolite ZSM-11 1 is described in U.S. Specification 3,709,979. Zeolite ZSM-12 is described in U.S. Specification 3,970,544. Zeolite ZSM-35 is described in U.S. Specification 4,016,245. Zeolite ZSM-38 is described in U.S. Specification 4,046,859. The significance and definition of "Constraint Index" is also well known from extensive patent literature such as DTOS 2,438,252.
  • the catalysts hereof are selected as those having a crystal framework density, in the dry hydrogen form, of not substantially below 1.6 grams per cubic centimeter. It has been found that zeolites which satisfy all three of these criteria are most desired for the present process. Therefore, the preferred catalysts of this invention are those having a constraint index as defined above of 1 to 12, a silica to alumina ratio of at least 12 and a dried crystal density of not less than 1.6 grams per cubic centimeter.
  • the crystal framework density may be determined by classical pyknometer techniques. For example, it may be determined by immersing the dry hydrogen form of the zeolite in an organic solvent which is not sorbed by the crystal. It is possible that the unusual sustained activity and stability of this class of zeolite is associated with its high crystal anionic framework density of not less than 1.6 grams per cubic centimeter. This high density of course must be associated with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, is important as the locus of catalytic activity.
  • Crystal framework densities of some typical zeolites are: The amount of ethylbenzene in the feedstock is usually from 5 to 30 weight percent, more usually from 10 to 25 weight percent.
  • Specific compounds contemplated for isomerisation include para-xylene, meta-xylene, ortho-xylene, mesitylene (1,3,5-trimethylbenzene) durene (1,2,4,5-tetramethyibenzene), hemimellitene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethy)benzene), prehnitene (1,2,3,4-tetramethylbenzene) and isodurene ( 1,2,3,5-tetramethylbenzene) with the xylene isomers and pseudocumene especially preferred.
  • the nitrogen-containing compounds useful in the present process are ones which neither react with the charge materials nor possess catalytic activity contrary to the purpose for their use.
  • Said nitrogen-containing compounds may be gaseous, liquid or in the form of a solid dissolved in a suitable solvent, such as, for example, toluene.
  • the nitrogen compounds useful in this invention are ammonia, alkylamines of from 1 to about 40 carbon atoms, and preferably from 1 to 10 carbon atoms, e.g. n-propylamine, alkylenediamines of from 2 to 40 carbon atoms, and preferably from 6 to 20 carbon atoms, aromatic amines of from 6 to 40 carbon atoms, e.g. aniline, and heterocyclic nitrogen compounds, such as pyridine and pyrrolidine.
  • the catalyst may be contacted in the reactor with the nitrogen compound in a variety of ways.
  • the nitrogen compound can be contacted with the catalyst by adding it to the feedstock periodically or continuously.
  • Example 1 the preparation of a zeolite for use in the later Examples, and in Examples 2 to 6 embodiments of the process of the present invention, as well as comparative procedures.
  • Example 2 to 6 the preparation of a zeolite for use in the later Examples, and in Examples 2 to 6 embodiments of the process of the present invention, as well as comparative procedures.
  • the single Figure of the Drawing summarises the data of Examples 2 to 4.
  • a sodium silicate solution was prepared by mixing 16 parts water and 27.7 parts sodium silicate (28.7 wt.% Si0 2 , 8.9 wt.% Na 2 0, 62.4% H 2 0). The solution was cooled to approximately 15°C.
  • An acid solution was prepared by adding 1 part aluminum sulfate (17.2 wt.% AI 2 0 3 ) to 16.4 parts water followed by 2.4 parts sulfuric acid (93 wt.% H 2 SO 4 ) and 1.2 parts NaCI.
  • An organic solution was prepared by adding 1.6 parts n-propyl bromide and 3.1 parts methyl ethyl ketone to 1.9 parts tri-n-propylamine.
  • the zeolite slurry product was diluted with 4-5 parts water per part slurry, allowed to settle and supernatent liquid was drawn off. The settled solids were reslurried to the original volume of the preceding step with water. After settling, the aqueous phase was decanted. This procedure was repeated until the sodium level of the zeolite was less than 1.0 wt.%. The washed zeolite was then filtered, dried and identified as ZSM-5 having a silica/alumina mole ratio of about 70 and a constraint index of about 8.3.
  • the dried zeolite was then mixed with alumina and water. It was then extruded into 2.9 cm (1.16") pellets and dried. The extruded material contained 65 parts ZSM-5 per 35 parts alumina, by weight.
  • the dried extrudate was calcined for three hours at 538°C in flowing nitrogen. After cooling, the extrudate was contacted with an ammonium nitrate exchange solution (about 0.08 kg NH 4 NO 3 /kg extrudate) for one hour at ambient temperature. This exchange was then repeated until the sodium level was less than 0.05 wt.%. The extrudate was then contacted with a nickel nitrate exchange solution (about 0.1 kg Ni (Ni(N03)2. 6H.0/kg extrudate) for two hours at about 80-90°C. After this exchange, the extrudate was washed, dried and calcined in a flowing 10% air-90% nitrogen mixture at 538°C for six hours.
  • an ammonium nitrate exchange solution about 0.08 kg NH 4 NO 3 /kg extrudate
  • the extrudate was then contacted with a nickel nitrate exchange solution (about 0.1 kg Ni (Ni(N03)2. 6H.0/kg extrudate) for two hours at about
  • 25 cc of the catalyst of Example 1 was further calcined at 538°C (1000°F) in airfor24 hours and placed in an isothermal one galion/day reactor. Pure hydrogen was continuously passed through the reactor without recycle in order to maintain a constant molar ratio between hydrogen and hydrocarbon feedstock at the reactor inlet. A feedstock comprising the components listed in Table 2 was then passed through the reactor under the conditions listed in Table 3, hereinafter presented. Also listed in Table 3 are the results of ten separate material balances over the period of 10.5 days on stream.
  • the zeolite is preferably employed in association with a support or binder material which acts as diluent such as, for example, a porous inorganic oxide support or a clay binder.
  • a support or binder material which acts as diluent
  • binder materials include alumina, zirconia, silica, magnesia, thoria, titania, boria and combinations thereof, generally in the form of dried inorganic oxide gels and gelatinous precipitates.
  • Suitable clay materials include, by way of example, bentonite and kieselguhr.
  • the relative proportion of suitable crystalline aluminosilicate zeolite of the total composition of catalyst and binder or support may vary with the zeolite content ranging from between 10 to 90 percent by weight and more usually in the range of 20 to 80 percent by weight of the composition.
  • WHSV Weight hourly space velocity
  • Example 2 After 10.5 days on stream, the catalyst used in Example 2 was contacted in the same reactor as for Example 2 with a feedstock containing a nitrogen containing compound, i.e., 1.10-decane diamine as indicated in Table 4, hereinafter presented.
  • the feedstock containing the nitrogen-containing compound was pumped through the reactor for 24 hours at operating conditions of 316°C (600°F), 1480 kPa (200 psig) a WHSV of 7 hr -1 ' and a hydrogen/hydrocarbon mole ratio of 4.
  • the ratio of nitrogen atoms provided in the feed per aluminum atom in the zeolite component was 3.4.
  • Example 2 Thereafter, the above feedstock without the nitrogen-containing compound was charged to the reactor and at the reaction conditions of Example 2, the catalyst was found to be inactive.
  • the reaction temperature was increased, through increments, up to about 399°C (750°F), where a rapid reactivation of the catalyst was observed, as a result of desorption of part of the nitrogen from the catalyst, bringing the ratio of nitrogen atoms/aluminum atom in the zeolite component within the range of 0.01 to 1.0.
  • the temperature was then reduced to 371 °C (700 0 F) where gradual recovery of catalyst activity was still observable.
  • the reaction conditions and results from 8 material balances over the period of about 8 days on stream appear in Table 5.
  • Example 3 The experiment of Example 3 was continued with a feedstock composed as indicated in Table 6. The conditions for and results from 10 material balances over a period of about 10 days on stream appear in Table 7.
  • Example 9 A catalyst prepared as in Example 1, but not contacted with the nickel nitrate solution, was placed in the reactor used in Examples 2-4. A feedstock composed as described in Table 8 was then passed through the reactor at 273.7 kPa (25 psig), 316°C (600°F), a WHSV of 5 hr-1 and a hydrogen/hydrocarbon mole ratio of 0 (absence of added hydrogen). The results of this experiment are presented in Table 9.
  • Example 5 The feedstock for Example 5 is then injected with ammonia to the extent that the ratio of nitrogen atoms/aluminum atom in the zeolite is 0.1.
  • the injection of ammonia into the feedstock is stopped after a time and the reaction temperature is increased to 399°C (750°F). Results of this experiment are also presented in Table 9 for comparison with the results from Example 5.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
EP78300119A 1977-07-08 1978-07-05 A process for effecting catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon compounds Expired EP0000432B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US81391177A 1977-07-08 1977-07-08
US813911 1977-07-08

Publications (2)

Publication Number Publication Date
EP0000432A1 EP0000432A1 (en) 1979-01-24
EP0000432B1 true EP0000432B1 (en) 1983-05-25

Family

ID=25213739

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78300119A Expired EP0000432B1 (en) 1977-07-08 1978-07-05 A process for effecting catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon compounds

Country Status (11)

Country Link
US (1) US4158676A (es)
EP (1) EP0000432B1 (es)
JP (1) JPS6024771B2 (es)
AR (1) AR223821A1 (es)
CA (1) CA1098918A (es)
DE (1) DE2862267D1 (es)
ES (1) ES471561A1 (es)
IN (1) IN149346B (es)
IT (1) IT1109966B (es)
MX (1) MX4173E (es)
ZA (1) ZA783919B (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190079385A (ko) * 2017-12-27 2019-07-05 한화케미칼 주식회사 탄화수소 함유 용액 내의 방향족 함량의 측정 방법

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1121967B (it) * 1979-06-29 1986-04-23 Montedison Spa Zeolite mb 28 particolarmente adatta per la catalisi dell'isomerizzazione degli xileni
US4300011A (en) * 1980-04-28 1981-11-10 Mobil Oil Corporation Selective production of aromatics
US4302323A (en) * 1980-05-12 1981-11-24 Mobil Oil Corporation Catalytic hydroconversion of residual stocks
US4533298A (en) * 1982-12-02 1985-08-06 Westinghouse Electric Corp. Turbine blade with integral shroud
US5100535A (en) * 1987-12-03 1992-03-31 Mobil Oil Corporation Method for controlling hydrocracking operations
US5419830A (en) * 1985-07-26 1995-05-30 Mobil Oil Corporation Method for controlling hydrocracking and isomerization dewaxing
US5043512A (en) * 1988-10-06 1991-08-27 Mobil Oil Corp. Alkylaromatic isomerization process
US5030787A (en) * 1990-01-24 1991-07-09 Mobil Oil Corp. Catalytic disproportionation/transalkylation utilizing a C9+ aromatics feed
US5905181A (en) * 1997-12-29 1999-05-18 Uop Llc Process for the isomerization of paraffins
US6313363B1 (en) 1998-04-10 2001-11-06 Institut Francais Du Petrole Process for isomerizing aromatic compounds containing eight carbon atoms
FR2777207B1 (fr) * 1998-04-10 2000-05-19 Inst Francais Du Petrole Procede d'activation des catalyseurs d'isomerisation des composes aromatiques a huit atomes de carbone
US6333289B1 (en) 1998-04-10 2001-12-25 Institut Francais Du Petrole Process for activating catalysts for isomerizing aromatic compounds containing eight carbon atoms
FR2784686B1 (fr) 1998-09-10 2001-02-23 Inst Francais Du Petrole Procede d'isomerisation des composes aromatiques a huit atomes de carbone en deux etapes successives et utilisant un catalyseur active
US6051744A (en) * 1998-12-17 2000-04-18 Chevron Chemical Company Llc Low pressure hydrodealkylation of ethylbenzene and xylene isomerization
FR2795343B1 (fr) * 1999-06-22 2001-08-03 Inst Francais Du Petrole Procede de pretraitement dans des conditions severes d'un catalyseur a base de zeolithe euo

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3293314A (en) * 1965-03-04 1966-12-20 Chevron Res Equilibration of lower alkyl substituted aromatic hydrocarbons
US3644200A (en) * 1968-12-23 1972-02-22 Union Oil Co Ammoniated zeolite catalysts
US3856872A (en) * 1973-09-13 1974-12-24 Mobil Oil Corp Xylene isomerization
US3856873A (en) * 1973-09-13 1974-12-24 Mobil Oil Corp Xylene isomerization
US3992466A (en) * 1975-08-13 1976-11-16 Mobil Oil Corporation Hydrocarbon conversion
DE2558035A1 (de) * 1975-12-22 1977-06-23 Mobil Oil Corp Kombiniertes verfahren zur katalytischen umwandlung und hydrodealkylierung von kohlenwasserstoffen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190079385A (ko) * 2017-12-27 2019-07-05 한화케미칼 주식회사 탄화수소 함유 용액 내의 방향족 함량의 측정 방법

Also Published As

Publication number Publication date
CA1098918A (en) 1981-04-07
MX4173E (es) 1982-01-15
IT1109966B (it) 1985-12-23
JPS5419921A (en) 1979-02-15
ZA783919B (en) 1980-02-27
IT7825466A0 (it) 1978-07-07
ES471561A1 (es) 1979-01-16
DE2862267D1 (en) 1983-07-07
AR223821A1 (es) 1981-09-30
JPS6024771B2 (ja) 1985-06-14
IN149346B (es) 1981-10-31
EP0000432A1 (en) 1979-01-24
US4158676A (en) 1979-06-19

Similar Documents

Publication Publication Date Title
US4029716A (en) Selective production of para-xylene
US4007231A (en) Selective production of para-xylene
US4113788A (en) Selective production of para-xylene
US4375573A (en) Selective production and reaction of p-Disubstituted aromatics over zeolite ZSM-48
US4117026A (en) Selective production of para dialkyl substituted benzenes
EP0000432B1 (en) A process for effecting catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon compounds
US4094921A (en) Selective ethylation of mono alkyl benzenes
US3965207A (en) Selective production of para-xylene
US4465886A (en) Silica-modified catalyst and use for selective production of para-dialkyl substituted benzenes
US3965209A (en) Selective production of para-xylene
US4001346A (en) Selective production of para-xylene
US4098836A (en) Vapor-phase isomerization process
US4100214A (en) Isomerization of monocyclic alkyl aromatic hydrocarbons
US4152363A (en) Vapor phase isomerization of methyl-substituted aromatic hydrocarbons improved by using highly diluted zeolite catalyst
US3965210A (en) Selective production of para-xylene and catalyst therefor
EP0014545B1 (en) Method of preparing a zeolitic catalyst composition of improved shape selectivity and thermal stability, and use thereof in catalytic hydrocarbon conversion process
US4101596A (en) Low pressure xylene isomerization
US20060122445A1 (en) Process for the preparation of 2,6-dimethylnaphthalene
US5034362A (en) Zeolitic catalyst composition of improved shape selectivity
EP0036704B1 (en) Improved aromatics processing
US4159283A (en) Isomerization process
CA1142552A (en) Selective alkylation of xylenes with ethylene
US4899007A (en) Aromatic conversion reactions with zeolitic catalyst composition of improved shape selectivity
EP0582108B1 (en) Process for production of dimethyltetralin
USRE31781E (en) Isomerization of monocyclic alkyl aromatic hydrocarbons

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB NL

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB NL

ET Fr: translation filed
REF Corresponds to:

Ref document number: 2862267

Country of ref document: DE

Date of ref document: 19830707

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19840604

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19840630

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19840703

Year of fee payment: 7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19870731

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19890705

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19890731

BERE Be: lapsed

Owner name: MOBIL OIL CORP.

Effective date: 19890731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19900201

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19900330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19900403

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST