CN110813366A - Cerium oxide/HZSM-5 molecular sieve composite catalytic material, preparation method thereof and application thereof in decomposing carbon tetrafluoride - Google Patents
Cerium oxide/HZSM-5 molecular sieve composite catalytic material, preparation method thereof and application thereof in decomposing carbon tetrafluoride Download PDFInfo
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- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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Abstract
The invention discloses a cerium oxide/HZSM-5 molecular sieve composite catalytic material, a preparation method thereof and application thereof in catalytic decomposition of carbon tetrafluoride, wherein the composite catalytic material is formed by loading cerium oxide on an HZSM-5 molecular sieve, and the catalyst can realize high-efficiency catalytic conversion of carbon tetrafluoride into carbon dioxide under mild conditions, thereby overcoming the defects that the traditional carbon tetrafluoride decomposition catalyst is easy to inactivate at relatively high temperature and has low-temperature activity.
Description
Technical Field
The invention relates to a composite catalytic material, in particular to a cerium oxide/HZSM-5 molecular sieve composite catalytic material and a preparation method thereof, and also relates to an application of the cerium oxide/HZSM-5 molecular sieve composite catalytic material as a carbon tetrafluoride decomposition catalyst, belonging to the technical field of catalysis.
Background
Carbon tetrafluoride is a low-carbon hydrocarbon in which hydrogen atoms are completely replaced by fluorine atoms, has the advantages of stability, safety, no spontaneous combustion, low toxicity, no chemical reaction at normal temperature and the like, and the stability of carbon tetrafluoride is mainly reflected in two aspects, namely high symmetry of the structure, extremely strong bond energy of C-F bonds, strong infrared light absorption capacity and thermal stability, and very long retention life in the atmosphere due to the fact that carbon tetrafluoride is difficult to decompose in the environment. Although the concentration of carbon tetrafluoride in the atmosphere is much lower than that of CO2However, its effect on global warming is quite profound: one is the extremely long shelf life in the atmosphere due to stability (50000 years); secondly, the greenhouse effect potential value (global warming potential (GWP) index, defined as the ratio of infrared adsorption to carbon dioxide equivalent adsorption of gas for more than 100 years) is equivalent to CO26500 times of the original product.
The source of atmospheric carbon tetrafluoride derives mainly from three aspects: the aluminum industry, the semiconductor industry and the rare earth metal smelting are the most main emission sources, so that the limitation of the emission of carbon tetrafluoride in the aluminum electrolysis flue gas is very important. At present, the greenhouse effect is an environmental problem which is seriously concerned by people and is artificially dischargedThe released gas causes the global climate to become warm day by day, the temperature rise causes the ice river to melt, the ice layers of the two poles to shrink, the rainfall form changes, abnormal phenomena such as hurricane, drought, tsunami and the like and natural disasters to frequently occur, and more people pay attention to the global warming problem. Representative of 149 countries and regions in the 1997 12 th month at the third meeting of the treaty's prescription for climate Change framework convention in United nations, held in Japan, passed the intent to limit carbon dioxide (CO)2) Methane (CH)4) Dinitrogen monoxide (N)2O), Hydrofluorocarbons (HFCs), Perfluorocarbons (PFCs), sulfur hexafluoride (SF)6) And the Kyoto protocol of six main greenhouse gas emissions. China signed the protocol at 29.5.1998 and formally validated at 16.2.2005.
At present, the control of the discharge amount of perfluorocarbon can be divided into three categories, namely substitution, end treatment and recycling, wherein the recycling and substitution technology is mainly used for the perfluorocarbon discharge control technology in the semiconductor industry and is not suitable for the treatment of carbon tetrafluoride in aluminum electrolysis flue gas. The thermal catalytic decomposition technology is generally used for treating carbon tetrafluoride in aluminum electrolysis flue gas, so that the development of a catalyst with high activity and good stability is necessary. The technology of thermal catalytic decomposition of carbon tetrafluoride began in the 90 s of the 20 th century, and the catalysts mainly involved were metal phosphates, metal sulfates, metal oxides (mainly alumina), molecular sieves, rare earth metal and metal oxides, alkali metal and alkali metal oxide composites, and the like. The relatively low catalytic temperature of the thermal catalytic decomposition method is concerned by many scholars, but one of the main reasons limiting the development of the thermal catalytic decomposition method is that HF is generated in the catalytic process, and then the catalyst is poisoned, so that the activity of the catalyst is reduced and the catalytic capability is lost.
Molecular sieves have attracted attention due to their complex structures and characteristics. At present, the molecular sieve is mainly used as a catalytic hydrogenation catalyst, an adsorbent and the like. The composite material of the molecular sieve is mostly used as a catalytic material for catalytic cracking of organic matters, for example, Chinese patent (CN106140266B) discloses La2O3ZSM-5 complexThe modified catalyst of the invention has obviously improved diene yield or propylene selectivity. In addition, compared with the traditional impregnation method, the service life and the diene selectivity are also obviously improved. Among the selection of various modification conditions, the method using water or the mixture of water and acetic acid as the modifying element solvent has the best effect, and the diene has higher yield and longer service life.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a cerium oxide/HZSM-5 molecular sieve composite catalytic material formed by loading cerium oxide on an HZSM-5 molecular sieve, wherein the catalytic material can realize the high-efficiency catalytic conversion of carbon tetrafluoride in flue gas into carbon dioxide under the relatively low temperature condition, and solves the technical problems of low activity and poor stability of the traditional carbon tetrafluoride decomposition catalyst under the relatively low temperature condition.
The second purpose of the invention is to provide a method for preparing the cerium oxide/HZSM-5 molecular sieve composite catalytic material simply and at low cost.
The third purpose of the invention is to provide the application of the cerium oxide/HZSM-5 molecular sieve composite catalytic material in catalytic decomposition of carbon tetrafluoride in flue gas, the cerium oxide/HZSM-5 molecular sieve composite material can realize catalytic conversion of carbon tetrafluoride into carbon dioxide by using high-temperature flue gas waste heat and a small amount of water vapor, has the characteristics of high catalytic efficiency and good stability, and is particularly suitable for decomposition and conversion of carbon tetrafluoride in aluminum electrolysis flue gas, semiconductor industry flue gas and rare earth metal smelting flue gas.
In order to achieve the technical purpose, the invention provides a cerium oxide/HZSM-5 molecular sieve composite catalytic material which is formed by loading cerium oxide on an HZSM-5 molecular sieve.
The HZSM-5 molecular sieve in the cerium oxide/HZSM-5 molecular sieve composite catalytic material has rich pore structures and larger specific surface area, and can well disperse and load cerium oxide, so that the cerium oxide shows higher catalytic activity.
In a preferable scheme, the cerium oxide/HZSM-5 molecular sieve composite material contains 5-12.5% of cerium oxide by mass. The content of the cerium oxide is preferably 10% by mass.
The invention also provides a preparation method of the cerium oxide/HZSM-5 molecular sieve composite catalytic material, which comprises the steps of demoulding the HZSM-5 molecular sieve, adding the demoulded molecular sieve into a cerium salt solution for ultrasonic treatment, and drying and calcining the obtained product.
In the preferable scheme, the HZSM-5 molecular sieve is calcined at 500-600 ℃ for 3-8 hours to remove the residual template agent. The HZSM-5 molecular sieve can be a commercial raw material, and is mainly used for removing a template agent remained in the HZSM-5 molecular sieve through high-temperature calcination, so that the loading of cerium oxide is facilitated.
In a preferable scheme, the concentration of the cerium salt solution is 0.015-0.15 mol/L. The cerium salt is mainly water-soluble cerium salt such as cerium nitrate.
In a preferred embodiment, the calcination treatment conditions are as follows: calcining at 650-750 ℃ for 2-4 hours.
The invention also provides application of the cerium oxide/HZSM-5 molecular sieve composite catalytic material in catalyzing carbon tetrafluoride to be decomposed and converted into carbon dioxide.
In a preferable scheme, the cerium oxide/HZSM-5 molecular sieve composite catalytic material is applied to catalyzing carbon tetrafluoride in carbon tetrafluoride-containing flue gas to decompose and convert carbon tetrafluoride into carbon dioxide.
In a preferred scheme, the carbon tetrafluoride-containing flue gas comprises at least one of aluminum electrolysis flue gas, semiconductor industrial flue gas and rare earth metal smelting flue gas.
Preferably, the CF in the carbon tetrafluoride-containing flue gas4The concentration is 5000-10000 ppm, H2The content of O in percentage by volume is 10 to 50 percent.
In a preferred scheme, the temperature of the carbon tetrafluoride-containing flue gas is 550-750 ℃. The smooth proceeding of the carbon tetrafluoride decomposition reaction can be ensured in the temperature range.
The cerium oxide/HZSM-5 molecular sieve composite catalytic material is arranged in a fixed bed reactor in a packed bed mode, the packing amount of the cerium oxide/HZSM-5 molecular sieve composite catalytic material is 0.5-1 g, and the corresponding reaction space velocity is50000～100000h-1. The filling amount of the cerium oxide/HZSM-5 molecular sieve composite catalytic material is in inverse proportion to the reaction space velocity, and the reaction space velocity can be controlled by properly adjusting the filling amount of the cerium oxide/HZSM-5 molecular sieve composite catalytic material.
The preparation method of the cerium oxide/HZSM-5 molecular sieve composite catalytic material comprises the following steps:
in the preparation process of the cerium oxide/HZSM-5 molecular sieve composite catalytic material, cerium salt is adsorbed by the HZSM-5 molecular sieve, the porous structure of the HZSM-5 molecular sieve is used for adsorbing and loading the cerium salt, and then the dispersion and the stable loading of the cerium oxide are realized by drying and calcining.
The reaction principle of catalyzing decomposition of carbon tetrafluoride by using the cerium oxide/HZSM-5 molecular sieve composite catalytic material is that cerium oxide firstly reacts with carbon tetrafluoride to generate cerium tetrafluoride and carbon dioxide, and the cerium tetrafluoride then continuously reacts with water to generate cerium oxide and hydrogen fluoride, so that a complete catalytic reaction is formed, and the specific reaction is as follows:
CeO2+CF4＝CeF4+CO2；
CeF4+2H2O＝CeO2+2HF。
the preparation method of the cerium oxide/HZSM-5 molecular sieve composite catalytic material comprises the following specific preparation steps:
1) analytically pure cerium nitrate (Ce (NO)3)3·6H2O) into deionized water to prepare Ce3+A colorless solution with the concentration of 0.015-0.15 mol/L, wherein the obtained solution is marked as A;
2) heating an HZSM-5 molecular sieve (Si/Al is 18) to 550 ℃ at the heating rate of 2 ℃/min, and preserving heat for 5h to remove a template agent remained in the commercial HZSM-5 molecular sieve to obtain a solid A;
3) adding the solid A into the solution A, stirring for 3 hours at the rotating speed of 500rpm/min, and carrying out ultrasonic treatment for 3 hours to obtain a solution B;
3) standing the solution B for 12h, and drying in an oven at 80 ℃ to obtain a sample C;
4) placing the sample C in a tube furnace at 650-750 ℃, roasting for 3-5 h under nitrogen atmosphere, wherein the heating rate is 2-10 ℃/min;
5) and after roasting, naturally cooling to room temperature in a nitrogen atmosphere, and taking out from a roasting tube to obtain the white cerium oxide/HZSM-5 molecular sieve composite material.
The cerium oxide/HZSM-5 molecular sieve composite material is particularly suitable for being used as a catalyst to catalyze and decompose carbon tetrafluoride in flue gas, and a small amount of water vapor in the flue gas is utilized to catalyze and decompose the carbon tetrafluoride into carbon dioxide under the action of the cerium oxide/HZSM-5 molecular sieve composite material. The flue gas generally refers to flue gas containing carbon tetrafluoride, such as aluminum electrolysis flue gas, semiconductor flue gas, rare earth metal smelting flue gas and the like.
The invention relates to a method for removing carbon tetrafluoride by catalytic decomposition of a cerium oxide/HZSM-5 molecular sieve composite material, which comprises the following steps:
introducing the flue gas into a device (such as a fixed bed reactor) provided with a cerium oxide/HZSM-5 molecular sieve composite material catalyst to perform catalytic decomposition reaction; the reaction space velocity is adjusted by controlling the adding amount of the cerium oxide/HZSM-5 molecular sieve composite material catalyst in the fixed bed reactor, the mass of the added catalyst is 0.5-1 g, and the space velocity can reach 50000-100000 h under the catalytic atmosphere condition-1。
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the cerium oxide/HZSM-5 molecular sieve composite catalytic material provided by the invention is used for catalytically decomposing carbon tetrafluoride to generate carbon dioxide, and develops a new idea for catalytic treatment of carbon tetrafluoride flue gas.
2. The cerium oxide/HZSM-5 molecular sieve composite catalytic material provided by the invention is simple in preparation process, easy in raw material obtaining, mild in condition and beneficial to industrial production.
3. The cerium oxide/HZSM-5 molecular sieve composite catalytic material provided by the invention has relatively mild catalytic conditions and high catalytic activity, and the catalytic efficiency is maintained at 40% when the temperature is 550 ℃.
4. The cerium oxide/HZSM-5 molecular sieve composite catalytic material provided by the invention has stable catalytic performance, and can still maintain 40% of decomposition efficiency after running for 24 hours under the catalytic condition of 550 ℃.
5. The cerium oxide/HZSM-5 molecular sieve provided by the invention uses the HZSM-5 molecular sieve raw material as a carrier, so that the cerium oxide has good dispersibility and the catalytic activity of the cerium oxide/HZSM-5 molecular sieve is improved.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the cerium oxide/HZSM-5 molecular sieve composite prepared in example 1.
FIG. 2 is a diagram showing the effect of cerium oxide/HZSM-5 molecular sieve on the catalytic decomposition activity of carbon tetrafluoride.
FIG. 3 is a diagram showing the catalytic decomposition effect of cerium oxide/HZSM-5 molecular sieve on carbon tetrafluoride under the condition of different loading amounts of cerium oxide.
FIG. 4 is a diagram showing the effect of the cerium oxide/HZSM-5 molecular sieve on the catalytic stability of the catalyst under a long-term condition.
FIG. 5 is a diagram showing the catalytic decomposition effect of cerium oxide/HZSM-5 molecular sieve on carbon tetrafluoride.
FIG. 6 is a graph showing the catalytic decomposition stability effect of cerium oxide/HZSM-5 molecular sieve on carbon tetrafluoride.
Detailed Description
The following examples are intended to illustrate the present invention in further detail with reference to the accompanying drawings, and are not intended to limit the scope of the invention as claimed.
Example 1
Analytically pure cerium nitrate (Ce (NO)3)3·6H2O) into deionized water to prepare Ce3+A colorless solution with the concentration of 0.015-0.15 mol/L, wherein the obtained solution is marked as A; heating an HZSM-5 molecular sieve (Si/Al is 18) to 550 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for 5h to remove a template agent remained in the commercial HZSM-5 molecular sieve to obtain a solid A; adding 3g of solid A into 30mL of solution A, stirring at the rotating speed of 500rpm/min for 3 hours, and carrying out ultrasonic treatment for 3 hours to obtain solution B; standing the solution B for 12h, and drying in an oven at 80 ℃ to obtain a sample C; placing the sample C in a 700 ℃ tubular furnace, roasting for 4h under the nitrogen atmosphere, wherein the heating rate is 5 ℃/min; naturally cooling to room temperature in nitrogen atmosphere after roasting, and taking out from the roasting tube to obtain white oxideThe cerium/HZSM-5 molecular sieve composite material is prepared by adjusting the concentration of a cerium nitrate solution to obtain the cerium oxide/HZSM-5 molecular sieve composite catalytic material with the cerium oxide mass percent contents of 5%, 7.5%, 10% and 12.5% respectively. The sample obtained is analyzed by a Japanese science D/Max 2500 VB + XX type X-ray diffractometer, the crystal phase of the obtained product is found to be the cerium oxide/HZSM-5 molecular sieve composite catalytic material, and the XRD diffraction pattern can well correspond to the main peak position of a standard card (PDF No.34-0394), as shown in figure 1.
Example 2
Heating a commercial HZSM-5 molecular sieve (Si/Al is 18) to 550 ℃ at a heating rate of 2 ℃/min, and keeping the temperature for 5h to remove a template agent remained in the commercial HZSM-5 molecular sieve to obtain the solid HZSM-5 molecular sieve. The experiment was carried out in a fixed bed reactor with a HZSM-5 molecular sieve packing of 1g and nitrogen as CF4The flow rate of the carrier gas (2.5 mL/min (10000ppm) was controlled, the flow rate of the other path of nitrogen gas was controlled to 30mL/min (60 vol%) as an equilibrium gas, the flow rate of the vaporized water vapor was 17.5mL/min (35 vol%), the total flow rate of the gas was kept at 50mL/min, and the experimental temperature was 550 ℃. After the flue gas is treated, the catalyst treatment efficiency is recorded after the concentration of carbon tetrafluoride reaches a stable state. The results are shown in FIG. 2, from which it can be seen that a single HZSM-5 molecular sieve is used for CF4The catalytic conversion of (a) is only around 5%.
Example 3
Analytically pure cobalt nitrate (Ce (NO)3)3·6H2And O) placing the cerium oxide powder into a crucible, placing the crucible into a tubular furnace, and roasting at 650-750 ℃ to obtain pure cerium oxide solid. Experiment pure cerium oxide was loaded in a fixed bed reactor in an amount of 1g, using nitrogen as CF4The flow rate of the carrier gas (2.5 mL/min (10000ppm) was controlled, the flow rate of the other path of nitrogen gas was controlled to 30mL/min (60 vol%) as an equilibrium gas, the flow rate of the vaporized water vapor was 17.5mL/min (35 vol%), the total flow rate of the gas was kept at 50mL/min, and the experimental temperature was 550 ℃. After the flue gas is treated, the catalyst treatment efficiency is recorded after the concentration of carbon tetrafluoride reaches a stable state. The results are shown in FIG. 3, from which it can be seen that a single cerium oxide is used for CF4The catalytic conversion of (2) is only around 7%.
Example 4
Effect of cerium oxide loading on catalyst activity test:
the experiment was carried out in a fixed bed reactor with a catalyst (prepared in example 1) packing of 1g and nitrogen as CF4The flow rate of the carrier gas (2.5 mL/min (10000ppm) was controlled, the flow rate of the other path of nitrogen gas was controlled to 30mL/min (60 vol%) as an equilibrium gas, the flow rate of the vaporized water vapor was 17.5mL/min (35 vol%), the total flow rate of the gas was kept at 50mL/min, and the experimental temperature was 550 ℃. After the flue gas is treated, the catalyst treatment efficiency is recorded after the concentration of carbon tetrafluoride reaches a stable state. The results are shown in FIG. 4.
Example 5
Temperature effect on catalyst activity test:
the experiment was carried out in a fixed bed reactor with a catalyst of 10 wt% CeO2the/HZSM-5 (prepared in example 1) had a packing volume of 1g and nitrogen was used as CF4The flow rate of the carrier gas (2.5 mL/min (10000ppm) was controlled, the flow rate of the other nitrogen gas was controlled to 30mL/min (60 vol%) as an equilibrium gas, the flow rate of the vapor after vaporization was 17.5mL/min (35 vol%), and the total flow rate of the gas was kept at 50 mL/min. Setting reaction temperature conditions, reaction 1: 550 ℃; reaction 2: 600 ℃; reaction 3: 650 ℃; reaction 4: 700 ℃. After the flue gas is treated, the catalyst treatment efficiency is recorded after the concentration of carbon tetrafluoride reaches a stable state. The results are shown in FIG. 5.
Example 6
And (3) testing the catalytic stability:
the experiment was carried out in a fixed bed reactor with a catalyst of 10 wt% CeO2the/HZSM-5 (prepared in example 1) had a packing volume of 1g and nitrogen was used as CF4The flow rate of the carrier gas (2.5 mL/min (10000ppm) was controlled, the flow rate of the other nitrogen gas was controlled to 30mL/min (60 vol%) as an equilibrium gas, the flow rate of the vapor after vaporization was 17.5mL/min (35 vol%), and the total flow rate of the gas was kept at 50 mL/min. The reaction temperature is 550 ℃, the reaction time is 24h, and the test data are shown in figure 6.
Claims (10)
1. A cerium oxide/HZSM-5 molecular sieve composite catalytic material is characterized in that: is composed of cerium oxide loaded on HZSM-5 molecular sieve.
2. The cerium oxide/HZSM-5 molecular sieve composite catalytic material of claim 1, wherein: the cerium oxide/HZSM-5 molecular sieve composite catalytic material contains 5-12.5% of cerium oxide by mass percentage.
3. A method for preparing the cerium oxide/HZSM-5 molecular sieve composite catalytic material of claim 1 or 2, characterized in that: and (3) demoulding the HZSM-5 molecular sieve, adding the demoulded molecular sieve into a cerium salt solution for ultrasonic treatment, and drying and calcining the obtained product to obtain the catalyst.
4. The method for preparing the cerium oxide/HZSM-5 molecular sieve composite catalytic material of claim 3, wherein the method comprises the following steps: calcining the HZSM-5 molecular sieve at 500-600 ℃ for 3-8 hours to remove the residual template agent.
5. The method for preparing the cerium oxide/HZSM-5 molecular sieve composite catalytic material of claim 3, wherein the method comprises the following steps: the concentration of the cerium salt solution is 0.015-0.15 mol/L.
6. The method for preparing the cerium oxide/HZSM-5 molecular sieve composite catalytic material of claim 3, wherein the method comprises the following steps: the conditions of the calcination treatment are as follows: calcining at 650-750 ℃ for 3-5 hours.
7. The use of the ceria/HZSM-5 molecular sieve composite catalytic material of claim 1 or 2, wherein: the catalyst is applied to catalyzing the decomposition and conversion of carbon tetrafluoride into carbon dioxide.
8. The use of the ceria/HZSM-5 molecular sieve composite catalytic material of claim 7, wherein: the method is applied to catalyzing carbon tetrafluoride in the carbon tetrafluoride-containing flue gas to decompose and convert the carbon tetrafluoride into carbon dioxide.
9. The use of the ceria/HZSM-5 molecular sieve composite catalytic material of claim 7, wherein: the carbon tetrafluoride-containing smoke comprises at least one of aluminum electrolysis smoke, semiconductor industrial smoke and rare earth metal smelting smoke.
10. The use of the ceria/HZSM-5 molecular sieve composite catalytic material of claim 8 or 9, wherein: CF in the carbon tetrafluoride-containing flue gas4The concentration is 5000-10000 ppm, H2The content of O in percentage by volume is 10 to 50 percent; the temperature of the carbon tetrafluoride-containing flue gas is 550-750 ℃.
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| CN115382504A (en) * | 2022-09-13 | 2022-11-25 | 河南宣和钧釉环保材料有限公司 | Novel Li-LSX type oxygen generation molecular sieve capable of releasing negative oxygen ions and preparation method thereof |
| CN116328824A (en) * | 2023-03-28 | 2023-06-27 | 上海翊嘉生物科技有限公司 | Cerium oxide cluster nano-enzyme anchored by defective molecular sieve, and preparation method and application thereof |
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