WO2010137504A1 - Procédé d'activation d'un catalyseur pour la production de chlore et procédé de production de chlore - Google Patents

Procédé d'activation d'un catalyseur pour la production de chlore et procédé de production de chlore Download PDF

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Publication number
WO2010137504A1
WO2010137504A1 PCT/JP2010/058434 JP2010058434W WO2010137504A1 WO 2010137504 A1 WO2010137504 A1 WO 2010137504A1 JP 2010058434 W JP2010058434 W JP 2010058434W WO 2010137504 A1 WO2010137504 A1 WO 2010137504A1
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Prior art keywords
catalyst
chlorine
reaction
gas
oxygen
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PCT/JP2010/058434
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English (en)
Japanese (ja)
Inventor
洋平 内田
航平 関
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住友化学株式会社
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Priority to CN2010800198309A priority Critical patent/CN102413927A/zh
Publication of WO2010137504A1 publication Critical patent/WO2010137504A1/fr

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    • 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
    • B01J23/90—Regeneration or reactivation
    • B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble 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
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for activating a catalyst for chlorine production with reduced activity, and a method for producing chlorine using a catalyst for chlorine production activated by this method.
  • Chlorine is useful as a raw material for vinyl chloride, phosgene, and the like, and is conventionally produced by a reaction in which hydrogen chloride is oxidized with oxygen in the presence of a catalyst for producing chlorine.
  • the catalyst for chlorine production used in the reaction described above may have a reduced catalytic activity when subjected to a heat load, for example, under steady or unsteady conditions.
  • a method for activating a chlorine production catalyst (hereinafter also referred to as “degraded catalyst”) having a decreased activity
  • a method in which the degraded catalyst is brought into contact with a gas substantially consisting of only oxygen and / or inert gas Japanese Patent Laid-Open No. 2007-7521 (Patent Document 1)] and a method of contacting a deteriorated catalyst with a reducing gas containing carbon monoxide and / or hydrogen [Japanese Patent Laid-Open No. 2009-22917 (Patent Document 2)]
  • Patent Document 1 Japanese Patent Laid-Open No. 2007-7521
  • Patent Document 2 Japanese Patent Laid-Open No. 2009-22917
  • the catalyst for chlorine production activated by the above-described conventional activation method sometimes fails to obtain sufficiently satisfactory catalytic activity.
  • the subject of this invention is activating the catalyst for chlorine production in which activity fell, and the activation method of the catalyst for chlorine production which can recover
  • the inventors of the present invention have intensively studied to solve the above problems. As a result, it has been found that the catalyst activity can be effectively recovered by a simple method in which the catalyst having decreased activity is brought into contact with the acidic liquid, and the present invention has been completed.
  • the present invention has the following configuration.
  • a method for activating a catalyst for producing chlorine used in a reaction for oxidizing hydrogen chloride with oxygen comprising activating a catalyst for producing chlorine having reduced activity in contact with an acidic liquid. .
  • a method for producing chlorine by oxidizing hydrogen chloride with oxygen in the presence of a catalyst wherein the catalyst is activated by the activation method according to any one of (1) to (4) above Method for producing chlorine using
  • the present invention it is possible to effectively activate a catalyst for chlorine production whose activity has been reduced and to recover its catalytic activity satisfactorily. This makes it possible to reuse the catalyst for producing chlorine whose activity has been lowered for the reaction of oxidizing hydrogen chloride with oxygen, so that chlorine can be advantageously produced in that the catalyst cost can be reduced.
  • the catalyst to be activated is produced when chlorine is produced by a reaction of oxidizing hydrogen chloride with oxygen (hereinafter also referred to simply as “oxidation reaction”).
  • Any catalyst may be used as long as it is a catalyst used (that is, a catalyst for producing chlorine), and examples thereof include a copper catalyst, a chromium catalyst, and a ruthenium catalyst.
  • the copper catalyst include a catalyst obtained by adding various compounds as a third component to copper chloride and potassium chloride, generally referred to as a Deacon catalyst.
  • the chromium catalyst contains chromium oxide as disclosed in JP-A-61-136902, JP-A-61-275104, JP-A-62-1113701, and JP-A-62-270405.
  • a catalyst is preferred.
  • the ruthenium catalyst as disclosed in JP-A-9-67103, JP-A-10-338502, JP-A-2000-281314, JP-A-2002-79093, JP-A-2002-292279, an oxidation catalyst is used.
  • Preferred is a catalyst containing ruthenium.
  • the catalyst for producing chlorine to be activated is preferably a ruthenium catalyst, particularly a catalyst containing ruthenium oxide, among the above-mentioned catalysts.
  • the catalyst containing ruthenium oxide for example, may be substantially composed of only ruthenium oxide, or ruthenium oxide is supported on a support such as alumina, titania, silica, zirconia, niobium oxide, activated carbon or the like. It may be a supported ruthenium oxide or a complex oxide composed of ruthenium oxide and other oxides such as alumina, titania, silica, zirconia, niobium oxide and the like.
  • the catalyst to be activated is a catalyst for chlorine production (deteriorated catalyst) with reduced activity.
  • a catalyst for chlorine production deteriorated catalyst
  • the catalytic activity of the catalyst for producing chlorine used in the reaction of oxidizing hydrogen chloride with oxygen (oxidation reaction) is reduced, but usually the reaction time of the oxidation reaction (that is, the catalyst use time)
  • the catalyst activity gradually decreases with the passage of time. In addition to this, for example, i) it becomes difficult to control the reaction temperature due to equipment failure, etc., and the heat load when the catalyst is exposed to high temperature for a long time, ii) oxygen due to equipment failure, etc.
  • Catalyst poisoning when the supply is stopped and the catalyst is in contact with hydrogen chloride for a long time in the absence of oxygen iii)
  • the source gas contains sulfur (specifically, for example, oxidation
  • the gas generated in the reaction is washed with concentrated sulfuric acid and dehydrated, and then chlorine is separated. The remaining gas is recovered and reused as a raw material gas for the oxidation reaction.
  • a catalyst for producing chlorine (deteriorated catalyst) having reduced activity is brought into contact with an acidic solution.
  • an acidic solution By performing the contact treatment in contact with the acidic liquid in this way, for example, a catalyst for chlorine production whose activity has been lowered due to heat load or catalyst poisoning can be effectively activated, and the catalytic activity can be recovered well.
  • the recovery of the catalyst activity is caused by the removal of the inert component soluble in the acid on the catalyst surface by the contact treatment with the acidic solution.
  • a supported catalyst having an alumina carrier is subjected to a heat load for a long time, and thus alumina partially scatters and covers the active sites. It is inferred that the alumina covering the dots is well removed.
  • the acidic liquid may be, for example, an aqueous solution in which an inorganic acid such as hydrogen chloride, sulfuric acid, or nitric acid is dissolved, or an aqueous solution in which an organic acid such as acetic acid, propionic acid, butyric acid, or valeric acid is dissolved.
  • an acid that is in a liquid state under the temperature and pressure at the time of contact with the deteriorated catalyst may be used alone as the acidic liquid.
  • the acidic liquid is preferably an aqueous solution in which an inorganic acid is dissolved from the viewpoint of washing efficiency when washing with water later.
  • the pH of the acidic solution is preferably 5 or less, more preferably 3 or less.
  • the pH of the acidic liquid exceeds 5 and approaches the neutral region, the activation effect becomes insufficient, and the catalytic activity may not be sufficiently recovered.
  • the supply rate of the acidic liquid is usually about 0.01 to 100 h ⁇ 1 in terms of the volume supply rate of the acidic liquid per volume of the catalyst (that is, LHSV), and the contact treatment time is Usually, it is about 0.5 to 100 hours.
  • the acidic liquid can be circulated.
  • the amount of the acidic liquid used is usually about 1 to 100 parts by weight with respect to 1 part by weight of the catalyst, and the contact treatment time is usually about 0.5 to 120 hours.
  • the contact treatment temperature is usually 0 to 100 ° C., preferably 10 to 90 ° C., and the number of contact treatments is usually about 1 to 10 times.
  • the amount of water used for rinsing is preferably at least 1 times the amount of the previously contacted acidic solution, more preferably at least 3 times the weight.
  • the water used for washing is preferably water having a high purity such as ultrapure water.
  • drying may be performed after the deteriorated catalyst is brought into contact with the acidic solution or after washing.
  • the drying method is not particularly limited.
  • the activated catalyst for chlorine production exhibits excellent catalytic activity in the reaction of oxidizing hydrogen chloride with oxygen, and can be reused in such oxidation reaction. Thereby, catalyst cost can be reduced and chlorine can be produced advantageously in terms of cost.
  • the method for producing chlorine of the present invention is a method of oxidizing hydrogen chloride with oxygen in the presence of the catalyst activated by the activation method of the present invention described above.
  • the reaction of oxidizing hydrogen chloride with oxygen using an activated catalyst is usually carried out in a fixed bed reactor filled with the catalyst or a fluidized bed reactor in which the catalyst is fluidized. Gas) and oxygen (gas containing oxygen) while supplying a raw material gas under a gas phase condition.
  • gas gas containing oxygen
  • the gas containing hydrogen chloride is not particularly limited.
  • a gas generated by a reaction between hydrogen and chlorine a gas generated by heating hydrochloric acid, a pyrolysis reaction or a combustion reaction of a chlorine compound, or phosgene.
  • any gas containing hydrogen chloride such as carbonylation reaction of organic compounds, chlorination reaction of organic compounds with chlorine, various by-product gases generated by the production of chlorofluoroalkanes, and combustion exhaust gas generated from incinerators. be able to.
  • Specific examples of the various reactions described above for generating the gas containing hydrogen chloride include, for example, a reaction in which vinyl chloride is generated from 1,2-dichloroethane, a tetrafluoroethylene from chlorodifluoromethane, as a thermal decomposition reaction of a chlorine compound.
  • Examples of the carbonylation reaction of organic compounds with phosgene include reactions that produce isocyanates from amines, reactions that produce carbonates from hydroxy compounds, and chlorination reactions of organic compounds with chlorine.
  • a reaction in which allyl chloride is produced from propylene a reaction in which ethyl chloride is produced from ethane, and a reaction in which chlorobenzene is produced from benzene.
  • chlorofluoroalkane examples include dichlorodifluoromethane and trichloromonofluoromethane by the reaction of carbon tetrachloride and hydrogen fluoride, dichlorodifluoromethane and trichloro by the reaction of methane, chlorine and hydrogen fluoride.
  • production of monofluoromethane examples include dichlorodifluoromethane and trichloromonofluoromethane by the reaction of carbon tetrachloride and hydrogen fluoride, dichlorodifluoromethane and trichloro by the reaction of methane, chlorine and hydrogen fluoride.
  • production of monofluoromethane examples include dichlorodifluoromethane and trichloromonofluoromethane by the reaction of carbon tetrachloride and hydrogen fluoride.
  • gas containing oxygen air or pure oxygen may be used. Pure oxygen can be obtained by ordinary industrial methods such as air pressure swing method or deep cold separation.
  • the ratio of hydrogen chloride (a gas containing hydrogen chloride) to oxygen (a gas containing oxygen) is theoretically set to 1 oxygen per mole of hydrogen chloride in order to completely oxidize hydrogen chloride to chlorine. / 4 mol is required, but usually 0.1 to 10 times the theoretical amount of oxygen is used.
  • the supply rate of the gas containing hydrogen chloride is usually about 10 to 20000 h ⁇ 1 in terms of the volume supply rate of the gas per volume of the catalyst layer (converted to 0 ° C. and 1 atm), that is, GHSV.
  • the supply rate of the gas containing oxygen is usually about 10 to 20000 h ⁇ 1 in terms of the volume supply rate of the gas per volume of the catalyst layer (0 ° C., converted to 1 atm), that is, GHSV.
  • reaction conditions and the like in the oxidation reaction are not particularly limited, but the reaction temperature is usually 100 to 500 ° C., preferably 200 to 400 ° C., and the reaction pressure is usually about 0.1 to 5 MPa.
  • the activation treatment for activating the deteriorated catalyst by the activation method of the present invention described above and the oxidation reaction.
  • the oxidation reaction is carried out while supplying a raw material gas consisting of hydrogen chloride and oxygen into a reactor filled with the catalyst, and the catalyst is made to the extent that it is difficult to continue the operation.
  • the activation treatment and the oxidation reaction may be repeated as necessary.
  • the oxidation reaction is performed in a fluidized bed format, while performing the oxidation reaction, a part of the catalyst is continuously or intermittently extracted from the reactor, and the activation treatment is performed in another container. Then, the catalyst is returned to the reactor, and the catalyst is circulated between the reactor and the container for the activation treatment, so that the catalyst is alternately supplied to the activation treatment and the oxidation reaction.
  • the gas supply rate (mL / min) is shown as a converted value at 0 ° C. and 1 atm unless otherwise specified.
  • This kneaded product was extruded into a cylindrical shape having a diameter of 3.0 mm ⁇ , dried, and then crushed to a length of about 4 to 6 mm.
  • the obtained molded body was fired in air at 800 ° C. for 3 hours to obtain a carrier made of a mixture of titanium oxide and ⁇ -alumina.
  • this carrier is impregnated with an aqueous solution of ruthenium chloride in an amount to give a predetermined loading rate, dried, and then fired in air at 250 ° C. for 2 hours, so that the ruthenium oxide has a loading rate of 2% by weight.
  • a blue-gray-supported ruthenium oxide catalyst (new catalyst) supported on a carrier was obtained.
  • the obtained supported ruthenium oxide catalyst (new catalyst) is charged into a reactor, and an oxidation reaction is performed at 280 to 390 ° C. for a long period of time while supplying a raw material gas containing hydrogen chloride and oxygen to the reactor.
  • a deteriorated catalyst was prepared.
  • Example 1 5 g of the deteriorated catalyst obtained in Reference Example 1 and 45 g of a 36% hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a container, mixed, and allowed to stand at 25 ° C. for 24 hours to be brought into contact with each other. Thereafter, the supernatant liquid is removed by decantation, and the obtained solid is washed three times with 150 g of ion-exchanged water and then dried at 60 ° C. until a constant weight (2 hours or more). A catalyst activated by the activation method (activation catalyst) was obtained. The pH of the 36% aqueous hydrochloric acid solution used here was -2.0.
  • ⁇ Catalyst activity evaluation> 1 g of the obtained catalyst was filled into a nickel reaction tube having an inner diameter of 13 mm, and 12 g of ⁇ -alumina sphere (“SSA995” manufactured by Nikkato Co., Ltd.) was filled as a preheating layer on the gas inlet side of the catalyst layer. While supplying nitrogen gas into the reaction tube at a rate of 80 mL / min, the reaction tube is immersed in a salt bath using a molten salt (potassium nitrate / sodium nitrite 1/1 (weight ratio)) as a heat medium to form a catalyst layer. The temperature of was 281 to 282 ° C.
  • hydrogen chloride gas and oxygen gas are supplied at a rate of 80 mL / min (0.21 mol / h) for hydrogen chloride gas and 40 mL / min (0.11 mol / h) for oxygen gas.
  • the oxidation reaction was carried out at a catalyst layer temperature of 281 to 282 ° C.
  • the gas at the outlet of the reaction tube was sampled by flowing it through a 30 wt% aqueous potassium iodide solution for 20 minutes, and the amount of chlorine produced was measured by an iodine titration method.
  • the production rate (mol / h) of was determined. From the chlorine production rate and the hydrogen chloride supply rate (mol / h), the conversion rate (%) of hydrogen chloride was calculated by the following equation.
  • Hydrogen chloride conversion (%) [Chlorine production rate (mol / h) ⁇ 2 ⁇ hydrogen chloride supply rate (mol / h)] ⁇ 100 (Example 2)
  • 36% hydrochloric acid aqueous solution used in Example 1 45 g of 20% hydrochloric acid aqueous solution (prepared by diluting 25 g of 36% hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) with 20 g of ion-exchanged water) was used. Except for this, a catalyst (activated catalyst) activated by the activation method of the present invention was obtained in the same manner as in Example 1. The pH of the 20% aqueous hydrochloric acid solution used here was measured to be ⁇ 1.7.
  • Example 3 In place of the 36% hydrochloric acid aqueous solution used in Example 1, prepared by diluting 3.125 g of a 2.5% aqueous hydrochloric acid solution (36% hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) with 41.875 g of ion-exchanged water. Except for using 45 g, a catalyst (activated catalyst) activated by the activation method of the present invention was obtained in the same manner as in Example 1. The pH of the 2.5% aqueous hydrochloric acid solution used here was 0.2.
  • carbon monoxide gas and nitrogen gas were supplied at a rate of 3.2 mL / min (0.009 mol / h) for carbon monoxide gas and 28.8 mL / min for nitrogen gas ( 0.08 mol / h) was supplied and kept at 350 ° C. for 2 hours to perform contact treatment with a reducing gas.
  • the contact treatment with the oxidizing gas was performed following the contact treatment with the reducing gas. That is, after the supply of carbon monoxide gas is stopped, oxygen gas and nitrogen gas are supplied at a rate of 40 mL / min (0.009 mol / h) for oxygen gas and 160 mL / min (0.43 mol / h) for nitrogen gas.
  • the catalyst was subjected to contact treatment with an oxidizing gas by maintaining at 350 ° C. for 2 hours, and a catalyst subjected to contact treatment with an oxidizing gas after contact treatment with a reducing gas was obtained.
  • the catalytic activity when the reaction of oxidizing hydrogen chloride with oxygen was performed following the contact treatment with the oxidizing gas was evaluated. That is, the supply of oxygen gas was stopped, the supply rate of nitrogen gas was set to 80 mL / min (0.21 mol / h), and then the temperature of the catalyst layer was set to 281 to 282 ° C. Subsequently, after the supply of nitrogen gas was stopped in the same manner as the catalyst activity evaluation in Example 1, hydrogen chloride gas and oxygen gas were supplied to perform an oxidation reaction, and the amount of chlorine produced was measured. The hydrogen conversion (%) was calculated. The results are shown in Table 1.

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

Abstract

La présente invention concerne un procédé d'activation d'un catalyseur pour la production de chlore qui est utilisé dans une réaction d'oxydation de chlorure d'hydrogène avec de l'oxygène, comprenant une étape dans laquelle on met en contact un catalyseur pour la production de chlore ayant une activité réduite, avec un liquide acide. Cette invention porte également sur un procédé de production de chlore dans lequel du chlore est produit par oxydation de chlorure d'hydrogène avec de l'oxygène en présence d'un catalyseur pour la production de chlore, qui est activé au moyen du procédé décrit précédemment. Le liquide acide utilisé dans le procédé a de préférence un pH ne dépassant pas 5 et se présente de préférence sous forme d'une solution aqueuse dans laquelle un acide inorganique est dissous. De plus, le catalyseur pour la production de chlore contient de l'oxyde de ruthénium
PCT/JP2010/058434 2009-05-29 2010-05-19 Procédé d'activation d'un catalyseur pour la production de chlore et procédé de production de chlore WO2010137504A1 (fr)

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CN2010800198309A CN102413927A (zh) 2009-05-29 2010-05-19 氯制造用催化剂的活化方法和氯的制造方法

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JP2009-130989 2009-05-29
JP2009130989A JP2010274216A (ja) 2009-05-29 2009-05-29 塩素製造用触媒の賦活方法および塩素の製造方法

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CN111495359A (zh) * 2020-04-01 2020-08-07 浙江师范大学 一种用于氯化氢氧化制氯气的成型催化剂及其制备方法

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JPS506592A (fr) * 1973-05-22 1975-01-23
JPH02144149A (ja) * 1988-11-22 1990-06-01 Ube Ind Ltd 白金族金属担持触媒の再活性化方法
JPH03221145A (ja) * 1989-11-22 1991-09-30 Mitsui Toatsu Chem Inc 触媒の再生方法
JP2005270910A (ja) * 2004-03-26 2005-10-06 Sumitomo Chemical Co Ltd 還元触媒の再生方法及び（アルキルアミノ）ジフェニルアミン類の製造方法。
JP2009022917A (ja) * 2007-07-23 2009-02-05 Sumitomo Chemical Co Ltd 塩素製造用触媒の賦活方法及び塩素の製造方法

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JPS506592A (fr) * 1973-05-22 1975-01-23
JPH02144149A (ja) * 1988-11-22 1990-06-01 Ube Ind Ltd 白金族金属担持触媒の再活性化方法
JPH03221145A (ja) * 1989-11-22 1991-09-30 Mitsui Toatsu Chem Inc 触媒の再生方法
JP2005270910A (ja) * 2004-03-26 2005-10-06 Sumitomo Chemical Co Ltd 還元触媒の再生方法及び（アルキルアミノ）ジフェニルアミン類の製造方法。
JP2009022917A (ja) * 2007-07-23 2009-02-05 Sumitomo Chemical Co Ltd 塩素製造用触媒の賦活方法及び塩素の製造方法

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LOPEZ, N. ET AL.: "Mechanism of HC1 oxidation (Deacon process) over RuO2", JOURNAL OF CATALYSIS, vol. 255, no. 1, 1 April 2008 (2008-04-01), pages 29 - 39, XP022518262, DOI: doi:10.1016/j.jcat.2008.01.020 *
ZWEIDINGER, S. ET AL.: "Reaction Mechanism of the Oxidation of HC1 over RuO2(110)", J. PHYS. CHEM. C, vol. 112, no. 27, 13 June 2008 (2008-06-13), pages 9966 - 9969 *

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