CN102008953A - Manganese dioxide catalyst - Google Patents
Manganese dioxide catalyst Download PDFInfo
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- CN102008953A CN102008953A CN2010102089929A CN201010208992A CN102008953A CN 102008953 A CN102008953 A CN 102008953A CN 2010102089929 A CN2010102089929 A CN 2010102089929A CN 201010208992 A CN201010208992 A CN 201010208992A CN 102008953 A CN102008953 A CN 102008953A
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- catalyst
- manganese dioxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 21
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 20
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 6
- 150000004678 hydrides Chemical class 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000011572 manganese Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003205 fragrance Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012695 Ce precursor Substances 0.000 claims description 2
- 239000012691 Cu precursor Substances 0.000 claims description 2
- 239000012692 Fe precursor Substances 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical group [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 5
- 239000012855 volatile organic compound Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KTZSFYNCPSAEKK-UHFFFAOYSA-N CP(C)(C)C Chemical compound CP(C)(C)C KTZSFYNCPSAEKK-UHFFFAOYSA-N 0.000 description 2
- 229910017566 Cu-Mn Inorganic materials 0.000 description 2
- 229910017871 Cu—Mn Inorganic materials 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- RWACICCRNCPMDT-UHFFFAOYSA-N cerium sulfuric acid Chemical compound [Ce].S(O)(O)(=O)=O RWACICCRNCPMDT-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01D53/46—Removing components of defined structure
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/08—Heat treatment
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- Chemical Kinetics & Catalysis (AREA)
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- Environmental & Geological Engineering (AREA)
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Abstract
The present invention relates to a method for preparing a catalyst which is impregnated with oxide particles of more than one metal selected from a group consisting of Ag, Ce, Co, Cr, Cu and Fe in mesoporous manganese dioxide that has a BET specific surface area larger than 180m<2>/g and an average airhole diameter within 4-10nm. The catalyst of the invention can effectively remove ozone and carbon monoxide in the presence of moisture at a low temperature which is lower than -20 DEG C., and can effectively remove hydride gas, nitrogen oxide and volatile organic compound.
Description
Technical field
The present invention relates to a kind of is 180m in the BET specific area
2Contain in the mesopore manganese dioxide that/g is above, average pore diameter is 4～10nm and be soaked with more than one the manufacture method of catalyst of metal oxide particle that is selected from the group that constitutes by Ag, Ce, Co, Cr, Cu and Fe.
In more detail, relate to a kind of manufacture method of catalyst, described catalyst is the manganese dioxide (MnO that makes in the mode with high specific area and mesopore (mesoporous)
2) high-dispersion load is selected from more than one metal oxide composition of the group that is made of Ag, Ce, Co, Cr, Cu and Fe in the particle, so that the effect of performance co-catalyst and oxygen supply, and add the K composition and increase catalyst catalyst activity, the structure physical properties excellent.
Background technology
Long term exposure is under the situation of ozone or carbon monoxide in confined space, and people's cognition is subjected to fatal harm.Therefore, need under atmospheric temperature, also effectively to remove the catalyst of these ozone or carbon monoxide.But, as the catalyst component of removing ozone and carbon monoxide at normal temperatures, noble metal (Au, Pt) and Ce-Mn[Appl.Catal.A are arranged, 142 (1996) 279], Cu-Mn[Appl.Catal.A, 302 (2006) 257], Fe-Mn (J Mol.Catal.A, 280 (2008) 43].But under the situation of using noble metal,, cause economy to reduce (Catal.Today, 144 (2009) 292) owing to need the above gold of load 1wt% (every kg load 10g).
Using under the situation of noble metal, there are the following problems: because of price expensive and universal limited, though and the removal efficient height of carbon monoxide at high temperature, efficient can reduce at low temperatures, can not long term maintenance remove efficient.Compare with Cu (Fe)-Mn, (the BET specific area is 50m to the natural manganese dioxide ore
2/ g is following) only utilize and synthesize MnO
2The time its performance of removing ozone or carbon monoxide low, have only among the Mn and add the removal efficient that Cu (Fe) just can improve ozone and carbon monoxide with adequate rate.In addition, owing to be difficult to synthetic bulk MnO
2(bulk MnO
2), so sometimes at Al
2O
3, SiO
2, TiO
2, impregnation Mn composition and make [Chemical PhysicsLetters, 408 (2005) 377] in the zeolite (zeolite), active carbon, but compare and can not effectively remove with bulk Cu (Fe)-Mn catalyst.In addition, the trial [Catal.Today, 119 (2007) 321, Fuel, 87 (2008) 1177] of bulk Cu (the Fe)-Mn that makes high specific area is arranged], but can not manufacture 180m
2The specific area that/g is above, it is not high to remove efficient yet.In addition, there is following shortcoming in bulk Cu (Fe)-Mn catalyst: when moisture was arranged, performance sharply reduced.Industrially be set up in parallel two reactors, make during the catalyst reaction of a reactor, the catalyst that makes another reactor is dry and remove moisture.
Therefore, not only as industrial but also in order to be widely used in multiple application, need be when moisture be arranged also long term maintenance remove the catalyst of efficient.In addition, make under the further situation about increasing of oxidizing force, removal [Appl.Catal.B, 51 (2004) 93] performance of removing stench and VOC is improved, can replace the high noble metal catalyst of price.
In addition, the titanium dioxide manganese catalyst is used for removing the hydride gas (AsH that semiconductor spreads, ion injects, the CVD operation is discharged
3, PH
3, SiH
2Cl
2, SiH
4) and TEOS (tetraethyl orthosilicate; tetraethylorthosilicate), TMB (tetramethyl borine; tetramethylborane), TMP (tetramethyl phosphine; tetramethylphosphine) etc. (United States Patent (USP) 4578256,4910001); when the gentle pore volume in pore footpath is little; can stop up pore according to the such As that reaction produced of following formula, Si metallic particles, thereby finish its life-span.
AsH
3→As+3/2H
2
PH
3→P+3/2H
2
SiH
2Cl
2→Si+H
2+Cl
2
SiH
4→Si+2H
2
Titanium dioxide manganese catalyst [Appl.Catal.B, 62 (2006) 311] can be used in NH
3Spray in the low temperature removal of carrying out in nitrogen oxide, but need high specific area.
Summary of the invention
In the transition metal, the oxidizing force excellence of Mn, but be difficult to manufacture porous bulk oxide, be dipped in as Al so also contain
2O
3, SiO
2, TiO
2, use behind the such carrier of zeolite (zeolite), but activity of such catalysts is relatively low.
Even manufacture porous Mn bulk oxide, the surface of Mn can continue reduction when also can make ozone and carbon monoxide oxidation, therefore must Cu (Fe) is oxide carried in the Mn oxide, make its performance oxygen supply effect, and suppress the reduction of Mn in the reaction.
In addition, under the situation of Cu oxide, having pointed out is having the problem that activity of such catalysts reduces under the situation of moisture.
Therefore, the present invention desires to provide the catalyst with high-specific surface area and mesopore in order to solve aforesaid problem.For this reason, its purpose is, by MnO is provided
2New manufacture method, make metallic particles such as Cu with nanometer state high-dispersion load in above-mentioned MnO
2, existing with physical mixed state and to compare with multiple oxide, Cu, Mn, K are interact with each other, and catalyst and manufacture method thereof with new electromagnetism, chemical rerum natura are provided.
As mentioned above, the present invention's mixing KMnO
4The aqueous solution and Mn (CH
3COO)
2The aqueous solution, synthetic MnO with high-specific surface area and mesopore
2After, impregnation is selected from more than one metal oxide of the group that is made of Ag, Ce, Co, Ar, Cu and Fe, fires then, and the oxide high-dispersion load in manganese dioxide, and is not added the K composition in addition, makes KMnO
4K make an addition to catalyst system and make, thereby can in the low temperature more than-20 ℃, have under the condition of moisture, also effectively remove ozone and carbon monoxide, simultaneously, more effectively remove hydride gas, carbon monoxide, ozone, nitrogen oxide, VOC etc.
Description of drawings
Fig. 1: be the figure that the X-ray diffraction analysis result of catalyst is shown.
Fig. 2 and Fig. 3: be the figure that the carbon monoxide removal experimental result is shown.
The specific embodiment
The invention provides a kind of is 180m in the BET specific area
2Contain in above mesopore (mesopore) manganese dioxide of/g and be soaked with more than one the catalyst of metal oxide particle that is selected from the group that constitutes by Ag, Ce, Co, Cr, Cu and Fe.
In the catalyst of the present invention, for example, the BET specific area is 210～320m
2/ g more specifically is 220～290m
2/ g.In addition, average pore diameter is specially 5～8nm, and for example, the pore volume is 0.2～0.6cm
3/ g more specifically is 0.3～0.5cm
3/ g.
In the catalyst of the present invention, for example, the size of the metal oxide particle of impregnation is below the 3nm in the manganese dioxide.
In the catalyst of the present invention, to consider from the impurity removal efficacy aspect, the mol ratio of manganese dioxide and metal oxide is preferably 6: 4～and 9: 1, but impurity and removal condition that above-mentioned mol ratio is removed according to desire can change arbitrarily.
The present invention also provides a kind of manufacture method of catalyst, and it comprises the steps:
(a) making the BET specific area is 180m
2/ g is above, average pore diameter is the mesopore manganese dioxide of 4～10nm; With
(b) more than one the metal precursor that is selected from the group that is made of Ag, Ce, Co, Cr, Cu and Fe is contacted with above-mentioned manganese dioxide.
In the manufacture method of catalyst of the present invention, mesopore manganese dioxide is preferably and mixes KMnO
4The aqueous solution and Mn (CH
3COO)
2The aqueous solution and making, wherein, KMnO
4Solution: Mn (CH
3COO)
2The mol ratio of solution is 1: 3～1: 1, more specifically is about 2: 3.
Not with the above-mentioned KMnO of above-mentioned mixed in molar ratio
4Solution and Mn (CH
3COO)
2During solution, excessive Mn
+Ion should be removed in the wastewater treatment operation.
2KMnO
4+3Mn(CHCOO)
2＝5MnO
2+2CH
3COOK+4CH
3COOH
Make under the situation of manganese dioxide with aforesaid precursor and condition, unlike previous technologies, can make the specific area with manganese dioxide is 200m
2/ g is above, be specially 250m
2/ g is above, more specifically be 300m
2The mesopore manganese dioxide of the high-specific surface area that/g is above.
Simultaneously, the invention provides a kind of manufacture method, described manufacture method was added solution such as Ag, Ce, Cr, Cu, Fe and is stirred and heat before making the precipitation stabilisation of Mn oxide, metals such as Cu and K oxide are contained be dipped in the Mn oxide, so that it has interaction.
The precursor of above-mentioned metal is not subjected to special qualification, but temperature is when surpassing 500 ℃, MnO
2Become mutually and remove inefficient Mn
2O
3, be not preferred therefore in the use that surpasses the metal precursor of phase transformation under 500 ℃ the temperature.
Specifically, the Cu precursor uses copper acetate [Cu (CH
3COO)
2H
2O] or copper nitrate [Cu (NO
3)
23H
2O] in any is all harmless.Use copper sulphate (CuSO
45H
2O) under the situation, at high temperature become CuO mutually, so MnO
2Specific area reduce, the oxysulfide that sintering procedure produced significantly corrodes baking furnace, and is therefore not preferred.
When replaced C u and impregnation Ag, Ce, Co, Cr or Fe,, specifically can use silver nitrate (AgNO as the Ag precursor
3); As the Ce precursor, can use cerium acetate [Ce (C
2H
3O
2)
31.5H
2O]; As the Co precursor, can use cobalt nitrate [Co (NO
3)
26H
2O], cobalt acetate [Co (CH
3COO)
24H
2O]; As the Cr precursor, can use chromic nitrate [Cr (NO
3)
39H
2O]; As the Fe precursor, can use ferric nitrate [Fe (NO
3)
39H
2O].Because with the above-mentioned copper sulphate (CuSO of use
45H
2O) reason that situation is identical, also preferably sulfuric acid cerium [Ce (SO not
4)
24H
2O], ferric sulfate [Fe
2(SO
4)
35H
2O].When Ag was carried out impregnation, (1.2g/100ml) was low for the solubility of silver sulfate, is difficult to impregnation, had been oxidized to AgO more than 600 ℃, and the sulfur oxide corrosion baking furnace that is produced when firing is therefore not preferred.
Simultaneously, the invention provides a kind of method, after described method water cleans the compound of sedimentation, carry out drying so that only remaining 20～35 weight % of water manufacture coarse grain then, perhaps adding binding agent and extrusion molding is pelletizing (pellet).
The K precursor is not added in addition, produces the K oxide in stabilization step.But, the K that 5wt% is above
+Ion plays a part to make catalyst poisoning, therefore must fully clean.
In addition, in the manufacture method of catalyst of the present invention, after the above-mentioned steps (b), can also comprise step of heat treatment, and the coarse grain made or pelletizing are made air circulation and heat-treat under 150～500 ℃ temperature, make residual CH
3COOH and CH
3The COOK oxidation, the pollutant of removal catalyst surface.
When under the temperature below 150 ℃, heat-treating, CH
3Not oxidation of COOK, when heat-treating under the temperature more than 500 ℃, amorphous Cu oxide is by crystallization, it is big that granular size becomes, thus from the Mn divided oxide from, activity of such catalysts is sharply reduced.
The invention provides a kind of removal method of polluter, it comprises the steps: to make catalyst of the present invention to contact with the polluter that is selected from the group that is made of hydride gas, odorant, ozone, carbon monoxide, nitrogen oxide and VOC.
In the removal method of above-mentioned polluter, above-mentioned contact procedure can be carried out under the temperature of (for example, more than 0 ℃ or normal temperature) more than-20 ℃.That is, the catalyst according to invention also has excellent effect under the quite low temperature conditions that is not hot conditions.In addition, as record in the following embodiments like that, be below the 5vol%, be specially the effect that also shows excellence under the condition below the 3vol% at moisture.
Below, by according to embodiments of the invention with not according to comparative example of the present invention, be described in more detail the present invention, but scope of the present invention is not limited to embodiment as described below.
The manufacturing of embodiment 1.K-Cu-Mn catalyst
10, the KMnO of dissolving 710g in the ion exchange water of 595g
4(SILVER REAGENT, SAMCHUM chemical) (solution 1.).4, dissolve 1 in the ion exchange water of 493g, the Mn (CH of 652g
3COO)
24H
2O (SILVER REAGENT, Junsei) (solution 2.).1. little by little drop into solution at solution and stir (solution 3.) in 2..8, the Cu (CH of dissolving 561g in the ion exchange water of 410g
3COO)
2H
2O (SILVER REAGENT, Junsei) (solution 4.).4. agitating solution little by little drops into solution 3. the time.After 6 hours, use 30, the water of 000g cleans, and carries out drying then so that the only remaining 30wt% of water.In agitator (R02, Eirich), drop into cataloid AS-40 (the W.R.Grace ﹠amp of 150g; Co) after, stirred 30 minutes with the rotating speed of 25rpm.With its extrusion molding in extrusion shaping machine (Vanho) is the pelletizing of 3mm.To the pelletizing that generates 120 ℃ following 2 hours, 280 ℃ extraneous air was flowed in following 4 hours and circulation in heat-treat.
The catalyst of above-mentioned manufacturing is carried out X-ray diffraction analysis (DMAX2500H, Rigaku, CuK α, 20kV, 15A, 0.1 °/min), it the results are shown in Fig. 1.
As shown in Figure 1, although with 8: 2 MnO
2: CuO or MnO
2: Fe
2O
3The ratio of theoretical molar ratio makes Cu or Fe oxide carried in MnO
2The surface, but only detect unbodied γ-MnO
2The peak of (ICSD 78331) does not detect the relevant peaks of Cu or Fe.As can be known this be because the oxide of Cu or Fe be with as the mode high-dispersion load below the 3nm of the minimum detection size of X-ray diffraction analysis in MnO
2The surface.The K composition is also undetected, thereby K also is a high-dispersion load as can be known.
The manufacturing of embodiment 2.K-Fe-Mn catalyst
Except corresponding with the solution manufacture process 4. of embodiment 1 " 2, dissolves 1 in the ion exchange water of 000g, the Fe (NO of 159g
3)
39H
2The step of O (SILVER REAGENT, Junsei) " in addition, other are made in an identical manner.
To sample according to present embodiment, carry out X-ray diffraction analysis in the same manner with embodiment 1, it the results are shown in Fig. 1.
The manufacturing of embodiment 3.K-Ce-Mn catalyst
Except corresponding with the solution manufacture process 4. of embodiment 1 " 2, dissolved [Ce (the C of 440g in the ion exchange water of 500g
2H
3O
2)
31.5H
2O] step of (SILVER REAGENT, Junsei) " in addition, other are made in an identical manner.
Comparative example 1.
3. little by little drop into 4. step of solution [impregnation Cu (CH not the time except the step of omitting solution manufacturing 4. among the embodiment 1 and agitating solution
3COO)
2H
2O] in addition, experience the sample that identical process is made comparative example 1.
Comparative example 2.
When agitating solution little by little drops into 4. process of solution 3. the time in embodiment 1 and KOH (SILVER REAGENT, Junsei) pH of solution is adjusted into 7.0 when together dropping into, experience the sample that identical process is made comparative example 2.
Experimental example 1.BET analyzes
To the sample of embodiment 1,2 and comparative example 1,2, carry out BET and analyze (ASAP2020M, Micromeritics), it the results are shown in following table 1.
The porosity that table 1. is analyzed according to BET
| Project | Specific area (m 2/g) | Average pore diameter (nm) | Pore volume (cm 3/g) |
| Embodiment 1 | 245 | 6.7 | 0.38 |
| Embodiment 2 | 239 | 6.9 | 0.37 |
| Comparative example 1 | 313 | 5.5 | 0.44 |
| Comparative example 2 | 221 | 7.2 | 0.35 |
From the result of above-mentioned table 1, MnO as can be known
2When (comparative example 1) middle loaded Cu (embodiment 1) or Fe (embodiment 2), the gentle pore volume of specific area reduces.
Experimental example 2. drying conditions are measured carbon monoxide removal efficient down
In order to measure carbon monoxide removal efficient, be 3 at CO, 000ppmv (using CO, the Air Korea of 5vol%), H
2O is that 0vol%, pelletizing catalyst are that 50g, total flow are 16,000cm
3/ min, weight space velocity are 16,000h
-1, temperature is to experimentize under 25 ℃ the condition, measures the concentration of CO with CO analyzer (7500CO IR Analyzer, Teledyne).Its experiment the results are shown in Fig. 2.
From the result of Fig. 2, MnO as can be known
2When (comparative example 1) middle loaded Cu (embodiment 1) or Fe (embodiment 2), the gentle pore volume of specific area reduces, but carbon monoxide removal efficient significantly increases.But, shown in comparative example 2, when making the CuO precipitation when injecting the KOH as precipitating reagent, under drying condition, to compare with comparative example 1, carbon monoxide removal efficient significantly increases.
Experimental example 2. wet conditions are measured carbon monoxide removal efficient down
Except constituting the H of 2.5vol%
2Beyond the O, under the condition identical, experimentize with experimental example 1.Its experiment the results are shown in Fig. 3.
From the result of Fig. 3, MnO as can be known
2When (comparative example 1) middle loaded Cu (embodiment 1) or Fe (embodiment 2), carbon monoxide removal efficient significantly increases.In addition, shown in comparative example 2, when injection makes the CuO precipitation as the KOH of precipitating reagent the time, under the condition of humidity, compare with comparative example 1, carbon monoxide removal efficient increases, and to show ozone removal efficient under the situation of its high-dispersion load very high but make by impregnation manufactured (embodiment 1).
Experimental example 3. is measured ozone and is removed efficient
Remove efficient in order to measure ozone, at O
3Be 130ppmv (using ozone generator, LabTech), H
2O is that 2.5vol%, pelletizing catalyst are that 50g, total flow are 19,000cm
3/ min, weight space velocity are 19,000h
-1, temperature is to experimentize under 25 ℃ the condition, uses O
3Analyzer (UV-100, Eco Sensors) is measured O
3Concentration.Its experiment the results are shown in following table 2.
Table 2. ozone conversion ratio
From the result of table 2, MnO as can be known
2When (comparative example 1) middle loaded Cu (embodiment 1) or Fe (embodiment 2) or Ce (embodiment 3), ozone is removed efficient significantly to be increased.In addition, shown in comparative example 2, make under the situation of CuO precipitation when injecting the KOH as precipitating reagent, with comparative example 1 relatively the time, ozone is removed efficient to be increased, but utilizes impregnation manufactured (embodiment 1) and make and show ozone under the situation of its high-dispersion load to remove efficient very high.
Claims (10)
1. the manufacture method of a catalyst, it comprises the steps:
(a) making the BET specific area is 180m
2/ g is above, average pore diameter is the mesopore manganese dioxide of 4～10nm; With
(b) more than one the metal precursor that is selected from the group that is made of Ag, Ce, Co, Cr, Cu and Fe is contacted with described manganese dioxide.
2. the manufacture method of catalyst as claimed in claim 1 is characterized in that, mesopore manganese dioxide is to mix KMnO
4The aqueous solution and Mn (CH
3COO)
2The aqueous solution is made.
3. the manufacture method of catalyst as claimed in claim 1 is characterized in that, the phase transition temperature of metal precursor is below 500 ℃.
4. the manufacture method of catalyst as claimed in claim 1 is characterized in that,
The silver precursor is a silver nitrate;
The cerium precursor is a cerous acetate;
Cobalt precursors is cobalt nitrate or cobalt acetate;
The chromium precursor is a chromic nitrate;
Copper precursors is copper acetate or copper nitrate;
The iron precursor is a ferric nitrate.
5. the manufacture method of catalyst as claimed in claim 1 is characterized in that, after step (b), also comprises step of heat treatment.
6. the manufacture method of catalyst as claimed in claim 5 is characterized in that, heat treatment is carried out under 150 ℃～500 ℃.
7. the removal method of a polluter, it comprises the steps: to make the catalyst that utilizes the described method manufacturing of claim 1 to contact with the polluter that is selected from the group that is made of hydride gas, odorant, ozone, carbon monoxide, nitrogen oxide and VOC.
8. the removal method of polluter as claimed in claim 7 is characterized in that, described contact procedure is to carry out under the temperature more than-20 ℃.
9. catalyst, wherein, described catalyst is to be 180m in the BET specific area
2More than one the metal precursor that impregnation is selected from the group that is made of Ag, Ce, Co, Cr, Cu and Fe in the above mesopore manganese dioxide of/g obtains.
10. the removal method of a polluter, it comprises the steps: to make the described catalyst of claim 9 to contact with the polluter that is selected from the group that is made of hydride gas, odorant, ozone, carbon monoxide, nitrogen oxide and VOC.
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|---|---|---|---|
| KR10-2009-0084316 | 2009-09-08 | ||
| KR1020090084316A KR101008350B1 (en) | 2009-09-08 | 2009-09-08 | Manganese dioxide catalyst |
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| JPH0957107A (en) * | 1995-08-18 | 1997-03-04 | Sakai Chem Ind Co Ltd | Nitrogen oxide oxidizing catalyst |
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-
2009
- 2009-09-08 KR KR1020090084316A patent/KR101008350B1/en not_active IP Right Cessation
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