CN106964348B - A kind of formaldehyde pollutants room temperature catalytic oxidation catalyst and its preparation method and application - Google Patents
A kind of formaldehyde pollutants room temperature catalytic oxidation catalyst and its preparation method and application Download PDFInfo
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- CN106964348B CN106964348B CN201710243810.3A CN201710243810A CN106964348B CN 106964348 B CN106964348 B CN 106964348B CN 201710243810 A CN201710243810 A CN 201710243810A CN 106964348 B CN106964348 B CN 106964348B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
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Abstract
A kind of formaldehyde pollutants room temperature catalytic oxidation catalyst and its preparation method and application, the catalyst is with a water aluminium oxide (AlOOH) for carrier, precious metals pt, Pd are supported on AlOOH using the methods of infusion process, be prepared it is a kind of under atmospheric pressure at room can will pollute formaldehyde in air efficiently catalyzing and oxidizing at harmless carbon dioxide and water catalyst.AlOOH carrier is as obtained by aluminium hydroxide roasting direct, and preparation process is simply repeatable, large specific surface area, hydroxyl are more；When the present invention uses nitrate as precursor solution, Pt/AlOOH or Pd/AlOOH catalyst obtained has higher noble metal dispersion degree, to obtain more excellent room temperature purifying formaldehyde effect.Experiment test shows that in the air that relative humidity RH is 0~80%, concentration of formaldehyde 80ppm, catalyst oxidation formaldehyde conversion can maintain 100% in a long time.
Description
Technical field
The invention belongs to catalyst and environmental protection technical field, and in particular to a kind of room temperature of indoor pollutant formaldehyde is urged
Change oxidation catalyst and its preparation method and application.
Background technique
In recent years, formaldehyde poisoning event took place frequently.2014, Zhejiang Normal University's bedroom formaldehyde poisoning event, Nanchang
Fort kindergarten there is collective's formaldehyde poisoning；2015, Shanghai Chongming Yu An primary school new camupus formaldehyde, ammonia were exceeded；In July, 2016
1, there are the symptoms such as nausea, high fever, bronchial inflammation successively in the several childs in Jilin kindergarten, the reason is that newly-built child
Caused by the formaldehyde of garden.Currently, formaldehyde is confirmed as possibility carcinogenic substance by Environmental Protection Agency (EPA), defended by the world
The international cancer research institution (IARC) of raw tissue subordinate is determined as 1 class carcinogen.And formaldehyde derive from extensively construction material,
The release of decorative article and furniture material etc..In order to meet increasingly strict Law on Environmental Protection Laws & Regulations and meet people to more
The pursuit of high-quality life, being effectively removed indoor formaldehyde gas becomes current problem in the urgent need to address.
Currently, the method for administering formaldehyde has ventilation method, the green plants method of purification, active carbon adsorption, Ozonation, light
The methods of catalysis method, anion fine-purification method, room-temperature catalytic oxidation method, plasma technology method, molecular complex technology law.In these sides
In method, ventilation method is the content for reducing harmful substance in room air with outdoor air flowing by indoor, however formaldehyde
Pollution sources generally require three to ten five years deenergized periods, and deenergized period is too long；The green plants method of purification is the light by plant
The cooperation indoor formaldehyde of absorption, but act on limited；Active carbon adsorption is adsorbed using the high-ratio surfaces such as active carbon substance
Formaldehyde, but secondary pollution can be generated；Ozonation is that decomposition is oxidized the formaldehyde into using the strong oxidizing property of ozone, but ozone itself
With toxicity；Photocatalytic method be using photochemical catalyst under specific light source irradiation catalysis oxidation formaldehyde, but this method low efficiency, and need
Additional energy is provided；Anion fine-purification method is negative aeroion by condensation suction-operated, is attached on formaldehyde, is formed big
Ion settles down, but this method because caused by decorations the pollution such as formaldehyde, benzene homologues clean-up effect it is limited；Plasma technology
Method is a large amount of plasma oxidation formaldehyde to be generated by electric discharge, but this method generates ozone and causes secondary pollution；Molecular complex technology
Method utilizes the molten water characteristic of formaldehyde and ammonia, and room air is introduced into clarifier, toxic gas therein is passed through molecular complex
The complexing decomposing solution of agent (formaldehyde catching agent) and water composition, finally converts the pollutant in room air in irreversible
Property macromolecular chain solid matter, but this method solution needs Chang Genghuan, energy consumption big.
Conventional catalyst oxidizing process be using catalyst catalysis oxidation formaldehyde under the action of thermal energy, but this method need temperature compared with
Height, energy consumption are big.The catalytic oxidation technologies of efficient degradation formaldehyde have many advantages, such as energy saving, efficient, sustainable at room temperature, in recent years at
For the research hotspot of this field.As referred to a kind of urging for catalysis oxidation formaldehyde at room temperature in 103736484 A of Chinese patent CN
Agent, the catalyst are made of carried noble metal on Nano tube array of titanium dioxide, the catalyst life is short, it is active relatively
Poor activity under difference, anhydrous condition.A kind of anodised aluminium of Metal Substrate is referred in 106040230 A of Chinese patent CN except first
The integrated catalyst of aldehyde, the catalyst are with a kind of special orderly anodic oxidation aluminum material of the self-growing self assembly of metallic aluminium
Substrate, but its carrier and catalyst preparation are complicated, have secondarily polluted water generation in preparation process, and purifying formaldehyde is imitated at room temperature
Fruit is poor, " when platinum content is 2-2.5wt%, formaldehyde conversion reaches 72% " at normal temperature, and bullion content is higher, at
This height is unfavorable for promoting.
Summary of the invention
The pernicious gas formaldehyde high-efficiency polluted in air is urged at room temperature, at a normal the purpose of the present invention is to provide a kind of
Change the catalyst for being oxidized to harmless carbon dioxide and water.
It is a further object to provide a kind of methods and applications for preparing above-mentioned catalyst.
For achieving the above object, the invention adopts the following technical scheme:
A kind of formaldehyde pollutants room temperature catalytic oxidation catalyst, is noble metal carrier catalyst, in the catalyst
Active component is Pt or Pd, and carrier is a water aluminium oxide AlOOH, and the load capacity of active component is 0.05~5.0wt%.
The catalyst uses AlOOH carrier, and large specific surface area, hydroxyl are more, are conducive to the expansion of formaldehyde molecule and product
Dissipate, the dispersion of noble metal and formaldehyde molecule catalyst surface absorption and oxidation.Preferably, hydroxyl oxygen in the catalyst
Ratio (the O of the total oxygen of ZhanOH/OTotal) it is 40~80%.
Catalyst of the present invention, one water aluminium oxide (AlOOH) of carrier can be under the conditions of 250~450 DEG C (preferably
Temperature range is 300~400 DEG C) by aluminium hydroxide (Al (OH)3, self-control or business) roasting and be made, or use it is commercially available
AlOOH is carrier.Using using the methods of infusion process, the precipitation method by noble-metal-supporteds such as Pt, Pd on AlOOH, active component
The load capacity of the noble metals such as Pt, Pd is 0.05~5.0% (preferably 0.2~2.0%), and noble metals such as active component Pt, Pd
Most probable partial size be less than 5nm (preferably smaller than 1nm).
The present invention also provides the preparation methods of the catalyst, and the methods of infusion process, precipitation method can be used and prepared, packet
Include following steps:
(1) by aluminium hydroxide Al (OH)3Roasting preparation AlOOH carrier under the conditions of 250~450 DEG C；
(2) in a solvent, precious metals pt or the precursor solution and AlOOH carrier of Pd is added, controls the solid-liquid of mixed liquor
Than stirring is to uniformly mixed so that Active components distribution is uniform；
(3) under room temperature or heating condition, continue stirring and dried afterwards to sticky (starchiness)；
(4) desciccate is ground into powdery, 250~450 DEG C are roasted；
(5) reduction treatment of precious metals pt or Pd.
In step (2), the precursor solution of the noble metals such as Pt, Pd, Pt precursor solution can be Pt (NH3)2(NO2)2、Pt
(NO3)2、H2PtCl6·6H2O；Pd precursor solution can be PdCl2、Pd(NO3)2·nH2O、Pd(OAc)2；Before noble metal used
Driving liquid solution can be the one or more of the above solution.It is preferred that precursor solution is the nitrate of Pt or Pd, such as Pt (NH3)2
(NO2)2、Pt(NO3)2、Pd(NO3)2·nH2O), the most probable partial size of its noble metal of catalyst obtained is less than 1nm.
In step (2), one of the solvent preferred alcohol, deionized water, benzene or a variety of, solid-to-liquid ratio are controlled 1
~80% (preferably 10~40%).Mixing time is no less than 0.1h, and the temperature of stirring is not less than 20 DEG C.
In step (3), the temperature of drying process can be 50~200 DEG C (preferably 90~130 DEG C), drying time 0.05
~60h (preferably 6~12h).
In step (4), in the roasting apparatus such as Muffle furnace carry out maturing temperature can for 250~450 DEG C (preferably 300~
400 DEG C), calcining time is 0.05~120h (preferably 1~5h).
In step (5), reduction treatment be can be used in pure hydrogen or hydrogen-containing gas atmosphere, (the preferable temperature at 250-450 DEG C
Section is 300~400 DEG C) vapour phase reduction processing is carried out to catalyst obtained；Or in the reproducibilities solvent such as sodium borohydride,
Liquid-phase reduction processing is carried out to catalyst obtained using liquid phase reduction.
According to the above scheme, it in step (2), after solvent being added into the precursor solution of the noble metals such as Pt, Pd, is stirring
Under the conditions of mixing, AlOOH carrier is added, controls the solid-to-liquid ratio of mixed solution, and continuing stirring keeps Active components distribution uniform；Also
It can be used and AlOOH carrier is added in solvent after stirring preparation AlOOH slurry first, then addition noble metal precursor body is molten thereto
The method of liquid.
According to the above scheme, in preparation method step (3), heating stirring can be omitted to paste process, directly adopt filtering etc.
Mode is separated by solid-liquid separation, and is then dried.
The invention further relates to application of the catalyst in formaldehyde through catalytic oxidation.
Formaldehyde pollution gas complete catalysts oxidation in air can be two under room temperature (5~40 DEG C) by the catalyst
Carbonoxide and water.The application method of catalyst of the invention are as follows: directly can directly be used with powder or particulate form；Or it adopts
With coating, impregnating conventional method, be coated onto the metal of different shapes such as honeycomb, threadiness, netted, plate, fabric,
On the supporter of the unlike materials such as ceramics, papery, the molding of catalyst is easily realized, be applied to air purifier, air-conditioning etc.
In equipment.
The utility model has the advantages that the present invention is to make by oneself or the Al of business (OH)3AlOOH prepared by roasting direct is carrier, is used
By noble-metal-supporteds such as Pt, Pd on AlOOH, preparing one kind will pollute in air at room temperature, at a normal for the methods of coating, dipping
Pernicious gas formaldehyde high-efficiency be catalytically oxidized to the catalyst of harmless carbon dioxide and water, be suitable for workshop, room, office
There are the environment of formaldehyde pollution in room, classroom, building materials market etc..
Compared with prior art, the invention has the advantages that
(1) present invention is recommended using self-control or the AlOOH carrier of business by self-control or business Al (OH)3Roasting direct institute
The AlOOH of preparation, purity are higher；Its preparation process is simply repeatable, easy to spread.X-ray diffraction (XRD) analyzes result table
Bright (Fig. 3), in 150-500 DEG C of roasting, Al (OH)3Crystal phase very big change has occurred: in 250-450 DEG C of roasting, Al
(OH)3AlOOH is formed because of dehydration；And in 500 DEG C of roastings, further dehydration forms γ-Al2O3；
AlOOH carrier large specific surface area provided by the invention, the more (O of hydroxylOH/OTotalHeight, as shown in table 4 and Fig. 7), have
Conducive to the diffusion of formaldehyde molecule and product, the dispersion of noble metal and formaldehyde molecule catalyst surface absorption and oxidation, thus
Higher purifying formaldehyde effect can be provided；
(2) so far, H is usually used2PtCl6·6H2O、PdCl2As noble metal precursor liquid solution, and it is of the invention
It is preferable to use Pt (NO3)2、Pt(NH3)2(NO2)2Or Pd (NO3)2·nH2O is as precursor solution.Through scanning electron microscope
(TEM) it is tested with BET specific surface area (BET), with H2PtCl6·6H2O、PdCl2Etc. comparing, such noble metal precursor is used
The active component good dispersion degree of Pt/AlOOH or Pd/AlOOH catalyst made from liquid solution, partial size are small (as shown in Figure 4, Figure 5),
Thus the catalyst is still able to maintain very high active (as shown in table 1, table 2, table 3) in anhydrous conditions, it is hereby achieved that
More excellent room temperature purifying formaldehyde effect；
(3) catalyst provided by the invention, can be in the case where not needing any additional energy, can at room temperature will be in air
Formaldehyde pollution gas complete catalysts oxidation is carbon dioxide and water, in control N2:O2=4:1 (volume ratio), relative humidity RH are 0
~80%, concentration of formaldehyde 80ppm, air speed are 180 000mlg-1·h-1, Pt/AlOOH or Pd/AlOOH catalyst
Conversion rate of oxidation is maintained at 100% (as shown in Figure 6) within considerable time；
(4) Pt/AlOOH or Pd/AlOOH catalyst life provided by the invention is long, high-efficient；The catalyst preparation of offer
Method is simple, easily operated, and catalyst performance repeatability is good, large-scale production easy to accomplish.
Detailed description of the invention
Fig. 1 is catalyst activity evaluating apparatus figure: 1 is oxygen；2 be nitrogen；3 be formaldehyde generating device；4 be mixing chamber；5
For quartz tube reactor；6 be formaldehyde detector；7: mass flow controller；8 be humidity generator；
Fig. 2 is the schematic diagram of honeycombed catalyst: (a) be honeycombed catalyst device figure: 1 is gas access；2 be quartz
Pipe, 3 be silica wool；4 be honeycombed catalyst；5 be ceramic fiber paper；6 be thermocouple；7 be gas vent；It (b) is honeycomb
Catalyst packing figure；
Fig. 3 is to roast Al (OH) under different temperatures in embodiment 13And 1Pt (N)/AlOOH catalyst XRD in embodiment 2
Figure；
Fig. 4 is 1Pt (N)/AlOOH catalyst (a) scanning electron microscope (TEM) figure and (b) partial size point in embodiment 2
Butut；
Fig. 5 is 1Pt (Cl)/AlOOH catalyst (a) TEM figure and (b) grain size distribution in embodiment 5；
Fig. 6 is 1Pt (N)/AlOOH catalyst activity durability test figure in embodiment 10；
Fig. 7 is x-ray photoelectron spectroscopy analysis (XPS) figure that different carriers prepare catalyst in comparative example 1: (a) being 1Pt
(N)/Al2O3With 1Pt (N)/AlOOH；It (b) is 1Pt (N)/P25 and 1Pt (N)/CC.
Specific embodiment
With reference to the accompanying drawing, further details of theory is given to technical solutions according to the invention by specific embodiment
It is bright, but it is necessary to note that following embodiment is served only for the description to summary of the invention, do not constitute the limit to the scope of the present invention
System.
In following embodiment, catalyst activity evaluating apparatus figure of the invention as shown in Figure 1, a kind of method be with powder or
Particulate form is directly used in catalyst activity evaluation, and another way is to be coated on honeycomb support body to form, system
Activity rating is carried out at honeycomb catalyst.
Wherein, the preparation and test of beaded catalyst: 40-60 mesh catalyst is fitted into the U-tube of 6mm internal diameter, U pipe is set
In constant temperature in 5-40 DEG C of water bath.The entrance of U-shaped reaction tube is passed through certain density formaldehyde, and exit gas passes through dedicated first
Aldehyde analyzer on-line analysis concentration of formaldehyde；
The preparation and test of honeycombed catalyst: the catalyst fines after milling are mixed by 30% solid-to-liquid ratio with water,
It is formulated as slurry；Then it is coated on honeycomb-typed steel, honeycomb catalyst sample is made after drying roasting；It will
U-shaped reaction tube in Fig. 1 device replaces with straight tube, and it is 30mm that the catalyst of 1in*1in (inch, about 25.4mm), which is packed into internal diameter,
Straight tube in, the filling figure of catalyst is as shown in Fig. 2, straight tube is placed in constant temperature in 25 DEG C of water bath.The entrance of straight tube is passed through
Certain density formaldehyde, exit gas pass through special-purpose formaldehyde analyzer on-line analysis concentration of formaldehyde.
Catalyst activity evaluation experimental condition is as follows: under room temperature, volume forms (volume ratio): oxygen: 20%,
Nitrogen: 80%, relative humidity RH are 0~50%, and formaldehyde gas is blown into reaction system by nitrogen, and control concentration of formaldehyde is 80ppm,
Reaction velocity (GHSV) is 180 000mlg-1·h-1。
The preparation method of 1: one water aluminium oxide (AlOOH) of embodiment
Make or buy first the Al (OH) of business by oneself3.Make Al (OH) by oneself in laboratory3Method there are mainly two types of: it is soluble
Aluminium salt reacts with ammonia water, sodium metaaluminate is reacted with excess carbon dioxide.
Preparation Al (OH) is reacted with ammonia water with aluminum soluble salt3The step of are as follows: measure the AlCl that 10ml concentration is 1mol/L3
Solution enters the weak aqua ammonia that concentration is 0.5mol/L under stirring conditions dropwise thereto, and the instillation time controls in 2h or more,
Until occurring there is no precipitating, then by respectively centrifuge washing 3 times of gained precipitating deionized water and ethyl alcohol, then done
It is dry to get arrive Al (OH)3。
Preparation Al (OH) is reacted with excess carbon dioxide with sodium metaaluminate3The step of are as follows: 5.0g sodium metaaluminate solid is weighed,
It is dissolved in deionized water, stirs evenly, by excessive CO2Gas is passed through wherein, until occurring there is no precipitating, is connect
By gained precipitating deionized water and ethyl alcohol respectively centrifuge washing 3 times, then be dried to get to Al (OH)3。
By above-mentioned preparation or business Al (OH)3Respectively in 150 DEG C, 200 DEG C, 250 DEG C, 300 DEG C, 400 DEG C, 450
DEG C, roast 3h under the different temperatures such as 500 DEG C or do not roast, it is as shown in Figure 3 through the resulting result of XRD analysis.The result shows that
When 150-500 DEG C of roasting, Al (OH)3Crystal phase very big change has occurred: in 250-450 DEG C of roasting, Al (OH)3Because of dehydration
And form AlOOH；And in 500 DEG C of roastings, further dehydration forms γ-Al2O3。
The preparation of embodiment 2:1Pt (N)/AlOOH catalyst and its active testing
2ml Pt (NO is measured with pipette3)2(10g Pt/L, the same below) is placed in 50ml beaker；Stirring is added thereto
Rotor, puts to stirring on blender, appropriate amount of deionized water is added, and 300 DEG C of roastings in 2.0g embodiment 1 are added into beaker and prepare
AlOOH carrier；12h is stirred at room temperature, keeps Active components distribution uniform；After stirring, two parts of samples are heated
70 DEG C are warming up to, continues stirring to sticky (starchiness)；Sample is put into drying box, (110 DEG C, 12h) are dried；It is dry
After dry, sample is taken out, after being cooled to room temperature, is ground into powdery；Sample is placed in crucible, Muffle furnace is put into
In roasted (300 DEG C, 3h)；After calcination, after Muffle in-furnace temperature is cooled to room temperature, by sample tabletting and screening is
40~60 mesh are to be restored.
Using vapour phase reduction in pure hydrogen or hydrogen-containing gas atmosphere.In reduction process, reducing gas is hydrogen and nitrogen
Mixed gas, gas composition: hydrogen: 30%, nitrogen: 70%, reaction velocity (GHSV) is 30 000mlg-1·h-1, reduction
Temperature is 300 DEG C, and the recovery time is 1~2h to get 1Pt (N)/AlOOH catalyst.Its scanning electron microscope (TEM) and grain
Diameter distribution such as Fig. 4.
The catalyst that will be prepared is placed in the U-shaped quartz ampoule that diameter is 6mm and carries out catalyst activity evaluation, experiment
Condition is as follows: under the conditions of 25 DEG C, gas composition: and oxygen: 20%, nitrogen: 80%, relative humidity RH are 0~50%, formaldehyde
Gas is blown into reaction system by nitrogen, and control concentration of formaldehyde is 80ppm, and reaction velocity (GHSV) is 180 000mlg-1·h-1.The results are shown in Table 1.
The preparation of embodiment 3:0.5Pt (N)/AlOOH catalyst and its active testing
1ml Pt (NO is measured with pipette3)2(10g Pt/L) is placed in 50ml beaker；Subsequent preparation step can press
Prepared by step described in embodiment 2, active testing step is also tested by step described in embodiment 2.As a result such as 1 institute of table
Show.
The preparation of embodiment 4:0.2Pt (N)/AlOOH catalyst and its active testing
0.4ml Pt (NO is measured with pipette3)2(10g Pt/L) is placed in 50ml beaker；Subsequent preparation step can
It is prepared by step described in embodiment 2, active testing step is also tested by step described in embodiment 2.As a result such as table 1
It is shown.
The preparation of embodiment 5:1Pt (Cl)/AlOOH catalyst and its active testing
6.32ml H is measured with pipette2PtCl6·6H2O (3.76g Pt/L) is placed in 50ml beaker, next system
Standby step can be prepared by step described in embodiment 2, and active testing step is also tested by step described in embodiment 2.
The scanning electron microscope (TEM) and particle diameter distribution such as Fig. 5 of obtained catalyst.The results are shown in Table 1.
The preparation of embodiment 6:1Pd (Cl)/AlOOH catalyst and its active testing
10ml PdCl is measured with pipette2(2.0g Pd/L) is placed in 50ml beaker, and subsequent preparation step can press
Prepared by step described in embodiment 2, active testing step is also tested by step described in embodiment 2.Activity review knot
Fruit is as shown in table 1.
The preparation of embodiment 7:0.5Pd (Cl)/AlOOH catalyst and its active testing
5ml PdCl is measured with pipette2(2.0g/Pd/L) is placed in 50ml beaker, and subsequent preparation step can be by reality
It applies step described in example 2 to be prepared, active testing step is also tested by step described in embodiment 2.As a result such as 1 institute of table
Show.
The oxidation of formaldehyde Activity Results of 1 different catalysts of tablea
Note: 1, the oxidation of formaldehyde Activity Results of different catalystsaIt indicates when data are taken from reaction balance 1h (similarly hereinafter)
2、RHbIt indicates relative humidity (similarly hereinafter)
3、1cIndicate that noble metal quality accounts for the degree (similarly hereinafter) of catalyst gross mass
4、NdIndicate element (similarly hereinafter) contained by precursor solution used
5、100eIt indicates that concentration of formaldehyde is lower than the lower limit (0.5ppm) of on-line checking, is defaulted as conversion ratio 100% (similarly hereinafter)
Embodiment 8: the preparation of the catalyst of liquid-phase reduction method and its active testing
Before reduction process, it is catalyzed in embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and embodiment 7
The preparation step of agent can respectively prepared by step by its, is carried out at liquid-phase reduction using sodium borohydride to catalyst in reduction
Reason, active testing step also tested by step described in embodiment 2, and the results are shown in Table 2.
Table 2 is through NaBH4The oxidation of formaldehyde Activity Results of the catalyst of reduction
Embodiment 9: the preparation of honeycombed catalyst and its active testing
Its being pressed in embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and embodiment 7, respectively prepared by step
Catalyst is coated in honeycomb support surface, is placed on carrying out activity rating in straight tube, experiment condition by good catalyst
It is as follows: under room temperature, volume composition: oxygen: 20%, nitrogen: 80%, relative humidity RH are 0~50%, formaldehyde gas
Reaction system is blown by nitrogen, control concentration of formaldehyde is 80ppm, and reaction velocity (GHSV) is 180 000mlg-1·h-1, urge
Agent usage amount is 0.1g, and the results are shown in Table 3.
Table 3 is coated in the oxidation of formaldehyde Activity Results of the catalyst on honeycomb
The active durability test of embodiment 10:1Pt (N)/AlOOH catalyst
1Pt (N)/AlOOH catalyst is prepared by step described in embodiment 2, is placed on the U-shaped quartz that diameter is 6mm
Guan Zhong, experiment condition are as follows: under room temperature, volume composition: oxygen: 20%, nitrogen: 80%, relative humidity RH are
5%, formaldehyde gas is blown into reaction system by nitrogen, and control concentration of formaldehyde is 80ppm, and reaction velocity (GHSV) is 180
000ml·g-1·h-1。
As a result as shown in fig. 6, can body find out that 1Pt (N)/AlOOH catalyst in the atmosphere of RH=5%, is urged in 150h
Change the conversion ratio of oxidation formaldehyde still close to 100%.This shows that 1Pt (N)/AlOOH catalyst has good catalytic activity.
Comparative example 1: the catalyst and its active testing and result prepared using different carriers
Carrier in embodiment 2 is changed to TiO2(P25)、TiO2(super color), γ-Al2O3Equal carriers, remaining preparation step and
Activity test method and embodiment 2 are same, respectively obtain 1Pt (N)/P25,1Pt (N)/CC, 1Pt (N)/Al2O3Equal catalyst and its
Activity Results.
The wherein x-ray photoelectron spectroscopy analysis chart (XPS) of the catalyst of different carriers preparation such as Fig. 7, shows 1Pt
(N)/AlOOH catalyst has many advantages, such as that surface hydroxyl is more, noble metal dispersion degree is good.
By carrier in embodiment 2 be changed under the different temperatures such as 200 DEG C, 250 DEG C, 400 DEG C, 450 DEG C, 500 DEG C roasting and
The Al (OH) not roasted3Equal carriers, remaining preparation step and activity test method and embodiment 2 are same, respectively obtain 1Pt (N)/
AlOOH-200 DEG C, 1Pt (N)/AlOOH-300 DEG C, 1Pt (N)/AlOOH-400 DEG C, 1Pt (N)/AlOOH-500 DEG C and 1Pt (N)/
Al(OH)3Equal catalyst and its Activity Results.Catalyst correlation properties are tested by BET and XPS analysis obtains, and analyze its OOH/
OTotalValue, the results are shown in Table 4.
The XPS test related data and oxidation of formaldehyde Activity Results of 4 different catalysts of table
Note: 1, SBET aIndicate the specific surface area (similarly hereinafter) of catalyst
2、OOH/OTotal bIndicate the degree (similarly hereinafter) of the total oxygen of hydroxyl oxygen Zhan contained by catalyst
3、200℃cIt indicates Al (OH)3Maturing temperature (similarly hereinafter)
Comparative example 2: different preparation sequences and method prepare catalyst and its active testing
In example 2, heating stirring is omitted to paste process, is directlyed adopt the modes such as filtering and is separated by solid-liquid separation,
It is remaining same with embodiment 2, it obtains catalyst and is named as 1Pt (N)/AlOOH-a.
Appropriate amount of deionized water is first added into beaker, the AlOOH carrier that 2.0g is prepared is added, then with pipette amount
Take 2ml Pt (NO3)2(10g/L) is placed in 50ml beaker；Stirring rotator is added thereto, puts to stirring on blender, remaining with
Embodiment 2 is same, obtains catalyst and is named as 1Pt (N)/AlOOH-b.
Catalyst 1Pt (N)/AlOOH-b preparation process is omitted into heating stirring to paste process, directlys adopt filtering etc.
Mode is separated by solid-liquid separation, remaining is same with embodiment 2, is obtained catalyst and is named as 1Pt (N)/AlOOH-c.Measurement result
See Table 5 for details.
The different preparation sequences of table 5 and method prepare the Activity Results of catalyst
Comparative example 3: the Activity Results of different catalysts under the same test conditions
The catalyst and Chinese patent prepared as described in Example 2 discloses a kind of gold mentioned in 106040230 A of CN
Belong to the anodised aluminium of base except the integrated catalyst of formaldehyde carries out active comparison.According to the active testing condition of the patent: "
At room temperature, formaldehyde is that 37% formalin occurs, catalyst amount 0.3g, concentration of formaldehyde 200ppm, air speed 3000~
150000ml·g-1·h-1.", the results are shown in Table 6 (partial results disclose 106040230 A of CN from Chinese patent).
The Activity Results of 6 different catalysts of table under the same test conditions
Note: 1, Pt (N)/AlOOHaIndicate that catalyst is provided by the present invention with preceding method
2、Cat 6b、Cat 9cIndicate that Chinese patent discloses two catalyst that activity is best in 106040230 A of CN.
Claims (7)
1. a kind of formaldehyde pollutants room temperature catalytic oxidation catalyst, which is characterized in that catalyst system noble metal support type is urged
Agent, wherein active component is Pt, and carrier is that water aluminium oxide an AlOOH, the AlOOH is by aluminium hydroxide Al (OH)3?
It roasts and is made under the conditions of 300~450 DEG C, the load capacity of active component Pt is 0.05~5.0wt%, and most probable partial size is less than 5nm；
The ratio O of the total oxygen of hydroxyl oxygen Zhan in the catalystOH/OTotalIt is 50.6~80%；The catalyst the preparation method is as follows:
(1) by aluminium hydroxide Al (OH)3It is roasted under the conditions of 300~450 DEG C and carrier AlOOH is made；
(2) in a solvent, the precursor solution and AlOOH carrier of precious metals pt is added, controls the solid-to-liquid ratio of mixed liquor, stirring is extremely
It is uniformly mixed, the precursor solution is Pt (NH3)2(NO2)2Or Pt (NO3)2；
(3) dry after continuing stirring to starchiness under room temperature or heating condition；Or it is dry after being directly separated by solid-liquid separation；
(4) desciccate is ground into powdery, 250~450 DEG C are roasted；
(5) reduction treatment is carried out to the precious metals pt in product of roasting.
2. formaldehyde pollutants room temperature catalytic oxidation catalyst according to claim 1, which is characterized in that the active component
The most probable partial size of Pt is less than 1nm.
3. a kind of preparation method of formaldehyde pollutants room temperature catalytic oxidation catalyst described in claim 1, includes the following steps:
(1) by aluminium hydroxide Al (OH)3It is roasted under the conditions of 300~450 DEG C and carrier AlOOH is made；
(2) in a solvent, the precursor solution and AlOOH carrier of precious metals pt is added, controls the solid-to-liquid ratio of mixed liquor, stirring is extremely
It is uniformly mixed, the precursor solution is Pt (NH3)2(NO2)2Or Pt (NO3)2；
(3) dry after continuing stirring to starchiness under room temperature or heating condition；Or it is dry after being directly separated by solid-liquid separation；
(4) desciccate is ground into powdery, 250~450 DEG C are roasted；
(5) reduction treatment is carried out to the precious metals pt in product of roasting.
4. preparation method according to claim 3, which is characterized in that in step (2), the solvent be ethyl alcohol, go from
The solid-to-liquid ratio of one or more of sub- water, benzene, mixed liquor is controlled 1~80%.
5. preparation method according to claim 3, which is characterized in that in step (4), maturing temperature is 300~400 DEG C,
Calcining time is 1~5h.
6. preparation method according to claim 3, which is characterized in that in step (5), reduction treatment is using pure hydrogen or contains
In hydrogen atmosphere, vapour phase reduction processing is carried out to catalyst obtained at 250-450 DEG C；Or in sodium borohydride reduction
In solution, liquid-phase reduction processing is carried out to catalyst obtained using liquid phase reduction.
7. application of the formaldehyde pollutants room temperature catalytic oxidation catalyst described in claim 1 in formaldehyde through catalytic oxidation.
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| CN108445141B (en) * | 2018-01-30 | 2019-12-10 | 北京联合大学 | Low-temperature formaldehyde catalytic luminescent sensitive material |
| CN109012695A (en) * | 2018-08-17 | 2018-12-18 | 华东理工大学 | A kind of preparation method, thus obtained structural catalyst and its application of the structural catalyst of catalysis oxidation formaldehyde |
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| CN114100605A (en) * | 2020-09-01 | 2022-03-01 | 宁波方太厨具有限公司 | Room temperature catalytic formaldehyde oxidation catalyst and preparation method thereof |
| CN112158866B (en) * | 2020-09-04 | 2021-12-03 | 厦门大学 | Preparation method of hydroxy alumina and catalyst thereof |
| CN112121792A (en) * | 2020-09-29 | 2020-12-25 | 运城学院 | Catalyst for formaldehyde catalytic oxidation reaction and preparation method thereof |
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| CN115301231A (en) * | 2022-08-15 | 2022-11-08 | 中国科学院生态环境研究中心 | Noble metal catalyst for catalytic oxidation of formaldehyde and preparation method thereof |
| CN115739113A (en) * | 2022-11-23 | 2023-03-07 | 大气(广东)科技发展有限公司 | Catalyst for catalyzing formaldehyde at room temperature and preparation method thereof |
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