CN112691542B - Metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs (volatile organic compounds), and preparation method and application thereof - Google Patents

Metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs (volatile organic compounds), and preparation method and application thereof Download PDF

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CN112691542B
CN112691542B CN202011641203.0A CN202011641203A CN112691542B CN 112691542 B CN112691542 B CN 112691542B CN 202011641203 A CN202011641203 A CN 202011641203A CN 112691542 B CN112691542 B CN 112691542B
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molecular sieve
waste gas
metal composite
vocs
composite molecular
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CN112691542A (en
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胡芸
杜玥莹
肖高飞
李剑晗
付名利
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South China University of Technology SCUT
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Abstract

The invention discloses a metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs (volatile organic compounds), and a preparation method and application thereof. The method comprises the following steps: dissolving the molecular sieve in water, and dipping or performing photo-deposition on the metal precursor on the molecular sieve to prepare the metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs. The material prepared by the invention can efficiently adsorb, capture and concentrate VOCs in waste gas, and the captured organic matters are catalytically oxidized into H at the active center of metal 2 O and CO 2 The integration of adsorption and catalytic oxidation is realized, so that the aim of degrading the low-concentration VOCs in the waste gas is fulfilled. Compared with the existing VOCs purification material, the invention has the advantages of high adsorption performance, high activity, high selectivity and the like. The prepared material can be widely applied to industrial conventional organic waste gas containing NO and NH 3 、SO 2 The industrial organic waste gas and the organic waste gas in the coal-fired flue gas and the like.

Description

Metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs (volatile organic compounds), and preparation method and application thereof
Technical Field
The invention belongs to the technical field of environmental functional materials, and particularly relates to a preparation method of a metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs (volatile organic compounds) and application of the metal composite molecular sieve material in atmospheric environmental pollution treatment.
Background
VOCs are an important group of atmospheric pollutants, the sources of which mainly comprise man-made sources and natural sources, and due to the uncontrollable nature of natural sources, people are more concerned about emissions of man-made sources, wherein the emissions of industrial sources account for more than 70% of the total emissions of man-made sources, and may be accompanied by NH 3 、NO、SO 2 And the like. The types of VOCs are complex, and the VOCs participate in the formation of ozone and photochemical smog in the atmospheric environment, so that serious atmospheric pollution can be caused, and meanwhile, most VOCs have a 'three-cause' effect and harm the life health of human beings. Therefore, the treatment of VOCs is not slow.
The common treatment technologies of VOCs mainly include adsorption, combustion (direct combustion, catalytic combustion and regenerative incineration), biological oxidation and the like. At present, a control technology based on a zeolite rotating wheel adsorption concentration system is applied more in VOCs treatment, and the VOCs is mainly adsorbed through zeolite, and then catalytic combustion equipment is connected in series to purify desorbed waste gas. But the method has the defects of large floor area, high investment, operation and maintenance cost and the like, and has the defects of narrow range (20-35 ℃) of exhaust gas temperature which can be treated by the adopted zeolite adsorbent, high price of the adopted commercial Pt-based catalyst, low catalytic oxidation performance of the commercial Mn-based catalyst and the like. The molecular sieve selected by the invention has adjustable aperture, abundant and various pore channel structures and good thermal stability, so that the molecular sieve has certain adsorption capacity at high temperature, and compared with the existing adsorbent, the molecular sieve has the advantages of improving the adsorption capacity and widening the temperature range of the treatable waste gas; meanwhile, the metal composite molecular sieve material has a plurality of surface acid sites, good thermal stability and high catalytic oxidation efficiency. Therefore, the metal composite molecular sieve material can be applied to adsorption and catalytic oxidation of VOCs.
In view of the above, the invention aims at the industrial conventional organic waste gas containing NO and NH 3 、SO 2 The metal composite molecular sieve material has excellent adsorption performance, widens the temperature range of waste gas treatment, has high dispersion degree of active components, reduces the temperature required by catalytic oxidation of the organic waste gas, improves the selectivity of carbon oxide in the catalytic oxidation of the VOCs, enables the adsorption-in-situ catalytic oxidation of the organic waste gas to be realized, achieves the integration of an adsorbent and a catalyst material, and reduces the cost and the using amount of industrial application. The invention is industrial conventional organic waste gas containing NO and NH 3 、SO 2 The preparation of the adsorption-catalytic oxidation material of the industrial organic waste gas and the organic waste gas in the coal-fired flue gas and the pollution treatment of the VOCs in the atmosphere provide a new idea and method.
Disclosure of Invention
The invention aims to develop a catalyst containing NO and NH, which can be applied to industrial conventional organic waste gas 3 、SO 2 The metal composite molecular sieve material for adsorbing and catalytically oxidizing the industrial organic waste gas and the organic waste gas in the coal-fired flue gas can simultaneously realize high adsorption performance of an adsorbent and high conversion rate and high selectivity of a catalyst, and provides a preparation method of the metal composite molecular sieve material for adsorbing and catalytically oxidizing VOCs and application thereof in VOCs pollution treatment.
The purpose of the invention is realized by the following technical scheme:
a process for preparing the composite metal molecular sieve used to adsorb and catalytically oxidize VOCs includes dissolving molecular sieve in water, immersing or optical depositing the precursor of transition metal or noble metal on the molecular sieve to obtain the composite metal molecular sieve used to prepare the organic waste gas containing NO and NH 3 、SO 2 The adsorption and catalytic oxidation of industrial organic waste gas and organic waste gas in coal-fired flue gas.
Further, the metal comprises transition metal copper or noble metal platinum, and the molecular sieve is Beta.
Furthermore, the transition metal load accounts for 1-20 wt% of the mass of the molecular sieve; the noble metal loading accounts for 0.1-1.0 wt% of the mass of the molecular sieve.
Further, the preparation method of the metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs comprises one of the following three methods;
1. dissolving copper acetate, copper nitrate or copper sulfate in deionized water, adding a Beta molecular sieve, and drying and calcining to obtain a transition metal composite molecular sieve material;
2. adding a Beta molecular sieve into water introduced with nitrogen, adding chloroplatinic acid, methanol and ethanol, using an ultraviolet lamp or a xenon lamp as a light source, continuously stirring under irradiation, centrifuging, and drying in vacuum to obtain a noble metal composite molecular sieve material;
3. the honeycomb ceramic is dipped in a solution consisting of deionized water, copper acetate, a Beta molecular sieve, methyl cellulose and glass fiber, and the metal composite molecular sieve material is obtained after drying and calcining.
Further, the preparation method of the Beta molecular sieve comprises the following steps:
slowly dripping tetraethyl ammonium hydroxide into tetraethoxysilane, heating and stirring for 2-6 hours in a constant-temperature magnetic stirrer at 60 ℃, then dropwise adding 0.1g of sodium metaaluminate dissolved by 20mL of deionized water, continuously stirring at room temperature after forming a mixed solution, then transferring to a liner of a polytetrafluoroethylene reaction kettle, finally putting the liner of the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, carrying out hydrothermal reaction in a blast drying box, naturally cooling to room temperature, centrifugally washing with deionized water, carrying out vacuum freeze drying, and finally calcining in a muffle furnace to obtain a Beta molecular sieve;
the addition amount of the tetraethyl ammonium hydroxide is 10-30 mL, and the addition amount of the tetraethoxysilane is 20-25 mL; stirring at room temperature for 1-3 h; the hydrothermal reaction temperature is 120-180 ℃, and the hydrothermal reaction pressure is 0.1-0.5 Mpa; the vacuum freeze drying temperature is-10 to-50 ℃, the vacuum pressure is 1.3 to 13Pa, and the vacuum freeze drying time is 12 to 24 hours; the calcination temperature is 400-550 ℃, the calcination time is 1-5 h, and the heating rate is 1-5 ℃/min; the specific calcining method comprises the following steps: the temperature raising procedure is that the temperature is raised from the room temperature to 400-550 ℃ at the speed of 2-5 ℃/min, the temperature is kept constant at 400-550 ℃ for 2-6 h, and finally the temperature is lowered to the room temperature at the speed of 2-10 ℃/min;
further, the preparation method of the transition metal composite molecular sieve material comprises the following steps:
(1) Dissolving a transition metal precursor:
adding a transition metal precursor into 20-40 mL of water, and magnetically stirring at a constant temperature to prepare a transition metal precursor solution; the transition metal precursor comprises copper acetate, copper nitrate or copper sulfate;
(2) Preparing a transition metal composite molecular sieve catalyst by an impregnation method:
adding a Beta molecular sieve into the transition metal precursor solution obtained in the step (1) in the stirring process, stirring by using a constant-temperature magnetic stirrer until the mixture is evaporated to dryness, performing vacuum freeze drying, and calcining by using a muffle furnace to obtain different transition metal-based molecular sieve catalysts;
the constant-temperature magnetic stirring time in the step (1) is 2-4 h; in the step (2), the addition amount of the transition metal precursor is 1-20 wt% of the total mass of the material, and the mass of the added molecular sieve is 1-3 g; the stirring temperature is 60-80 ℃, and the stirring time is 2-4 h; the vacuum freeze drying temperature is-10 to-50 ℃, the vacuum pressure is 1.3 to 13Pa, and the vacuum freeze drying time is 12 to 24 hours; the calcination temperature is 300-550 ℃, the calcination time is 3-6 h, and the heating rate is 2-5 ℃/min.
Further, the preparation method of the noble metal composite molecular sieve material by the photo-deposition comprises the following steps:
introducing nitrogen into deionized water, removing oxygen in the water, adding a Beta molecular sieve, stirring on a magnetic stirrer at room temperature, and then adding a noble metal precursor, wherein the load capacity on the final catalyst is 0.1-1.0 wt%; dropwise adding methanol and ethanol solution, using an ultraviolet lamp or a xenon lamp as a light source, stirring for several hours while irradiating to obtain a reduced catalyst, centrifuging for several times by using a centrifugal machine, performing vacuum freeze drying, and grinding to obtain a light deposition prepared precious metal composite molecular sieve material;
the deionized water is 20-60 mL; the added molecular sieve amount is 2-4 g; the volume of the solution used by the methanol solution is 20-40 mL, and the volume of the ethanol solution is 5-20 mL; the light intensity of the ultraviolet lamp or the xenon lamp is 100-400mW/cm 2 The irradiation stirring time is 6 to 12 hours; the rotating speed of the centrifugal washing centrifuge is 6000 to 8000r/min, the centrifugation time is 3 to 6 min/time, and the washing times are 4 to 6 times; the vacuum freeze drying temperature is-10 to-50 ℃, the vacuum pressure is 1.3 to 13Pa, and the vacuum freeze drying time is 12 to 24 hours.
Further, the preparation method of the metal composite molecular sieve material by the honeycomb ceramic impregnation method comprises the following steps:
dissolving a transition metal precursor in deionized water, adding a Beta molecular sieve, methylcellulose and glass fiber, uniformly stirring, adding honeycomb ceramic, soaking for 6-8 h, taking out, drying, putting into a forced air drying box, drying, and calcining in a muffle furnace to obtain a metal composite molecular sieve material;
the volume of the deionized water is 50-70 mL, the addition amount of the molecular sieve is 8-10g, and the addition amount of the metal precursor is 1-20 wt% of the addition amount of the molecular sieve; the addition amount of the methyl cellulose is 0.5-1 g, and the addition amount of the glass fiber is 0.1-0.5 g; the drying temperature is 100-150 ℃, and the drying time is 12-24 h; the muffle furnace is used for calcining at the temperature of 400-600 ℃, the calcining time is 1-3 h, and the heating rate is 2-5 ℃/min.
Metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs (volatile organic compounds) applied to industrial conventional organic waste gas and containing NO and NH 3 、SO 2 And pollution control of organic waste gas in industrial organic waste gas and coal-fired flue gas.
The invention dissolves the molecular sieve in water, and the precursor of the transition metal or the noble metal is dipped or photo-deposited on the molecular sieve to prepare the metal composite molecular sieve material. The material has excellent adsorption capacity and catalytic oxidation toluene activity and selectivity.
Compared with the prior art, the invention has the following advantages:
(1) The invention adopts a simple preparation method, so that the metal is dispersed on the molecular sieve carrier to a high degree, and the method is easy for industrial application.
(2) The material prepared by the invention has excellent adsorption performance and catalytic oxidation activity, can realize the integration of adsorption and catalysis of the material, and reduces the industrial application cost while degrading VOCs.
(3) The material prepared by the invention can be widely applied to industrial conventional organic waste gas containing NO and NH 3 、SO 2 The field of adsorption-catalytic oxidation of industrial organic waste gas and organic waste gas in coal-fired flue gas shows high-efficiency adsorption performance, high-efficiency catalytic oxidation activity, high selectivity and long-term stability.
Drawings
FIG. 1 is a penetration curve of toluene adsorption at 30 ℃ of the metal composite molecular sieve material and the zeolite wheel adsorbent for adsorbing-catalytically oxidizing VOCs according to the invention.
FIG. 2 is a penetration curve of the adsorbent of zeolite wheel and metal composite molecular sieve for adsorbing-catalytically oxidizing VOCs according to the present invention for toluene adsorption at 150 ℃.
FIG. 3 is a graph showing the evaluation of the catalytic oxidative degradation activity of toluene by the metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs, the commercial Pt-based catalyst and the commercial Mn-based catalyst of the present invention.
Fig. 4 is a graph showing the evaluation of selectivity of the metal composite molecular sieve material for adsorption-catalytic oxidation of VOCs, a commercial Pt-based catalyst, and a commercial Mn-based catalyst according to the present invention for carbon oxides in toluene catalytic oxidation.
FIG. 5 is a graph showing the evaluation of the adsorption-catalytic oxidation of toluene by the metal composite molecular sieve material for adsorbing-catalytic oxidizing VOCs according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
Preparation of Beta molecular sieve:
slowly dropwise adding 22mL of tetraethylammonium hydroxide into 25mL of tetraethoxysilane, heating and stirring for 2h in a constant-temperature magnetic stirrer at 60 ℃, then dropwise adding 0.23g of sodium metaaluminate dissolved in water, stirring the formed mixed solution at room temperature for 3h, then transferring the mixed solution into a liner of a polytetrafluoroethylene reaction kettle, finally putting the liner of the polytetrafluoroethylene reaction kettle into a high-pressure reaction kettle, carrying out hydrothermal reaction for 3d at 140 ℃, then naturally cooling, centrifugally washing for 5 times by using deionized water, carrying out vacuum freeze drying at-30 ℃, and finally calcining for 5h in a muffle furnace at 550 ℃ to obtain the Beta molecular sieve.
Example 2
Preparation of CuOx/Beta molecular sieve:
0.22g of copper acetate (Cu) 2 (CH 3 COO) 4 ) Mixing with 20mL of deionized water, placing the mixture in a constant-temperature magnetic stirrer, fully stirring the mixture for 10min at the stirring speed of 450r/min at 60 ℃ for dissolving the mixture, adding 1g of Beta molecular sieve in the stirring state, stirring the mixture until the mixture is dried, transferring the dried mixture to a vacuum freeze dryer at the temperature of minus 25 ℃ for freeze drying for 24h, grinding the dried mixture, placing the calcined mixture in a muffle furnace for high-temperature calcination, wherein the temperature rise procedure is to firstly rise from room temperature to 450 ℃ at the speed of 3 ℃/min, keep the temperature at the constant temperature of 450 ℃ for 4h, and then reduce the temperature to the room temperature at the speed of 3 ℃/min to obtain the CuOx/Beta molecular sieve.
Example 3
Preparation of Pt/Beta molecular sieve:
adding 4g Beta molecular sieve carrier into 40mL deionized water with nitrogen, stirring at constant temperature and strong force continuously, dropwise adding 5.23mL chloroplatinic acid solution, continuously adding 5mL methanol and 5mL ethanol, using xenon lamp (Perfect light, PLS-SXE300/300 UV) as light source, and light intensity of 350mW/cm 2 Continuously stirring and irradiating for 10h, centrifuging for 5 times by a centrifugal machine with the rotating speed of 6500r/min, and putting into a vacuum freeze dryer at the temperature of-25 ℃ for freeze drying for 24h to obtain the Pt/Beta molecular sieve catalyst prepared by the light deposition method.
Example 4
Preparing a Cu-Beta/honeycomb ceramic molecular sieve:
3g of copper acetate powder is added into 70mL of deionized water and dissolved in the deionized water, 5g of Beta molecular sieve is added and then stirred continuously, and then 0.8g of methyl cellulose and 0.2g of glass fiber are added and dissolved in the water. And (3) putting the honeycomb ceramic into the solution, soaking for 30min, taking out, putting into a forced air drying oven for drying for 12h, and then putting into a muffle furnace for calcining for 3h at 500 ℃ to obtain the Cu/Beta molecular sieve catalyst impregnated by the honeycomb ceramic.
Example 5
Evaluation of catalytic oxidation of VOCs: toluene is used as a target pollutant for research, and the catalytic oxidation activity and selectivity of the metal composite molecular sieve material to toluene at different temperatures are researched. The reaction conditions are as follows: the concentration of toluene is 50ppm, the dosage of catalyst is 200mg, the reaction temperature is 150-390 ℃, the reaction flow is 200mL/min, and the space velocity is 60000h -1 ，5vol％O 2 ，N 2 Is a balance gas; the concentrations of toluene and carbon oxides were measured using a flame detector with hydrogen ions and a gas chromatograph.
Fig. 1 and fig. 2 are the penetration curves of the transition metal composite molecular sieve material and the zeolite wheel adsorbent at 30 ℃ and 150 ℃ for toluene respectively. The result shows that the prepared metal composite molecular sieve material has better adsorption performance on VOCs at low temperature and high temperature than zeolite rotary wheel adsorbents. Therefore, compared with zeolite wheel adsorbents, the metal composite molecular sieve material prepared by the invention widens the temperature range of the waste gas capable of being treated.
Fig. 3 and 4 are graphs showing the catalytic oxidation activity and selectivity of the metal composite molecular sieve material for toluene (carbon oxide selectivity is replaced by carbon dioxide selectivity due to the very small amount of carbon monoxide generated) compared with the commercial Pt-based catalyst and the commercial Mn-based catalyst, and it can be seen that the metal composite molecular sieve material has higher catalytic oxidation efficiency and carbon oxide selectivity for toluene than the commercial Pt-based catalyst and the commercial Mn-based catalyst.
FIG. 5 shows the process of first adsorbing and then catalytically oxidizing toluene with the metal composite molecular sieve material. It can be seen that the concentration of toluene is always kept at 0ppm, therefore, the material prepared by the invention has excellent adsorption performance and catalytic oxidation activity, and can realize adsorption-catalysis integration.
Example 6
Containing NO and NH 3 、SO 2 Evaluation of catalytic oxidation of VOCs (b): toluene is taken as a target pollutant for research, and the temperature of the metal composite molecular sieve material is researched at different temperaturesThe catalytic oxidation activity and selectivity of toluene. The reaction conditions are as follows: the concentration of toluene is 50ppm, the dosage of catalyst is 200mg, the reaction temperature is 150-390 ℃, the reaction flow is 200mL/min, and the space velocity is 60000h -1 ，NH 3 50ppm concentration of NO, 50ppm concentration of SO, and 2 concentration of 500ppm,5vol% 2 ，N 2 Is a balance gas; the concentration of toluene and carbon oxides was measured using a flame detector with hydrogen ions and a gas chromatograph.
Under the condition of simulating flue gas, the prepared transition metal composite molecular sieve material catalyzes and oxidizes T of toluene 90 305 ℃ corresponding to a selectivity of 85% over the T of the commercial Pt-based catalyst for the catalytic oxidation of toluene 90 The temperature was 20 ℃ lower. Indicating that the prepared transition metal composite molecular sieve material contains NO and NH 3 、SO 2 The treatment of industrial organic waste gas and organic waste gas in coal-fired flue gas has excellent activity and selectivity of catalyzing and oxidizing VOCs.
The above examples are merely illustrative of the technical solutions of the present invention and not restrictive, and it will be understood by those of ordinary skill in the art that various changes in the details or forms thereof may be made without departing from the spirit and scope of the present invention as defined by the claims.

Claims (1)

1. A preparation method of a metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs is characterized by comprising the following steps:
the method I comprises the following specific steps:
introducing nitrogen into deionized water to remove oxygen in the water, adding a Beta molecular sieve, stirring at room temperature on a magnetic stirrer, and adding a noble metal precursor, wherein the load capacity on the catalyst is 0.1-1.0 wt%; dropwise adding methanol and ethanol solution, using an ultraviolet lamp or a xenon lamp as a light source, stirring for several hours while irradiating to obtain a reduced catalyst, centrifuging for several times by using a centrifugal machine, and then carrying out vacuum freeze drying and grinding to obtain a precious metal composite molecular sieve material prepared by light deposition;
the deionized water is 20 to 60mL; the added Beta molecular sieve has the weight of2 to 4g; the volume of the solution used by the methanol solution is 20 to 40mL, and the volume of the ethanol solution is 5 to 20mL; the light intensity of the ultraviolet lamp or xenon lamp is 100-400mW/cm 2 The irradiation stirring time is 6 to 12 hours; the rotating speed of the centrifugal washing centrifuge is 6000 to 8000r/min, the centrifugation time is 3 to 6 min/time, and the washing times are 4~6; the vacuum freeze drying temperature is-10 to-50 ℃, the vacuum pressure is 1.3 to 13Pa, and the vacuum freeze drying time is 12 to 24 hours; the noble metal precursor is chloroplatinic acid;
the method II comprises the following specific steps:
dissolving a transition metal precursor in deionized water, adding a Beta molecular sieve, methylcellulose and glass fibers, uniformly stirring, adding honeycomb ceramic, soaking for 6-8 h, taking out, drying, putting into a forced air drying oven, drying, and calcining by a muffle furnace to obtain a metal composite molecular sieve material;
the volume of the deionized water is 50-70 mL, the addition amount of the Beta molecular sieve is 8-10g, and the addition amount of the metal precursor is 1-20 wt% of the addition amount of the molecular sieve; the addition amount of the methyl cellulose is 0.5 to 1g, and the addition amount of the glass fiber is 0.1 to 0.5g; the drying temperature is 100 to 150 ℃, and the time is 12 to 24 hours; the muffle furnace calcining temperature is 400-600 ℃, the calcining time is 1-3 h, and the heating rate is 2-5 ℃/min; the transition metal precursor is copper acetate;
the metal composite molecular sieve material is used for industrial conventional organic waste gas, contains NO and NH 3 、SO 2 The adsorption and catalytic oxidation field of industrial organic waste gas and organic waste gas in coal-fired flue gas.
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