US3202723A - Process for the catalytic hydrogenation of aromatic hydrocarbons - Google Patents

Process for the catalytic hydrogenation of aromatic hydrocarbons Download PDF

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US3202723A
US3202723A US223393A US22339362A US3202723A US 3202723 A US3202723 A US 3202723A US 223393 A US223393 A US 223393A US 22339362 A US22339362 A US 22339362A US 3202723 A US3202723 A US 3202723A
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hydrocarbon
reaction
aromatic hydrocarbon
reaction zone
cycloaliphatic hydrocarbon
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US223393A
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English (en)
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Thonon Clement
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals

Definitions

  • the vapor phase processes yield an undesirably low output per unit volume of reaction zone. This is due not only to the low density of the treated product but also to the difficulties encountered in attempting to cool said reaction zone efiiciently. It is necessary either to use a bulky apparatus comprising critical and costly internal cooling circuits so as to completely avoid local overheating of the catalyst which if uncontrolled would result in a reduction of catalyst activity; or, on the other hand, to dilute the aromatic hydrocarbons in a large volume of gases or vapors, for instance, in the corresponding hydrogenated products, which requires the recycling of a large portion of the latter and accordingly leads to a poor hourly rate of production of the plant.
  • liquid phase processes are not easily applicable when it is desired to get a large output of cycloaliphatic hydrocarbons of a high purity, since such a result is only achieved by use of either of a very bulky apparatus or of a series of reaction vessels of substantially equal volumes in the first of which the major part (for instance 95%) of the aromatic hydrocarbon is converted, whereas in the other reaction vessels the conversion is limited to decreasing portions of the aromatic hydrocarbons (for instance 3.5% in a second reaction vessel, 1% in a third one, 0.3% in a fourth one, etc.), the cycloaliphatic hydrocarbon produced being eventua United States Patent reaction.
  • an object of this invention to provide for the converison of aromatic hydrocarbons, such as, for instance, benezene, toluene and/or xylene, to the corresponding cycloaliphatic hydrocarbons, under such conditions as to obtain the latter with a high degree of purity.
  • aromatic hydrocarbons such as, for instance, benezene, toluene and/or xylene
  • It is still another object of this invention to carry out the conversion of aromatic hydrocarbons to the corresponding cycloaliphatic hydrocarbons without dilution of said aromatic hydrocarbons in the vapor phase with a large volume of gases or vapors which have to be recycled.
  • the aromatic hydrocarbon is introduced together with hydrogen in excess or in amount at least a stoichiometric ratio, in a first reaction zone containing the corresponding cycloaliphatic hydrocarbon in the liquid phase having suspended therein a catalyst for liquid phase hydrogenation, the molar ratio of said aromatic hydrocarbon to the corresponding cycloaliphatic hydrocarbon being maintained at a substantially constant value comprised between 0.003 and 0.1; and,
  • a cycloaliphatic hydrocarbon of high purity is obtained with a high output rate. Furthermore, the heat necessary for vaporizing the hydrocarbons in view of their treatment in the second reaction zone, is only that heat generated by the reaction conducted in the first reaction zone, so that any addition of external heat may be avoided.
  • the molar ratio between the aromatic hydrocarbon and the cycloaliphatic hydrocarbon may be easily determined by conventional means, for instance, by ultraviolet spectrography and gas chromatography.
  • the molar ratio of aromatic to cycloaliphatic hydrocarbons is 0.003-0.l:l, preferably (LOGS-0.05:1
  • the intermediate product stream which is fed to the gas phase reaction zone generally contains the aromatic to cycloaliphatic hydrocarbons in a molar ratio of about 0.003-0.1:1, preferably 0005-005: 1, respectively.
  • the catalysts used in each of the two stages of reaction are conventional hydrogenation catalysts.
  • the catalyst in the first reaction zone is a solid conventional catalyst for liquid phase hydrogenation, and it is suspended in the liquid hydrocarbon.
  • a conventional catalyst for gaseous phase hydrogenation may be used in the form of a stationary, a moving or a fluid bed, the stationary bed being, however, preferred. These catalysts may be used either as such, or deposited on any carrier.
  • a metal of the 8th group of Mendeleefis periodic table particularly nickel, cobalt, platinum, palladium, rhodium, or ruthenium
  • alumina silica, pumice stone, asbestos, clays and the like.
  • the reaction temperature and pressure are selected in the range of the temperatures and pressures commonly used when operating with the previously mentioned hydrogenation catalysts, and at such a level within said range as to maintain a liquid phase during the first step of the process and a gaseous phase during the second step.
  • the operating temperature will preferably be about 10 C. to 100 C., preferably about 30 C. to 70 C. below the actual boiling temperature of the cycloaliphatic hydrocarbon under the prevailing total pressure.
  • satisfactory reaction velocities for an industrial plant may be obtained at temperatures between 80 and 250 C. and under pressures in the range of from 1 to 100 atmospheres, these limits being not, however, strictly obligatory.
  • the temperature and pressure used for the first step may be difierent from those selected for conducting the second step.
  • the two steps may be, if desired, conducted under substantially the same temperature and pressure conditions, provided that the partial pressure of the hydrocarbons in the outflow of the first stage he reduced, for instance by dilution of the same with hydrogen or recycled gas so as to avoid any undesirable condensation of the hydrocarbons during the second stage of the reaction.
  • condensation may be prevented by operating the second reaction zone at a lower pressure or higher temperature than the first zone.
  • the amount of hydrogen used is at least equal to the stoichiometric proportion corresponding to the desired degree of saturation, for instance 3 mols of hydrogen per mol of benzene, toluene or xylene and 2 or 5 mols of hydrogen per mol of naphthalene, etc. An excess of 100% is preferred.
  • Hydrogen may be used either in pure form or in admixture with other diluent gases such as, for instance, methane, or nitrogen. Furthermore, it is of advantage to recycle the excess hydrogen separated from the outflow of the second reaction zone, said hydrogen stream containing significant proportions of such diluent gases.
  • the schematically illustrated apparatus comprises essentially, a first reactor 1 wherein is conducted the first hydrogenation step, a heat exchanger 2, a second reactor 3, a condenser 4, a separating unit 5 for separation of incondensable gases from the liquid product, and pump means 6, 7, 8 and 9.
  • the reaction vessel 1 containing the cycloaliphatic hydrocarbon having the catalyst suspended therein, is fed with the corresponding aromatic hydrocarbon through the pipe 10, the circulating pump 7, and the pipe 11. Hydrogen is conveyed through pipe 12, the circulating benzene.
  • the outflow is partially condensed and caused to pass through pipe 17 to the separating unit 5 from where the pure liquid cycloaliphatic hydrocarbon is removed through pipe 18 whereas the incondensable gases are recycled to the input of the first reaction vessel through pipe 19.
  • reaction vessel 1 A part of the reaction mixture contained in the reaction vessel 1 is continuously withdrawn through pipe 20, passes through the pump 8, the pipe 21 and the heat exchanger 2 and is recycled to the reaction vessel 1 so as to maintain the temperature therein substantially constant. It is to be appreciated, however, that other circulation systems for removal of heat may be used such as thermo-siphon cooling, heat exchange means internal to the reaction vessel Or the like.
  • the reaction vessel 3 may be juxtaposed to the upper part of the reaction vessel 1.
  • a portion of the gases recycled through pipe 19 may be conveyed through pipe 23 to the reaction vessel 3, said gases constituting a diluent which prevents any undesirable condensation of hydrocarbon vapors in the reaction vessel 3.
  • Another improvement consists of withdrawing from the pipe 24 a part of the recycled gases so as to avoid any excessive accumulation of inert gases such as CH CO, N and the like.
  • Example 1 A conversion is conducted in an apparatus corresponding to the fiowsheet of FIGURE 1, at a temperature of 200 C. and under a. pressure of 40 kg./cm. in both reaction vessels 1 and 3.
  • reaction vessel 1 Forty-five kg. of cyclohexane are introduced together with 5 kg. of divided Raney nickel into the reaction vessel 1 which is thereafter fed with benzene at a rate of kg./hour and with hydrogen in 30 %excess of the stoichiometric ratio. Under these conditions, the reaction volume is kept constant, with a molar ratio benzene/cyclo hexene in the liquid and gaseous phases of about 0.015.
  • the gaseous outflow from reaction vessel 1 is then passed through the reaction vessel 3 containing 2.5 kg. of a catalyst consisting of activated carbon having a 20% nickel content deposited thereon, said catalyst being used in the form of a stationary bed.
  • the cyclohexane product is obtained in a substantially quantitative yield by condensation of the effluent from the reaction vessel 3 and the product contains only 0.01% Furthermore, no additional heat is required during the reaction.
  • Example 2 the liquid phase in a single reaction vessel 1. It is thus 1500% increase in the undesired impurity.
  • Example 3 Example 2 is repeated with a reaction'mass consisting of 20 kg. of R-aney nickel and 180 kg. of cyclohexane. Under these conditions, the cyclohexane obtained as reaction product still contains 0.12% benzene, which is equivalent to a 230% increase in the undesired impurity.
  • Example 4 Example 1 is repeated except that 'thereaction vessel 3 is replaced by another reaction vessel for liquid phase operation which is identical to the reaction vessel 1, each of the two reaction vessels initially containing- 5 kg. of Raney nickel and 45 kg. of cyclohexane.
  • Example 5 there is used only one reaction vessel for operation in the vapor phase.
  • a reaction vessel having a volume corresponding to about 20 times the volume of the reaction vessel 3 for operation in the vapor phase according to Example 1, and of 50 kg. of a catalyst consisting of nickel deposited on active carbon and used in the form of a stationary bed. It is also necessary to recycle and cool the eflluent flow from the reaction vessel at a rate of 1500 kg./hour so as to remove the heat generated by the reaction. 7
  • the cyclohexane obtained as reaction product still contains a 0.09% benzene content, which amounts to an 80% increase in the content of the undesired impurity, which is of course again highly dele terious.
  • Example 6 Example 1 is repeated, except that there is initially introduced into the reactionvessel ,1, 67.5 kg. of'cyclohexane and 75 kg. of a divided catalyst consisting of 35% by weight kieselguhr and 65% by weight nickel deposited? thereon, and except that the reaction vessel 3 contains. 3.5 kg. of a catalyst consisting of 15% by weight. nickel and 85% by Weight alumina, said catalyst having been previously activated at a temperature of about 340". C. for 6 hours in hydrogen.
  • Example 7 Into an apparatus corresponding to theflowsheet of FIGURE .1, there is introduced 90 kg. of methylcyclohexane and 10 kg. of divided Raney nickel, and then toluene at a rate of 100 kg./hour and hydrogen in excess over the stoichiometric ratio.
  • a process for the catalytic, non-destructive hydrogenation of at least one aromatic hydrocarbon which process comprises the steps of:
  • a continuous process for the catalytic, non-destructive hydrogenation of an aromatic hydrocarbon which process comprises the steps of:
  • step (2) withdrawing from the reaction medium of step (1), a gaseous product stream comprising cycloaliphatic hydrocarbon, hydrogen, and unreacted aromatic hydrocarbon starting material;

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US223393A 1961-09-13 1962-09-13 Process for the catalytic hydrogenation of aromatic hydrocarbons Expired - Lifetime US3202723A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR873243A FR1419557A (fr) 1961-09-13 1961-09-13 Nouveau procédé d'hydrogénation catalytique des hydrocarbures aromatiques

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FR (1) FR1419557A (fr)
GB (1) GB955926A (fr)
OA (1) OA01615A (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484496A (en) * 1965-10-04 1969-12-16 British Petroleum Co Desulphurisation and hydrogenation of aromatic hydrocarbons
US3484501A (en) * 1965-10-04 1969-12-16 British Petroleum Co Operation of reactor systems
US3505421A (en) * 1967-03-24 1970-04-07 Inst Francais Du Petrole Process of hydrogenating benzene
US4160745A (en) * 1977-12-01 1979-07-10 Exxon Research & Engineering Co. Method of preparing highly active nickel catalysts and catalysts prepared by said method
WO2003010119A1 (fr) * 2001-07-20 2003-02-06 Basf Aktiengesellschaft Procede d'hydrogenation de composes aromatiques au moyen d'hydrogene comprenant des gaz residuaires
US20040024273A1 (en) * 2000-10-13 2004-02-05 Arnd Bottcher Method for the hydrogenation of aromatics by means of reactive distillation
US20040024274A1 (en) * 2000-10-13 2004-02-05 Boettcher Arnd Method for the hydrogenation of unsubstituted or alkyl substituted aromatics using a catalyst with a structured or monolithic support
US20040199033A1 (en) * 2001-06-11 2004-10-07 Arnd Bottcher Method for hydrogenating organic compounds by means of ru/sio2 catalysts
US20070299294A1 (en) * 2006-06-27 2007-12-27 Amt International, Inc. Integrated process for removing benzene from gasoline and producing cyclohexane
US20100186636A1 (en) * 2007-05-31 2010-07-29 Basf Se Use of isoalkane mixtures for dedusting construction chemistry products

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4036734A (en) * 1973-11-02 1977-07-19 Exxon Research And Engineering Company Process for manufacturing naphthenic solvents and low aromatics mineral spirits

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2952625A (en) * 1957-08-05 1960-09-13 Union Oil Co Mixed-phase hydrofining of hydrocarbon oils
US2979546A (en) * 1958-07-16 1961-04-11 Standard Oil Co Manfuacture of cycloparaffin hydrocarbons
US3054833A (en) * 1960-01-25 1962-09-18 Universal Oil Prod Co Hydrogenation of aromatic hydrocarbons
US3070640A (en) * 1958-12-29 1962-12-25 Kellogg M W Co Preparation of cyclohexane

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2952625A (en) * 1957-08-05 1960-09-13 Union Oil Co Mixed-phase hydrofining of hydrocarbon oils
US2979546A (en) * 1958-07-16 1961-04-11 Standard Oil Co Manfuacture of cycloparaffin hydrocarbons
US3070640A (en) * 1958-12-29 1962-12-25 Kellogg M W Co Preparation of cyclohexane
US3054833A (en) * 1960-01-25 1962-09-18 Universal Oil Prod Co Hydrogenation of aromatic hydrocarbons

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484496A (en) * 1965-10-04 1969-12-16 British Petroleum Co Desulphurisation and hydrogenation of aromatic hydrocarbons
US3484501A (en) * 1965-10-04 1969-12-16 British Petroleum Co Operation of reactor systems
US3505421A (en) * 1967-03-24 1970-04-07 Inst Francais Du Petrole Process of hydrogenating benzene
US4160745A (en) * 1977-12-01 1979-07-10 Exxon Research & Engineering Co. Method of preparing highly active nickel catalysts and catalysts prepared by said method
US20040024274A1 (en) * 2000-10-13 2004-02-05 Boettcher Arnd Method for the hydrogenation of unsubstituted or alkyl substituted aromatics using a catalyst with a structured or monolithic support
US20040024273A1 (en) * 2000-10-13 2004-02-05 Arnd Bottcher Method for the hydrogenation of aromatics by means of reactive distillation
US20040199033A1 (en) * 2001-06-11 2004-10-07 Arnd Bottcher Method for hydrogenating organic compounds by means of ru/sio2 catalysts
US7355084B2 (en) 2001-06-11 2008-04-08 Basf Aktiengesellschaft Method for hydrogenating organic compounds by means of Ru/SiO2 catalysts
WO2003010119A1 (fr) * 2001-07-20 2003-02-06 Basf Aktiengesellschaft Procede d'hydrogenation de composes aromatiques au moyen d'hydrogene comprenant des gaz residuaires
US20040215042A1 (en) * 2001-07-20 2004-10-28 Arnd Bottcher Method for the hydrogenation of aromatic compounds with hydrogen containing residual gas
US7388119B2 (en) 2001-07-20 2008-06-17 Basf Aktiengesellschaft Method for the hydrogenation of aromatic compounds with hydrogen containing residual gas
US20070299294A1 (en) * 2006-06-27 2007-12-27 Amt International, Inc. Integrated process for removing benzene from gasoline and producing cyclohexane
US7790943B2 (en) 2006-06-27 2010-09-07 Amt International, Inc. Integrated process for removing benzene from gasoline and producing cyclohexane
US20100186636A1 (en) * 2007-05-31 2010-07-29 Basf Se Use of isoalkane mixtures for dedusting construction chemistry products
US8232439B2 (en) 2007-05-31 2012-07-31 Basf Se Use of isoalkane mixtures for dedusting construction chemistry products

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FR1419557A (fr) 1965-12-03
OA01615A (fr) 1969-09-20
GB955926A (en) 1964-04-22

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