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EP2558197A1 - Catalyseur d'oxydation de so2 en so3 - Google Patents

Catalyseur d'oxydation de so2 en so3

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Publication number
EP2558197A1
EP2558197A1 EP11768535A EP11768535A EP2558197A1 EP 2558197 A1 EP2558197 A1 EP 2558197A1 EP 11768535 A EP11768535 A EP 11768535A EP 11768535 A EP11768535 A EP 11768535A EP 2558197 A1 EP2558197 A1 EP 2558197A1
Authority
EP
European Patent Office
Prior art keywords
diatomaceous earth
catalyst
naturally occurring
oxidation
carrier
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Withdrawn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
EP11768535A
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German (de)
English (en)
Other versions
EP2558197A4 (fr
Inventor
Michael Krämer
Markus Schubert
Thomas Lautensack
Thomas Hill
Reinhard KÖRNER
Frank Rosowski
Jürgen ZÜHLKE
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
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11768535.4A priority Critical patent/EP2558197A4/fr
Publication of EP2558197A1 publication Critical patent/EP2558197A1/fr
Publication of EP2558197A4 publication Critical patent/EP2558197A4/fr
Withdrawn legal-status Critical Current

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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/102—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/202—Alkali metals
    • B01D2255/2022—Potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/30—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9205—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides

Definitions

  • the invention relates to a catalyst for the oxidation of SO2 to SO3 as well as a process for its preparation and its use in a method for the oxidation of S0 2 to S0 3
  • V2O5 vanadium pentoxide
  • M2O alkali metal oxides
  • K2O potassium oxide K2O but also sodium oxide Na2Ü and / or cesium oxide CS2O
  • sulfate As supports for the aforementioned components, porous oxides such as silica S1O2 are usually used. Under reaction conditions, an alkali metal pyrosulfate melt forms on the support material, in which the active component is dissolved in the form of oxosulfate complexes (Catal. Rev. - Sei. Eng., 1978, Vol. 17 (2), pages 203 to 272).
  • V2O5 contents of V2O5 are usually between 3 and 10 wt .-%, the alkali metal oxides depending on the species used or depending on the combination of different alkali metals between 6 and 26 wt .-%, wherein the molar ratio of alkali metal to vanadium (M / V Ratio) is usually between 2 and 5.5.
  • the content of K 2 O is usually between 7 and 14 wt .-% and sulfate between 12 and 30
  • the porous carrier material used is predominantly S1O2.
  • the preparation of such catalysts on an industrial scale is usually carried out by mixing aqueous solutions or suspensions of the various active components, for example corresponding vanadium compounds (V2O5, ammonia).
  • alkali metal salts nitrates, carbonates, oxides, hydroxides, sulfates
  • sulfuric acid and other components which can act as pore formers or lubricants such as sulfur, starch or graphite
  • the properties of the catalyst are determined on the one hand by the active material content, the type and amount of the alkali metal used, the M / V ratio and by the use of any further promoters, but also by the nature of the carrier material used.
  • a stable under reaction conditions support material helps to increase the surface of the melt and thus the number of accessible dissolved active component complexes.
  • the pore structure of the carrier material has a central importance. Small pores stabilize the liquid state of aggregation and therefore lower the melting point of the molten salt (React. Kinet. Catal. Lett, 1986, Vol. 30 (1), pages 9 to 15) and, moreover, bring about a particularly high surface area. Both effects result in increased reactivity in the lower temperature range, i. according to the classification made in DD92905 in the temperature range ⁇ 400 ° C. Large pores are particularly relevant at high temperatures (reaction temperatures> 440 ° C) to avoid transport limitation.
  • the lifetime is influenced by toxins which enter the reactor from the outside with the feed gas and gradually accumulate on the bed, but also by impurities contained in the feedstocks, such as the silica carrier, which become mobile under reaction conditions and can react with sulfate ions and thus adversely affect the properties of the catalyst.
  • impurities are alkaline earth metal compounds (such as calcium compounds), iron or aluminum compounds.
  • the catalyst can simply sinter in the extreme conditions and thus gradually lose its active surface.
  • the pressure drop across the bed which should be as low as possible and should increase as little as possible over the lifetime.
  • a freshly prepared catalyst has the best possible mechanical properties.
  • Typical parameters for this are, for example, the abrasion stability or the resistance to the penetration of a cutting edge (cutting hardness).
  • the Haittelêt the catalyst plays a central role, as only so can be ensured that a certain necessary mass of active material is filled in the given reactor volume.
  • inert carrier materials for commercial sulfuric acid catalysts especially cost-effective, porous materials based on S1O2 are used.
  • synthetic variants of S1O2 as well as natural forms of S1O2 use.
  • the desired carrier properties such as pore structure or mechanical stability, can generally be set well.
  • 2186620 describes the use of precipitated silica gel as a carrier for a sulfuric acid catalyst.
  • DE 1235274 discloses a process for the oxidation of SO 2 using a catalyst based on V 2 O 5 K 2 O / S 2 O 2, which is characterized in that catalysts are used with a respectively corresponding pore structure at different operating temperatures.
  • These compounds can be exemplified by use of certain synthetic S1O2 components such as precipitated sodium water glass.
  • SU 1616-688 describes the use of high surface area amorphous synthetic S1O2.
  • the disadvantage of such components is the relatively high production and material costs.
  • silicon dioxides also called kieselguhr or diatomaceous earth
  • kieselguhr as a carrier for a corresponding catalyst.
  • CN 1417110 discloses a catalyst for the oxidation of SO2 based on V2O5 and K2SO4 in which the kieselguhr used comes from a particular province in China.
  • the properties of a sulfuric acid catalyst can also be influenced by the nature of the pretreatment of the pure natural support material. Fedoseev et al.
  • SU 1824235 describes a catalyst for the oxidation of SO 2 to SO 3 for a high-temperature process, characterized in that the diatomaceous earth carrier used contains between 10 and 30 wt .-% clay minerals, calcined at 600 to 1000 ° C and then before mixing with the actual active components are comminuted, with at least 40% of the calcined diatomaceous earth having a particle size have diameter of ⁇ 10 ⁇ . Again, in this example, an additional step (crushing) is necessary.
  • No. 4,000,609 discloses a catalyst for the oxidation of SO2 consisting of vanadium and alkali metal compounds on a support material with a defined pore structure, which is characterized in that different S1O2 components with different pore diameters are mixed in defined proportions, so that the resulting support a high proportion of pores with a diameter ⁇ 200 nm.
  • a similar approach is followed in WO 2006/033588, WO 2006/033589 and RU 2244590.
  • catalysts for the oxidation of SO2 based on V2O5 alkali metal oxides, sulfur oxide and S1O2 are described with an oligomodal pore distribution adapted to the respective working temperature range.
  • RU 2080176 describes a positive effect on the hardness and activity of a sulfuric acid catalyst based on V2O5 / K2O / SO4 / S1O2 by an admixture of S1O2 waste resulting from the recovery of silicon to the silica gel.
  • a similar effect is found in SU 1558-463 by the addition of silica sols to diatomaceous earth.
  • DE 2500264 discloses a vanadium-based catalyst for the oxidation of SO2, wherein as a carrier mixed with potassium waterglass solution mixture of diatomaceous earth with asbestos and bentonite are used as carrier components with increased mechanical stability.
  • PL 72384 claim a S1O2 natural diatomaceous earth support for a vanadium catalyst, characterized in that 20-35% of the particles are between 1 and 5 ⁇ , 10-25% between 5 and 10 ⁇ , 10-25% between 20 and 40 ⁇ , 10-25% between 40 and 75 ⁇ and 1-7% are greater than 75 ⁇ and by calcination of the diatomaceous earth at 900 ° C with subsequent mixing with the uncalcined diatomaceous earth in the ratio 1: 1 to 1: 4 is shown.
  • DE 2,640,169 describes a vanadium-based sulfuric acid catalyst having high durability and effectiveness, which uses as carrier a finely divided freshwater diatomaceous earth containing at least 40% by weight of a calcined, diatomaceous earth
  • Melatira granulata diatomaceous earth wherein the diatomaceous earth was calcined at a temperature between 510 and 1010 ° C before mixing with the active component, suitable accelerators and promoters.
  • the catalysts thus prepared have a higher catalytic activity and mechanical resistance compared to the catalysts which consist exclusively of the corresponding diatomaceous earth in uncalcined and / or comminuted form, wherein it is irrelevant whether the proportion of diatomaceous earth to be comminuted before or after the Calcination is crushed.
  • the diatomaceous earth used can be mechanically comminuted prior to the catalyst preparation and uncalcined diatomaceous earth can be treated with corresponding calcined or calcined and crushed diatomaceous earth or with synthetic SiO 2 variants.
  • the known approaches for improving the catalyst properties, in particular the mechanical stability have at least one of the following disadvantages:
  • This object is achieved by a catalyst whose carrier contains at least one softer naturally occurring non-calcined diatomaceous earth.
  • the invention thus relates to a catalyst for the oxidation of SO 2 to SO 3, comprising active substance comprising vanadium, alkali metal compounds and sulfate applied to a carrier containing naturally occurring diatomaceous earth, characterized in that the carrier contains at least one softer naturally occurring non-calcined diatomaceous earth, which has a percentage decrease of its in a pond size determination by the dry method in comparison to the determined by the wet method D50 value of at least 35%.
  • a preferred embodiment of the invention is a catalyst for the oxidation of SO 2 to SO 3, comprising on a support containing naturally occurring diatomaceous earth applied active substance containing vanadium, alkali metal compounds and sulfate, characterized in that the carrier contains at least one softer naturally occurring non-calcined diatomaceous earth which has a percentage decrease in its dry-method pond size compared to the wet-method D50 value of at least 35% and also contains at least one harder naturally-occurring undecalcified diatomaceous earth which has a percentage decrease in its at least Pond size determination according to the dry method in comparison to the determined by the wet method D50 value.es of less than 35%.
  • inventive catalysts according to the preferred embodiment whose support contains at least one uncalcined harder diatomaceous earth and also another non-calcined softer diatomaceous earth, which has a significantly lower mechanical stability than the other diatomaceous earth, have significantly better properties, in particular over one improved mechanical stability, as the previously known catalysts.
  • the harder diatomaceous earth mainly on the cylindrical diatom Melosira granulata such as the commercially available types MN or LCS from EP Minerals LLC or on a plate-shaped diatom same or similar to the coscinodicineae type such as those commercially available Types Celite 209, Celite 400, Masis, AG-WX1, AG-WX3 or CY-100 or is based on other variants, or is a corresponding mixture of different variants of harder diatomaceous earth with similar mechanical stabilities.
  • An example of a softer diatomaceous earth having markedly lower mechanical stability is diatomite diatomaceous earth from Mineral Resources Co.
  • Diatomaceous earths suitable for preparing the catalysts of the invention should have a content of aluminum oxide Al 2 O 3 of less than 5% by weight, preferably less than 2, 6 wt .-% and in particular less than 2.2 wt .-% have.
  • Your salary Iron (III) oxide Fe 2 O 3 should be less than 2% by weight, preferably less than 1.5% by weight and in particular less than 1.2% by weight.
  • Their content of the sum of alkaline earth metal oxides (magnesium oxide MgO + calcium oxide CaO) should be less than 1.8% by weight, preferably less than 1.4% by weight and in particular less than 1.0% by weight.
  • non-calcined diatomaceous earth means that a diatomaceous earth was not treated at temperatures above 500 ° C., preferably not above 400 ° C. and especially not above 320 ° C., before mixing with the active components.
  • a characteristic feature of uncalcined diatomaceous earth is that the material is quasi amorphous, i. the content of cristobalite is ⁇ 5% by weight, preferably ⁇ 2% by weight and particularly preferably ⁇ 1% by weight (determined by means of X-ray diffraction analysis).
  • An advantage of the present invention is that the non-calcined diatomaceous earth with the lower mechanical stability is not subjected to further process steps such as calcination or comminution, so that the production process remains virtually unchanged.
  • the measure of the hardness or mechanical stability of a diatomaceous earth is the percentage decrease in its particle size determination by the so-called dry method in comparison to the D 5 o value determined by the so-called wet method.
  • the particle size determination can be carried out, for example, with an apparatus such as the Mastersizer 2000 from Malvern Instruments.
  • D 5 o is the mean particle diameter, that is to say 50% of the particles have a maximum diameter of the value indicated as D 5 o.
  • Particle size determination by the wet method is a very gentle method, in which the samples to be examined are not exposed to any significant mechanical stresses.
  • the samples to be examined are not exposed to any significant mechanical stresses.
  • about 0.1 to 2 g of the sample are dispersed in water by means of a dispersing device such as the Hydro 2000G from Malvern Instruments (pump capacity: 2000 rpm, stirrer setting: 500 rpm) and as a suspension in the Mastersizer 2000 introduced.
  • the particles size determination by the dry method the samples are dispersed in an air jet, for example by means of the dispersing module Scirocco 2000A from Malvern Instruments at a pressure of 1 bar.
  • diatomaceous earths are said to be hard when the percentage decrease of their Dox value determined in a pond size determination by the dry method is smaller than 35% as compared to the Dso value determined by the wet method.
  • a diatomaceous earth is said to be soft if its percentage decrease in its dry-method pond size compared to the Dso value determined by the wet method is at least 35%.
  • a soft diatomaceous earth with low mechanical stability generally has a particle size determination by means of the dry method in the Mastersizer 2000 combined with the dispersing unit Scirocco 2000A at 1 bar D 5 o of at most 6 ⁇ , preferably of at most 5 ⁇ while the corresponding value in the harder diatomaceous earth with higher mechanical stability is generally at least 7 ⁇ .
  • the median volume-related pore diameter ie the pore diameter above and below which in each case 50% of the total pore volume, determined by means of mercury porosimetry) of the various diatomaceous earth usable in the context of this invention should be between 0.1 ⁇ and 10 ⁇ , preferably between 0.5 ⁇ and 9 ⁇ and in particular between 0.7 ⁇ and 7 ⁇ are.
  • the median volume-related pore diameter of inventive mixtures of uncalcined diatomaceous earths should be between 0.5 ⁇ and 9 ⁇ , preferably between 0.8 and 7 ⁇ and in particular between 0.9 and 5 ⁇ .
  • the shape of the pore distribution of the mixtures according to the invention can differ significantly from that of the individual diatomaceous earth. Oligomodal or bimodal
  • Pore distributions or monomodal pore distributions with pronounced shoulders can result depending on the combination of different diatomaceous earths.
  • Diatomaceous earth in different proportions is possible in principle.
  • the median volume men-related pore diameter is for the sulfuric acid catalysts according to the invention between 0.1 ⁇ and 5 ⁇ , preferably between 0.2 ⁇ and 4 ⁇ and in particular between 0.3 ⁇ and 3.2 ⁇ , wherein the shape of the pore distribution of the catalysts, their support to mixtures are based on uncalcined diatomaceous earths, can be adjusted by the nature and the ratio of the different diatomaceous earths, so that also here oligomodal or bimodal pore distributions or monomodal pore distributions with pronounced shoulders can result.
  • catalysts are obtained when using a carrier material in which the proportion of softer diatomaceous earths based on the total carrier mass in the range of 10 wt .-% and 42 wt .-%, preferably in the range of 14 wt .-% and 37 wt .-% and particularly preferably in the range of 18 wt .-% and 32 wt .-% is.
  • the catalysts according to the invention generally have a cutting hardness of at least 60 N, preferably of at least 70 N and particularly preferably of at least 80 N. Their abrasion is usually ⁇ 4 wt .-%, preferably ⁇ 3% by weight.
  • Their shaking density is generally in the range of 400 g / l to 520 g / l, preferably in the range of 425 g / l to 500 g / l.
  • Their porosity is at least 0.38 ml / g, preferably at least 0.4 ml / g and more preferably at least 0.45 ml / g.
  • the characteristic physical catalyst parameters cutting hardness, abrasion and porosity were determined in analogy to the instructions described in EP 0019174.
  • the determination of the catalytic activity was carried out according to the method described in DE4000609.
  • the reference catalyst used was a commercially available catalyst according to DE 4000609, Example 3.
  • Another object of the invention is a process for the preparation of the above-described catalysts for the oxidation of SO 2 to SO 3, characterized in that a carrier comprising at least one softer naturally occurring non-calcined diatomaceous earth, which a percentage decrease in their in a Teichenificat after the Drying method compared to the determined by the wet method D50- value.es of at least 35%, with a solution or suspension containing vanadium, alkali metal compounds and sulfate added.
  • a preferred embodiment of the invention is a process for the preparation of the catalysts described above for the oxidation of SO 2 to SO 3, characterized in that a carrier containing at least one softer naturally occurring non-calcined diatomaceous earth, which a percentage decrease in their in a pond size determination according to the dry method in Compared to the determined by the wet method D50- value.es of at least 35% and also contains at least one harder naturally occurring non-calcined diatomaceous earth, which is a percentage decrease in their pond size determination by the dry method compared to the determined by the wet method D 5 o- Value of less than 35%, mixed with a solution or suspension containing vanadium, alkali metal compounds and sulfate.
  • Another object of the invention is a method for the oxidation of SO 2 to SO 3 using the catalysts described above.
  • a gas mixture containing oxygen and sulfur dioxide SO 2 is brought into contact with the catalyst at temperatures in the range from 340 to 680 ° C., with at least part of the sulfur dioxide being converted to sulfur trioxide SO 3.
  • All of the diatomaceous earths used below contain less than 4% by weight of aluminum oxide Al 2 O 3, less than 1.5% by weight of iron (II) oxide Fe 2 O 3 and less than 1.0% by weight of alkaline earth metal oxides (sum of magnesium oxide MgO and calcium oxide CaO).
  • the proportion of crystalline cristobalite was below the limit of quantification of about 1 wt .-%.
  • the loss on ignition at 900 ° C was typically between 5 and 12% by weight.
  • Table 1 Mean particle size D 5 o of different diatomaceous earths determined by the wet method and by the dry method
  • the catalyst thus prepared had a porosity of 0.49 ml / g.
  • the cutting hardness was 74.3 N, the abrasion 3.0 wt .-% and the bulk volume 431 g / l (see Table 2).
  • Example 2 Comparative Example 3.51 kg of a Masis diatomaceous earth from Diatomite SP CJSC, Armenia, was mixed with a suspension of 1.705 kg of 40% KOH, 0.575 kg of 25% NaOH and 0.398 kg of 90% ammonium polyvanadate and 2.35 kg 48% sulfuric acid mixed. Subsequently, 250 g of a 7.4 wt .-% aqueous starch solution was added, the mixture mixed thoroughly and deformed to 1 1 x 5 mm star strands. These strands were then dried at 120 ° C and calcined at 650 ° C.
  • Example 3 Comparative Example 3.51 kg of a Masis diatomaceous earth from Diatomite SP CJSC, Armenia, was mixed with a suspension of 1.705 kg of 40% KOH, 0.575 kg of 25% NaOH and 0.398 kg of 90% ammonium polyvanadate and 2.35 kg 48% sulfuric acid mixed. Subsequently, 250 g of a 7.4 wt .
  • the catalyst was prepared in analogy to Examples 1 to 3 using a mixture of diatomaceous earth, which to 70 wt .-% of the type MN from. EP Minerals and to 30 wt .-% of the type Diatomite 1 of the Fa. Mineral Resources Co. existed.
  • the composition of the actual active component was not varied except for process-related slight fluctuations (deviations ⁇ 5% relative, S0 4 ⁇ 9% relative).
  • Example 5
  • the catalyst was prepared in analogy to Examples 1 to 3 using a mixture of diatomaceous earths containing 20% by weight of the MN type from EP Minerals LLC, to 50% by weight of the Masis Fa diatomite type SP CJSC and to 30 wt .-% of the type Diatomite 1 from the company Mineral Resources Co. was.
  • the composition of the actual active component was not varied except for process-related slight fluctuations (deviations ⁇ 5% relative, S0 4 ⁇ 9% relative).
  • Examples 6 and 7 describe the influence of a partial replacement of the more stable diatomaceous earth by a mechanically unstable diatomaceous earth on the properties of cesium-containing sulfuric acid catalysts.
  • the catalyst was prepared in analogy to Example 6 using a mixture of diatomaceous earths containing up to 50% by weight of the MN type from EP Minerals LLC, to 20% by weight from the Celite 400 from the Fa. Lehmann & Voss & Co., Hamburg, and to 30 wt .-% of the type Diatomite 1 of the Fa. Mineral Resources Co. was.
  • the composition of the actual active component was not varied except for process-related slight fluctuations (deviations ⁇ 5% relative, S0 4 ⁇ 9% relative).
  • Table 2 Pore volume, cutting hardness, abrasion, Hinttel Why and catalytic properties of the catalysts prepared according to Examples 1 to 7.

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Abstract

L'invention concerne un catalyseur d'oxydation de SO2 en SO3, ainsi que son procédé de préparation et son utilisation dans un procédé d'oxydation de SO2 en SO3. Ce catalyseur comprend une substance active comprenant du vanadium, des composés métalliques alcalins et du sulfate, cette substance active étant appliquée sur un support comprenant des terres de diatomées d'origine naturelle. Selon l'invention, le support comprend au moins une terre de diatomées non calcinée d'origine naturelle relativement molle présentant une réduction en pourcentage d'au moins 35 % de sa valeur D50 déterminée lors d'une détermination de la taille des particules selon le procédé par voie sèche comparativement au procédé par voie humide.
EP11768535.4A 2010-04-12 2011-04-12 Catalyseur d'oxydation de so2 en so3 Withdrawn EP2558197A4 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11768535.4A EP2558197A4 (fr) 2010-04-12 2011-04-12 Catalyseur d'oxydation de so2 en so3

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10159647 2010-04-12
EP11768535.4A EP2558197A4 (fr) 2010-04-12 2011-04-12 Catalyseur d'oxydation de so2 en so3
PCT/IB2011/051553 WO2011128830A1 (fr) 2010-04-12 2011-04-12 Catalyseur d'oxydation de so2 en so3

Publications (2)

Publication Number Publication Date
EP2558197A1 true EP2558197A1 (fr) 2013-02-20
EP2558197A4 EP2558197A4 (fr) 2014-03-26

Family

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Family Applications (1)

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EP11768535.4A Withdrawn EP2558197A4 (fr) 2010-04-12 2011-04-12 Catalyseur d'oxydation de so2 en so3

Country Status (7)

Country Link
EP (1) EP2558197A4 (fr)
JP (1) JP5833630B2 (fr)
KR (1) KR20130097071A (fr)
CN (1) CN102892501B (fr)
BR (1) BR112012026246A2 (fr)
CL (1) CL2012002875A1 (fr)
WO (1) WO2011128830A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
UA118163C2 (uk) 2015-08-14 2018-11-26 Оріон Інджинірд Карбонз Гмбх Способи і системи для видалення матеріалу частинок з потоку технологічних відпрацьованих газів
EP3838393A1 (fr) * 2019-12-19 2021-06-23 Basf Se Procédé d'oxydation de dioxyde de soufre en trioxyde de soufre impliquant un lit de catalyseur structuré
CN119857503A (zh) * 2023-10-20 2025-04-22 中国石油化工股份有限公司 钒基催化剂及其制备方法和应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1080205A (fr) * 1975-09-11 1980-06-24 Stauffer Chemical Company Catalyseur actif et durable de la synthese d'acide sulfurique
DE3322940A1 (de) * 1983-06-25 1985-01-03 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung eines katalysators fuer die oxidation von schwefeldioxid zu schwefeltrioxid
DE4000609B4 (de) * 1990-01-11 2005-09-15 Basf Ag Katalysator für die Oxidation von Schwefeldioxid zu Schwefeltrioxid
JP2002285691A (ja) * 2001-03-26 2002-10-03 Toto Ltd 内装材
JP2003073997A (ja) * 2001-08-31 2003-03-12 Toto Ltd 機能性内装材及びその製造方法
CN1226184C (zh) * 2002-12-11 2005-11-09 南化集团研究院 一种硫酸生产用钒催化剂的活性相及钒催化剂的制备方法
CN101462048B (zh) * 2008-06-21 2011-08-24 康喆 一种含钨的氧化制酸钒催化剂及其制备方法

Also Published As

Publication number Publication date
KR20130097071A (ko) 2013-09-02
CN102892501B (zh) 2015-04-08
CN102892501A (zh) 2013-01-23
BR112012026246A2 (pt) 2016-07-12
EP2558197A4 (fr) 2014-03-26
JP5833630B2 (ja) 2015-12-16
CL2012002875A1 (es) 2012-12-14
JP2013523447A (ja) 2013-06-17
WO2011128830A1 (fr) 2011-10-20

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