CN111330563B - Ordered mesoporous carbon-titanium oxide composite material catalyst and preparation method thereof - Google Patents

Ordered mesoporous carbon-titanium oxide composite material catalyst and preparation method thereof Download PDF

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CN111330563B
CN111330563B CN202010217769.4A CN202010217769A CN111330563B CN 111330563 B CN111330563 B CN 111330563B CN 202010217769 A CN202010217769 A CN 202010217769A CN 111330563 B CN111330563 B CN 111330563B
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CN111330563A (en
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陈步东
曹飞飞
王书红
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Hangzhou Chuhuan Science And Technology Co ltd
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract

The invention discloses an ordered mesoporous carbon-titanium oxide composite catalyst and a preparation method thereof, wherein the catalyst comprises the following components: the active component is a mesoporous carbon-titanium oxide composite material with an ordered structure as an active component carrier; the specific surface area of the catalyst is 500-1200m 2 (ii)/g; the formula comprises the following components; the preparation method comprises the following steps of (1) preparing a phenolic resin precursor, a phenolic resin precursor and a titanium source; the catalyst prepared by using the formula and matching with an evaporation-induced self-synthesis method is low in production cost, uniform in pore structure, good in sulfur resistance, high in low-temperature catalytic activity and high in thermal stability; and the structure of the pores can be adjusted by changing the proportion of the components, so that the catalyst has controllability.

Description

Ordered mesoporous carbon-titanium oxide composite material catalyst and preparation method thereof
Technical Field
The invention relates to the field of environmental materials, in particular to an ordered mesoporous carbon-titanium oxide composite material catalyst and a preparation method thereof.
Background
Nitrogen oxides are one of the major atmospheric pollutants recognized by various countries in the world and are important precursors for inducing photochemical smog and acid rain. The nitrogen oxides discharged by fire coal in China are main artificial sources for causing the environmental pollution of the nitrogen oxides. The most applied technology for treating nitrogen oxides at present is a Selective Catalytic Reduction (SCR) technology. The SCR technology can effectively remove NO in the flue gas x However, the SCR flue gas denitration technology has the defects of low activity at low temperature, secondary pollution, poor sulfur resistance, high investment cost and the like.
The carbon-based catalyst is an important low-temperature SCR catalyst, and is related to patents CN1475305A, CN102614917A and CN101417223B, for example, patent CN1475305A discloses that the weight percentage of the carbon-based catalyst using vanadium as an active component is as follows: the honeycomb active carbon (90-99.9%) and vanadium pentoxide (0.1-10%) can make the NO conversion rate be 50% -100% at reaction temp. of 150-250 deg.C. In recent years, ordered mesoporous carbon materials have attracted attention of researchers due to their unique pore structures, large specific surface areas and other characteristics, for example, chentian et al introduced selective adsorption behavior of functionalized ordered mesoporous carbon on heavy metal ions Cu (II) and Cr (VI) in "that triblock copolymer F127 is used as a template agent, phenolic resin is used as a carbon source, tetraethoxysilane is used as a silicon source, three components are co-assembled to synthesize a mesoporous carbon-silicon oxide nano composite, and then silicon oxide is removed by HF to prepare the ordered mesoporous carbon. Zhanya, zhang scholar, in the influence of the template agent on the pore structure and order of mesoporous carbon, three-block polymers F127, P123 and P123/F127 are respectively used as template agents, phenolic resin is used as an organic carbon source, and a solvent volatilization self-assembly method is adopted to prepare the ordered mesoporous carbon material. Patent ZL 201110110498.3 describes a preparation method and denitration activity of ordered mesoporous carbon with cerium and vanadium as active components. However, the thermal stability of the above materials is yet to be further improved; the market needs a product which can overcome the defects of poor activity and low stability at low temperature of the existing mesoporous activated carbon denitration catalyst, and the invention solves the problems.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide an ordered mesoporous carbon-titanium oxide composite material catalyst and a preparation method thereof, and the catalyst prepared by the evaporation-induced self-synthesis method has the advantages of low production cost, uniform pore structure, good sulfur resistance, high low-temperature catalytic activity and high thermal stability; and the structure of the pores can be adjusted by changing the proportion of the components, so that the catalyst has adjustability.
In order to achieve the above object, the present invention adopts the following technical solutions:
an ordered mesoporous carbon-titania composite catalyst, comprising: the active component is a mesoporous carbon-titanium oxide composite material with an ordered structure as a carrier of the active component; the specific surface area of the catalyst is 500-1200m 2 /g；
The formula comprises the following components; the preparation method comprises the following steps of (1) preparing a surfactant, an acid solution, tetraethoxysilane, a titanium source, an active component precursor and a phenolic resin precursor;
surfactant (B): ethyl orthosilicate: the mass ratio of the ethanol solution of the phenolic resin precursor is 2.5-3; the active component precursor is Cu or V oxide, the mass fraction of the Cu oxide is 2.0-10.0%, and the mass fraction of the V oxide is 2.0-40.0%.
In the ordered mesoporous carbon-titanium oxide composite material catalyst, the formula of the phenolic resin precursor comprises the following components in molar mass ratio: 1, phenol: 1-2NaOH: 1.8-2-Formaldehyde.
In the foregoing ordered mesoporous carbon-titanium oxide composite catalyst, the active component precursor includes: copper nitrate, copper acetate, copper sulfate, vanadyl acetylacetonate and ammonium metavanadate.
The ordered mesoporous carbon-titanium oxide composite catalyst comprises the following titanium sources: titanium tetrachloride, titanium sulfate, titanyl sulfate, difluorotitanyl, tetrabutyl titanate, titanium isopropoxide and metatitanic acid.
The ordered mesoporous carbon-titanium oxide composite catalyst comprises an acid solution and a catalyst component, wherein the acid solution comprises: hydrochloric acid, sulfuric acid, nitric acid.
In the ordered mesoporous carbon-titanium oxide composite material catalyst, the surfactant is a triblock copolymer substance.
A preparation method of an ordered mesoporous carbon-titanium oxide composite material catalyst comprises the following steps:
dissolving a surfactant in ethanol, stirring until a solid is completely dissolved, then adding 0.2-0.5mol/L acid solution, heating in a water bath, and continuously stirring fully to obtain a solution A;
step two, adding ethyl orthosilicate, a titanium source, an active component precursor and an ethanol solution of a phenolic resin precursor into the solution A in sequence, keeping water bath heating, and stirring fully to obtain a solution B; wherein the surfactant: TEOS: the mass ratio of the ethanol solution of the phenolic resin precursor is = 2.5-3; the active component precursor is Cu or V oxide, the mass fraction of the Cu oxide is 2.0-10.0%, and the mass fraction of the V oxide is 2.0-40.0%;
step three, fully volatilizing the ethanol in the solution B;
step four, drying the solution B after the ethanol is completely volatilized to obtain a mixture B;
step five, calcining the dried mixture B;
and step six, finally soaking the calcined mixture B in an ethanol water solution containing NaOH, filtering, washing and drying in vacuum to obtain the catalyst.
In the preparation method of the ordered mesoporous carbon-titanium oxide composite material catalyst, the conditions of water bath heating in the first step and the second step are as follows: the constant temperature heating temperature is 40-50 ℃.
And fourthly, after the ethanol is completely volatilized and evaporated, drying the B in an oven at the constant temperature of 100 ℃ for more than 24 hours to obtain a mixture B.
And fifthly, transferring the dried mixture B into a tubular furnace for calcination, and heating the mixture B from room temperature to 700-850 ℃ at the speed of 2 ℃/min under the protection of nitrogen.
The invention has the advantages that:
the catalyst prepared by the invention has better catalytic activity in a low-temperature area;
the catalyst prepared by the invention has a uniform pore structure;
the catalyst prepared by the method can obtain catalysts with different pore structures by changing the proportion of substances, so that the catalyst has adjustability;
compared with the catalyst using the mesoporous carbon material as the carrier, the thermal stability of the catalyst prepared by the invention is greatly improved.
Drawings
FIG. 1 is a small angle XRD spectrum of the catalyst of sample 1 and sample 2 of the present invention (FIG. 1 (a) is the small angle XRD spectrum of sample 1, and FIG. 1 (b) is the small angle XRD spectrum of sample 2);
fig. 2 shows TEM and STEM images of samples 1 and 3 according to the present invention (fig. 2 (a) and (b) show TEM and STEM images of sample 1, and fig. 2 (c) and (d) show TEM and STEM images of sample 3).
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
An ordered mesoporous carbon-titanium oxide composite catalyst comprising: the active component is a mesoporous carbon-titanium oxide composite material with an ordered structure as a carrier of the active component; the specific surface area of the catalyst is 500-1200m 2 /g；
The formula comprises the following components; the preparation method comprises the following steps of (1) preparing a surfactant, an acid solution, tetraethoxysilane, a titanium source, an active component precursor and a phenolic resin precursor;
surfactant (b): ethyl orthosilicate: the mass ratio of the ethanol solution of the phenolic resin precursor is 2.5-3; the active component precursor is Cu or V oxide, the mass fraction of the Cu oxide is 2.0-10.0%, and the mass fraction of the V oxide is 2.0-40.0%.
The formula of the phenolic resin precursor comprises the following components in molar mass ratio: 1, phenol: 1-2NaOH: 1.8-2-carbaldehyde.
As an example, the active ingredient precursor includes: copper nitrate, copper acetate, copper sulfate, vanadyl acetylacetonate, ammonium metavanadate; the titanium source comprises: titanium tetrachloride, titanium sulfate, titanyl difluoride, n-tetrabutyl titanate, titanium isopropoxide and metatitanic acid; the acid solution comprises: hydrochloric acid, sulfuric acid, nitric acid; the surfactant is a triblock copolymer material.
The samples 1-4 prepared according to the following method were subjected to performance testing to verify the effect;
example 1:
preparing the ordered mesoporous carbon-titanium oxide catalyst carrier.
1. Dissolving 4.8g of surfactant in 40ml of ethanol, stirring until the solid is completely dissolved, then adding 3g of 0.2mol/L HCl solution, heating in a water bath at 40 ℃, and continuing stirring for 1h to obtain a solution A;
2. adding ethyl orthosilicate TEOS, tetra-n-butyl titanate and an ethanol solution of a phenolic resin Precursor (PF) into the solution A in sequence, wherein the mass ratio of the three components in the solution is surfactant: TEOS: the ethanol solution of the phenolic resin precursor = 4. Keeping the water bath for heating, and stirring for 2 hours to obtain a mixture B;
3. transferring the B into a culture dish to ensure that the active components are uniformly distributed, and standing at room temperature to volatilize and evaporate ethanol;
4. after the ethanol is basically volatilized and completely evaporated, putting the B into a 100 ℃ oven for drying, and keeping the temperature for 24 hours;
5. then transferring the dried B into a tubular furnace for calcination in N 2 Under the protection, the temperature is raised from the room temperature to 850 ℃ at the speed of 2 ℃/min for calcination;
6. and finally, dissolving the calcined B in an ethanol solution containing sodium hydroxide, soaking in a water bath for 5 hours to remove the template on the surface, washing with deionized water for 3-4 times, and drying in vacuum to obtain the denitration catalyst Ti10-OMC.
Sample 1 was obtained.
Example 2:
1. 4.8g of surfactant was dissolved in 40ml of ethanol and stirred until the solid was completely dissolved. Then adding 3g of 0.2mol/L HCl solution, heating in a water bath at 40 ℃, and continuously stirring for 1h to obtain a solution A;
2. and sequentially adding TEOS, titanyl sulfate, copper sulfate and an ethanol solution of a phenolic resin Precursor (PF) into the solution. Wherein the mass ratio of the three components is surfactant: TEOS: the ethanol solution of the phenolic resin precursor = 2. The mass of copper sulfate and a phenolic resin Precursor (PF) conforms to Cu/PF =10%, heating in a water bath is kept, and stirring is carried out for 2 hours to obtain a mixture B;
3. transferring the B into a culture dish to ensure that the active components are uniformly distributed, and standing at room temperature to volatilize and evaporate ethanol;
4. after the ethanol is basically volatilized and completely evaporated, putting the B into a 100 ℃ oven for drying, and keeping the temperature for 24 hours;
5. then the dried B is transferred into a tube typeCalcining in a furnace in N 2 Under protection, heating from room temperature to 800 ℃ at the speed of 2 ℃/min for calcination;
6. and finally, dissolving the calcined B in an ethanol solution containing sodium hydroxide, soaking in a water bath for 5 hours to remove the template on the surface, washing with deionized water for 3-4 times, and drying in vacuum to obtain the denitration catalyst Cu10Ti10-OMC.
Sample 2 was obtained.
Example 3:
1. 4.8g of surfactant was dissolved in 40ml of ethanol and stirred until the solid was completely dissolved. Then adding 3g of 0.3mol/L HCl solution, heating in a water bath at 45 ℃, and continuously stirring for 1h to obtain a solution A;
2. and (2) adding ethyl orthosilicate TEOS, titanium sulfate, ammonium metavanadate and an ethanol solution of a phenolic resin Precursor (PF) into the solution in sequence, wherein the mass ratio of the three components is surfactant: TEOS: the ethanol solution of the phenolic resin precursor = 2. The mass of ammonium metavanadate and a phenolic resin Precursor (PF) follows V/PF =5%, water bath heating is kept, and a mixture B is obtained after stirring for 2 hours;
3. transferring the B into a culture dish to ensure that the active components are uniformly distributed, and standing at room temperature to volatilize and evaporate ethanol;
4. after the ethanol is basically volatilized and completely evaporated, putting the B into a 100 ℃ oven for drying, and keeping the temperature for 24 hours;
5. then transferring the dried B into a tubular furnace for calcination in N 2 Under protection, the temperature is raised from room temperature to 850 ℃ at the speed of 2 ℃/min for calcination;
6. and finally, dissolving the calcined B in an ethanol solution containing sodium hydroxide, soaking in a water bath for 5 hours to remove the template on the surface, washing with deionized water for 3-4 times, and drying in vacuum to obtain the denitration catalyst V5Ti10-OMC.
Sample 3 was obtained.
Example 4:
1. 4.8g of surfactant was dissolved in 40ml of ethanol and stirred until the solid was completely dissolved. Then adding 3g of 0.2mol/L HCl solution, heating in a water bath at 40 ℃, and continuously stirring for 1h to obtain a solution A;
2. and sequentially adding tetraethoxysilane TEOS, tetra-n-butyl titanate, vanadyl acetylacetonate and an ethanol solution of a phenolic resin Precursor (PF) into the solution, wherein the mass ratio of the three components is as follows: TEOS: the ethanol solution of the phenolic resin precursor = 4. The mass of vanadyl acetylacetonate and a phenolic resin Precursor (PF) conforms to V/PF =10%, heating in a water bath is kept, and stirring is carried out for 2 hours to obtain a mixture B;
3. transferring the B into a culture dish to ensure that the active components are uniformly distributed, and standing at room temperature to volatilize and evaporate ethanol;
4. evaporating ethanol basically, drying B in a 100 ℃ oven, and keeping the temperature for 24h;
5. then transferring the dried B into a tubular furnace for calcination in N 2 Under protection, the temperature is raised from room temperature to 700 ℃ at the speed of 2 ℃/min for calcination;
6. and finally, dissolving the calcined B in an ethanol solution containing sodium hydroxide, soaking in a water bath for 5 hours to remove the template on the surface, washing with deionized water for 3-4 times, and drying in vacuum to obtain the denitration catalyst V10Ti20-OMC.
Sample 4 was obtained.
A mesoporous carbon supported catalyst was prepared as a comparative sample.
The preparation process comprises the following steps:
1. 4.8g of surfactant was dissolved in 40ml of ethanol and stirred until the solid was completely dissolved. Then adding 3g of 0.2mol/L HCl solution, heating in a water bath at 40 ℃, and continuously stirring for 1h to obtain a solution A;
2. and sequentially adding ethyl orthosilicate TEOS, ammonium metavanadate and an ethanol solution of a phenolic resin Precursor (PF) into the solution, wherein the mass ratio of the three components is surfactant: TEOS: the method comprises the following steps of (1) heating in a water bath, stirring for 2 hours to obtain a mixture B, wherein the ethanol solution of the phenolic resin precursor = 4;
3. transferring the B into a culture dish to ensure that the active components are uniformly distributed, and standing at room temperature to volatilize and evaporate ethanol;
4. the ethanol is basically volatilized and completely evaporated, and the B is put into an oven at 100 ℃ for drying and is kept at the constant temperature for 24 hours;
5. then transferring the dried B into a tubular furnace for calcination in N 2 Under protection, the temperature is raised from room temperature to 700 ℃ at the speed of 2 ℃/min for calcination;
6. and finally, dissolving the calcined B in an ethanol solution containing sodium hydroxide, soaking in a water bath for 5 hours to remove a template on the surface, washing with deionized water for 3-4 times, and drying in vacuum to obtain the denitration catalyst V5-OMC.
A comparative sample was obtained.
The performance test verifies that the invention has the beneficial effects that:
experiment I, denitration experiment under low temperature environment (150-250 ℃), mass loss and thermal stability test:
the experimental process comprises the following steps:
the simulated smoke components adopt 500ppm of NO and 500ppm of NH 3 5% of O 2 Nitrogen as background gas, reaction temperature of 150-250 ℃, space velocity of 36000h -1 And (4) carrying out a denitration experiment, and testing the concentration difference of NO before and after the reaction in the reaction process to measure the reaction efficiency of denitration. After the experiment is finished, the mass loss of the catalyst before and after the reaction is weighed by an electronic balance, so that the thermal stability of the catalyst is measured.
Experiment two, pore structure test;
the catalyst carrier and the catalyst prepared by the invention both utilize a nitrogen adsorption instrument to test the specific surface area of a sample, utilize small-angle XRD to represent the formation condition of the ordered mesoporous structure of the sample, and utilize a transmission electron microscope to directly observe the internal structure of the sample from a microscopic angle. Fig. 1 is small-angle XRD spectrograms of embodiment 1 and embodiment 2 of the present invention, and it can be seen from the graphs that both samples have distinct diffraction peaks at diffraction angles of about 1 °, indicating that both samples effectively form ordered structures. FIG. 2 is a transmission electron microscope image of embodiment 1 and embodiment 3 of the present invention, which can visually observe that the microstructures of the two samples are composed of uniform pore sizes, and the ordered mesoporous structure is well preserved after the catalyst carrier loads the active component.
Results of the first and second experiments:
specific surface area (m) 2 /g) Denitration efficiency (%) Mass loss (%)
Sample 1 1140 3 5
Sample 2 550 75 10
Sample 3 830 57 12
Sample No. 4 524 64 10
Comparative sample 876 61 55
And (4) analyzing results:
as can be seen from FIGS. 1 and 2, the catalyst prepared by the method has an ordered catalyst structure with developed mesopores, large specific surface area and uniform pore diameter; the catalyst has better catalytic activity in a low-temperature area, and is generally more than 55%; compared with the mesoporous carbon carrier catalyst, the catalyst prepared by the invention has the advantages that the oxidation resistance of the catalyst carrier is enhanced due to the addition of the metal titanium element in the catalyst carrier, so that the quality loss is reduced, and the thermal stability is obviously improved.
The catalyst prepared by the method has a uniform pore structure, so that the sulfur resistance is effectively improved, and the catalytic activity and the thermal stability in a low-temperature environment are improved; and the structure of the pores can be adjusted by changing the proportion of the components, so that the catalyst has adjustability.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.

Claims (9)

1. An ordered mesoporous carbon-titania composite catalyst, comprising: an active component, a mesoporous carbon-titanium oxide composite material with an ordered structure as a carrier of the active component; the specific surface area of the catalyst is 500-1200m 2 /g；
The formula comprises the following components; the preparation method comprises the following steps of (1) preparing a phenolic resin precursor, a phenolic resin precursor and a titanium source; the active component precursor is copper sulfate or vanadyl acetylacetonate;
surfactant (B): ethyl orthosilicate: the mass ratio of the ethanol solution of the phenolic resin precursor is 2.5-3; the active component is Cu or V oxide, the mass fraction of the Cu oxide is 2.0-10.0%, and the mass fraction of the V oxide is 2.0-40.0%;
the preparation method of the ordered mesoporous carbon-titanium oxide composite material catalyst comprises the following steps:
dissolving a surfactant in ethanol, stirring until a solid is completely dissolved, then adding 0.2-0.5mol/L acid solution, heating in a water bath, and continuously stirring fully to obtain a solution A;
step two, adding ethyl orthosilicate, a titanium source, an active component precursor and an ethanol solution of a phenolic resin precursor into the solution A in sequence, keeping water bath heating, and stirring fully to obtain a solution B; wherein the surfactant: TEOS: the mass ratio of the ethanol solution of the phenolic resin precursor is = 2.5-3; the active component is Cu or V oxide, the mass fraction of the Cu oxide is 2.0-10.0%, and the mass fraction of the V oxide is 2.0-40.0%;
transferring the B into a culture dish to ensure that the active components are uniformly distributed, and standing at room temperature to volatilize and evaporate ethanol;
step four, drying the solution B after the ethanol is completely volatilized and evaporated to obtain a mixture B;
step five, calcining the dried mixture B;
and step six, finally soaking the calcined mixture B in an ethanol water solution containing NaOH, filtering, washing and drying in vacuum to obtain the catalyst.
2. The ordered mesoporous carbon-titanium oxide composite catalyst according to claim 1, wherein the formula of the phenolic resin precursor comprises, in terms of molar mass ratio: 1, phenol: 1-2NaOH: 1.8-2-Formaldehyde.
3. The ordered mesoporous carbon-titanium oxide composite catalyst of claim 1, wherein the titanium source comprises: titanium tetrachloride, titanium sulfate, titanyl difluoride, n-tetrabutyl titanate, titanium isopropoxide, and metatitanic acid.
4. The ordered mesoporous carbon-titanium oxide composite catalyst of claim 1, wherein the acid solution comprises: hydrochloric acid, sulfuric acid, nitric acid.
5. The ordered mesoporous carbon-titania composite catalyst of claim 1, wherein the surfactant is a triblock copolymer.
6. A method for preparing the ordered mesoporous carbon-titanium oxide composite catalyst of claim 1, comprising the steps of:
dissolving a surfactant in ethanol, stirring until a solid is completely dissolved, then adding 0.2-0.5mol/L acid solution, heating in a water bath, and continuously stirring fully to obtain a solution A;
step two, adding ethyl orthosilicate, a titanium source, an active component precursor and an ethanol solution of a phenolic resin precursor into the solution A in sequence, keeping water bath heating, and stirring fully to obtain a solution B; wherein the surfactant: TEOS: the mass ratio of the ethanol solution of the phenolic resin precursor is = 2.5-3; the active component is Cu or V oxide, the mass fraction of the Cu oxide is 2.0-10.0%, and the mass fraction of the V oxide is 2.0-40.0%;
transferring the B into a culture dish to ensure that the active components are uniformly distributed, and standing at room temperature to volatilize and evaporate ethanol;
step four, drying the solution B after the ethanol is completely volatilized and evaporated to obtain a mixture B;
step five, calcining the dried mixture B;
and step six, finally soaking the calcined mixture B in an ethanol water solution containing NaOH, filtering, washing and drying in vacuum to obtain the catalyst.
7. The method for preparing the ordered mesoporous carbon-titanium oxide composite catalyst according to claim 6, wherein the conditions of water bath heating in the first step and the second step are as follows: the constant temperature heating temperature is 40-50 ℃.
8. The preparation method of the ordered mesoporous carbon-titanium oxide composite catalyst according to claim 6, wherein in the fourth step, after the ethanol is completely volatilized and evaporated, the mixture B is dried in an oven at a constant temperature of 100 ℃ for more than 24 hours to obtain a mixture B.
9. The preparation method of the ordered mesoporous carbon-titanium oxide composite catalyst according to claim 6, wherein in the fifth step, the dried mixture B is transferred to a tubular furnace for calcination, and the temperature is raised from room temperature to 700-850 ℃ at a rate of 2 ℃/min under the protection of nitrogen.
CN202010217769.4A 2020-03-25 2020-03-25 Ordered mesoporous carbon-titanium oxide composite material catalyst and preparation method thereof Active CN111330563B (en)

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