US3665047A - Method for the simultaneous preparation of a diolefin and an olefin - Google Patents

Method for the simultaneous preparation of a diolefin and an olefin Download PDF

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US3665047A
US3665047A US40278A US3665047DA US3665047A US 3665047 A US3665047 A US 3665047A US 40278 A US40278 A US 40278A US 3665047D A US3665047D A US 3665047DA US 3665047 A US3665047 A US 3665047A
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hydrocarbon
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dehydrated
diolefin
isoprene
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Andre Gislon
Joseph-Edouard Weisang
Jean Maurin
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Compagnie Francaise de Raffinage SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/08—Alkenes with four carbon atoms
    • C07C11/09—Isobutene
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/12—Alkadienes
    • C07C11/173—Alkadienes with five carbon atoms
    • C07C11/18—Isoprene
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
    • C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
    • C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
    • C07C15/46—Styrene; Ring-alkylated styrenes
    • 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
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
    • 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
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    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C07C2527/16—Phosphorus; Compounds thereof containing oxygen
    • C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
    • 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
    • Y10S585/905—Catalyst and recycle considerations by-product conversion to feed
    • 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
    • Y10S585/929—Special chemical considerations
    • Y10S585/93—Process including synthesis of nonhydrocarbon intermediate
    • Y10S585/934—Chalcogen-containing

Definitions

  • ABSTRACT A method of preparing a diolefin and an olefin or an alkenyl benzene hydrocarbon simultaneously from more highly saturated hydrocarbons, said latter respectively having the same carbon structure as the desired end product pair, wherein the more highly saturated hydrocarbon precursors are reacted with oxygen to form respective hydroperoxides, the latter are reacted with an ethylenic hydrocarbon having the same carbon structure as the diolefin precursor to form an epoxide or glycol which are in turn dehydrated to the desired diolefin; the first hydroperoxide forms an alcohol which is dehydrated to reform the ethylenic hydrocarbon for recycling; the second hydroperoxide forms an alcohol which is dehydrated to the desired olefin or alkenylbenzene (depending upon the form of the precursor); and the ketone byproducts formed during the reaction of said hydroperoxides with said ethylenic hydrocarbon (these
  • the foregoing process is particularly advantageous in the simultaneous production of isoprene and isobutylene from isopentane and isobutane or of isoprene and styrene from isopentane and ethyl benzene.
  • the present invention relates to a method for producing a diolefin and an olefin simultaneously from more highly saturated compounds.
  • One of these processes consists in hydroperoxidizing isopentane with oxygen and reacting the resultant hydroperoxide with 2-methyl-2-butylene to form methyl 2,3- epoxy butane. The latter is then isomerized to form alcohol, which is finally dehydrated to isoprene. isomerization and dehydration are usually combined in a single operation with the use of a suitable catalyst. This method has the drawback of giving a poor yield of isoprene as compared with the quantity of isopentane used because of the formation of various byproducts.
  • the isomerization-dehydration operation is accompanied by an isomerization into compounds with carbonyl function (formation of methyl isopropylketone) and even of a structural isomerization (formation of trimethyl acetaldehyde); on the other hand, both during the isopentane oxidation phase and during the following operations, other byproducts are formed, particularly tertiary amyl alcohol and methyl isopropyl ketone. Since not all of these products can be converted further into isoprene and since the different phases of the process are of poor selectivity, one therefore obtains only a poor conversion of the isopentane into isoprene.
  • This process has the same drawbacks as the preceding process.
  • One object of the present invention is to improve the profitability of the processes for the production of isoprene or other diolefin by utilizing the byproducts of the intermediate reactions.
  • Another object of the invention is to propose a method for the simultaneous preparation of an olefin or an alkenyl benzene hydrocarbon.
  • alpha glycols diols, the two hydroxyl functions of which are attached to two adjacent carbon atoms of the molecule.
  • olefin oxides the oxygen atom of which is bound to two adjacent carbon atoms.
  • the method of the present invention comprises separately contacting with molecular oxygen under peroxidation conditions 21 first hydrocarbon, for example a branched saturated hydrocarbon, having the same carbon structure as the diolefin which it is desired to prepare and a second hydrocarbon, for example a branched saturated hydrocarbon or alkylbenzene hydrocarbon having the same carbon structure as the olefin or alkenylbenzene, desired, so as to produce a first and a second hydroperoxide respectively; reacting the said first and second hydroperoxides with the same ethylenic hydrocarbon having the same carbon structure as the first hydrocarbon in the presence of a suitable catalyst so as to obtain from said ethylenic hydrocarbon an alpha epoxide or an alpha glycol of the same carbon structure as the first hydrocarbon; said alpha epoxide or alpha glycol is then converted by dehydration to the corresponding diolefin; (with the alpha epoxide first being separately, or simultaneously, isomerized) the first
  • the process in accordance with the present invention therefore has the great advantage over the conventional processes directed at the simultaneous preparation of a diolefin and an olefin or an alkenylbenzene of avoiding discarding large quantities of byproducts thereby adversely affecting the economy of such processes.
  • the ketones formed are converted into an intermediate product which is used in the very process of production of the diolefin and olefin or alkenylbenzene; namely the ethylenic hydrocarbon, which is thus recycled in full (except for leakage).
  • the process in accordance with the present invention can be applied in principle to the production of any olefin/diolefin or alkenylbenzene/diolefin pairing.
  • the invention is more particularly useful in the preparation of diolefins derived from a preferably branched condensation hydrocarbon having four or more carbon atoms.
  • the olefin or alkenylbenzene can be obtained either from paraffins, for instance isobutane or from alkyl aromatic hydrocarbons such as ethyl benzene, cumene, etc. or from any hydrocarbon which can give a hydroperoxide.
  • the conversion of the ketone into the corresponding ethylenic hydrocarbon can be effected by any known method for the hydrogenation of a ketone to the corresponding alcohol and the dehydration of said alcohol.
  • alpha-glycol can be obtained in the presence of water by the process described by the applicant in its U.S. application, Ser. No. 866,357 filed Oct. 14, 1969 based upon its priority French Pat. application, Ser. No. PV 169,862 filed on Oct. 14, 1968.
  • the diol obtained in this manner can also be dehydrated in known fashion, particularly in the presence of lithium phosphate prepared under acid conditions atomic Li/P ratio of less than three in the reaction medium for the preparation of the catalystby the process described by the applicant in its U.S. application, Ser. No. 30,276 filed Apr. 20, 1970 based upon its priority French Pat. application filed on Apr. 22, 1969 under National Registration No. 69/12684.
  • alpha-epoxide or alpha glycol can also be converted into the corresponding diolefin by any known means, and particularly by preparing the monoacetate corresponding to the glycol and pyrolyzing said monoacetate to olefinic alcohol, which can then easily be dehydrated by the process described by the applicant in its US. application, Ser. No. 34,172 filed May 4, 1970 based upon its priority French Pat. application filed on May 8, 1969 under National Registration No. 69/14751.
  • FIG. 1 illustrates the simultaneous preparation of isoprene and isobutylene from isopentane and isobutane
  • FIG. 2 refers to the simultaneous production of isoprene and styrene from isopentane and ethyl benzene.
  • FIG. 1 Referring, first of all, to FIG. 1:
  • lsopentane and air are introduced by the lines 1 and 2 respectively into a reactor 3 where they are heated. to a temperature of about 150 C to form the corresponding hydroperoxide.
  • the latter is transferred via a line 4 with the excess isopentane, to a film evaporator 5 from which the hydroperoxide is evacuated through a line 6 while the excess isopentane is recycled through the line 7 to the feed of the reactor 3.
  • the lines 8 and 9 feed a reactor 10 at a temperature of 140 with isobutane and air respectively, line 11 evacuating the resultant hydroperoxide and the excess isobutane from said reactor towards a film evaporator 12.
  • the hydroperoxide which has been separated out is evacuated by a line 13 which joins the line 6 while the excess isobutane is recycled via a line 14 to the feed of the reactor 10.
  • the epoxidation/hydration reactor 15 is fed via the line 6 on the one hand and on the other hand via lines 16 and 17 which conduct water and a mixture of 2-methyl-2-butylene and catalyst respectively.
  • the catalyst consists for instance of molybdenum napthenate, it being understood that the use of other catalysts falls within the scope of the invention.
  • the temperature of the reactor is about 120 C and the dwell time of the products introduced is about 1 hour, during which time the conversion of the hydroperoxides is practically complete.
  • a line 18 evacuates the products emerging from the reactor 15 towards the distillation column 19; at the top of said column the 2-methyl-2-butylene which has not undergone epoxidation/hydration in the reactor 15 is evacuated via a line 20; the line 20 connects up with the line 17.
  • the line 21 collects the other products formed in 15 and introduces them into a distillation column 22.
  • a mixture of methyl 2,3-butanediol and epoxidation/hydration catalyst is collected by the line 23. The catalyst is eliminated by passage through the filter 24.
  • the methyl 2,3-butanediol is introduced through the line 25 into a reactor 26 where it passes at 500 C over lithium phosphate, Li PO which has been prepared in accordance with the method described in the aforementioned French Pat. application filed on Apr. 22, 1969.
  • the products emerging from the reactor 26 via the line 27 are separated in a distillation column 28 at the top of which at 29 isoprene emerges and at the bottom of which small quantities primarily of methyl isopropylketone are collected by the line 30.
  • a mixture composed primarily of methyl isopropyl ketone, tertiary butyl alcohol and 2-methyl Z-butanol is collected by the line 31.
  • the line 31 connects up with the line via the line 32, hydrogen is fed; and the mixture from these three lines is introduced via the line 33 into a hydrogenation reactor 34 containing nickel on pumice stone support; the pressure is 50 kg/cm2, the temperature 250 C, and the time of contact 1 hour.
  • FIG. 2 A second embodiment of the invention is illustrated in FIG. 2.
  • a reactor 44 which is heated to 150 C is fed with isopentane and air through the lines 45 and 46 respectively.
  • the mixture of hydroperoxide formed and of excess isopentane is discharged through a line 47 into a flash distillation column 48 at the bottom of which the hydroperoxide is collected by the line 49, while at the top the excess isopentane is recovered and recycled via the line 50 to the feed of the reactor 44.
  • a reactor 51 heated to a temperature of 140 C, is fed via the lines 52 and 53 respectively with ethyl benzene and air, the outgoing mixture being evacuated by a line 54 to a flash distillation tower 55 at the base of which the hydroperoxide is collected which is then evacuated through a line 56 which connects up with the line 49 while at the top the excess ethyl benzene is collected and recycled by the line 57 to the feed of the reactor 5 l.
  • the line 49 feeds an epoxidation reactor 58 at a temperature of 120 C, also fed with 2-methyl 2-butylene and with an epoxidation catalyst, for instance one having a base of molybdenum, via a line 59.
  • the mixture emerging at 60 from this reactor 58 is separated in a distillation column 61 at the top of which via 62 the excess Z-methyl Z-butylene is collected and recycled to the feed of the reactor 58 while at the bottom of the column 61 a mixture of methyl 2,3-epoxy butane, methyl benzyl alcohol, tertiary amyl alcohol and methyl isopropyl ketone is recovered at 63.
  • This mixture is itself separated in a column 64 at the top of which the epoxide is collected in the line 65.
  • methyl 2,3-epoxy butane is mixed in the reactor 66 with a slight excess of acetic acid introduced through the line 67 so as to form a monoacetate in the presence of a suitable catalyst, for instance ferric chloride, also introduced through the line 67, as described in the aforementioned French Patent application filed on May 8, 1969.
  • a suitable catalyst for instance ferric chloride
  • the resultant mixture is transferred via the line 68 to a pyrolysis reactor 69.
  • the efflux evacuated through the line 70 is diluted with water arriving at 71 and introduced via a line 72 into a distillation column 73.
  • azeotropic distillation makes it possible to recover acetic acid at the bottom of the tower.
  • the acetic acid is recycled via 67, while the olefin alcohols are collected from the top of the column at 74.
  • These alcohols are catalytically dehydrated over thorium oxide at 400 C in the reactor 75.
  • the efflux is transferred via the line 76 into an enclosure 77 where a light phase consisting essentially of isoprene is separated by settling and collected at 78.
  • the pure isoprene is separated from this phase by distillation in a column 80.
  • the isoprene passes off from the top of the column through the line 81.
  • the other components are introduced via the line 82 into a distillation column 83 at the top of which themethyl isopropyl ketone passes over via 84.
  • the olefin alcohols which have not been dehydrated are located at the bottom of the column and are recycled via the line 85 into the reactor 75.
  • the heavy phase separated at 79 contains unconverted olefin alcohols primarily 2-methyl 3-butylene 2-ol. These alcohols are recycled via the line 86 into the reactor after possible distillation in a column 87; the distillation residue being eliminated at 88.
  • the mixture emerges at 91; the line 84 connects up with the line 91; thus all the methyl isopropyl ketone formed is recycled; after injection of hydrogen in 92, the mixture enters a hydrogenation reactor 93 containing a catalyst formed of nickel on pumice stone.
  • the pressure is 50 kg/cm2, the temperature 250 C and the time of contact 1 hour.
  • the reduction products are collected by the line 94 and introduced into a catalytic dehydration reactor 95 formed of thorium oxide brought to 400 C.
  • the mixture is introduced via the line 96 into a distillation column 97. At the top of the column 97, the 2-methyl 2-butylene passes off and is recycled via the line 98 to the epoxidation reactor 58; the styrene is extracted via line 99.
  • EXAMPLE II The simultaneous preparation of isoprene and styrene is effected from isopentane and ethyl benzene as illustrated in FIG. 2.
  • a method for simultaneously preparing a diolefin and an olefin or an alkenyl benzene hydrocarbon comprising separately contacting with molecular oxygen under peroxidation conditions a first saturated hydrocarbon having the same carbon structure as the diolefin end product and a second saturated hydrocarbon or alkyl benzene hydrocarbon having the same carbon structure as the desired olefin or alkenyl benzene end product to produce a first and a second hydroperoxide respectively; reacting both the said first and second hydroperoxides with an ethylenic hydrocarbon having the same carbon structure as the said first hydrocarbon in the presence of a suitable catalyst to obtain from said ethylenic hydrocarbon an alpha-epoxide or an alpha glycol of the same carbon structure as the first hydrocarbon; converting the alpha epoxide by an isomerization-dehydration process to the diolefin end product; or dehydrating the alpha-glycol into the corresponding diolefin end

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US40278A 1969-05-30 1970-05-25 Method for the simultaneous preparation of a diolefin and an olefin Expired - Lifetime US3665047A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4203926A (en) * 1978-12-18 1980-05-20 Gulf Research & Development Company Hydroxidation of gaseous olefins with ethylbenzene hydroperoxide in a heterogeneous liquid system
US4255599A (en) * 1980-03-12 1981-03-10 Gulf Research & Development Company Preparation of styrene from ethylbenzene
US4255596A (en) * 1980-02-25 1981-03-10 Gulf Research & Development Company Preparation of ethylene glycol from ethylene
US4308409A (en) * 1978-10-03 1981-12-29 Gulf Research & Development Company Preparation of propylene glycol from propylene
US4982029A (en) * 1988-12-16 1991-01-01 The Dow Chemical Company Method for the direct preparation of olefins from ketones and Grignard reagents
US5319114A (en) * 1993-09-23 1994-06-07 Arco Chemical Technology, L. P. Olefin epoxidation using a carbon molecular sieve impregnated with a transition metal
US5539131A (en) * 1995-07-13 1996-07-23 Arco Chemical Technology, L.P. Olefin epoxidation process

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4308409A (en) * 1978-10-03 1981-12-29 Gulf Research & Development Company Preparation of propylene glycol from propylene
US4203926A (en) * 1978-12-18 1980-05-20 Gulf Research & Development Company Hydroxidation of gaseous olefins with ethylbenzene hydroperoxide in a heterogeneous liquid system
US4255596A (en) * 1980-02-25 1981-03-10 Gulf Research & Development Company Preparation of ethylene glycol from ethylene
US4255599A (en) * 1980-03-12 1981-03-10 Gulf Research & Development Company Preparation of styrene from ethylbenzene
US4982029A (en) * 1988-12-16 1991-01-01 The Dow Chemical Company Method for the direct preparation of olefins from ketones and Grignard reagents
US5319114A (en) * 1993-09-23 1994-06-07 Arco Chemical Technology, L. P. Olefin epoxidation using a carbon molecular sieve impregnated with a transition metal
US5539131A (en) * 1995-07-13 1996-07-23 Arco Chemical Technology, L.P. Olefin epoxidation process

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GB1276039A (en) 1972-06-01
ZA703535B (en) 1971-01-27
DE2026094A1 (de) 1970-12-17
BE750663A (fr) 1970-11-20
LU60945A1 (xx) 1970-07-20
FR2045074A5 (xx) 1971-02-26
AT297670B (de) 1972-04-10
NL7007814A (xx) 1970-12-02
CA935443A (en) 1973-10-16

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