CN102892501A - Catalyst for the oxidation of so2 to so3 - Google Patents

Catalyst for the oxidation of so2 to so3 Download PDF

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CN102892501A
CN102892501A CN2011800235213A CN201180023521A CN102892501A CN 102892501 A CN102892501 A CN 102892501A CN 2011800235213 A CN2011800235213 A CN 2011800235213A CN 201180023521 A CN201180023521 A CN 201180023521A CN 102892501 A CN102892501 A CN 102892501A
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catalyst
diatomite
carrier
naturally occurring
weight
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CN102892501B (en
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M·克拉梅尔
M·舒伯特
T·劳滕扎克
T·希尔
R·科尔纳
F·罗索夫斯基
J·齐尔克
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BASF SE
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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
    • 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
    • B01J23/16—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
    • 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
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    • 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
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    • 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

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Abstract

A catalyst for the oxidation of SO2 to SO3, a process for producing it and its use in a process for the oxidation of SO2 to SO3 are provided. The catalyst comprises active substance comprising vanadium, alkali metal compounds and sulfate applied to a support comprising naturally occurring diatomaceous earths, wherein the support comprises at least one relatively soft naturally occurring uncalcined diatomaceous earth which has a percentage reduction of at least 35% in its D50 value determined in a particle size determination according to the dry method in comparison with the wet method.

Description

Be used for SO 2Be oxidized to SO 3Catalyst
The present invention relates to a kind of for SO 2Be oxidized to SO 3Catalyst and production method with and with SO 2Be oxidized to SO 3Method in purposes.
Sulfuric acid only passes through in contact/secondary contact method sulfur dioxide (SO basically current 2) be oxidized to sulfur oxide (SO 3) and be hydrolyzed subsequently and obtain.In the method, in the heat insulation layer (bed) of a plurality of arranged in series on vanadium containing catalysts by molecular oxygen with SO 2Be oxidized to SO 3The SO of feed gas 2Content is generally 0.01-50 volume % and O 2/ SO 2Than being 0.5-5.Preferred oxygen source is air.This gas (contact method) is wherein cooled off in part sulfur dioxide reaction in each in each case between each.The SO that forms 3Can be removed by air-flow by centre absorption, to realize higher total conversion (secondary contact method).This reaction depends on that this carries out in the temperature range of 340-680 ° of C, maximum temperature is because SO 2Content increases with the implantation number and reduces.
Current commercial catalyst comprises active component vanadic anhydride (V usually 2O 5) and alkali metal oxide (M 2O), potassium oxide K especially 2O, but also have sodium oxide molybdena Na 2O and/or cesium oxide Cs 2O, and also have sulfate.Porous oxide such as silica SiO 2Be typically used as the carrier of said components.Under reaction condition, be dissolved in wherein (Catal.Rev. – Sci.Eng. at carrier material formation alkali metal pyrosulfate melt and active component with Hydroxysulfate (oxo sulfate complex) complex form, 1978, the 17 volumes (2), the 203-272 page or leaf).This catalyst is called supported liquid phase catalyst.
V 2O 5Content be generally the 3-10 % by weight, and the content of alkali metal oxide depends on used kind and the various alkali-metal 6-26 of being combined as % by weight, wherein the mol ratio of alkali metal and vanadium (M/V ratio) is generally 2-5.5.K 2O content is generally the 7-14 % by weight, and sulphates content is the 12-30 % by weight.In addition, reported and used many other extra elements, for example chromium, iron, aluminium, phosphorus, manganese and boron.As porous carrier materials, mainly use SiO 2
Such catalyst passes through usually with various active components, for example suitable vfanadium compound (V 2O 5, ammonium vanadate, alkali metal vanadate or vanadic sulfate) with alkali metal salt (nitrate, carbonate, oxide, hydroxide, sulfate), sometimes with sulfuric acid with can play other components of pore former or lubricant such as the aqueous solution of sulphur, starch or graphite or aqueous suspension mix with carrier material and with industrial-scale production.Machining gets viscous composition and obtains required formed body and finally heat-treat (dry and calcining) in following step.
The performance of this catalyst at first determines by the use of active compound content, used alkali metal type and amount, M/V ratio and any other promoter, secondly also by the type decided of used carrier material.The active component complex number that stable carrier material helps to increase the surface area of this melt and therefore increases available dissolving under reaction condition.The pore structure of this carrier material is most important here.Aperture makes liquid stableization and therefore reduces the fusing point (React.Kinet.Catal.Lett., 1986, the 30 volumes (1), 9-15 page or leaf) of molten salt bath and also produce extra high surface area.These two kinds of effects are in the lower temperature scope, namely according to causing reactive the raising in the temperature range of being determined in DD92905＜400 ° C.Macropore is suitable especially under high temperature (reaction temperature〉440 ° C), to avoid the transmission restriction.
Except the catalytic activity of catalyst, its life-span is also very important.Life-span at first is subjected to be entered in the reactor by the outside and assemble in this gradually and also affect via being included in raw material such as the silica supports and becoming removable under reaction condition and can and therefore have the poisonous substance that the impurity of adverse effect enters in the reactor to the performance of this catalyst with the sulfate ion reaction with feed gas.The example of such impurity is alkaline earth metal compound (for example calcium compound), iron compound or aluminium compound.In addition, this catalyst can also be simply sintering and therefore lose gradually its active surface area under extreme conditions.Pressure drop on this is particular importance also; This pressure drop should very low and seldom raising in the life-span of this catalyst.For this reason, the catalyst of new production must have extraordinary mechanical performance.The canonical parameter that this purpose is measured for example is wear resistence or anti-cutter penetrability (cutting hardness).In addition, the bulk density of this catalyst also plays an important role, because only can guarantee in this way active compound specific, necessary amount is introduced in the given reactor volume.
As the inert material of commercial sulfuric acid catalyst, mainly use based on SiO 2Cheap porous material.Synthetic SiO 2Modification and natural SiO 2Form is all in this use.
Synthetic modification can suitably be set required carrier property such as pore structure or mechanical stability usually.For example, RU 2186620 has described and has used precipitation silica gel as the carrier of sulfuric acid catalyst.DE 1235274 discloses a kind of use based on V 2O 5/ K 2O/SiO 2Catalyst oxidation SO 2Method, wherein under the different operating temperature, use the catalyst of the hole micro-structural with suitable coupling.These compounds for example can be by using specific synthetic SiO 2Component as the precipitation sodium silicate and obtain.SU 1616-688 has described and has used the amorphous synthetic SiO with high surface 2Yet the shortcoming of such component is higher production cost and material cost.
Owing to this reason, in industrial practice, usually use to can be used as that natural products significantly obtains more at an easy rate but the naturally occurring silica (being also referred to as tripoli or diatomite) that usually departs from required optimum value in its performance.The author of SU 1803180 uses tripoli as catalyst carrier.CN1417110 discloses a kind of for oxidation SO 2Catalyst, it is based on V 2O 5And K 2SO 4And wherein used tripoli comes from the specific province of China.
The performance of sulfuric acid catalyst also can be by the preliminary treatment type impact of pure natural carrier material.For example, Fedoseev etc. have reported pore structure (maximum is shifted to less hole) (the Sbornik Nauchnykh Trudov-Rossiiskii Khimiko-Tekhnologicheskii Universitet im.D.I.Mendeleeva (2000) of modification vanadium base sulfuric acid catalyst by the mechanical crushing tripoli, (178, Protsessy i Materialy Khimicheskoi Promyshlennosti), 34-36CODEN:SNTRCV).This causes improved mechanical stability.The shortcoming of this modification at first is to use extra operating procedure (pulverize this carrier 12 hour), secondly is that the catalytic activity that causes thus reduces.
SU 1824235 described a kind of for high temperature process with SO 2Be oxidized to SO 3Catalyst, wherein used tripoli carrier comprises 10-30 % by weight clay mineral and calcines under 600-1000 ° of C, then with pulverize the particle diameter that has of at least 40% calcining tripoli＜10 μ m wherein before the substantial activity component is mixed.In this embodiment, also must extra operating procedure (pulverizing).
Many document descriptions use natural and synthetic SiO by uniting 2Modification is come the optimization of catalysts performance.DE 400609 discloses a kind of for oxidation SO 2Catalyst, it comprises vfanadium compound and alkali metal compound at the carrier material with limiting hole structure, wherein will have the different SiO of different pore size 2Component is mixed mutually with the ratio that limits, thereby makes the gained carrier have the hole of a high proportion of diameter＜200nm.Similar approach is described among WO 2006/033588, WO 2006/033589 and the RU2244590.Described therein and be used for oxidation SO 2Catalyst, it is based on V 2O 5, alkali metal oxide, oxysulfide and SiO 2And has low mode (oligomodal) pore size distribution with corresponding operating temperature range coupling.The hole micro-structural of this restriction for example can be by setting synthetic silica and the combination of natural diatom rock.RU 2080176 has described by be added in the SiO that obtains in the production of silicon in tripoli 2Waste material and to based on V 2O 5/ K 2O/SO 4/ SiO 2The hardness of sulfuric acid catalyst and active positive impact.Similar effect is found in SU 1558-463 owing to adding Ludox in tripoli.
US 1952057, FR 691356, GB 337761 and GB 343441 have described the synthetic SiO that is used in combination the natural diatom rock and is suitable KP1 form 2Should be applied to tripoli by the aqueous solution by synthetic silicon components, for example by precipitation, can be with the embedding SiO of suitable active dipping thereby finally obtain 2The tripoli particle.The catalyst of producing in this way demonstrates improved performance such as hardness or catalytic activity.
DE 2500264 discloses a kind of for oxidation SO 2Catalytic component based on vanadium, wherein tripoli is mixed with KP1 solution with asbestos and bentonitic mixture, then as the carrier component of mechanical stability with raising.
Except only using synthetic or natural SiO 2Modification or use are synthesized and natural SiO 2Outside the mixture of modification, can also use different natural SiO 2The mixture of modification.J í ru and Br ü ll have described the pore structure of modification particular type tripoli by adding 30 % by weight from the thick tripoli waste material of same vehicle, this causes average pore size to be displaced to 80nm (Chemicky Prumysl (1957) by 56nm, 7,652-4CODEN:CHPUA4; ISSN:0009-2789).PL 72384 claimed a kind of SiO based on the natural diatom rock for vanadium catalyst 2Carrier, wherein this carrier granular of 20-35% is 1-5 μ m, 10-25% is 5-10 μ m, 10-25% is 20-40 μ m, and 10-25% is 40-75 μ m and 1-7% greater than 75 μ m and this carrier by this tripoli of calcining under 900 ° of C and mix with the ratio of 1:1-1:4 with the tripoli of calcining not subsequently and produce.DE 2640169 has described a kind of vanadium base sulfuric acid catalyst, its have high stability and validity and the fresh water diatomite in small, broken bits that comprises at least 40 % by weight calcined diatomites that wherein will be formed by diatom-particle melosira (Melosira granulata) as carrier, wherein diatomite with before active component, suitable accelerator and promoter are mixed at the temperature lower calcination of 510-1010 ° of C.The catalyst of producing in this way than only with calcining not and/or not pulverised form comprise corresponding diatomaceous catalyst and have more high catalytic activity and mechanical stability, whether before or after calcining, grind irrelevant with diatomite ratio to be pulverized.
Therefore, the mechanical stability of known sulfuric acid catalyst can by the used tripoli of mechanical crushing before Catalyst Production and the tripoli that will not calcine and corresponding calcining calcining and the tripoli of pulverizing or with the SiO that synthesizes 2Modification is mixed and is optimized.Yet the known method of finding to improve catalyst performance, especially mechanical stability has at least one in the following shortcoming:
(i) remarkable higher preparation cost, because essential extra operating procedure such as pulverizing or the calcining of carrier or part carrier, precipitation is filtered or washing;
(ii) by formerly calcining the conversion of natural diatom rock carrier or Partial Conversion are become cristobalite, this is a problem with regard to human health;
(iii) when with natural diatom rock carrier higher cost of material when expensive synthetic vectors mixes;
(iv) improvement owing to mechanical performance reduces catalytic activity (pulverizing of natural diatom rock carrier).
The purpose of this invention is to provide a kind of for SO 2Be oxidized to SO 3Catalyst, it can be used for the temperature range of non-constant width and can produce very economically and especially have improved mechanical stability.
This purpose realizes by a kind of catalyst with the carrier that comprises at least a softer naturally occurring not calcined diatomite.
Therefore, the invention provides a kind of for SO 2Be oxidized to SO 3Catalyst, this catalyst comprises to put on to comprise and contains vanadium active material, alkali metal compound and sulfate on the naturally occurring diatomaceous carrier, wherein this carrier comprises at least a softer naturally occurring not calcined diatomite, and the latter is at its D that measures in granulometry according to dry method 50Compare with wet method on the value and have at least 35% percentage and reduce.
The preferred embodiments of the invention are a kind of for SO 2Be oxidized to SO 3Catalyst, comprise to put on to comprise and contain vanadium active material, alkali metal compound and sulfate on the naturally occurring diatomaceous carrier, wherein this carrier comprises at least a softer naturally occurring not calcined diatomite (at its D that measures according to dry method in granulometry 50Compare with wet method on the value and have at least 35% percentage and reduce) and comprise in addition at least a harder naturally occurring not calcined diatomite (at its D that in granulometry, measures according to dry method 50Comparing the percentage that has less than 35% with wet method on the value reduces).
Comprise the harder diatomite of at least a not calcining and comprise in addition mechanical stability according to its carrier of this preferred embodiment and significantly be lower than another diatomaceous catalyst softer diatomaceous of the present invention that another is not calcined and have significantly better performance, especially improved mechanical stability than known up to now catalyst.This moment, harder diatomite mainly came from cylindrical diatom-particle melosira (Melosira granulata), for example from commercially available type MN or the LCS of EP Minerals LLC, perhaps come from and the same or analogous sheet diatom of rotary strainer algae guiding principle (Coscinodicineae) type, for example commercially available Type C elite 209, Celite 400, Masis, AG-WX1, AG-WX3 or Cy-100, perhaps be derived from other modification, perhaps unimportant for the hard diatomaceous suitable mixture with similar mechanical stability of different modification.Softer diatomaceous example with remarkable lower mechanical stability is the Diatomite type diatomite from Mineral Resources Co..
The diatomite that is fit to production catalyst of the present invention should have less than 5 % by weight, preferably less than 2.6 % by weight, especially less than the aluminium oxide Al of 2.2 % by weight 2O 3Content.Its iron oxide (III) Fe 2O 3Content should be less than 2 % by weight, preferably less than 1.5 % by weight, especially less than 1.2 % by weight.The total content of its alkaline earth oxide (magnesia MgO+ calcium oxide CaO) should be less than 1.8 % by weight, preferably less than 1.4 % by weight, especially less than 1.0 % by weight.
For the purpose of the present invention, not calcined diatomite be with before active component is mixed not yet in the temperature that surpasses 500 ° of C, preferred not yet in the temperature that surpasses 400 ° of C, especially not yet surpassing the diatomite of processing under the temperature of 320 ° of C.The characteristic features of calcined diatomite is not that this material is essentially amorphous, and namely cristobalite content＜5 % by weight are preferred＜2 % by weight, particularly preferably＜1 % by weight (measuring by X-ray diffraction analysis).
Advantage of the present invention be not calcined diatomite with low mechanical stability without successive what further processing step such as calcining or pulverize, substantially constant thereby this production method keeps.
For the purpose of the present invention, the tolerance for diatomite hardness or mechanical stability is its D that measures by the granulometry of dry method 50Value and the D that measures by wet method 50The percentage that value is compared reduces.Granulometry for example can be used from the equipment of Malvern Instruments such as Mastersizer2000 and carry out.D 50Be average grain diameter, namely the diameter that has of 50% particle is no more than with D 50The value of expression.
Granulometry by wet method is a kind of method as mild as a dove, and wherein detected sample is without successive what significant mechanical stress.In wet method, by from the dispersing apparatus of Malvern Instruments such as Hydro 2000G (pump power: 2000rpm, agitator setting: 500rpm) about this sample dispersion of 0.1-2g is introduced among the Mastersizer 2000 in water and as suspension.
In the granulometry by dry method, sample dispersion in air-spray, is for example disperseed under the pressure of 1 bar by the dispersed components thereof Scirocco 2000A from Malvern Instruments.For this reason, about 0.5-2g sample is placed on the vibra shoot of dispersal unit and slowly introduce this jet (1 bar).Depend on various diatomaceous mechanical stabilities, in measuring process, form larger particles than granule and in harder diatomaceous situation forming in the softer diatomaceous situation, therefore in softer diatomite situation at D 50Exist larger percentage to reduce on the value.In this analytic process diatomite particle to be detected by frictional force mechanically stressed and mutually collision or with the chamber wall collision, this causes breaking of particle and wears away.Diatomite is more stable, particle mean size and so D 50The percentage of value reduces less.
For the purpose of the present invention, the D that in its granulometry by dry method, measures 50Value and the D that measures by wet method 50Percentage that value is compared reduces less than 35% the time diatomite is called firmly.The D that in its granulometry by dry method, measures 50Value and the D that measures by wet method 50When the percentage that value is compared is reduced to 35% diatomite is called soft at least.
Soft diatomite with low mechanical stability usually has and is no more than 6 μ m, preferably is no more than the D of 5 μ m 50, under 1 bar, measure at the Mastersizer 2000 of being combined with dispersal unit Scirocco 2000A according to the granulometry by dry method, and be generally at least 7 μ m in the respective value that has than in the harder diatomite situation of high mechanical stability.
Operable various diatomaceous mean pore sizes based on volume (namely in each case on it and under record total pore volume 50% aperture, measure by the mercury porosimetry) should be for the purpose of the present invention 0.1-10 μ m, preferred 0.5-9 μ m, especially 0.7-7 μ m.The mixture-base diatomaceous of the present invention of calcining not should be 0.5-9 μ m in the mean pore sizes of volume, preferred 0.8-7 μ m, especially 0.9-5 μ m.The shape of the at this moment cell size of mixture of the present invention distribution can significantly depart from each diatomaceous shape.Can obtain low mode or bimodal pore size distribution or have the single mode pore size distribution of remarkable acromion by various more diatomaceous combinations.Will specific mean pore sizes based on volume to be arranged on be possible in principle in the above-mentioned limit by with various ratios different diatomite being mixed.
In the production of sulfuric acid catalyst of the present invention, owing in blend step or forming step process and also have the partial rupture of the diatom structure that the result of mechanical stress occurs in the process that active compound is put on the diatomite support to cause being offset based on the mean pore sizes of volume, thereby make the gained catalyst usually have the remarkable lower mean pore sizes based on volume than parent carrier.The mean pore sizes based on volume of sulfuric acid catalyst of the present invention is 0.1-5 μ m, preferred 0.2-4 μ m, especially 0.3-3.2 μ m, wherein its carrier can be set via various diatomaceous types and ratio based on the shape of the not cell size distribution of the catalyst of the mixture of calcined diatomite, thereby can also be in this single mode cell size distribution that obtains low mode or the distribution of bimodal cell size or have remarkable acromion.
When the gross mass of using softer diatomaceous ratio wherein based on this carrier is the 10-42 % by weight, preferred 14-37 % by weight particularly preferably obtains particularly preferred catalyst during the carrier material of 18-32 % by weight.
Catalyst of the present invention has at least 60N usually, preferred 70N at least, the particularly preferably cutting hardness of 80N at least.It wears away usually＜4 % by weight, and is preferred＜3 % by weight.Its bulk density is generally 400-520g/l, preferred 425-500g/l.Its porosity is 0.38ml/g at least, preferred 0.4ml/g at least, particularly preferably 0.45ml/g at least.
In order to measure the bulk density of catalyst, via vibra shoot about 1 liter of formed body being introduced volume is in 2 liters the measurement cylinder.Should measure cylinder and place on the tamped volume meter, this stereometer raps within the time that limits and therefore in this measurement cylinder formed body is compressed.Determine bulk density by weight and volume at last.
Measure characteristic physical property cutting hardness, abrasion and the porosity of catalyst by being similar to those method described in the EP 0019174.Catalyst activity is measured by method described in the DE 4000609.DE 4000609 embodiment 3 described commercial catalyst are used as reference catalyst.
Having the present invention further provides a kind of production is used for SO 2Be oxidized to SO 3The method of above-mentioned catalyst, wherein make to comprise at least a softer naturally occurring not calcined diatomite (at its D that in granulometry, measures according to dry method 50Compare with wet method on the value and have at least 35% percentage and reduce) carrier mix with the solution that comprises vanadium, alkali metal compound and sulfate or suspension.
The preferred embodiments of the invention are that a kind of production is used for SO 2Be oxidized to SO 3The method of above-mentioned catalyst, wherein make to comprise at least a softer naturally occurring not calcined diatomite (at its D that in granulometry, measures according to dry method 50Compare with wet method on the value and have at least 35% percentage and reduce) and comprise in addition at least a harder naturally occurring not calcined diatomite (at its D that in granulometry, measures according to dry method 50Compare the percentage that has less than 35% on the value reduces with wet method) carrier mix with the solution that comprises vanadium, alkali metal compound and sulfate or suspension.
The present invention further provides the above-mentioned catalyst of a kind of use with SO 2Be oxidized to SO 3Method.In a preferred embodiment of the invention, make and comprise oxygen and sulfur dioxide SO 2Admixture of gas under the temperature of 340-680 ° of C, contact with this catalyst, wherein at least part of Sulphur Dioxide becomes sulfur trioxide SO 3
Embodiment:
Below used all diatomite comprise aluminium oxide Al less than 4 % by weight 2O 3, less than iron oxide (III) Fe of 1.5 % by weight 2O 3With the alkaline earth oxide (summation of magnesia MgO and calcium oxide CaO) less than 1.0 % by weight.The ratio of crystallization cristobalite is lower than the approximately detectable limit of 1 % by weight.Loss on ignition under 900 ° of C is generally the 5-12 % by weight.
Synthesizing by carrying out based on the method for DE 4000609 embodiment 3 of all catalyst.The mensuration of catalyst activity is equally by carrying out based on the method described in the DE 4000609.
Table 1: by the various diatomaceous mean particle size D of wet method and dry method mensuration 50
Figure BDA00002386891100091
1): measure size distribution (Mastersizer 2000, disperse) by wet method in Hydro 2000G.
2): under 1 bar, measure size distribution (Mastersizer 2000, disperse) by dry method in Scirocco 2000A under 1 bar.
Embodiment 1: Comparative Examples
With 3.926kg from EP Minerals LLC, Reno, the MN type diatomite of USA and the KOH, the 0.563kg concentration that by 1.701kg concentration are 40% are that 25% NaOH and 0.398kg concentration are that 90% ammonium poly-vanadate and 2.35kg concentration are that the suspension that 48% sulfuric acid consists of mixes.Then add the amidin that 250g concentration is 7.4 % by weight, with this mixture powerful mixing and extrude and obtain 11 * 5mm star extrudate.Then with these extrudates dry under 120 ° of C and under 650 ° of C, calcine.
The catalyst of producing in this way has the porosity of 0.49ml/g.Cutting hardness is 74.3N, and abrasion are that 3.0 % by weight and bulk density are 431g/l (referring to table 2).
Embodiment 2: Comparative Examples
From Diatomite SP CJSC, the Masis type diatomite of Armenia and the KOH, the 0.575kg concentration that by 1.705kg concentration are 40% are that 25% NaOH and 0.398kg concentration are that 90% ammonium poly-vanadate and 2.35kg concentration are that the suspension that 48% sulfuric acid consists of mixes with 3.51kg.Then add the amidin that 250g concentration is 7.4 % by weight, with this mixture powerful mixing and extrude and obtain 11 * 5mm star extrudate.Then with these extrudates dry under 120 ° of C and under 650 ° of C, calcine.
Embodiment 3: Comparative Examples
With 3.565kg from Mineral Resources Co., Lima, the Diatomite 1 type diatomite of Peru and the KOH, the 0.559kg concentration that by 1.666kg concentration are 40% are that 25% NaOH and 0.396kg concentration are that 90% ammonium poly-vanadate and 2.35kg concentration are that the suspension that 48% sulfuric acid consists of mixes.Then add the amidin that 250g concentration is 7.4 % by weight, with this mixture powerful mixing and extrude and obtain 11 * 5mm star extrudate.Then with these extrudates dry under 120 ° of C and under 650 ° of C, calcine.
Embodiment 4:
This catalyst uses by the method that is similar to embodiment 1-3 and comprises 70 % by weight from the diatomaceous mixture production of Diatomite 1 type from Mineral Resources Co. of the MN type diatomite of EPMinerals and 30 % by weight.The composition of substantial activity component is constant, but (deviation＜5% is relative except the relevant fluctuation of slight technique; SO 4＜9% is relative).
Embodiment 5:
This catalyst by the method that is similar to embodiment 1-3 use comprise 20 % by weight from the MN type diatomite of EPMinerals LLC, 50 % by weight from the diatomaceous mixture production of Diatomite 1 type from Mineral Resources Co. of the Masis type diatomite of Diatomite SP CJSC and 30 % by weight.The composition of substantial activity component is constant, but (deviation＜5% is relative except the relevant fluctuation of slight technique; SO 4＜9% is relative).
Embodiment 6 and 7 describes mechanically more unsettled diatomite and partly replaces more stable diatomite to the impact of the performance of the sulfuric acid catalyst that contains caesium.
Embodiment 6:
With 2.753kg from the MN type diatomite of EP Minerals LLC with by 0.956kgCs 2SO 4, 1.394kg concentration is that 47% KOH, 0.417kg concentration are that 90% ammonium poly-vanadate and 1.906kg concentration are that the suspension that 48% sulfuric acid consists of mixes.Then add the amidin that 177g concentration is 10.68 % by weight, with this mixture powerful mixing and extrude and obtain 11 * 5mm star extrudate.Then with these extrudates dry under 120 ° of C and under 510 ° of C, calcine.
Embodiment 7:
This catalyst by the method that is similar to embodiment 6 use comprise 50 % by weight from the MN type diatomite of EPMinerals LLC, 20 % by weight from Lehmann; Voss ﹠amp; Co., the Celite 400 type diatomite of Hamburg and 30 % by weight are from the diatomaceous mixture production of Diatomite 1 type of Mineral Resources Co..The composition of substantial activity component is constant, but (deviation＜5% is relative except the relevant fluctuation of slight technique; SO 4＜9% is relative).
The shown significantly improved mechanical performance of the catalyst of producing according to embodiment 4,5 and 7 and the combination of similar in the whole temperature range that detects or the catalytic activity that improves show the superiority of catalyst of the present invention.
Figure BDA00002386891100121

Claims (7)

1. one kind is used for SO 2Be oxidized to SO 3Catalyst, comprise to put on to comprise and contain vanadium active material, alkali metal compound and sulfate on the naturally occurring diatomaceous carrier, wherein said carrier comprises at least a softer naturally occurring not calcined diatomite, and the latter is at its D that measures in granulometry according to dry method 50Compare with wet method on the value and have at least 35% percentage and reduce.
2. according to claim 1 catalyst, wherein said carrier comprises at least a harder naturally occurring not calcined diatomite, and the latter is at its D that measures in granulometry according to dry method 50Comparing the percentage that has less than 35% with wet method on the value reduces.
3. according to claim 1 and 2 catalyst, wherein softer diatomite is the 10-42 % by weight based on the ratio of described carrier gross mass.
4. a production is used for SO 2Be oxidized to SO 3The method of catalyst, the carrier that wherein will comprise at least a softer naturally occurring not calcined diatomite mixes with a kind of solution or suspension that comprises vanadium, alkali metal compound and sulfate, and wherein said not calcined diatomite is at its D that measures in granulometry according to dry method 50Compare with wet method on the value and have at least 35% percentage and reduce.
5. according to claim 4 method, wherein said carrier comprises at least a harder naturally occurring not calcined diatomite, and the latter is at its D that measures in granulometry according to dry method 50Comparing the percentage that has less than 35% with wet method on the value reduces.
In the use according to claim 1-3 each catalyst with SO 2Be oxidized to SO 3Method.
7. according to claim 6 method wherein makes to comprise oxygen and sulfur dioxide SO 2Admixture of gas under the temperature of 340-680 ° of C, contact with described catalyst.
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