EP1546032A1 - Catalyseur pour l'oxydation catalytique de chlorure d'hydrogene - Google Patents

Catalyseur pour l'oxydation catalytique de chlorure d'hydrogene

Info

Publication number
EP1546032A1
EP1546032A1 EP03748085A EP03748085A EP1546032A1 EP 1546032 A1 EP1546032 A1 EP 1546032A1 EP 03748085 A EP03748085 A EP 03748085A EP 03748085 A EP03748085 A EP 03748085A EP 1546032 A1 EP1546032 A1 EP 1546032A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrogen chloride
weight
gold
metals
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Withdrawn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
EP03748085A
Other languages
German (de)
English (en)
Inventor
Christian Kuhrs
Christian Walsdorff
Martin Fiene
Eckhard Ströfer
Klaus Harth
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
Publication of EP1546032A1 publication Critical patent/EP1546032A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/04—Preparation of chlorine from hydrogen chloride

Definitions

  • the invention relates to a catalyst for the catalytic oxidation of hydrogen chloride with oxygen to chlorine and a method for the catalytic oxidation of hydrogen chloride.
  • EP-A 0 743 277 discloses a process for the production of chlorine by catalytic oxidation of hydrogen chloride, in which a supported catalyst containing ruthenium is used. Ruthenium is applied to the support in the form of ruthenium chloride, ruthenium oxychlorides, chlororuthenate complexes, ruthenium hydroxide, ruthenium amine complexes or in the form of further ruthenium complexes.
  • the catalyst can contain, as further metals, palladium, copper, chromium, vanadium, manganese, alkali, alkaline earth and rare earth metals.
  • rutherdum (DI) chloride on silicon dioxide is used as a catalyst in a process of catalytic hydrogen chloride oxidation.
  • a disadvantage of the catalysts containing ruthenium is the high volatility of the ruthenium compounds. Furthermore, it is desirable to carry out the exothermic hydrogen chloride oxidation because of the then more favorable equilibrium position at lower temperatures. This requires catalysts with high low-temperature activity.
  • the object of the present invention is to provide an improved process for the catalytic oxidation of hydrogen chloride.
  • a catalyst for the catalytic oxidation of hydrogen chloride comprising on a support a) 0.001 to 30% by weight of gold, b) 0 to 3% by weight of one or more alkaline earth metals, c) 0 to 3% by weight. % of one or more alkali metals, d) 0 to 10% by weight of one or more rare earth metals, e) 0 to 10% by weight of one or more further metals, selected from the group consisting of ruthenium, palladium, platinum, osmium, Iridium, silver, copper and rhenium, each based on the total weight of the catalyst.
  • the gold-containing supported catalysts according to the invention have a significantly higher activity than the ruthenium-containing catalysts of the prior art, in particular at temperatures of ⁇ 250 ° C. in the oxidation of hydrogen chloride.
  • the catalysts of the invention contain gold on a support.
  • Suitable carriers are silicon dioxide, graphite, titanium dioxide, preferably with a rutile or anatase structure, zirconium dioxide, aluminum oxide or mixtures thereof, titanium dioxide, zirconium dioxide, aluminum oxide or mixtures thereof are preferred.
  • the catalysts according to the invention can be obtained by applying gold in the form of the aqueous solution of a soluble gold compound, then drying or drying and calcining.
  • Gold is preferably applied to the support as an aqueous solution of AuCl 3 or HAuCl 4 .
  • the catalysts according to the invention contain 0.001 to 30% by weight, preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight of gold.
  • the catalysts of the invention can additionally contain compounds of other noble metals selected from ruthenium, palladium, platinum, osmium, iridium, silver, copper or rhenium.
  • the catalysts of the invention can also be doped with other metals.
  • Suitable promoters for doping are alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, particularly preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and calcium, particularly preferably magnesium, rare earth metals such as Scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yttrium, lanthanum and cerium, particularly preferably lanthanum and cerium, or mixtures thereof.
  • alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, particularly preferably potassium, alkaline earth metals such as magnesium, calcium, strontium and barium, preferably magnesium and calcium, particularly preferably magnesium, rare earth metals such as Scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium,
  • the catalysts of the invention are obtained by impregnating the support material with aqueous solutions of salts of the metals.
  • the metals other than gold are usually applied to the support as aqueous solutions of their chlorides, oxychlorides or oxides.
  • the catalyst can be shaped after or preferably before the support material is impregnated.
  • the specific surface area of the carrier substance before the metal salt deposit is preferably in the range from 20 to 400 m 2 / g, particularly preferably from 75 to 250 m / g.
  • the pore volume is usually in the range of 0.15 to 0.75 cmVg.
  • the moldings can then be dried at temperatures of 100 to 400 ° C., preferably 100 to 300 ° C., for example under a nitrogen, argon or air atmosphere and optionally calcined.
  • the moldings are preferably first dried at 100 to 150 ° C. and then calcined at 200 to 400 ° C. If necessary, the catalyst is then reduced.
  • the present invention also relates to a process for the catalytic oxidation of hydrogen chloride with oxygen to chlorine on the catalyst according to the invention.
  • a hydrogen chloride stream and an oxygen-containing stream are fed into an oxidation zone and hydrogen chloride is partially oxidized to chlorine in the presence of a catalyst, a product gas stream being obtained which contains chlorine, unreacted oxygen, unreacted hydrogen chloride and water vapor.
  • Usual reaction temperatures are between 150 and 500 ° C, usual reaction pressures are between 1 and 25 bar. Since it is an equilibrium reaction, it is advisable to work at the lowest possible temperatures at which the catalyst still has sufficient activity.
  • the reaction temperature is preferably ⁇ 350.degree. C., particularly preferably from 200 to 250.degree.
  • oxygen in excess of stoichiometric amounts. For example, a two to four-fold excess of oxygen is common. Since there is no fear of loss of selectivity, it can be economically advantageous to work at relatively high pressures and, accordingly, with longer residence times compared to normal pressure.
  • Common reaction apparatuses in which the catalytic hydrogen chloride oxidation according to the invention is carried out are fixed bed or fluidized bed reactors.
  • the hydrogen chloride oxidation can be carried out in one or more stages.
  • the catalytic hydrogen chloride oxidation can be adiabatic or preferably isothermal or approximately isothermal, discontinuous, preferably continuously as a fluidized bed or fixed bed process, preferably as a fixed bed process, particularly preferably in tube bundle reactors on heterogeneous catalysts at reactor temperatures of 150 to 500 ° C., preferably 150 to 250 ° C. particularly preferably 200 to 250 ° C. and a pressure of 1 to 25 bar, preferably 1.2 to 20 bar, particularly preferably 1.5 to 17 bar and in particular 2.0 to 15 bar.
  • a preferred embodiment consists in using a structured catalyst bed in which the catalyst activity increases in the direction of flow. Such structuring of the catalyst bed can be carried out by impregnating the catalyst support with an active composition or by diluting the catalyst differently with an inert material.
  • rings, cylinders or balls made of titanium dioxide, zirconium dioxide or mixtures thereof, aluminum oxide, steatite, ceramic, glass, graphite or stainless steel can be used as the inert material.
  • the inert material should preferably have similar external dimensions.
  • the conversion of hydrogen chloride in a single pass can be limited to 15 to 90%, preferably 40 to 85%. Unreacted hydrogen chloride can be partially or completely recycled into the catalytic hydrogen chloride oxidation after the separation.
  • the volume ratio of hydrogen chloride to oxygen at the reactor inlet is generally between 1: 1 and 20: 1, preferably between 1.5: 1 and 8: 1, particularly preferably between 1.5: 1 and 5: 1.
  • the chlorine formed can subsequently be separated off in the customary manner.
  • the removal usually comprises several stages, namely the removal and, if appropriate, recycling of unreacted hydrogen chloride from the product gas stream of the catalytic hydrogen chloride oxidation, the drying of the residual gas stream obtained essentially consisting of chlorine and oxygen and the removal of chlorine from the dried stream.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur pour l'oxydation catalytique de chlorure d'hydrogène, ce catalyseur contenant sur un support a) 0,001 à 30 % en poids d'or, b) 0 à 3 % en poids d'un ou de plusieurs métaux alcalino-terreux, c) 0 à 3 % en poids d'un ou de plusieurs métaux alcalins, d) 0 à 10 % en poids d'un ou de plusieurs métaux des terres rares, e) 0 à 10 % en poids d'un ou de plusieurs autres métaux, choisis dans le groupe comprenant le ruthénium, le palladium, le platine, l'osmium, l'iridium, l'argent, le cuivre et le rhénium, chacun de ces pourcentages se rapportant au poids total du catalyseur.
EP03748085A 2002-09-26 2003-09-25 Catalyseur pour l'oxydation catalytique de chlorure d'hydrogene Withdrawn EP1546032A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10244996 2002-09-26
DE10244996A DE10244996A1 (de) 2002-09-26 2002-09-26 Katalysator für die katalytische Chlorwasserstoff-Oxidation
PCT/EP2003/010657 WO2004031074A1 (fr) 2002-09-26 2003-09-25 Catalyseur pour l'oxydation catalytique de chlorure d'hydrogene

Publications (1)

Publication Number Publication Date
EP1546032A1 true EP1546032A1 (fr) 2005-06-29

Family

ID=31969626

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03748085A Withdrawn EP1546032A1 (fr) 2002-09-26 2003-09-25 Catalyseur pour l'oxydation catalytique de chlorure d'hydrogene

Country Status (9)

Country Link
US (1) US20060140849A1 (fr)
EP (1) EP1546032A1 (fr)
JP (1) JP2006500216A (fr)
KR (1) KR100976437B1 (fr)
CN (1) CN1314581C (fr)
AU (1) AU2003267407A1 (fr)
DE (1) DE10244996A1 (fr)
MX (1) MXPA05003170A (fr)
WO (1) WO2004031074A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090274612A1 (en) * 2005-04-08 2009-11-05 Sumitomo Chemical Company, Limited. Process for producing supported ruthenium oxide and process for producing chlorine
DE102006024546A1 (de) * 2006-05-23 2007-11-29 Bayer Materialscience Ag Verfahren zur Herstellung von Chlor durch Gasphasenoxidation
DE102007020143A1 (de) * 2007-04-26 2008-10-30 Bayer Materialscience Ag Verfahren zur Erhöhung der Langzeitstabilität und Aktivität von Ruthenium-Katalysatoren
JP5169047B2 (ja) * 2007-07-23 2013-03-27 住友化学株式会社 塩素の製造方法
DE102008052012A1 (de) * 2008-10-17 2010-04-22 Bayer Materialscience Ag Katalysator und Verfahren zur Herstellung von Chlor durch Gasphasenoxidation
KR20110119736A (ko) * 2009-02-26 2011-11-02 바스프 에스이 염화수소의 산화를 위한, 루테늄 및 은 및/또는 칼슘을 포함하는 촉매
WO2011015503A1 (fr) 2009-08-05 2011-02-10 Basf Se Procédé de production de chlore par oxydation en phase gazeuse de chlorure d'hydrogène dans un réacteur à lit fluidisé
CN102000583B (zh) * 2010-11-18 2012-08-15 烟台万华聚氨酯股份有限公司 一种氯化氢氧化制氯气的催化剂及其制备方法
CN104549360B (zh) * 2014-04-01 2017-05-24 上海方纶新材料科技有限公司 一种用于催化氧化氯化氢生产氯气的催化剂
CN105642318B (zh) * 2014-11-11 2018-08-21 上海氯碱化工股份有限公司 氯化氢催化氧化制氯气的催化剂制法及应用
CN105126930B (zh) * 2015-08-28 2017-12-12 烟台大学 一种催化剂载体的制备方法及其在氯化氢催化氧化中的应用
CN106902848B (zh) * 2017-02-09 2019-06-28 西安近代化学研究所 一种氯化氢转化催化剂

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6404460A (fr) * 1964-04-23 1965-10-25
US3667913A (en) * 1967-08-15 1972-06-06 Bayer Ag Chromium-dioxide-catalyst
CA920775A (en) * 1968-05-13 1973-02-13 Vadekar Mohan Oxidation of hydrogen chloride using molecular sieve catalysts
US4774070A (en) * 1986-02-19 1988-09-27 Mitsui Toatsu Chemicals, Incorporated Production process of chlorine
DE4241696A1 (de) * 1992-12-10 1994-06-16 Wacker Chemie Gmbh Verfahren zur Entfernung von wasserstoffhaltigen Silanen aus Silanen
SG67942A1 (en) * 1995-05-18 1999-10-19 Sumitomo Chem Ind Process for producing chlorine
DE19533484A1 (de) * 1995-09-12 1997-03-13 Basf Ag Monomodale und polymodale Katalysatorträger und Katalysatoren mit engen Porengrößenverteilungen und deren Herstellverfahren
WO2000043313A1 (fr) * 1999-01-22 2000-07-27 Sumitomo Chemical Company, Limited Procede de fabrication du chlore
BR9917285A (pt) * 1999-03-10 2001-12-26 Du Pont Processo de decomposição de hidroperóxidos
RU2232636C2 (ru) * 1999-04-08 2004-07-20 Дау Глобал Текнолоджиз Инк. Способ получения катализатора, содержащего золото и титан
US6534438B1 (en) * 2000-07-26 2003-03-18 Bp Chemicals Limited Catalyst composition
DE10309799A1 (de) * 2003-03-05 2004-09-23 Sgl Acotec Gmbh Verfahren und Vorrichtung zur Herstellung von Chlorwasserstoff

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004031074A1 *

Also Published As

Publication number Publication date
CN1314581C (zh) 2007-05-09
KR20050059204A (ko) 2005-06-17
CN1684903A (zh) 2005-10-19
DE10244996A1 (de) 2004-04-01
WO2004031074A1 (fr) 2004-04-15
KR100976437B1 (ko) 2010-08-18
MXPA05003170A (es) 2005-06-08
JP2006500216A (ja) 2006-01-05
US20060140849A1 (en) 2006-06-29
AU2003267407A1 (en) 2004-04-23

Similar Documents

Publication Publication Date Title
EP2257372B1 (fr) Procédé de régénération d'un catalyseur contenant du ruthénium ou des composés de ruthénium contaminés par du soufre sous forme de composés de soufre
DE102005040286A1 (de) Mechanisch stabiler Katalysator auf Basis von alpha-Aluminiumoxid
WO2010076262A1 (fr) Catalyseur pour l'oxydation de chlorure d'hydrogène contenant du ruthénium et du nickel
EP1529033A1 (fr) Procede integre de production d'isocyanates
WO2006089877A1 (fr) Procede pour produire du chlore
EP2027062A2 (fr) Procédé de production de chlore par oxydation en phase gazeuse
EP2391740B1 (fr) Procédé de récupération de ruthénium dans des catalyseurs usagés contenant de l'oxyde de ruthénium
EP2178636A1 (fr) Catalyseur thermiquement stable pour l'oxydation de chlorure d'hydrogene en phase gazeuse
EP2608879B1 (fr) Catalyseur et procédé pour produire du chlore par une oxydation catalytique en phase gazeuse de chlorure d'hydrogène
EP2157198A1 (fr) Procédé de production de ruthénium métallique ou de composés de ruthénium à partir de matières solides contenant du ruthénium
EP2142296A1 (fr) Catalyseurs au ruthénium pour l'oxydation catalytique en phase gazeuse du chlorure d'hydrogène avec de l'oxygène (procédé deacon)
WO2004026761A1 (fr) Procede a lit fixe pour produire du chlore par oxydation catalytique en phase gazeuse de chlorure d'hydrogene
WO2004031074A1 (fr) Catalyseur pour l'oxydation catalytique de chlorure d'hydrogene
EP2401072B1 (fr) Catalyseur pour l'oxydation de chlorure d'hydrogène contenant du ruthénium et de l'argent et/ou du calcium
EP3403723A1 (fr) Procédé de régénération d'un catalyseur contenant du ruthénium contaminé ou des composés de ruthénium
EP2177268A1 (fr) Catalyseur et procédé de fabrication de chlore par oxydation en phase gazeuse
EP2608880B1 (fr) Procédé pour produire du chlore par une oxydation catalytique en phase gazeuse de chlorure d'hydrogène
EP2440490A1 (fr) Procédé d'oxydation de gaz chlorhydrique sur un catalyseur à faible rugosité superficielle
DE102007033113A1 (de) Temperaturstabiler Katalysator für die Chlorwasserstoffgasphasenoxidation
EP2054340A2 (fr) Procédé de production de chlore par oxydation en phase gazeuse
WO2007125004A1 (fr) Procédé de fabrication de catalyseurs pour l'oxydation catalytique de chlorure d'hydrogène
EP1506133B1 (fr) Procede de fabrication de chlore a partir de gaz chlorhydrique
DE102007033114A1 (de) Verfahren zur Herstellung von Chlor durch Gasphasenoxidation von Chlorwasserstoff
DE102011005897A1 (de) Verfahren zur Bereitstellung von Chlor für chemische Umsetzungen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050426

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: HARTH, KLAUS

Inventor name: STROEFER, ECKHARD

Inventor name: FIENE, MARTIN

Inventor name: WALSDORFF, CHRISTIAN

Inventor name: KUHRS, CHRISTIAN

17Q First examination report despatched

Effective date: 20070316

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20070727