CN114534797B - Continuous flow purification and separation method of nanofiber supported catalyst - Google Patents
Continuous flow purification and separation method of nanofiber supported catalyst Download PDFInfo
- Publication number
- CN114534797B CN114534797B CN202210230936.8A CN202210230936A CN114534797B CN 114534797 B CN114534797 B CN 114534797B CN 202210230936 A CN202210230936 A CN 202210230936A CN 114534797 B CN114534797 B CN 114534797B
- Authority
- CN
- China
- Prior art keywords
- nanofiber
- supported catalyst
- continuous flow
- metal
- cellulose ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002121 nanofiber Substances 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000000926 separation method Methods 0.000 title claims abstract description 40
- 238000000746 purification Methods 0.000 title claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 42
- 239000012528 membrane Substances 0.000 claims abstract description 36
- 229920002678 cellulose Polymers 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000011068 loading method Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 13
- 239000002082 metal nanoparticle Substances 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000006250 one-dimensional material Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000003917 TEM image Methods 0.000 description 12
- 229910018575 Al—Ti Inorganic materials 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000010041 electrostatic spinning Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000520 microinjection Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
Classifications
-
- 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
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Water Supply & Treatment (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a continuous flow purification and separation method of a nanofiber supported catalyst, which specifically comprises the following steps: (1) mixing and stirring the nanofiber and the metal to carry out loading; (2) filtering the loaded mixed solution by sucking the loaded mixed solution into a syringe; (3) And collecting solids remained on the mixed cellulose ester membrane after the filtration is completed, thus obtaining the separated nanofiber supported catalyst. The method can perform solid-liquid separation, and can obtain nanofiber supported catalyst with good separation effect, and meanwhile, the complexity of the operation in the preparation process is reduced, and the experimental efficiency is remarkably improved; the filter membrane with proper aperture is selected for filtering the nanofiber, so that the operation time is reduced, the catalyst yield is obviously improved, the problem that the catalyst is easy to agglomerate is solved, and the integral forming of the nanofiber supported catalyst filter cake is realized.
Description
Technical Field
The invention belongs to catalyst separation and purification, and in particular relates to a continuous flow purification and separation method of a nanofiber supported catalyst.
Background
The metal/nanofiber catalyst prepared by taking the nanofiber as a carrier and carrying out metal nanoparticle loading has a series of excellent characteristics and catalytic performance, and is an important research direction in the field of catalysts. In the prior art, after metal is loaded on the nanofiber, for removing metal nano particles which cannot be loaded, a solvent washing and centrifuging method is generally adopted, and the method is complicated in operation process, long in time consumption, high in energy consumption, low in yield, easy to cause agglomeration and unfavorable for efficient development of experiments. The labor required in the experimental process is more, which is a hindrance to realizing industrialization. Meanwhile, the prior art has more solvent consumption and more types in the separation process, and the required centrifuge has higher energy consumption, which is not beneficial to green production and environmental protection. Therefore, development of a purification and separation method which is simple and convenient to operate and can effectively improve experimental efficiency is urgently needed.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a continuous flow purification and separation method of a nanofiber supported catalyst, which is simple to operate, short in time consumption and high in yield.
A second object of the present invention is to provide an integrally formed nanofiber supported catalyst obtained by a continuous flow purification and separation method of nanofiber supported catalyst.
The third object of the invention is to provide the application of the continuous flow purification and separation method of the nanofiber supported catalyst in the nano synthesis with a one-dimensional material as a framework.
The technical scheme is as follows: in order to achieve the above purpose, the continuous flow purification and separation method of the nanofiber supported catalyst comprises the following specific steps:
(1) Mixing and stirring the nanofiber and metal in a solvent at room temperature, and loading;
(2) Sucking the loaded mixed solution into a syringe for filtering;
(3) And collecting solids remained on the mixed cellulose ester membrane after the filtration is completed, thus obtaining the separated nanofiber supported catalyst.
Wherein the metal in step (1) may be one or more of Au, ag, pt, pd; the metal nanoparticle diameter is less than the nanofiber diameter.
Preferably, the metal in step (1) is Pt.
Wherein the nanofiber in the step (1) is TiO 2 Nanofibers, al 2 O 3 Nanofiber, al-Ti composite nanofiber or CeO 2 A nanofiber.
Wherein the mixing and stirring time in the step (1) is 1-3 hours.
Preferably, the stirring time in step (1) is 2 hours.
Preferably, a filter head is connected below the injector in the step (2), and the filter head is internally provided with a mixed cellulose ester film.
Preferably, the filtration described in step (3) is performed using a continuous flow device at a flow rate of 1-3 mL/min.
Wherein the mixed cellulose ester membrane has a pore size of 0.20-0.50 μm, and the mixed cellulose ester membrane has a pore size between the diameter of the metal nanoparticle and the diameter of the nanofiber.
The invention provides a nanofiber supported catalyst which is integrally formed into a filter cake and is obtained by a continuous flow purification and separation method of a nanofiber supported catalyst.
The invention also provides an application of the continuous flow purification and separation method of the nanofiber supported catalyst in nano synthesis with a one-dimensional material as a framework.
The mechanism of the invention is as follows: according to the invention, the matching degree of the nanofiber size, the metal nanoparticle diameter and the mixed cellulose ester membrane pore diameter is taken as a design idea, a filtering separation principle is adopted, and the mixed cellulose ester membrane with the pore diameter between the metal nanoparticle diameter and the nanofiber diameter size is selected, so that the mixed cellulose ester membrane can be penetrated with liquid during filtering because the nanoparticle diameter is smaller than the mixed cellulose ester membrane pore diameter, the diameter size of the nanofiber is larger than the mixed cellulose ester membrane pore diameter, and the nanofiber can not be penetrated and stays on the mixed cellulose ester membrane during filtering, so that the metal nanoparticle which is not loaded on the fiber can be removed, and the separation and purification of the supported nanofiber catalyst are realized. Based on the size matching principle, the technology can be applied to the nano synthesis process with various one-dimensional materials as frameworks, and compared with the centrifugation process, the technology is simple and convenient to operate, reduces manpower, has high efficiency and low energy consumption, and is beneficial to the industrialized process.
The beneficial effects are that: compared with the prior art, the method has the following advantages:
(1) The invention adopts a washing and filtering method to carry out solid-liquid separation, reduces the operational complexity of the preparation process while obtaining the nanofiber supported catalyst with better separation effect, obviously improves the experimental efficiency, and only takes ten minutes when the centrifugal washing process is carried out for a certain amount of the same separation tasks, and the required time is about one tenth of that of the centrifugal method when the filtering and separation are adopted;
(2) According to the continuous flow separation method for the nanofiber supported catalyst, the mixed cellulose ester membrane with the aperture is selected for filtering the nanofiber precipitate, so that the operation time is shortened, the catalyst yield is obviously improved, and meanwhile, the problem that the catalyst is easy to agglomerate is solved;
(3) The invention realizes the integral molding of the nanofiber supported catalyst filter cake, and the catalyst obtained by centrifugation is dispersed powder or particle block, so that the invention is more convenient for the subsequent catalysis experiment to be directly carried out.
Drawings
FIG. 1 is a diagram of a continuous filtration apparatus of the present invention;
FIG. 2 is a diagram of the structure of a filter needle of the present invention;
FIG. 3 is a physical diagram of a filter cake after filtration according to the present invention, A is a Pt/Al-Ti composite fiber filter cake, B is Pt/CeO 2 A filter cake;
FIG. 4 is a diagram of a TiO according to the invention 2 A nanofiber TEM image;
FIG. 5 is a diagram of a TiO according to the invention 2 TEM image of nanofiber-supported Pt catalyst;
FIG. 6 is a view of the Al of the present invention 2 O 3 TEM image of nanofiber-supported Pt catalyst;
FIG. 7 is a TEM image of an Al-Ti composite nanofiber supported Pt catalyst of the present invention (titanium to aluminum molar ratio of 15:1);
FIG. 8 shows CeO according to the present invention 2 TEM image of nanofiber supported Pt catalyst.
Detailed Description
The invention is further described below with reference to the drawings and examples.
In the examples, PVP is polyvinylpyrrolidone, TTIP is tetraisopropyl titanate, and Al (acac) 3 Aluminum acetylacetonate, ce (acac) 3 Is cerium acetylacetonate. Mixed cellulose ester membranes of different pore sizes were purchased from Shanghai peninsula industries, inc. purification equipment.
Example 1
Separation of TiO by washing and filtering 2 Nanofiber-supported Pt catalyst
(1) Dissolving 0.3g PVP (molecular weight: 55000) in 4.5mL ethanol, stirring overnight, adding 3mL acetic acid and 2.5mL TTIP, stirring to obtain clear precursor solution, transferring to a syringe equipped with a metal needle, electrostatic spinning under the conditions of voltage of 17.5kV, distance between the metal needle and a wire collector of 12.5cm and flow rate of 0.5mL/h, heating the obtained nanofiber to 700 ℃ at a speed of 2.8 ℃/min in air, and roasting for 2h to obtain TiO 2 A nanofiber.
(2) Preheating 4mL of ethylene glycol in an oil bath at 110 ℃ for 30min; 22.5mg PVP (molecular weight 55000) was then dissolved in 2mL of ethylene glycol at room temperature to give solution A; re-formulation of 8.25mg/mL H 2 PtCl 6 Is liquid B. Then takeA. And (3) simultaneously injecting 0.5mL of each solution B into the preheated glycol, and continuously reacting for about 1h at the temperature of 110 ℃ in an oil bath to obtain Pt suspension.
(3) Weigh 5mg TiO 2 The nanofibers were dispersed in 1.8mL of purified water, and then 0.2mL of Pt suspension (0.392 mg/mL) was added dropwise to form TiO with a concentration of 0.0025g/mL 2 Nanofiber solution, tiO by mixing and stirring 2 The nanofiber and the metal Pt are loaded, and the mixture is mixed and stirred for 2 hours at normal temperature to finish loading.
(4) As shown in FIG. 1, the solution (0.0025 g/mL,2 mL) after the stirring and loading was sucked into a syringe, the syringe was fixed on a microinjection pump (Shenzhen Ruiword life technologies Co., ltd.) and the flow rate was set, a filter head was connected below the syringe, and a mixed cellulose ester membrane having a pore size of 0.45 μm was filled into the filter head. As shown in FIG. 2, the filter head can be unscrewed to fill the mixed cellulose ester membrane.
(5) And filtering the loaded mixed solution at a flow rate of 3mL/min by utilizing a microinjection pump in a continuous filtering device, and collecting solids remained on the mixed cellulose ester membrane after the filtration is completed to obtain the nanofiber supported catalyst which is completely separated and becomes a filter cake. The diameter of the Pt nano-particles is about 3nm, the diameter of the nano-fibers is about 0.1-0.3 μm, the length of the nano-fibers is about 0.5-2 μm, and the pore diameter of the mixed cellulose ester membrane is 0.45 μm, so that the separation of the unsupported Pt nano-particles and the nano-fibers can be realized.
(6) Observation of the electrospun raw, unsupported TiO using a transmission electron microscope 2 Nanofiber sample, obtaining TiO as shown in FIG. 4 2 A nanofiber TEM image. TiO after loading metal Pt is observed by adopting a transmission electron microscope 2 Sample of nanofiber supported catalyst to obtain TiO as shown in FIG. 5 2 TEM image of nanofiber supported Pt catalyst. And the TiO of FIG. 4 without metal 2 The comparison of nanofibers can show that the Pt nanoparticles in FIG. 5 are successfully loaded on the surface of the fibers, and the back area outside the fibers is clean and free of residual Pt nanoparticles, thus proving that the separation and purification technology is effective.
Example 2
Separating Al by washing and filtering 2 O 3 Nanofiber-supported Pt catalyst
(1) 0.3g PVP (molecular weight 55000) was dissolved in 2mL ethanol, stirred overnight, and 0.3g Al (acac) was added 3 And 3mL of acetone, stirring until the solution is a clear precursor solution, transferring the solution into a syringe provided with a metal head, carrying out electrostatic spinning under the conditions that the voltage is 16.5kV, the distance between the metal needle and a wire collector is 12cm, the flow rate is 0.3mL/h, heating the prepared nanofiber to 900 ℃ at a speed of 2.8 ℃/min in air, and roasting for 2h to obtain Al 2 O 3 A nanofiber.
(2) Pt suspension was prepared by the method of example 1.
(3) Weigh 5mg Al 2 O 3 Dispersing the nanofiber in 1.8mL of pure water, and dropwise adding 0.2mL of Pt (0.392 mg/mL) to form Al with a concentration of 0.0025g/mL 2 O 3 Nanofiber solution, al was mixed and stirred 2 O 3 The nanofiber and the metal Pt are loaded, and the mixture is mixed and stirred for 2 hours at normal temperature to finish loading.
(4) A continuous flow filtration apparatus as described in example 1 was constructed, and the solution (0.0025 g/mL,2 mL) after the stirring and loading was sucked into a syringe, a filter head was connected below the syringe, and a mixed cellulose ester membrane having a pore size of 0.22 μm was filled in the filter head.
(5) And filtering the loaded mixed solution at a flow rate of 1mL/min by utilizing a microinjection pump in a continuous filtering device, and collecting solids remained on the mixed cellulose ester membrane after the filtration is completed to obtain the separated nanofiber supported catalyst. The diameter of the Pt nano-particles is about 3nm, the diameter of the nano-fibers is about 0.1-0.3 μm, the length of the nano-fibers is about 0.5-2 μm, and the pore diameter of the mixed cellulose ester membrane is 0.22 μm, so that the separation of the unsupported Pt nano-particles and the nano-fibers can be realized.
(6) Observing the obtained Al by using a transmission electron microscope 2 O 3 A sample of the nanofiber-supported catalyst gave Al as shown in FIG. 6 2 O 3 TEM image of nanofiber supported Pt catalyst, compared to TiO with no supported metal in FIG. 4 2 Compared with the nanofiber, the Pt nano particles can be successfully loaded on the surface of the fiber, the back bottom area outside the fiber is clean, and no residual Pt nano particles exist, so that the separation and purification technology is proved to be effective.
Example 3
Separating Al-Ti composite nano fiber supported Pt catalyst by adopting washing filtration method
(1) 0.6g PVP (molecular weight 55000) was dissolved in ethanol, stirred overnight, and then a certain amount of Al (acac) was added 3 And 5mL of acetone, uniformly stirring, adding 3mL of acetic acid and 2.5mL of TTIP, stirring until the mixture is clarified, transferring the spinning solution into an injector provided with a metal head, carrying out electrostatic spinning under the conditions that the voltage is 18.5kV, the distance between the metal needle and a wire collector is 12.5cm and the flow rate is 0.3mL/h, heating the obtained nanofiber to 600 ℃ in air at the speed of 2.0 ℃/min, and roasting for 2h to obtain the Al-Ti composite nanofiber. By adjusting Al (acac) 3 The amount of (C) was 0.74g to control the molar ratio of titanium to aluminum to 15:1.
(2) Pt suspension was prepared by the method of example 1.
(3) 5mg of Al-Ti composite nanofiber is weighed and dispersed in 1.8mL of pure water, then 0.2mL of Pt (0.392 mg/mL) is added dropwise to form an Al-Ti composite nanofiber solution with the concentration of 0.0025g/mL, the Al-Ti composite nanofiber and the metal Pt are loaded through mixing and stirring, and the loading is completed after mixing and stirring for 2 hours at normal temperature.
(4) A continuous flow filtration apparatus as described in example 1 was constructed, and the solution (0.0025 g/mL,2 mL) after the stirring and loading was sucked into a syringe, a filter head was connected below the syringe, and a mixed cellulose ester membrane having a pore size of 0.22 μm was filled in the filter head.
(5) And (3) filtering the loaded mixed solution at a flow rate of 2mL/min by using a continuous flow device, and collecting solids remained on a filter membrane after the filtration is completed to obtain the separated nanofiber supported catalyst, wherein a filter cake after the filtration is shown in fig. 3 (A). The diameter of the Pt nano-particles is about 3nm, the diameter of the nano-fibers is about 0.1-0.3 μm, the length is about 0.5-2 μm, and the pore diameter of the mixed cellulose ester membrane is 0.22 μm, so that the separation of the unsupported Pt nano-particles and the nano-fibers can be realized theoretically.
(6) The obtained Al-Ti composite nanofiber supported catalyst sample is observed by a transmission electron microscope to obtain a TEM image of the Al-Ti composite nanofiber supported Pt catalyst shown in figure 7, and the TEM image of the Al-Ti composite nanofiber supported Pt catalyst is compared with TiO of figure 4 which is not supported with metal 2 Compared with the nanofiber, the Pt nano particles can be successfully loaded on the surface of the Al-Ti composite nanofiber, the back area except the fiber is clean, and no residual Pt nano particles exist, so that the separation and purification technology is proved to be effective.
Example 4
CeO separation by washing and filtering 2 Nanofiber-supported Pt catalyst
(1) 0.6g PVP (molecular weight 55000) was dissolved in 3mL ethanol, stirred overnight, and 0.3g Ce (acac) was added 3 And 3mL of acetone, stirring until the solution is a clear precursor solution, transferring the solution into a syringe provided with a metal head, carrying out electrostatic spinning under the conditions that the voltage is 17kV, the distance between the metal needle and a wire collector is 12cm, the flow rate is 0.3mL/h, heating the prepared nanofiber to 500 ℃ at the speed of 4.2 ℃/min in air, and roasting for 2h to obtain CeO 2 A nanofiber.
(2) Pt suspension was prepared by the method of example 1.
(3) Weigh 5mg CeO 2 Dispersing the nanofiber in 1.8mL of pure water, and dropwise adding 0.2mL of Pt (0.392 mg/mL) to form CeO with the concentration of 0.0025g/mL 2 Nanofiber solution, ceO was mixed and stirred 2 The nanofiber and the metal Pt are loaded, and the mixture is mixed and stirred for 2 hours at normal temperature to finish loading.
(4) A continuous flow filtration device as described in example 1 was constructed, the solution after stirring and loading was sucked into a syringe, a filtration needle was connected below the syringe, and the filtration needle was filled with a mixed cellulose ester film having a pore diameter of 0.22. Mu.m.
(5) And filtering the loaded mixed solution at a flow rate of 2mL/min by using a microinjection pump in a continuous filtering device, and collecting the precipitate remained on the mixed cellulose ester membrane after the filtration is completed to obtain the separated nanofiber supported catalyst, wherein a filter cake after the filtration is shown in a figure 3 (B). The diameter of the Pt nano-particles is about 3nm, the diameter of the nano-fibers is about 0.1-0.3 μm, the length is about 0.5-2 μm, and the pore diameter of the mixed cellulose ester membrane is 0.22 μm, so that the separation of the unsupported Pt nano-particles and the nano-fibers can be realized theoretically.
(6) The obtained nanofiber-supported catalyst sample was observed by a transmission electron microscope to obtain CeO as shown in FIG. 8 2 TEM image of nanofiber supported Pt catalyst, compared to TiO with no supported metal in FIG. 4 2 Compared with the nanofiber, the Pt nano particles can be successfully loaded on the surface of the fiber, the back bottom area outside the fiber is clean, and no residual Pt nano particles exist, so that the separation and purification technology is proved to be effective.
Comparative example 1
With the method of example 1, the difference is that when the mixed cellulose ester membrane having a pore diameter of 0.6 μm or more is packed in the filter head, as a result, since the mixed cellulose ester membrane has a pore diameter larger than the metal nanoparticle diameter and the nanofiber size, a part of nanofibers or all of nanofibers pass through the pore diameter together with the liquid, and loss of catalyst occurs even completely cannot be separated. If the pore diameter of the mixed cellulose ester membrane filled in the filter head is too small, the filtration resistance increases, which increases the difficulty in the filtration process, and at the same time, the nanofibers continuously accumulated on the mixed cellulose ester membrane during the filtration process affect the pore diameter of the filter membrane to a certain extent, so that the diameter of the filter membrane can pass through the filter membrane is smaller, and the possibility of residual nanoparticles is increased. If the separation is not complete, metal nanoparticles appear in the back of the TEM image of the supported fibers, and during the catalytic reaction, these metal nanoparticles that are not supported on the fibers are more prone to sintering, affecting the catalytic activity.
Claims (7)
1. A continuous flow purification and separation method of nanofiber supported catalyst is characterized by comprising the following specific steps:
(1) Mixing and stirring the nanofiber and metal, and loading;
(2) Sucking the loaded mixed solution into a syringe for filtering;
(3) Collecting solids remained on the mixed cellulose ester membrane after the filtration is completed, and obtaining a separated nanofiber supported catalyst;
the metal in the step (1) is one or more of Au, ag, pt, pd; the diameter of the metal nano-particles is smaller than that of the nano-fibers;
the nanofiber in the step (1) is TiO 2 Nanofibers, al 2 O 3 Nanofiber, al-Ti composite nanofiber or CeO 2 A nanofiber;
the mixed cellulose ester membrane has a pore size of 0.20-0.50 μm, and the mixed cellulose ester membrane has a pore size between the diameter of the metal nanoparticle and the diameter of the nanofiber.
2. The continuous flow purification and separation process of a nanofiber supported catalyst according to claim 1, wherein the metal in step (1) is Pt.
3. The continuous flow purification and separation method of the nanofiber supported catalyst according to claim 1, wherein the mixing and stirring time in the step (1) is 1-3 hours.
4. The method for continuous flow purification and separation of a nanofiber supported catalyst according to claim 1, wherein a filter head is connected below the injector in the step (2), and a mixed cellulose ester membrane is arranged in the filter head.
5. The continuous flow purification and separation process of nanofiber supported catalyst according to claim 1, wherein the filtration in step (2) is performed at a flow rate of 1-3mL/min using a continuous flow device.
6. An integrally formed nanofiber supported catalyst obtained by the continuous flow purification and separation method of nanofiber supported catalyst of claim 1.
7. Use of the continuous flow purification and separation method of the nanofiber supported catalyst according to claim 1 in nano synthesis with one-dimensional materials as a framework.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210230936.8A CN114534797B (en) | 2022-03-09 | 2022-03-09 | Continuous flow purification and separation method of nanofiber supported catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210230936.8A CN114534797B (en) | 2022-03-09 | 2022-03-09 | Continuous flow purification and separation method of nanofiber supported catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114534797A CN114534797A (en) | 2022-05-27 |
| CN114534797B true CN114534797B (en) | 2024-02-27 |
Family
ID=81663215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210230936.8A Active CN114534797B (en) | 2022-03-09 | 2022-03-09 | Continuous flow purification and separation method of nanofiber supported catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114534797B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721705A (en) * | 2014-01-14 | 2014-04-16 | 武汉理工大学 | Porous TiO2 fiber loaded noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN108193500A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Catalyst that composite nano fiber and composite nano fiber support and its preparation and application |
| CN110038452A (en) * | 2019-04-23 | 2019-07-23 | 东南大学 | Load the ceramic nanofibers base compound purifying film and its preparation method and application of silver |
| CN110075834A (en) * | 2019-04-26 | 2019-08-02 | 东南大学 | C-shaped cerium oxide nano fiber of Supported Pt Nanoparticles and its preparation method and application |
-
2022
- 2022-03-09 CN CN202210230936.8A patent/CN114534797B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103721705A (en) * | 2014-01-14 | 2014-04-16 | 武汉理工大学 | Porous TiO2 fiber loaded noble metal formaldehyde room-temperature oxidation catalyst and preparation method thereof |
| CN108193500A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Catalyst that composite nano fiber and composite nano fiber support and its preparation and application |
| CN110038452A (en) * | 2019-04-23 | 2019-07-23 | 东南大学 | Load the ceramic nanofibers base compound purifying film and its preparation method and application of silver |
| CN110075834A (en) * | 2019-04-26 | 2019-08-02 | 东南大学 | C-shaped cerium oxide nano fiber of Supported Pt Nanoparticles and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| Concurrent filtration and solar photocatalytic disinfection/degradation using high-performance Ag/TiO2 nanofiber membrane;Lei Liu等;《Water research》;1101-1112 * |
| Porous ceramic nanofibers as new catalysts toward heterogeneous reactions;Zhihui Li等;《Composites Communications》;168-178 * |
| Surface-Functionalized Electrospun Titania Nanofibers for the Scavenging and Recycling of Precious Metal Ions;Yunqian Dai等;《ChemSusChem》;2912-2916 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114534797A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103272576B (en) | Vanadate nanofiber photocatalyst and preparation method thereof | |
| CN111348676B (en) | Porous metal oxide nanosheet and preparation method and application thereof | |
| CN114534797B (en) | Continuous flow purification and separation method of nanofiber supported catalyst | |
| CN109943920A (en) | A kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber | |
| CN101590435A (en) | A kind of rare-earth zirconium doped alumina nano fiber catalyst carrier material and preparation method thereof | |
| WO2021232648A1 (en) | Device for macro-purifying metal-based nanowire | |
| CN110240723B (en) | Ultraviolet high-shielding cellulose membrane and preparation method and application thereof | |
| CN110038642A (en) | A kind of TiO with ultra-deep desulfuration performance2@NH2- MIL-125 (Ti) nanofiber | |
| CN101590434A (en) | A kind of rare-earth cerium doped alumina nano fiber catalyst carrier material and preparation method thereof | |
| CN105622675B (en) | A kind of preparation method of high activity metal organic framework material | |
| CN114558571A (en) | Spherical composite catalyst for generating methyl isopropyl ketone by reacting isobutyric acid with acetic acid and preparation method thereof | |
| CN112452165B (en) | Ag/AgBr/AgVO 3 Composite nano-fiber filtering membrane and preparation method and application thereof | |
| CN107754493B (en) | Photocatalytic transparent PM2.5 filtering membrane and preparation method thereof | |
| WO2024066446A1 (en) | Method for preparing cyclohexanone compound by photocatalysis of biomass phenolic compound | |
| CN103977779B (en) | Aluminum oxide titanium white hetero-junctions nano fibre carrier and its preparation method and application in anti-sintering noble metal catalyst system | |
| KR100990216B1 (en) | Method of manufacturing organic or inorganic nanoparticles with electrospinning and the product thereby | |
| CN111545180B (en) | Preparation method of cellulose acetate modified montmorillonite composite nanofiber | |
| CN107376512A (en) | A kind of water filtration filter element with antibacterial effect | |
| CN107469819B (en) | Supported catalyst for preparing cyclohexene by benzene hydrogenation and preparation method thereof | |
| CN114045608B (en) | Flexible polycrystalline titanium oxide-aluminum oxide composite nanofiber membrane and preparation method thereof | |
| CN110614124B (en) | Nano-gold catalyst with multi-stage structure and preparation method thereof | |
| JP3436267B2 (en) | Purification device and photocatalyst cartridge | |
| CN104307518B (en) | Preparation method for palladium-doped cerium-zirconium composite oxide | |
| CN114797934A (en) | Nitrogen-doped carbon nanotube supported palladium platinum catalyst and preparation method and application thereof | |
| CN109174193B (en) | Cross-linked polystyrene embedded palladium nanofiber catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |