CN107233893B - Non-noble metal CO catalytic purification material for gas water heater and preparation method thereof - Google Patents
Non-noble metal CO catalytic purification material for gas water heater and preparation method thereof Download PDFInfo
- Publication number
- CN107233893B CN107233893B CN201710501794.3A CN201710501794A CN107233893B CN 107233893 B CN107233893 B CN 107233893B CN 201710501794 A CN201710501794 A CN 201710501794A CN 107233893 B CN107233893 B CN 107233893B
- Authority
- CN
- China
- Prior art keywords
- sio
- tio
- solution
- cuo
- ceo
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000000746 purification Methods 0.000 title claims abstract description 25
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 33
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 claims abstract description 20
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 49
- 229910052681 coesite Inorganic materials 0.000 claims description 33
- 229910052906 cristobalite Inorganic materials 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052682 stishovite Inorganic materials 0.000 claims description 33
- 229910052905 tridymite Inorganic materials 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl glycoside Chemical class 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 229930182470 glycoside Natural products 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 239000006260 foam Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000003483 aging Methods 0.000 claims description 5
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229930182478 glucoside Natural products 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 abstract description 6
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052726 zirconium 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
-
- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- B01J35/40—
-
- B01J35/615—
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a non-noble metal CO catalytic purification material for a gas water heater, wherein a catalyst carrier is CuO-TiO2‑SiO2The active group comprising CeO2、Sb2O3Or Nb2O5One or more of them. The invention also discloses a preparation method of the non-noble metal CO catalytic purification material for the gas water heater. The non-noble metal CO catalytic purification material has the advantages of low cost, high temperature resistance, good hydrothermal stability, good sulfur and fluorine-chlorine poisoning resistance, long service life, capability of reducing the CO content to be below 20ppm and the like.
Description
Technical Field
The invention relates to a gas water heater, in particular to a non-noble metal CO catalytic purification material for the gas water heater and a preparation method thereof.
Background
With the progress of the times and the transformation of life forms, the water heater is an indispensable necessary device for common household life at present. Wherein, the gas heater is owing to have the heating rapidly, and purchase and use cost are low, and no matter weather all need not to wait for, but direct use, and advantages such as small, the most adopts for general masses. However, when a gas water heater is used, the amount of oxygen in a closed room is insufficient, so that the gas is not completely combusted to release carbon monoxide, and poisoning is caused. Therefore, the carbon monoxide purifier is generally arranged in the gas water heater, and the emission of CO is ensured to reach the standard during gas combustion, so that the life safety of a user is ensured.
Patent publication No. CN 104556032 a discloses a CO purifier for a gas water heater, which includes a honeycomb ceramic substrate and a catalyst layer attached to the surface of the honeycomb ceramic substrate, but the active component thereof is composed of one or more of noble metals of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, or platinum, and the production cost is high.
Patent document No. CN 101143321B discloses a non-noble metal catalyst for CO oxidation, which has a simple preparation process, but the reaction temperature is-30 to 50 ℃. Patent publication No. CN 103362613 a discloses a carbon monoxide selective cerium oxide, zirconium and copper mixed oxide (CeZrCuOx) catalyst, but its use temperature is in the range of 200 to 400 ℃. Patent document publication No. CN 103831111B discloses Co having a core-shell structure3O4-CeO2-ZrO2The catalyst has a complex preparation process, and the temperature required by the complete oxidation of CO is less than or equal to-65 ℃. The three catalysts are non-noble metal catalysts, have low raw material cost, but are not suitable for being used in the working condition environment (150-200 ℃) of the gas water heater.
The patent publication No. CN 101485984B discloses a CO oxidation catalyst made of CeO2-TiO2The composite oxide consists of a composite oxide carrier and an active component CuO, and can reduce CO within the temperature range of 80-170 DEG CAs little as 100ppm, but the CO concentration at the outlet of the CO purifier of the gas water heater needs to be reduced to below 50ppm, and the CO conversion rate is reduced in the range of 170 ℃ and 200 ℃, so that the smoke emission requirement of the water heater cannot be met.
In conclusion, the CO purifier for the gas water heater has the problems of high production cost, high use environment temperature (150-200 ℃), low requirement on CO discharge (less than or equal to 50ppm), short service life and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a non-noble metal CO catalytic purification material for a gas water heater and a preparation method thereof, and the material has the advantages of low cost, high temperature resistance, good hydrothermal stability, good sulfur and fluorine-chlorine poisoning resistance, long service life, capability of reducing the CO content to be below 20ppm and the like.
The technical scheme is as follows:
a CO catalytic purifying non-noble metal material for gas water heater contains CuO-TiO as carrier2-SiO2The active group comprising CeO2、Sb2O3Or Nb2O5One or more of them.
Further: in the catalyst carrier, CuO and TiO2And SiO2In a mass ratio of 5-9:1-5, SiO2With TiO2In a mass ratio of 1: 19.
Further: active component CeO2With a carrier CuO-TiO2-SiO2Is 1:1 or 1: 2.
Further: active component Sb2O3Or Nb2O5With CeO2Is 1:4.3 or 1: 6.2.
Further: the specific surface area of the catalyst is 180-220m2/g。
Further: the grain size is 25-30 nm.
A preparation method of non-noble metal CO catalytic purification material for a gas water heater adopts a surfactant template method, wherein a template agent is alkyl glycoside; the catalyst carrier of the material is CuO-TiO2-SiO2The active group comprising CeO2、Sb2O3Or Nb2O5One or more of them.
Preferably: according to the formula CuO and TiO2+SiO2The mass ratio of SiO to SiO is 7:12With TiO2With the mass ratio of 1:19, 3303g of Cu (NO) were weighed out separately3)2·3H2O and 125g SiO2With TiO2The mixture was stirred well in 3L of water according to CeO2With CuO-TiO2-SiO26625.7g Ce (NO) was weighed in a molar ratio of 1:13)3·6H2Adding O into the mixed solution, stirring uniformly, adding 500mL of 0.23mol/L alkyl glycoside solution, and after completely dispersing in the solution, according to the formula of Sb2O3With CeO2In a molar ratio of 1:4.3 of Sb2O3Slowly adding into the above solution with ammonia water to pH 9, stirring, aging for 4 hr, hydrothermal reacting at 110 deg.C for 12 hr, filtering, washing, and calcining at 500 deg.C for 4 hr to obtain catalyst powder.
Preferably: taking 3L of 0.28mol/L alkyl glycoside solution, stirring until the foam size in the solution is 1-2mm according to CuO/TiO2+SiO2Mass ratio of 6.5:1, SiO2With TiO2In a mass ratio of 1:19, 3263g of Cu (NO) was weighed3)2·3H2O and 133g SiO2With TiO2The mixture of (A) and (B) is stirred uniformly in the above solution according to the formula of CeO2With CuO-TiO2-SiO2In a molar ratio of 1:2 3300g of Ce (NO) was weighed3)3·6H2O is put into the mixed solution and stirred for 2 hours until the alkyl glucoside foam completely covers the added substances, according to the Sb2O3With CeO2The molar ratio of antimony acetate to ammonia water is 1:4.3, the hot glycol solution of antimony acetate and ammonia water are respectively and slowly added into the solution until the pH value is 9, the mixture is stirred and aged for reaction for 4 hours, hydrothermal reaction is carried out for 12 hours at 110 ℃, and the catalyst powder can be obtained by suction filtration, washing and roasting for 4 hours at 500 ℃.
Preferably: taking 3L of 0.18mol/L alkyl glycoside solution, stirring until the foam size in the solution is 1-2mm according to CuO/TiO2+SiO2The mass ratio of SiO to SiO is 7:12With TiO23303g of Cu (1: 19) were weighed in a weight ratio of 1:19, respectivelyNO3)2·3H2O and 125g SiO2With TiO2The mixture was stirred well in 3L of water according to CeO2With CuO-TiO2-SiO26625.7g Ce (NO) was weighed in a molar ratio of 1:13)3·6H2O in the above mixed solution according to Nb2O5With CeO2The molar ratio of niobium acetate solution to ammonia water is 1:6.2, the niobium acetate solution and the ammonia water are respectively and slowly added into the solution until the pH value is 9, the mixture is stirred and aged for reaction for 4 hours, hydrothermal reaction is carried out for 12 hours at 110 ℃, the mixture is filtered, washed and roasted for 4 hours at 500 ℃, and then the catalyst powder can be obtained.
Compared with the prior art, the invention has the technical effects that:
the invention has the advantages of low cost, high temperature resistance, good hydrothermal stability, good sulfur and fluorine-chlorine poisoning resistance, long service life, capability of reducing the content of CO to be below 20ppm and the like.
1. The CO catalytic purifier provided by the invention can reduce the emission of CO to below 20ppm within the range of 120-270 ℃ for non-fully premixed and fully premixed gas water heaters.
2. After the CO catalytic purifier provided by the invention is installed, the pressure increase of the air duct is less than 60Pa, and the service life of the CO catalytic purifier can reach 2200 h.
Detailed Description
The technical solution of the present invention will be described in detail with reference to exemplary embodiments. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art.
The non-noble metal CO catalytic purifying material for gas water heater is honeycomb and is formed through extrusion, and the catalyst carrier is CuO-TiO2-SiO2The active component is CeO2、Sb2O3Or Nb2O5One or more of them.
In the catalyst carrier, CuO and TiO2And SiO2In a mass ratio of 5-9:1-5, SiO2With TiO2In a mass ratio of 1: 19. The specific surface area of the catalyst is 180-220m2(ii) in terms of/g. The grain size is 25-30 nm.
CeO2With a carrier CuO-TiO2-SiO2Is 1:1 or 1: 2. Active component Sb2O3Or Nb2O5With CeO2Is 1:4.3 or 1: 6.2.
The preparation method is a surfactant template method, wherein the template agent is alkyl glycoside. From CeO2-Sb2O3(Nb2O5)/CuO-TiO2-SiO2The catalyst powder is extruded by itself.
Example 1:
(1) according to the formula CuO and TiO2+SiO2The mass ratio of SiO to SiO is 7:12With TiO2With the mass ratio of 1:19, 3303g of Cu (NO) were weighed out separately3)2·3H2O and 125g SiO2With TiO2The mixture was stirred well in 3L of water according to CeO2With CuO-TiO2-SiO26625.7g Ce (NO) was weighed in a molar ratio of 1:13)3·6H2Adding O into the mixed solution, stirring uniformly, adding 500mL of 0.23mol/L alkyl glycoside solution, and after completely dispersing in the solution, according to the formula of Sb2O3With CeO2In a molar ratio of 1:4.3 of Sb2O3Slowly adding into the above solution with ammonia water to pH 9, stirring, aging for 4 hr, hydrothermal reacting at 110 deg.C for 12 hr, filtering, washing, and calcining at 500 deg.C for 4 hr to obtain catalyst powder.
(2) The honeycomb-shaped CO catalytic purification material can be obtained by carrying out traditional mud refining, ageing, extrusion, drying, firing, cutting and packaging on the catalyst.
By using N2The specific surface area of the obtained catalyst was 183.6m in the adsorption-desorption test2(ii) in terms of/g. The catalyst was analyzed by XRD and had a crystallite size of 27.9 nm.
Example 2:
(1) taking 3L of 0.28mol/L alkyl glycoside solution, stirring until the foam size in the solution is 1-2mm according to CuO/TiO2+SiO2Mass ratio of 6.5:1, SiO2With TiO2In a mass ratio of 1:19, 3263g of Cu (NO) was weighed3)2·3H2O and 133g SiO2With TiO2The mixture of (A) and (B) is stirred uniformly in the above solution according to the formula of CeO2With CuO-TiO2-SiO2In a molar ratio of 1:2 3300g of Ce (NO) was weighed3)3·6H2O is put into the mixed solution and stirred for 2 hours until the alkyl glucoside foam completely covers the added substances, according to the Sb2O3With CeO2The molar ratio of antimony acetate to ammonia water is 1:4.3, the hot glycol solution of antimony acetate and ammonia water are respectively and slowly added into the solution until the pH value is 9, the mixture is stirred and aged for reaction for 4 hours, hydrothermal reaction is carried out for 12 hours at 110 ℃, and the catalyst powder can be obtained by suction filtration, washing and roasting for 4 hours at 500 ℃.
(2) The honeycomb-shaped CO catalytic purification material can be obtained by carrying out traditional mud refining, ageing, extrusion, drying, firing, cutting and packaging on the catalyst.
By using N2The specific surface area of the obtained catalyst was 209.7m in the adsorption-desorption test2(ii) in terms of/g. The catalyst was analyzed by XRD and had a crystallite size of 25.4 nm.
Example 3:
(1) taking 3L of 0.18mol/L alkyl glycoside solution, stirring until the foam size in the solution is 1-2mm according to CuO/TiO2+SiO2The mass ratio of SiO to SiO is 7:12With TiO2With the mass ratio of 1:19, 3303g of Cu (NO) were weighed out separately3)2·3H2O and 125g SiO2With TiO2The mixture was stirred well in 3L of water according to CeO2With CuO-TiO2-SiO26625.7g Ce (NO) was weighed in a molar ratio of 1:13)3·6H2O in the above mixed solution according to Nb2O5With CeO2The molar ratio of niobium acetate solution to ammonia water is 1:6.2, the niobium acetate solution and the ammonia water are respectively and slowly added into the solution until the pH value is 9, the mixture is stirred and aged for reaction for 4 hours, hydrothermal reaction is carried out for 12 hours at 110 ℃, the mixture is filtered, washed and roasted for 4 hours at 500 ℃, and then the catalyst powder can be obtained.
(2) The honeycomb-shaped CO catalytic purification material can be obtained by carrying out traditional mud refining, ageing, extrusion, drying, firing, cutting and packaging on the catalyst.
By using N2The specific surface area of the obtained catalyst is 181.0m in an adsorption-desorption test2(ii) in terms of/g. The catalyst was analyzed by XRD and had a crystallite size of 29.5 nm.
Example 4:
(1) taking 3L of 0.2mol/L alkyl glycoside solution, stirring until the foam size in the solution is 1-2mm according to CuO/TiO2+SiO2Mass ratio of 5.3:1, SiO2With TiO2In a mass ratio of 1:19, 3176g of Cu (NO) was weighed in each case3)2·3H2O and 159g SiO2With TiO2The mixture of (A) and (B) is stirred uniformly in the above solution according to the formula of CeO23292.8g Ce (NO) was weighed in a 1:2 molar ratio to CuO3)3·6H2O in the above mixed solution according to Nb2O5With CeO2The molar ratio of niobium oxalate solution to ammonia water is 1:4.3, the niobium oxalate solution and the ammonia water are respectively and slowly added into the solution until the pH value is 10, the mixture is stirred and aged for reaction for 4 hours, hydrothermal reaction is carried out for 12 hours at 110 ℃, the mixture is filtered, washed and roasted for 4 hours at 500 ℃, and then the catalyst powder can be obtained.
(2) The honeycomb-shaped CO catalytic purification material can be obtained by carrying out traditional mud refining, ageing, extrusion, drying, firing, cutting and packaging on the catalyst.
By using N2The specific surface area of the obtained catalyst was 183.7m in the adsorption-desorption test2(ii) in terms of/g. The catalyst was analyzed by XRD and had a crystallite size of 26.8 nm. The CO elimination performance test is carried out, and the specific reaction conditions are as follows: 20-40ppm NO, 60-150ppm CO, 10-15% O2，10-15％H2O，30-100ppm SO2，7％CO2100-1000ppm fluorine-chlorine mixed gas, Ar is carrier gas, and space velocity (GHSV) is 90000-120000 h-1. The gas detection system is a Fourier transform infrared analyzer equipped with a gas cell.
The catalysts in the above examples were subjected to CO elimination performance testing: the catalyst size was 1 inch by 1 inch, and the reaction gas composition (by volume): 40ppm NO, 100ppm CO, 10% O2，12％H2O，80ppm SO2，7％CO2800ppm of fluorine-chlorine mixed gas, Ar is carrier gas, and the space velocity (GHSV) is 90000 h-1. The gas detection system is a Fourier transform infrared analyzer equipped with a gas cell.
From the detection results, the concentrations of CO at the outlet of the catalyst in the temperature range of 120-270 ℃ in examples 1-4 are respectively 16ppm, 7ppm, 10ppm and 15ppm, and the detection shows that the non-noble metal catalyst provided by the invention has a good CO purification effect.
The CO purifier of examples 1-4 was heated to 1000 ℃, naturally cooled to room temperature, and the heating-cooling process was repeated 53 times (corresponding to about 2200 hours of normal operation of a gas water heater), after which the catalyst was subjected to a performance test. The detection shows that the CO concentration air at the outlet of the catalyst in the embodiment 1-4 is 19ppm, 14ppm, 18ppm and 19ppm within the temperature range of 120-270 ℃, which indicates that the non-noble metal catalyst has good thermal stability.
After the CO catalytic purifiers in the embodiments 1 to 4 are installed, the pressure of the air duct is detected, and the pressure increase after the installation is smaller than 60Pa, so that the use requirements of water heater manufacturers on the CO catalytic purifiers are met.
The detection results show that the non-noble metal CO purification catalyst has the characteristics of low cost, high temperature resistance, good hydrothermal stability, good sulfur and fluorine-chlorine poisoning resistance, long service life, capability of reducing the CO content to be below 20ppm, small use air pressure and the like, and meets the use requirements of water heater manufacturers on the CO purification catalyst.
The terminology used herein is for the purpose of description and illustration, rather than of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.
Claims (7)
1. Non-noble metal CO catalytic purification material for gas water heaterThe catalyst comprises a catalyst carrier and an active component, and is characterized in that: the catalyst carrier is CuO-TiO2-SiO2The active component comprises CeO2And Sb2O3Or Nb2O5One or two of them; CuO and TiO2And SiO2In a mass ratio of 5-9:1-5, SiO2With TiO2The mass ratio of (A) to (B) is 1: 19; the specific surface area of the catalyst is 180-220m2The grain diameter of the catalyst is 25-30 nm.
2. The non-noble metal CO catalytic purification material for the gas water heater as claimed in claim 1, wherein: active component CeO2With a carrier CuO-TiO2-SiO2Is 1:1 or 1: 2.
3. The non-noble metal CO catalytic purification material for the gas water heater as claimed in claim 1, wherein: active component Sb2O3With CeO2In a molar ratio of 1:4.3, an active component Nb2O5With CeO2In a molar ratio of 1: 6.2.
4. A method for preparing non-noble metal CO catalytic purification material for a gas water heater as claimed in claim 1, characterized in that: preparing catalyst powder by adopting a surfactant template method, wherein the template is alkyl glycoside; the non-noble metal CO catalytic purifying material for the gas water heater is honeycomb-shaped and is made of CeO2-Sb2O3/CuO-TiO2-SiO2Or CeO2-Nb2O5/CuO-TiO2-SiO2Extruding and forming catalyst powder; the catalyst carrier of the material is CuO-TiO2-SiO2The active component comprises CeO2And Sb2O3Or Nb2O5One or two of them; CuO and TiO2And SiO2In a mass ratio of 5-9:1-5, SiO2With TiO2The mass ratio of (A) to (B) is 1: 19; the specific surface area of the catalyst is 180-220m2The grain diameter of the catalyst is 25-30 nm.
5. The method for preparing non-noble metal CO catalytic purification material for gas water heater as claimed in claim 4, wherein: according to the formula CuO and TiO2+SiO2The mass ratio of SiO to SiO is 7:12With TiO2With the mass ratio of 1:19, 3303g of Cu (NO) were weighed out separately3)2·3H2O、125g SiO2With TiO2The mixture was stirred well in 3L of water according to CeO2With CuO-TiO2-SiO26625.7g Ce (NO) was weighed in a molar ratio of 1:13)3·6H2Adding O into the mixed solution, stirring uniformly, adding 500mL of 0.23mol/L alkyl glycoside solution, and after completely dispersing in the solution, according to the formula of Sb2O3With CeO2In a molar ratio of 1:4.3 of Sb2O3Slowly adding into the above solution with ammonia water to pH 9, stirring, aging for 4 hr, hydrothermal reacting at 110 deg.C for 12 hr, filtering, washing, and calcining at 500 deg.C for 4 hr to obtain catalyst powder; the catalyst is subjected to traditional mud refining, staling, extrusion, drying, firing, cutting and packaging to obtain the honeycomb-shaped CO catalytic purification material.
6. The method for preparing non-noble metal CO catalytic purification material for gas water heater as claimed in claim 4, wherein: taking 3L of 0.28mol/L alkyl glycoside solution, stirring until the foam size in the solution is 1-2mm according to CuO/TiO2+SiO2Mass ratio of 6.5:1, SiO2With TiO2In a mass ratio of 1:19, 3263g of Cu (NO) was weighed3)2·3H2O and 133g SiO2With TiO2The mixture of (A) and (B) is stirred uniformly in the above solution according to the formula of CeO2With CuO-TiO2-SiO23300gCe (NO) weighed in a molar ratio of 1:23)3·6H2O is put into the mixed solution and stirred for 2 hours until the alkyl glucoside foam completely covers the added substances, according to the Sb2O3With CeO2In the molar ratio of 1:4.3, adding a hot glycol solution of antimony acetate and ammonia water into the solution slowly to reach the pH value of 9, stirring and ageing for reactionCarrying out hydrothermal reaction for 12h at 110 ℃, carrying out suction filtration and washing, and roasting for 4h at 500 ℃ to obtain catalyst powder; the catalyst is subjected to mud refining, staleness, extrusion, drying, firing, cutting and packaging to obtain the honeycomb-shaped CO catalytic purification material.
7. The method for preparing non-noble metal CO catalytic purification material for gas water heater as claimed in claim 4, wherein: taking 3L of 0.18mol/L alkyl glycoside solution, and stirring until the foam size in the solution is 1-2 mm; according to CuO/TiO2+SiO2The mass ratio of SiO to SiO is 7:12With TiO2With the mass ratio of 1:19, 3303g of Cu (NO) were weighed out separately3)2·3H2O、125g SiO2With TiO2The mixture of (a) is stirred evenly in the solution; according to CeO2With CuO-TiO2-SiO26625.7g Ce (NO) was weighed in a molar ratio of 1:13)3·6H2O in the above mixed solution according to Nb2O5With CeO2The molar ratio of niobium acetate solution to ammonia water is 1:6.2, the niobium acetate solution and the ammonia water are respectively and slowly added into the solution until the pH value is 9, the solution is stirred, aged and reacted for 4 hours, hydrothermal reaction is carried out for 12 hours at 110 ℃, the solution is filtered, washed and roasted for 4 hours at 500 ℃ to obtain catalyst powder; the catalyst is subjected to mud refining, staleness, extrusion, drying, firing, cutting and packaging to obtain the honeycomb-shaped CO catalytic purification material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710501794.3A CN107233893B (en) | 2017-06-27 | 2017-06-27 | Non-noble metal CO catalytic purification material for gas water heater and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710501794.3A CN107233893B (en) | 2017-06-27 | 2017-06-27 | Non-noble metal CO catalytic purification material for gas water heater and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107233893A CN107233893A (en) | 2017-10-10 |
| CN107233893B true CN107233893B (en) | 2020-09-01 |
Family
ID=59987344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710501794.3A Active CN107233893B (en) | 2017-06-27 | 2017-06-27 | Non-noble metal CO catalytic purification material for gas water heater and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107233893B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485984B (en) * | 2009-02-11 | 2010-12-08 | 中国科学院山西煤炭化学研究所 | CO low-temperature oxidation catalyst and preparation method thereof |
| US10792647B2 (en) * | 2009-04-21 | 2020-10-06 | Johnson Matthey Public Limited Company | Base metal catalysts for the oxidation of carbon monoxide and volatile organic compounds |
| CN103007970A (en) * | 2012-12-13 | 2013-04-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Carbon monoxide room-temperature catalytic oxidation catalyst and preparation method thereof |
-
2017
- 2017-06-27 CN CN201710501794.3A patent/CN107233893B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Kinetic study of CO oxidation over CuO/MO2(M=Si,Ti and Ce) catalysts;Ji-Qing Lu et al.;《Applied Surface Science》;20130923;第287卷;第124-134页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107233893A (en) | 2017-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4969843B2 (en) | Exhaust gas purification catalyst and exhaust gas purification catalyst member | |
| CN103157491B (en) | One is used for being catalyzed voloxidation organic mesopore metal oxide loaded palladium catalyst | |
| US20050221978A1 (en) | Catalyst powder, method of producing the catalyst powder, and exhaust gas purifying catalyst | |
| CN106540741A (en) | It is used at room temperature eliminating catalyst of formaldehyde and preparation method thereof | |
| WO2003082461A1 (en) | Catalyst for production of hydrogen | |
| JPH01168343A (en) | Exhaust gas purifying catalyst | |
| CN106390983A (en) | CeO2 catalyst with Ce-based metal-organic framework used as precursor, method for preparing CeO2 catalyst and application of CeO2 catalyst to preventing and remedying air pollution | |
| US5002920A (en) | Catalyst for ozone decomposition | |
| CN110773158A (en) | Material for room-temperature catalytic purification of VOCs (volatile organic compounds) based on metal monoatomic atoms and preparation method thereof | |
| WO1995009047A1 (en) | Adsorption material for nitrogen oxides and exhaust emission control catalyst | |
| CN108187690A (en) | A kind of cobalt manganese composite oxide loaded catalyst that formaldehyde is removed for room temperature and preparation method thereof | |
| US20070249496A1 (en) | Catalyst for Production of Hydrogen | |
| WO2009054728A1 (en) | Catalyst for production of nitric oxide | |
| CN113797935A (en) | Catalyst for low-temperature efficient treatment of VOCs and preparation method thereof | |
| CN107233893B (en) | Non-noble metal CO catalytic purification material for gas water heater and preparation method thereof | |
| CN107303468A (en) | By the method for removing oxidable gaseous compound from admixture of gas containing platinum oxidation catalyst | |
| CN108380222B (en) | Method for fixing active component of noble metal catalyst and application thereof | |
| CN114570435A (en) | Honeycomb catalyst and preparation method and application thereof | |
| KR101839778B1 (en) | A method for producing an metal aluminate oxidation catalyst having improved endotoxicity against organic chloro compounds and an oxidation catalyst | |
| JP4525909B2 (en) | Water gas shift reaction catalyst, method for producing the same, and method for producing water gas | |
| US20040147394A1 (en) | Catalyst for production of hydrogen | |
| US20090185961A1 (en) | Oxygen storage component | |
| TWI398298B (en) | Preparation of copper oxide-titania-supported nano-gold catalysts and its application in preferential oxidation of carbon monoxide in hydrogen stream | |
| JP2010221091A (en) | Composite oxide for exhaust gas cleaning catalyst, coating material for exhaust gas cleaning catalyst and diesel exhaust gas cleaning filter | |
| JP2014061461A (en) | Exhaust gas cleaning catalyst, method for manufacturing an exhaust gas cleaning catalyst, and exhaust gas cleaning catalyst component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |