CN102218311A - Ordered structure mesoporous carbon material denitrification catalyst and preparation method thereof - Google Patents
Ordered structure mesoporous carbon material denitrification catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ordered structure mesoporous carbon material denitrification catalyst applicable to preparation of a medium-pore catalyst and a preparation method thereof. The active components of the ordered structure mesoporous carbon material denitrification catalyst are oxides of Ce or V; and a mesoporous carbon material with an ordered structure is used as a final carrier for the active components. The preparation method for the catalyst comprises the following steps of mixing and dissolving an organism F127(EO106-PO70-EO106) and dilute hydrochloric acid; sequentially adding tetraethyl orthosilicate, a former body of the active compenonts and a former body of phenol formaldehyde resin into the solution; mixing and drying the solution; then transferring dried mixture in a tubular furnace; and roasting the mixture under the protection of inert gas, thus obtaining the catalyst, wherein the former body of the active components is Ce-contained nitrate or V-contained inorganic salt. The catalyst prepared by the method has a uniform porous structure, and has good catalytic activity in a low-temperature region; and furthermore, by changing the proportion of substances, the catalysts with different porous structures can be obtained so that the catalyst has adjustability.
Description
Technical field
The invention belongs to environmentally conscious materials, environmental catalysis and environmental protection technical field, relate to a kind of denitrating catalyst, specifically is a kind of ordered structure meso-porous carbon material denitrating catalyst that is applicable to the preparation medium-pore catalyst and preparation method thereof.
Background technology
Nitrogen oxide is one of generally acknowledged main atmosphere pollution in countries in the world, is the important presoma that brings out photochemical fog and acid rain.It can damage the ozone layer, influence ecological environment, harm humans health.The nitrogen oxide that combustion of fossil fuel produces is the main artificial source of causing the nitrogen oxide environmental pollution, and China is the developing country based on fire coal, and coal fire discharged nitrogen oxide is the main artificial source of causing the nitrogen oxide environmental pollution.What the application of improvement nitrogen oxide was maximum at present is the SCR technology.The SCR technology can remove the NOx in the flue gas effectively, but the SCR gas denitrifying technology exists shortcomings such as secondary pollution, anti-sulphur difference cost of investment height.In order to address the above problem, all over the world all at the novel denitrating catalyst of research.The catalyst of research mainly concentrates on molecular sieve catalyst, noble metal catalyst, transition-metal catalyst etc. at present, but every kind of catalyst all exists deficiency separately: molecular sieve catalyst only shows high temperature active, almost do not have activity at a lower temperature, anti-middle toxicity and stability are also undesirable; Noble metal catalyst costs an arm and a leg, and has exceeded the receptible scope of commercial Application, and much toxic reaction all can make the irreversible inactivation of catalyst, and this has caused the increase of catalyst cost again; Traditional transition-metal catalyst also exists problems such as sulfur resistance difference.
For example Chinese patent application number is a kind of high-temperature flue gas SCR denitrating catalyst of CN201010298125.9, and its activity of such catalysts scope is 250 ℃～400 ℃; Notification number is a kind of low-vanadium denitration catalyst of CN101590404B, also be aimed at the catalytic reaction (more than 200 ℃) of high-temperature area, all poor in the low-temperature region catalytic activity, in order to reduce of the influence of impurity such as SO2 to denitration, and the production cost that reduces denitrating technique, the catalyst of seeking low-temperature region is imperative.
Summary of the invention
The denitrating catalyst that the present invention is directed to prior art exists that sulfur resistance is poor, poor activity under the low temperature, defective that stability is not high, and the ordered structure meso-porous carbon material that a kind of cost is lower, mesopore is flourishing, anti-sulphur is good, low temperature active is higher denitrating catalyst is provided.
The present invention also provides a kind of preparation method of this ordered structure meso-porous carbon material denitrating catalyst.
Above-mentioned technical problem of the present invention is implemented by the following technical programs:
A kind of ordered structure meso-porous carbon material denitrating catalyst, this activity of such catalysts component is the oxide of Ce or V, is the final carrier of active component with the meso-porous carbon material with ordered structure.
A kind of preparation method of described ordered structure meso-porous carbon material denitrating catalyst, this method are with organism F127(EO
106-PO
70-EO
106) mix with watery hydrochloric acid and to make its dissolving, add ethyl orthosilicate, active component precursor and phenolic resins precursor then successively, to stir, oven dry changes in the tube furnace and calcines under inert gas shielding, obtains catalyst; Described active component precursor is to contain the nitrate of Ce or the inorganic salts of V.The present invention adopts evaporation to induce synthetic certainly method to prepare catalyst of the present invention, adopts organism F127(EO
106-PO
70-EO
106) mix with the weak solution of hydrochloric acid; add ethyl orthosilicate (TEOS) and phenolic resins precursor with certain proportion then; after stirring, drying; change in the tube furnace and under inert gas shielding, rise to about 850 ℃ by room temperature, can obtain mesopore prosperity, specific area is big, the aperture is unified orderly catalyst structure with given pace.By in preparation process, adding V or Ce element, obtain the good catalyst of sulfur resistance efficiently.In addition, change the ratio of F127, ethyl orthosilicate and phenolic resins, can obtain the catalyst carrier of Different Pore Structures.
As preferably, the preparation method of described phenolic resins precursor is as follows:
A. under 40 ~ 50 ℃ of water-baths, phenol is dissolved in the conical flask, adds the NaOH solution of 50wt% subsequently, stir 10min;
B. the formalin with 37wt% at the uniform velocity is added dropwise to above-mentioned solution, and 70 ℃ of stirring in water bath 1h are cooled to room temperature, and wherein the molal weight of phenol, NaOH, formaldehyde is than being 5:10:9 ~ 5:1:10;
C. the HCl solution of 1.5mol/L is dropwise added in the solution that the b step obtains, treat that the pH value just arrives at 7 o'clock, solution is transferred to vacuum drying chamber, manifest thickness until solution;
D. in solution, add small amount of ethanol, filter lower floor's white precipitate, filtrate is put into vacuum drying chamber once more, continue drying, obtain described phenolic resins precursor to remove ethanol.
As preferably, described active component precursor is cerous nitrate or cerous nitrate, ceric nitrate or ammonium metavanadate.
As preferably, the preparation method of ordered structure meso-porous carbon material denitrating catalyst of the present invention specifically comprises the steps:
A. F127 is dissolved in the ethanol, is stirred to the F127 solid and dissolves fully, add the hydrochloric acid solution of 0.2 ~ 0.5mol/L then, make solution become clarification by white, the water-bath heating continues to stir fully, obtains solution A;
B. the ethanolic solution that in solution A, adds ethyl orthosilicate (TEOS), active component precursor and phenolic resins precursor (PF) successively, make that the mass ratio of three kinds of compositions is F127:TEOS in the solution: the ethanolic solution=4:5:10 of phenolic resins precursor ~ 2:3:5, the amount of active component precursor is regulated according to concrete activity of such catalysts percentage composition, keep the water-bath heating, obtain mixture B after the stirring fully;
As further preferred, F127:TEOS: the mass ratio of the ethanolic solution of phenolic resins precursor is 8:10.4:20;
C. B is transferred in the culture dish, guarantee that active component is evenly distributed (can not use evaporating dish) in the mixture B, the room temperature placement makes the ethanol evaporation of fully volatilizing;
D. treat ethanol volatilization evaporation fully, B is put into baking oven more than 100 ℃ of freeze-day with constant temperature 24h;
E. more dried B is changed in the tube furnace and calcine, at N
2Protection is warming up to 850 ℃ of calcinings with 2 ℃/min from room temperature down, and keeps more than the 1h at 850 ℃;
F. the B after will calcining at last soaks with the dissolve with ethanol solution that contains NaOH, water-bath, filters, and washing, vacuum drying obtains catalyst.
As preferably, the ethanolic solution of described phenolic resins precursor (PF) is the ethanolic solution that contains 25wt% phenolic resins precursor.The phenolic resins precursor preparation becomes 25% ethanolic solution, mainly is the oxidation deterioration that prevents phenolic resins in the preparation process.
As preferably, the water-bath heating process described in step a, the b is heated at constant temperature, and heating-up temperature is 40 ~ 50 ℃.The water-bath heating mainly is to keep reactant to be heated evenly, and all remains on liquid state.The too high meeting of temperature is partly evaporated reactant.
As preferably, the mass ratio of active component precursor and phenolic resins precursor (PF) is followed Ce/PF=2%～8%, or V/PF=2%～8%.The ratio of active component in catalyst is generally all less than 8 ~ 10%, in order to seek the catalyst that best active quantities the present invention prepares active component 2 ~ 8% respectively.
As preferably, the volume ratio of ethanol and water is 1:1 in the described ethanolic solution.Ethanol is used for removing organic matter, and water is mainly used to remove the surface inorganic thing, and both mix the effect with the best with volume.
Catalyst of the present invention can improve anti-sulphur effectively, and low temperature active also is enhanced, and the structure that can come adjustment hole by the ratio that changes component, makes catalyst have Modulatory character.
Compare with existing denitrating catalyst, the catalyst that the inventive method makes has unified pore structure, at low-temperature region catalytic activity is preferably arranged, and can obtain the catalyst of Different Pore Structures by changing the ratio of material, make catalyst have controllability.
Description of drawings
Fig. 1 is the specific area of the catalyst of embodiment 2 preparations.Specific area s=1456 (m
2g
-1).
Fig. 2 is the graph of pore diameter distribution of the catalyst of embodiment 2 preparations.Pore-size distribution D
Avg=7.41nm.
Fig. 3 is the catalyst carrier and the load active component catalyst S EM figure of embodiment 6 preparations.Wherein, (a) being catalyst carrier, (b) is the catalyst of load active component.
The specific embodiment
Below be specific embodiments of the invention; These embodiment can do further to replenish and explanation to the present invention; But the present invention is not limited to these embodiment.
Employed technology in following examples unless stated otherwise, is routine techniques known to those skilled in the art; Employed instrument and equipment, reagent etc., only this specification specifies, is that the research of this area and technical staff can be by public approach acquisition.
The source of F127: model Pluronic F-127, P2443-250G, the Sigma-Aldrich of producer;
The preparation method of the phenolic resins precursor of using among the embodiment (PF) (oneself is prepared from, and producer is not provided at present) is as follows:
A. under 40 ~ 50 ℃ of water-baths, phenol is dissolved in the conical flask, adds the NaOH solution of 50wt% subsequently, stir 10min;
B. the formalin with 37wt% at the uniform velocity is added dropwise to above-mentioned solution, and 70 ℃ of stirring in water bath 1h are cooled to room temperature, and wherein the molal weight of phenol, NaOH, formaldehyde is than being 5:1:9 ~ 5:1:10; For better saying something, following examples all adopt the molal weight of phenol, NaOH, formaldehyde than the phenolic resins precursor that makes for 5:1:9;
C. the HCl solution of 1.5mol/L is dropwise added in the solution that the b step obtains, treat that the pH value just arrives at 7 o'clock, solution is transferred to vacuum drying chamber, manifest thickness until solution;
D. in solution, add small amount of ethanol, filter lower floor's white precipitate, filtrate is put into vacuum drying chamber once more, continue drying, obtain described phenolic resins precursor to remove ethanol.
Embodiment 1:
1. the F127 with 1.6g is dissolved in the 20ml ethanol, is stirred to the F127 solid and dissolves fully, adds the HCl solution of the 0.2mol/L of 1g then, makes solution become clarification by white, and 40 ℃ of water-bath heating continue to stir 1h, obtain solution A;
2. the ethanolic solution that in solution A, adds ethyl orthosilicate TEOS, cerous nitrate and phenolic resins precursor (PF) successively, the mass ratio of three kinds of compositions is F127:TEOS in the solution: the ethanolic solution=4:5:10 of phenolic resins precursor, the quality of cerous nitrate and phenolic resins precursor (PF) is followed Ce/PF=2%, keep the water-bath heating, obtain mixture B behind the stirring 2h; The ethanolic solution of phenolic resins precursor is the ethanolic solution that contains 25wt% phenolic resins precursor.
3. B is transferred in the culture dish, guarantee that active component is evenly distributed, room temperature is placed the volatilization ethanol evaporation;
4. treat that ethanol volatilizees evaporation fully substantially, it is dry that B is put into 100 ℃ of baking ovens, constant temperature 24h;
5. more dried B is changed in the tube furnace and calcine, at N
2Protection is warming up to 850 ℃ of calcinings with 2 ℃/min from room temperature down, and keeps 2h at 850 ℃;
6. the B after will calcining at last contains ethanolic solution (the NaOH 10g of NaOH with 100ml, ethanol: the volume ratio of water=1:1) dissolving, the template that 5h removes the surface is soaked in water-bath, it is yellow partially to soak the back solution colour, filter, washed with de-ionized water 2-3 time, vacuum drying obtain denitrating catalyst Ce2F.
Sample carries out nitrogen BET test, and specific area is 950 ㎡/g, and pore size distribution mainly is present in the mesoporous stage.The present invention adopts the NO of 500ppm and the NH of 500ppm
3, 5% O
2, nitrogen is background gas, air speed 36000h
-1Carry out the denitration experiment, be up to 60% at 150 ℃ ~ 250 ℃ denitration efficiencies.
Embodiment 2:
1. the F127 with 1.6g is dissolved in the 20ml ethanol, is stirred to the F127 solid and dissolves fully.Add the HCl solution of the 0.5mol/L of 1g then, make solution become clarification by white, 50 ℃ of water-bath heating continue to stir 1h, obtain solution A;
2. the ethanolic solution that in above-mentioned solution, adds ethyl orthosilicate TEOS, cerous nitrate and phenolic resins precursor (PF) successively. wherein the mass ratio of three kinds of compositions is F127:TEOS: the ethanolic solution=2:3:5 of phenolic resins precursor, the quality of cerous nitrate and phenolic resins precursor (PF) is followed Ce/PF=4%, keep the water-bath heating, obtain mixture B behind the stirring 2h; The ethanolic solution of phenolic resins precursor is the ethanolic solution that contains 20wt% phenolic resins precursor.
3. B is transferred in the culture dish, guarantee that active component is evenly distributed, room temperature is placed the volatilization ethanol evaporation;
4. treat that ethanol volatilizees evaporation fully substantially, it is dry that B is put into 100 ℃ of baking ovens, constant temperature 24h.;
5. more dried B is changed in the tube furnace and calcine, at N
2Protection is warming up to 850 ℃ of calcinings with 2 ℃/min from room temperature down, and keeps 2h at 850 ℃;
6. the B after will calcining at last contains ethanolic solution (the NaOH 10g of NaOH with 100ml, ethanol: the volume ratio of water=1:1) dissolving, the template that 5h removes the surface is soaked in water-bath, it is yellow partially to soak the back solution colour, filter, washed with de-ionized water 2-3 time, vacuum drying obtain denitrating catalyst Ce4F.
Sample carries out nitrogen BET test, and specific area is 1150 ㎡/g, and pore size distribution mainly is present in the mesoporous stage.The specific area of the catalyst that present embodiment makes is seen Fig. 1, and graph of pore diameter distribution is seen Fig. 2.The present invention adopts the NO of 500ppm and the NH of 500ppm
3, 5% O
2, nitrogen is background gas, air speed 36000h
-1Carry out the denitration experiment, be up to 58% at 150 ℃ ~ 250 ℃ denitration efficiencies.
Embodiment 3:
1. the F127 with 1.6g is dissolved in the 20ml ethanol, is stirred to the F127 solid and dissolves fully.Add the HCl solution of the 0.3mol/L of 1g then, make solution become clarification by white, 45 ℃ of water-bath heating continue to stir 1h, obtain solution A;
2. the ethanolic solution that in above-mentioned solution, adds ethyl orthosilicate TEOS, cerous nitrate and phenolic resins precursor (PF) successively. wherein the mass ratio of three kinds of compositions is F127:TEOS: the ethanolic solution=8:10.4:20 of phenolic resins precursor, the quality of cerous nitrate and phenolic resins precursor (PF) is followed Ce/PF=8%, keep the water-bath heating, obtain mixture B behind the stirring 2h; The ethanolic solution of phenolic resins precursor is the ethanolic solution that contains 30wt% phenolic resins precursor.
3. B is transferred in the culture dish, guarantee that active component is evenly distributed, room temperature is placed the volatilization ethanol evaporation;
4. treat that ethanol volatilizees evaporation fully substantially, it is dry that B is put into 100 ℃ of baking ovens, constant temperature 24h;
5. more dried B is changed in the tube furnace and calcine, at N
2Protection is warming up to 850 ℃ of calcinings with 2 ℃/min from room temperature down, and keeps 2h at 850 ℃;
6. the B after will calcining at last contains ethanolic solution (the NaOH 10g of NaOH with 100ml, ethanol: the volume ratio of water=1:1) dissolving, the template that 5h removes the surface is soaked in water-bath, it is yellow partially to soak the back solution colour, filter, washed with de-ionized water 2-3 time, vacuum drying obtain denitrating catalyst Ce8F.
Sample carries out nitrogen BET test, and specific area is 1030 ㎡/g, and pore size distribution mainly is present in the mesoporous stage.The present invention adopts the NO of 500ppm and the NH of 500ppm
3, 5% O
2, nitrogen is background gas, air speed 36000h
-1Carry out the denitration experiment, be up to 60% at 150 ℃ ~ 250 ℃ denitration efficiencies.
Embodiment 4:
1. the F127 with 1.6g is dissolved in the 20ml ethanol, is stirred to the F127 solid and dissolves fully.Add the HCl solution of the 0.2mol/L of 1g then, make solution become clarification by white, 40 ℃ of water-bath heating continue to stir 1h, obtain solution A;
2. the ethanolic solution that in above-mentioned solution, adds ethyl orthosilicate TEOS, ammonium metavanadate and phenolic resins precursor (PF) successively. wherein the mass ratio of three kinds of compositions is F127:TEOS: the ethanolic solution=4:5:10 of phenolic resins precursor, the quality of ammonium metavanadate and phenolic resins precursor (PF) is followed V/PF=2%, keep the water-bath heating, obtain mixture B behind the stirring 2h; The ethanolic solution of phenolic resins precursor is the ethanolic solution that contains 25wt% phenolic resins precursor.
3. B is transferred in the culture dish, guarantee that active component is evenly distributed, room temperature is placed the volatilization ethanol evaporation;
4. ethanol volatilizees evaporation fully substantially, and it is dry that B is put into 100 ℃ of baking ovens, constant temperature 24h;
5. more dried B is changed in the tube furnace and calcine, at N
2Protection is warming up to 850 ℃ of calcinings with 2 ℃/min from room temperature down, and keeps 2h at 850 ℃;
6. the B after will calcining at last contains ethanolic solution (the NaOH 10g of NaOH with 100ml, ethanol: the volume ratio of water=1:1) dissolving, the template that 5h removes the surface is soaked in water-bath, it is yellow partially to soak the back solution colour, filter, washed with de-ionized water 2-3 time, vacuum drying obtain denitrating catalyst V2F.
Sample carries out nitrogen BET test, and specific area is 1024 ㎡/g, and pore size distribution mainly is present in the mesoporous stage.The present invention adopts the NO of 500ppm and the NH of 500ppm
3, 5% O
2, nitrogen is background gas, air speed 36000h
-1Carry out the denitration experiment, be up to 50% at 150 ℃ ~ 250 ℃ denitration efficiencies.
Embodiment 5:
1. the F127 with 1.6g is dissolved in the 20ml ethanol, is stirred to the F127 solid and dissolves fully.Add the HCl solution of the 0.5mol/L of 1g then, make solution become clarification by white, 50 ℃ of water-bath heating continue to stir 1h, obtain solution A;
2. the ethanolic solution that in above-mentioned solution, adds ethyl orthosilicate TEOS, ammonium metavanadate and phenolic resins precursor (PF) successively. wherein the mass ratio of three kinds of compositions is F127:TEOS: the ethanolic solution=2:3:5 of phenolic resins precursor, the quality of ammonium metavanadate and phenolic resins precursor (PF) is followed V/PF=4%, keep the water-bath heating, obtain mixture B behind the stirring 2h; The ethanolic solution of phenolic resins precursor is the ethanolic solution that contains 20wt% phenolic resins precursor.
3. B is transferred in the culture dish, guarantee that active component is evenly distributed, room temperature is placed the volatilization ethanol evaporation;
4. ethanol volatilizees evaporation fully substantially, and it is dry that B is put into 100 ℃ of baking ovens, constant temperature 24h;
5. more dried B is changed in the tube furnace and calcine, at N
2Protection is warming up to 850 ℃ of calcinings with 2 ℃/min from room temperature down, and keeps 2h at 850 ℃;
6. the B after will calcining at last contains ethanolic solution (the NaOH 10g of NaOH with 100ml, ethanol: the volume ratio of water=1:1) dissolving, the template that 5h removes the surface is soaked in water-bath, it is yellow partially to soak the back solution colour, filter, washed with de-ionized water 2-3 time, vacuum drying obtain denitrating catalyst V4F.
Sample carries out nitrogen BET test, and specific area is 1310 ㎡/g, and pore size distribution mainly is present in the mesoporous stage.The present invention adopts the NO of 500ppm and the NH of 500ppm
3, 5% O
2, nitrogen is background gas, air speed 36000h
-1Carry out the denitration experiment, be up to 55% at 150 ℃ ~ 250 ℃ denitration efficiencies.
Embodiment 6:
1. the F127 with 1.6g is dissolved in the 20ml ethanol, is stirred to the F127 solid and dissolves fully.Add the HCl solution of the 0.3mol/L of 1g then, make solution become clarification by white, 45 ℃ of water-bath heating continue to stir 1h, obtain solution A;
2. the ethanolic solution that in above-mentioned solution, adds ethyl orthosilicate TEOS, ammonium metavanadate and phenolic resins precursor (PF) successively. wherein the mass ratio of three kinds of compositions is F127:TEOS: the ethanolic solution=8:10:4:20 of phenolic resins precursor, the quality of ammonium metavanadate and phenolic resins precursor (PF) is followed V/PF=8%, keep the water-bath heating, obtain mixture B behind the stirring 2h; The ethanolic solution of phenolic resins precursor is the ethanolic solution that contains 30wt% phenolic resins precursor.
3. B is transferred in the culture dish, guarantee that active component is evenly distributed, room temperature is placed the volatilization ethanol evaporation;
4. ethanol volatilizees evaporation fully substantially, and it is dry that B is put into 100 ℃ of baking ovens, constant temperature 24h.;
5. more dried B is changed in the tube furnace and calcine, at N
2Protection is warming up to 850 ℃ of calcinings with 2 ℃/min from room temperature down, and keeps 2h at 850 ℃;
6. the B after will calcining at last contains ethanolic solution (the NaOH 10g of NaOH with 100ml, ethanol: the volume ratio of water=1:1) dissolving, the template that 5h removes the surface is soaked in water-bath, it is yellow partially to soak the back solution colour, filter, washed with de-ionized water 2-3 time, vacuum drying obtain denitrating catalyst V8F.
Sample carries out nitrogen BET test, and specific area is 1250 ㎡/g, and pore size distribution mainly is present in the mesoporous stage.The present invention adopts the NO of 500ppm and the NH of 500ppm
3, 5% O
2, nitrogen is background gas, air speed 36000h
-1Carry out the denitration experiment, be up to 60% at 150 ℃ ~ 250 ℃ denitration efficiencies.Catalyst carrier and load active component catalyst S EM figure see Fig. 3.
Specific embodiment described in the present invention only is that the present invention's spirit is illustrated.The technical staff of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.More than active component precursor in each embodiment step 2 also can be cerous nitrate or ceric nitrate because concrete grammar is identical with effect, do not do tired stating at this paper.
Although the present invention has been made detailed explanation and has quoted some instantiations as proof, to those skilled in the art, only otherwise leave that the spirit and scope of the present invention can be done various variations or correction is obvious.
Claims (10)
1. ordered structure meso-porous carbon material denitrating catalyst, it is characterized in that: this activity of such catalysts component is the oxide of Ce or V, is the final carrier of active component with the meso-porous carbon material with ordered structure.
2. the preparation method of an ordered structure meso-porous carbon material denitrating catalyst as claimed in claim 1 is characterized in that: with organism F127(EO
106-PO
70-EO
106) mix with watery hydrochloric acid and to make its dissolving, add ethyl orthosilicate, active component precursor and phenolic resins precursor then successively, to stir, oven dry changes in the tube furnace and calcines under inert gas shielding, obtains catalyst; Described active component precursor is to contain the nitrate of Ce or the inorganic salts of V.
3. preparation method according to claim 2 is characterized in that: the preparation method of described phenolic resins precursor is as follows:
A. under 40 ~ 50 ℃ of water-baths, phenol is dissolved in the conical flask, adds the NaOH solution of 50wt% subsequently, stir 10min;
B. the formalin with 37wt% at the uniform velocity is added dropwise to above-mentioned solution, and 70 ℃ of stirring in water bath 1h are cooled to room temperature, and wherein the molal weight of phenol, NaOH, formaldehyde is than being 5:1:9 ~ 5:1:10;
C. the HCl solution of 1.5mol/L is dropwise added in the solution that the b step obtains, treat that the pH value just arrives at 7 o'clock, solution is transferred to vacuum drying chamber, manifest thickness until solution;
D. in solution, add small amount of ethanol, filter lower floor's white precipitate, filtrate is put into vacuum drying chamber once more, continue drying, obtain described phenolic resins precursor to remove ethanol.
4. preparation method according to claim 2 is characterized in that: described active component precursor is cerous nitrate or cerous nitrate, ceric nitrate or ammonium metavanadate.
5. according to claim 2 or 3 or 4 described preparation methods, it is characterized in that specifically comprising the steps:
A. F127 is dissolved in the ethanol, is stirred to the F127 solid and dissolves fully, add the hydrochloric acid solution of 0.2 ~ 0.5mol/L then, make solution become clarification by white, the water-bath heating continues to stir fully, obtains solution A;
B. the ethanolic solution that in solution A, adds ethyl orthosilicate (TEOS), active component precursor and phenolic resins precursor (PF) successively, make that the mass ratio of three kinds of compositions is F127:TEOS in the solution: the ethanolic solution=4:5:10 of phenolic resins precursor ~ 2:3:5, the amount of active component precursor is regulated according to concrete activity of such catalysts percentage composition, keep the water-bath heating, obtain mixture B after the stirring fully;
C. B is transferred in the culture dish, guarantee that active component is evenly distributed in the mixture B, room temperature is placed and is made the ethanol evaporation of fully volatilizing;
D. treat ethanol volatilization evaporation fully, B is put into baking oven more than 100 ℃ of freeze-day with constant temperature 24h;
E. more dried B is changed in the tube furnace and calcine, at N
2Protection is warming up to 850 ℃ of calcinings with 2 ℃/min from room temperature down, and keeps more than the 1h at 850 ℃;
F. the B after will calcining at last soaks with the dissolve with ethanol solution that contains NaOH, water-bath, filters, and washing, vacuum drying obtains catalyst.
6. preparation method according to claim 5 is characterized in that: the ethanolic solution of described phenolic resins precursor (PF) is the ethanolic solution that contains 25wt% phenolic resins precursor.
7. preparation method according to claim 5 is characterized in that: the water-bath heating process described in step a, the b is heated at constant temperature, and heating-up temperature is 40 ~ 50 ℃.
8. preparation method according to claim 5 is characterized in that: the mass ratio of active component precursor and phenolic resins precursor (PF) is followed Ce/PF=2%～8%, or V/PF=2%～8%.
9. preparation method according to claim 5 is characterized in that: the volume ratio of ethanol and water is 1:1 in the described ethanolic solution.
10. preparation method according to claim 5 is characterized in that: in the b step, F127:TEOS: the mass ratio of the ethanolic solution of phenolic resins precursor is 8:10.4:20.
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| CN102794165A (en) * | 2012-07-25 | 2012-11-28 | 大连交通大学 | Preparation method of carbon-supported vanadium oxide |
| CN105597777A (en) * | 2015-12-24 | 2016-05-25 | 浙江大学 | Ordered mesoporous carbon loading Cu-Mn bi-metal denitration catalyst and preparation method thereof |
| CN106861740A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | N doping is classified the preparation and its C catalyst and application of gold/mesoporous carbon catalyst in order |
| CN110013829A (en) * | 2019-01-21 | 2019-07-16 | 北京工业大学 | Order mesoporous CMK-3 load Ba/Rh or K/Mo adsorbent of a kind of cryogenic absorption NOx and preparation method thereof |
| CN110368923A (en) * | 2019-07-23 | 2019-10-25 | 龙净科杰环保技术（上海）有限公司 | A kind of mesoporous denitration of middle low temperature takes off dioxin catalyst and preparation method thereof |
| CN111330563A (en) * | 2020-03-25 | 2020-06-26 | 杭州楚环科技股份有限公司 | Ordered mesoporous carbon-titanium oxide composite material catalyst and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794165A (en) * | 2012-07-25 | 2012-11-28 | 大连交通大学 | Preparation method of carbon-supported vanadium oxide |
| CN106861740A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | N doping is classified the preparation and its C catalyst and application of gold/mesoporous carbon catalyst in order |
| CN106861740B (en) * | 2015-12-13 | 2019-05-28 | 中国科学院大连化学物理研究所 | N doping is orderly classified the preparation and its C catalyst and application of gold/mesoporous carbon catalyst |
| CN105597777A (en) * | 2015-12-24 | 2016-05-25 | 浙江大学 | Ordered mesoporous carbon loading Cu-Mn bi-metal denitration catalyst and preparation method thereof |
| CN110013829A (en) * | 2019-01-21 | 2019-07-16 | 北京工业大学 | Order mesoporous CMK-3 load Ba/Rh or K/Mo adsorbent of a kind of cryogenic absorption NOx and preparation method thereof |
| CN110013829B (en) * | 2019-01-21 | 2022-03-15 | 北京工业大学 | Low-temperature NOx adsorption ordered mesoporous CMK-3 loaded Ba/Rh or K/Mo adsorbent and preparation method thereof |
| CN110368923A (en) * | 2019-07-23 | 2019-10-25 | 龙净科杰环保技术（上海）有限公司 | A kind of mesoporous denitration of middle low temperature takes off dioxin catalyst and preparation method thereof |
| CN111330563A (en) * | 2020-03-25 | 2020-06-26 | 杭州楚环科技股份有限公司 | Ordered mesoporous carbon-titanium oxide composite material catalyst and preparation method thereof |
| CN111330563B (en) * | 2020-03-25 | 2022-12-06 | 杭州楚环科技股份有限公司 | Ordered mesoporous carbon-titanium oxide composite material catalyst and preparation method thereof |
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