CN100389873C - Load type gold catalyst with stabilized catalyzing performance and its preparation process - Google Patents
Load type gold catalyst with stabilized catalyzing performance and its preparation process Download PDFInfo
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- CN100389873C CN100389873C CNB2004100245096A CN200410024509A CN100389873C CN 100389873 C CN100389873 C CN 100389873C CN B2004100245096 A CNB2004100245096 A CN B2004100245096A CN 200410024509 A CN200410024509 A CN 200410024509A CN 100389873 C CN100389873 C CN 100389873C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000010931 gold Substances 0.000 title claims abstract description 60
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 43
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 101150089916 Miox gene Proteins 0.000 claims abstract description 11
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000001802 infusion Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910052596 spinel Inorganic materials 0.000 abstract description 2
- 239000011029 spinel Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000029058 respiratory gaseous exchange Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 210000000481 breast Anatomy 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000003434 inspiratory effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910002710 Au-Pd Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 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
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
-
- 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
- B01J23/005—Spinels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The present invention relates to a load type gold catalyst with stable catalytic performance, and a preparation method thereof. The load type gold catalyst takes Au as an active constituent, and Al2O3 and TiO2/Al2O3 that are modified by MIOx and MIIOx as carriers, wherein the atomic ratio of Au to (MI+MII) is 1.0:1.0 to 1.0:10, the atomic ratio of MI to MII is 2.0:1.0 to 0.2:1.0, and the atomic ratio of Au and Al is 1.0:1.0*103 to 1.0:10. The load type gold catalyst has the substantive feature that the strong interaction between gold nanoparticles on the surface of the catalyst and transition metal oxide with a spinel structure, and an alloy structure formed by transitional metal and part of the gold nanoparticles jointly stabilize both structure and catalytic activity of the load type nano-gold catalyst during long-term use and storage.
Description
Technical field
The present invention relates to a kind of Au catalyst, specifically, tie up under environment temperature, the ambient humidity that trace (0.1%～1.0%) CO becomes CO in the catalytic oxidation air
2, the stable and pressure of catalytic performance falls and satisfies load type gold catalyst breathing mask and air cleaning requirement, the tool industrial applicibility and its preparation method.
Background technology
At present, the breathing mask of China is used the Hopcalite catalyst more, and it is to be composite oxide catalysts (Lamb, A.B., Bray, W.C, Frazer, the J.C.W. of Main Ingredients and Appearance with CuO-MnOx; INd. Eng.Chem., 1920,12,213), be used breathing mask catalyst material just in the World War I.Its fatal shortcoming is that water-resistance is poor, therefore " oxidation tank " preceding must to add a volume bigger, " drying chamber " that weight is heavier.Load type gold catalyst can be eliminated CO (An Lidun, Qi Shixue, Zou Xuhua, rope palm bosom under environment temperature (10 ℃～40 ℃) and ambient humidity; Practical low-temperature CO oxidizing catalyst; Chinese invention patent ZL 00 1 22829.3), be applied to breathing mask and can remove the preceding drying chamber of catalyst from.But the stability of load type gold catalyst is one of key factor that influences its commercial Application.The TEM photo shows, decaying catalyst Au/TiO
2Gold grain obviously greater than fresh Au/TiO
2Gold grain.The calculating of Wronski shows, (fusing point particularly＜10nm) has obvious reduction than the reguline metal to nanogold particle, for example, the fusing point of Φ 3nm gold grain is near 850K (Huettig Temperature～10 ℃), promptly use and storage process in growing up of gold grain be one of major reason of this class catalysqt deactivation.Other reason of inactivation may also have generation (the Kim Chang Hwan ﹠amp of catalyst surface carbonate; Thompson L T; " Gold 2003 "), water is to the negative effect (Wang Gui-ying, etal. chemistry journal 58,1557-1562,2000) of catalyst stability, and Yi Yujin forms the ion of complex (as Cl
-, CN
-Ion) poisoning.
Some stabilisation measure of load type gold catalyst is advised and is tested, and for example, adopts generation (the G C Bond of acid carrier to prevent catalyst surface carbonate; D T Thompson, Catal.Rev.-Sci.Eng., 41,319-388,1999), add other oxides additive or generate alloy and in use and storage process, grow up to stop gold grain with other transition metal, for example, Au/TiO
2-CeO
2(PetrovL A, 1998), Au/ZrO
2-CeO
2(Plzak, V, WO 03/068389 A1,21 Aug 2003), Au/Fe
2O
3(or MnOx)-MgO/Al
2O
3(Grisel, R, et al., Catalysis Today, 72,123-132,2002) and Au-Pd/support (DEGUSA AG, 2001), Au-PGMs/ZrO
2-CeO
2(MarecotP, 1999), or employing does not contain Cl
-The metallic compound presoma of ion.Holger Falke, et al. (USP5068217, Nov 26 1991) once uses Fe
2O
3/ Al
2O
3Composite oxide carrier is prepared highly active load type gold catalyst.Grisel, R J H et al. (Catalysis Today, 64,69-81,2001) also find, add MOx (M=Cr, Mn, Fe, Co, Ni, Cu and Zn) to Au/Al
2O
3In can improve the heat endurance of little gold grain on the carrier.This scheme all is to add the single oxide auxiliary agent, tests without long-time stability.
Usually the CO that will eliminate low concentration in the air that runs into, for example gas mask, indoor (workshop, spacecraft, submarine, room, shop etc.) air cleaning etc. must be carried out under environment temperature and humidity.This just requires catalyst not only high low temperature active will be arranged, and enough good stability will be arranged in relative humidity under near 100% situation.Authorize (An Lidun, Qi Shixue, Zou Xuhua, rope palm bosom; Practical low-temperature CO oxidizing catalyst; ZL 00 1 22829.3) and carry out patent (An Lidun, Qi Shixue, Zou Xuhua, the rope palm bosom of substantive examination; The load type nano gold catalyst that is used for the CO low-temperature catalytic oxidation; PCT international application no: PCT/CN01/01582; International filing date: November 23 calendar year 2001) the patent catalyst of inscribing can in storing year, keep high catalytic activity, its activity just reduces gradually later on, until not satisfying instructions for use, promptly the extended storage stability of catalyst still has some deficits.
Summary of the invention
The objective of the invention is to seek a kind of environment temperature (10 ℃～50 ℃) and ambient humidity (relative humidity 60%～100%) down catalytic reaction activity height, stable performance, pressure fall satisfy breathing mask and the practical catalyst that requires of air cleaning with and preparation method thereof.Be called stable load type gold catalyst of catalytic performance and preparation method thereof.
Technical scheme: the load type gold catalyst that a kind of catalytic performance is stable is characterized in that: active component is Au, and carrier is the Al that MIOx and MIIOx modify
2O
3Or the TiO of MIOx and MIIOx modification
2/ Al
2O
3, Au and atomic ratio (MI+MII) they are 1.0: 1.0～1.0: 10, the atomic ratio of MI and MII is 2.0: 1.0～0.2: 1.0; The atomic ratio of Au and Al is 1.0: 1.0 * 10
3～1.0: 10;
Wherein MI is Cu, and MII is Fe or Co or Ni.Carrier can be the moulding oxide carrier.
Carrier is to adopt dipping method or coprecipitation method preparation, Al
2O
3Or TiO
2/ Al
2O
3Load MIOx, behind the MIIOx, through 800 ℃-1000 ℃ roasting, to generate spinelle or perovskite structure, catalyst precarsor is behind hydrogen reducing, and the part A u and the MIOx of easily reduction generate alloy A uMI.
The preparation method of the load type gold catalyst that catalytic performance is stable is: the deposition-precipitation method or anion infusion process are adopted in the load of Au; Wherein, deposition-the precipitation method are in the active component precursor solution of 350K for the oxide carrier with high-specific surface area of moulding is in advance inserted the control temperature after vacuum drying treatment, in continuous stirring, dropwise add aqueous slkali, control pH value of solution value is 4.5～8.5 under constant temperature, until precipitation fully, get finished catalyst through sedimentation, filtration, washing, drying, roasting or activation processing;
Said aqueous slkali is Na
2CO
3Or K
2CO
3Or the solution of NaOH or KOH.
The Al that the present invention adopts composite oxides to modify
2O
3Or TiO
2Be carrier, the preparation load type nano gold catalyst, its substantive distinguishing features is: between the nanogold particle of catalyst surface and the spinel structure transition metal oxide strong interaction, and part gold grain and transition metal form alloy structure, thus stablized load type nano gold catalyst long-term use and storage process in structure and the stability of catalytic activity.
Compared with the prior art, the substantive distinguishing features that also has of the present invention is: 1. have good CO catalytic oxidation under low temperature and become CO
2Catalytic activity; 2. have the performance that good anti-water vapour is poisoned, activity stabilized under relative humidity≤100% (23 ℃) situation, can save drying chamber before the beds.3. have good anti-long term storage performance, long-term (several years) sealed storage under the room temperature, catalyst catalytic performance is constant.4. bed layer pressure is fallen and is met the practical requirement of breathing mask.5. has good sulfur poisoning-resistant ability.
The specific embodiment
It below is detailed description of the present invention.
Activity of such catalysts component of the present invention is a gold, and carrier is MIOx, the Al that MIIOx modifies
2O
3, TiO
2/ SiO
2Or TiO
2/ Al
2O
3
The precursor compound of above-mentioned active component gold can be metallic gold (silk, bar, piece), gold chloride (HAuCl
4H
2O), gold trichloride (AuCl
3) etc.
The precursor compound of carrier can be nitrate, sulfate, acetate, chloride or the metal alkoxide etc. of corresponding oxide, or in type oxide.The transition metal oxide MIOx that modifies, the predecessor of MIIOx can be nitrate, sulfate, acetate, the chloride of corresponding oxide, and wherein MI is Cu, and MII is Fe, or Co, or Ni.
Catalyst system therefor of the present invention is with Al
2O
3When being carrier, the atomic ratio of Au and Al etc. is 1.0: 1.0 * 10
3～1.0: 10.Au and atomic ratio (MI+MII) are 1.0: 1.0～1.0: 10, and the atomic ratio of MI and MII is 2.0: 1.0～0.2: 1.0,
The preparation method of catalyst system therefor carrier of the present invention can be a coprecipitation, infusion process.
The coprecipitation preparation process of catalyst carrier can be: the salting liquid of an amount of MI and MII metal salt solution and carrier metal is added drop-wise to Na in stirring
2CO
3(or K
2CO
3) in the solution, through leave standstill, separation, roasting, activation processing promptly get required catalyst carrier.
The immersion process for preparing process of catalyst carrier can be: use the carrier of moulding (as Al an amount of MI and MII metal salt solution
2O
3) dipping, leave standstill at least 1h after, drying, roasting get composite oxide carrier.
Deposition-the precipitation method or anion infusion process are adopted in the load of nm of gold.
The deposition of catalyst-precipitation method preparation process can be: the oxide carrier with high-specific surface area of moulding is in advance inserted after vacuum drying treatment in the active component precursor solution of controlling under the temperature (for example 350K), dropwise add aqueous slkali (as Na in continuous stirring
2CO
3, K
2CO
3, NaOH, KOH etc.), control pH value of solution value is 4.5～8.5 under constant temperature, until precipitation fully, gets finished catalyst through sedimentation, filtration, washing, drying, roasting or activation processing.
The anion infusion process loading process of nm of gold adopts applicant laboratory patented technology (An Lidun, Qi Shixue, rope palm bosom, Weng Yonggen, Zou Xuhua; A kind of preparation method of new load type nano gold catalyst, the Chinese invention patent application number: 03138796.1, the applying date: on July 8th, 2003).
Catalyst of the present invention carries out CO catalytic oxidation performance evaluation on atmospheric fixed bed reactor, raw materials used gas consists of: CO:0.25-1.0%, all the other are air.
The conversion ratio of CO is obtained by the gas chromatographic analysis result, and the minimum detectable range of CO is measured and is 50ppm.
The part catalyst has carried out Performance Detection by practical national standard requirement on the CO of Shanxi Xinhua Chemical Plant inspection center barrier propterty experimental rig.Unstripped gas consists of: CO:0.25-1.0%, air are balance gas, and controlled humidity is the saturated humidity under 23 ℃.
The heat resistanceheat resistant performance test of catalyst: place the drying box air atmosphere to heat 72h, the activity change of detecting catalyst down for 120 ℃ finished catalyst.
The anti humility performance experiment of catalyst: finished catalyst is placed the unstripped gas successive reaction 72h of reaction tube with water-vapo(u)r saturation under the room temperature, or handle 72h, the activity change of detecting catalyst continuously with the same gas speed of evaluation response with the air of water-vapo(u)r saturation under the room temperature.
Implementation of the present invention and most preferred embodiment:
Example 1: with 0.0325g CuCl
22H
2O and 0.0419g FeCl
36H
2O is fused in the 2.6ml water, with the 2.0g Al of moulding
2O
3Spheroid carrier joins in the above-mentioned solution, leaves standstill 1h after shaking up, and dry 4h under 80-120 ℃ in 800 ℃ of roasting 3h, is chilled to room temperature under the air atmosphere naturally.Measure 0.75mlHAuCl
4Solution (20gAu/L) adds the 0.2ml deionized water, adds 0.25ml NaOH (1M) solution, the pH=9-10 of regulator solution, pour above-mentioned complex carrier into dipping, mixing leaves standstill 1h, soak 24h with 20ml ammoniacal liquor (pH=10-11), the elimination stillness of night, be washed till to detect with deionized water and (use AgNO
3Solution) Cl
-Ion, 60 ℃ of dry 12h, 300 ℃ of following hydrogen reducing 1h get light brown finished catalyst.
Consist of at unstripped gas: CO:1%; O
2: 12%; N
2: 87% (percent by volume), gas volume air speed are 1.5 * 10
4h
-1Situation under, CO transforms (remaining CO is lower than Qi Xiang Se Spectrum detectable limit 50ppm) fully for CO
2Permission minimum response temperature (being called " minimum full conversion temperature ", as follows) be-18 ℃ (255K).In 27 ℃ of following successive reaction 3h, minimum full conversion temperature is-18.5 ℃.
The heat resistanceheat resistant performance test of catalyst: finished catalyst is placed 120 ℃ of drying box air atmospheres heating 72h down, be chilled to after the room temperature its catalytic activity of test and be minimum full conversion temperature-20.0 ℃.
The anti humility performance experiment of catalyst: place reaction tube to handle 72h continuously with the same gas speed of evaluation response finished catalyst with the air of water-vapo(u)r saturation under the room temperature, the activity of detecting catalyst, its minimum full conversion temperature is-14.0 ℃.
Example 2: adopt the used complex carrier of example 1.Measure 0.75mlHAuCl
4Solution (20gAu/L) adds the 0.75ml deionized water, with this gold solution direct impregnation complex carrier.Mixing leaves standstill 1h, soaks 24h with 20ml ammoniacal liquor (pH=10-11), the elimination stillness of night, is washed till to detect with deionized water and (uses AgNO
3Solution) Cl
-Ion, 60 ℃ of dry 12h, 300 ℃ of following hydrogen reducing 1h get light brown finished catalyst.Its minimum full conversion temperature is-24.0 ℃.
Example 3: take by weighing 100g Al
2O
3Spheroid carrier adopts example 1 method to prepare complex carrier, measures 75mlHAuCl
4Solution (20gAu/L) adds the 20ml deionized water, adds 30ml Na OH (1M) solution, the pH=9-10 of regulator solution, pour above-mentioned complex carrier into dipping, mixing leaves standstill 1h, soak 24h with 500ml ammoniacal liquor (pH=10-11), the elimination stillness of night, be washed till to detect with deionized water and (use AgNO
3Solution) Cl
-Ion, 60 ℃ of dry 12h, 300 ℃ of following hydrogen reducing 1h get light brown finished catalyst.Its minimum full conversion temperature is-17.5 ℃.
Consist of at unstripped gas: CO:1.0%; Air is a balance gas, and relative humidity 100% (23 ℃) than speed is: 0.75L/min.cm
2Test with Shanxi Xinhua Chemical Plant metrology and measurement center C O barrier propterty experimental rig, successive reaction 300 minutes, the CO penetrating concentration be lower than 54ppm (standard-required:＜100ppm), 30L examination back inspiratory resistance≤159Pa (standard-required :≤350Pa), 85L examination back inspiratory resistance≤682Pa (standard-required :≤880Pa).
Example 4: example 3 catalyst are put under the wide-mouth bottle room temperature air place and revalue its catalytic performance after 1 year.Consist of at unstripped gas: CO:0.25%; Air is a balance gas, and relative humidity 100% (23 ℃) than speed is: 0.65 L/min.cm
2Test with Shanxi Xinhua Chemical Plant metrology and measurement center C O barrier propterty experimental rig, successive reaction 30 minutes, the CO penetrating concentration be lower than 2ppm (standard-required:＜100ppm), 30L examination back inspiratory resistance≤184Pa (standard-required :≤350Pa), 85L examination back inspiratory resistance≤768Pa (standard-required :≤880Pa).
Claims (5)
1. load type gold catalyst that catalytic performance is stable, it is characterized in that: active component is Au, carrier is the Al that MIOx and MIIOx modify
2O
3Or the TiO of MIOx and MIIOx modification
2/ A1
2O
3, Au and atomic ratio (MI+MII) they are 1.0: 1.0～1.0: 10, the atomic ratio of MI and MII is 2.0: 1.0～0.2: 1.0; The atomic ratio of Au and Al is 1.0: 1.0 * 10
3～1.0: 10;
Wherein MI is Cu, and MII is Fe or Co or Ni.
2. as the stable load type gold catalyst of the said catalytic performance of claim 1, it is characterized in that: carrier is the moulding oxide carrier.
3. as the preparation method of the stable load type gold catalyst of claim 1 or 2 said catalytic performances, it is characterized in that: carrier is to adopt dipping method or coprecipitation method preparation, Al
2O
3Or TiO
2/ Al
2O
3Load MIOx, behind the MIIOx, through 800 ℃-1000 ℃ roasting, to generate spinelle or perovskite structure, catalyst precarsor is behind hydrogen reducing, and the part A u and the MIOx of easily reduction generate alloy A uM I.
4. as the preparation method of the stable load type gold catalyst of claim 1 or 2 said catalytic performances, it is characterized in that: the deposition-precipitation method or anion infusion process are adopted in the load of Au; Wherein, deposition-the precipitation method are in the active component precursor solution of 350K for the oxide carrier with high-specific surface area of moulding is in advance inserted the control temperature after vacuum drying treatment, in continuous stirring, dropwise add aqueous slkali, control pH value of solution value is 4.5～8.5 under constant temperature, until precipitation fully, get finished catalyst through sedimentation, filtration, washing, drying, roasting or activation processing;
Said aqueous slkali is Na
2CO
3Or K
2CO
3Or the solution of NaOH or KOH.
5. as the preparation method of the stable load type gold catalyst of the said catalytic performance of claim 3, it is characterized in that: the deposition-precipitation method or anion infusion process are adopted in the load of Au; Wherein, deposition-the precipitation method are in the active component precursor solution of 350K for the oxide carrier with high-specific surface area of moulding is in advance inserted the control temperature after vacuum drying treatment, in continuous stirring, dropwise add aqueous slkali, control pH value of solution value is 4.5～8.5 under constant temperature, until precipitation fully, get finished catalyst through sedimentation, filtration, washing, drying, roasting or activation processing;
Said aqueous slkali is Na
2CO
3Or K
2CO
3Or the solution of NaOH or KOH.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100245096A CN100389873C (en) | 2004-07-21 | 2004-07-21 | Load type gold catalyst with stabilized catalyzing performance and its preparation process |
| PCT/CN2005/000602 WO2006007774A1 (en) | 2004-07-21 | 2005-04-29 | Catalyst with stable catalytic performance and the preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100245096A CN100389873C (en) | 2004-07-21 | 2004-07-21 | Load type gold catalyst with stabilized catalyzing performance and its preparation process |
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| CN1724153A CN1724153A (en) | 2006-01-25 |
| CN100389873C true CN100389873C (en) | 2008-05-28 |
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| WO (1) | WO2006007774A1 (en) |
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| CN101204655B (en) * | 2006-12-21 | 2010-12-01 | 中国人民解放军63971部队 | Process for preparing nanometer gold catalyst |
| CN101698149B (en) * | 2009-10-14 | 2012-11-07 | 安立敦 | Supported gold-PGM alloy catalyst with stable storage property and preparation method thereof |
| CN106334555A (en) * | 2016-11-15 | 2017-01-18 | 烟台大学 | High-activity and high-stability supported nanometer gold catalyst, preparation and application method |
| CN114984940B (en) * | 2022-06-02 | 2023-06-06 | 宁波方太厨具有限公司 | PGM-Au alloy and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068217A (en) * | 1989-04-29 | 1991-11-26 | Gutec | Carrier catalysts for oxidizing carbon monoxide and process for their production |
| JPH05228367A (en) * | 1992-02-17 | 1993-09-07 | Idemitsu Kosan Co Ltd | Waste gas purifying catalyst |
| CN1326811A (en) * | 2000-08-29 | 2001-12-19 | 烟台大学 | Practical low-temperature CO oxidizing catalyst |
| CN1498680A (en) * | 2002-11-08 | 2004-05-26 | 中国人民解放军63971部队 | Catalyst for purifying CO under environmental condition |
-
2004
- 2004-07-21 CN CNB2004100245096A patent/CN100389873C/en not_active Expired - Fee Related
-
2005
- 2005-04-29 WO PCT/CN2005/000602 patent/WO2006007774A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5068217A (en) * | 1989-04-29 | 1991-11-26 | Gutec | Carrier catalysts for oxidizing carbon monoxide and process for their production |
| JPH05228367A (en) * | 1992-02-17 | 1993-09-07 | Idemitsu Kosan Co Ltd | Waste gas purifying catalyst |
| CN1326811A (en) * | 2000-08-29 | 2001-12-19 | 烟台大学 | Practical low-temperature CO oxidizing catalyst |
| CN1498680A (en) * | 2002-11-08 | 2004-05-26 | 中国人民解放军63971部队 | Catalyst for purifying CO under environmental condition |
Non-Patent Citations (4)
| Title |
|---|
| 常温常湿条件下Au/MeOx催化剂上CO 氧化性能. 王桂英等.化学学报，第58卷第12期. 2000 |
| 常温常湿条件下Au/MeOx催化剂上CO 氧化性能. 王桂英等.化学学报，第58卷第12期. 2000 * |
| 纳米金催化剂上Co低(常)温氧化的研究. 王东辉等.化学进展，第14卷第5期. 2002 |
| 纳米金催化剂上Co低(常)温氧化的研究. 王东辉等.化学进展，第14卷第5期. 2002 * |
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|---|---|
| WO2006007774A1 (en) | 2006-01-26 |
| CN1724153A (en) | 2006-01-25 |
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