US3838179A - Process for manufacturing alcohols by oxidation of saturated hydrocarbons containing from 5 to 8 carbon atoms per molecule - Google Patents

Process for manufacturing alcohols by oxidation of saturated hydrocarbons containing from 5 to 8 carbon atoms per molecule Download PDF

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Publication number
US3838179A
US3838179A US00638719A US63871967A US3838179A US 3838179 A US3838179 A US 3838179A US 00638719 A US00638719 A US 00638719A US 63871967 A US63871967 A US 63871967A US 3838179 A US3838179 A US 3838179A
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hydrocarbon
vapor
carbon atoms
oxidation
mixture
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US00638719A
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English (en)
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B Cha
J Alagy
C Busson
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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
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C07C29/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only in the presence of mineral boron compounds with, when necessary, hydrolysis of the intermediate formed
    • 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

Definitions

  • the present disclosure is directed to a process for converting saturated hydrocarbons containing from to 8 carbon atoms in the molecule to corresponding alcohols and ketones of the same number of carbon atoms which comprises contacting said hydrocarbons in the liquid phase with an oxidizing gas in the presence of a boron compound, said oxidizing gas being introduced at a temperature between about 100 to 220 C., hydrolysing the reaction product and separating the obtained alcohols and ketones, said oxidizing gas containing a mixture of air and a vapor of the hydrocarbon to be oxidized which has been preliminary preheated to a temperature of about 140 to 190 C.
  • Oxygen is usually emplyed at a concentration of 1 to 25% in admixture with an inert gas such as nitrogen.
  • oxidizing cyclohexane provides for a cyclohexy borate.
  • the oxidizable hydrocarbons are essentially alkanes and cycloalkanes which contain from 5 to 8 carbon atoms per molecule, for example hexane, heptane, octane, isooctane, cycloheptane, cyclooctane, methylcyclohexane and dimethycyclohexanes (ortho-, meta-, para-).
  • the oxidation temperature is usually comprised between 100 and 220 C. preferably between 140 and 190 C., the pressure being suflicient to maintain a liquid phase, for example between 1 and 40 atmospheres.
  • This invention relates to a process of this kind wherein, by hydrolysis of the reaction product, before or after having separated a part or the whole of the non-converted hydrocarbon, there is recovered boric acid either directly in the solid state or an aqueous solution which may be submitted to crystallization, as well as an organic phase containing the required alcohol having the same number of carbon atoms as the oxidized hydrocarbon usually with a minor'amount of corresponding ketone.
  • hydrolysis agent there is used for example water or the mother-waters of boric acid crystallization.
  • the amount of used water is at least the stoichiometrical amount for the hydrolysis reaction; as an average there is used from 0.1 to 2 parts by volume of aqueous phase per part by volume of liquid efiluent from the oxidation zone, and the operating temperature is usually between 20 and 170 C. approximately.
  • the non-converted hydrocarbon may be recycled.
  • the recovered solid boric acid (essentially orthoboric acid) may be used again in a new oxidation operation, preferably after dehydration, so as to be at least in part under the form of alower hydrate of boric acid.
  • This invention also relates to several improvements to the above process, which improvements may be used alone or as various combinations.
  • the process of this invention consists of using an oxidizing gas containing oxygen and vapor of the hydrocarbon to be oxidized, for example as an intimate mixture of oxygen, nitrogen and vapor of the hydrocarbon to be oxidized.
  • this mixture must be warm, for example at a temperature of about to 220 C., when it is introduced into the reactor.
  • the nitrogen and/or oxygen gas for example at about -190 -'C., before admixing the same with the hydro carbon vapor.
  • the nitrogen-oxygen mixture is saturated only partly with vapor of hydrocarbon to be oxidized; the saturation rate is advantageously comprised between 20 and 90%, preferably between 30 and 55%.
  • the saturation rate S at a given temperature, is the ratio between the partial pressure p of the hydrocarbon in the oxidizing mixture and the saturating vapor pressure of the hydrocarbon p at the same temperature. The latter is given by the constants tables.
  • p is proportional to the concentration c of the hydrocarbon in the oxidizing mixture:
  • the improvement, object of this invention, and which remedies to the above defects consists of feeding the reactor with an oxidizing gas consisting of an intimate mixture of oxygen, nitrogen and vapor of the hydrothrough one or several injectors, through a distributor or any equivalent means.
  • a volumetric ratio of the vaporized hy- .drocarbon to the mixture oxygen nitrogen comprised between 0.5/1 and 10/1.
  • the process which is the object of this invention may be used together with all known and compatible processes for oxidizing saturated hydrocarbons in the presence of boron compounds.
  • an inert gas for example the recycle gas.
  • Example 1-7 illustrate the process of this invention whereas Example 1A is given by way of comparison.
  • EXAMPLE 1 In an autoclave of stainless steel of 4 liters capacity is introduced a mixture of 1,800 grams of cyclohexane and 130 grams of meta-boric acid.
  • the autoclave is provided with a blade stirrer and with inlet ducts for introduction of gas in the vicinity of the bottom of the apparatus.
  • the autoclave is surmounted with a condenser and a decanter placed on the circuit of the gas evacuation in order to allow removal of water formed in the reaction.
  • the cyclohexane which has been condensed an separated from water is returned to the reaction vessel.
  • the temperature is brought to 165 C. and the pressure to 12 kg./cm. as absolute pressure.
  • the oxidizing gas consists of an intimate, previously formed mixture of air with cyclohexane vapor prior to its introduction into the reaction vessel, the ratio by volume of the cyclohexane vapor to the air being equal to 1.5, which corresponds substantially to the complete saturation of this air.
  • the reaction is stopped when 60 liters of oxygen have been absorbed.
  • the reaction product is hydrolyzed by water at a temperature of 100 C., in a conventional manner.
  • the molar yield of cyclohexanol+cyclohexanone mixture with respect to the converted cyclohexane is equal to 89% and the conversion rate of cyclohexane attains 12.4%.
  • EXAMPL'E 1A The same apparatus as in Example 1 is used with the same starting amounts of cyclohexanone and metaboric acid, the same temperature and the same pressure.
  • Cyclohexane oxidation is carried out continuously in a cylindrical vertical reaction vessel of stainless steel in which the liquid phase (i.e. cyclohexane containing in suspension metaboric acid) is maintained at C., the pressure prevailing inside the reaction vessel being of 10.5 kg./cm.
  • the respective feeding rates of cyclohexane and metaboric acid are of 50 liters per hour and 2 kg. per hour.
  • the bottom of the reaction vessel is perforated with holes through which oxidizing gas is allowed to pass.
  • This gas is obtained by admixing previously, air preheated to C., with cyclohexane vapor also brought to the same temperature.
  • the mixture effected outside of the oxidation reaction vessel contains 57% by volume of cyclohexane vapor and 43 by volume of air, which corresponds to a saturation rate of 70%.
  • the experiment lasts 50 hours. During this entire time the gaseous mixture is regularly injected into the reaction vessel.
  • EXAMPLE 3 The experiment described in Example 2 is repeated under the same operating conditions except that air at the ambient temperature is admixed with the stream of cyclohexane, vaporized at 175 C.
  • the oxidizing mixture consists of 4% oxygen, 68% nitrogen and 28% cyclohexane vapor (by volume), which corresponds to a saturation rate of about 40% of the mixture oxygen-nitrogen by means of hydrocarbon vapor.
  • Example 5 is repeated with the same operating conditions except that the saturation rate of the oxidizing mixture oxygen-nitrogen with cyclohexane vapor is about
  • Example 5 is repeated with the same saturation rate of the hydrocarbon vapor, however, with different hydrocarbons. The following results are obtained:
  • a process for converting saturated hydrocarbons containing from 5 to 8 carbon atoms in the molecules to corresponding alcohols and ketones to the same number of carbon atoms which comprises contacting said hydrocarbons in the liquid phase With an oxidizing gas in the presence of a boron compound, said oxidizing gas being introduced at a temperature between about 100 to 220 C., hydrolyzing the reaction product and separating the obtained alcohols and ketones, said oxidizing gas containing a mixture of air and a vapor of the hydrocarbon to be oxidized, said mixture containing by volume, 2-14% oxygen, 33-70% nitrogen and 2858% said hydrocarbon vapor, and said air and hydrocarbon vapor being preliminarily and separately preheated, before being admixed, to a temperature of about 140 to 190 C.
  • a process for converting saturated hydrocarbons containing from 5 to 8 carbon atoms in the molecules to corresponding alcohols and ketones or the same number of carbon atoms which comprises contacting said hydrocarbons in the liquid phase With an oxidizing gas in the presence of a boron compound, said oxidizing gas being introduced at a temperature between about to 220 C., hydrolyzing the reaction product and separating the obtained alcohols and ketones, said oxidizing gas containa mixture of air and a vapor of the hydrocarbons to be oxidized, said oxidizing gas being characterized by a ratio by volume of the vaporized hydrocarbon to oxygen-l-nitrogen between 0.5 :1 and 10: 1, and said air and hydrocarbon vapor being preliminarily and separately preheated, before being admixed to a temperature of about to C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00638719A 1966-05-25 1967-05-16 Process for manufacturing alcohols by oxidation of saturated hydrocarbons containing from 5 to 8 carbon atoms per molecule Expired - Lifetime US3838179A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR62988A FR1497522A (fr) 1966-05-25 1966-05-25 Procédé d'oxydation d'hydrocarbures aliphatiques saturés
FR91680A FR1509367A (fr) 1966-05-25 1967-01-18 Procédé perfectionné d'oxydation d'hydrocarbures saturés

Publications (1)

Publication Number Publication Date
US3838179A true US3838179A (en) 1974-09-24

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US00638719A Expired - Lifetime US3838179A (en) 1966-05-25 1967-05-16 Process for manufacturing alcohols by oxidation of saturated hydrocarbons containing from 5 to 8 carbon atoms per molecule

Country Status (5)

Country Link
US (1) US3838179A (fr)
DE (1) DE1618561A1 (fr)
FR (2) FR1497522A (fr)
GB (1) GB1141724A (fr)
NL (1) NL6707164A (fr)

Also Published As

Publication number Publication date
FR1497522A (fr) 1967-10-13
DE1618561A1 (de) 1970-12-23
GB1141724A (en) 1969-01-29
FR1509367A (fr) 1968-01-12
NL6707164A (fr) 1967-11-27

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