CN107008227B - Metal ion modified hierarchical pore zeolite nano adsorbent and preparation method thereof - Google Patents
Metal ion modified hierarchical pore zeolite nano adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a metal ion modified hierarchical pore zeolite nano adsorbent and a preparation method thereof, wherein metal in the metal modified hierarchical pore zeolite nano adsorbent is highly dispersed in a hierarchical pore zeolite framework and mesoporous pore canals in the form of ions and/or oxides. Compared with the existing adsorption material, the metal modified hierarchical pore zeolite nano adsorbent has the advantages that the hierarchical pore zeolite nano adsorbent has high specific surface area which is more than 500m2(iv)/g, to facilitate high dispersion of the active ingredient; the modified hierarchical pore zeolite adsorbs gas pollutants through intrinsic acidity and metal ion/oxide synergy; the modified hierarchical pore zeolite can adsorb CO and C with low concentration3H8Can also adsorb CO and C with high concentration3H8(ii) a The adsorbent does not contain noble metals, is low in cost and can be reused through heat treatment.
Description
Technical Field
The invention belongs to the technical field of materials, relates to a metal modified hierarchical pore zeolite nano adsorbent and a preparation method thereof, and particularly relates to an adsorbent for efficiently removing low-concentration and high-concentration CO and HC compounds in semi-closed spaces (tunnels, parking lots and the like) and diesel vehicle exhaust purification, and a preparation method thereof.
Background
The exhaust gas from urban semi-enclosed spaces and diesel vehicles contains a large amount of CO and HC compounds, which seriously affect our living environment and human health. Therefore, with public calls for high quality environments, efficient treatment and purification of these contaminant gases is imperative. Generally, for the exhaust gas discharged from urban semi-closed spaces and diesel vehicles, the exhaust gas is mainly removed by adsorption catalysis, and the premise of the material exerting the catalytic effect is to effectively adsorb pollutant gas. Therefore, it is a significant effort to develop adsorbent materials that have high efficiency in adsorbing gaseous pollutants. Generally, the concentration of exhaust gas discharged from urban semi-enclosed spaces such as tunnels, parking lots and the like is relatively low, while the concentration of exhaust gas discharged from diesel vehicles is relatively high. It is very difficult to achieve the removal of harmful gases in both low and high concentrations in a single material due to the interplay of thermodynamics and kinetics.
The adsorbing material is generally an oxide with high specific surface area such as alumina, silica and the like, and generally only plays a role of dispersing the active component.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a metal modified hierarchical pore zeolite molecular sieve adsorbent which can realize low-concentration and high-concentration CO and C at normal temperature3H8Effective adsorption and repeated use performance.
In order to achieve the purpose, the invention provides a metal modified hierarchical pore zeolite nano-adsorbent, wherein metals in the metal modified hierarchical pore zeolite nano-adsorbent are highly dispersed in the hierarchical pore zeolite framework or/and mesoporous pore channels in the form of ions or/and oxides.
Here, we use metal-modified hierarchical pore zeolites as the adsorbent material, whose high specific surface area acts to highly disperse the active components, thereby allowing efficient contact with gaseous contaminants; meanwhile, metal ions and/or metal oxides in the zeolite framework and the mesoporous pore canal can be used as active components to effectively adsorb normal-temperature pollutant gas; meanwhile, the intrinsic acidity of the zeolite is also an active component, and plays a role in improving the adsorption performance of the material at normal temperature, so that the metal modified hierarchical pore zeolite shows excellent catalytic performance in the field of adsorption catalysis.
Preferably, the hierarchical pore zeolite can be ZSM-5, Beta, TS. The preferred mesoporous aperture is 2-30nm, and the preferred molar ratio of Si to Al is 20-40; more preferably, the mesoporous pore diameter of the hierarchical pore zeolite is 3-7nm, and Si/Al is 25.
The multiwell zeolites are highly dispersed and have a particle size of less than 500 nm. Preferably, the particle size is 300-400 nm.
The metal is at least one of Mg, K, Ca, Na and Mn, and is preferably Mg.
Preferably, the metal loading is from 2wt% to 15 wt%. Preferably 5wt% to 10 wt%.
The invention also provides a preparation method of the metal modified hierarchical pore zeolite nano adsorbent, which comprises the following steps:
(1) adding potassium chloride, a silicon source, an aluminum source and metal salt into water to prepare a mixed solution, and then adding a structure directing agent to enable the silicon source, the aluminum source and the metal salt to perform hydrolytic polycondensation reaction under an alkaline condition;
(2) adding a mesoporous template agent, performing hydrothermal crystallization treatment, then performing centrifugal washing to collect a product, and then roasting at 550-600 ℃ to obtain the metal modified hierarchical pore zeolite nano adsorbent.
The nano adsorbent disclosed by the invention is simple in preparation process, excellent in adsorption capacity and low in preparation cost, and not only can be used for removing low-concentration CO, hydrocarbons and the like at normal temperature in a semi-closed space (a tunnel, a parking lot and the like), but also can be used for adsorbing and enriching gas pollutants in an idling stage of a diesel vehicle.
Preferably, the silicon source is selected from metasilicic acid, and the aluminum source is selected from sodium aluminate, and the concentration is preferably 1-2.5mol/L and 0.06-0.12mol/L respectively.
Preferably, the metal salt is an alkali metal or alkaline earth metal nitrate, and the concentration is preferably 0.1-0.2 mol/L.
Preferably, the concentration of the potassium chloride is preferably 0.2-0.4 mol/L.
Preferably, in the step (2), the mesoporous template is selected from cetyl trimethyl ammonium bromide CTAB, and the added amount is 0.05-0.1 mol/L.
The invention provides an application of a metal modified hierarchical pore zeolite nano adsorbent for efficiently removing CO and HC compounds, wherein simulated reaction gas is introduced into a reactor, a metal modified hierarchical pore zeolite molecular sieve is used as an adsorbent, and O in the air is used as the adsorbent2Is used as oxidant for simulating CO and C in semi-closed space exhaust gas and diesel vehicle exhaust gas under room temperature condition3H8Adsorption performance studies were performed.
Preferably, the total flow of the simulated semi-closed space waste gas is 600-3H8The content was below 10 ppmv.
Preferably, the total flow of the simulated diesel vehicle tail gas is 600-1800mL/min, the content of CO is 5000ppmv, and C is3H8The content was 500 ppmv.
Preferably, the adsorbent is present in an amount of 0.1 to 0.2 g.
Compared with the existing adsorbing material, the metal modified hierarchical pore zeolite nano adsorbent has the advantages that:
1. the porous zeolite nano adsorbent has high specific surface area of more than 500m2(iv)/g, to facilitate high dispersion of the active ingredient;
2. the modified hierarchical pore zeolite adsorbs gas pollutants through intrinsic acidity and metal ion/oxide synergy;
3. the modified hierarchical pore zeolite can adsorb CO and C with low concentration3H8Can also adsorb CO and C with high concentration3H8；
4. The adsorbent does not contain noble metals, is low in cost and can be reused through heat treatment.
The metal modified hierarchical pore Beta molecular sieve has good normal-temperature low-concentration and high-concentration CO and C3H8And the like, and the high-efficiency adsorption performance of pollutant gas. The adsorbent has excellent cyclic use performance, strong applicability and high preparation efficiencySimple and easy preparation and use, and can economically and efficiently remove low-concentration CO and C in semi-closed space and high-concentration CO and C in tail gas of diesel vehicles at normal temperature3H8And the like, and has important practical application value.
Drawings
FIG. 1 is a low magnification TEM photograph of the metal modified hierarchical pore Beta molecular sieve adsorbent prepared in example 1;
FIG. 2 is a high magnification TEM photograph of the metal modified hierarchical pore Beta molecular sieve adsorbent prepared in example 1;
FIG. 3 shows the results of the metal-modified hierarchical pore Beta zeolite adsorbent prepared in example 2 for high concentrations of CO and C at room temperature and low flow rate3H8The adsorption catalysis effect of (3);
FIG. 4 shows the results of the metal-modified hierarchical pore Beta zeolite adsorbent prepared in example 3 for high concentrations of CO and C at room temperature and high flow rate3H8The adsorption catalysis effect of (3);
FIG. 5 shows the results of the metal-modified hierarchical pore Beta zeolite adsorbent prepared in example 4 under operating conditions for low concentrations of CO and C3H8The adsorption catalysis effect of (3);
FIG. 6 shows the results of the heat treatment at 100 ℃ of the metal modified hierarchical pore Beta zeolite adsorbent prepared in example 5 at room temperature and high flow rate for high concentrations of CO and C3H8The adsorption catalytic effect of (3).
Detailed Description
The invention provides a metal modified hierarchical pore zeolite nano adsorbent and a preparation method thereof. The metal in the metal modified hierarchical pore zeolite nano-adsorbent is highly dispersed in a zeolite framework and mesoporous pore canals in the form of ions or/and oxides. The metal can be highly dispersed in the zeolite framework in the form of ions, and also can be highly dispersed in mesoporous channels in the form of oxides. The metal ion modified hierarchical pore nano zeolite is a nano adsorbent for efficiently adsorbing low-concentration and high-concentration CO and HC compounds. The hierarchical pore zeolite nano adsorbent has high specific surface area, thus being beneficial to high dispersion of active components, being capable of fully contacting with reaction gas and improving adsorption and catalytic capability. The hierarchical pore zeolite can be ZSM-5, Beta and TS. The molar ratio of Si to Al is 20-40. The hierarchical pore zeolite is highly dispersed, and the particle size is less than 500nm and is mostly distributed at 200-300 nm. The mesoporous aperture of the hierarchical pore zeolite is preferably 3-7nm, and the Si/Al value is preferably 25. The metal may be at least one of Mg, K, Ca, Na, Mn, etc., preferably Mg. The loading of the metal may be from 2 to 15 wt%. The loading is preferably 5wt% to 10 wt%.
The following further illustrates the preparation process of the metal modified hierarchical pore zeolite nano-adsorbent of the present invention.
Reacting a silicon source, an aluminum source and corresponding metal salt at a certain temperature for a certain time in the presence of a structure directing agent and a mesoporous template agent, then carrying out hydrothermal crystallization, and calcining at a certain temperature after centrifugal washing and drying treatment to remove organic matters in the solution.
More specifically, potassium chloride, a silicon source, an aluminum source, and a metal salt are added to the aqueous solution. And then adding a structure directing agent tetraethylammonium hydroxide (TEAOH) to perform hydrolytic polycondensation reaction on the silicon source, the aluminum source and the metal salt under an alkaline condition. The silicon source is selected from metasilicic acid, the aluminum source is selected from sodium aluminate, and the metal salt is alkali metal or alkaline earth metal nitrate. The concentrations of the added potassium chloride, the silicon source, the aluminum source and the TEAOH are respectively 0.2-0.4mol/L, 2.5mol/L, 0.06-0.12mol/L and 0.4-0.7mol/L, and the concentration of the nitrate or the sulfate is 0.1-0.2 mol/L. The metal salt may be 1 or 2 kinds of metal ions including Mg, K, Ca, Na, etc. Preferably, the metal ions comprise Mg; more preferably, the Mg loading is from 5wt% to 10 wt%. After reacting for a period of time, adding a mesoporous template, performing 135-DEG C hydrothermal crystallization treatment at 150 ℃, performing centrifugal washing to collect a product, and then roasting at 550-DEG C and 600 ℃ to remove organic matters, thereby obtaining a metal modified hierarchical pore Beta molecular sieve adsorbent powder material; wherein the mesoporous template is selected from cetyl trimethyl ammonium bromide CTAB, and the addition amount is 0.05-0.1 mol/L.
The invention also relates to the application of the modified hierarchical pore Beta molecular sieve adsorbent in removing low concentrationHigh concentration of CO and C3H8The use of (1). Introducing simulated reaction gas into a reactor, taking a metal modified hierarchical pore zeolite molecular sieve as an adsorbent, and taking O in the air2Is used as oxidant for simulating CO and C in semi-closed space exhaust gas and diesel vehicle exhaust gas under room temperature condition3H8The adsorption performance study is carried out on the exhaust environment of the simulated semi-closed space, the temperature is room temperature, air is taken as carrier gas, the total flow of the exhaust gas is 600-1800mL/min, the content of CO is lower than 20ppmv, and C is3H8The content is less than 10 ppmv. The exhaust environment of the simulated diesel vehicle tail gas has room temperature, wherein air is used as carrier gas, the total flow of the waste gas is 600-1800mL/min, the content of CO is 5000ppmv, and C3H8The content was 500 ppmv. Preferably, when the metal modified hierarchical pore Beta molecular sieve adsorbent is used, the content of the adsorbent is 0.1-0.2 g.
Removal of CO and C3H8The activity evaluation adopts the continuous monitoring and recording of gas chromatography to record CO and C under the conditions of certain atmosphere and room temperature3H8In the case of the amount of (A), carbon CO and carbon C are used for the removing ability of the adsorbent3H8Expressed by the actual adsorption efficiency and the duration of the adsorption of not less than 50%, CO and C under the action of the adsorbent3H8The higher the adsorption efficiency of the adsorbent is, the longer the duration of the adsorption amount of not less than 50% is, the better the adsorption performance of the adsorbent is.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Preparation examples
Example one
Adding 0.005mol tetraethylammonium hydroxide (TEAOH) and 0.005mol KCl into a certain amount of water, stirring uniformly at 40 ℃, adding 0.025mol metasilicic acid, and stirring until the mixture is clear; adding 2mL of 0.001mol of sodium aluminate and 0.001mol of magnesium nitrate, then adding the mixed aqueous solution into 2mL of a 0.03mol/L surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) aqueous solution, violently stirring for 3 hours at 80 ℃, then putting the formed solution into a polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal crystallization reaction for 24 hours at 150 ℃, centrifuging, washing a sample, drying overnight at 100 ℃, and finally roasting for 8 hours at 550 ℃ to remove inorganic salts and organic matters, thus preparing the metal modified hierarchical pore Beta molecular sieve material;
FIGS. 1 and 2 are low and high power TEM photographs of the metal modified hierarchical pore Beta molecular sieve prepared in this example. As can be seen from FIG. 1, the size of the modified hierarchical pore zeolite is 300-400nm, and is highly dispersed, and no oxide agglomerates are observed, which indicates that the metal is highly dispersed in the hierarchical pore zeolite in the form of ions or oxides, which is beneficial to improving the catalytic activity of the adsorbent. In addition, obvious zeolite lattice stripes and mesoporous channels can be observed in a high-power TEM (TEM) electron microscope. The nitrogen adsorption/desorption experiment is carried out by a Micromeritics Tristar 3000 analyzer, and the test result shows that the specific surface area of the prepared metal modified hierarchical pore Beta molecular sieve is up to 578m2/g。
Effects of the embodiment
To verify the metal modified hierarchical pore Beta molecular sieves of the present invention are paired with low and high concentrations of CO and C3H8The adsorption catalysis effect of the method particularly simulates the semi-closed underground space and the tail gas emission condition of the diesel vehicle, and the following experiments are carried out under the laboratory condition and the working condition.
Example two
A fixed bed reactor was charged with 0.1g of the adsorbent prepared in the example, and the following mixed gas was introduced at room temperature: the CO content was 5000ppmv, C3H8The content is 500ppmv, the carrier gas is air, and the total flow is 0.6L/min;
test adsorbents for CO and C at room temperature3H8The adsorption catalysis effect is shown inFIG. 3;
as can be seen from fig. 3: at room temperature and under the flow rate of 600mL/min, the adsorbent can obviously adsorb HC, and 80% of adsorption energy lasts for 10 min; the CO adsorption time is short, and 50% adsorption lasts for 6 min. Because the diesel vehicle discharges a large amount of harmful gas during cold start, but the time required by the cold start is short, the adsorption effect of the diesel vehicle can meet the requirement of purifying the harmful gas during the cold start of the diesel vehicle;
the previous experimental results show that the zeolite without metal modification has almost no adsorption activity on CO and HC, and the zeolite after metal modification shows excellent adsorption performance, which indicates that a synergistic catalytic action mechanism exists between the metal species and the intrinsic acidity of the zeolite.
EXAMPLE III
A fixed bed reactor was charged with 0.1g of the adsorbent prepared in the example, and the following mixed gas was introduced at room temperature: the CO content was 5000ppmv, C3H8The content is 500ppmv, the carrier gas is air, and the total flow is 1.8L/min;
test adsorbents for CO and C at room temperature3H8The adsorption catalysis effect of (a), the results are shown in FIG. 4;
as can be seen from fig. 4: at room temperature and a flow rate of 1800mL/min, the adsorbent has obvious adsorption on HC, 80% of adsorption energy lasts for 10min, and 50% of adsorption time on CO is only 2 min. Because the cold start time of the diesel vehicle is shorter, the adsorption effect of the adsorption device can also meet the purification of harmful gas when the diesel vehicle is cold started to a certain extent.
Example four
And (3) simulation working condition testing: the temperature is 29 ℃; relative humidity: 80% -85%; reaction channel wind speed: 0.28m/s, volume space velocity: 10000h-1. The adsorbent was 10 x 10cm honeycomb ceramic coated at 10 wt%. The order of placing the adsorbents is as follows: day 1: THC (10X 10cm Si in C)7-1) + alkali-treated activated carbon (10 x 10cm) + NOx adsorbent (10 x 10cm silica C5-3) + alkali-treated activated carbon (10 x 10 cm);
day 1: alkali-treated activated carbon (10X 10cm) + THC (10X 10cm Si in C7-1) + NOx adsorbent (10 x 10cm silicon C5-3) + alkali-treated activated carbon (10 x 10cm), test results as in figure 5;
as can be seen from FIG. 5, 10000h at 29 ℃ are observed-1The 50% adsorption efficiency time of the adsorbent to HC can last for 8 h.
EXAMPLE five
The adsorbent tested in example three was dried in an oven at 100 ℃ for 30min and then loaded into a fixed bed reactor, and mixed gas was introduced at room temperature: the CO content was 5000ppmv, C3H8The content was 500ppmv, the carrier gas was air, and the total flow rate was 1.8L/min. Test adsorbents for CO and C at room temperature3H8The test results after the adsorbent is activated are shown in fig. 6;
from fig. 6, it can be seen that the adsorbent still can maintain the initial adsorption performance of the adsorbent after the activation treatment, which indicates that the metal modified hierarchical pore zeolite has excellent recycling performance.
Claims (5)
1. The application of a metal modified hierarchical pore zeolite nano-adsorbent for adsorbing CO and HC compounds with low concentration and high concentration is characterized in that the metal in the metal modified hierarchical pore zeolite nano-adsorbent is highly dispersed in the hierarchical pore zeolite framework and mesoporous pore canals in the form of ions and/or oxides, and the metal is one of Mg, Ca and Na, and K; the loading amount of the metal is 2-15 wt%; the metal-modified hierarchical pore zeolite nano-adsorbent has intrinsic acidity;
the preparation method of the metal modified hierarchical pore zeolite nano adsorbent comprises the following steps:
(1) adding potassium chloride, a silicon source, an aluminum source and metal salt into water to prepare a mixed solution, and then adding a structure directing agent to enable the silicon source, the aluminum source and the metal salt to perform hydrolytic polycondensation reaction under an alkaline condition; the silicon source is selected from metasilicic acid, and the concentration is 1-2.5 mol/L; the aluminum source is selected from sodium aluminate, and the concentration is 0.06-0.12 mol/L; the metal salt is alkali metal nitrate or alkaline earth metal nitrate, and the concentration is 0.1-0.2 mol/L;
(2) adding a mesoporous template agent, performing hydrothermal crystallization treatment, centrifuging, washing with water, collecting a product, and roasting at 550-600 ℃ to obtain the metal modified hierarchical pore zeolite nano adsorbent.
2. The use of claim 1, wherein the mesoporous pore diameter of the hierarchical pore zeolite is 2-30nm, and the molar ratio of Si to Al is 20-40.
3. The use of claim 2, wherein the mesoporous pore size of the hierarchical pore zeolite is 3 to 7nm, and the molar ratio of Si to Al is 25.
4. Use according to claim 1, wherein the metal loading is from 5wt% to 10 wt%.
5. The use according to claim 1, wherein the potassium chloride is present in a concentration of 0.2 to 0.4 mol/L.
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