CN112691542A - 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 PDFInfo
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- CN112691542A CN112691542A CN202011641203.0A CN202011641203A CN112691542A CN 112691542 A CN112691542 A CN 112691542A CN 202011641203 A CN202011641203 A CN 202011641203A CN 112691542 A CN112691542 A CN 112691542A
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- molecular sieve
- temperature
- metal composite
- stirring
- sieve material
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 111
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000002905 metal composite material Substances 0.000 title claims abstract description 51
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 47
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 31
- 239000010815 organic waste Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000003546 flue gas Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 34
- 229910052723 transition metal Inorganic materials 0.000 claims description 28
- 150000003624 transition metals Chemical class 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000010354 integration Effects 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 238000002256 photodeposition Methods 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 59
- 239000003463 adsorbent Substances 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 230000010718 Oxidation Activity Effects 0.000 description 6
- 239000011865 Pt-based catalyst Substances 0.000 description 6
- 229910002090 carbon oxide Inorganic materials 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910016553 CuOx Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
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 metal2O and CO2The 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 NH3、SO2The industrial organic waste gas and the organic waste gas in the coal-fired flue gas and the like.
Description
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 artificial sources and natural sources, and due to the uncontrollable nature of natural sources, people pay more attention to emissions of artificial sources, wherein the emissions of industrial sources account for more than 70% of the total emissions of artificial sources, and may be accompanied by NH3、NO、SO2And the like. VOCs of complex species, participate inThe formation of ozone and photochemical smog in the atmospheric environment can cause serious atmospheric pollution, and meanwhile, most VOCs have a 'triple effect' and harm human life and health. 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 NH3、SO2The 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 relates to industrial conventional organic waste gas containing NO and NH3、SO2In industrial organic waste gas and coal-fired flue gasThe preparation of the adsorption-catalytic oxidation material of the organic waste gas and the pollution control of 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 gas3、SO2The 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 NH3、SO2The 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;
dissolving copper acetate, copper nitrate or copper sulfate in deionized water, adding a Beta molecular sieve, drying and calcining to obtain a transition metal composite molecular sieve material;
secondly, adding a Beta molecular sieve into water with introduced 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;
and thirdly, soaking the honeycomb ceramic in a solution consisting of deionized water, copper acetate, a Beta molecular sieve, methyl cellulose and glass fiber, drying and calcining to obtain the metal composite molecular sieve material.
Further, the preparation method of the Beta molecular sieve comprises the following steps:
slowly dripping tetraethylammonium 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, carrying out centrifugal washing by using 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 rise 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 reduced 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 at room temperature on a magnetic stirrer, and adding a noble metal precursor, wherein the loading 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, 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 accounts for 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/cm2The irradiation stirring time is 6-12 h; the rotating speed of the centrifugal washing centrifuge is 6000-8000 r/min, the centrifugation time is 3-6 min/time, and the washing times are 4-6 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, methyl cellulose and glass fiber, uniformly stirring, adding honeycomb ceramic, soaking for 6-8 hours, taking out, drying, putting into a forced air drying oven, 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 hours; 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 NH3、SO2And 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 has high dispersion degree on the molecular sieve carrier, 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 NH3、SO2The 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 the selectivity of carbon oxides for catalytic oxidation of toluene by using 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.
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 dripping 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 at 140 ℃ for 3d, then naturally cooling, carrying out centrifugal washing for 5 times by 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(CH3COO)4) Mixing with 20mL of deionized water, placing in a constant temperature magnetic stirrer at 60 ℃ and stirring speed of 45Fully stirring for 10 min at the speed of 0r/min to dissolve the CuOx/Beta molecular sieve, adding 1g of Beta molecular sieve in a stirring state, stirring until the mixture is dried, transferring the mixture to a vacuum freeze dryer at the temperature of minus 25 ℃ for freeze drying for 24h, grinding the dried mixture, placing the ground mixture in a muffle furnace for high-temperature calcination, raising the temperature from room temperature to 450 ℃ at the speed of 3 ℃/min, keeping the temperature at the constant temperature of 450 ℃ for 4h, and then reducing 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-SXE300/300UV) as light source, and light intensity of 350mW/cm2Continuously stirring and irradiating for 10h, centrifuging for 5 times by a centrifugal machine with the rotating speed of 6500r/min, and freeze-drying in a vacuum freeze dryer at the temperature of-25 ℃ 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) placing the honeycomb ceramic into the solution, soaking for 30min, taking out, placing into a forced air drying oven for drying for 12h, and then placing 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 the catalyst is 200mg, the reaction temperature is 150-390 ℃, the reaction flow is 200mL/min, and the space velocity is 60000h-1,5vol%O2, N2Is 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 substituted for carbon dioxide selectivity due to very small amount of carbon monoxide generated) with a commercial Pt-based catalyst and a 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 NH3、SO2Evaluation of catalytic oxidation of VOCs (b): 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 the catalyst is 200mg, the reaction temperature is 150-390 ℃, the reaction flow is 200mL/min, and the space velocity is 60000h-1,NH3Concentration 50ppm, NO concentration 50ppm, SO2The concentration was 500ppm, 5 vol% O2,N2Is a balance gas; the concentrations of toluene and carbon oxides were 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 toluene90305 ℃ corresponding to a selectivity of 85% over the T of the commercial Pt-based catalyst for the catalytic oxidation of toluene90The temperature was 20 ℃ lower. Shows that the prepared transition metal composite molecular sieve materialContaining NO and NH3、SO2The 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 (10)
1. A preparation method of a metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs is characterized in that a molecular sieve is dissolved in water, and a metal precursor is soaked or photo-deposited on the molecular sieve to prepare the obtained metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs.
2. The method of claim 1, wherein the metal comprises copper or platinum, and the molecular sieve is Beta.
3. The method for preparing the metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs according to claim 2, wherein the transition metal loading 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.
4. The method of claim 1, wherein the method comprises one of the following three methods:
dissolving copper acetate, copper nitrate or copper sulfate in deionized water, adding a Beta molecular sieve, drying and calcining to obtain a metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs;
secondly, adding a Beta molecular sieve into water with introduced nitrogen, adding chloroplatinic acid, methanol and ethanol, using an ultraviolet lamp or a xenon lamp as a light source, irradiating under continuous stirring, centrifuging, and drying in vacuum to obtain a noble metal composite molecular sieve material;
and thirdly, soaking the honeycomb ceramic in a solution consisting of deionized water, copper acetate, a Beta molecular sieve, methyl cellulose and glass fiber, drying and calcining to obtain the metal composite molecular sieve material.
5. The method for preparing the metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs according to claim 1, wherein the Beta molecular sieve is prepared by the following steps:
slowly dripping tetraethylammonium 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 the formed mixed solution at room temperature, transferring the mixed solution into a polytetrafluoroethylene reaction kettle inner container, finally putting the polytetrafluoroethylene reaction kettle inner container into a high-pressure reaction kettle, carrying out hydrothermal reaction in a blast drying box, naturally cooling to room temperature, carrying out centrifugal washing by using deionized water, carrying out vacuum freeze drying, and finally calcining by using 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.
6. The method of claim 1 for preparing a metal composite molecular sieve material for adsorption-catalytic oxidation of VOCs, comprising the steps of:
(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 material 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 materials;
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 catalyst, 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.
7. The method for preparing the metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs according to claim 1, comprising the following steps:
introducing nitrogen into deionized water, removing 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 loading 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 20-60 mL; the added Beta molecular sieve accounts for 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/cm2The irradiation stirring time is 6-12 h; the rotating speed of the centrifugal washing centrifuge is 6000-8000 r/min, the centrifugation time is 3-6 min/time, and the washing time is 4-6 times(ii) a 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.
8. The method for preparing the metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs according to claim 1, comprising the following steps:
dissolving a transition metal precursor in deionized water, adding a Beta molecular sieve, methyl cellulose and glass fiber, uniformly stirring, adding honeycomb ceramic, soaking for 6-8 hours, taking out, drying, putting into a forced air drying oven, 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 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 0.5-1 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 hours; 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.
9. A metal composite molecular sieve material for adsorbing-catalytically oxidizing VOCs is prepared by the preparation method of any one of claims 1 to 8.
10. The metal composite molecular sieve material of claim 9, which is used for industrial conventional organic waste gas, and contains NO and NH3、SO2The adsorption and catalytic oxidation field of industrial organic waste gas and organic waste gas in coal-fired flue gas.
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CN115178076A (en) * | 2022-07-27 | 2022-10-14 | 美埃(中国)环境科技股份有限公司 | Method for cooperatively realizing storage-oxidation regeneration cyclic purification of gaseous benzene or toluene molecules |
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