US3387049A - Catalytic hydrogenation of aromatic hydrocarbons - Google Patents

Catalytic hydrogenation of aromatic hydrocarbons Download PDF

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Publication number
US3387049A
US3387049A US493415A US49341565A US3387049A US 3387049 A US3387049 A US 3387049A US 493415 A US493415 A US 493415A US 49341565 A US49341565 A US 49341565A US 3387049 A US3387049 A US 3387049A
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US
United States
Prior art keywords
reaction zone
hydrogenation
zone
hydrocarbon
effluent
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Expired - Lifetime
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US493415A
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English (en)
Inventor
Robert G Craig
Zulueta Javier
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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Publication date
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Priority to US493415A priority Critical patent/US3387049A/en
Priority to DE19661568043 priority patent/DE1568043A1/de
Priority to GB44698/66A priority patent/GB1152710A/en
Priority to JP6548166A priority patent/JPS5521017B1/ja
Priority to ES0331995A priority patent/ES331995A1/es
Application granted granted Critical
Publication of US3387049A publication Critical patent/US3387049A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • 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
    • C07C2601/14—The ring being saturated
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/8995—Catalyst and recycle considerations
    • Y10S585/901—Catalyst and recycle considerations with recycle, rehabilitation, or preservation of solvent, diluent, or mass action agent
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/8995—Catalyst and recycle considerations
    • Y10S585/903—Catalyst and recycle considerations with hydrocarbon recycle to control synthesis reaction, e.g. by cooling, quenching

Definitions

  • Cycloaliphatic hydrocarbons such as cyclohexane, having a purity of at least 99.5% and often 99.9%, are presently required for many industrial uses. Due to the similarity in boiling points of hydrocarbons found in petroleum fractions as well as the tendency of cyclic hydrocarbons to form azeotropes, high purity cyclohexane cannot be obtained from petroleum fractions by distillation. Accordingly, various processes have been proposed for obtaining cyclohexane of the desired purity by the catalytic hydrogenation of substantially pure benzene. Known continuous catalytic processes, however, suffer from various disadvantages, including: a minimum number of at least four reactors in some suggested systems, low conversion at high space rates and diflicult temperature control due to the exothermic nature of the hydrogenation reaction.
  • cycloaliphatic hydrocarbons such as cyclohexane
  • cyclohexane may be obtained at a purity of approximately 99.9% at substantially 100% conversion of the feed material in operations conducted at space velocities of approximately two.
  • unique process design of the present invention avoids the necessity for complex and expensive internal or external reactor zone cooling means.
  • the effluent, at a temperature within the range of 425 to 485 F., is blended witha mixture of recycle cyclohexane and the remainder of the benzene feed stock, having a temperature of about 100 F.
  • the blended mixture at a temperature of 275 to 375 F., is then contacted with hydrogenation catalyst in a second reaction bed which is approximately a quarter to a third the volume of the first reaction zone. Conversion in the second reaction zone is maintained substantially within the range of to 60 percent and preferably to percent by control of the amount and type of hydrogenation catalyst employed.
  • Reactants withdrawn from the second reaction zone at a temperature of about 425 to about 485 F., are cooled by indirect heat exchange with the benzene feed stock supplied to the first reaction zone and then passed to the third and last reaction zone wherein substantially complete hydrogenation occurs.
  • the third reaction bed is ice about one and a quarter to about two times the volume of the first reaction bed.
  • the ettluent stream from the last reaction zone is withdrawn, cooled to a temperature which is usually between to 150 F. and passed through a flash drum for separation into a gaseous phase and a liquid phase All or a portion of the gaseous phase, which comprises substantially pure hydrogen, is combined with make-up hydrogen and recycled to the first reaction zone. A portion of the liquid phase, which comprises substantially pure cyclohexane, is recycled back to the first and second reaction zones.
  • the ratio of the cyclohexane recycle to total benzene feed stock is maintained between 0.5 to 3 and preferably is about 2.
  • the remaining portion of cyclohexane is recovered as final product, which may be subjected to such additional treatment, if any, as desired.
  • the effluent from the first reaction zone passes through line 11 and is combined with a 100 F. mixture (from line 14) of 453 mols of cyclohexane (line 12) and 272 mols of benzene (line 13).
  • the combined materials in line 15, at a temperature of 300 F. are then passed to the second reaction zone 16 where 40 to 50 percent conversion is effected in the presence of catalyst bed 17.
  • the effluent from the second reaction zone, at a temperature of 470 F. in line 18, is subjected to indirect heat exchange with the line 6 material in heat exchanger 7.
  • the cooled efiluent is then transmitted through line 19 and further cooled by injection of recycle cyclohexane in means not shown or by cooler 20 to provide a material having a temperature of 300 F. in line 21 which is introduced into the third and final reaction zone 22.
  • Complete hydrogenation is effected in this last reaction zone in the presence of catalyst bed 23.
  • the efiluent from the third reaction zone (line 24), at a temperature of about 445 F. is condensed by cooler 25 and passed through line 26 into a high pressure flash drum 27. Liquid and vapor phases are separated in flash drum 27.
  • the vapor phase (line 28) consists substantially of hydrogen. A portion of this vapor phase is vented in line 29, while the remainder is recycled in line 30 and combined with a make-up gas mixture of 1200 mols of hydrogen and 62 mols of methane from line 31.
  • a portion of the liquid phase (in line 32), at 100 F. and 530 p.s.i. is recycled through line 33 to lines 5 and 12 While the remainder is recovered in line 34 as final product having .a composition of 362 mols of cyclohexane and 3 mols of methane.
  • the catalyst employed is conventional hydrogenation catalyst and may 'be the same or different in each reaction zone.
  • Such catalysts include nickel, cobalt, platinum,
  • catalysts may be used in the form of a stationary, moving or fluid bed. However, the stationary or fixed bed is preferred.
  • hydrogen may be used either in pure form or in admixture with diluent gases such as nitrogen or methane. If desired, a portion of the recycled gases may be liquefied to separate one or more of the inert or diluent gases from the hydrogen.
  • diluent gases such as nitrogen or methane.
  • the process of this invention provides a means of obtaining substantially pure cycloaliphatic hydrocarbons in a continuous process that is well adapted to large scale commercial operation. It is also seen that the exothermic hydrogenation reaction is completely and effectively controlled-thereby avoiding local over-heating of the catalyst and destructive temperatures within the reaction zones which could result in degradation reactions causing product contamination. This temperature control is accomplished by the present invention WlthOUt the necessity for either internal or external reaction zone cooling means.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US493415A 1965-10-06 1965-10-06 Catalytic hydrogenation of aromatic hydrocarbons Expired - Lifetime US3387049A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US493415A US3387049A (en) 1965-10-06 1965-10-06 Catalytic hydrogenation of aromatic hydrocarbons
DE19661568043 DE1568043A1 (de) 1965-10-06 1966-10-05 Verfahren zur katalytischen Hydrierung von aromatischen Kohlenwasserstoffen
GB44698/66A GB1152710A (en) 1965-10-06 1966-10-06 Catalytic Hydrogenation.
JP6548166A JPS5521017B1 (enExample) 1965-10-06 1966-10-06
ES0331995A ES331995A1 (es) 1965-10-06 1966-10-10 Un proceso para la hidrogenacion catalitica de un hidrocarburo aromatico al correspondiente hidrocarburo cicloalifatico.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US493415A US3387049A (en) 1965-10-06 1965-10-06 Catalytic hydrogenation of aromatic hydrocarbons

Publications (1)

Publication Number Publication Date
US3387049A true US3387049A (en) 1968-06-04

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US493415A Expired - Lifetime US3387049A (en) 1965-10-06 1965-10-06 Catalytic hydrogenation of aromatic hydrocarbons

Country Status (5)

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US (1) US3387049A (enExample)
JP (1) JPS5521017B1 (enExample)
DE (1) DE1568043A1 (enExample)
ES (1) ES331995A1 (enExample)
GB (1) GB1152710A (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3541169A (en) * 1968-01-09 1970-11-17 Ashland Oil Inc Naphthalene hydrogenation
US3992464A (en) * 1974-11-08 1976-11-16 Uop Inc. Hydroprocessing aromatics to make cycloparaffins
US3996304A (en) * 1974-06-19 1976-12-07 Universal Oil Products Company Hydroprocessing of hydrocarbons
US4003954A (en) * 1975-01-02 1977-01-18 Uop Inc. Hydroprocessing aromatics to make cycloparaffins
US4036734A (en) * 1973-11-02 1977-07-19 Exxon Research And Engineering Company Process for manufacturing naphthenic solvents and low aromatics mineral spirits
US4849093A (en) * 1987-02-02 1989-07-18 Union Oil Company Of California Catalytic aromatic saturation of hydrocarbons

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3254134A (en) * 1965-04-05 1966-05-31 Texaco Inc Plural stage hydrogenation of aromatics

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3254134A (en) * 1965-04-05 1966-05-31 Texaco Inc Plural stage hydrogenation of aromatics

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3541169A (en) * 1968-01-09 1970-11-17 Ashland Oil Inc Naphthalene hydrogenation
US4036734A (en) * 1973-11-02 1977-07-19 Exxon Research And Engineering Company Process for manufacturing naphthenic solvents and low aromatics mineral spirits
US3996304A (en) * 1974-06-19 1976-12-07 Universal Oil Products Company Hydroprocessing of hydrocarbons
US3992464A (en) * 1974-11-08 1976-11-16 Uop Inc. Hydroprocessing aromatics to make cycloparaffins
US4003954A (en) * 1975-01-02 1977-01-18 Uop Inc. Hydroprocessing aromatics to make cycloparaffins
US4849093A (en) * 1987-02-02 1989-07-18 Union Oil Company Of California Catalytic aromatic saturation of hydrocarbons

Also Published As

Publication number Publication date
ES331995A1 (es) 1967-11-16
GB1152710A (en) 1969-05-21
JPS5521017B1 (enExample) 1980-06-06
DE1568043A1 (de) 1970-04-30

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