CN104998553A - Preparation method of palladium-modified coal composite film - Google Patents
Preparation method of palladium-modified coal composite film Download PDFInfo
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Abstract
The invention discloses a preparation method of a palladium-modified coal composite film. According to the method, in-hole palladium deposition is conducted on a carrier through a chemical vapor deposition method, a carbon film is loaded through a dipping-pulling method, and after loading is successful, in-hole palladium deposition is conducted again; when a plurality of layers of carbon films are prepared, in-hole palladium deposition is conducted on the carrier, the carbon films are loaded through the dipping-pulling method, in-hole palladium deposition is conducted every time one layer of carbon film is prepared, and then the next layer of carbon film is prepared; palladium deposition modification is conducted on the carrier or the previous carbon film in advance, needle-eye-shaped defects and cracks of the carrier and the carbon film can be repaired, and the film forming rate is obviously increased; meanwhile, palladium has the hydrogen penetrating characteristic, and therefore the hydrogen conveying paths can be increased through the palladium contained in the combined film. The method can solve the problems that film forming fails or hydrogen selectivity is low due to the fact that the number of the carrier defects or the number of carbon film layer defects is large in the common film forming process, and the high hydrogen selectivity can be reached when the number of the film layers is small even only a single film layer exists.
Description
Technical field
The present invention relates to the preparation method of the carbon composite membrane that a kind of palladium is modified, belong to chemical materials preparation and technical field of chemical separation.
Background technology
Carbon membrane is by the porous film material of the polymer substances such as phenolic resins, polyimides, cellulose, poly furfuryl alcohol through pyrolysis carbonization.As a kind of inoranic membrane, carbon membrane has excellent characteristic in gas separaion field.With regard to film to regard to the separating mechanism of gas, mainly come by the diffusion of gas in rete micropore; Because gas with various has different transmission speeds, which results in the separation of carbon membrane to gaseous mixture.From microcosmic, the separating mechanism of gas in perforated membrane depends primarily on the interaction between film and gas molecule, and key factor is wherein relation and the characterization of adsorption of gas molecule on membrane material surface etc. between the aperture of film and gas molecule size.4 kinds are mainly contained: Knudsen diffusion, diffusion into the surface, capillary condensation and molecule screening in the separation mechanism of membrane that current people propose.When prepared carbon membrane aperture is between 0.3 ~ 0.5nm, be then referred to as carbon molecular sieve membrance (CMSM).CMSM is due to its pore size distribution characteristics specified, the sieving actoion of main dependence molecule is separated the gas of different molecular size, the pore size of such carbon membrane and the molecular diameter of separated gas are quite (generally between 0.3 ~ 0.5nm), the little molecule of diameter is by film, the large molecule of diameter then tunicle dams, thus reaches separating effect.
The structure of film, carbon membrane is divided into non-supported body film (homogeneous membrane) and support film (composite membrane).Non-supported body carbon membrane comprises hollow-fibre membrane, without supporting body flat-plate film etc., and supporter carbon membrane can be divided into flat support body film and tubular support film according to supporter shape, and the carbon membrane layer by its surface plays centrifugation.No matter which kind of carbon membrane, its separating property is all using permeability and permselective property as primary evaluation index, and people obviously wish to obtain and not only had high osmosis to object gas but also had the carbon membrane of high selectivity.From current research conditions, although the non-supported body films such as hollow fiber carbon membrane have also shown good application prospect, in general, the advantage of supporter carbon membrane in mechanical strength, makes it have higher industrial application value.
Comprise the carbon membrane of carbon molecular sieve membrance, outstanding performance and good application prospect is shown in gas separaion, this is because it has good selective, permeability, high temperature resistant and chemical corrosion resistance, and the aperture size of carbon membrane regulates by multiple methods such as gas activation, thermal contraction, vapour depositions simultaneously.But, for the carbon membrane be carried on the carrier such as porous ceramics, porous carbon pipe, be faced with the problems such as masking difficulty, masking yield rate ventilative speed that is low, gained film is on the low side.Cause the reason of above problem, mainly due to carbon membrane, particularly carbon molecular sieve membrance is very high to the requirement of preparation technology, gained finished film aperture is less, must avoid large needle-like, rimiform defect, and this is when preparing large area film, is difficult to avoid.People attempt to adopt the method preparing multilayer film, needle-like defect, crack are covered, but this structure of multilayer film makes a lot of duct be blocked by follow-up film forming matter, and formed " carbon pile plug ", the via count of final whole film greatly reduces, and the ventilative speed of film significantly declines.
The existence of above problem, thus the high finished product rate making carbon membrane be difficult to realize producing and extensive preparation, also hinder its extensive use.
Summary of the invention
The preparation method of the carbon composite membrane that the object of the present invention is to provide a kind of palladium to modify, to overcome the masking failure caused because supporter defect is more in conventional carbon membrane preparation process, and the film finished product blind hole handing over the factor such as lid to cause due to the multilayer film shortcomings such as hydrogen resistance is large too much, thoroughly, thus realize the high finished product rate of producing and prepare on a large scale.
Technical scheme of the present invention is as follows:
The preparation method of the monolayer carbon composite membrane that a kind of palladium provided by the invention is modified, is characterized in that the method is carried out as follows:
A. select tubular porous material or sheet-like porous material as carrier;
B. pre-heat carrier control its temperature, this temperature is the temperature during material generation pyrolysis of palladium source; Pass into carrier gas to side, carrier masking face, between the inside and outside two sides making tubular carrier, or form gas pressure difference between two of chip carrier sides;
C. make palladium source material masking face close to carrier under the carrying of carrier gas, and under the driving of pressure differential, enter the duct of carrier, the deposition reaction of palladium occurs;
D. take out the carrier after depositing Pd, carbon membrane is prepared in masking face;
E. by the carbon membrane material made according to the method in step b and step c, again carry out the deposition of palladium, obtain monolayer carbon composite membrane.
The preparation method of the multilayer carbon composite membrane that a kind of palladium provided by the invention is modified, is characterized in that the method is carried out as follows:
A. select tubular porous material or sheet-like porous material as carrier;
B. pre-heat carrier control its temperature, this temperature is the temperature during material generation pyrolysis of palladium source; Pass into carrier gas to side, carrier masking face, between the inside and outside two sides making tubular carrier, or form gas pressure difference between two of chip carrier sides;
C. make palladium source material under the carrying of carrier gas, close to the masking face of carrier, and under the driving of pressure differential, enter the duct of carrier, the deposition reaction of palladium occurs;
D. take out the carrier after depositing Pd, prepare one deck carbon membrane;
E. by the carbon membrane material made according to the method in step b and step c, again carry out the deposition of palladium, the lower one deck carbon membrane of then preparation;
F. repeat the operation of step e many times, obtain multilayer carbon composite membrane.
In technique scheme, the method for described mineralization pressure difference adopts the method for pressurizeing to carrier gas or vacuumizing in the non-masking side of carrier, or adopts carrier gas pressurization and vacuumize the method for simultaneously carrying out in the non-masking side of carrier.
In technique scheme, the described method preparing carbon membrane adopts one or more in dip-coating method, spin-coating method, spread coating, spraying process and chemical vapour deposition technique.
Preferably, described palladium source material adopts one or more in palladium acetylacetonate, acid chloride, oxalic acid palladium, the hexafluoroacetylacetonate ketonic compound of palladium or the chloride of palladium.
Preferably, described carrier adopts earthenware, charcoal pipe, stainless steel tube, potsherd, graphite flake or stainless steel substrates.
Preferably, during depositing Pd, in carrier gas, the content of palladium source material is 2mg/l to 500mg/l, and palladium sedimentation time is at least 5 minutes.
The present invention is compared with traditional process, have the following advantages and outstanding technique effect: 1. in prior art, supporter carbon membrane prepares failure and carbon membrane exists the defect such as crack, large perforate, often existing defects own is relevant with carrier, particularly needle-like, the slit-like defect of those permeabilities.Adopt the method that the present invention proposes, when carrying out palladium deposition in hole to carrier, palladium deposition preferentially can be there is in macropore on carrier and crack, therefore needle-like, rimiform defect can be repaired, the aperture of macropore is conditioned and diminishes, finally make the overall pore-size distribution of carrier become more tight, eliminate defect and macropore, this is obviously conducive to the preparation of high-quality carbon membrane on carrier.2. carbon membrane also can be sprawled the factors such as uneven, partial film forming, pyrolysis be too fast due to precursor liquid and produce various defect and large through hole in preparation process, causes the gas-selectively of film to decline.The method adopting the application to propose can repair these defects equally.3. for the defect of above-mentioned carrier and carbon membrane, the method taked traditionally is preparation multilayer carbon membrane, each layer carbon membrane is allowed to hand over lid each other, the defect of specific rete is sheltered from, although in raising gas-selectively effectively, the mutual friendship lid crossing multilayer film makes through hole ratio in whole carbon membrane significantly decline to this method, a lot of through hole has been blocked into blind hole along with the increase of rete number, the gas transmision rate of such material can significantly decline, and has a strong impact on its effective utilization.And the method adopting the application to propose, although define palladium " embolism " in a lot of duct, even blocked, but because palladium has unique affinity characteristic to hydrogen, it is concerning being still " unobstructed " hydrogen, and with " hydrogen permeation selectivity ", when therefore composite membrane uses as Hydrogen Separation film, palladium contained in rete will increase the transport path of hydrogen with its distinctive hydrogen characteristic.Above advantage, can overcome the masking failure caused because supporter defect is more in conventional carbon membrane preparation process, and the film finished product blind hole handing over the factor such as lid to cause due to multilayer film too much, the shortcoming such as saturating hydrogen resistance is large.Therefore, adopt the method to prepare carbon membrane, having the selective hydrogen permeability of high, the made composite membrane of yield rate can wait advantage well, and importantly, the method obtains hydrogen throughout curve and all high carbon membrane of through-rate by less masking number of times and carbon membrane thickness.
Accompanying drawing explanation
Fig. 1 is the equipment schematic diagram that uses of carbon composite membrane that the present invention prepares palladium and modifies, for the preparation of tubulose carbon composite membrane.
In figure: 1-tubular carrier; 2-carrier gas inlet pipe; 3-reaction tube; 4-heating furnace; 5-carrier gas outlet; A and B is the two ends of tubular carrier 1; C is the port of reaction tube 3.
Fig. 2 is another equipment schematic diagram of using of carbon composite membrane that the present invention prepares palladium and modifies, for the preparation of sheet carbon composite membrane.
In figure: 6-chip carrier; Wireway before 7-; Wireway after 8-; 9-heating furnace.
Detailed description of the invention
First method provided by the invention adopts carrier gas to pressurize, or in the mode that the offside in carrier masking face vacuumizes, utilizes certain pressure to force and carry the carrier gas of palladium source gas by carrier duct, carrier is carried out to the chemical vapour deposition (CVD) (CVD) of palladium.The defect such as crack, pin hole of the penetrating type on carrier, because aperture is larger, under the existence of pressure differential, preferential can there is palladium deposition in its duct, i.e. palladium deposition in hole, therefore after CVD the aperture of carrier by adjusted, the large number of perforations of carrier significantly reduces, pore-size distribution is tending towards even, and particularly needle-like, rimiform defect obtain repairing, and this is conducive to the load of follow-up carbon membrane.Then prepare carbon membrane via dipping-pulling method.During preparation multilayer carbon molecular sieve membrance, also first the palladium CVD under above-mentioned pressure reduction existence condition is carried out to carrier, often prepare one deck carbon membrane, all carry out palladium deposition in a secondary aperture, then carry out the preparation of lower one deck carbon membrane again.The palladium deposition of carrying out in advance is modified, can the needle-like defect on Efficient software patching carrier and front one deck carbon membrane surface and crack, improves the success rate of masking.Although define palladium " embolism " in a lot of duct, even blocked, but because palladium has unique affinity characteristic to hydrogen, it is concerning being still " unobstructed " hydrogen, and with " hydrogen permeation selectivity ", there is when therefore composite membrane uses as Hydrogen Separation film the selective and high transmission rates of very strong hydrogen.Above advantage, can overcome the masking failure caused because supporter defect is more in conventional film-forming process, and the film finished product blind hole handing over the factor such as lid to cause due to multilayer film too much, the shortcoming such as saturating hydrogen resistance is large.Therefore, adopt the method to prepare carbon membrane, having the selective hydrogen permeability of high, the made composite membrane of yield rate can wait advantage well, and importantly, the method obtains hydrogen throughout curve and all high carbon membrane of through-rate by less coating times/coating thickness.
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further details.
The preparation method of the monolayer carbon composite membrane that a kind of palladium provided by the invention is modified, the method is carried out as follows:
A. select tubular porous material or sheet-like porous material as carrier, such as carrier adopts earthenware, charcoal pipe, stainless steel tube, potsherd, graphite flake or stainless steel substrates etc.
B. pre-heat carrier control its temperature, this temperature is the temperature during material generation pyrolysis of palladium source; Pass into carrier gas to side, carrier masking face, between the inside and outside two sides making tubular carrier, or form gas pressure difference between two of chip carrier sides; Adopt the method that carrier gas is pressurizeed or vacuumized in the non-masking side of carrier, or adopt carrier gas pressurization and vacuumize the method for simultaneously carrying out in the non-masking side of carrier.
C. make palladium source material masking face close to carrier under the carrying of carrier gas, and under the driving of pressure differential, enter the duct of carrier, the deposition reaction of palladium occurs; Palladium source material adopts one or more in palladium acetylacetonate, acid chloride, oxalic acid palladium, the hexafluoroacetylacetonate ketonic compound of palladium or the chloride of palladium.During depositing Pd, in carrier gas, the content of palladium source material is generally 2mg/l to 500mg/l, and palladium sedimentation time is at least 5 minutes;
D. take out the carrier after depositing Pd, carbon membrane is prepared in masking face; Prepare one or more in method employing dip-coating method, spin-coating method, spread coating, spraying process and the chemical vapour deposition technique of carbon membrane;
E. by the carbon membrane material made according to the method in step b and step c, again carry out the deposition of palladium, obtain monolayer carbon composite membrane.
The preparation method of the multilayer carbon composite membrane that a kind of palladium provided by the invention is modified, the method is carried out as follows:
A. select tubular porous material or sheet-like porous material to select tubular porous material or sheet-like porous material as carrier as carrier, such as carrier adopts earthenware, charcoal pipe, stainless steel tube, potsherd, graphite flake or stainless steel substrates etc.;
B. pre-heat carrier control its temperature, this temperature is the temperature during material generation pyrolysis of palladium source, and the chemical property according to palladium source material is selected, general close with its pyrolysis temperature; Carrier gas is passed into side, carrier masking face, between the inside and outside two sides making tubular carrier, or form gas pressure difference between two of chip carrier sides, the method forming gas pressure difference can adopt the method for pressurizeing to carrier gas or vacuumizing in the non-masking side of carrier, or adopts carrier gas pressurization and vacuumize the method for simultaneously carrying out in the non-masking side of carrier.
C. make palladium source material under the carrying of carrier gas, close to the masking face of carrier, and under the driving of pressure differential, enter the duct of carrier, the deposition reaction of palladium occurs; Described palladium source material adopts one or more in palladium acetylacetonate, acid chloride, oxalic acid palladium, the hexafluoroacetylacetonate ketonic compound of palladium or the chloride of palladium; During depositing Pd, in carrier gas, the content of palladium source material is 2mg/l to 500mg/l, and palladium sedimentation time is at least 5 minutes;
D. take out the carrier after depositing Pd, prepare one deck carbon membrane; Prepare one or more in method employing dip-coating method, spin-coating method, spread coating, spraying process and the chemical vapour deposition technique of carbon membrane.
E. the carbon membrane material made is carried out again the deposition of palladium according to the method in step b and step c, the lower one deck carbon membrane of then preparation;
F. repeat the operation of step e many times, obtain multilayer carbon composite membrane.
Embodiment 1
In the present embodiment, with micropore α-Al
2o
3earthenware 1 is carrier, and its internal diameter is 6mm, and external diameter is 9mm, length 150mm, and the micropore average pore size of this carrier is about 5nm.By earthenware 1 washed with de-ionized water post-drying, then operate according to following steps:
1) as shown in Figure 1, by α-Al
2o
3the A end sealing of earthenware 1, B end inserts the rear sealing of carrier gas inlet pipe 2.According to shown in Fig. 1, earthenware 1 is placed on quartz reaction tube 3 processed in and by the C port sealing of quartz reaction tube 3, after this crystal reaction tube 3 is positioned in heating furnace 4 heat, control in-furnace temperature be 190 DEG C, the actual length of being heated of earthenware 1 is 100mm.Take argon gas as carrier gas, when pressurizeing, the inside of earthenware 1 is introduced by carrier gas inlet pipe 2, regulate argon pressure, argon gas can be purged earthenware 1 with the flow velocity of 50ml/min, and residual gas is discharged by carrier gas outlet 5, after 20min, introduce in earthenware 1 by the argon carrier containing palladium acetylacetonate via carrier gas inlet pipe 2, the content controlling palladium acetylacetonate in carrier gas is 15mg/l, regulates carrier gas air pressure so that controlling gas flow is 30ml/min.After 2h, stop the introducing of palladium acetylacetonate, but keep carrier gas flux to be still 30ml/min, and stop the heating of heating furnace 4, after in-furnace temperature reduces to room temperature, cut off carrier gas supply, when pipeline internal gas pressure reaches normal pressure, take out earthenware 1.
2) A, B two ends sealer of earthenware 1 is removed, and the air inlet pipe 2 of B end, the outer wall teflin tape of pipe is closely wound around.Take the polyimides 20g that phosphorus content is 20wt% respectively, 1-METHYLPYRROLIDONE 20g, mixing is placed in beaker, is placed on and carries out ultrasonic in ultrasonic cleaner, make it mix, make the polybenzazole precursor liquid solution of carbon containing 10wt%.Pulling machine carries out dipping film to earthenware: be dipped vertically into by pipe in polybenzazole precursor liquid solution, flood and lift with the speed of 6cm/min after 5 minutes, take off the teflin tape of pipe outer wall, by earthenware dry 12 hours at ambient temperature, then in electric tube furnace and vacuum condition under, with the heating rate of 1 DEG C/min by room temperature to 800 DEG C, keep 4h carry out charing process, then in stove, naturally cool to room temperature, now the inwall of earthenware load individual layer carbon membrane.
3) by step 2) in obtain earthenware again according to 1) described by scheme carry out palladium deposition, finally obtain Al
2o
3earthenware is the palladium modified monolayer carbon composite membrane material of carrier.
With H
2, CO
2and N
2for measuring gas, detect the gas separating property of carbon membrane.At room temperature, H
2gas permeation rate reach 155.7 × 10
-9molm
-2s
-1pa
-1; , in selective penetrated property, film is to H
2selective penetrated property very high, reach H
2/ N
2=390, and through ratio CO
2/ N
2=89.And at 200 DEG C, H
2gas permeation rate reach 500.8 × 10
-9molm
-2s
-1pa
-1; , in selective penetrated property, gas permeation ratio H
2/ N
2=743.
Embodiment 2
In the present embodiment, with coal-based Microporous Carbon pipe for carrier, its internal diameter is 10mm, and external diameter is 15mm, length 500mm, and the micropore average pore size of this carrier is about 900nm.By effective for charcoal washed with de-ionized water post-drying, then operate according to following steps:
1) as shown in Figure 1, the A of Microporous Carbon pipe 1 is held sealing, B end inserts the rear sealing of carrier gas inlet pipe 2.According to shown in Fig. 1, charcoal pipe pipe 1 is placed on quartz reaction tube 3 processed in and by the C port sealing of 3, after this crystal reaction tube 3 is positioned in heating furnace 4 heat, control in-furnace temperature be 230 DEG C, the actual length of being heated of Microporous Carbon pipe 1 is 460mm.Take argon gas as carrier gas, in carrier gas outlet 5 side, vacuum extractor is installed, under vacuumized conditions, carrier gas introduces the inside of charcoal pipe 1 by carrier gas inlet pipe 2, regulates the air pressure of carrier gas, and the vacuum of carrier gas outlet 5 side, carrier gas is purged charcoal pipe 1 with the flow velocity of 50ml/min, after 20min, the argon carrier containing acid chloride is introduced in charcoal pipe 1 by carrier gas inlet pipe 2 side, the content controlling acid chloride in carrier gas is 10mg/l, and adjustment carrier gas flux is 50ml/min.After 2h, stop the introducing of acid chloride, but keep carrier gas flux to be still 50ml/min, and stop the heating of heating furnace 4, after in-furnace temperature reduces to room temperature, cut off carrier gas supply, be communicated with air and make pipeline internal gas pressure reach normal pressure, take out charcoal pipe 1.
2) remove A, B two ends sealer of charcoal pipe 1, the outer wall teflin tape of pipe is closely wound around.Take the polyimides 300g that phosphorus content is 20wt% respectively, 1-METHYLPYRROLIDONE 300g, mixing is placed in beaker, is placed on and carries out ultrasonic in ultrasonic cleaner, make it mix, make the polybenzazole precursor liquid solution of carbon containing 10wt%.With pulling machine, dipping film is carried out to charcoal pipe: be dipped vertically into by pipe in polybenzazole precursor liquid solution, flood and lift with the speed of 6cm/min after 5 minutes, take off the teflin tape of pipe outer wall, by charcoal pipe dry 15 hours at ambient temperature, then in electric tube furnace and under vacuum condition, with the heating rate of 1 DEG C/min by room temperature to 900 DEG C, keep 5h carry out charing process, then in stove, naturally cool to room temperature.
3) by step 2) in obtain charcoal pipe again according to 1) described by scheme carry out palladium deposition, and again by 1), 2) in describe operating procedure carry out palladium modify and carbon membrane prepare, repeat 2 times altogether, finally obtain modifying carbon composite membrane material with the palladium that charcoal pipe is carrier, the carbon membrane that haves three layers is gathered around in the inner side of this tubular material.
With H
2and N
2for measuring gas, detect the gas separating property of carbon membrane.At room temperature, H
2gas permeation rate be 105.2 × 10
-9molm
-2s
-1pa
-1; , at H
2selective penetrated property aspect, H
2/ N
2=130.At 200 DEG C, H
2gas permeation rate be 300 × 10
-9molm
-2s
-1pa
-1; , in selective penetrated property, gas permeation ratio H
2/ N
2=190.
Embodiment 3
In the present embodiment, with porous stainless steel disc for carrier, concrete shape is the disk 1 of the diameter 50mm of thickness 3mm, and the micropore average pore size of this carrier is about 900nm.Stainless steel substrates is used washed with de-ionized water post-drying, then operates according to following steps:
1) as shown in Figure 2, front wireway 7 and rear wireway 8 are bonded together with porous stainless steel disc 6, guarantee that abutting edge has gas tightness in 300 DEG C.When bonding, stainless steel substrates 1 needs the surface (hereinafter referred to as " masking face ") of preparing carbon membrane towards wireway 7.Heat according to bonding front wireway 7, rear wireway 8 and stainless steel substrates (hereinafter referred to as wireway carrier convered structure) being placed on shown in Fig. 2 in heating furnace 4, controlling in-furnace temperature is 190 DEG C.Nitrogen buffer gas, when pressurizeing, the internal cavities of wireway carrier convered structure is introduced into by front wireway 7, regulate nitrogen pressure to make its flow velocity reach 50ml/min, purge carrier, residual gas is discharged by rear wireway 8, after 10min, introduced via front wireway 7 by nitrogen carrier gas containing palladium acetylacetonate, the content controlling palladium acetylacetonate in carrier gas is 5mg/l, regulates carrier gas air pressure to make gas flow be 10ml/min.After 1h, stop the introducing of palladium acetylacetonate, but keep carrier gas flux to be still 10ml/min, and stop the heating of heating furnace 4, after in-furnace temperature reduces to room temperature, cut off carrier gas supply, when pipeline internal gas pressure reaches normal pressure, take out wireway carrier convered structure.
2) stainless steel substrates is taken off from wireway carrier convered structure.Take the polyimides 20g that phosphorus content is 20wt% respectively, 1-METHYLPYRROLIDONE 20g, mixing is placed in beaker, is placed on and carries out ultrasonic in ultrasonic cleaner, make it mix, make the polybenzazole precursor liquid solution of carbon containing 10wt%.Adopt spread coating to prepare carbon membrane, namely dip above-mentioned precursor solution with small brushes, be coated on the masking face of stainless steel substrates, then stainless steel substrates vertical hanging is placed 3h, unnecessary precursor solution is dripped by carrier.Take off stainless steel substrates and place under 60 DEG C of conditions dry 12 hours in an oven, then in electric tube furnace and under vacuum condition, with the heating rate of 1 DEG C/min by room temperature to 800 DEG C, 4h is kept to carry out charing process, then in stove, naturally cool to room temperature, now the masking face load individual layer carbon membrane of stainless steel substrates.
3) by 2) in the stainless steel substrates that obtains again according to 1) described by scheme carry out palladium deposition, finally obtaining porous stainless steel is that the palladium of carrier modifies carbon composite membrane material.
Claims (7)
1. a preparation method for the monolayer carbon composite membrane of palladium modification, is characterized in that the method is carried out as follows:
A. select tubular porous material or sheet-like porous material as carrier;
B. pre-heat carrier control its temperature, this temperature is the temperature during material generation pyrolysis of palladium source; Pass into carrier gas to side, carrier masking face, between the inside and outside two sides making tubular carrier, or form gas pressure difference between two of chip carrier sides;
C. make palladium source material masking face close to carrier under the carrying of carrier gas, and under the driving of pressure differential, enter the duct of carrier, the deposition reaction of palladium occurs;
D. take out the carrier after depositing Pd, carbon membrane is prepared in masking face;
E. by the carbon membrane material made according to the method in step b and step c, again carry out the deposition of palladium, obtain monolayer carbon composite membrane.
2. a preparation method for the multilayer carbon composite membrane of palladium modification, is characterized in that the method is carried out as follows:
A. select tubular porous material or sheet-like porous material as carrier;
B. pre-heat carrier control its temperature, this temperature is the temperature during material generation pyrolysis of palladium source; Pass into carrier gas to side, carrier masking face, between the inside and outside two sides making tubular carrier, or form gas pressure difference between two of chip carrier sides;
C. make palladium source material under the carrying of carrier gas, close to the masking face of carrier, and under the driving of pressure differential, enter the duct of carrier, the deposition reaction of palladium occurs;
D. take out the carrier after depositing Pd, prepare one deck carbon membrane;
E. by the carbon membrane material made according to the method in step b and step c, again carry out the deposition of palladium, the lower one deck carbon membrane of then preparation;
F. repeat the operation of step e many times, obtain multilayer carbon composite membrane.
3. the preparation method of the carbon composite membrane of palladium modification according to claim 1 and 2, it is characterized in that, the method of described mineralization pressure difference adopts the method for pressurizeing to carrier gas or vacuumizing in the non-masking side of carrier, or adopts carrier gas pressurization and vacuumize the method for simultaneously carrying out in the non-masking side of carrier.
4. the preparation method of the carbon composite membrane of palladium modification according to claim 1 and 2, is characterized in that, the described method preparing carbon membrane adopts one or more in dip-coating method, spin-coating method, spread coating, spraying process and chemical vapour deposition technique.
5. the preparation method of the carbon composite membrane of palladium modification according to claim 1 and 2, it is characterized in that, described palladium source material adopts one or more in palladium acetylacetonate, acid chloride, oxalic acid palladium, the hexafluoroacetylacetonate ketonic compound of palladium or the chloride of palladium.
6. the preparation method of the carbon composite membrane of palladium modification according to claim 1 and 2, it is characterized in that, described carrier adopts earthenware, charcoal pipe, stainless steel tube, potsherd, graphite flake or stainless steel substrates.
7. the preparation method of the carbon composite membrane of palladium modification according to claim 1 and 2, it is characterized in that, during depositing Pd, in carrier gas, the content of palladium source material is 2mg/l to 500mg/l, and palladium sedimentation time is at least 5 minutes.
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| JP2019514666A (en) * | 2016-04-29 | 2019-06-06 | ダウ グローバル テクノロジーズ エルエルシー | Improved transition metal-containing carbon molecular sieve membranes and methods of making them |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640530A (en) * | 2004-01-09 | 2005-07-20 | 中国科学院大连化学物理研究所 | Composite metal palladium membrane or alloy palladium membrane and its preparing method |
| JP2008246299A (en) * | 2007-03-29 | 2008-10-16 | Noritake Co Ltd | Method of manufacturing hydrogen gas separation material |
| CN102527259A (en) * | 2012-02-10 | 2012-07-04 | 南京工业大学 | Composite carbon molecular sieve membrane and preparation method and application thereof |
-
2015
- 2015-05-21 CN CN201510262740.7A patent/CN104998553B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1640530A (en) * | 2004-01-09 | 2005-07-20 | 中国科学院大连化学物理研究所 | Composite metal palladium membrane or alloy palladium membrane and its preparing method |
| JP2008246299A (en) * | 2007-03-29 | 2008-10-16 | Noritake Co Ltd | Method of manufacturing hydrogen gas separation material |
| CN102527259A (en) * | 2012-02-10 | 2012-07-04 | 南京工业大学 | Composite carbon molecular sieve membrane and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019514666A (en) * | 2016-04-29 | 2019-06-06 | ダウ グローバル テクノロジーズ エルエルシー | Improved transition metal-containing carbon molecular sieve membranes and methods of making them |
| JP7078544B2 (en) | 2016-04-29 | 2022-05-31 | ダウ グローバル テクノロジーズ エルエルシー | Improved transition metal-containing carbon molecular sieve membranes and methods for making them |
| US11471824B2 (en) | 2016-04-29 | 2022-10-18 | Dow Global Technologies Llc | Transition metal containing carbon molecular sieve membranes and method to make them |
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| CN104998553B (en) | 2017-07-07 |
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