CN110841633B - Preparation method of catalytic membrane - Google Patents
Preparation method of catalytic membrane Download PDFInfo
- Publication number
- CN110841633B CN110841633B CN201911180578.9A CN201911180578A CN110841633B CN 110841633 B CN110841633 B CN 110841633B CN 201911180578 A CN201911180578 A CN 201911180578A CN 110841633 B CN110841633 B CN 110841633B
- Authority
- CN
- China
- Prior art keywords
- membrane
- ceramic membrane
- catalytic
- time
- temperature
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 162
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 119
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- 239000000919 ceramic Substances 0.000 claims abstract description 74
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 54
- 238000000151 deposition Methods 0.000 claims abstract description 50
- 238000001354 calcination Methods 0.000 claims abstract description 43
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 31
- 230000008021 deposition Effects 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 69
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 65
- 239000002243 precursor Substances 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000004140 cleaning Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical group FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 31
- 238000005516 engineering process Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000012159 carrier gas Substances 0.000 description 24
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 14
- 239000000306 component Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229910003074 TiCl4 Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011070 membrane recovery Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2475—Membrane reactors
-
- 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
- B01J23/44—Palladium
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a catalytic membrane, belonging to the technical field of catalyst preparation. And placing the ceramic membrane into a reaction cavity of the atomic layer deposition equipment, depositing a titanium dioxide coating on the ceramic membrane, placing the ceramic membrane into a tubular furnace for calcination, placing the ceramic membrane into the reaction cavity of the atomic layer deposition equipment, and depositing Pd nano-particles to obtain the Pd catalytic membrane. The invention adopts the atomic layer deposition technology to deposit TiO2The surface and the pore channels of the ceramic membrane are modified, the modified ceramic membrane is calcined, the surface characteristics of the ceramic membrane are regulated and controlled, the subsequent deposition of Pd active components is facilitated, the prepared catalytic membrane can be used for a flow-through membrane reaction device, the reaction separation coupling of a catalyst and a reactant is realized, the catalytic membrane is good in repeated use effect and can be simply washed, the catalytic membrane is repeatedly used for multiple times, and the activity is not obviously reduced. Ceramic membrane is adopted as a carrier, and the unit is improved through treatmentThe catalytic efficiency of the Pd is improved, and the utilization rate of the heavy metal Pd is improved.
Description
Technical Field
The invention relates to a process for preparing a catalytic film by an atomic layer deposition method, belonging to the technical field of preparation of catalytic films.
Background
Membrane catalysis is an important branch in the membrane process and is an important field influencing the development of chemical and petrochemical industries. The membrane catalysis technology has the advantages of breaking the chemical equilibrium limitation, improving the reaction conversion rate, realizing in-situ separation of products and catalysts, realizing the coupling of separation and reaction processes and the like, and has attracted extensive attention of people.
The catalytic membrane is a core component constituting the membrane catalytic reactor. Researchers have focused on improving catalytic membrane performance in terms of membrane surface characteristics, membrane configuration, preparation methods, etc., however, few studies have been made on the effect of catalytic membrane active components themselves on catalytic membrane performance. The method for loading active components on the catalytic membrane mainly comprises the following steps: organometallic chemical vapor deposition, ion exchange, in situ growth, surface impregnation, phase inversion, and the like. Compared with the method that the microscopic size of the active component can not be accurately regulated and controlled by the method for loading the active component, the atomic layer deposition technology has the unique advantage of accurately regulating the deposited object, can theoretically regulate and control the microscopic size of the deposited object at the atomic level, has good conformality and basically has no influence on the specific surface area of the film carrier before and after deposition. Researchers have conducted some research work utilizing the characteristics of atomic layer deposition techniques. The patent (CN 110042365A) reports an atomic layer deposition method for growing alumina on the surface of a two-dimensional material, the atomic layer deposition method is used to grow alumina on the surface of the two-dimensional material, and the alumina is deposited on the surface of the two-dimensional material by physical adsorption, so that not only impurities and defects are prevented from being introduced on the surface of the two-dimensional material, but also the intrinsic characteristics of the two-dimensional material are maintained. Patent (CN 109675609A) reports a preparation method and application of a nanoporous gold-based catalyst modified by atomic layer deposition of ultrathin titanium oxide, and the method of atomic layer deposition is adopted to deposit ultrathin titanium oxide on the nanoporous gold-based catalyst, thereby greatly improving the catalytic performance of the nanoporous gold-based catalyst. At present, no report of preparing a catalytic film by adopting an atomic layer deposition technology is found.
The present invention is directed to a method for preparing a catalytic film by atomic layer deposition, which is used to prepare a high performance catalytic film.
Disclosure of Invention
The invention aims to modify the surface of a ceramic membrane by adopting an atomic layer deposition technology, then load Pd nano-particles to prepare a Pd catalytic membrane, and develop a novel catalytic membrane preparation method.
The technical scheme of the invention is as follows: a Pd catalytic membrane prepared by an atomic layer deposition technology comprises the following steps:
the method comprises the following steps: putting a ceramic membrane into a reaction cavity of the atomic layer deposition equipment, and depositing a titanium dioxide coating on the ceramic membrane to prepare TiO2A modified ceramic membrane;
step two: adding TiO into the mixture2Calcining the modified ceramic membrane in a tube furnace with model number of TL1200 to prepare TiO2Calcining the modified ceramic membrane;
step three: adding TiO into the mixture2And placing the calcined and modified ceramic membrane into a reaction cavity of atomic layer deposition equipment, and depositing Pd nano particles to obtain the Pd catalytic membrane.
Preferably, the ceramic membrane is a sheet type alumina ceramic membrane, the aperture is 1-3.5 mu m, and the thickness is 1.5-3 mm.
Preferably, the deposition temperature of the titanium dioxide on the ceramic membrane in the first step is 100-150 ℃; titanium tetrachloride and water are used as precursors, the pulse time of the titanium tetrachloride is 0.03-0.06s, the exposure time is 10-30s, and the cleaning time is 20-60 s; the pulse time of water is 0.06-0.12s, the exposure time is 10-30s, and the cleaning time is 20-60 s; the cycle number is 10-50.
Preferably, the calcination conditions in step two are: under the hydrogen-argon mixed atmosphere with the hydrogen volume fraction of 10%, the temperature rise rate is increased to 400-475 ℃ at the speed of 2-3 ℃/min, and the calcination is carried out for 120-210 min.
Preferably, the deposition temperature of the Pd active component in the step three is 200 ℃; the precursors used for depositing the active component Pd were palladium hexafluoroacetylacetonate and formalin solution with a formaldehyde concentration of 37%.
Preferably, the temperature of the hexafluoroacetylacetone palladium is 80 ℃ to ensure that enough vapor pressure exists in the steel cylinder, formalin is at normal temperature, the pulse time of the hexafluoroacetylacetone palladium is 0.3-1s, the exposure time is 80-150s, and the cleaning time is 100-150 s; the pulse time of the formalin precursor is 0.6-2s, the exposure time is 80-150s, and the cleaning time is 100-150 s; the cycle number is 2-80.
Preferably, the optimal parameters for preparing the catalytic membrane are as follows: the thickness of the ceramic film is 1.75mm, the aperture is 2.5 mu m, two precursors for depositing titanium dioxide are titanium tetrachloride and water, the two precursors are kept at normal temperature in a steel cylinder, the pulse time, the exposure time and the cleaning time of the titanium tetrachloride are respectively 0.06s, 10s and 20s, and the pulse time, the exposure time and the cleaning time of the water are respectively 0.12s, 10s and 20 s; the number of titanium dioxide cycles was 10. The calcination temperature of the ceramic membrane modified by titanium dioxide in a TL1200 tubular furnace is 450 ℃, the heating rate is 2 ℃/min, and the calcination time is 120 min; the deposition temperature of the Pd active component is 200 ℃, the steel cylinder of the precursor of the hexafluoroacetylacetone palladium is maintained at 80 ℃, the formalin solution is maintained at normal temperature, the pulse time, the exposure time and the cleaning time of the hexafluoroacetylacetone palladium are respectively 0.5s, 120s and 100s, and the pulse time, the exposure time and the cleaning time of the formalin precursor are respectively 1s, 120s and 100 s; the number of Pd cycles was 64.
The catalytic membrane prepared by the method is applied to a flow-through membrane reaction device.
The catalyst recovered after the reaction can be used as the catalytic membrane, and the recovery method is to wash the catalytic membrane for more than 5 seconds by using clean water without obvious reduction of activity.
Has the advantages that:
1. the invention adopts the atomic layer deposition technology to deposit TiO2Modifying the surface and the pore channel of the ceramic membrane, and then putting the modified ceramic membrane at 10% H2Calcining is carried out, the surface characteristics of the ceramic membrane are regulated, and the subsequent deposition of Pd active components is facilitated, so that the catalytic membrane with excellent catalytic performance is prepared.
2. The catalytic membrane prepared by the invention can be used for a flow-through membrane reaction device, realizes the reaction separation coupling of a catalyst and a reactant, has good repeated use effect, only needs simple washing, can be repeatedly used for many times, and has no obvious reduction of activity.
3. According to the invention, the ceramic membrane is used as a carrier, and the catalytic efficiency of Pd per unit mass is improved and the utilization rate of heavy metal Pd is improved through treatment.
Drawings
FIG. 1 is a schematic view of an atomic layer deposition apparatus.
FIG. 2 is a schematic of a flow-through catalytic membrane reactor.
FIG. 3 shows the results of the catalytic performance of each catalytic membrane prepared in example 1 in the reaction of preparing p-aminophenol by catalytic reduction of p-nitrophenol.
The reference number is 1 reaction cavity, 2 air inlet pipeline, 3 ALD valve, 4 manual valves, 5 precursor steel bottle, 6 carrier gas flowmeter, 7 carrier gas inlet, 8 vacuum gauge, 9 tail valve, 10 tail gas outlet, 11 vacuum pump, A constant temperature water bath, B storage tank, C membrane module, D peristaltic pump.
Detailed Description
The method and the effect of using the catalyst of the present invention will be specifically described below by way of examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
The atomic layer deposition apparatus used in this embodiment has a model number E100-M6, and a schematic diagram of the apparatus is shown in fig. 1, which mainly includes: the device comprises a reaction chamber 1, an air inlet pipeline 2, a manual valve 4, a carrier gas flowmeter 6, a vacuum gauge 8, a tail valve 9, a tail gas outlet 10, a vacuum pump 11, an ALD valve 3, a precursor steel cylinder 5, a carrier inlet 7 and the like. The atomic layer deposition device is connected with a computer, and each deposition parameter is controlled by software. The deposition flow comprises the following steps: the deposition mode is set to be Close-Type on the ALD software interface, high-purity nitrogen enters through the air inlet pipeline, the flow rate of the high-purity nitrogen is controlled by the carrier gas flowmeter 6 connected with the air inlet pipeline 2, the manual valve 4 and the ALD valve 3 are sequentially connected to the outlet of the precursor steel cylinder 5 and then connected with the high-purity nitrogen air inlet pipeline 2, the pulse time of the precursor is controlled by the ALD valve 3, and specific parameters can be regulated and controlled on the ALD software interface. The ceramic membrane is placed in a reaction cavity, the periphery of the reaction cavity 1 is surrounded by a heating belt, the temperature of the heating belt is controlled at an ALD software interface to enable the reaction cavity to maintain the reaction temperature, a vacuum gauge 8, a tail valve 9 and a vacuum pump 11 are sequentially connected to an air outlet of the reaction cavity, the exposure time of a deposition process is achieved when the tail valve 9 is closed, the cleaning time of an organic process is achieved when the tail valve 9 is opened, and specific parameters are controlled by the ALD software interface.
In the embodiment, sodium borohydride is used as a reducing agent, and p-aminophenol prepared by catalyzing reduction of p-nitrophenol is used as a model reaction to evaluate the catalytic performance of the prepared catalytic membrane. The p-nitrophenol reduction reaction was carried out in a flow-through catalytic membrane reactor as shown in figure 2. The reactor consists of a membrane component C, a storage tank B, a peristaltic pump D and a temperature-controlled water bath A. Firstly, preparing 60 mL of reaction solution (0.45 g of p-nitrophenol is dissolved in 10 mL of absolute ethyl alcohol, then adding 50 mL of deionized water to reach a constant volume of 60 mL, and then adding 0.65 g of sodium borohydride to stir uniformly) and adding the reaction solution into a storage tank B; then starting a peristaltic pump D, and reacting the reaction liquid with the loaded active component by flowing through the surface and pore channels of the membrane catalyst through the peristaltic pump D; and returning the reaction liquid passing through the membrane catalyst from the bottom end of the membrane component C to the storage tank B for circular reaction for 60 min. Analyzing the content of p-nitrophenol in the reaction solution by adopting high performance liquid chromatography, calculating the conversion rate of the p-nitrophenol, and evaluating the catalytic activity of the catalytic membrane by using the conversion rate of the p-nitrophenol.
EXAMPLE 1 Pd catalytic Membrane preparation
(1) Titanium dioxide modification of ceramic membrane surface
The first step is to deposit titanium dioxide: setting the reaction temperature in the reaction chamberSet at 100 ℃, the inlet pipeline is heated to 100 ℃ by a heating belt, and the temperature of the outlet pipeline at the tail valve 9 is set to 80 ℃. TiO 22The precursor used is TiCl4And H2And O, the two are maintained in a normal temperature state and are automatically and alternately carried out. The carrier gas is high-purity nitrogen, and the flow of the carrier gas in the four pipelines is set to be 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. TiCl (titanium dioxide)4The pulse time and the exposure time of the two precursors are respectively set to be 0.06s and 10s, the pulse time and the exposure time of the water are respectively set to be 0.12s and 10s, and the cleaning time after the two precursors are exposed is 20 s. And depositing 10 cycles of titanium dioxide on the surface of the ceramic membrane (the carbon tetrachloride and the water are alternately reacted for 10 times).
And a second step of titanium dioxide calcination: the ceramic membrane with the titanium dioxide deposited in the first step is put into a tube furnace at 10% H2Calcining at 450 deg.C for 120min under atmosphere, and heating rate is 2 deg.C/min. After calcining, naturally cooling, and taking out for later use.
(2) Deposition of Pd
Depositing Pd by using an atomic layer deposition technology: the reaction temperature in the reaction chamber is set to 200 ℃, the inlet pipeline 2 is heated to 150 ℃ by a heating belt, and the temperature of the outlet pipeline at the tail valve 9 is set to 100 ℃. The precursor of Pd is Pd (hfac)2Purity was 99.999%, and heating was carried out to 80 ℃ with a heating belt to maintain sufficient vapor pressure. The reducing agent was Formalin (aqueous solution with formaldehyde concentration of 37% and containing 15% methanol), and was maintained at room temperature. The carrier gas was high purity nitrogen gas, and the carrier gas flow meter 6 was set to 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity 1 in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. Pd (hfac)2The pulse time and the exposure time of (1) are set to 0.5s and 120s respectively, and the pulse time and the exposure time of Formalin are set to 1s and 120s respectively; the two precursors are automatically and alternately carried out, and the cleaning time after exposure is 100 s. Deposition 64 cycles Pd (hfac)2And Formalin) were reacted alternately 64 times. Finally obtaining the catalytic membrane which is modified by titanium dioxide calcination, and numberingIs c.
(3) Preparation of comparative example
Ceramic membrane without TiO2Carrying out surface modification, wherein the rest operations are completely the same as the steps (1) and (2), and the prepared catalytic membrane is marked as a; only titanium dioxide is adopted for deposition on the surface of the ceramic membrane without calcination, the rest of the operation is completely the same as the steps (1) and (2), and the prepared catalytic membrane is marked as b; and (3) depositing titanium dioxide on the surface of the ceramic membrane, calcining in a pure Ar atmosphere, and completely performing the same operations as the steps (1) and (2) to prepare the catalytic membrane, wherein the label is marked as d.
The prepared catalytic membrane is used for the reaction of preparing p-aminophenol by catalytic reduction of p-nitrophenol, and the catalytic performance of the catalytic membrane is considered, and the result is shown in figure 3, the performance of the membrane catalyst prepared by calcining titanium dioxide under hydrogen is the best, 63 percent, which is obviously superior to that of the membrane catalyst prepared under other conditions, and the membrane catalyst with excellent performance can be prepared by the method of calcining and modifying a ceramic membrane by titanium dioxide under hydrogen.
EXAMPLE 2 Pd catalytic Membrane preparation
(1) Modifying titanium dioxide on the surface of the ceramic membrane:
the first step is to deposit titanium dioxide: the reaction temperature in the reaction chamber is set to 100 ℃, the inlet pipeline 2 is heated to 100 ℃ by a heating belt, and the temperature of the outlet pipeline at the tail valve 9 is set to 80 ℃. TiO 22The precursor used is TiCl4And H2And O, and keeping the two in a normal temperature state. The carrier gas is high-purity nitrogen, and the carrier gas flow meters 6 are all set to be 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity 1 in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. TiCl (titanium dioxide)4The pulse time and the exposure time of the two precursors are respectively set to be 0.03 s and 30s, the pulse time and the exposure time of the water are respectively set to be 0.06s and 30s, and the cleaning time after the two precursors are exposed is 60 s. 50 cycles of titanium dioxide were deposited on the ceramic membrane surface.
And a second step of titanium dioxide calcination: placing the ceramic membrane deposited with the titanium dioxide in the first step into a tube furnace in H2Under the mixed atmosphere of hydrogen and argon with the volume fraction of 10 percentCalcining at 400 deg.C for 120min, and heating at 2 deg.C/min. After calcining, naturally cooling, and taking out for later use.
(2) Depositing Pd by using an atomic layer deposition technology:
the reaction temperature in the reaction chamber 1 is set to 200 ℃, the air inlet pipeline 2 is heated to 150 ℃ by a heating belt, and the temperature of the air outlet pipeline at the tail valve 9 is set to 80 ℃. The precursor of Pd is Pd (hfac)2Purity was 99.999%, and heating was carried out to 80 ℃ with a heating belt to maintain sufficient vapor pressure. The reducing agent was Formalin (aqueous solution with formaldehyde concentration of 37% and containing 15% methanol), and was maintained at room temperature. The carrier gas is high-purity nitrogen, and the flow of the carrier gas in the four pipelines is set to be 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity 1 in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. Pd (hfac)2The pulse time and the exposure time of (2) are set to 0.3 s and 80s respectively, and the pulse time and the exposure time of Formalin are set to 2s and 150s respectively; the cleaning time after exposure of the two precursors was 150 s. Deposit 80 cycles Pd. Finally, a catalytic membrane modified by titanium dioxide calcination is obtained, the prepared catalytic membrane is used for the reaction of preparing p-aminophenol by catalytic reduction of p-nitrophenol, the catalytic performance of the catalytic membrane is inspected, and the result shows that the conversion rate of the membrane catalyst prepared by calcining the titanium dioxide under hydrogen is 58.3%.
EXAMPLE 3 Pd catalytic Membrane preparation
(1) Modifying titanium dioxide on the surface of the ceramic membrane:
the first step is to deposit titanium dioxide: the reaction temperature of the reaction chamber 1 is set to 100 ℃, the air inlet pipeline 2 is heated to 100 ℃ by a heating belt, and the temperature of the air outlet pipeline at the tail valve 9 is set to 100 ℃. TiO 22The precursor used is TiCl4And H2And O, and keeping the two in a normal temperature state. The carrier gas is high-purity nitrogen, and the carrier gas flow meters 6 are all set to be 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity 1 in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. TiCl (titanium dioxide)4The pulse time and the exposure time of (2) were set to 0.06s and 10s, respectively, and the pulse time and the exposure time of water were set to 0.12s,The cleaning time after exposure of the two precursors was 20s for 10 s. Depositing 10 circulating titanium dioxide on the surface of the ceramic membrane.
And a second step of titanium dioxide calcination: the ceramic membrane with the titanium dioxide deposited in the first step is put into a tube furnace at 10% H2Calcining at 475 deg.C for 210min under atmosphere, and heating rate of 3 deg.C/min. After calcining, naturally cooling, and taking out for later use.
(2) Deposition of Pd: depositing Pd by using an atomic layer deposition technology: the reaction temperature in the reaction chamber is set to 200 ℃, the inlet pipeline 2 is heated to 150 ℃ by a heating belt, and the temperature of the outlet pipeline at the tail valve 9 is set to 80 ℃. The precursor of Pd is Pd (hfac)2Purity was 99.999%, and heating was carried out to 80 ℃ with a heating belt to maintain sufficient vapor pressure. The reducing agent was Formalin (aqueous solution with formaldehyde concentration of 37% and containing 15% methanol), and was maintained at room temperature. The carrier gas is high-purity nitrogen, and the flow of the carrier gas in the four pipelines is set to be 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity 1 in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. Pd (hfac)2The pulse time and the exposure time of (1.0 s) and (150 s) respectively, and the pulse time and the exposure time of Formalin are respectively set to (0.6 s) and (80 s); the purge time after exposure of both precursors was 80s and 64 cycles of Pd were deposited. Finally obtaining the catalytic membrane modified by titanium dioxide calcination.
The prepared catalytic membrane is used for the reaction of preparing p-aminophenol by catalytic reduction of p-nitrophenol, the catalytic performance is inspected, and the result is as follows: the conversion of the membrane catalyst prepared after calcination of the titanium dioxide under hydrogen was 65.2%.
EXAMPLE 4 Pd catalytic Membrane preparation
(1) Modifying titanium dioxide on the surface of the ceramic membrane:
the first step is to deposit titanium dioxide: the reaction temperature in the reaction cavity 1 is set to 100 ℃, the air inlet pipeline 2 is heated to 100 ℃ by a heating belt, and the temperature of the air outlet pipeline at the tail valve 9 is set to 80 ℃. TiO 22The precursor used is TiCl4And H2And O, and keeping the two in a normal temperature state. High purity nitrogen for carrier gas, carrier gas flow in four-way pipeThe amounts were all set at 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. TiCl (titanium dioxide)4The pulse time and the exposure time of the two precursors are respectively set to be 0.06s and 10s, the pulse time and the exposure time of the water are respectively set to be 0.12s and 10s, and the cleaning time after the two precursors are exposed is 20 s. Depositing 10 circulating titanium dioxide on the surface of the ceramic membrane.
And a second step of titanium dioxide calcination: the ceramic membrane with the titanium dioxide deposited in the first step is put into a tube furnace at 10% H2Calcining at 450 deg.C for 120min under atmosphere, and heating rate is 2 deg.C/min. After calcining, naturally cooling, and taking out for later use.
(2) Deposition of Pd: depositing Pd by using an atomic layer deposition technology: the reaction temperature in the reaction chamber 1 is set to 200 ℃, the air inlet pipeline 2 is heated to 150 ℃ by a heating belt, and the temperature of the air outlet pipeline at the tail valve 9 is set to 80 ℃. The precursor of Pd is Pd (hfac)2Purity was 99.999%, and heating was carried out to 80 ℃ with a heating belt to maintain sufficient vapor pressure. The reducing agent was Formalin (aqueous solution with formaldehyde concentration of 37% and containing 15% methanol), and was maintained at room temperature. The carrier gas is high-purity nitrogen, and the carrier gas flow meters 6 are all set to be 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity 6 in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. Pd (hfac)2The pulse time and the exposure time of (1) are set to 0.5s and 120s respectively, and the pulse time and the exposure time of Formalin are set to 1s and 120s respectively; the purge time after exposure of both precursors was 100s and 64 cycles of Pd were deposited. Finally obtaining the catalytic membrane modified by titanium dioxide calcination.
The prepared catalytic membrane is used for the reaction of preparing p-aminophenol by catalytic reduction of p-nitrophenol, the catalytic performance of the catalytic membrane is examined, and the result is that the conversion rate of the membrane catalyst prepared by calcining titanium dioxide under hydrogen is 63 percent.
EXAMPLE 5 this example examines the Pd catalyst membrane conversion frequency
In the catalytic membrane c prepared in example one, the total content of Pd is 0.01484 mg, the concentration of p-nitrophenol is 0.54 mol/L, and the molar ratio of the corresponding p-nitrophenol to sodium borohydride is 1: and 5, evaluating the performance of the catalyst by using a conversion frequency TOF of the catalyst to a substrate, wherein the conversion frequency TOF is expressed as:
See the following two documents:
[1] sunzeiling, allowability, naughty, influence of reducing agent on size and particle size distribution of nano gold particles [ J ]. proceedings of Zhengzhou university (science edition), 2014 (1).
[2] Guoshualong, yangyuan, lyxiu, nestixiu, yangyiwei, wangchuan, countryside, preparation, characterization and hydrocatalytic performance research of Au/Co _3O _4 [ J ] noble metals, 2018, (2).
Example 5 this example examines the stability of the Pd-catalyzed membrane
(1) Titanium dioxide modification of ceramic membrane surface
The first step is to deposit titanium dioxide: the reaction temperature in the reaction chamber is set to 100 ℃, the gas inlet pipeline is heated to 100 ℃ by a heating belt, and the temperature of the gas outlet pipeline at the tail valve 9 is set to 80 ℃. TiO 22The precursor used is TiCl4And H2And O, the two are maintained in a normal temperature state and are automatically and alternately carried out. The carrier gas is high-purity nitrogen, and the flow of the carrier gas in the four pipelines is set to be 50 mL/min. In the state that the deposition mode is close-type, the deposition mode isAnd placing the ceramic membrane in the reaction chamber, and waiting for 20min to allow the ceramic membrane to reach the reaction temperature. TiCl (titanium dioxide)4The pulse time and the exposure time of the two precursors are respectively set to be 0.06s and 10s, the pulse time and the exposure time of the water are respectively set to be 0.12s and 10s, and the cleaning time after the two precursors are exposed is 20 s. And depositing 10 cycles of titanium dioxide on the surface of the ceramic membrane (the carbon tetrachloride and the water are alternately reacted for 10 times).
And a second step of titanium dioxide calcination: the ceramic membrane with the titanium dioxide deposited in the first step is put into a tube furnace at 10% H2Calcining at 450 deg.C for 120min under atmosphere, and heating rate is 2 deg.C/min. After calcining, naturally cooling, and taking out for later use.
(2) Deposition of Pd
Depositing Pd by using an atomic layer deposition technology: the reaction temperature in the reaction chamber is set to 200 ℃, the inlet pipeline 2 is heated to 150 ℃ by a heating belt, and the temperature of the outlet pipeline at the tail valve 9 is set to 100 ℃. The precursor of Pd is Pd (hfac)2Purity was 99.999%, and heating was carried out to 80 ℃ with a heating belt to maintain sufficient vapor pressure. The reducing agent was Formalin (aqueous solution with formaldehyde concentration of 37% and containing 15% methanol), and was maintained at room temperature. The carrier gas was high purity nitrogen gas, and the carrier gas flow meter 6 was set to 50 mL/min. And (3) placing the ceramic membrane in the reaction cavity 1 in a close-type deposition mode, and waiting for 20min to enable the ceramic membrane to reach the reaction temperature. Pd (hfac)2The pulse time and the exposure time of (1) are set to 0.5s and 120s respectively, and the pulse time and the exposure time of Formalin are set to 1s and 120s respectively; the two precursors are automatically and alternately carried out, and the cleaning time after exposure is 100 s. Deposition 64 cycles Pd (hfac)2And Formalin) were reacted alternately 64 times. Finally obtaining the catalytic membrane modified by titanium dioxide calcination.
The prepared catalytic membrane is used for the reaction of preparing p-aminophenol by catalytic reduction of p-nitrophenol, the catalytic performance of the catalytic membrane is inspected, and the result is shown in the following table, wherein the performance of the membrane catalyst prepared by calcining titanium dioxide under hydrogen is the best, and is 63%.
The membrane catalyst prepared by calcining titanium dioxide under hydrogen is used for testing, after one-time reaction is finished, the catalytic membrane is taken out, is simply washed for more than 5 seconds by clear water, is naturally dried or is placed in an oven for drying for 10-30min at 50-200 ℃, then the same reaction condition is adopted for reaction, and the stability of the membrane catalyst in repeated use is tested; the above process was repeated until the catalytic membrane was continuously used 5 times, and the reaction results are shown in table 1:
table 1 catalytic membrane recycle test results
From the recycling result, the activity of the catalyst is only reduced by about 2% after the catalyst is repeatedly used for 5 times, the activity is not obviously reduced, and the catalytic membrane recovery method is simple and only needs absolute ethyl alcohol and clean water for washing.
Claims (8)
1. A preparation method of a catalytic membrane is characterized by comprising the following steps:
the method comprises the following steps: putting a ceramic membrane into a reaction cavity of the atomic layer deposition equipment, and depositing a titanium dioxide coating on the ceramic membrane to prepare TiO2A modified ceramic membrane;
step two: adding TiO into the mixture2Calcining the modified ceramic membrane in a tubular furnace to prepare TiO2Calcining the modified ceramic membrane;
step three: adding TiO into the mixture2Placing the calcined and modified ceramic membrane into a reaction cavity of atomic layer deposition equipment, and depositing Pd nano particles to obtain a Pd catalytic membrane;
the calcination conditions in the second step are as follows: under the hydrogen-argon mixed atmosphere with the hydrogen volume fraction of 10%, the temperature rise rate is increased to 400-475 ℃ at the speed of 2-3 ℃/min, and the calcination is carried out for 120-210 min.
2. A catalytic membrane preparation method according to claim 1, wherein the ceramic membrane is a sheet alumina ceramic membrane having a pore size of 1 to 3.5 μm and a thickness of 1.5 to 3 mm.
3. The method of claim 1, wherein the deposition temperature of titania on the ceramic membrane in the first step is 100-150 ℃; titanium tetrachloride and water are used as precursors, the pulse time of the titanium tetrachloride is 0.03-0.06s, the exposure time is 10-30s, and the cleaning time is 20-60 s; the pulse time of water is 0.06-0.12s, the exposure time is 10-30s, and the cleaning time is 20-60 s; the cycle number is 10-50.
4. The method of claim 1, wherein the Pd active component is deposited at a temperature of 200 ℃ in step III; the precursors used for depositing the active component Pd were palladium hexafluoroacetylacetonate and formalin solution with a formaldehyde concentration of 37%.
5. The method of claim 4, wherein the temperature of the hexafluoroacetylacetonatopalladium is 80 ℃, formalin is normal temperature, the pulse time of the hexafluoroacetylacetonatopalladium is 0.3-1s, the exposure time is 80-150s, and the cleaning time is 100-150 s; the pulse time of the formalin precursor is 0.6-2s, the exposure time is 80-150s, and the cleaning time is 100-150 s; the cycle number is 2-80.
6. The catalytic membrane preparation method according to claim 1, wherein the ceramic membrane has a thickness of 1.75mm and a pore size of 2.5 μm, normal-temperature titanium tetrachloride and water are used for depositing titanium dioxide, the pulse time, the exposure time and the cleaning time of titanium tetrachloride are respectively 0.06s, 10s and 20s, and the pulse time, the exposure time and the cleaning time of water are respectively 0.12s, 10s and 20 s; the titanium dioxide cycle number is 10; through TiO 22The calcination temperature of the modified ceramic membrane in a TL1200 tube furnace is 450 ℃, the heating rate is 2 ℃/min, and the calcination time is 120 min; the deposition temperature of the Pd active component is 200 ℃, the precursor for depositing the Pd active component is hexafluoroacetylacetone palladium with the temperature of 80 ℃ and normal-temperature formalin solution, the pulse time, the exposure time and the cleaning time of the hexafluoroacetylacetone palladium are respectively 0.5s, 120s and 100s, and the pulse time, the exposure time and the cleaning time of the formalin are respectively 1s, 120s and 100 s; the number of cycles was 64.
7. Use of a catalysed membrane prepared by the process according to any one of claims 1 to 6 in a flow-through membrane reactor.
8. The use according to claim 7, wherein the catalytic membrane is recovered after the reaction is finished by washing the catalytic membrane with clean water for more than 5 seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911180578.9A CN110841633B (en) | 2019-11-27 | 2019-11-27 | Preparation method of catalytic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911180578.9A CN110841633B (en) | 2019-11-27 | 2019-11-27 | Preparation method of catalytic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110841633A CN110841633A (en) | 2020-02-28 |
| CN110841633B true CN110841633B (en) | 2022-04-29 |
Family
ID=69605271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911180578.9A Active CN110841633B (en) | 2019-11-27 | 2019-11-27 | Preparation method of catalytic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110841633B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114452975B (en) * | 2021-12-27 | 2024-05-10 | 西安近代化学研究所 | Honeycomb ceramic supported palladium-based catalyst and application thereof in HBIW hydrogen debenzylation |
| CN114588894B (en) * | 2022-03-22 | 2023-06-16 | 中国科学院赣江创新研究院 | Rhodium-based catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478114A (en) * | 2015-12-01 | 2016-04-13 | 南京工业大学 | Preparation method of palladium catalyst loaded on ceramic membrane |
| CN105536851A (en) * | 2016-02-22 | 2016-05-04 | 西安近代化学研究所 | Method for preparing acetylene selective hydrogenation catalyst |
| CN108786793A (en) * | 2018-06-05 | 2018-11-13 | 南京工业大学 | Preparation method of supported catalyst for flow-through catalytic reaction |
| CN109694128A (en) * | 2019-01-14 | 2019-04-30 | 南京工业大学 | Method for treating high-concentration p-nitrophenol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011119469A1 (en) * | 2010-03-22 | 2011-09-29 | T3 Scientific Llc | Hydrogen selective protective coating, coated article and method |
-
2019
- 2019-11-27 CN CN201911180578.9A patent/CN110841633B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105478114A (en) * | 2015-12-01 | 2016-04-13 | 南京工业大学 | Preparation method of palladium catalyst loaded on ceramic membrane |
| CN105536851A (en) * | 2016-02-22 | 2016-05-04 | 西安近代化学研究所 | Method for preparing acetylene selective hydrogenation catalyst |
| CN108786793A (en) * | 2018-06-05 | 2018-11-13 | 南京工业大学 | Preparation method of supported catalyst for flow-through catalytic reaction |
| CN109694128A (en) * | 2019-01-14 | 2019-04-30 | 南京工业大学 | Method for treating high-concentration p-nitrophenol |
Non-Patent Citations (4)
| Title |
|---|
| High Catalytic Efficiency of Pd Nanoparticles lmmobilized on TiO2 Nanorods-Coated Ceramic Membranes;Shuai Zhang et al.;《The Canadian Journal of Chemical Engineering》;20171231;第95卷;1-9 * |
| Towards ALD thin film stabilized single-atom Pd1 catalysts;Mar Piernavieja-Hermida et al.;《Nanoscale》;20160727;第8卷(第33期);15348-15356 * |
| 一种TiO2修饰的Pd/Al2O3选择性加氢用催化剂的研究;南军等;《催化学报》;20050831;第26卷(第8期);672-676 * |
| 钯/陶瓷膜催化剂的制备及其催化性能;孙晓旭等;《化学反应工程与工艺》;20130430;第29卷(第2期);152-156 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110841633A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111632596B (en) | High-dispersion metal-oxide bifunctional catalyst and preparation method and application thereof | |
| CN109174085B (en) | Atomic-level dispersed palladium-based nano-diamond/graphene composite material catalyst and preparation method and application thereof | |
| Pal et al. | A review on types, fabrication and support material of hydrogen separation membrane | |
| CN110841633B (en) | Preparation method of catalytic membrane | |
| O’Neill et al. | Catalyst design with atomic layer deposition | |
| CN105406087B (en) | A kind of preparation method and application of low-temperature fuel cell nucleocapsid elctro-catalyst | |
| CN105536851B (en) | A kind of preparation method of selective hydrocatalyst of acetylene | |
| CN112191111B (en) | Ionic liquid/metal organic framework ZIF-8 composite membrane and preparation method and application thereof | |
| CN103194731B (en) | Method for preparing nitrogen-doped titanium dioxide porous membrane | |
| CN101135052B (en) | Method for preparing metallic complex film | |
| CN112337509A (en) | MOF-based transition metal monatomic catalyst for carbon-carbon triple bond selective hydrogenation and preparation method thereof | |
| Liu et al. | Fabrication of ceramic membrane supported palladium catalyst and its catalytic performance in liquid-phase hydrogenation reaction | |
| TW201330918A (en) | A method of preparing or reconditioning a leak stable gas separation membrane system | |
| CN106914200A (en) | A kind of capillary type efficiently carries palladium zirconium-based metallic organic framework film microreactor, dynamic in-situ preparation method and applications | |
| CN110694690A (en) | Method for preparing metal monatomic catalyst | |
| Braun et al. | Optimization and characterization of electroless co-deposited PdRu membranes: Effect of the plating variables on morphology | |
| CN110152735B (en) | Carbon dioxide reduction catalyst, preparation method and reduction reaction method | |
| CN113694921B (en) | Nano-diamond/graphene composite carrier loaded atomic-scale dispersed iridium cluster catalyst and preparation method and application thereof | |
| CN104998637B (en) | A kind of preparing ethylene by selective hydrogenation of acetylene catalyst and preparation method thereof | |
| CN103977817B (en) | A kind of preparation method of the netted integer catalyzer of silver-bearing copper composite wire with surface porosity | |
| CN110508290B (en) | High-dispersion palladium/cobalt hydroxide catalyst and preparation method and application thereof | |
| US9901917B2 (en) | Enclosed-channel reactor method to manufacture catalysts or support materials | |
| CN101161342B (en) | Method for preparing high activity loading type RhxAu-x/Y nanometer catalyst | |
| CN106622248A (en) | Porous nickel and carbon compound and preparation method of porous nickel and carbon compound | |
| CN108117046A (en) | A kind of hydrogen manufacturing metal membrane reactor |
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 |