CN113289598A - FePO4-SiO2Preparation method of aerogel catalyst material - Google Patents
FePO4-SiO2Preparation method of aerogel catalyst material Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 126
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 34
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 34
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 43
- 239000011259 mixed solution Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 17
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000006073 displacement reaction Methods 0.000 claims description 7
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002131 composite material Substances 0.000 abstract description 9
- 229910000399 iron(III) phosphate Inorganic materials 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000000352 supercritical drying Methods 0.000 abstract description 3
- 239000004965 Silica aerogel Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to FePO4‑SiO2Method for preparing aerogel catalyst material using SiO2Aerogel as matrix, FePO4Uniformly loading the particles in silica aerogel cavities, and performing sol-gel process and impregnation method to obtain FePO by ethanol supercritical drying4With SiO2Aerogel composite to prepare FePO with high specific surface area and excellent catalytic performance4‑SiO2An aerogel. Wherein, FePO4Providing catalytic activity for the composite material and being loaded on SiO2Promotion of methane conversion on aerogels, SiO2The aerogel provides a high specific surface area for the composite material and avoids FePO to a certain extent4The aggregation of the active substance allows the active component to more fully contact the reactants. The catalyst material can effectively overcome the defects of single-component materials, thereby greatly improving the catalytic efficiency and the selectivity of target products. Prepared FePO4‑SiO2The specific surface area of the aerogel catalyst material is 282.7-476.8 g/cm370ml/min of CH at a temperature of 200-650 DEG C4/O2Under the mixed flow rate of 32/4.3/63.7/He, the conversion rate of methane reaches 2.63-3.59%, and the selectivity of formaldehyde reaches 19.7-29.8%.
Description
Technical Field
The invention belongs to the field of preparation technology of nano porous materials, and relates to FePO with low density, high specific surface area and catalytic activity4-SiO2A method for preparing aerogel catalyst material.
Background
Methane is the main component of natural gas, and in the face of the increasing depletion of petroleum resources, it is a great challenge to research how to efficiently convert methane into liquid fuel which is easier to store and transport and is also cleaner. Silicon oxide (SiO)2) Aerogel materials are the least dense man-made materials known in the world, and are known as "solid smoke". In addition to very low density, aerogels have high porosity, very low thermal conductivity and large specific surface area, which makes SiO possible2Aerogels have a wide range of applications in a wide variety of fields, such as thermal insulation materials, sound insulation materials, optical devices, supercapacitors, and the like. Iron phosphate (FePO)4) Catalyst in CH4Or C2H6And O2-H2Or N2The oxidation process of O can show high selectivity to the target product oxygen-containing compound. While using O alone2In FePO4On catalyst with CH4And O2During the partial oxidation, there is also the possibility of selective conversion to formaldehyde. Thus FePO4Has attracted attention in the field of catalytic oxidation of methane.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide FePO4-SiO2A method for preparing aerogel catalyst material.
The technical scheme of the invention is as follows: using SiO2Aerogel as matrix, FePO4The particles are uniformly loaded in the silica aerogel hollow space and are based on SiO2Aerogel high porosity, large specific surface area and FePO4The advantages in the field of methane catalysis are that FePO is prepared by a sol-gel process and an impregnation method and by adopting an ethanol supercritical drying technology4With SiO2Aerogel composite to prepare FePO with high specific surface area and excellent catalytic performance4-SiO2An aerogel. Wherein, FePO4Providing catalytic activity for the composite material and being loaded on SiO2Promotion of methane conversion on aerogels, SiO2The aerogel provides a high specific surface area for the composite material and avoids FePO to a certain extent4The aggregation of the active substance allows the active component to more fully contact the reactants. The catalyst material can effectively overcome the defects of single-component materials, thereby greatly improving the catalytic efficiency and the selectivity of target products.
The specific technical scheme of the invention is as follows: FePO4-SiO2The preparation method of the aerogel catalyst material comprises the following specific steps:
(1) dissolving tetraethyl orthosilicate in ethanol during stirring, and uniformly stirring at room temperature to obtain a uniform mixed solution A;
(2) dissolving ammonium fluoride and ammonia water in a mixed solution of deionized water and ethanol, and uniformly stirring at room temperature to obtain a mixed solution B;
(3) slowly dripping the solution B in the step (2) into the solution A in the step (1), stirring at room temperature until the mixed solution becomes transparent sol, continuously stirring for a period of time, and pouring the sol into a mold until the sol is gelled;
(4) adding ethanol solvent into the gel to perform gel aging and solvent replacement, and replacing deionized water at intervals to perform solvent replacement;
(5) dissolving ferric nitrate nonahydrate and ammonium dihydrogen phosphate in ethanol according to a certain molar ratio, and stirring at room temperature for a period of time to obtain a mixed salt solution;
(6) taking out the gel from the displacement solvent, placing the gel in a mixed salt solution, completely soaking the gel in the mixed salt solution at room temperature for a period of time, taking out the gel from the mixed salt solution, and placing the gel in an ethanol solution for cleaning;
(7) putting the cleaned gel into a supercritical reaction kettle, drying with ethanol as a drying medium and nitrogen as an atmosphere at a certain temperature and pressure, maintaining at a constant temperature and pressure for a period of time, discharging gas, and cooling to obtain FePO4-SiO2An aerogel catalyst material.
Preferably, the volume ratio of the tetraethyl orthosilicate to the ethanol in the step (1) is 2.5-0.8.
Preferably, the concentration of the ammonium fluoride in the step (2) is 0.1-0.8 mol/L; the volume of ammonium fluoride in the mixed solution B is 0.5-2%, the volume of ammonia water is 0.1-0.5%, the volume of deionized water is 40-80%, and the volume of ethanol is 17.9-59%.
Preferably, the volume ratio of the solution A to the mixed solution of the solution A and the solution B in the step (3) is 0.4-0.8; the continuous stirring time is 10-50 min.
Preferably, in the step (4), the solvent replacement interval time is 4-12 h, and the replacement times are 3-9.
Preferably, the molar ratio of Fe to P of the ferric nitrate nonahydrate and the ammonium dihydrogen phosphate in the step (5) is 0.5-3; the volume ratio of the mixed salt in the mixed salt solution is 3-12%; the stirring time is 10-50 min.
Preferably, the complete immersion time in the step (6) is 12-48 h.
Preferably, in the step (7), the drying temperature is 250-290 ℃, the drying pressure is 8-12 MPa, and the maintaining time is 2-4 hours.
Prepared FePO4-SiO2The specific surface area of the aerogel catalyst material is 282.7-476.8 g/cm370ml/min of CH at a temperature of 200-650 DEG C4/O2Under the mixing flow rate of 32/4.3/63.7 (volume ratio) of/He, the methane conversion rate reaches 2.63-3.59%, and the formaldehyde selectivity reaches 19.7-29.8%.
Has the advantages that:
(1) FePO is prepared by sol-gel process, soaking method, and ethanol supercritical drying technology4With SiO2Aerogel composite to prepare FePO with high specific surface area, excellent catalytic performance and excellent selectivity4-SiO2An aerogel catalyst material.
(2) Wherein, FePO4Providing catalytic activity for the composite material and being loaded on SiO2The conversion of methane is promoted on the aerogel.
(3)SiO2The aerogel provides a high specific surface area for the composite material and avoids FePO to a certain extent4The aggregation of the active substance allows the active component to more fully contact the reactants.
(4) The catalyst material can effectively overcome the defects of single-component materials, thereby greatly improving the catalytic efficiency and the selectivity of target products.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of protection.
Example 1
Tetraethyl orthosilicate is dissolved in ethanol in the stirring process, wherein the volume ratio of the tetraethyl orthosilicate to the ethanol is 2.5, and the tetraethyl orthosilicate and the ethanol are uniformly stirred at room temperature to obtain a uniform mixed solution A. Dissolving 0.1mol/L ammonium fluoride and ammonia water in a mixed solution of deionized water and ethanol, wherein the addition amount of the ammonium fluoride is 2%, the addition amount of the concentrated ammonia water is 0.1%, the addition amount of the deionized water is 80%, and the addition amount of the ethanol is 17.9%, and uniformly stirring at room temperature to obtain a mixed solution B. Slowly dripping the solution B into the solution A, wherein the volume ratio of the solution A to the mixed solution AB is 0.8, stirring at room temperature until the mixed solution becomes transparent sol, continuously stirring for 10min, and pouring the sol into a mold until gelation; adding ethanol solvent into the gel for gel aging and solvent replacement, and replacing deionized water every 4h for solvent replacement for 9 times; mixing the nine water nitreDissolving ferric salt and ammonium dihydrogen phosphate in ethanol at a molar ratio of 0.5:1, wherein the volume ratio of the salt is 3%, and stirring at room temperature for 50min to obtain mixed salt solution; taking out the gel from the displacement solvent, placing the gel in a mixed salt solution, completely soaking the gel for 12 hours at room temperature, taking out the gel from the mixed salt solution, and placing the gel in an ethanol solution for cleaning; putting the cleaned gel into a supercritical reaction kettle, drying at 250 deg.C under 12MPa with ethanol as drying medium and nitrogen as atmosphere, maintaining at constant temperature and constant pressure for 4 hr, and cooling to room temperature to obtain FePO4-SiO2An aerogel catalyst material. Prepared FePO4-SiO2The specific surface area of the aerogel catalyst material is 282.7g/cm370ml/min CH4/O2At a mixed flow rate of 32/4.3/63.7 (volume ratio)/He, the methane conversion rate reaches 2.63% at 450 ℃, and the formaldehyde selectivity reaches 29.8%.
Example 2
Tetraethyl orthosilicate is dissolved in ethanol in the stirring process, wherein the volume ratio of the tetraethyl orthosilicate to the ethanol is 2.1, and the tetraethyl orthosilicate and the ethanol are uniformly stirred at room temperature to obtain a uniform mixed solution A. Dissolving 0.3mol/L ammonium fluoride and ammonia water in a mixed solution of deionized water and ethanol, wherein the addition amount of the ammonium fluoride is 1.6%, the addition amount of concentrated ammonia water is 0.2%, the addition amount of the deionized water is 70%, and the addition amount of the ethanol is 28.2%, and uniformly stirring at room temperature to obtain a mixed solution B. Slowly dripping the solution B into the solution A, wherein the volume ratio of the solution A to the mixed solution AB is 0.7, stirring at room temperature until the mixed solution becomes transparent sol, continuously stirring for 20min, and pouring the sol into a mold until gelation; adding ethanol solvent into the gel for gel aging and solvent replacement, and replacing deionized water every 6h for solvent replacement for 8 times; mixing ferric nitrate nonahydrate and ammonium dihydrogen phosphate in a ratio of 1: dissolving 1mol ratio of salt in ethanol, wherein the volume ratio of the salt is 6%, and stirring at room temperature for 40min to obtain a mixed salt solution; taking out the gel from the displacement solvent, placing the gel in a mixed salt solution, completely soaking the gel for 18 hours at room temperature, taking out the gel from the mixed salt solution, and placing the gel in an ethanol solution for cleaning; will clear awayPutting the washed gel into a supercritical reaction kettle, drying at 260 deg.C under 11MPa with ethanol as drying medium and nitrogen as atmosphere, maintaining at constant temperature and constant pressure for 3.5 hr, and cooling to room temperature to obtain FePO4-SiO2An aerogel catalyst material. Prepared FePO4-SiO2The specific surface area of the aerogel catalyst material is 312.7g/cm370ml/min CH4/O2Under the mixed flow rate of 32/4.3/63.7 (volume ratio) of/He, the methane conversion rate reaches 2.89% at 470 ℃, and the formaldehyde selectivity reaches 28.9%.
Example 3
Tetraethyl orthosilicate is dissolved in ethanol in the stirring process, wherein the volume ratio of the tetraethyl orthosilicate to the ethanol is 1.6, and the tetraethyl orthosilicate and the ethanol are uniformly stirred at room temperature to obtain a uniform mixed solution A. Dissolving 0.5mol/L ammonium fluoride and ammonia water in a mixed solution of deionized water and ethanol, wherein the addition amount of the ammonium fluoride is 1.2%, the addition amount of concentrated ammonia water is 0.3%, the addition amount of the deionized water is 60%, the addition amount of the ethanol is 38.7%, and uniformly stirring at room temperature to obtain a mixed solution B. Slowly dripping the solution B into the solution A, wherein the volume ratio of the solution A to the mixed solution AB is 0.6, stirring at room temperature until the mixed solution becomes transparent sol, continuously stirring for 30min, and pouring the sol into a mold until the sol is gelled; adding ethanol solvent into the gel for gel aging and solvent replacement, and replacing deionized water once every 8h for solvent replacement for 6 times; iron nitrate nonahydrate and ammonium dihydrogen phosphate were mixed at a ratio of 1.5: dissolving 1mol ratio of salt in ethanol, wherein the volume ratio of the salt is 8%, and stirring at room temperature for 30min to obtain a mixed salt solution; taking out the gel from the displacement solvent, placing the gel in a mixed salt solution, completely soaking the gel for 24 hours at room temperature, taking out the gel from the mixed salt solution, and placing the gel in an ethanol solution for cleaning; putting the cleaned gel into a supercritical reaction kettle, drying at 270 deg.C under 10MPa with ethanol as drying medium and nitrogen as atmosphere, maintaining at constant temperature and constant pressure for 3 hr, and cooling to room temperature to obtain FePO4-SiO2An aerogel catalyst material. Prepared FePO4-SiO2The specific surface area of the aerogel catalyst material is 374.7g/cm370ml/min CH4/O2Under the mixed flow rate of 32/4.3/63.7 (volume ratio) of/He, the methane conversion rate reaches 3.12% at 465 ℃, and the formaldehyde selectivity reaches 26.1%.
Example 4
Tetraethyl orthosilicate is dissolved in ethanol in the stirring process, wherein the volume ratio of the tetraethyl orthosilicate to the ethanol is 1.2, and the tetraethyl orthosilicate and the ethanol are uniformly stirred at room temperature to obtain a uniform mixed solution A. Dissolving 0.7mol/L ammonium fluoride and ammonia water in a mixed solution of deionized water and ethanol, wherein the addition amount of the ammonium fluoride is 0.8%, the addition amount of concentrated ammonia water is 0.4%, the addition amount of the deionized water is 50%, the addition amount of the ethanol is 48.8%, and uniformly stirring at room temperature to obtain a mixed solution B. Slowly dripping the solution B into the solution A, wherein the volume ratio of the solution A to the mixed solution AB is 0.5, stirring at room temperature until the mixed solution becomes transparent sol, continuously stirring for 40min, and pouring the sol into a mold until the sol is gelled; adding ethanol solvent into the gel for gel aging and solvent replacement, and replacing deionized water every 10h for solvent replacement for 4 times; mixing ferric nitrate nonahydrate and ammonium dihydrogen phosphate in a ratio of 2: dissolving 1mol ratio of salt in ethanol, wherein the salt accounts for 10% by volume, and stirring at room temperature for 20min to obtain a mixed salt solution; taking out the gel from the displacement solvent, placing the gel in a mixed salt solution, completely soaking the gel for 36 hours at room temperature, taking out the gel from the mixed salt solution, and placing the gel in an ethanol solution for cleaning; putting the cleaned gel into a supercritical reaction kettle, drying at 280 deg.C under 9MPa with ethanol as drying medium and nitrogen as atmosphere, maintaining at constant temperature and constant pressure for 2.5 hr, and cooling to room temperature to obtain FePO4-SiO2An aerogel catalyst material. Prepared FePO4-SiO2The specific surface area of the aerogel catalyst material is 426.8g/cm370ml/min CH4/O2At a mixed flow rate of 32/4.3/63.7 (volume ratio)/He, the methane conversion rate reaches 3.44% and the formaldehyde selectivity reaches 23.7% at 475 ℃.
Example 5
Stirring tetraethyl orthosilicateDissolving in ethanol during stirring, wherein the volume ratio of tetraethyl orthosilicate to ethanol is 0.8, and uniformly stirring at room temperature to obtain a uniform mixed solution A. Dissolving 0.8mol/L ammonium fluoride and ammonia water in a mixed solution of deionized water and ethanol, wherein the addition amount of the ammonium fluoride is 0.5%, the addition amount of concentrated ammonia water is 0.5%, the addition amount of the deionized water is 40%, the addition amount of the ethanol is 59%, and uniformly stirring at room temperature to obtain a mixed solution B. Slowly dripping the solution B into the solution A, wherein the volume ratio of the solution A to the mixed solution AB is 0.4, stirring at room temperature until the mixed solution becomes transparent sol, continuously stirring for 50min, and pouring the sol into a mold until gelation; adding ethanol solvent into the gel for gel aging and solvent replacement, and replacing deionized water once every 12h for solvent replacement for 3 times; mixing ferric nitrate nonahydrate and ammonium dihydrogen phosphate in a ratio of 3: dissolving 1mol ratio of salt in ethanol, wherein the volume ratio of the salt is 12%, and stirring at room temperature for 10min to obtain a mixed salt solution; taking out the gel from the displacement solvent, placing the gel in a mixed salt solution, completely soaking the gel for 48 hours at room temperature, taking out the gel from the mixed salt solution, and placing the gel in an ethanol solution for cleaning; putting the cleaned gel into a supercritical reaction kettle, drying at 290 deg.C under 8MPa with ethanol as drying medium and nitrogen as atmosphere, maintaining at constant temperature and constant pressure for 2 hr, and cooling to room temperature to obtain FePO4-SiO2An aerogel catalyst material. Prepared FePO4-SiO2The aerogel catalyst material had a specific surface area of 476.8g/cm370ml/min CH4/O2At a mixed flow rate of 32/4.3/63.7 (volume ratio)/He, the methane conversion rate reaches 3.59% and the formaldehyde selectivity reaches 19.7% at 480 ℃.
Claims (8)
1. FePO4-SiO2The preparation method of the aerogel catalyst material comprises the following specific steps:
(1) dissolving tetraethyl orthosilicate in ethanol during stirring, and uniformly stirring to obtain a uniform mixed solution A;
(2) dissolving ammonium fluoride and ammonia water in a mixed solution of deionized water and ethanol, and uniformly stirring to obtain a mixed solution B;
(3) slowly dripping the solution B in the step (2) into the solution A in the step (1), stirring until the mixed solution becomes transparent sol, continuously stirring for a period of time, and pouring the sol into a mold until the sol is gelled;
(4) adding ethanol solvent into the gel to perform gel aging and solvent replacement, and replacing deionized water at intervals to perform solvent replacement;
(5) dissolving ferric nitrate nonahydrate and ammonium dihydrogen phosphate in ethanol according to a certain molar ratio, and stirring for a period of time to obtain a mixed salt solution;
(6) taking out the gel from the displacement solvent, placing the gel in a mixed salt solution, completely soaking for a period of time, taking out the gel from the mixed salt solution, and placing the gel in an ethanol solution for cleaning;
(7) putting the cleaned gel into a supercritical reaction kettle, drying with ethanol as a drying medium and nitrogen as an atmosphere at a certain temperature and pressure, maintaining at a constant temperature and pressure for a period of time, discharging gas, and cooling to obtain FePO4-SiO2An aerogel catalyst material.
2. The method according to claim 1, wherein the volume ratio of tetraethyl orthosilicate to ethanol in step (1) is 2.5 to 0.8.
3. The method according to claim 1, wherein the concentration of ammonium fluoride in the step (2) is 0.1 to 0.8 mol/L; the volume of ammonium fluoride in the mixed solution B is 0.5-2%, the volume of ammonia water is 0.1-0.5%, the volume of deionized water is 40-80%, and the volume of ethanol is 17.9-59%.
4. The preparation method according to claim 1, wherein the volume ratio of the solution A to the mixed solution of the solution A and the solution B in the step (3) is 0.4 to 0.8; the continuous stirring time is 10-50 min.
5. The method according to claim 1, wherein the solvent replacement in step (4) is carried out for 4 to 12 hours and the number of replacements is 3 to 9.
6. The method according to claim 1, wherein the molar ratio of Fe to P of the ferric nitrate nonahydrate and the ammonium dihydrogen phosphate in the step (5) is 0.5 to 3; the volume ratio of the mixed salt in the mixed salt solution is 3-12%; the stirring time is 10-50 min.
7. The method according to claim 1, wherein the time for the complete impregnation in the step (6) is 12 to 48 hours.
8. The method according to claim 1, wherein the drying temperature in the step (7) is 250 to 290 ℃, the drying pressure is 8 to 12MPa, and the holding time is 2 to 4 hours.
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| CN115624988B (en) * | 2022-10-25 | 2024-03-26 | 贵州大学 | Organic iron-SiO 2 Aerogel-like catalyst and preparation method thereof |
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