CN106984301B - Manganese cerium titanium catalyst with ordered mesoporous structure, preparation method and application thereof - Google Patents
Manganese cerium titanium catalyst with ordered mesoporous structure, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of catalyst preparation, and particularly relates to a manganese-cerium-titanium catalyst with an ordered mesoporous structure, a preparation method and application thereof. Adopting a solvent evaporation induced self-assembly synthesis method, taking a triblock copolymer as a template agent, and introducing Mn/Ce active substances into TiO in an assembly way 2The manganese cerium titanium catalyst with an ordered mesoporous structure is prepared in the pore wall framework of the carrier. The catalyst has the advantages of high dispersion of active components, good pore permeability, stability, order and large specific surface area. Can be used in the fields of low-temperature denitration, heterogeneous catalytic degradation of organic matters and the like.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a manganese-cerium-titanium catalyst with an ordered mesoporous structure, a preparation method and application thereof.
Background
In recent years, ordered mesoporous materials have been selected as catalyst carriers or active components due to their advantages of ordered pore arrangement, uniform size and large specific surface area, and are widely used in catalytic reaction processes. However, to prepare TiO with long-range order and good thermal stability 2Ordered mesoporous materials are extremely difficult. In the prior art, a medium with good thermal stability is obtained by adopting an organic template agent assembly method A pore material. However, the method has long assembly time and drying time of the template agent, the solvent and the inorganic precursor, and adopts a multi-step heating and sintering procedure in the process of removing the template agent, so that the synthesis period and the working procedure are complicated, and the method is not beneficial to large-scale production.
Except optimizing and improving TiO on synthesis control process 2In addition to the thermal stability of the ordered mesoporous material, other metal elements are doped to stabilize TiO 2The ordered mesoporous channel of the ordered mesoporous material is another effective method. In addition, other elements can be introduced to improve or endow TiO 2Some new properties (such as catalytic capability, photoelectric effect, conductive property and the like) of the mesoporous material, but the introduction of other elements also causes the problems of poor distribution uniformity of the introduced elements, poor pore size matching, poor multi-element co-doping synergetic catalysis and the like.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems existing at present, the manganese-cerium-titanium catalyst with the ordered mesoporous structure is provided, has the advantages of long-range order, good thermal stability, few preparation procedures and the like, and solves the problems caused by the introduction of other elements.
The technical scheme of the invention is as follows: the invention provides a manganese cerium titanium catalyst with an ordered mesoporous structure, which adopts a solvent evaporation induced self-assembly synthesis method, takes a triblock copolymer as a template agent, and introduces Mn/Ce active substances into TiO through assembly 2The manganese cerium titanium catalyst with an ordered mesoporous structure is prepared in the pore wall framework of the carrier. The preparation method of the manganese-cerium-titanium catalyst with the ordered mesoporous structure is provided, and comprises the following specific operations:
(1) Dissolving a triblock copolymer template agent, cerium salt and manganese salt in an alcohol solvent to obtain a solution A;
(2) Slowly adding concentrated hydrochloric acid into the titanium precursor, and reacting for 15-20 min to obtain a solution B;
(3) Slowly adding the solution A into the solution B, and mixing and reacting at the temperature of 20-60 ℃ for 2-6 hours to obtain a solution C;
(4) Spreading the solution C in a culture dish, and drying for 24-48 h under the conditions that the drying temperature is 20-40 ℃ and the drying humidity is 60-80% RH to obtain a solid D;
(5) And sintering the solid D in a muffle furnace for 2-4 h at the sintering temperature of 300-700 ℃ and the heating rate of 0.5-10 ℃/min to obtain the manganese-cerium-titanium catalyst with the ordered mesoporous structure.
Wherein, the temperature and the humidity in the step (4) are key process parameters, both the temperature and the humidity can influence the self-assembly effect of the ordered mesopores, and the conditions of the drying temperature of 20-40 ℃ and the drying humidity of 60-80% RH are favorable for the formation of the pore canal order degree; in the step (5), the heating rate is 0.5-10 ℃/min, which is beneficial to the formation of ordered pore channels.
preferably, the triblock copolymer template in the step (1) is P123, F127 or L64, the alcohol solvent in the step (1) is one or two of n-butyl alcohol, isobutyl alcohol, n-propyl alcohol, isopropyl alcohol and ethanol, the cerium salt in the step (1) is cerium chloride, cerium nitrate or cerium acetate, and the manganese salt in the step (1) is manganese nitrate, manganese chloride, manganese sulfate or manganese acetate.
Preferably, the titanium precursor in step (2) is one or two of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate and titanium tetrachloride.
Preferably, the molar ratio of the titanium precursor, the concentrated hydrochloric acid, the alcohol solvent, the triblock copolymer template, the cerium salt and the manganese salt in the steps (1) and (2) is 1: 6: 9-25: 0.001-0.3: 0.01-0.5: 0.01 to 0.5.
The manganese cerium titanium catalyst with the ordered mesoporous structure prepared by the invention is used for low-temperature denitration and heterogeneous catalytic degradation of organic matters.
The invention has the technical effects that:
1) The mesoporous material with different pore channel structures (such as a long-range ordered hexagonal structure or a cubic structure) can be prepared by regulating and controlling the pore channel structure of the catalyst by selecting the type and the content of the template agent. Incorporation of Mn/Ce active mass assembly into TiO 2In the pore wall skeleton of the support, TiO 2The high specific surface area and porosity of the carrier can provide more active sites, can realize high dispersion and fixation of active components of the catalyst, improve the catalytic performance, and have better catalytic activity in a low-temperature area. From the examples 1-5, the problems of poor element distribution uniformity, poor pore size matching, poor multi-element co-doping synergistic catalysis and the like caused by the introduction of other elements are avoided.
2) The catalyst prepared by the invention has the advantages of high dispersion of active components, good pore permeability, ordered pore channels, high thermal stability and large specific surface area. Can inhibit the deposition of sulfate on the surface of the catalyst, has better anti-poisoning capability, and can be used in the field of low-temperature denitration. In addition, the method has good applicability in the field of heterogeneous catalytic degradation of organic matters, and can degrade different types of organic matters. Meanwhile, the preparation method is also suitable for preparing other soluble active salt catalysts and has universality.
Drawings
Fig. 1 is a TEM image of the ordered mesoporous structure manganese cerium titanium catalyst prepared in example 1, and fig. 1 shows that the catalyst has a long-range ordered hexagonal structure.
FIG. 2 is a BET diagram of the Mn-Ce-Ti catalyst with ordered mesoporous structure prepared in example 1, wherein FIG. 2 shows that the specific surface area of the catalyst is 194.59m 2·g-1The pore diameter is mainly distributed in the range of 8-14nm, and experimental data show that the mesoporous material with large specific surface area is prepared by the method.
Fig. 3 is a TEM image of the manganese cerium titanium catalyst having an ordered mesoporous structure prepared in example 2, and fig. 3 shows that the catalyst has a highly ordered cubic structure.
Fig. 4 is a BET diagram of the manganese cerium titanium catalyst of the ordered mesoporous structure prepared in example 2. FIG. 4 shows that the specific surface area of the catalyst is 245.6m 2·g-1The pore distribution is mainly distributed in the range of 6-12nm, and experimental data show that the mesoporous material with large specific surface area is prepared by the method.
Detailed Description
Example 1
Dissolving 0.013mol of P123, 0.4mol of cerium nitrate and 0.12mol of manganese nitrate into 9mol of n-butanol (BuOH) to obtain solution A, dissolving the solution A by using an ultrasonic instrument, slowly adding 6mol of concentrated hydrochloric acid dropwise into 1mol of tetraethyl titanate Ti (OET) 4In the reaction, the solution is obtained after 15min of reaction And (B) liquid. Slowly dripping the solution A into the solution B, and mixing and reacting for 3 hours at 25 ℃ to obtain a stable solution C. 40g of solution C were spread on a petri dish and dried at 25 ℃ and 80% RH for 48h to give solid D. And (3) placing the solid D in a muffle furnace, and sintering for 3h at the temperature of 400 ℃ at the temperature rise speed of 0.5 ℃/min to prepare the manganese-cerium-titanium catalyst with the ordered mesoporous structure. The prepared catalyst samples were subjected to TEM topography analysis (see fig. 1). The prepared catalyst samples were subjected to specific surface area BET analysis (see fig. 2).
Evaluation of catalyst Performance: grinding and screening the prepared catalyst to 40-60 meshes, and putting the catalyst into a catalyst evaluation bed, wherein the inner diameter of a reactor is 0.8 cm. The simulated smoke is 500ppmNO and 500ppmNH 3、5vol％O2And 10 vol% H 2O, balance gas N 2The space velocity is 30000h -1And the reaction temperature is 150-350 ℃, and the catalytic activity test is carried out under the conditions, so that the denitration efficiency is over 90 percent.
Example 2
Mixing and dissolving 0.005mol of F127, 0.5mol of cerium acetate and 0.2mol of manganese acetate into 10mol of isobutanol to obtain a solution A, dissolving the solution A by using an ultrasonic instrument, slowly dripping 6mol of concentrated hydrochloric acid into 1mol of isopropyl titanate, and reacting for 20min to obtain a solution B. Slowly dripping the solution A into the solution B, and mixing and reacting for 4 hours at the temperature of 20 ℃ to obtain a stable solution C. 40g of solution C were spread on a petri dish and dried at 20 ℃ and 75% RH for 24h to give solid D. And (3) placing the solid D in a muffle furnace, and sintering for 4h at the temperature of 420 ℃ at the heating speed of 1 ℃/min to prepare the manganese-cerium-titanium catalyst with the ordered mesoporous structure. The prepared catalyst samples were subjected to TEM topography analysis (see fig. 3). The prepared catalyst samples were subjected to specific surface area BET analysis (see fig. 4).
Evaluation of catalyst Performance: grinding and screening the prepared catalyst to 40-60 meshes, and putting the catalyst into a catalyst evaluation bed, wherein the inner diameter of a reactor is 0.8 cm. The simulated smoke is 500ppmNO and 500ppmNH 3、5vol％O2And 10 vol% H 2O, balance gas N 2Airspeed of 30000h -1The reaction temperature is 150-350 ℃, and the catalytic activity test and the denitration efficiency are carried out under the conditions More than 90 percent.
Example 3
0.073mol of L64, 0.42mol of cerium nitrate and 0.28mol of manganese chloride are mixed and dissolved in 15mol of isopropanol to obtain a solution A, the solution A is dissolved by an ultrasonic instrument, 6mol of concentrated hydrochloric acid is slowly dripped into 1mol of titanium tetrachloride (TiCl) 4) And reacting for 20min to obtain a solution B. Slowly dripping the solution A into the solution B, and mixing and reacting for 4 hours at the temperature of 20 ℃ to obtain a stable solution C. 40g of solution C were spread on a petri dish and dried at 25 ℃ and 80% RH for 36h to give solid D. And (3) placing the solid D in a muffle furnace, and sintering for 2h at the temperature of 600 ℃ at the temperature rise speed of 5 ℃/min to prepare the manganese-cerium-titanium catalyst with the ordered mesoporous structure. The prepared catalyst sample was subjected to BET analysis of specific surface area, and the specific surface area of the sample was 164.5m 2·g-1The pore distribution is mainly distributed in the range of 12-18 nm.
and (3) evaluating the performance of the catalyst, namely grinding and screening the prepared catalyst to 40-60 meshes by taking methyl orange as a model degradation product, weighing 0.5g of the catalyst, adding the catalyst into a methyl orange solution (100ml, 5 mg/L and pH 3), suspending the catalyst in the solution under magnetic stirring, placing the solution in an opaque container, and performing degradation reaction at normal temperature, wherein after 100min, the degradation rate of the methyl orange can reach 95%.
Example 4
0.009mol of P123, 0.3mol of cerium nitrate and 0.5mol of manganese sulfate are mixed and dissolved in 17mol of n-propanol to obtain a solution A, the solution A is dissolved by an ultrasonic instrument, 6mol of concentrated hydrochloric acid is slowly dripped into 1mol of tetrabutyl titanate to react for 20min to obtain a solution B. Slowly dripping the solution A into the solution B, and mixing and reacting for 4 hours at the temperature of 20 ℃ to obtain a stable solution C. 40g of solution C were spread on a petri dish and dried at 25 ℃ and 75% RH for 30h to give solid D. And (3) placing the solid D in a muffle furnace, and sintering for 3h at the temperature of 700 ℃ at the temperature rise speed of 10 ℃/min to prepare the manganese-cerium-titanium catalyst with the ordered mesoporous structure. The prepared catalyst is subjected to BET analysis of specific surface area, and the specific surface area of the catalyst is 143.2m 2·g-1The pore distribution is mainly distributed in the range of 16-20 nm.
Evaluation of catalyst Performance grinding and screening the prepared catalyst powder to 40-60 meshes, weighing 0.5g of sample, and putting the sample into 1L of 50 mg.L -1The ozone is introduced into the solution, the solution is stirred and reacted for 1 hour, the degradation rate of phenol reaches 92 percent, and the TOC removal rate reaches 85 percent.
Example 5
0.009mol of F127, 0.075mol of cerium chloride and 0.06mol of manganese chloride are mixed and dissolved in 20mol of ethanol to obtain a solution A, the solution A is dissolved by an ultrasonic instrument, 6mol of concentrated hydrochloric acid is slowly dripped into 1mol of tetraethyl titanate to react for 20min to obtain a solution B. Slowly dripping the solution A into the solution B, mixing at 20 ℃ and reacting for 4h to obtain a stable solution C. 40g of solution C was spread on a petri dish and dried at 25 ℃ and 60% RH for 40h to give solid D. And (3) placing the solid D in a muffle furnace, and sintering for 4h at the temperature of 300 ℃ at the temperature rise speed of 2 ℃/min to prepare the manganese-cerium-titanium catalyst with the ordered mesoporous structure. The prepared catalyst is subjected to BET analysis of specific surface area, and the specific surface area of the catalyst is 221.68m 2·g-1The pore distribution is mainly distributed in the range of 8-14 nm.
the performance evaluation of the catalyst comprises the steps of grinding and screening the prepared catalyst to 40-60 meshes, weighing 0.5g of the catalyst, and putting the catalyst into 1L of 50 mg.L -1Introducing ozone into the p-nitrophenol (PNP) solution, stirring and reacting for 1h, wherein the degradation rate of the p-phenol reaches 95%, and the removal rate of the TOC reaches 88%.
Claims (4)
1. The application of the manganese-cerium-titanium catalyst with the ordered mesoporous structure is characterized in that the catalyst is used for catalyzing and degrading phenol or p-nitrophenol solution in an ozone oxidation reaction; the catalyst is prepared by the following specific steps:
(1) Dissolving a triblock copolymer template agent, cerium salt and manganese salt in an alcohol solvent to obtain a solution A;
the triblock copolymer template agent in the step (1) is F127 or L64;
(2) Slowly adding concentrated hydrochloric acid into the titanium precursor, and reacting for 15-20 min to obtain a solution B;
(3) Slowly adding the solution A into the solution B, and mixing and reacting at the temperature of 20-60 ℃ for 2-6 hours to obtain a solution C;
(4) Spreading the solution C in a culture dish, and drying for 24-48 h under the conditions that the drying temperature is 20-40 ℃ and the drying humidity is 60-80% RH to obtain a solid D;
(5) And sintering the solid D in a muffle furnace for 2-4 h at the sintering temperature of 300-700 ℃ and the heating rate of 0.5-10 ℃/min to obtain the manganese-cerium-titanium catalyst with the ordered mesoporous structure.
2. The use of the manganese cerium titanium catalyst with ordered mesoporous structure as claimed in claim 1, wherein the alcohol solvent in step (1) is one or two of n-butanol, isobutanol, n-propanol, isopropanol and ethanol; the cerium salt in the step (1) is cerium chloride, cerium nitrate or cerium acetate; the manganese salt in the step (1) is manganese nitrate, manganese chloride, manganese sulfate or manganese acetate.
3. The use of the Mn-Ce-Ti catalyst with ordered mesoporous structure according to claim 1, wherein the Ti precursor in step (2) is one or two of tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate and titanium tetrachloride.
4. The use of the ordered mesoporous manganese cerium titanium catalyst of claim 1, wherein the molar ratio of the titanium precursor, concentrated hydrochloric acid, alcohol solvent, triblock copolymer template agent, cerium salt and manganese salt in steps (1) and (2) is 1: 6: 9-25: 0.001-0.3: 0.01-0.5: 0.01 to 0.5.
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| CN109126817B (en) * | 2018-11-07 | 2021-07-16 | 东北大学 | Iron, tungsten and zinc modified cerium oxide/manganese oxide SCR denitration catalyst and preparation method thereof |
| CN109201043A (en) * | 2018-11-14 | 2019-01-15 | 清华大学盐城环境工程技术研发中心 | A method of preparing mesoporous manganese titanium low-temperature denitration catalyst |
| CN109331802B (en) * | 2018-11-16 | 2021-04-02 | 内蒙古工业大学 | Nano-porous TiO prepared from polyether2Preparation method of vanadium-based denitration catalyst as carrier |
| CN111558394A (en) * | 2020-05-20 | 2020-08-21 | 佛山科学技术学院 | Titanium dioxide mesoporous film material, preparation method and application |
| CN111905709A (en) * | 2020-07-31 | 2020-11-10 | 江南大学 | Mesoporous cerium-titanium-based low-temperature denitration catalyst and preparation method thereof |
| CN114950467A (en) * | 2021-02-22 | 2022-08-30 | 复旦大学 | VOCs catalytic combustion catalyst and preparation method and application thereof |
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