CN108126708A - A kind of CO room-temperature catalytic oxidation catalysts - Google Patents

A kind of CO room-temperature catalytic oxidation catalysts Download PDF

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CN108126708A
CN108126708A CN201711296350.7A CN201711296350A CN108126708A CN 108126708 A CN108126708 A CN 108126708A CN 201711296350 A CN201711296350 A CN 201711296350A CN 108126708 A CN108126708 A CN 108126708A
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catalyst
aqueous slkali
iron
value
washing
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CN108126708B (en
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唐志诚
韩维亮
张国栋
董芳
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/8906—Iron and noble metals
    • 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
    • B01J23/89—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
    • B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • 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 kind of CO room-temperature catalytic oxidation catalysts, which is prepared by the following method to obtain：1）PH is adjusted by aqueous slkali again after molysite is mixed with aqueous slkali, iron hydroxide is obtained after reacted, filtering, washing, drying, iron oxide is obtained after roasting；2）Palladium salt solution, iron oxide or/and iron hydroxide, polyalcohol are mixed, pH, reacted, filtering, washing, drying are adjusted by aqueous slkali；In step 1）Or 2）In include or the situation not comprising rare earth reactant salt and in step 2）In the situation that includes or reacted not comprising the salting liquid of alkali metal or/and alkaline-earth metal.Catalyst of the present invention possesses that catalytic activity is high and stability is good, can at ambient temperature by CO complete oxidations the features such as.

Description

A kind of CO room-temperature catalytic oxidation catalysts
Technical field
The present invention relates to a kind of CO room-temperature catalytic oxidation catalysts, belong to environmental catalysis Material Field.
Background technology
In various atmosphere pollutions, CO is one of its important composition ingredient.CO is mainly by the incomplete of carbon-containing fuel Burning is generated or is generated under the high temperature of internal combustion engine, the burning condition of high pressure.The main harm of CO is that influencing the mankind is good for Health, such as：Make visual impairment, headache etc..Therefore, eliminate CO be many aspects such as industrial processes and environmentally friendly process all urgently It solves the problems, such as.
At present, CO catalytic oxidation is to eliminate one of the most frequently used of CO, most efficient method.CO oxidation catalysts can be divided into two Major class：Noble metal catalyst and non-precious metal catalyst.Noble metal catalyst is paid close attention to its good catalytic activity by people, but The high cost of noble metal catalyst, limits its large-scale application.At present, people bear noble metal often through carrier It carries, prepares loaded noble metal catalyst.
Loaded noble metal catalyst is for CO oxidation catalysts since automobile industry.Earliest people apply Pt- Pd/γ-Al2O3, the CO complete oxidations in vehicle exhaust can be made.The discoveries such as Stark later, Pt/SnO2In the range of 30 ~ 100 DEG C With higher CO oxidation activities, but it is still necessary to further improve for stability.Until Wacker is by PdCl2-CuCl2Aqueous solution loads In Al2O3Or on the carriers such as activated carbon, the CO oxidation activities that catalyst adds in moisture in feeding gas can be made to improve 1 ~ 3 quantity Grade just has greater activity in 300K.But Cl is remained in catalyst-, the Activity and stabill of catalyst can be impacted, Secondary pollution can be caused to environment.
Another kind of more important noble metal catalyst is Au catalyst.Heruta in 1989 et al. first reported nanoscale Au/ metal oxide catalyst CO catalytic oxidations can reach the low temperature of 203K.Scientists are since then caused twenties years Carry out the further investigation to Au catalyst.But gold catalysis stability it is poor, illumination or storage a period of time after, can all lead to it Inactivation.Furthermore the preparation condition of Au catalyst is typically complex harshness, catalyst poor repeatability, and the gold in preparation process Loss amount it is big, it is of high cost.
In recent years, CO low-temperature oxidation catalysts are prepared as carrier using the oxide of iron and hydroxide, shown good Catalytic activity and stability, such as Shinji Kudo（S. Kudo, Y. Maki, M. Yamada, K. Mae, Chemical Engineering Science 2010, 65, 214-219）Au/Fe (OH) is prepared using coprecipitationxCatalysis Agent is reacted for CO low-temperature oxidations, when air speed is 36000h-1It can make 400ppmCO in 50 DEG C of conversions completely.Qiao Botao etc.（B. T. Qiao, L. Q. Liu, J. Zhang, Y. Q. Deng, Journal of Catalysis 2009, 261, 241- 244）The catalyst of iron hydroxide supported palladium and/or gold is prepared using coprecipitation, for CO low-temperature catalytic oxidations, catalyst exhibition Revealing the low-temperature catalyzed performances of good CO, such catalyst is when Pd contents are 4.4%, air speed 15000ml/gh, 10000ppmCO 5 DEG C completely conversion, and pass through hydrogen reducing catalyst, Pd contents be 4.1% when, -15 DEG C can will CO is converted completely.It can be seen that by catalyst reduction, make the atom of the noble metal loaded in catalyst generation lower valency, catalysis Agent activity higher.
CN101579635A discloses the catalyst that infusion process prepares room temperature CO catalytic oxidation.The catalyst is with 0.5 ~ 1.0% PdCl2With 99.5 ~ 99.0% γ-Al2O3It is made by infusion process.Catalyst activity prepared by this method is more than 98%, but its The successive reaction 15h under water saturation vapour pressure, activity are just down to 77.7%, and the catalyst water resistant stability is poor.
CN101618328A discloses a kind of load type nano gold catalyst.The catalyst activity component is nanogold, is helped Agent is Fe2O3、MnO2、CuO、Co2O3、CeO2With the one or more of NiO, carrier is γ-Al2O3.At the beginning of this method prepares catalyst Activity begin preferably, but activity is down to 88.2% after reaction 40h at room temperature.
CN102059115A discloses a kind of attapulgite clay loaded nanometer palladium catalyst.The catalyst is with attapulgite clay For carrier, load active component Technique of Nano Pd and auxiliary agent vanadic anhydride or molybdenum trioxide, active component content are 0.5 ~ 3%, auxiliary agent Content is 0.1 ~ 2%, remaining is carrier.The catalyst stability and mithridatism are preferable, but activity is poor, makes 10 at 30 DEG C ~ The CO conversion ratios of 200ppm are 99.4%.
CN102059127A reports a kind of CO catalytic oxidation under low temperature catalyst.The catalyst activity component is palladium and transition Metal（Iron, cerium, cobalt, manganese, copper, lanthanum, nickel, molybdenum）One or more of compositions of oxide, carrier is aluminium oxide, is used with citric acid Sol-gal process for raw material prepares catalyst.The catalyst is carrier 2.2% in the mass fraction of palladium, and transition metal is Fe oxygen Activity highest during compound.
Invention content
The purpose of the present invention is to provide it is a kind of under room temperature and wet condition can in catalysis oxidation flue gas CO catalyst.
A kind of CO room-temperature catalytic oxidation catalysts, it is characterised in that the catalyst is prepared by following two methods：
Method one：
1）It is 7 ~ 12 to adjust pH value by aqueous slkali again after molysite is mixed with aqueous slkali, and in room temperature ~ 80 DEG C, reaction 0.5 ~ 5 is small When, filtered, washing obtains iron hydroxide after 50 ~ 100 DEG C of dryings, and oxygen is obtained after being roasted 0.5 ~ 10 hour at 300 ~ 600 DEG C Change iron；
2）In the situation comprising or not comprising rare-earth salts and the salting liquid comprising or not comprising alkali metal or/and alkaline-earth metal In the case of, palladium salt solution, iron oxide or/and iron hydroxide, polyalcohol are mixed, it is 8 ~ 13 to adjust pH value by aqueous slkali, is turned Autoclave is moved to, in 80 ~ 200 DEG C of hydro-thermal reactions 0.1 ~ 4 hour, catalyst is obtained after filtered, washing, 60 ~ 120 DEG C of dryings；
Method two：
1）After molysite, rare-earth salts are mixed with aqueous slkali, then it is 7 ~ 12 to adjust pH value by aqueous slkali, is reacted in room temperature ~ 80 DEG C 0.5 ~ 5 hour, filtered, washing obtained rare earth modified iron hydroxide after 50 ~ 100 DEG C of dryings, in 300 ~ 600 DEG C of roastings Rare earth modified iron oxide is obtained after 0.5 ~ 10 hour；
2）In the case of the salting liquid comprising or not comprising alkali metal or/and alkaline-earth metal, by palladium salt solution, polyalcohol and dilute After the iron oxide of land reform or/and the mixing of rare earth modified iron hydroxide, it is 8 ~ 13 to adjust pH value by aqueous slkali, and transfer is supreme Kettle is pressed, in 80 ~ 200 DEG C of hydro-thermal reactions 0.1 ~ 4 hour, catalyst is obtained after filtered, washing, 60 ~ 120 DEG C of dryings.
The mass percentage of Pd is 0.05 ~ 3% in the catalyst, the mass percentage of rare earth oxide for 0 ~ 30%, the mass percentage of the oxide of alkali metal or/and alkaline-earth metal is 0 ~ 10%.
Two step 1 of the method one and method）In pH value be 7.5 ~ 10.
Two step 2 of the method one and method）In pH value be 8 ~ 10.
Step 1 in the method one and method two）Drying temperature be 60 ~ 100 DEG C.
Step 2 in the method one and method two）Hydro-thermal reaction in autoclave, temperature be 80-170 DEG C.
The palladium salt is one or both of palladium bichloride, palladium nitrate, chlorine palladium acid.
The molysite is ferric nitrate, iron chloride, ferric sulfate, ferrous nitrate, frerrous chloride, one kind in ferrous sulfate or several Kind.
Nitrate, chloride or oxide of the rare-earth salts for one or more of La, Ce, Pr, Nd, Y.
The rare-earth salts is the nitrate of La and Ce.
The aqueous slkali is one or more of sodium hydroxide, urea, ammonium hydroxide, ammonium carbonate, sodium carbonate.
The polyalcohol is ethylene glycol, the one or two of glycerine.
The salting liquid of the alkali metal or/and alkaline-earth metal is nitrate solutions one or more of in K, Na, Ca, Mg.
The modified condition that the preparation method of catalyst of the present invention is different from conventional dipping, ion exchange requires, point It is polyalcohol to dissipate solvent, and by the reduction of polyalcohol under alkaline condition, precious metal salt solution is reduced to the expensive gold of zeroth order Belong to, and polyalcohol is conducive to dispersion of the noble metal in carrier surface, makes noble metal uniform in carrier surface as dispersion solvent Dispersion, is conducive to contact of the CO molecules with catalyst.
The preparation method of catalyst of the present invention is different from conventional circumfluence method, and reaction condition is autoclave, is utilized The pressure that autoclave generates in temperature-rise period can reduce noble metal grain size to 10 nanometers hereinafter, and noble metal nano particles point It dissipates uniform.
Catalyst of the present invention containing rare earth oxide is mutually acted synergistically by rare earth oxide with noble metal, Advantageously reduce the content that noble metal is concentrated in catalysis.
One or more of catalyst of oxide of the present invention containing K, Na, Ca, Mg, K, Na, Ca, Mg oxide New species are generated to provide effective activated centre with carrier function, weaken the interaction in carrier and activated centre.
Compared with prior art, catalyst of the present invention has following advantages：
（1）Effectively eliminating for CO can be realized under normal temperature condition；
（2）Good moisture resistance properties.
（3）Low bullion content.
（4）Not easy in inactivation, service life are long.
Description of the drawings
Fig. 1 is the stability test of catalyst of the present invention.
Specific embodiment
The assay method of various embodiments of the present invention and comparative example is：
Evaluating catalyst method：CO catalytic oxidations are atmospheric fixed bed（Internal diameter is 6mm）Middle carry out performance evaluation.Used Unstripped gas forms：CO is 1000 ~ 30000ppm, remaining is air, air speed 6000mlg-1·h-1, unstripped gas first passes through one A bubbler equipped with water, brings the saturated steam under reaction temperature into（30 DEG C of saturated water is brought in 30 DEG C or more of reaction into Steam）, then using catalyst bed.Using GC-7890II gas chromatographs, CO in thermal conductivity detector (TCD) on-line analysis tail gas Concentration.The complete conversion temperatures of CO（Remaining CO is 1ppm less than the gas chromatographic detection limit）For the minimum response temperature of CO, claim For minimum full conversion temperature, T is used100It represents.
Embodiment one
The preparation of carrier：1.81 grams of iron chloride is taken to be added in 15 grams of distilled water, is added dropwise and fills 27.2mL mass point Number is in 25% ammonia spirit, then it is 10 to adjust pH value with ammonium hydroxide；At room temperature, it stirs 4 hours, then filtering and washing, in 60 DEG C Lower drying, 400 DEG C of roastings, is denoted as carrier Z-1.
The preparation of Pd/Z-1 catalyst：100mL ethylene glycol is measured in three-necked flask, it is a concentration of that 3mL is added in stirring 6mg/mL palladium bichlorides and a concentration of 1mol/L solution of cerium chloride by oxidation of 0.20mL add in three-necked flask, and pH is adjusted with 0.4mol/L sodium carbonate It is 12 to be worth, and adds in 1gZ-1 carriers；It is transferred in autoclave, 130 DEG C are reacted 1 hour, are filtered, and washing, 60 DEG C of dryings are urged Agent.
Evaluating catalyst test shows that using catalyst prepared by this method be the complete of 30000ppm in carbonomonoxide concentration Full conversion temperature（T100）It is 30 DEG C.
Embodiment two
The preparation of carrier：2.70 grams of ferric nitrates is taken to be added in 15 grams of distilled water, is added dropwise and fills 40mL concentration In 0.4mol/L sodium carbonate liquors, and it is 8.5 to adjust pH value with 0.4mol/L sodium carbonate；At room temperature, stirring 3 hours, then Filtering and washing, it is dry at 60 DEG C, it is denoted as carrier Z-2.
The preparation of Pd/Z-2 catalyst：50mL ethylene glycol is measured in three-necked flask, 4.35mL concentration is added in stirring Three-necked flask is added in for 2.3mg/mL palladium nitrate solutions, it is 10.5 to adjust pH value with 1mol/L sodium hydroxides, adds in 1gZ-2 and carries Body；It is transferred in autoclave, 170 DEG C are reacted 3 hours, are filtered, and washing, 100 DEG C of dryings obtain catalyst.
Evaluating catalyst test show using catalyst prepared by this method carbonomonoxide concentration for 10000ppm when T100It is 27 DEG C.
Embodiment three
The preparation of carrier：4.46 grams of ferric sulfate is taken to be added in 15 grams of distilled water, is added dropwise and fills ammonium carbonate and ammonium hydroxide Mixed solution（By metering ratio, molar ratio 1:1）, and it is 7 to adjust pH value with 25% ammonium hydroxide；At 60 DEG C, stirring 4 hours, so Filtering and washing afterwards, dry at 80 DEG C, 500 DEG C of roastings are denoted as carrier Z-3.
The preparation of Pd/Z-3 catalyst：10mL ethylene glycol and 10mL glycerine are measured in three-necked flask, is added in stirring Enter a concentration of 2.3mg/mL palladium nitrates of 0.50mL, 0.34mL concentration 2.3mol/L praseodymium nitrates and 0.32 concentration 2mol/L cerous nitrates Mixed solution adds in three-necked flask, with ammonium carbonate and ammonium hydroxide（Molar ratio is 1:1）It is 9 to adjust pH value, adds in 1gZ-3 carriers；Turn It moves in autoclave, 90 DEG C are reacted 4 hours, are filtered, and washing, 100 DEG C of dryings obtain catalyst.
Evaluating catalyst test show using catalyst prepared by this method carbonomonoxide concentration for 2000ppm when T100It is 23 DEG C.
Example IV
The preparation of carrier：2.70 grams of ferric nitrates is taken to be added in 15 grams of distilled water, is added dropwise and fills 0.4mol/L carbonic acid Sodium solution, and it is 8.5 to adjust pH value with 0.4mol/L sodium carbonate liquors；At room temperature, it stirs 3 hours, then filtering and washing, in It is dry at 60 DEG C, it is denoted as carrier Z-4.
The preparation of Pd/Z-4 catalyst：25mL ethylene glycol is measured in three-necked flask, 4.35mL concentration is added in stirring Three-necked flask is added in for 2.3mg/mL palladium nitrates and a concentration of 2mol/L cerous nitrates mixed solutions of 0.73mL, with 1mol/L hydroxides It is 10.5 that sodium, which adjusts pH value, adds in 1gZ-4 carriers；It is transferred in autoclave, 160 DEG C are reacted 3 hours, are filtered, washing, 100 DEG C It is dry, obtain catalyst.
Evaluating catalyst test show using catalyst prepared by this method carbonomonoxide concentration for 5000ppm when T100It is 26 DEG C.
Embodiment five
The preparation of carrier：Take a concentration of 2mol/L cerous nitrates of 2.70 grams of ferric sulfate, 0.41mL and a concentration of 2mol/L nitre of 0.41mol Sour lanthanum is added in 15 grams of distilled water, is added dropwise and fills 0.4mol/L sodium carbonate liquors, and with ammonium carbonate and ammonium hydroxide It is 10 that mixed solution, which adjusts pH value,；At 60 DEG C, stir 4 hours, then filtering and washing, dry at 60 DEG C, is denoted as carrier Z- 5,500 DEG C of roasting 4h, are denoted as carrier Z-5 '.
The preparation of Pd/Z-5 catalyst：15mL ethylene glycol and 135mL glycerine are measured in three-necked flask, is added in stirring Enter a concentration of 2.3mg/mL palladium nitrate solutions of 4.35mL, 0.19 gram of magnesium nitrate and 0.15 gram of potassium nitrate and add in three-necked flask, use It is 8 that 1mol/L sodium hydroxides, which adjust pH value, adds in 1gZ-5 and Z-5 ' mixed carriers（Mass ratio is 1:1）；It is transferred to autoclave In, 170 DEG C are reacted 1 hour, are filtered, and washing, 100 DEG C of dryings obtain catalyst.
Evaluating catalyst test show using catalyst prepared by this method carbonomonoxide concentration for 30000ppm when T100It is 30 DEG C.
Embodiment six
The preparation of carrier：A concentration of 2mol/L cerous nitrates of 2.70 grams of iron chloride, 0.73mL is taken to be dissolved in 15 grams of distilled water, and will This solution is added in reactor.1mol/L urea is added dropwise to above-mentioned solution, until pH is value 7；At room temperature, stirring 1 is small When, then filtering and washing, dry at 100 DEG C, and 500 DEG C of roasting 4h are denoted as carrier Z-6.
The preparation of Pd/Z-6 catalyst：Glycerine 150mL is measured in three-necked flask, 5.43mL concentration is added in stirring Three-necked flask is added in for 2.3mg/mL palladium nitrate solutions and 0.23 gram of potassium nitrate, it is 8 to adjust pH value with 1mol/L sodium hydroxides, is added Enter 1gZ-6 mixed carriers；It is transferred in autoclave, 130 DEG C are reacted 4 hours, are filtered, and washing, 100 DEG C of dryings obtain catalyst.
Evaluating catalyst test show using catalyst prepared by this method carbonomonoxide concentration for 2000ppm when T100It is 25 DEG C.
Embodiment seven
The preparation of carrier：Take 4.46 grams of ferric sulfate and a concentration of 2mol/L yttrium chlorides of 0.21mL and a concentration of 0.2mol/L of 0.2mL Sodium chloride is added in 15 grams of distilled water, is added dropwise and fills 0.4mol/L sodium carbonate liquors, and adjusts pH value with ammonium hydroxide It is 8.5；At room temperature, it stirs 3 hours, then filtering and washing, dry at 100 DEG C, is denoted as carrier Z-7.
The preparation of Pd/Z-7 catalyst：Ethylene glycol 10mL is measured in three-necked flask, 5.43mL concentration is added in stirring Three-necked flask is added in for 2.3mg/mL chlorine palladium acid and a concentration of 2mol/L solution of cerium chloride by oxidation of 0.73mL, with 1mol/L urea liquid tune It is 10.5 to save pH value, adds in 1gZ-7 carriers；It is transferred in autoclave, 150 DEG C are reacted 3 hours, are filtered, washing, 100 DEG C of dryings, Obtain catalyst.
Evaluating catalyst test show using catalyst prepared by this method carbonomonoxide concentration for 5000ppm when T100It is 22 DEG C.
Comparative example one
The preparation of carrier：A concentration of 2mol/L aluminum nitrates of 55mL are taken, is added dropwise and fills 0.4mol/L sodium carbonate liquors, and It is 8.5 to adjust pH value with ammonium hydroxide；At room temperature, it stirs 3 hours, then filtering and washing, dry at 100 DEG C, 600 DEG C of roastings 4h is denoted as carrier DZ-1.
The preparation of Pd/DZ-1 catalyst：Ethylene glycol 50mL is measured in three-necked flask, 5.43mL concentration is added in stirring Three-necked flask is added in for 2.3mg/mL palladium nitrates and a concentration of 2mol/L cerous nitrate solutions of 0.73mL, it is molten with 1mol/L sodium hydroxides It is 10.5 that liquid, which adjusts pH value, adds in 1g DZ-1 carriers；170 DEG C are reacted 3 hours, are filtered, and washing, 100 DEG C of dryings are catalyzed Agent.
Evaluating catalyst test show using catalyst prepared by this method carbonomonoxide concentration for 10000ppm when T100It is 45 DEG C.
Comparative example two
The preparation of carrier：2.70 grams of ferric nitrates and a concentration of 2mol/L cerous nitrates of 0.73mL is taken to be added in 15 grams of distilled water, it will It is added dropwise in the mixed solution for filling ammonium carbonate and ammonium hydroxide, and it is 8.5 to adjust pH value with 25% ammonium hydroxide；At room temperature, it stirs 3 hours, then filtering and washing, dry at 60 DEG C, is denoted as carrier DZ-2.
The preparation of Pd/DZ-2 catalyst：1gDZ-2 carriers are weighed in beaker, add in a concentration of 2.3mg/mL nitre of 5.43mL Sour palladium impregnates 4h, and 100 DEG C of dryings obtain catalyst.
Evaluating catalyst test show using catalyst prepared by this method carbonomonoxide concentration for 10000ppm when T100It is 55 DEG C.
Carry out hydrosphere steadiness investigation to the optimal catalyst of screening, catalyst amount 0.3g, CO contents are in unstripped gas 10000ppm, remaining is air.Reaction temperature is 35 DEG C, relative humidity 5%, and reaction gas air speed is 10000mLg-1·h-1, Catalyst activity in 500h declines seldom.

Claims (10)

1. a kind of CO room-temperature catalytic oxidation catalysts, it is characterised in that the catalyst is prepared by following two methods：
Method one：
1）It is 7 ~ 12 to adjust pH value by aqueous slkali again after molysite is mixed with aqueous slkali, and in room temperature ~ 80 DEG C, reaction 0.5 ~ 5 is small When, filtered, washing obtains iron hydroxide after 50 ~ 100 DEG C of dryings, and oxygen is obtained after being roasted 0.5 ~ 10 hour at 300 ~ 600 DEG C Change iron；
2）In the situation comprising or not comprising rare-earth salts and the salting liquid comprising or not comprising alkali metal or/and alkaline-earth metal In the case of, palladium salt solution, iron oxide or/and iron hydroxide, polyalcohol are mixed, it is 8 ~ 13 to adjust pH value by aqueous slkali, is turned Autoclave is moved to, in 80 ~ 200 DEG C of hydro-thermal reactions 0.1 ~ 4 hour, catalyst is obtained after filtered, washing, 60 ~ 120 DEG C of dryings；
Method two：
1）After molysite, rare-earth salts are mixed with aqueous slkali, then it is 7 ~ 12 to adjust pH value by aqueous slkali, is reacted in room temperature ~ 80 DEG C 0.5 ~ 5 hour, filtered, washing obtained rare earth modified iron hydroxide after 50 ~ 100 DEG C of dryings, in 300 ~ 600 DEG C of roastings Rare earth modified iron oxide is obtained after 0.5 ~ 10 hour；
2）In the case of the salting liquid comprising or not comprising alkali metal or/and alkaline-earth metal, by palladium salt solution, polyalcohol and dilute After the iron oxide of land reform or/and the mixing of rare earth modified iron hydroxide, it is 8 ~ 13 to adjust pH value by aqueous slkali, and transfer is supreme Kettle is pressed, in 80 ~ 200 DEG C of hydro-thermal reactions 0.1 ~ 4 hour, catalyst is obtained after filtered, washing, 60 ~ 120 DEG C of dryings.
2. catalyst as described in claim 1, it is characterised in that in the catalyst mass percentage of Pd for 0.05 ~ 3%, the mass percentage of rare earth oxide is 0 ~ 30%, the mass percentage of the oxide of alkali metal or/and alkaline-earth metal It is 0 ~ 10%.
3. catalyst as described in claim 1, it is characterised in that two step 1 of the method one and method）In pH value be 7.5 ~10；Two step 2 of the method one and method）In pH value be 8 ~ 10；Step 1 in the method one and method two）Dry temperature Spend is 60 ~ 100 DEG C；Step 2 in the method one and method two）Hydro-thermal reaction in autoclave, temperature be 80-170 DEG C.
4. catalyst as described in claim 1, it is characterised in that the palladium salt is one in palladium bichloride, palladium nitrate, chlorine palladium acid Kind or two kinds.
5. catalyst as described in claim 1, it is characterised in that the molysite is ferric nitrate, iron chloride, ferric sulfate, nitric acid are sub- One or more of iron, frerrous chloride, ferrous sulfate.
6. catalyst as described in claim 1, it is characterised in that the rare-earth salts is one kind or several in La, Ce, Pr, Nd, Y Nitrate, chloride or the oxide of kind.
7. catalyst as claimed in claim 6, it is characterised in that the rare-earth salts is the nitrate of La and Ce.
8. catalyst as described in claim 1, it is characterised in that the aqueous slkali is sodium hydroxide, urea, ammonium hydroxide, carbonic acid One or more of ammonium, sodium carbonate.
9. catalyst as described in claim 1, it is characterised in that the polyalcohol is ethylene glycol, one kind of glycerine or two Kind.
10. catalyst as described in claim 1, it is characterised in that the salting liquid of the alkali metal or/and alkaline-earth metal for K, One or more of nitrate solution in Na, Ca, Mg.
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