EP1049685A1 - Procede pour la production d'oxyde de propene - Google Patents

Procede pour la production d'oxyde de propene

Info

Publication number
EP1049685A1
EP1049685A1 EP98963536A EP98963536A EP1049685A1 EP 1049685 A1 EP1049685 A1 EP 1049685A1 EP 98963536 A EP98963536 A EP 98963536A EP 98963536 A EP98963536 A EP 98963536A EP 1049685 A1 EP1049685 A1 EP 1049685A1
Authority
EP
European Patent Office
Prior art keywords
reactor
propene
propene oxide
oxygen
oxide
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.)
Withdrawn
Application number
EP98963536A
Other languages
German (de)
English (en)
Inventor
Rolf Peter Schulz
Uwe Dingerdissen
Holger Orzesek
Wilhelm Maier
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.)
Evonik Operations GmbH
Original Assignee
Aventis Research and Technologies GmbH and Co KG
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 Aventis Research and Technologies GmbH and Co KG filed Critical Aventis Research and Technologies GmbH and Co KG
Publication of EP1049685A1 publication Critical patent/EP1049685A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for the production of propene oxide by direct oxidation of propene with oxygen or gases containing oxygen in the gas phase with or without the participation of an extra catalyst in a temperature range of 150 to 500 ° C in a reactor which is lined with inert materials or is modified.
  • Propene oxide is one of the most important intermediates in the chemical industry; it is mainly required for the production of propylene glycols, which are predominantly processed into polyurethanes.
  • Bifunctional polypropylene glycols with highly viscous properties or mixed adducts of propene and ethylene oxide or the monoalkyl ethers of these compounds are important raw materials that are used to manufacture a wide variety of products (e.g. defoamers, mold release agents, desmulsifiers, brake fluids, metalworking aids, textile auxiliaries, lubricants and adhesives).
  • Propenoxide itself is a good solvent for cellulose acetate, nitrocellulose, adhesives, resins and other substances and is used as a stabilizer for chlorine-containing polymers, as a corrosion additive for coolants and pesticides, as well as for weed control and as a disinfectant and sterilizing agent.
  • the chlorohydrin is reacted with NaOH from the cell liquid of the chlor-alkali electrolysis; this creates a NaOH / NaCI solution, which has to be concentrated and cleaned of organic substances before it can be returned to the electrolytic cell.
  • propene oxide by indirect oxidation with peroxides or peracids is also a two-stage process, which differs from the chlorohydrin process in that the resulting coupling products are often obtained in larger quantities than propene oxide itself and an outlet must also be available for this.
  • Hydrogen peroxide, organic peracids and organic hydroperoxides are used for the epoxidation of propene.
  • the epoxidation with H 2 O 2 is usually carried out in the liquid phase (e.g. methanol / water) in the presence of a catalyst (MoO 3 ) or titanium oxide on SiO 2 or Ti-containing zeolites such as TS-1 (Enichem) at 40 - 50 ° C and a pressure of 4 bar.
  • a catalyst MoO 3
  • Ti-containing zeolites such as TS-1 (Enichem)
  • Oxidation with organic hydroperoxides has become increasingly important in recent years because there is an increasing demand on the world market for the by-products which are formed, especially styrene or methyl tert-butyl ether (MTBE).
  • Tert-butyl hydroperoxide, ethylbenzene hydroperoxide and cumene hydroperoxide are preferably used, which, as coproducts, provide isobutene (or methyl tert-butyl ether), styrene or methylstyrene.
  • Oxidations in the liquid phase which are carried out with or without a catalyst (homogeneous or, heterogeneous) (FR-A-2 1 15 752, DE-A-4 447 231) often provide better yields than the gas phase processes, but they are also difficult separation tasks, corrosion problems and complicated technologies, so that no large-scale application has become known.
  • a catalyst homogeneous or, heterogeneous
  • a Canadian publication (CA 986127) describes a gas phase reaction of propene (93.9%) with oxygen (6.1%) in a steel autoclave with a glass insert at a temperature of 226 ° C at 5 bar pressure. After 90 minutes, the selectivity to propene oxide is 64% (no information is given on the conversion).
  • the main disadvantage of this method is the excessively long dwell time and the use of relatively expensive pure oxygen, which represents a very high safety risk.
  • the object of the present invention is therefore to provide a process for the preparation of propene oxide by direct oxidation of propene which does not have the disadvantages of the known processes, i.e. with which propene oxide selectivities> 60% can be achieved without the by-products or by-products in stoichiometric amounts.
  • propene oxide can be produced very selectively, effectively and inexpensively in a continuous gas phase process in a reactor lined with inert materials.
  • the inner walls of the reactor and / or internals for directing the gas flow or internals which control the flow of the reactances in the tubular reactor, such as Thermocouples be coated with an inert material or consist of such a material.
  • the present invention thus relates to a process for the preparation of propene oxide, a mixture of propene and oxygen or an oxygen-containing gas, optionally in the presence of a catalyst, being reacted in a reactor at a temperature in the range from 150 to 500 ° C., wherein the interior of the reactor is completely or partially lined with inert materials. Surprisingly, it was found that an inside coated with inert materials
  • Standard steel e.g. V2A
  • V2A Standard steel
  • the product selectivity can be increased even further via the moisture and CO 2 content of the air or gas mixture used for the oxidation.
  • inert materials are understood to mean those materials which have no or only minimal interactions or chemical reactions with the reactants and which do not allow any chemical or physical sorption on their surface.
  • Inert materials which are suitable for coating the interior of the reactor or for coating reactor internals can, for example, be selected from the materials of the following group: one or more precious metals of the 8th subgroup of the periodic system, in particular gold, titanium, tantalum, glass, enamel , Quartz, ceramic or teflon.
  • the process according to the invention is preferably operated continuously, air being used as the oxidizing agent for propene. This eliminates the need for complex processing. Unreacted propene is preferably recycled into the feed stream of the reactor after the propene oxide, the inert gases and the by-products have been separated off.
  • the reaction temperature is in the range from 150 to 500 ° C., preferably in the range from 220 to 380 ° C., at a pressure in the reactor in the range from 1 to 100 bar, in particular 10 to 55 bar.
  • the residence times for the gas mixture in the reactor are 0.1 to 15 minutes, preferably one to 1000 seconds, particularly preferably 2.5 to 500 seconds.
  • the described method also differs from the gas phase oxidation processes known hitherto in that the Reaction is carried out continuously in a pressure operated reactor with hydrodynamic residence times in the range of seconds - in contrast to many autoclave processes described with residence times in the minutes to hours range.
  • the feed gas stream preferably has the following composition: 50 to 95% by volume of propene and 5 to 50% by volume of a gas containing oxygen, e.g. Air, or a mixture of oxygen and inert gases (ratio 0.1 to 1.0).
  • a gas containing oxygen e.g. Air
  • a mixture of oxygen and inert gases ratio 0.1 to 1.0
  • the inert gases are e.g. Propane, carbon dioxide, water vapor, methane, nitrogen or argon are possible.
  • Another advantage of the process according to the invention is that it is possible to dispense with the addition of any catalyst material, so that there is no need to separate, work up, dispose of or regenerate the catalyst material at a later time, which results in considerable cost and time advantages (reactor dead times largely eliminated) continuous driving style.
  • catalysts Compounds based on transition metals, very particularly based on titanium, vanadium, chromium, iron, cobalt, nickel, copper, molybdenum, ruthenium, palladium, tungsten, rhenium and silver, are particularly preferred as catalysts.
  • the conversion and selectivity of the process can even be optimized by optimizing the design of the flow tube and the internals of the reactor.
  • tube bundle reactors By using tube bundle reactors, the process can be scaled up to technically interesting volume flows.
  • air of suitable purity or with the addition of agents to suppress certain side reactions enables a further increase in the selectivity Propene oxide.
  • Such reagents or inhibitors are familiar to the person skilled in the art; chlorine-containing organic compounds, in particular alkyl chlorides, in particular 1,2-dichloroethane, are often used for this purpose.
  • the yields in the process according to the invention are above 7%, in particular above 8%, preferably> 9%, with selectivities to propene oxide of> 60%, in particular> 61.5%.
  • the propene sales are> 13%, in particular> 14%, preferably> 15%.
  • the reactor consists of a vertically downward positioned steel tube (length: 30 cm, thereof 5.4 cm reaction chamber length; inner diameter: 9.5 mm; reaction volume: 3.8 ml; steel no .: 1.4571) and is with a heated outer jacket.
  • the propene is metered in with the aid of a pump which conveys the liquefied alkene into the reactor at a pressure of 1 00 bar; the air is supplied via a mass flow controller, which enables the reactor to operate under a constant volume flow.
  • the pressure constancy inside the reactor is through an overflow valve at the reactor outlet ewirxt.
  • a gas chromatograph is used to determine the composition of the product gas stream, which enables continuous analysis at any time interval (taking into account the retention times of the products on the capillary column).
  • Test 1 was installed in a flow reactor made of standard steel
  • * - Sales include oligomerization and polymerization products.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé pour la production d'oxyde de propène, dans lequel on fait réagir un mélange de propène et d'oxygène ou bien d'un gaz contenant de l'oxygène, éventuellement en présence d'un catalyseur, dans un réacteur à une température allant de 150 à 500 DEG C, la chambre intérieure du réacteur étant revêtue totalement ou partiellement de matériaux inertes. On utilise comme matériau inerte au moins l'un des matériaux du groupe suivant: un ou plusieurs métaux précieux du 8ème sous-groupe de la classification périodique des éléments, notamment de l'or, du titane, du tantale, du verre, de l'émail, du quartz, de la céramique ou du téflon. La sélectivité vis-à-vis de l'oxyde de propène est > 60 %.
EP98963536A 1997-12-08 1998-12-03 Procede pour la production d'oxyde de propene Withdrawn EP1049685A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19754303A DE19754303A1 (de) 1997-12-08 1997-12-08 Verfahren zur Herstellung von Propenoxid
DE19754303 1997-12-08
PCT/EP1998/007862 WO1999029679A1 (fr) 1997-12-08 1998-12-03 Procede pour la production d'oxyde de propene

Publications (1)

Publication Number Publication Date
EP1049685A1 true EP1049685A1 (fr) 2000-11-08

Family

ID=7851061

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98963536A Withdrawn EP1049685A1 (fr) 1997-12-08 1998-12-03 Procede pour la production d'oxyde de propene

Country Status (6)

Country Link
US (1) US6303800B1 (fr)
EP (1) EP1049685A1 (fr)
JP (1) JP2001525402A (fr)
CA (1) CA2313318A1 (fr)
DE (1) DE19754303A1 (fr)
WO (1) WO1999029679A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2169730C1 (ru) * 2000-02-22 2001-06-27 Российский научный центр "Прикладная химия" Способ получения окиси гексафторпропилена
DE10044538A1 (de) * 2000-09-05 2002-04-04 Ift Inst Fuer Troposphaerenfor Verfahren zur Herstellung von Epoxiden durch Oxidation von Olefinen
WO2003027086A1 (fr) * 2001-08-22 2003-04-03 Sumitomo Chemical Company, Limited Procede permettant de produire de l'oxyde de propylene
US7557225B2 (en) * 2006-12-06 2009-07-07 E.I. Du Pont De Nemours And Company Process for preparing hexafluoroisobutene epoxide

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2530509A (en) * 1950-11-21 Production of propylene oxide
US3026333A (en) * 1962-03-20 Process for the continuous production of propylene oxide
CA986127A (en) * 1970-07-15 1976-03-23 Nazar S. Aprahamian Process for the production of propylene oxide
FR2115752A5 (en) * 1970-11-26 1972-07-07 Progil Propylene oxide - from propylene and oxygen in contact with titanium surfaces
AU2399992A (en) * 1991-08-07 1993-03-02 Olin Corporation Loop reactor for the oxidation of olefins
US5241088A (en) * 1991-08-07 1993-08-31 Olin Corporation Non-catalytic oxidation of alkylene to alkylene oxide in the presence of recycled aldehyde by-products

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9929679A1 *

Also Published As

Publication number Publication date
WO1999029679A1 (fr) 1999-06-17
US6303800B1 (en) 2001-10-16
CA2313318A1 (fr) 1999-06-17
JP2001525402A (ja) 2001-12-11
DE19754303A1 (de) 1999-06-10

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