EP0025787A1 - Procedes catalytiques et catalyseurs - Google Patents

Procedes catalytiques et catalyseurs

Info

Publication number
EP0025787A1
EP0025787A1 EP19800900497 EP80900497A EP0025787A1 EP 0025787 A1 EP0025787 A1 EP 0025787A1 EP 19800900497 EP19800900497 EP 19800900497 EP 80900497 A EP80900497 A EP 80900497A EP 0025787 A1 EP0025787 A1 EP 0025787A1
Authority
EP
European Patent Office
Prior art keywords
copper
support
catalyst
process according
redox couple
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Withdrawn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
EP19800900497
Other languages
German (de)
English (en)
Inventor
Robert William Dale
John Joseph Rooney
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.)
GALLAHER GROUP Ltd
Gallaher Ltd
Original Assignee
GALLAHER GROUP Ltd
Gallaher Ltd
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 GALLAHER GROUP Ltd, Gallaher Ltd filed Critical GALLAHER GROUP Ltd
Publication of EP0025787A1 publication Critical patent/EP0025787A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
    • C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
    • 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
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • 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
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • 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
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene

Definitions

  • a catalytic process for the oxidation or oxydehydrochlorination of an aliphatic hydrocarbon comprises passing a gas stream comprising the hydrocarbon, oxygen and, optionally, hydrogen chloride over a catalyst that is selected from (a) catalysts that comprise a_ support, copper chemically bonded to the support, and a minor amount of a redox couple for the support and (b) catalysts that are stable redox catalysts and which comprise a support carrying divalent copper and in which the exposed surfaces of the catalyst comprises monovalent . copper.
  • Preferred processes according to the invention are oxydehydrochlorination processes and in particular by the invention it is possible to produce vinyl chloride.
  • the hydro ⁇ carbon can be an unsaturated hydrocarbon, for instance ethylene, but preferably it is a saturated hydrocarbon.
  • the hydrocarbon preferably contains at least two carbon atoms and the process is of most value applied to hydrocarbons containing up to six carbon atoms.
  • Preferred hydrocarbons are propane, butane, (preferably straight chain) and, especially, ethane. Numerous attempts have been made to subject ethane and other saturated hydrocarbons to catalytic oxydehydrochlorination processes but these processes have generally involved very high temperatures, low conversions and large amounts of unwanted by-products. In the invention we surprisingly find that it is possible to carry out the oxydehydrochlorination process with satisfactory conversions at lower temperatures than normal, for instance temperatures below 350°C and
  • the oxydehydrochlorination is best conducted by forming a gaseous mixture of the hydrocarbon, hydrogen chloride and air (or pure oxygen or other oxygen providing gas) and passing this gas stream through a reaction tube containing the selected catalyst.
  • the gas mixture is conveniently generated by passing a mixture of the hydrocarbons and air or other oxygen providing gas through concentrated aqueous hydrochloric acid and thereby entraining hydrogen chloride in the gas stream.
  • the degree of oxydehydrochlorination can be varied from onochloro substitution to replacement with chlorine of all the hydrogen atoms in the resultant unsaturated molecule by appropriate selection of reaction conditions.
  • the relative proportions of hydrocarbon, oxygen and hydrogen chloride may be varied to optimise the yield of a chosen product.
  • the catalyst may significantly affect the degree of oxydehydrochlorina ⁇ tion at any particular temperature. For instance at a given temperature and with a given gas mixture a catalyst having a support of small pore size may give more- chlorination than a similar catalyst formed on a support having a larger pore size.
  • catalysts on a support having an average pore size below 50 Angstroms, and preferably below 30 Angstroms (for instance 4 to 16 Angstroms, e.g. Zeolite 13X) are preferred when high chlorine substitution is-desired and catalysts on a s.upport having an average pore size above 50 Angstroms and preferably above 100 Angstroms (for instance conventional activated alumina or ⁇ -alumina) are preferred when low substitution is desired, e.g. for the formation of vinylchloride from ethylene.
  • the product When the starting hydrocarbon is ethane the product may be any of vinylchloride, 1,1-dichloroethylene, cis- or trans-l,2-dichloroethylene, trichloroethylene or tetrachloroethylene.
  • the products can be subjected to subsequent reactions in conventional manner. For instance the higher chlorinated products, such as dichloro- ethylene can be converted to vinylchloride in known manner.
  • the hydrocarbon should be unsaturated, preferably at a terminal position, and generally contains from 2 to 6 carbon atoms, usually 2 to 4 carbon atoms and is preferably ethylene.
  • Reaction- of ethylene with air in accordance with the invention can easily be conducted to give high yields of acetaldehyde with substantially nc formation of tars or other inconvenient by-products. Since the reaction product is free of such by-products any ethylene that remains unconverted in the process can easily be recycled for subsequent reaction. Higher terminally unsaturated hydrocarbons generally form the corresponding methyl ketones.
  • the support for catalysts for use in the oxidation processes preferably has a small average pore size, e.g below 50 Angstroms and preferably below 50 Angstroms, supports having a pore size of 4 to 16 Angstroms (e.g. Zeolite 13X) being preferred. All processes of the invention are preferably conducted by passing the chosen gas stream over the catalyst contained in a tube maintained at substantially atmospheric pressure, although higher or lower pressures may be used if desired.
  • the * catalyst may be in any form that ensures good contact between the gas stream and the catalyst and may be in traditional catalyst shape but is preferably in granular or powder' form, most preferably in the form of particles below 1 mm in size, often below 10 mesh in size.
  • the catalysts used in the process comprise a support, copper chemically bonded to the support and a minor amount of a redox couple for the support.
  • a substantial part at least of the copper should be chemically bonded to the support as opposed to being merely adsorbed onto the support as an adsorbed copper salt, e.g. copper chloride.
  • the support should therefore contain sites at which bonding of-copper can occur.
  • the bonding generally is mainly electrovalent.
  • the support can be formed initially with ionically bonded copper in it, for instance by precipitation of aluminium hydroxide gel from an alkaline liquor containing a copper salt followed by drying the gel, but generally the copper is ionically bonded into the support as a result of ion exchange. Accordingly the support should be one that is capable of undergoing
  • Supports such as activated carbon or normal silica can be used but are less satisfactory than supports containing a greater number of ion exchange sites.
  • the support is preferably alumina .. or an alumino silicate, for instance a zeolite.
  • the support may include substantial amounts of copper compound that is not chemically bonded to the support and the support may also carry the ions that the copper should have replaced.
  • the support is impregnated 5 with a solution of a copper salt, ion exchange is permitted to occur, excess solution is removed and the impregnation is then repeated at least once and usually more, e.g. 3 to 6 times. Finally the catalyst is washed and dried.
  • the copper salt solution should not 0 be too concentrated as otherwise the activity may be impaired, the concentration generally being below 50 grams per litre, preferably 20 to 40 grams per litre.
  • the solvent is generally water. Since the anion of the copper salt is removed together with the cation that ** - * is being replaced and the excess solution the particular
  • OMPI salt is not critical, but the nitrate or chloride is generally preferred.
  • cupric chloride can subsequently be added by a conventional impregnation and dehydration technique the amount is always relatively low compared to the amount of copper that is bonded to the support.
  • At least 501 by weight of the copper on the support usually at least 70% and preferably at least 90%, is bonded to the support.
  • the activity of the final catalyst may be inferior if the amount of ionically bonded copper is low,, and in particular if it is significantly below the maximum amount that can be ion exchanged into the support.
  • the support is chemically substantially saturated with such copper, for instance containing at least 501 and preferably at least 75% of the maximum amount that can be ionically exchanged into the support.
  • the support Before conducting the ion exchange with the copper solution, the support may have its balancing cations exchanged with lithium or other ions.
  • Any compound capable of serving as a redox couple with copper may be used. It may consist of a single compound or of a mixture of compounds in which event it is sometimes convenient to look upon one compound of the mixture as the redox couple and another compound of the mixture as a promoter for the redox couple.
  • the redox couple is generally an inorganic compound and this compound and any promoter for it are generally in the form of an acetate or, preferably, a chloride. Suitable promoters include stannic and calcium compourlds but lithium compounds are preferred. Cupric compounds may also be used aspromoter. It is possible that the promotion effect (i.e. improvement in activity) is caused partly and perhaps mainly by the anion, which is preferably chloride, that is introduced with the cation.
  • Suitable inorganic compounds as redox couples are noble metal compounds including iridiu , ruthenium or rhodium compounds, generally the trichloride, or palladium compounds.
  • Preferred redox couples include divalent palladium, i.e. Pd 2+.
  • Pd 2+ Preferably it is a chloride, generally being introduced onto the support as PdClJ " .
  • the inclusion of compounds of cerium and/or manganese in the catalyst is often beneficial.
  • the deposition of the redox couple or promoter is best effected by impregnating the support with a solution of the redox couple or promoter and evaporating to dryness.
  • the redox couple and promoter can be impregnated in succession in either order but preferably the redox couple and any promoter "that is to be introduced are impregnated together from a solution containing both and the support is then evaporated 'to . dryness. This method results in anions in the solution remaining in the support.
  • the solution may be in any suitable solvent, preferably substantially non-aqueous. Methanol and dichloromethane are particularly suitable and may be used as a mixture.
  • the concentration of the redox couple in the solution is generally below 2% , for instance 0.001 to 1% preferably 0.005 to 0.1% by weight measured as metal, e.g. palladium.
  • concentration of promoter, measured as metal, in this solution or any other impregnation solution used is generally within the same range.
  • the catalysts generally comprise from 1 to 10% of chemically bonded copper and a much smaller amount, generally less than 20% by weight based on the weight of copper, of the redox couple, the amount of redox couple being measured as metal when the couple is an inorganic compound.
  • the amount of palladium or other metallic component of redox couple may be from 0.1 or 1% up to 20%, preferably 5. to 20%, based on the weight of copper.
  • Preferred catalysts comprise 2 to 7%, most preferably 3 to 6%, by weight chemically bonded copper and 0.05 to 2%, preferably 0.1 to 0.5% by weight metal of palladium compound or other redox couple.
  • the amount is generally from 0.5 to 2.5 parts by.weight of the redox couple, all amounts being measured as metal.
  • the amount of promoter is about 1 part by weight or sometimes up to 2 parts by weight when the promoter is monovalent, for instance lithium, with double these amounts for higher valent promoters such as calcium.
  • a preferred way of making the catalysts comprise impregnating zeolite with an aqueous copper salt solution, permitting ion exchange to occur, removing the excess solution and repeating the impregnation at least twice, preferably then washing and drying the support, impregnating the support with a solution providing 0.1 to 0.5%, measured ' as ' metal and based on
  • the catalyst is preferably used without any of the chemical after treatments normally used in the prior art, e.g high temperature reduction. However we have found that the activity of the catalyst can often be increased by subsequently heating it under moderate conditions, namely 100 to 200 C preferably for half to 4 hours. Lower temperatures do not seem to increase activity and higher temperatures tend to damage the catalyst.
  • the temperature is preferably at least 120°C and preferably the heating is conducted for from 1 to 3 hours at about 150 C.
  • the catalyst is contacted with water vapour for at least 15 Or 30 seconds at the specified temperature at the end of the heating.
  • the contact with water % yapour is generally for at least 5 minutes, usually at least 10 minutes but it is generally unnecessary for the contact to be longer than 20 minutes.
  • a convenient way of carrying out the activation is to conduct most of the heating under vacuum in a closed vessel and then to introduce sufficient water vapour to raise the pressure to atmospheric and complete the heating in this atmosphere.
  • activating by heating in the presence of steam activation may also be achieved by exposing the catalyst resulting from substantially dry heating to atmospheric moisture for 1 to 2 days or activation may be completed during use of the catalyst. For instance it may be heated immediately prior to use.
  • the catalyst generally has a blue colour.
  • the contact with moisture may reduce the colour intensity of the catalyst and as soon as this has been observed the contact with water vapour can be terminated.
  • the amount of water vapour absorbed for optimum activation is generally at least 10 mg per gram catalyst. Preferably the amount is at least 25 mg, most preferably 50 to 100 mg, per gram catalyst. Amounts above 200 mg per gram are usually unnecessary.
  • OMPI and is capable of being stored for significant periods of time, for instance many hours or days or weeks, before use, for instance in a impermeable packet.
  • the substantially monovalent copper on the surface is in intimate contact with divalent copper, which forms a substrate for the substantially monovalent copper.
  • divalent copper which forms a substrate for the substantially monovalent copper.
  • substantially all the copper on the surface is in substantially monovalent form since although some divalent copper can be tolerated it tends to reduce the activity of the catalyst.
  • the amount of monovalent copper should be low, compared to the amount of divalent copper, and may be provided by, for instance, a mono- molecular layer. The amount should not be more than the amount required to form a layer a few molecules thick on the divalent copper.
  • the presence of bivalent copper in the catalyst can be observed by electron spin resonance measurements .(ESR) .
  • the valency state of the copper in the surfaces can be determined by electron spectroscopy chemical analysis (ESCA) .
  • ESCA electron spectroscopy chemical analysis
  • the surface, as determined by ESCA is substantially free of divalent copper.
  • the analysis may be by, for example, a Vacuum Generators E.S.C.A. 3 Spectrometer in which the base pressure of the analyser
  • _g chamber is 1 x 10 Torr and of the sample chamber is
  • Divalent copper (CuO) has a binding energy of about 933.6 eV.
  • the bindin energy is preferably between 932.2 and 933.4, most preferably
  • the copper containing deposit in the catalyst may be physically adsorbed onto the support but is preferably bonded to the support e.g. as described above.
  • the catalyst includes also a redox couple for copper, this redox couple generally being present as a minor amount compared to the amount of copper.
  • the catalyst which has substantially mono ⁇ valent copper on its exposed surfaces is a catalyst made from the materials and by the methods described in detail above. The activation by heating, especially in the presence of moisture vapour, appears to result in the formation of substantially monovalent copper.
  • the monovalent copper catalysts are best made by heating a catalyst comprising a support carrying a deposit comprising divalent copper under conditions such as to convert the exposed surface of the deposit to monovalent copper compound, preferably while leaving the underlying copper in the divalent state.
  • the catalyst may be reduced during or after its formation.
  • a reducing agent such as stannous tin, cerium as Ce 3+ or thallium Tl1+ may be deposited before the redox couple.
  • the amount of reducing agent is generally very small, e.g. 0.01 to
  • the divalent copper can be reduced by a gaseous reducing agent, for instance carbon monoxide. This is generally affected before the deposition of any redox couple and promoter.
  • OM useful not only for the processes described but also for other processes, such as pollution control, for instance in an automobile exhaust, production of hydrogen by the water gas reaction and carbon monoxide oxidation. They are particularly satisfactory in the low temperature catalytic oxidation of carbon monoxide to carbon dioxide with the result that they are of value incorporation in smoking products or filters for smoking products. Thus they may be used as the catalytic component of the smoking products or filters as described in British Patent Specification No. 2,014,376.
  • Example 1 illustrates the novel catalysts and their production while the remaining examples illustrate processes according to the invention.
  • Example 1 illustrates the novel catalysts and their production while the remaining examples illustrate processes according to the invention.
  • Zeolite 13X was immersed in" an aqueous solution of • 30 g/1 cupric nitrate, left to soak in that solution to permit ion exchange to occur and was then separated from the remaining solution. The separated product was then immersed in fresh solution and the whole process".repeated until it has been given three immersions. Analysis showed at that time that the catalyst contained from 3 to 6% copper based on the dry weight. The product was then washed with water and dried. It was then immersed in sufficient of a solution of Na-PdCl. in equal parts methanol and methylene dichloride to provide 0.5% Pd, measured as metal, in the catalyst, and the product dried at room temperature.
  • a typical solution contains 7.5 mg Pd, as Na 2 PdCl 4 , in 100 ml solvent. Different samples of this catalyst were then heated in air for two hours at various temperatures between 25 C and 300°C. As a guide to the activity of these catalysts a standard activity test was used in this and the following examples and consisted of passing a gas stream containing carbon monoxide and oxygen over the .catalyst at ambient temperature and observing the degree of conversion of carbon monoxide to
  • Example 1 The process of Example 1 was repeated using various palladium concentrations and with the incorporation of various promoters in the palladium solution and the 0 catalyst content of palladium and promoters was as follows
  • catalysts B,C,D,F,G and H had higher and longer lasting activity than catalysts A and E, catalysts B, D and H 5 being particularly satisfactory.
  • the processes necessary for the manufacture of catalysts B and H were repeated but with varying amounts of lithium and calcium and it was found that the values of lithium and calcium quoted in catalysts B and H were optimum.
  • Example 4 Zeolite molecular sieve, type 13X, was ion exchanged in triplicate with 3% aqueous cupric nitrate, washed with distilled water and dried in air at about 35 C. A solution containing Na 2 PdCl, and Li Cl in 50/50 methanol/meth lene chloride (or methanol alone) was applied and allowed to evaporate leaving a free flowing powder having Pd and Li loadings of between 0.1% and 0.-51.
  • the catalyst was activated by first heating in a bottle for 1 ⁇ hours at 150 C after which time a small sample tube is introduced and the bottle sealed with a rubber septum. Water at the rate of from 50 to 100 mg/g of catalyst was added through the septum via a syringe into the empty tube, where it evaporated. The contents were maintained at 150°C for a further 15 minutes. The resultant catalyst had good activity when determined as in Example 1.
  • Electron spin resonance examination of the catalyst before the heating steps showed that the catalyst contained divalent copper and ESCA determination, at this stage showed that there was substantially no monovalent copper present on the surface.
  • ESCA determination of the catalyst that had been activated by heating and steaming at 150 C showed that the surface consisted substantially only of substantially monovalent
  • Example 5 The process of Example 1 was repeated but modified by contacting the ion exchanged zeolite with a solution containing stannous chloride before contact with the palladium solution. The stannous chloride solution was evaporated to dryness. The amount of stannous chloride was about 1% based on the amount of copper in the support. Similar results could be
  • Example 6 The process of Example 1 was repeated but with some modifications. Cupri.c chloride was used instead of cupric nitrate. The process was repeated until the support had been given five immersions and analysis then showed that the catalyst contained from 5 to 6% copper based on the dry weight.
  • the methanol/methylene dichloride solution contained, in addition to the palladium compound, stannic chloride in an amount sufficient to provide 0.5% measured as Sn. The product was dried at room temperature and then heated at 150 C for two hours while exposed to the ambient atmosphere.
  • Example 7 Example 7
  • Example 8 The process of Example 2 is repeated, to form catalysts 7A to 7H, but using ⁇ -alumina (having a pore size well in excess of 100 Angstroms) instead of Zeolite 13X.
  • Example 8 The process of Example 2 is repeated, to form catalysts 7A to 7H, but using ⁇ -alumina (having a pore size well in excess of 100 Angstroms) instead of Zeolite 13X.
  • a gas mixture was formed of one part by volume ethylene and three parts by volume air and passed through a tube containing catalyst A of Example 2 in particulate form having a mesh size of 30 to 60 mesh.
  • the tube and the catalyst was held at a temperature ill the range 70 to 100°C, generally around 100°C.
  • the resultant gas mixture contained acetaldehyde in high yield, and was substantially free of tarry residue and other by-products . Although the conversion of ethylene was high a little remained unreacted and could easily be recycled.
  • a mixture of equal amounts by volume of air and ethane was bubbled through concentrated aqueous hydrochloric acid to produce a gas mixture of air, ethane and hydrogen chloride.
  • This gas mixture was passed through a reaction tube containing catalyst A of Example 2 in the form of particles having a mesh size of 30 to 60 mesh, the tube and the catalyst being maintained at a temperature of about 280°C.
  • Example 9 was repeated using catalyst A of Example 7 instead of catalyst A of Example
  • the product was mainly vinylchloride, but contained also small amounts of di-, tri- and tetra-chloroethylenes.

Abstract

Des catalyseurs comprenant un support et du cuivre sont utilises pour l'oxydation catalytique ou oxydeshydrochloruration d'hydrocarbures aliphatiques. L'oxydeshydrochloruration peut s'effectuer a des temperatures comprises entre 150 et 350 C et l'oxydation a des temperatures comprises entre 30 et 150 C. Les catalyseurs peuvent consister en un support, du cuivre chimiquement lie au support et une petite quantite d'un couple redox, tel que du palladium bivalent, pour le cuivre ou ils peuvent consister en des catalyseurs redox stables comprenant un support portant du cuivre bivalent et dans lequel les surfaces exposees du catalyseur consistent en du cuivre monovalent. Les catalyseurs eux-memes sont de nouveaux materiaux.
EP19800900497 1979-03-28 1980-10-08 Procedes catalytiques et catalyseurs Withdrawn EP0025787A1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
GB7910823 1979-03-28
GB7910823 1979-03-28
GB7924181 1979-07-11
GB7924181 1979-07-11
GB7940699 1979-11-24
GB7940699 1979-11-24
GB7941221 1979-11-29
GB7941221 1979-11-29
GB8006899 1980-02-29
GB8006900 1980-02-29
GB8006899 1980-02-29
GB8006900 1980-02-29

Publications (1)

Publication Number Publication Date
EP0025787A1 true EP0025787A1 (fr) 1981-04-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800900497 Withdrawn EP0025787A1 (fr) 1979-03-28 1980-10-08 Procedes catalytiques et catalyseurs

Country Status (2)

Country Link
EP (1) EP0025787A1 (fr)
WO (1) WO1980002023A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1216273A (fr) * 1982-10-18 1987-01-06 Ronald W. Diesen Catalyse du dichloro-ethylene
WO1993017787A1 (fr) * 1992-03-06 1993-09-16 Isp Investments Inc. Catalyseur et procede de production de pyrrolidones d'alkyle
US5262575A (en) * 1992-08-04 1993-11-16 The Dow Chemical Company Production of allylic chlorides
US20050061338A1 (en) * 2003-06-18 2005-03-24 Olegario Raquel M. Reduction of polycyclic aromatic hydrocarbons in tobacco smoke using palladium salts
TWI633206B (zh) 2013-07-31 2018-08-21 卡利拉股份有限公司 使用金屬氧化物之電化學氫氧化物系統及方法
EP3368502B1 (fr) 2015-10-28 2020-09-02 Calera Corporation Systèmes et procédés électrochimiques, d'halogénation, et d'oxyhalogénation
WO2019060345A1 (fr) * 2017-09-19 2019-03-28 Calera Corporation Systèmes et procédés utilisant un halogénure de lanthanide

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Publication number Priority date Publication date Assignee Title
NL292101A (fr) * 1962-04-30
FR1390470A (fr) * 1963-02-13 1965-02-26 Pittsburgh Plate Glass Co Perfectionnements au procédé d'oxychloration des hydrocarbures aliphatiques et de leurs dérivés incomplètement chlorés
US3365498A (en) * 1963-04-15 1968-01-23 Union Carbide Corp Redox catalytic oxidation of olefins to aldehydes and ketones
US3403108A (en) * 1964-06-24 1968-09-24 Pullman Inc Aluminosilicate catalyst containing a group viii metal compound and a metal halide
US3497462A (en) * 1967-09-20 1970-02-24 Union Carbide Corp Copper (i) zeolites
US3987118A (en) * 1971-03-08 1976-10-19 Stauffer Chemical Company Novel process for the oxychlorination of ethane
BE791183A (fr) * 1971-11-12 1973-05-10 Monsanto Co Catalyseurs ameliores de chloration par voie oxydante
US4034065A (en) * 1975-09-26 1977-07-05 Union Carbide Corporation Preparation of CU+ zeolites

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