EP2558197A1 - Catalyseur d'oxydation de so2 en so3 - Google Patents
Catalyseur d'oxydation de so2 en so3Info
- 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- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 230000003647 oxidation Effects 0.000 title claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 118
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000005909 Kieselgur Substances 0.000 claims abstract description 55
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 8
- 239000013543 active substance Substances 0.000 claims abstract description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 20
- 230000007423 decrease Effects 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 19
- 230000009467 reduction Effects 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 239000011148 porous material Substances 0.000 description 31
- 229910052906 cristobalite Inorganic materials 0.000 description 21
- 229910052681 coesite Inorganic materials 0.000 description 18
- 229910052682 stishovite Inorganic materials 0.000 description 18
- 229910052905 tridymite Inorganic materials 0.000 description 18
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 14
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 description 11
- 239000011707 mineral Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- -1 alkali metal vanadates Chemical class 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000814619 Aulacoseira granulata Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000256856 Vespidae Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
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EP11768535.4A EP2558197A4 (fr) | 2010-04-12 | 2011-04-12 | Catalyseur d'oxydation de so2 en so3 |
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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 |
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EP (1) | EP2558197A4 (fr) |
JP (1) | JP5833630B2 (fr) |
KR (1) | KR20130097071A (fr) |
CN (1) | CN102892501B (fr) |
BR (1) | BR112012026246A2 (fr) |
CL (1) | CL2012002875A1 (fr) |
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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 |
Citations (2)
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DE4000609A1 (de) * | 1990-01-11 | 1991-07-18 | Basf Ag | Katalysator fuer die oxidation von schwefeldioxid zu schwefeltrioxid |
CN1417110A (zh) * | 2002-12-11 | 2003-05-14 | 南化集团研究院 | 一种硫酸生产用钒催化剂的活性相的制备方法 |
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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 |
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 |
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 |
-
2011
- 2011-04-12 WO PCT/IB2011/051553 patent/WO2011128830A1/fr active Application Filing
- 2011-04-12 KR KR1020127029480A patent/KR20130097071A/ko not_active Application Discontinuation
- 2011-04-12 EP EP11768535.4A patent/EP2558197A4/fr not_active Withdrawn
- 2011-04-12 CN CN201180023521.3A patent/CN102892501B/zh not_active Expired - Fee Related
- 2011-04-12 JP JP2013504376A patent/JP5833630B2/ja not_active Expired - Fee Related
- 2011-04-12 BR BR112012026246A patent/BR112012026246A2/pt not_active IP Right Cessation
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4000609A1 (de) * | 1990-01-11 | 1991-07-18 | Basf Ag | Katalysator fuer die oxidation von schwefeldioxid zu schwefeltrioxid |
CN1417110A (zh) * | 2002-12-11 | 2003-05-14 | 南化集团研究院 | 一种硫酸生产用钒催化剂的活性相的制备方法 |
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See also references of WO2011128830A1 * |
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CN102892501A (zh) | 2013-01-23 |
JP5833630B2 (ja) | 2015-12-16 |
JP2013523447A (ja) | 2013-06-17 |
CN102892501B (zh) | 2015-04-08 |
KR20130097071A (ko) | 2013-09-02 |
WO2011128830A1 (fr) | 2011-10-20 |
CL2012002875A1 (es) | 2012-12-14 |
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