CN110756160A - Modified molecular sieve, preparation method, material and use method - Google Patents
Modified molecular sieve, preparation method, material and use method Download PDFInfo
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Abstract
The invention provides a modified molecular sieve, a preparation method, a material and a use method thereof, wherein the modified molecular sieve is used for treating volatile organic compounds and comprises a molecular sieve body and an active component attached to the molecular sieve body, the mole ratio of silicon to aluminum of the molecular sieve body is 20-150, a pore structure is arranged in the molecular sieve body, the active component comprises super acid, the super acid is attached to the outer surface of the molecular sieve body and the inner wall of the pore structure, the content of the super acid is 1.0-30% of the total mass of the modified molecular sieve, and the adsorption capacity of the volatile organic compounds is greater than or equal to 10%. The modified molecular sieve provided by the invention has the advantages of long service life, high adsorption efficiency and catalytic activity, strong stability, simple preparation process, less related raw material types and low cost.
Description
Technical Field
The invention relates to the technical field of volatile organic compound treatment, in particular to a modified molecular sieve, a preparation method, a material for treating volatile organic compounds and a use method.
Background
The emission of Volatile Organic Compounds (VOCs) has increasingly prominent influence on the atmospheric environment, and effective treatment of VOCs has become a focus of wide social attention, and adsorption concentration and catalytic oxidation are considered to be effective treatment methods among the existing main treatment methods. The adsorption material commonly used at present comprises activated carbon, a molecular sieve and the like, the activated carbon serving as an adsorbent has various problems, such as poor regeneration performance, difficult regeneration after use, poor stability, easy pore blockage, flammability, certain safety problem and the like, compared with the activated carbon, the molecular sieve has large specific surface area, regular pore channels and good thermal stability, and is more applied to the field of volatile organic matter treatment, but the existing molecular sieve has the problem of low catalytic efficiency.
In order to solve the problems, a supported catalyst is provided in the prior art, a noble metal silicon dioxide composite material is used as an active component to be supported on a molecular sieve, the catalyst needs to take silicon dioxide as a shell to protect noble metal, the preparation method is complex, the stability of the noble metal is poor, and the catalyst is easy to lose effectiveness.
Disclosure of Invention
Based on the above current situation, the main objective of the present invention is to provide a modified molecular sieve, a preparation method, a material and a use method thereof, so as to solve the technical problems of complex preparation method and poor stability in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a modified molecular sieve for treating volatile organic compounds, which comprises a molecular sieve body and an active component attached to the molecular sieve body, wherein the molar ratio of silicon to aluminum of the molecular sieve body is 20-150, a pore structure is arranged in the molecular sieve body, the active component comprises super acid, the super acid is attached to the outer surface of the molecular sieve body and the inner wall of the pore structure, the content of the super acid is 1.0-30% of the total mass of the modified molecular sieve, and the adsorption capacity of the volatile organic compounds is more than or equal to 10%.
Under the general condition, the load of the load type catalyst is only attached to the outer surface of the molecular sieve body, and because a large number of pore channel structures are arranged in the molecular sieve body, the content of the super acid in the molecular sieve can reach 1.0-30% of the total mass of the modified molecular sieve, the super acid can be attached to the inner wall of the pore channel structures, and the pore channel structures of the molecular sieve body are utilized to load the super acid, so that the catalytic oxidation efficiency of volatile organic compounds is greatly improved.
Optionally, the specific surface area of the molecular sieve body is 600-1200 m2/g。
The modified molecular sieve provided by the application can change the pore structure of the molecular sieve in the hydrophobic modification process of the molecular sieve, so that the specific surface area of the molecular sieve body in the molecular sieve is higher than 600m2The modified molecular sieve has the advantages that the modified molecular sieve can adsorb more volatile organic compounds, and the surface of the modified molecular sieve can be attached with more super acid due to the higher specific surface area, so that the adsorption efficiency and the catalytic activity of the modified molecular sieve are further improved.
Optionally, the channel structure has a channel cross-sectional area of
The pore channel of the existing molecular sieve is narrower, and the cross-sectional area of the pore channel of the modified molecular sieve provided by the application can reach the cross-sectional area
Therefore, more volatile organic compounds can be adsorbed, and the adsorption efficiency of the modified molecular sieve is further improved.
Optionally, the molecular sieve body comprises one or a combination of at least two of HY molecular sieve, ZSM-5, Beta, SAPO-34, MCM-41.
Preferably adopt HY molecular sieve, HY molecular sieve has great cavity structure, and adsorption capacity is great, especially to macromolecule volatile organic compounds component, also because HY molecular sieve after this kind of structure makes the super acid load has great catalytic oxidation area, and catalytic activity is good.
Optionally, the super acid is MnO2·H2SO4、ZrO2·H2SO4、Al2O3·H2SO4、 TiO2·H2SO4、MnO2·H2S2O8、ZrO2·H2S2O8、Al2O3·H2S2O8、TiO2·H2S2O8Or a combination of at least two thereof, wherein MnO is2、ZrO2、Al2O3、TiO20.8-30 wt% of the total mass of the modified molecular sieve, and SO4 2-、S2O8 2-The content of (b) is 0.2-30 wt% of the total mass of the modified molecular sieve.
Preferably, the super acid is MnO2·H2SO4Or MnO2·H2S2O8。
MnO2·H2SO4Or MnO2·H2S2O8The catalyst is a super acid component, has strong oxidation capacity, provides possibility for realizing catalytic oxidation of VOCs components at low temperature (less than or equal to 200 ℃), has low cost and high safety, has small influence on environment, and inevitably causes active groups along with the increase of the use time and times of materialsThe loss of the component and the reduction of the activity can be realized, but the active component can be loaded into the material again through the same loading process without influencing the performance of the material.
The invention also provides a preparation method of the modified molecular sieve, which comprises the following steps:
s100, preparing the molecular sieve body by using a silicon source, an aluminum source and a template agent, wherein the mass ratio of the aluminum source to the silicon source to the template agent is 1: 1-10: 1;
s200, depositing a precursor of the super acid on the outer surface of the molecular sieve body and the inner wall of the pore channel structure by a chemical liquid phase deposition method, and performing primary drying and primary roasting to obtain an intermediate;
s300, vulcanizing the intermediate, and performing secondary drying and secondary roasting to obtain the modified molecular sieve.
Preferably, the precursor of the super acid is one of permanganate, titanate, meta-aluminate and zirconate or a combination of at least two of the two.
Preferably, the S200 includes the steps of:
s210, dissolving a precursor of the super acid in absolute ethyl alcohol or a mixed solution of the absolute ethyl alcohol and water to obtain a precursor solution;
s220, adding the molecular sieve body into the precursor solution, stirring, filtering and drying to obtain a first solid;
s230, roasting the first solid, and naturally cooling to obtain an intermediate;
in S210, the concentration of the precursor solution is 1.0-20.0 g/mL.
Preferably, the S300 includes the steps of:
s310, adding the intermediate into a sulfur-containing solution, stirring, filtering and drying to obtain a second solid;
s320, roasting the second solid, and then cooling to obtain the modified molecular sieve;
wherein the concentration of the sulfur-containing solution is 1.0-20 wt%, and the vulcanizing time is 8-24 h.
The invention also provides a material for treating volatile organic compounds, which comprises the modified molecular sieve.
The invention also provides a method for using the material, which comprises an adsorption step and an oxidation desorption step,
in the adsorption step, gas to be treated passes through the material to be adsorbed;
in the step of oxidative desorption, the temperature of the adsorbed material is raised to a reaction temperature, and the oxidative desorption is carried out, wherein the reaction temperature is lower than 200 ℃ and higher than 60 ℃.
Preferably, in the adsorption step, the flow rate of the gas is 20-100 mL/min, and the adsorption temperature is 30-50 ℃.
The molecular sieve body of the modified molecular sieve has the silicon-aluminum molar ratio of 20-150, thereby ensuring that the molecular sieve body has good hydrophobicity, avoiding the influence of the modified molecular sieve on the service life of the modified molecular sieve due to the absorption of excessive water vapor in airflow, adopting super acid as an active component, and the super acid is attached to the outer surface of the molecular sieve body and the inner wall of the pore channel structure, so that the adsorption efficiency and the catalytic activity of the modified molecular sieve can be effectively improved, the adsorption capacity is more than or equal to 10 percent, the in-situ low-temperature oxidation desorption can be realized, the desorption of the coking precursor is effectively promoted, the inactivation caused by the surface carbon deposition is inhibited, the modified molecular sieve can keep stable adsorption and catalytic activity for a long time, and the structure ensures that the modified molecular sieve has strong stability, the preparation process of utilizing super acid load is simple, the quantity of related raw materials is small, the cost is low, and thus, the production cost of the modified molecular sieve can be greatly reduced.
Detailed Description
The present invention will be described below based on examples, but the present invention is not limited to only these examples. In the following detailed description of the present invention, certain specific details are set forth in order to avoid obscuring the nature of the present invention, well-known methods, procedures, and components have not been described in detail.
Unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is, what is meant is "including, but not limited to".
In the description of the present invention, it is to be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In addition, in the description of the present invention, "a plurality" means two or more unless otherwise specified.
Aiming at the technical problems of complex preparation method and poor stability of the molecular sieve in the prior art, the application provides a novel modified molecular sieve which comprises a molecular sieve body and an active ingredient attached to the molecular sieve body, wherein the active ingredient is super acid, although super acid is used as a load in the existing load type molecular sieve, the super acid does not achieve good adsorption effect and has short service life when being applied to volatile organic matter treatment, and the super acid loaded molecular sieve provided by the application has a silicon-aluminum molar ratio of 20-150, so that the molecular sieve body is ensured to have good hydrophobicity, and the service life of the modified molecular sieve is prevented from being influenced by excessive water vapor in adsorbed airflow. The molecular sieve body is internally provided with a pore channel structure, the super acid as an active ingredient is attached to the outer surface of the molecular sieve body and the inner wall of the pore channel structure, because the super acid of the application can be attached to the outer surface of the molecular sieve body and the inner wall of the pore channel structure, the content of the super acid can reach 1.0-20% of the total mass of the modified molecular sieve, the adsorption efficiency and the catalytic activity of the modified molecular sieve can be effectively improved, the adsorption capacity is more than or equal to 10 percent, the in-situ low-temperature oxidation desorption can be realized, the desorption of the coking precursor is effectively promoted, the inactivation caused by the surface carbon deposition is inhibited, the modified molecular sieve can keep stable adsorption and catalytic activity for a long time, and the structure ensures that the modified molecular sieve has strong stability, the preparation process of utilizing super acid load is simple, the quantity of related raw materials is small, the cost is low, and thus, the production cost of the modified molecular sieve can be greatly reduced.
Ratio of conventional molecular sieves presentThe surface area is basically 200-600m2In the range of/g, the modified molecular sieve provided by the application can change the pore channel structure in the hydrophobic modification process of the molecular sieve, so that the specific surface area of the molecular sieve body in the molecular sieve can be higher than 600m2g, specifically, washing the molecular sieve with strong acid aqueous solutions with different concentrations (concentration range is 0.1-5.0mol/L, and the concentration of the strong acid is preferably 1.0mol/L) at 40-90 ℃ (the temperature is preferably 80 ℃), the washing time is 1-10h (the time is preferably 2h), the strong acid can erode the material structure while dissolving the hydrophilic component in the molecular sieve structure, and additional pore channel structures can be formed, further improving the specific surface area of the modified molecular sieve, so that the modified molecular sieve provided by the application can adsorb more volatile organic compounds, the adsorption capacity is improved to more than 10 percent, the water absorption is reduced to less than 3 percent, in addition, the higher specific surface area can also enable more superacid to be attached to the surface of the modified molecular sieve, thereby further improving the adsorption efficiency and the catalytic activity of the modified molecular sieve.
The pore channels of the conventional molecular sieve are narrow, the narrow pore channels are not convenient for volatile organic compound adsorption, and the cross-sectional area of the pore channel structure of the modified molecular sieve provided by the application is
Therefore, more volatile organic compounds can be adsorbed, and the adsorption efficiency of the modified molecular sieve is further improved.
The molecular sieve body can be selected from conventional molecular sieves, such as HY molecular sieve, ZSM-5, Beta, SAPO-34, MCM-41 and the like, in a preferred embodiment, the molecular sieve body is selected from HY molecular sieves which have larger hole structures and larger adsorption capacity, and particularly for macromolecular volatile organic compounds, the HY molecular sieve after super acid loading has larger catalytic oxidation area and good catalytic activity due to the structure.
The super acid may be MnO2·H2SO4、ZrO2·H2SO4、Al2O3·H2SO4、TiO2·H2SO4、 MnO2·H2S2O8、ZrO2·H2S2O8、Al2O3·H2S2O8、TiO2·H2S2O8Or a combination of at least two thereof, wherein MnO is2、ZrO2、Al2O3、TiO2Is 0.8 to 30 weight percent of the total mass of the modified molecular sieve and SO4 2-、S2O8 2-In an amount of 0.2-30 wt% based on the total weight of the modified molecular sieve, in a preferred embodiment, the super acid is MnO2·H2SO4Or MnO2·H2S2O8，MnO2·H2SO4Or MnO2·H2S2O8The catalyst is a super acid component, has strong oxidizing capability, provides possibility for realizing catalytic oxidation of VOCs components at low temperature (less than or equal to 200 ℃), has low cost and high safety, has small influence on the environment, inevitably causes loss of active components and activity reduction of the components along with increase of the service time and times of materials, but can load the active components into the materials again through the same loading process without influencing the performance of the materials.
Further, the application also provides a preparation method of the modified molecular sieve, which comprises the following steps:
s100, preparing the molecular sieve body by using a silicon source, an aluminum source and a template agent, wherein the mass ratio of the aluminum source to the silicon source to the template agent is 1: 1-10: 1;
s200, depositing a precursor of the super acid on the surface of the molecular sieve body by a chemical liquid phase deposition method, and performing primary drying and primary roasting to obtain an intermediate;
s300, vulcanizing the intermediate, and performing secondary drying and secondary roasting to obtain the modified molecular sieve.
Wherein, S100 is a step of preparing the molecular sieve body, and a conventional preparation method can be adopted, in order to obtain a higher specific surface area and a larger cross-sectional area of the pore channel, in a preferred embodiment, S100 comprises the following steps:
s110, preparation of a guiding agent: placing a template agent, an aluminum source and deionized water in a beaker, stirring until the template agent, the aluminum source and the deionized water are completely dissolved to obtain a solution with the concentration of 5-50g/L (preferably 15g/L), mixing and stirring the solution and a first mass of silicon source, and aging at a predetermined temperature for a predetermined time to obtain a directing agent, wherein the predetermined temperature is 25-40 ℃, the predetermined time is 25 ℃, the predetermined time is 10-24 hours, the preferred time is 24 hours, and the mass ratio of the silicon source to a solute of the solution is 1: 1-10: 1, and the preferred time is 1: 1.
S120, mother liquor preparation: mixing and stirring the guiding agent and a silicon source with a second mass to obtain a first liquid, stirring and dissolving an aluminum source and water at room temperature to obtain a second liquid, wherein the concentration of the second liquid is 10-20 g/mL, preferably 12g/mL, pouring the first liquid into the second liquid, stirring to obtain a mixed solution, subpackaging the mixed solution into two hydrothermal synthesis reaction kettles, purifying at a preset temperature for a preset time, filtering, washing and drying to obtain a molecular sieve intermediate, wherein in the step, the preset temperature is 80-180 ℃, the preset time is 100 ℃, the preset time is 10-24 hours, preferably 16 hours, and the drying temperature is 40-100 ℃, preferably 80 ℃.
S130, modification: and (3) carrying out acid washing on the molecular sieve intermediate, and sequentially carrying out hydrothermal superstability and high-temperature roasting after the acid washing is finished to obtain the molecular sieve body.
Wherein the aluminum source is NaAlO2、Al(NO3)3、Al2O3Or a combination of at least two of the above, the silicon source being, for example, water glass, silica sol, SiO2For example tetraethylammonium hydroxide or NaOH or a combination of both. The stirring process in the above steps is preferably performed by using a magnetic rotor.
In S130, HNO is preferably used3The solution is pickled, preferably at 75 to 85 ℃ during pickling, and more preferablyThe temperature at which the hydrothermal superstability is carried out with stirring at 80 ℃ is preferably 550 ℃ to 650 ℃, and the flow rate is preferably 18 to 22mL/h, and more preferably, the temperature is 600 ℃, and the flow rate is 20 mL/h. The high-temperature calcination is preferably carried out at a temperature of 500 ℃ to 600 ℃ for a time period of 1.5h to 2.5h, and more preferably at a temperature of 550 ℃ for a time period of 2 h.
In S200, the precursor of the super acid may be, for example, one of permanganate, titanate, meta-aluminate, and zirconate, or a combination of at least two of them. Among them, titanates and zirconates are superior to other materials because of their good load uniformity and load particle size.
S200 specifically includes the following steps:
s210, dissolving a precursor of the super acid in absolute ethyl alcohol or a mixed solution of absolute ethyl alcohol and water to obtain a precursor solution, preferably mixing in a heating and stirring manner, wherein the stirring time is 0.5-2 h, preferably 1 h;
s220, adding the molecular sieve body into the precursor solution, stirring, filtering and drying to obtain a first solid, wherein the mass ratio of the molecular sieve body to the precursor is 100: 1-100: 20, and preferably 100: 3;
s230, roasting the first solid, and naturally cooling to obtain an intermediate, wherein the roasting temperature is 500-600 ℃, the roasting time is preferably 550 ℃, and the roasting time is 1-5 hours, and the roasting time is preferably 3 hours;
in S210, the concentration of the precursor solution is 1.0-20.0 g/mL. Precursors of superacids are for example sodium permanganate, titanate, sodium aluminate or zirconate.
Further, S300 includes the steps of:
s310, adding the intermediate into a sulfur-containing solution, stirring, filtering and drying to obtain a second solid, wherein the sulfur-containing solution is an aqueous solution of sulfuric acid, ammonium sulfate, persulfuric acid or ammonium persulfate, the concentration of the aqueous solution is 2-20 wt%, and the stirring time is 0.5-24 hours;
s320, roasting the second solid, and cooling to obtain modified molecules, wherein the roasting temperature of the sieve is 500-600 ℃, preferably 550 ℃, and the roasting time is 1-5 h, preferably 3 h;
wherein the concentration of the sulfur-containing solution is 1.0-20 wt%, and the vulcanizing time is 8-24 h. The mass ratio of the intermediate to the sulfur-containing solution is 2: 1-10: 1, preferably 5: 1.
More specifically, taking the molecular sieve body as an HY molecular sieve as an example, the preparation process of the modified molecular sieve comprises the following steps:
s210, dissolving 0.03-3 g of sodium permanganate, titanate, sodium aluminate or zirconate in 100-500 mL of absolute ethanol to obtain a precursor solution;
s220, adding 2-10 g of HY molecular sieve into the precursor solution, stirring for about 0.5-10 hours (preferably for 2 hours), filtering, and drying the obtained first solid;
s230, roasting the first solid at 500-600 ℃ for 1-5 hours, and naturally cooling to room temperature to obtain the product with MnO on the surface2、ZrO2、Al2O3Or TiO2The HY molecular sieve of (4);
s310, including MnO in the surface obtained in S2302、ZrO2、Al2O3Or TiO2Adding the HY molecular sieve into 50-500 mL of sulfur-containing solution, stirring for 0.5-24 hours, filtering, and drying to obtain a second solid;
s320, roasting the second solid at 500-600 ℃ for 1-5 hours, and naturally cooling to room temperature to obtain the super acid supported HY molecular sieve.
Specific preparation method examples are given.
The first embodiment is as follows:
the embodiment provides a preparation method of an HY molecular sieve, which specifically comprises the following steps:
(1) preparing a guiding agent: mixing 3.8g of NaOH and 2.1g of NaAlO2Mixing with 15.2g deionized water in a 100mL beaker, stirring until the solution is completely dissolved, weighing 21.5g water glass, mixing with the solution, stirring with a rotor under magnetic force, and aging for 24h at 25 ℃.
(2) Preparing mother liquor: mixing 110g of water glass and the guiding agent, quickly stirring (stirring by a magnetic rotor), weighing 85.4g of water and 10.7g of sodium aluminate, stirring and dissolving completely at room temperature, pouring the solution, quickly stirring for 20min, subpackaging the mixed solution into 2 hydrothermal synthesis reaction kettles, crystallizing for 16h at 100 ℃, filtering, washing and drying at 80 ℃ to obtain a NaY powder product.
(3) Modification: 15.0g of NaY molecular sieve and 150mL of HNO with the concentration of 0.4moL/L3And placing the solution into a 250mL flask, stirring and carrying out acid washing at 80 ℃, and after the acid washing is finished, sequentially carrying out hydrothermal superstability (temperature is 600 ℃, flow rate is 20mL/h) and high-temperature roasting (550 ℃, 2h) to obtain the hydrophobic molecular sieve.
Example two:
the embodiment provides a preparation method of a modified molecular sieve using the HY molecular sieve obtained in the embodiment one as a molecular sieve body, which specifically comprises the following steps:
0.25g of sodium permanganate was dissolved in 125mL of a mixed solvent of absolute ethanol and water (the volume ratio of water to ethanol was 1:4), 5g of the HY molecular sieve described in example 1 was added to the solution, and the mixture was stirred with heating for about 1 hour. Next, the solution was filtered, dried, and then calcined at 550 ℃ for 3 hours. 100mL of a 10 wt% aqueous ammonium sulfate solution was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 8 hours. Then, the solution is filtered and dried, and then roasted at 550 ℃ for 3 hours to obtain the modified molecular sieve MnO2·H2SO4Supported HY molecular sieve.
Example three:
the embodiment provides a preparation method of a modified molecular sieve using the HY molecular sieve obtained in the embodiment one as a molecular sieve body, which specifically comprises the following steps:
under a protective atmosphere, 0.30g of zirconium butoxide was dissolved in 125mL of absolute ethanol under air exclusion, 5g of the HY molecular sieve from example 1 was added to the solution, and the mixture was stirred for about 1 hour. Next, the solution was filtered, dried, and then calcined at 550 ℃ for 3 hours. 100mL of a 2 wt% aqueous solution of sulfuric acid was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 1 hour. Then, the solution is filtered and dried, and then roasted at 550 ℃ for 3 hours to obtain the modified molecular sieve ZrO2·H2SO4Supported HY molecular sieve.
Example four:
the embodiment provides a preparation method of a modified molecular sieve using the HY molecular sieve obtained in the embodiment one as a molecular sieve body, which specifically comprises the following steps:
0.15g of Al (OH)3Dissolved in 125mL of a mixed solvent of absolute ethanol and water (the volume ratio of water to ethanol is 1:4), 5g of the HY molecular sieve of example 1 was added to the solution, and the mixture was stirred with heating for about 1 hour. Next, the solution was filtered, dried, and then calcined at 550 ℃ for 3 hours. 100mL of a 2 wt% aqueous solution of sulfuric acid was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 8 hours. Then, the solution is filtered and dried, and then roasted for 3 hours at 550 ℃, and the obtained modified molecular sieve is Al2O3·H2SO4Supported HY molecular sieve.
Example five:
the embodiment provides a preparation method of a modified molecular sieve using the HY molecular sieve obtained in the embodiment one as a molecular sieve body, which specifically comprises the following steps:
0.15g of tetrabutyl titanate was dissolved in 125mL of absolute ethanol, 5g of the HY molecular sieve in example 1 was added to the solution, and the mixture was stirred with heating for about 1 hour. Next, the solution was filtered, dried, and then calcined at 550 ℃ for 3 hours. 100mL of a 10 wt% aqueous ammonium sulfate solution was taken, and the calcined sample was added to the solution, followed by stirring at room temperature for about 8 hours. Then, the solution is filtered and dried, and then the solution is roasted for 3 hours at 550 ℃, SO that the obtained modified molecular sieve is a TiO 2. H2SO4 supported HY molecular sieve.
Five materials obtained in the first to fifth examples are respectively used as a sample 1, a sample 2, a sample 3, a sample 4, a sample 5 and a comparative sample 6 to be subjected to static adsorption tests of water and VOCs, wherein the sample 6 is a Pd-supported ceramic catalyst, and the molecular sieve static water adsorption test method comprises the following steps:
the test is carried out according to the national standard GB6287-1986 molecular sieve static water adsorption determination method. Firstly, a weighing bottle with constant weight is weighed by an electronic balance
Weighing (accurate to 0.2mg), pouring 1.5g of molecular sieve sample into the bottle, and immediately covering the bottle cap for weighing; then, the bottle cap was opened, and the bottle was placed in a desiccator having a saturated aqueous solution of sodium chloride (about 1000mL) at the bottom, and after adsorbing at a constant temperature of 35 ℃ for 24 hours, the lid of the desiccator was opened, and the bottle cap was immediately closed and weighed (to an accuracy of 0.2 mg). The static water adsorption capacity of the molecular sieve was calculated as follows:
X＝(m3-m2)/(m2-m1)×100％
wherein, X represents the amount of static water adsorption,%;
m1-weighing the bottle weight, g;
m2-initial weight of molecular sieve (dry weight) plus weight of weighing bottle, g;
m3weight after molecular sieve reached stable adsorption (wet weight) plus weight of the weighing flask, g.
The method for testing the adsorption of the static VOCs components of the molecular sieve comprises the following steps:
firstly, a weighing bottle with constant weight is weighed by an electronic balance
Weighing (accurate to 0.2mg), pouring a proper amount of molecular sieve samples roasted at 550 ℃ for 1h into a bottle, and immediately covering the bottle and weighing; the bottle cap was then opened and the bottle was placed in a desiccator with a source of VOCs (about 1000mL) at the bottom and after 24 hours of adsorption at a constant temperature of 35 c, the lid of the desiccator was opened and the bottle cap was immediately closed and weighed (to an accuracy of 0.2 mg). Calculating the adsorption capacity of the static VOCs component of the molecular sieve according to the following formula:
X＝(m3-m2)/(m2-m1)×100％
wherein, X represents the adsorption amount of static VOCs,%;
m1-weighing the bottle weight, g;
m2-initial weight of molecular sieve plus weight of weighing bottle, g;
m3-weight after molecular sieve reaches stable adsorption plus weight of weighing bottle, g.
Typical organic molecules including dichloromethane, methanol, ethanol, propanol, isopropanol, ethyl acetate, cyclohexene, cyclohexane, benzene, toluene, cyclohexanone and xylene are selected as VOCs sources.
The test results are shown in the following table:
the data in the table show that the modified super-strong acid supported HY molecular sieve material has greatly improved adsorption capacity on various organic matters, and greatly reduced water absorption capacity, which indicates that the molecular sieve modification method is reasonable and feasible.
Five materials obtained in examples one to five were subjected to catalyst activity tests as sample 1, sample 2, sample 3, sample 4, sample 5, and comparative sample 6, respectively, sample 6 being a Pd-supported ceramic catalyst, under the test conditions: a reactor, a fixed bed reactor; a VOC component: ethanol, ethyl acetate, acetone, n-hexane, benzene, toluene, dichloromethane, and chlorobenzene; reaction time, 12 hours. The test results are shown in the following table:
from the above table, samples 2-5 greatly reduced the conversion temperature of VOCs components, especially the conversion temperature of the difficult-to-oxidize components such as ethyl acetate, n-hexane, and benzene, which were all lower than 200 ℃.
Further, the application also provides a material for treating volatile organic compounds, which comprises the modified molecular sieve.
Further, the application also provides a using method of the material, namely a method for treating volatile organic compounds by adopting the material, which specifically comprises the following steps:
an adsorption step, namely passing the gas to be treated through the material to adsorb;
and an oxidation desorption step, namely heating the adsorbed material to a reaction temperature, and carrying out oxidation desorption, wherein the reaction temperature is lower than 200 ℃ and higher than 60 ℃.
Preferably, in the adsorption step, the flow rate of the gas is 20-100 mL/min, the adsorption temperature is 30-50 ℃, the adsorption effect of the molecular sieve is best at the flow rate and the adsorption temperature, and the conditions are consistent with the discharge conditions of VOCs in the industry.
In a specific embodiment, the processing comprises: 1) roasting the above materials at 500-600 deg.C, preferably 550 deg.C for 2-4 h, preferably 3h, wherein the roasting pretreatment is to take out adsorbed water or organic matter in the materials to realize better adsorption performance, cooling to room temperature, loading the materials into an adsorption box, measuring the stacking height, calculating the stacking density, and the range is 200-3Preferably 600 kg/m3(ii) a 2) Adjusting the superficial linear velocity of the VOCs atmosphere to be 0.1-0.8m/s, preferably 0.3m/s, setting the adsorption temperature to be 20-70 ℃, preferably 40 ℃, and adjusting the atmosphere humidity to be 40-90 RH%, preferably 50 RH%; 3) VOCs are introduced for adsorption, and the inlet concentration is set to be 60-300mg/m3Preferably 120mg/m3(ii) a 4) Recording the concentration of VOCs at the outlet of the adsorption box at regular intervals (10min-24h), and when the concentration at the outlet is equal to the concentration at the inlet, indicating that the molecular sieve is saturated in adsorption, and ending the adsorption process; 5) heating the adsorption box, wherein the outlet atmosphere re-enters the adsorption box in a circulating manner, heating to 160-200 deg.C, preferably 180 deg.C, and detecting outlet CO2Concentration, CO at the outlet2Concentration and CO in air2The concentration is equivalent, namely the catalytic combustion process is finished, the adsorbing material is regenerated, and the next adsorption-catalytic combustion cycle is carried out.
It will be appreciated by those skilled in the art that the above-described preferred embodiments may be freely combined, superimposed, without conflict.
It will be understood that the embodiments described above are illustrative only and not restrictive, and that various obvious and equivalent modifications and substitutions for details described herein may be made by those skilled in the art without departing from the basic principles of the invention.
Claims (10)
1. The modified molecular sieve is used for treating volatile organic compounds and is characterized by comprising a molecular sieve body and an active ingredient attached to the molecular sieve body, wherein the molar ratio of silicon to aluminum of the molecular sieve body is 20-150, a pore structure is arranged in the molecular sieve body, the active ingredient comprises super acid, the super acid is attached to the outer surface of the molecular sieve body and the inner wall of the pore structure, the content of the super acid is 1.0-20% of the total mass of the modified molecular sieve, and the adsorption capacity of the volatile organic compounds is greater than or equal to 10%.
2. The modified molecular sieve of claim 1, wherein the molecular sieve body has a specific surface area of 600 to 1200m2/g；
Preferably, the channel structure has a channel cross-sectional area of
3. The modified molecular sieve of claim 1, wherein the molecular sieve body comprises one or a combination of at least two of HY molecular sieve, ZSM-5, Beta, SAPO-34, MCM-41;
preferably, the super acid is MnO2·H2SO4、ZrO2·H2SO4、Al2O3·H2SO4、TiO2·H2SO4、MnO2·H2S2O8、ZrO2·H2S2O8、Al2O3·H2S2O8、TiO2·H2S2O8Or a combination of at least two thereof, wherein MnO is2、ZrO2、Al2O3、TiO20.8-30 wt% of the total mass of the modified molecular sieve, and SO4 2-、S2O8 2-The content of (A) is 0.2-30 wt% of the total mass of the modified molecular sieve;
preferably, the super acid is MnO2·H2SO4Or MnO2·H2S2O8。
4. A process for the preparation of a modified molecular sieve according to any one of claims 1 to 3, wherein the process comprises:
s100, preparing the molecular sieve body by using a silicon source, an aluminum source and a guiding agent, wherein the mass ratio of the aluminum source to the silicon source to the guiding agent is 1: 1-10: 1;
s200, depositing a precursor of the super acid on the outer surface of the molecular sieve body and the inner wall of the pore channel structure by a chemical liquid phase deposition method, and performing primary drying and primary roasting to obtain an intermediate;
s300, vulcanizing the intermediate, and performing secondary drying and secondary roasting to obtain the modified molecular sieve.
5. The preparation method according to claim 4, wherein the precursor of the super acid is one of permanganate, titanate, meta-aluminate and zirconate or a combination of at least two of the above.
6. The method according to claim 4, wherein the step S200 comprises the steps of:
s210, dissolving a precursor of the super acid in absolute ethyl alcohol or a mixed solution of the absolute ethyl alcohol and water to obtain a precursor solution;
s220, adding the molecular sieve body into the precursor solution, stirring, filtering and drying to obtain a first solid;
s230, roasting the first solid, and naturally cooling to obtain an intermediate;
in S210, the concentration of the precursor solution is 1.0-20.0 g/mL.
7. The method according to claim 4, wherein the step S300 comprises the steps of:
s310, adding the intermediate into a sulfur-containing solution, stirring, filtering and drying to obtain a second solid;
s320, roasting the second solid, and then cooling to obtain the modified molecular sieve;
wherein the concentration of the sulfur-containing solution is 1.0-20 wt%, and the vulcanizing time is 8-24 h.
8. A material for treating volatile organic compounds, comprising the modified molecular sieve of any of claims 1 to 3.
9. A method of using the material of claim 8, wherein the method comprises an adsorption step and an oxidative desorption step,
in the adsorption step, gas to be treated passes through the material to be adsorbed;
in the step of oxidative desorption, the temperature of the adsorbed material is raised to a reaction temperature, and the oxidative desorption is carried out, wherein the reaction temperature is lower than 200 ℃ and higher than 60 ℃.
10. The use method according to claim 9, wherein in the adsorption step, the flow rate of the gas is 20-100 mL/min, and the adsorption temperature is 30-50 ℃.
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