CN109225319A - Pt/SAPO-34 molecular sieve catalyst and preparation method thereof for toluene catalytic oxidation - Google Patents
Pt/SAPO-34 molecular sieve catalyst and preparation method thereof for toluene catalytic oxidation Download PDFInfo
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- CN109225319A CN109225319A CN201811336018.3A CN201811336018A CN109225319A CN 109225319 A CN109225319 A CN 109225319A CN 201811336018 A CN201811336018 A CN 201811336018A CN 109225319 A CN109225319 A CN 109225319A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
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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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
A kind of Pt/SAPO-34 molecular sieve catalyst and preparation method thereof for toluene catalytic oxidation, belongs to environmental catalysis purification techniques field.The present invention is handled in conjunction with hydrogen reduction using the infusion process for introducing dispersing agent in alcohol system, is prepared the high support type Pt/SAPO-34 molecular sieve catalyst of Pt good dispersion, utilization rate.Utilize Pt/SAPO-34 molecular sieve catalyst catalysis oxidation toluene in fixed bed reactors recited above, reaction gas is the toluene of 500~1000ppm, background gas is the nitrogen oxygen atmosphere of percent by volume 1:4, the overall flow rate of reaction gas and background gas is 30~100mL/min, and 0.1~1g, tabletting are carried out at 140 DEG C~250 DEG C to catalytic activity test continuous operation at the Pt/SAPO-34 molecular sieve catalyst of 40~60 mesh.The experimental results showed that catalyst of the present invention has many advantages, such as that initiation temperature is low, catalytic activity is high.
Description
Technical field
The invention belongs to environmental catalysis purification techniques fields, and in particular to Pt/SAPO-34 points for toluene catalytic oxidation
Sub- sieve catalyst and preparation method thereof.
Background technique
Volatile organic compounds (VOCs, Volatile Organic Compounds) is main atmosphere pollution,
Serious harm is brought to atmospheric environment and human health.Benzene homologues such as toluene etc. is as a kind of typical volatile organic compounds
It is widely used in the chemicals manufacturing industry such as ornament materials and paint, this kind of compound can stimulate skin, mucous membrane, to maincenter
System has anesthetic effect, and damages to ecological environment.Therefore research and development effectively remove in air the method for toluene and
Technique is of great significance.
There is the main method of toluene in common elimination air: absorption method, thermal incineration method, photocatalytic degradation method, plasma
Body edman degradation Edman, catalysis oxidation (burning) method etc..Catalytic oxidation have it is easy to operate, low energy consumption, it is high-efficient, without secondary pollution,
The advantages that applied widely.Catalyst used in this method can be roughly divided into noble metal catalyst and transition metal oxide is urged
Agent.Transition metal oxide price is relatively cheap, but there are initiation temperatures it is high, catalytic activity is low the problems such as.The expensive gold of support type
Belong to (Pt, Pd etc.) catalyst to be concerned due to relatively high low-temperature catalytic activity.
In recent years, the research of noble metal catalyst, which is mainly concentrated in pass through, selects suitable carrier and preparation side
Method improves the dispersibility and utilization rate of noble metal, under the premise of reducing noble metal dosage, significantly improves the performance of catalyst.
Research finds that the carrier of high-specific surface area has vital work for improving catalytic activity and reducing the load capacity of noble metal
With；In addition, dispersibility, stability and catalysis that the property of carrier surface and the preparation method of catalyst also will affect noble metal are lived
Property.Molecular sieve and molecular sieve type materials (such as USY, Beta, MOR, ZSM-5, FAU and CHA) have large specific surface area, cellular structure
The features such as rule, stability are high and acid-base property is adjustable is used for catalytic cracking, alkane as catalyst and catalyst carrier
In the important catalytic reaction process such as base and catalysis oxidation.Wherein, Chen etc. report with Beta (C.Chen, J.Zhu,
F.Chen,X,et al.Enhanced performance in catalytic combustion of toluene over
mesoporous Beta zeolite-supported platinum catalyst[J].Applied Catalysis B:
Environmental, 140-141 (2013) 199-205) and ZSM-5 (C.Chen, J.Zhu, F.Chen, X, et
al.Superior Performance in Catalytic Combustion of Toluene over KZSM-5Zeolite
Supported Platinum Catalyst[J].Applied Catalysis B:Environmental,140-141
(2013) 199-205) molecular sieve shows toluene catalytic oxidation reaction for the supported Pt catalysts of carrier preparation good
Catalytic performance, development prospect are wide.It should be noted that molecular sieve carried Pt catalyst generallys use traditional dipping legal system
It is standby.However this method is generally difficult to realize that Pt nanoparticle in the evenly dispersed of molecular sieve carrier surface, easily causes reunion, from
And reduce the utilization rate and catalytic efficiency of noble metal.
Micro porous molecular sieve SAPO-34 with CHA type topological structure is important a member of molecular sieves, the molecular sieve
There are relatively small aperture, high-specific surface area and high stability, and acidity can regulate and control in a certain range.At present by success
For exhaust gas from diesel vehicle NH3In the fields such as SCR denitration technology and methanol-to-olefins.The present invention is mainly with SAPO-34 molecular sieve
Carrier is both introduced the mode of polyvinylpyrrolidone dispersing agent in alcohol system, is prepared using a kind of improved dipping method
A series of SAPO-34 molecular sieve catalyst of supporting Pts, to obtain more excellent performance of toluene catalytic oxidation catalyst.
Summary of the invention
The object of the present invention is to provide a kind of Pt/SAPO-34 molecular sieve catalyst for toluene catalytic oxidation and its
Preparation method.Catalyst of the present invention has many advantages, such as that initiation temperature is low, catalytic activity is high.Divided using being introduced in alcohol system
The infusion process of powder handles in conjunction with hydrogen reduction, prepares the high support type Pt/SAPO-34 molecular sieve of Pt good dispersion, utilization rate
Catalyst.In order to achieve the above objectives, The technical solution adopted by the invention is as follows:
A kind of Pt/SAPO-34 molecular sieve catalyst for toluene catalytic oxidation of the present invention, the catalyst be with
SAPO-34 molecular sieve with octatomic ring CHA structure is as carrier, and supporting Pt nanoparticle is as active component, the catalyst
Preparation step it is as follows:
1) platinum salt presoma is mixed with polyvinylpyrrolidone, dehydrated alcohol, it is molten is uniformly mixing to obtain platinum salt presoma
Liquid, wherein the concentration of polyvinylpyrrolidone is 0.003~0.01g/mL, the concentration of platinum salt precursor solution is 0.00223~
0.007g/mL；
2) the SAPO-34 molecular sieve carrier of silica alumina ratio 0.1~0.6 is immersed in the platinum salt precursor solution that step 1) obtains
In, dipping 0.5~for 24 hours；
3) obtained molecular sieve carrier after step 2) dipping is evaporated under 50~85 DEG C of water bath conditions, then 60~
In 100 DEG C of vacuum drying ovens drying 2~for 24 hours；
4) molecular sieve carrier obtained after step 3) drying is roasted into 1~12h under 250~500 DEG C of inert gas atmospheres,
Obtain platinum based catalyst presoma；
5) the platinum based catalyst presoma for obtaining step 4) is in H2/ Ar gaseous mixture (H2Percentage by volume is 8~15%) item
Under part, 1~8h is restored at 300~600 DEG C, to obtain the Pt/SAPO-34 of the present invention for toluene catalytic oxidation points
Sub- sieve catalyst, wherein the load capacity of platinum is 0.1~2.0wt%.
Platinum salt presoma is one of four ammino platinum nitrates, platinous chloride, chloroplatinic acid；
Utilize Pt/SAPO-34 molecular sieve catalyst catalysis oxidation toluene in fixed bed reactors recited above: reaction
Gas is the toluene of 500~1000ppm, and background gas is the nitrogen oxygen atmosphere of percent by volume 1:4, total stream of reaction gas and background gas
Speed be 30~100mL/min, by 0.1~1g, tabletting at 40~60 mesh Pt/SAPO-34 molecular sieve catalyst 140 DEG C~
Catalytic activity test continuous operation is carried out at 250 DEG C.
Pt/SAPO-34 molecular sieve catalyst provided by the invention can be catalyzed toluene at a lower temperature, make its complete oxygen
Change, but also is able to maintain very high stability.
Compared with prior art, present invention has an advantage that
1) present invention is simple to operation using preparation method, compared to using traditional aqueous systems infusion process, Pt species energy
It is enough to be preferably scattered on SAPO-34 molecular sieve, to effectively reduce the size of Pt nanoparticle and the load capacity of Pt.
2) select SAPO-34 molecular sieve as carrier in the present invention, by comparative study, which is very suitable to support
Pt generates the catalysis oxidation toluene catalytically agent with high activity, which can effectively go at lower reaction temperature (165 DEG C)
Except low concentration (500~1000ppm) toluene in air, there is actual application prospect.
Detailed description of the invention
Fig. 1 is that the toluene oxidation activity of the Pt/SAPO-34 molecular sieve catalyst of different silica alumina ratios in the embodiment of the present invention is bent
Line；
Fig. 2 is the toluene oxidation activity curve of different carriers supporting Pt in the embodiment of the present invention；
Fig. 3 is that the toluene oxidation of the molecular sieve carried Pt of SAPO-34 of different dipping method preparations in the embodiment of the present invention is living
Linearity curve；
Fig. 4 is the XRD diagram of the Pt/SAPO-34 molecular sieve catalyst of different silica alumina ratios in the embodiment of the present invention, and explanation is used for
The carrier of molecular sieve catalyst of the invention is SAPO-34.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, but the embodiment does not limit
Protection scope of the present invention.
Embodiment 1
Following example is to synthesize SAPO-34 molecular sieve with hydro-thermal method:
By aluminium isopropoxide, phosphoric acid, tetraethyl ammonium hydroxide, the silica solution of 40wt% and water according to 1.0 Al of molar ratio2O3:
1.2P2O5:2.0TEAOH:x SiO2:40H2The proportion of O (x=0.1,0.2,0.4,0.6) mixes, and is stirred at room temperature 6 hours
To formed gel, 170 DEG C crystallization 3 days.After the completion of crystallization, removed within roasting 5 hours by centrifugation, washing, drying, 550 DEG C
The SAPO-34 molecular sieve of different silica alumina ratios is obtained after organic formwork agent.
Embodiment 2
Tetra- ammino platinum nitrate of 0.0223g, 0.03g polyvinylpyrrolidone are weighed, is added in the dehydrated alcohol of 6mL, stirs
Mix uniformly, then weigh 1.0g Si/Al be 0.1 SAPO-34 molecular sieve be added in above-mentioned solution, 12h is stirred at room temperature
Afterwards, the sample after dipping is placed under 80 DEG C of water bath conditions and is evaporated, and dries in 80 DEG C of vacuum drying ovens overnight, then in argon atmospher
Enclose lower 300 DEG C of roasting 12h and in 300 DEG C of H2/Ar(H2Percentage by volume 10%) under atmosphere reduction 5h to get arriving 1wt%Pt/
SAPO-34 (0.1) catalyst.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the above-mentioned catalyst of 40~60 purposes, catalyst
It is placed in reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h,
Then the various impurity for removing catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, background gas is volume basis
The overall flow rate of nitrogen oxygen atmosphere than 1:4, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1,
140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller under normal pressure.Being packed into should
Catalyst carries out catalysis oxidation test to the toluene that concentration is 1000ppm, as shown in Figure 1, can reach under 180 DEG C of reaction temperatures
95% or more toluene removal rate.
Embodiment 3
Tetra- ammino platinum nitrate of 0.0223g, 0.03g polyvinylpyrrolidone are weighed, is added in the dehydrated alcohol of 6mL, stirs
Mix uniformly, then weigh 1.0g Si/Al be 0.2 SAPO-34 molecular sieve be added in above-mentioned solution, 12h is stirred at room temperature
Afterwards, the sample after dipping is placed under 80 DEG C of water bath conditions and is evaporated, and dries in 80 DEG C of vacuum drying ovens overnight, then in argon atmospher
Enclose lower 300 DEG C of roasting 12h and in 300 DEG C of H2/Ar(H2Percentage by volume 10%) under atmosphere reduction 5h to get arriving 1wt%Pt/
SAPO-34 (0.2) catalyst.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the above-mentioned catalyst of 40~60 purposes, catalyst
It is placed in reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h,
Then the various impurity for removing catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, background gas is volume basis
The overall flow rate of nitrogen oxygen atmosphere than 1:4, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1,
140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller under normal pressure.Being packed into should
Catalyst carries out catalysis oxidation test to the toluene that concentration is 1000ppm, as shown in Figure 1, can reach under 168 DEG C of reaction temperatures
95% or more toluene removal rate.
Embodiment 4
Tetra- ammino platinum nitrate of 0.0223g, 0.03g polyvinylpyrrolidone are weighed, is added in the dehydrated alcohol of 6mL, stirs
Mix uniformly, then weigh 1.0g Si/Al be 0.4 SAPO-34 molecular sieve be added in above-mentioned solution, 12h is stirred at room temperature
Afterwards, the sample after dipping is placed under 80 DEG C of water bath conditions and is evaporated, and dries in 80 DEG C of vacuum drying ovens overnight, then in argon atmospher
Enclose lower 300 DEG C of roasting 12h and in 300 DEG C of H2/Ar(H2Percentage by volume 10%) under atmosphere reduction 5h to get arriving 1wt%Pt/
SAPO-34 (0.4) catalyst.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the above-mentioned catalyst of 40~60 purposes, catalyst
It is placed in reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h,
Then the various impurity for removing catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, background gas is volume basis
The overall flow rate of nitrogen oxygen atmosphere than 1:4, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1,
140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller under normal pressure.Being packed into should
Catalyst carries out catalysis oxidation test to the toluene that concentration is 1000ppm, as shown in Figure 1, can reach 95% under 165 DEG C of reactions
The above toluene removal rate.
Embodiment 5
Tetra- ammino platinum nitrate of 0.0223g, 0.03g polyvinylpyrrolidone are weighed, is added in the dehydrated alcohol of 6mL, stirs
Mix uniformly, then weigh 1.0g Si/Al be 0.6 SAPO-34 molecular sieve be added in above-mentioned solution, 12h is stirred at room temperature
Afterwards, the sample after dipping is placed under 80 DEG C of water bath conditions and is evaporated, and dries in 80 DEG C of vacuum drying ovens overnight, then in argon atmospher
Enclose lower 300 DEG C of roasting 12h and in 300 DEG C of H2/Ar(H2Percentage by volume 10%) under atmosphere reduction 5h to get arriving 1wt%Pt/
SAPO-34 (0.6) catalyst.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the catalyst of 40~60 mesh, catalyst is placed in
In reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h, is removed
Then the various impurity of catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, and background gas is percent by volume 1:
The overall flow rate of 4 nitrogen oxygen atmosphere, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1, normal pressure
It is lower that 140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller.It is packed into the catalysis
Agent carries out catalysis oxidation test to the toluene that concentration is 1000ppm, as shown in Figure 1, can reach 95% under 175 DEG C of reaction temperatures
The above toluene removal rate.
Embodiment 6
Tetra- ammino platinum nitrate of 0.0223g, 0.03g polyvinylpyrrolidone are weighed, is added in the dehydrated alcohol of 6mL, stirs
Mix uniformly, then weigh 1.0g Si/Al be 1 SAPO-34 (C) molecular sieve (commercialization) be added in above-mentioned solution, stirred in room temperature
After mixing 12h, the sample after dipping is placed under 80 DEG C of water bath conditions and is evaporated, and dries overnight in 80 DEG C of vacuum drying ovens, then exists
Lower 300 DEG C of roasting 12h of argon atmosphere and in 300 DEG C of H2/ Ar atmosphere (H2Percentage by volume 10%) under reduction 5h to get arriving
1wt%Pt/SAPO-34 (C) catalyst.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the catalyst of 40~60 mesh, catalyst is placed in
In reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h, is removed
Then the various impurity of catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, and background gas is percent by volume 1:
The overall flow rate of 4 nitrogen oxygen atmosphere, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1, normal pressure
It is lower that 140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller.It is packed into the catalysis
Agent carries out catalysis oxidation test to the toluene that concentration is 1000ppm, as shown in Fig. 2, can be only achieved under 192 DEG C of reaction temperatures
95% or more toluene removal rate.
Embodiment 7
Tetra- ammino platinum nitrate of 0.0223g, 0.03g polyvinylpyrrolidone are weighed, is added in the dehydrated alcohol of 6mL, stirs
It mixes uniformly, then weighs 1.0g ZSM-5 molecular sieve (commercialization) and be added in above-mentioned solution, after 12h is stirred at room temperature, after dipping
Sample be placed under 80 DEG C of water bath conditions and be evaporated, and dried overnight, then 300 DEG C under argon atmosphere in 80 DEG C of vacuum drying ovens
Roast 12h and in 300 DEG C of H2/ Ar atmosphere (H2Percentage by volume 10%) under reduction 5h urged to get to 1wt%Pt/ZSM-5 (C)
Agent.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the catalyst of 40~60 mesh, catalyst is placed in
In reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h, is removed
Then the various impurity of catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, and background gas is percent by volume 1:
The overall flow rate of 4 nitrogen oxygen atmosphere, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1, normal pressure
It is lower that 140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller.The catalyst pair
The toluene that concentration is 1000ppm carries out catalysis oxidation test, as shown in Fig. 2, can be only achieved 95% under 190 DEG C of reaction temperatures
The above toluene removal rate.
Embodiment 8
Tetra- ammino platinum nitrate of 0.0223g, 0.03g polyvinylpyrrolidone are weighed, is added in the dehydrated alcohol of 6mL, stirs
It mixes uniformly, then weighs 1.0g γ-Al2O3(commercialization) is added in above-mentioned solution, the sample after 12h is stirred at room temperature, after dipping
It is placed under 80 DEG C of water bath conditions and is evaporated, and dried overnight in 80 DEG C of vacuum drying ovens, then 300 DEG C of roastings under argon atmosphere
12h, and in 300 DEG C of H2/ Ar atmosphere (H2Percentage by volume 10%) under reduction 5h to get arrive 1wt%Pt/Al2O3Catalyst.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the catalyst of 40~60 mesh, catalyst is placed in
In reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h, is removed
Then the various impurity of catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, and background gas is percent by volume 1:
The overall flow rate of 4 nitrogen oxygen atmosphere, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1, normal pressure
It is lower that 140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller.The catalyst pair
The toluene that concentration is 1000ppm carries out catalysis oxidation test, as shown in Fig. 2, can be only achieved 95% under 190 DEG C of reaction temperatures
The above toluene removal rate.
Embodiment 9
It takes suitable chloroplatinic acid (load capacity of platinum is 1wt%) to be dissolved in 10mL water, stirs to being completely dissolved, to above-mentioned solution
The middle SAPO-34 molecular sieve that 1.0g Si/Al is added and is 0.2, impregnates 12h, 80 DEG C are dried overnight, then 450 DEG C in Muffle furnace
4h is roasted, and in 400 DEG C of H2/ Ar atmosphere (H2Percentage by volume 10%) under reductase 12 h to get to Pt-SAPO-34 (0.2) be catalyzed
Agent.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the catalyst of 40~60 mesh, catalyst is placed in
In reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h, is removed
Then the various impurity of catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, and background gas is percent by volume 1:
The overall flow rate of 4 nitrogen oxygen atmosphere, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1, normal pressure
It is lower that 140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller.The catalyst pair
The toluene that concentration is 1000ppm carries out catalysis oxidation test, as shown in figure 3, can be only achieved 95% under 230 DEG C of reaction temperatures
The above toluene removal rate.
Embodiment 10
It takes suitable chloroplatinic acid (load capacity of platinum is 1wt%) to be dissolved in 10mL water, stirs to being completely dissolved, to above-mentioned solution
The middle SAPO-34 molecular sieve that 1.0g Si/Al is added and is 0.6, impregnates 12h, 80 DEG C are dried overnight, then 450 DEG C in Muffle furnace
4h is roasted, and in 400 DEG C of H2/ Ar atmosphere (H2Percentage by volume 10%) under reductase 12 h to get to Pt-SAPO-34 (0.6) be catalyzed
Agent.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the catalyst of 40~60 mesh, catalyst is placed in
In reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h, is removed
Then the various impurity of catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, and background gas is percent by volume 1:
The overall flow rate of 4 nitrogen oxygen atmosphere, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1, normal pressure
It is lower that 140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller.The catalyst pair
The toluene that concentration is 1000ppm carries out catalysis oxidation test, as shown in figure 3, can be only achieved 95% under 240 DEG C of reaction temperatures
The above toluene removal rate.
Embodiment 11
It takes suitable chloroplatinic acid (load capacity of platinum is 1wt%) to be dissolved in 10mL water, stirs to being completely dissolved, to above-mentioned solution
Middle addition 1.0g Beta molecular sieve (commercialization) impregnates 12h, and 80 DEG C are dried overnight, then 450 DEG C of roasting 4h in Muffle furnace, and
In 400 DEG C of H2/ Ar atmosphere (H2Percentage by volume 10%) under reductase 12 h to get arrive Pt-Beta catalyst.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the catalyst of 40~60 mesh, catalyst is placed in
In reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h, is removed
Then the various impurity of catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, and background gas is percent by volume 1:
The overall flow rate of 4 nitrogen oxygen atmosphere, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1, normal pressure
It is lower that 140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller.The catalyst pair
The toluene that concentration is 1000ppm carries out catalysis oxidation test, as shown in figure 3, can be only achieved 95% under 240 DEG C of reaction temperatures
The above toluene removal rate.
Embodiment 12
The ethylene glycol solution of 27mL sodium hydroxide (0.34M) is added dropwise to the chloroplatinic acid ethylene glycol solution being stirred continuously
In (8.5 × 10-4M), the solution obtained heats 30 minutes for 140 DEG C under argon atmosphere, obtains black Pt colloids.Si/Al is added
For 0.2 SAPO-34 molecular sieve, 2h is mixed, then by mixture 80 DEG C of heating under agitation, until platinum glue is whole
It is deposited on carrier.Obtained solid is filtered, and is washed with distilled water until chloride ion is cleaned (silver nitrate detection).
Solid after washing is dried overnight under the conditions of 100 DEG C, then in 20%O2The lower 200 DEG C of roastings 2h of/Ar atmosphere, obtains Pt-
SAPO-34 (J), the mass fraction of platinum is 1.0% in Pt-SAPO-34 (J) catalyst.
Weigh 0.10g, tabletting is placed in the quartz ampoule of fixed bed reactors at the catalyst of 40~60 mesh, catalyst is placed in
In reaction gas constant temperature zone.200 DEG C are heated to 10 DEG C/min heating rate in air atmosphere before reaction, pre-processes 2h, is removed
Then the various impurity of catalyst surface absorption are down to 140 DEG C, toluene is blown into reactor, and background gas is percent by volume 1:
The overall flow rate of 4 nitrogen oxygen atmosphere, reaction gas and background gas is 100mL/min, reaction velocity 60000mL-1g-1h-1, normal pressure
It is lower that 140~250 DEG C of successive reactions are warming up to from room temperature with the rate program of 10 DEG C/min by control temperature controller.The catalyst pair
The toluene that concentration is 1000ppm carries out catalysis oxidation test, as shown in figure 3, can be only achieved 95% under 220 DEG C of reaction temperatures
The above toluene removal rate.
Claims (3)
1. a kind of preparation method of the Pt/SAPO-34 molecular sieve catalyst for toluene catalytic oxidation, its step are as follows:
1) platinum salt presoma is mixed with polyvinylpyrrolidone, dehydrated alcohol, is uniformly mixing to obtain platinum salt precursor solution,
The concentration of middle polyvinylpyrrolidone is 0.003~0.01g/mL, the concentration of platinum salt precursor solution is 0.00223~
0.007g/mL；
2) the SAPO-34 molecular sieve carrier of silica alumina ratio 0.1~0.6 is immersed in the platinum salt precursor solution that step 1) obtains,
Dipping 0.5~for 24 hours；
3) molecular sieve carrier obtained after step 2) dipping is evaporated under 50~85 DEG C of water bath conditions, then at 60~100 DEG C
In vacuum drying oven drying 2~for 24 hours；
4) molecular sieve carrier obtained after step 3) drying is roasted under 250~500 DEG C of inert gas atmospheres 1~12h, obtained
Platinum based catalyst presoma；
5) the platinum based catalyst presoma for obtaining step 4) is in H2Under the conditions of/Ar gaseous mixture, 1~8h is restored at 300~600 DEG C,
To obtaining the Pt/SAPO-34 molecular sieve catalyst for toluene catalytic oxidation, wherein the load capacity of platinum be 0.1~
2.0wt%.
2. a kind of preparation side of the Pt/SAPO-34 molecular sieve catalyst for toluene catalytic oxidation as described in claim 1
Method, it is characterised in that: platinum salt presoma is one of four ammino platinum nitrates, platinous chloride or chloroplatinic acid.
3. a kind of Pt/SAPO-34 molecular sieve catalyst for toluene catalytic oxidation, it is characterised in that: be by claim 1 or
Method described in 2 is prepared.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052287A (en) * | 2019-05-17 | 2019-07-26 | 湘潭大学 | A kind of the core-shell structure molecular sieve catalyst and preparation method of Collaborative Control NO and toluene |
| CN110433855A (en) * | 2019-08-13 | 2019-11-12 | 华南理工大学 | It is a kind of for purifying the loaded catalyst and the preparation method and application thereof of volatile organic matter in coal-fired flue-gas |
| CN115414963A (en) * | 2022-09-21 | 2022-12-02 | 中国科学院生态环境研究中心 | Catalyst for removing VOCs (volatile organic compounds), preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052287A (en) * | 2019-05-17 | 2019-07-26 | 湘潭大学 | A kind of the core-shell structure molecular sieve catalyst and preparation method of Collaborative Control NO and toluene |
| CN110433855A (en) * | 2019-08-13 | 2019-11-12 | 华南理工大学 | It is a kind of for purifying the loaded catalyst and the preparation method and application thereof of volatile organic matter in coal-fired flue-gas |
| CN110433855B (en) * | 2019-08-13 | 2021-07-20 | 华南理工大学 | Supported catalyst for purifying volatile organic compounds in coal-fired flue gas and preparation method and application thereof |
| CN115414963A (en) * | 2022-09-21 | 2022-12-02 | 中国科学院生态环境研究中心 | Catalyst for removing VOCs (volatile organic compounds), preparation method and application thereof |
| CN115414963B (en) * | 2022-09-21 | 2023-11-21 | 中国科学院生态环境研究中心 | Catalyst for removing VOCs and preparation method and application thereof |
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