AT286245B - Verfahren zur umwandlung von kohlenwasserstoffen - Google Patents

Verfahren zur umwandlung von kohlenwasserstoffen

Info

Publication number
AT286245B
AT286245B AT03760/66A AT376066A AT286245B AT 286245 B AT286245 B AT 286245B AT 03760/66 A AT03760/66 A AT 03760/66A AT 376066 A AT376066 A AT 376066A AT 286245 B AT286245 B AT 286245B
Authority
AT
Austria
Prior art keywords
hydrocarbons
conversion
Prior art date
Application number
AT03760/66A
Other languages
English (en)
Original Assignee
Union Carbide 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 Union Carbide Corp filed Critical Union Carbide Corp
Application granted granted Critical
Publication of AT286245B publication Critical patent/AT286245B/de

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321Catalytic processes
    • C07C5/324Catalytic processes with metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16Alumino-silicates
    • B01J20/18Synthetic zeolitic molecular sieves
    • B01J20/186Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084Y-type faujasite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline 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
    • B01J29/42Crystalline 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 containing iron group metals, noble metals or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/60Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0089Ortho-para conversion
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B4/00Hydrogen isotopes; Inorganic compounds thereof prepared by isotope exchange, e.g. NH3 + D2 → NH2D + HD
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08Catalytic processes
    • C07C2/12Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/222Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/2206Catalytic processes not covered by C07C5/23 - C07C5/31
    • C07C5/226Catalytic processes not covered by C07C5/23 - C07C5/31 with metals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321Catalytic processes
    • C07C5/324Catalytic processes with metals
    • C07C5/325Catalytic processes with metals of the platinum group
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/367Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • C07C5/393Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
    • C07C5/41Catalytic processes
    • C07C5/415Catalytic processes with metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • C10G11/05Crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12Inorganic carriers
    • C10G47/16Crystalline alumino-silicate carriers
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/18Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/60Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00Catalysts comprising molecular sieves
    • C07C2529/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
AT03760/66A 1962-12-03 1963-12-03 Verfahren zur umwandlung von kohlenwasserstoffen AT286245B (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US24149462A 1962-12-03 1962-12-03

Publications (1)

Publication Number Publication Date
AT286245B true AT286245B (de) 1970-11-25

Family

ID=22910900

Family Applications (2)

Application Number Title Priority Date Filing Date
AT03760/66A AT286245B (de) 1962-12-03 1963-12-03 Verfahren zur umwandlung von kohlenwasserstoffen
AT966263A AT253469B (de) 1962-12-03 1963-12-03 Verfahren zur Herstellung eines neuen Katalysators

Family Applications After (1)

Application Number Title Priority Date Filing Date
AT966263A AT253469B (de) 1962-12-03 1963-12-03 Verfahren zur Herstellung eines neuen Katalysators

Country Status (7)

Country Link
AT (2) AT286245B (de)
BE (1) BE640629A (de)
DE (1) DE1467177A1 (de)
FR (1) FR1413872A (de)
GB (1) GB1074129A (de)
NL (1) NL301296A (de)
SE (2) SE309770B (de)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3470257A (en) * 1966-02-01 1969-09-30 Universal Oil Prod Co Alkylation of aromatic compounds
US4631123A (en) * 1982-02-01 1986-12-23 Chevron Research Company Method of dehydrocyclizing alkanes
US4634518A (en) * 1982-02-01 1987-01-06 Chevron Research Company Platinum-barium-type L zeolite
US4645588A (en) * 1982-02-01 1987-02-24 Chevron Research Company Reforming with a platinum-barium-zeolite of L family
US4636298A (en) * 1982-02-01 1987-01-13 Chevron Research Company Reforming process
US4721695A (en) * 1982-06-28 1988-01-26 Chevron Research Company Platinum-barium-zeolite of L family
US4721694A (en) * 1982-08-06 1988-01-26 Chevron Research Company Platinum-barium-type L zeolite
AU2455484A (en) * 1983-02-11 1984-08-16 Broken Hill Proprietary Company Limited, The Diesel fuel production from olefins
US4675460A (en) * 1983-02-11 1987-06-23 The Broken Hill Propietary Company Limited Process
FR2728806A1 (fr) * 1994-12-29 1996-07-05 Inst Francais Du Petrole Adsorbants utilisables dans les procedes d'epuration d'atmospheres polluees par un oxyde d'azote
US8137750B2 (en) 2006-02-15 2012-03-20 3M Innovative Properties Company Catalytically active gold supported on thermally treated nanoporous supports
EP2586524A1 (de) * 2011-10-24 2013-05-01 Borealis AG Katalysatorbettsystem für ein endothermes katalytisches Dehydrierverfahren und endothermes Dehydrierverfahren
CN111085243B (zh) * 2018-10-23 2022-06-28 中国石油化工股份有限公司 一种负载金属的rey分子筛催化剂、制备方法及其应用
CN113404573B (zh) * 2021-06-08 2023-04-07 大连理工大学 一种低温存储氮氧化物的负载型钯铈基催化剂在汽车冷启动反应中的应用
CN114832852A (zh) * 2022-04-20 2022-08-02 柳州华锡有色设计研究院有限责任公司 一种锑掺杂改性Mn/ZSM-5分子筛低温脱硝催化剂的制备方法
WO2024003290A1 (de) * 2022-06-30 2024-01-04 Eberle Hans Juergen Verfahren zur umwandlung von ortho-wasserstoff zu para-wasserstoff

Also Published As

Publication number Publication date
GB1074129A (en) 1967-06-28
SE309770B (de) 1969-04-08
NL301296A (de) 1900-01-01
DE1467177A1 (de) 1968-12-02
SE343568B (de) 1972-03-13
AT253469B (de) 1967-04-10
BE640629A (de) 1964-03-16
FR1413872A (fr) 1965-10-15

Similar Documents

Publication Publication Date Title
AT303239B (de) Verfahren zur Umwandlung von Kohlenwasserstoffen
AT257789B (de) Verfahren zur hydrokatalytischen Umwandlung von Kohlenwasserstoffen
CH405257A (de) Verfahren zur Halogenisierung von Kohlenwasserstoffen
AT286245B (de) Verfahren zur umwandlung von kohlenwasserstoffen
AT250548B (de) Verfahren zur einstufigen Reformierung von Kohlenwasserstoffen
AT242673B (de) Verfahren zur Herstellung von ein- oder mehrfach ungesättigten Kohlenwasserstoffen
CH396850A (de) Verfahren zur Regenerierung von Phthalocyanin-Katalysatoren
AT246344B (de) Verfahren zur Herstellung von L-Ornithin-L-Asparaginat
AT239945B (de) Verfahren zur Umwandlung von paraffinischen Kohlenwasserstoffen
AT251553B (de) Verfahren zur Isomerisierung von Paraffinkohlenwasserstoffen
CH519449A (de) Verfahren zur katalytischen Umwandlung von Kohlenwasserstoffen
AT239206B (de) Verfahren zur Reinigung von Glykolen
CH454327A (de) Verfahren zur Reinigung von Kohlenwasserstoffen
AT239776B (de) Verfahren zur Hydrodesalkylierung von Alkylaromaten
CH399479A (de) Verfahren zur Reinigung von Polymyxinen
DE2157447B2 (de) Verfahren zur umwandlung von kohlenwasserstoffen
AT250562B (de) Verfahren zur Gewinnung von Oxytetracyclin
CH434222A (de) Verfahren zur Spaltung von Kohlenwasserstoffen
AT249648B (de) Verfahren zur Herstellung von Tetraflouräthylen
AT241659B (de) Verfahren zur Umwandlung von Kohlenwasserstoffen
AT248685B (de) Verfahren zur Reinigung von Polyolefinen
AT250318B (de) Verfahren zur Herstellung von acetylenhaltigen Gasen
CH428707A (de) Verfahren zur Herstellung von Isonitrilen
AT240506B (de) Verfahren zur kontinuierlichen Spaltung von Benzinkohlenwasserstoffen
AT252914B (de) Verfahren zur Reinigung von Dipyridylen

Legal Events

Date Code Title Description
ELJ Ceased due to non-payment of the annual fee