US3459644A - Process for oxidizing olefins to carbonyl compounds - Google Patents

Process for oxidizing olefins to carbonyl compounds Download PDF

Info

Publication number
US3459644A
US3459644A US517959A US3459644DA US3459644A US 3459644 A US3459644 A US 3459644A US 517959 A US517959 A US 517959A US 3459644D A US3459644D A US 3459644DA US 3459644 A US3459644 A US 3459644A
Authority
US
United States
Prior art keywords
oxidation
ruthenium
acid
reaction
heptaldehyde
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 - Lifetime
Application number
US517959A
Other languages
English (en)
Inventor
Alexander F Maclean
Adin L Stautzenberger
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.)
Celanese Corp
Original Assignee
Celanese 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 Celanese Corp filed Critical Celanese Corp
Application granted granted Critical
Publication of US3459644A publication Critical patent/US3459644A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties

Definitions

  • Carbonyl compounds are produced by the oxidative cleavage of an unsaturated olifinic hydrocarbon by a process which comprises contacting the hydrocarbon with a neutral to acidic aqueous solution of a catalyst comprising ruthenium together with a cerium salt having an oxidation potential greater than 1.5 volts.
  • the cerium salt oxidizing agent is regenerated electrochemically.
  • This invention relates to improvements in the process for the production of carbonyl compounds including carboxylic acids, aldehydes and ketones, by the oxidation of olefinic hydrocarbons. More particularly, this invention relates to a process for the oxidative cleavage of olefinic hydrocarbons to aldehydes in the presence of a ruthenium catalyst and an oxidizing agent, the oxidizing agent being regenerated by electrochemical oxidation.
  • carbonyl compounds such as carboxylic acids, ketones and aldehydes can be obtained in good yield in a continuous manner, if desired, by contacting olefinic hydrocarbons with a catalytic amount of ruthenium in the presence of at least one oxidizing agent having a formal oxidation potential greater than 1.5 volts.
  • the oxidizing agents useful in the process of this invention include compounds of metals which appear in various oxidation states and which have formal oxidation potentials greater than 1.5 volts with reference to the standard hydrogen electrode. Compounds with potentials above about 1.5 volts are capable of oxidizing the lower states of ruthenium to ruthenium tetroxide [Ru(VIII)].
  • Some of the oxidizing agents which have been found applicable in this invention include compounds such as cerium perchlorate, cerium nitrate, cerium methanesulfonate, nitric acid and hypochlorous acid.
  • the ruthenium catalyst forms an addition compound or complex with the olefinic hydrocarbon, although the exact mechanism which cleaves olefins to aldehyde is speculative.
  • the stoichiometric reaction requires a four electron change.
  • olefinically unsaturated hydrocarbon which is free from steric hinderance
  • Compounds which are most useful in the process according to this invention are olefins such as butene, propene, hexene, heptene, octene cyclohexene, styrene and their substituted homologs such as Z-methyl propene.
  • oxidizing agent For a continuous process it is necessary to regenerate the oxidizing agent, which in turn facilitates the reformation of the higher oxidation state of the active ruthenium catalyst component necessary to carrying out the reaction.
  • Certain of the oxidizing agents applicable to the process of this invention can be regenerated by electrochemical oxidation.
  • solutions of cerium (IV) are conveniently made by electrolytic oxidation of cerium (III). In this process a diaphragm electrolytic cell need not be used.
  • Electrodes which may be used for the electrochemical process include inert materials such as platinum, graphite, lead, tantalum and others. Cerium (III) is oxidized at the anode to cerium (IV) in either a divided or undivided cell while hydrogen gas is produce in an undivided cell and caustic in a divided cell at the cathode.
  • the electrochemical oxidation of Ce(III) to Ce(IV) may be carried out at temperatures ranging from about 10 to C. and preferably from about 25 to 50 C. Anode current densities of 1040 milliamps per sq. cm. with cell terminal voltages of 3.2 to 3.5 volts are sufficient for high conversion rates.
  • the process according to this invention is preferably carried out in an aqueous system, however, the reaction media may be diluted with substances which act as coupling agents such as t-butyl alcohol or acetic acid which are inert under the reaction conditions. It is necessary that the reaction be carried out in a neutral to acidic medium.
  • the reaction is substantially pH independent from a pH of 1 to 5. When an undivided electrolytic cell is used, acid is consumed during the reaction. This necessitates the addition of acid during the course of the reac tion to assure adequate pH control.
  • the process of this invention can be carried out at temperatures ranging from about 0 to 200 C. and preferably from 25 to 50 C. An increase in temperature results in a corresponding increase in reaction rate. At higher temperatures side reactions occur which lower the yields of desired products.
  • the process of this invention can be carried out at atmospheric pressure, at subatmospheric pressure or at superatmospheric pressure, e.g. pressures ranging from 0 to 1500 p.s.i.
  • pressures greater than atmospheric may be used to promote the solubility of the olefin in the aqueous reaction medium.
  • the molar ratio of ruthenium to the oxidizing agent employed is not particularly critical to this process.
  • the amount of ruthenium necessary to catalyze the reaction is very small, ranging from about 1 1O Molar to 1 1O- Molar.
  • the oxidizing agent need only be present in amounts sufficient to oxidize ruthenium to its active catalytic state, e.g. a ruthenium/oxidizing agent molar ratio of at least 1:1.
  • An excess of olefin is normally used in the process of this invention to minimize secondary oxidation.
  • the secondary oxidation which occurs in this instance is the oxidation of the aldehyde, formed as a result of the oxidation of the olefin, to the corresponding acid.
  • a stirred two phase system may be used.
  • a liquid olefin such as octene-l, which is oxidized to heptaldehyde in the presence of ruthenium [Ru(VII-I)]
  • the heptaldehyde preferably concentrates in the olefin phase rather than the aqueous phase, thus minimizing secondary oxidation.
  • the aldehyde concentration is minimized in the aqueous phase, it will be relatively free from further oxidation.
  • the process may be carried out by a batchwise or continuous process, although a continuous process is preferred.
  • a continuous process the following description is given.
  • An oxidizing agent is fed to a reaction zone containing the desired olefinic hydrocarbon and an aqueous solution of ruthenium catalyst.
  • the organic phase is removed from the reaction zone and continuously fed to a distillation column where the olefinic hydrocarbon is separated from the desired aldehyde product and recycled to the reaction zone.
  • the aqueous spent oxidizing agent is recycled to the electrolytic cell for regeneration. Regeneration of the oxidizing agent may also be carried out in the reaction zone by electrochemical oxidation.
  • octene-l may be oxidized to give heptaldehyde and formaldehyde, heptaldehyde being a useful intermediate in the production of adipaldehyde and adipic acid, a useful nylon raw material intermediate.
  • EXAMPLE I A stirred electrolytic cell having an anode made of platinum gauze and a cathode of platinum wire was used as the reactor. A solution of 0.2 F cerium (III) in 1 N perchloric acid was added to the reactor-electrolytic cell. Three millifaradays of electricity were passed through the electrolyte. The current was 100 milliamperes and the cell voltage was about 2 volts. The current efficiency to ceric ion was about 90%. Twenty milliliters of octene-l and sufiicient ruthenium as ruthenium chloride were added to the reactor electrolytic cell. The concentration of ruthenium was 1 l0 F. The total aqueous phase was 80 milliliters.
  • the reaction was allowed to proceed until the solution was colorless indicating the absence of cerium (IV), which has a yellow color.
  • the products obtained were analyzed and the following results obtained: 3.6 oxidation equivalents heptaldehyde, 6.27 oxidation equivalents formic acid, 0.48 equivalents formaldehyde.
  • the efiiciency to heptaldehyde based on Ce(IV) was 36%
  • the efiiciency to heptaldehyde based on octene-l was approximately 95%.
  • EXAMPLE II was carried out in nitric acid.
  • methanesulfonic acid was used.
  • acetic acid was added to the reaction media as a coupling agent or solubilizer.
  • the higher proportion of heptanoic acid and formic acid indicates that secondary oxidation of the aldehyde to the corresponding acid occurred as the result of the, influence of the acetic acid coupling agent.
  • a higher concentration of ruthenium was used.
  • EXAMPLE III Employing the reactor-cell as described in Example 1 runs were made in which ceric was continuously reacted and regenerated electrolytically as shown by Table II. The runs were made by passing current through the well mixed octene-aqueous two phase mixture. The current density was adjusted to generate ceric (yellow color) at a rate approximating the organic oxidation rate. An attempt was made to keep the solution light yellow. After passing the desired quantity of electricity, the excess ceric was allowed to react to completion as indicated by decolorization. The products were removed and analyzed.
  • Run 1 was made with unpurified octene. Runs 2 and 3 gave very high current efiiciencies. In Run 4 the ruthenium concentration was reduced to 5 10 F and the temperature increased to 50 C. The conversion was relatively high and the current eificiency was 57%.
  • TABLE II.GERIC OXIDATION OF OCTENE-l IN A TWO- PHASE SYSTEM CONCURRENT ELECTROLYTIC GEN- ERATION OF CERIO [Pt screen anode:100 sq. cm.; Pt wire cathode:1 sq. cm.; stgrretl diaphragmless cell; 80 ml. ag. phase; 20 ml.
  • Heptene-3 was found to yield propionic acid and butyric acid instead of propionaldehyde and butyraldehyde because of the preference of the aldehydes for the aqueous phase in which secondary oxidation occurred.
  • Cyclohexene was oxidized to a mixture of adipaldehyde and adipic acid.
  • Methyl oleate was oxidized to give the following products according to the equation:
  • Nonanol was obtained along with some nonanoic acid.
  • Alpha-pinene was oxidized to a mixture of products including pinonic aldehyde.
  • EXAMPLE V A reactor-column arrangement for the continuous production of heptaldehyde from octene-l was set up using the electrolytic cell-reactor arrangement as described in Example I. The conditions under which the reaction took place are shown by Table III. Heptaldehyde boils at 155 C. while octene-l boils at 121.3 C. Heptaldehyde produced from the reaction with octene-l was introduced at an intermediate point on a distillation column.
  • the reboiler of the distillation column was kept at a tem perature sufiicient to remove unreacted octene-l overhead for recycle back to the reactor zone while the heptaldehyde was taken off at the bottom of the column.
  • Heptaldehyde 1. 44 4. 72 3.0 Heptanoic acid 0 0 Current efiiciency to heptaldehyde,
  • EXAMPLE VI Using the diaphragmless electrolytic cell and reaction conditions as described in Example I, octene-l was oxidized to heptaldehyde using manganese as the oxidizing agent for ruthenium instead of cerium. The manganese was electrolytically regenerated.
  • EXAMPLE VIII A continuous run was made as described in Example V using n-hexane saturated with butene-Z as the liquid oil phase instead of heptaldehyde. From the reactor the liquid oil phase was passed to the middle of the distillation column and butene, acetaldehyde and some hexane removed overhead. Stripped hexane, from the base of the column, was recycled to the reaction zone by way of a bubbler which saturated the hexane with butene-Z. The conditions and efiiciencies are given below.
  • a continuous process for the production of a carbonyl compound selected from the group consisting of aldehydes, carboxylic acids, and ketones by oxidative cleavage of an unsaturated olefinic hydrocarbon which comprises contacting said olefinic hydrocarbon in the presence of a neutral to acidic aqueous catalyst solution comprising a ruthenium catalyst and a cerium salt whose oxidation potential is greater than 1.5 volts at a temperature of 0 to 200 C., removing the reaction products from the reaction zone as they are formed, and regenerating the cerium salt by electrochemical oxidation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US517959A 1966-01-03 1966-01-03 Process for oxidizing olefins to carbonyl compounds Expired - Lifetime US3459644A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US51795966A 1966-01-03 1966-01-03

Publications (1)

Publication Number Publication Date
US3459644A true US3459644A (en) 1969-08-05

Family

ID=24061957

Family Applications (1)

Application Number Title Priority Date Filing Date
US517959A Expired - Lifetime US3459644A (en) 1966-01-03 1966-01-03 Process for oxidizing olefins to carbonyl compounds

Country Status (5)

Country Link
US (1) US3459644A (en)van)
BE (1) BE692143A (en)van)
DE (1) DE1568363A1 (en)van)
FR (1) FR1507137A (en)van)
NL (1) NL6700029A (en)van)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3946068A (en) * 1968-10-12 1976-03-23 Societa Italiana Resine S.I.R. S.P.A. Process for the production of vinyl acetate from ethylene
US3985794A (en) * 1968-10-12 1976-10-12 Societa' Italiana Resine S.I.R. S.P.A. Process for the production of vinyl acetate from ethylene
US3989742A (en) * 1968-10-12 1976-11-02 Societa' Italiana Resine S.I.R. S.P.A. Process for the production of vinyl acetate from ethylene
US5026461A (en) * 1990-01-19 1991-06-25 E. I. Du Pont De Nemours And Company Process for the preparation of dodecanedioic acid
US5236561A (en) * 1992-04-14 1993-08-17 E. I. Du Pont De Nemours And Company Process for the preparation of dicarboxylic acid

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3048636A (en) * 1959-05-20 1962-08-07 Dow Chemical Co Oxidation of olefins by thallium (iii)
US3080425A (en) * 1957-06-28 1963-03-05 Consortium Elektrochem Ind Process for the production of aldehydes and ketones compounds
US3087968A (en) * 1958-11-19 1963-04-30 Hoechst Ag Process for oxidizing olefins to aldehydes, ketones, and acids
US3106579A (en) * 1957-10-31 1963-10-08 Hoechst Ag Process for oxidizing olefins to aldehydes and ketones
US3122586A (en) * 1957-08-01 1964-02-25 Consortium Elektrochem Ind Process for oxidizing olefins to aldehydes and ketones
US3147203A (en) * 1961-09-21 1964-09-01 Pure Oil Co Process for the production of carbonyl compounds
US3152586A (en) * 1964-10-13 Cooking apparatus
US3303020A (en) * 1963-10-21 1967-02-07 Gulf Research Development Co Process for the removal of a platinum group metal from an organic reaction product

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3152586A (en) * 1964-10-13 Cooking apparatus
US3080425A (en) * 1957-06-28 1963-03-05 Consortium Elektrochem Ind Process for the production of aldehydes and ketones compounds
US3122586A (en) * 1957-08-01 1964-02-25 Consortium Elektrochem Ind Process for oxidizing olefins to aldehydes and ketones
US3106579A (en) * 1957-10-31 1963-10-08 Hoechst Ag Process for oxidizing olefins to aldehydes and ketones
US3087968A (en) * 1958-11-19 1963-04-30 Hoechst Ag Process for oxidizing olefins to aldehydes, ketones, and acids
US3048636A (en) * 1959-05-20 1962-08-07 Dow Chemical Co Oxidation of olefins by thallium (iii)
US3147203A (en) * 1961-09-21 1964-09-01 Pure Oil Co Process for the production of carbonyl compounds
US3303020A (en) * 1963-10-21 1967-02-07 Gulf Research Development Co Process for the removal of a platinum group metal from an organic reaction product

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3946068A (en) * 1968-10-12 1976-03-23 Societa Italiana Resine S.I.R. S.P.A. Process for the production of vinyl acetate from ethylene
US3985794A (en) * 1968-10-12 1976-10-12 Societa' Italiana Resine S.I.R. S.P.A. Process for the production of vinyl acetate from ethylene
US3989742A (en) * 1968-10-12 1976-11-02 Societa' Italiana Resine S.I.R. S.P.A. Process for the production of vinyl acetate from ethylene
US5026461A (en) * 1990-01-19 1991-06-25 E. I. Du Pont De Nemours And Company Process for the preparation of dodecanedioic acid
JP3001653B2 (ja) 1990-01-19 2000-01-24 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ドデカンジオン酸の製造方法
US5236561A (en) * 1992-04-14 1993-08-17 E. I. Du Pont De Nemours And Company Process for the preparation of dicarboxylic acid

Also Published As

Publication number Publication date
BE692143A (en)van) 1967-07-03
NL6700029A (en)van) 1967-07-04
DE1568363A1 (de) 1970-07-09
FR1507137A (fr) 1967-12-22

Similar Documents

Publication Publication Date Title
US4528403A (en) Hydroformylation process for preparation of aldehydes and alcohols
Green et al. Oxo complexes of ruthenium (VI) and (VII) as organic oxidants
EP0518977A1 (en) Process for the production of methyl ethyl ketone
SU1757458A3 (ru) Способ получени масл ного альдегида
US3147203A (en) Process for the production of carbonyl compounds
US4041082A (en) Process for producing aldehydes
US4537997A (en) Process for treating hydroformylation catalyst
US3953305A (en) Catalyst regeneration
JP2618389B2 (ja) 水性トリフルオロメタンスルホン酸中でセリウムイオンを使用する有機化合物の酸化
JP2916277B2 (ja) ｔｅｒｔ−ブチルヒドロペルオキシドからｔｅｒｔ−ブチルアルコールの触媒的製造法
US3459644A (en) Process for oxidizing olefins to carbonyl compounds
US3879467A (en) Catalytic oxidation of alkanes and alkenes with organic hydroperoxides
EP0643781B1 (en) Electrocatalytic asymmetric dihydroxylation of olefinic compounds
JP2633244B2 (ja) 水性有機溶液中でメタンスルホン酸セリウムを使用する有機化合物の酸化
Takita et al. Selective partial oxidation of propane over metal phosphate catalysts.
US3293291A (en) The oxidative conversion of olefinic hydrocarbons to carbonylic compounds
US3479262A (en) Olefin oxidation process
US4482763A (en) Process for hydroxylating olefins in the presence of an osmium containing catalyst and organic halogenated hydrocarbon co-catalyst
US4212711A (en) Electrochemical oxidation of alkyl aromatic compounds
CA1182127A (en) Rhodium-catalyzed oxidation process for producing carboxylic acids
US3245890A (en) Process for simultaneous production of carbonyl compounds and electrical energy
Horowitz Preliminary examination of an electrochemical process for converting olefins to ketones
US4085145A (en) Process for manufacturing carbonyl compounds by oxidation with molecular oxygen of olefinic compounds in liquid phase in the presence of soluble bimetallic catalysts
US3248312A (en) Electrolytic oxidation of olefins to unsaturated esters
Pletcher Indirect electrolysis involving phase transfer catalysis