US3392205A - Production of styrenes - Google Patents

Production of styrenes Download PDF

Info

Publication number
US3392205A
US3392205A US560092A US56009266A US3392205A US 3392205 A US3392205 A US 3392205A US 560092 A US560092 A US 560092A US 56009266 A US56009266 A US 56009266A US 3392205 A US3392205 A US 3392205A
Authority
US
United States
Prior art keywords
iodine
oxygen
ethylbenzene
conversion
mole
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
US560092A
Other languages
English (en)
Inventor
Platz Rolf
Nohe Heinz
Frank Gerhard
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Application granted granted Critical
Publication of US3392205A publication Critical patent/US3392205A/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
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/357—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by dehydrogenation
    • 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
    • Y10S585/90—Rehabilitation of H acceptor
    • 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
    • Y10S585/904—Catalyst rehabilitation by reversion from different compound

Definitions

  • This invention relates to a process for the production of styrenes by dehydrogenation of ethylbenzenes with oxygen in the presence of iodine.
  • styrene is obtained in a yield of 94.9% at a conversion of 60.2% by reacting ethylbenzene with oxygen in the presence of ammonium iodide and a large amount of steam as diluent at 700 C. in contact with stationary ceramic material. In this process also the conversion is not satisfactory and moreover the recovery of the catalyst offers difliculties. In particular, relatively large reactors are necessary owing to the use of large amounts of steam as diluent.
  • ethylbenzenes which are suitable starting materials are ethylbenzene itse1f,.ethylbenzenes in which the ethyl group bears an alkyl radical having one or two carbon atoms as a substituent, such as.isopropyl benzene and butylbenzene, and also nuclear-chlorinated ethylbenzenes which preferably have one to four chlorine atoms attached to the benzene ring, such as 2-chloroethylbenzene, 4-chloroethylbenzene, 2,5-dichloroethylbenzene and 2,4,6trichloroethylbenzene.
  • Oxygen is usually employed in amounts of 0.35 to 1 mole per mole of ethylbenzene.
  • Oxygen-containing gases such as air, may also be used but it is preferred to use pure oxygen so that the reaction may be carried out in a very small reaction space.
  • Iodine is usually required only in very small amounts, for example 0.005 to 0.05 mole per mole of ethylbenzene, as catalyst.
  • Inorganic or organic iodine compounds which are decomposed under the process conditions to form iodine or which are oxidized to iodine maybe used instead of iodine itself.
  • suitable compounds are hydrogen iodide, ammonium iodide, ethyliodide and u,fl-diiodoethylbenzene.
  • the inert heat carriers used have an internal surface area of 0.1 to 15 sq. m./g., particularly 0.5 to 10 sq. m./g., and an average pore size of 300 'to 30,000 A., particularly 600 to 20,000 A.
  • Those materials are regarded as inert which do not initiate any secondary reactions, particularly which do not initiate polymerization of the styrene, under the conditions of the process.
  • substances which when suspended in Water have a pH value of more than 5.5, particularly of from 5.5 to 10, are particuarly Well suited. Materials which are more strongly acid than this are not regarded as inert.
  • suitable inert materials are porcelain, alkaline earth metal silicates, aluminum oxide and Particularly pumice.
  • the reaction is carried out at temperatures of 400 to 700 C., particularly from 450 to 600 C.
  • Atmospheric pressure is generally used but slightly subatmospheric pressure or slightly superatmospheric pressure may be used, for example 0.1 to 1 atmosphere gauge.
  • the residence time may vary within wide limits, for example from 0.1 to 30 seconds, and it is preferably from 0.5 to 10 seconds.
  • the inert heat carrier may be stationarily arranged in the reaction chamber. Particulraly good results are achieved however in a fluidized bed, the particle size of the fluidized material usually being from 0.05 to 0.4 mm.
  • the process may advantageously be carried out by dissolving iodine or the iodine compound in the ethylbenzene, vaporizing the solution and passing the vapor together with oxygen into the reaction zone.
  • the oxygen is advantageously injected immediately before and direct into the fluidized bed.
  • the gas keeps the material in fluidized motion.
  • the amount of oxygen is advantageously regulated so that the lowest possible amount of off-gas escapes. If a diluent is not used, practically the Whole reaction product is condensable. It is separated into an aqueous phase and an organic phase and the styrene is separated from the organic phase by distillation. Unreacted ethylbenzene may be reused.
  • Iodine is either washed out from the combustion gases by means of Example 1 A total of 505 g. of ethylbenzene is passed through a. quartz fluidized-bed reactor having an internal diameter of 30 mm.
  • Example 8 Dehydrogenation is carried out as described in Example 1 but with a stationary pumice catalyst instead of in a fluidized bed. A styrene yield of 87.5% of the theory is obtained with a conversion of 78.3%.
  • Example 9 0.7 mole of 1-ethyl-2,5-dichlorobenzene, 0.5 mole of oxygen and 0.018 mole of iodine per hour are reacted in contact with 200 ml. of Italian pumice in a fluidizedbed reactor according to Example 1. The residence time is 9.3 seconds. The total throughput is 810 g. The organic reaction product is 798 g. containing 44.9% by weight of unreacted starting product and 49.85% by weight of dichlorostyrene (yield: 88.9%, conversion 56.6%).
  • Example 10 The procedure of Example 9 is followed but using 270 g. of 1-ethyl-2,4,6-trichlorobenzene.
  • the organic reaction product is 266 g. and contains 38.1% by weight of starting product and 41.6% by weight of trichlorostyrene.
  • the yield is 73.7% and the conversion 59%.
  • Example 11 1 mole of isopropylbenzene, 0.8 mole of oxygen and 0.03 mole of iodine per hour are reacted at mm. Hg at 550 C. in the fluidized-bed reactor according to Example 1 in contact with 400 m1. of Italian pumice having a particle size of 0.1 to 0.4 mm. The residence time is 1.5 seconds. The total throughput is 432 g. The organic reaction product is 425 g. having a content of 46.6% by weight of isopropylbenzene and 49.6% by weight of u-methylstyrene. The yield is 90.7% and the conversion is 54.4%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US560092A 1965-06-29 1966-06-24 Production of styrenes Expired - Lifetime US3392205A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB82592A DE1260460B (de) 1965-06-29 1965-06-29 Verfahren zur Herstellung von gegebenenfalls substituiertem Styrol

Publications (1)

Publication Number Publication Date
US3392205A true US3392205A (en) 1968-07-09

Family

ID=6981559

Family Applications (1)

Application Number Title Priority Date Filing Date
US560092A Expired - Lifetime US3392205A (en) 1965-06-29 1966-06-24 Production of styrenes

Country Status (5)

Country Link
US (1) US3392205A (en))
BE (1) BE683380A (en))
DE (1) DE1260460B (en))
GB (1) GB1144214A (en))
NL (1) NL6608919A (en))

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846472A (en) * 1971-09-03 1974-11-05 Basf Ag Dehydrogenation of organic compounds
US4471146A (en) * 1983-02-03 1984-09-11 The Dow Chemical Company Oxydehydrogenation process

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5948814B2 (ja) * 1976-10-01 1984-11-29 三菱油化株式会社 アルケニル置換芳香族化合物の製法及びその触媒

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3130241A (en) * 1959-12-28 1964-04-21 Shell Oil Co Dehydrogenation process
US3304329A (en) * 1960-03-09 1967-02-14 Exxon Research Engineering Co Oxidizing hydrocarbons in the presence of triggering agents
US3318967A (en) * 1963-02-28 1967-05-09 Internat Synthetic Rubber Comp Dehydrogennation of hydrocarbons

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1390135A (fr) * 1963-04-29 1965-02-19 Shell Int Research Production de styrène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3130241A (en) * 1959-12-28 1964-04-21 Shell Oil Co Dehydrogenation process
US3304329A (en) * 1960-03-09 1967-02-14 Exxon Research Engineering Co Oxidizing hydrocarbons in the presence of triggering agents
US3318967A (en) * 1963-02-28 1967-05-09 Internat Synthetic Rubber Comp Dehydrogennation of hydrocarbons

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3846472A (en) * 1971-09-03 1974-11-05 Basf Ag Dehydrogenation of organic compounds
US4471146A (en) * 1983-02-03 1984-09-11 The Dow Chemical Company Oxydehydrogenation process

Also Published As

Publication number Publication date
DE1260460B (de) 1968-02-08
BE683380A (en)) 1966-12-29
NL6608919A (en)) 1966-12-30
GB1144214A (en) 1969-03-05

Similar Documents

Publication Publication Date Title
US3350422A (en) Catalytic epoxidation of an olefinically unsaturated compound using an organic hydroperoxide as an epoxidizing agent
US2410541A (en) Polyhalogenated olefins
GB1017970A (en) Process for preparing olefinic hydrocarbons
US6852896B2 (en) Concerted process for the production of an alkenyl substituted aromatic compound
US2746844A (en) Catalytic hydrogen chloride oxidation process to produce chlorine
US3028440A (en) Production of butadiene
US3551506A (en) Vinyl chloride production
US3392205A (en) Production of styrenes
US3240834A (en) Dehydrohalogenation of hydrocarbon halides
US3010913A (en) Catalyst preparation
US2434289A (en) Manufacture of hydrocarbons
US3352935A (en) Dehydrohalogenation process
GB1414438A (en) Process for the production of primary normal monochlorparaffins
US2749368A (en) Production of aralkyl hydroperoxides
US3299155A (en) Oxidative dehydrogenation of alkyl benzenes with canipo4 and so2
US2779805A (en) Separation of acetylene from ethylene by hydrochlorination of the ethylene
JPH0354928B2 (en))
US2708208A (en) Production of phenols
US3530169A (en) Production of methacrylic esters
US2846450A (en) Preparation of maleic anhydride
US2792430A (en) Production of phenolic compounds
US2603650A (en) Preparation of heterocyclic compounds
US2553799A (en) Hydrogen-halogen exchange process
US3496243A (en) Production of dichloroethane and trichloroethane
US2553800A (en) Hydrogen-halogen exchange process