CN117899800A - Preparation method of metal hollow fiber catalytic membrane reactor, reactor and application thereof - Google Patents
Preparation method of metal hollow fiber catalytic membrane reactor, reactor and application thereof Download PDFInfo
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a metal hollow fiber catalytic membrane reactor, the metal hollow fiber catalytic membrane reactor and application thereof. The preparation method of the metal hollow fiber catalytic membrane reactor comprises the following steps: a metal powder casting solution preparation process, a temporary outer surface layer casting solution preparation process, a metal hollow fiber catalytic membrane reactor precursor preparation process and a roasting process. According to the preparation method of the metal hollow fiber catalytic membrane reactor, the size and depth of the pore channel structure exposed in the metal hollow fiber catalytic membrane reactor are regulated, and the pore density formed on the surface of the membrane is higher, so that the metal hollow fiber catalytic membrane reactor can be more accurately constructed and regulated.
Description
Technical Field
The invention belongs to the technical field of inorganic membranes, and particularly relates to a preparation method of a metal hollow fiber catalytic membrane reactor.
Background
Hydrogen has a dissolution-diffusion mechanism on part of the metal or alloy material, making such metal films 100% selective for hydrogen. The traditional hydrogen separation usually adopts low-temperature distillation or pressure swing adsorption technology, and the methods have the defects of high energy consumption, large occupied area, complex process and the like, and the metal film can well avoid the defects through a unique separation mode. In addition, most of the metal films have catalytic properties and are suitable for reforming hydrogen production. Therefore, the metal film with hydrogen permeability can form a catalytic film reactor, and the synchronous performance of hydrogen production reaction and hydrogen separation and purification is realized, which is helpful to overcome the limitation of thermodynamic equilibrium of the reaction and improve the reaction conversion rate and the hydrogen yield. Meanwhile, the method can reduce the reaction temperature, alleviate the reaction condition and directly obtain pure hydrogen, thereby simplifying the hydrogen production process and reducing the hydrogen production cost.
Patents similar to metal hollow fiber catalytic membrane reactors, such as "a hollow fiber catalytic hydrogen production membrane and membrane reactor and a preparation method thereof" (patent publication No. CN 112354511A) have been reported previously. However, in the preparation process of the metal hollow fiber catalytic membrane reactor described in the above patent, an organic solvent is used as a temporary external coagulation bath, and the metal hollow fiber precursor forms an open pore structure within an air distance range of 50-100 cm. Because the viscosity of the organic solvent used for the temporary external coagulation bath is very small, the fluidity is very strong, the problem of uneven outer pore channel structure caused by uneven coverage of the temporary external coagulation bath on the metal hollow fiber precursor exists in the operation process, the pore density of the surface of the membrane is also small, and the size and depth of the pore channel structure cannot be regulated and controlled.
Disclosure of Invention
Aiming at the problems, through intensive research, the application discloses a preparation method of a metal hollow fiber catalytic membrane reactor, which adopts a double-layer co-spinning technology to design and prepare a hollow fiber catalytic membrane reactor precursor comprising a metal powder layer and a temporary outer surface layer, and further removes the temporary outer surface layer and organic matters in the metal powder layer by sintering in an oxidizing atmosphere so as to expose finger-shaped pore channels in the membrane, thereby forming the metal hollow fiber catalytic membrane reactor with larger pore density on the surface of the membrane.
In order to achieve the purpose of the invention, the following technical scheme is adopted.
[1] A preparation method of a metal hollow fiber catalytic membrane reactor comprises the following steps:
Preparing a metal powder casting solution: dissolving an organic polymer in an organic solvent, adding metal powder in batches, and uniformly stirring to obtain a metal powder casting solution;
preparing a temporary outer skin layer casting solution: after dissolving an organic polymer in an organic solvent, adding a regulating agent in batches to obtain a temporary outer surface layer casting solution;
The preparation process of the precursor of the metal hollow fiber catalytic membrane reactor comprises the following steps: the metal powder casting film liquid and the temporary outer surface layer casting film liquid are respectively subjected to vacuum degassing, the metal powder casting film liquid, the temporary outer surface layer casting film liquid and the inner solidification liquid are extruded into the outer solidification liquid through a double-layer spinneret by using a high-pressure injection pump, and under the action of the inner solidification liquid and the outer solidification liquid, the metal powder casting film liquid and the temporary outer surface layer casting film liquid are respectively solidified and formed into a metal powder layer and a temporary outer surface layer, the temporary outer surface layer is coated on the outer surface of the metal powder layer, and a precursor of the metal hollow fiber catalytic film reactor is obtained after natural drying;
And (3) roasting: and roasting the precursor of the metal hollow fiber catalytic membrane reactor in an oxidizing atmosphere to remove the temporary outer surface layer and the organic matters in the metal powder layer, oxidizing part of metal in the metal powder layer, and roasting in a reducing atmosphere to reduce the oxidized metal to obtain the metal hollow fiber catalytic membrane reactor.
[2] The method for producing a metal hollow fiber catalytic membrane reactor according to [1], wherein the internal coagulation liquid is a mixture of a solvent and a non-solvent, the solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the non-solvent is at least one selected from the group consisting of water, ethanol, propanol and ethylene glycol;
The mass fraction of the non-solvent in the internal coagulation liquid is 20-80%.
[3] The method for producing a metal hollow fiber catalytic membrane reactor according to [1], wherein,
The temperature of the external solidification liquid is 20-80 ℃,
The external coagulation liquid is a mixture of a solvent and a non-solvent, wherein the solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the non-solvent is at least one selected from the group consisting of water, ethanol, propanol and ethylene glycol;
the mass ratio of the non-solvent in the external coagulation liquid is 20-100%.
[4] The method for producing a metal hollow fiber catalytic membrane reactor according to [1], wherein the metal powder casting solution preparation step satisfies at least one of the following conditions:
in the metal powder film casting liquid, the weight percentage of the organic polymer is 5-10%, the weight percentage of the organic solvent is 12-65%, and the weight percentage of the metal powder is 30-80%;
the organic polymer is at least one selected from the group consisting of polysulfone, polyethersulfone, polyacrylonitrile and polyetherimide;
The organic solvent is at least one selected from N-methylpyrrolidone, N-dimethylamide, N-dimethylacetamide and dimethyl sulfoxide;
the metal powder is at least one selected from nickel powder, iron powder, copper powder, silver powder, zinc powder, vanadium powder and niobium powder and alloy powder thereof;
The particle size of the metal powder is 0.1-5 mu m.
[5] The method for producing a metal hollow fiber catalytic membrane reactor according to [1], wherein the temporary outer skin layer casting solution preparation step satisfies at least one of the following conditions:
The mass ratio of the regulating agent in the temporary outer skin layer casting solution is 2% -40%;
the regulator is at least one selected from the group consisting of water, ethanol, polyvinylpyrrolidone, ammonium polymethacrylate, polymethyl methacrylate and phosphate.
[6] The method for producing a metal hollow fiber catalytic membrane reactor according to [1], wherein the metal hollow fiber catalytic membrane reactor precursor production process satisfies at least one of the following conditions:
The vacuum degassing is carried out under the condition of atmospheric pressure of 0.01-0.1 MPa;
the extrusion speed of the metal powder casting film liquid is 1-15 mL/min;
the extrusion speed of the temporary outer skin layer casting solution is 1-15 mL/min;
the flow rate of the internal coagulation liquid is 1-20 mL/min.
[7] The method for producing a metal hollow fiber catalytic membrane reactor according to [1], wherein the firing step satisfies at least one of the following conditions:
the oxidizing atmosphere is air;
heating to 300-800 ℃ in the roasting under the oxidizing atmosphere;
the roasting time in the roasting under the oxidizing atmosphere is 2-10 h;
In the roasting under the reducing atmosphere, the reducing atmosphere is H 2 -Ar or H 2-N2 mixed gas, and the volume fraction of H 2 in the mixed gas is 2-80%;
The roasting temperature in the roasting under the reducing atmosphere is 1100-1400 ℃;
and the roasting time in the roasting under the reducing atmosphere is 2-10 h.
[8] A metal hollow fiber catalytic membrane reactor prepared by the method for preparing the metal hollow fiber catalytic membrane reactor according to any one of [1] to [7 ].
[9] The use of the metal hollow fiber catalytic membrane reactor of [8] for reforming hydrogen production.
Effects of the invention
According to the preparation method of the metal hollow fiber catalytic membrane reactor, a precursor of the hollow fiber catalytic membrane reactor comprising a metal powder layer and a temporary outer surface layer is obtained by utilizing a double-layer co-spinning technology, and further organic matters in the temporary outer surface layer and the metal powder layer are removed by sintering in an oxidizing atmosphere, so that finger-shaped pore channels in the membrane are exposed, and the metal hollow fiber catalytic membrane reactor with larger pore density on the surface of the membrane is formed.
Drawings
FIG. 1 is a schematic illustration of a double layer spinneret used in a method of making a metal hollow fiber catalytic membrane reactor according to one embodiment.
Fig. 2 is a schematic structural diagram of a metal hollow fiber catalytic membrane reactor precursor obtained in the preparation method of the metal hollow fiber catalytic membrane reactor according to an embodiment.
FIG. 3 is an electron micrograph of the metal hollow fiber catalytic membrane reactor precursor prepared in example 1 and the metal hollow fiber catalytic membrane reactor, wherein A in FIG. 3 is a cross-sectional photograph of the precursor; FIG. 3B is a photograph of a cross section of a metal hollow fiber catalytic membrane reactor; FIG. 3C is a photograph of the exterior surface of a metal hollow fiber catalytic membrane reactor; fig. 3D is an enlarged view of fig. 3C.
FIG. 4 shows the hydrogen permeation capacity of the metal hollow fiber catalytic membrane reactor prepared in example 1 at different temperatures.
FIG. 5 is an electron micrograph of the metal hollow fiber catalytic membrane reactor precursor prepared in example 3 and the metal hollow fiber catalytic membrane reactor, wherein A in FIG. 5 is a cross-sectional photograph of the precursor; FIG. 5B is a photograph of a cross section of a metal hollow fiber catalytic membrane reactor; FIG. 5C is a photograph of the exterior surface of a metal hollow fiber catalytic membrane reactor; d of fig. 5 is an enlarged view of C of fig. 5.
Fig. 6 is a graph of methane conversion in steam reforming of methane at various temperatures for the metal hollow fiber catalytic membrane reactor prepared in example 3.
FIG. 7 is a graph showing the hydrogen permeation capacity of the metal hollow fiber catalytic membrane reactor prepared in example 3 at various temperatures.
Fig. 8 is an SEM image of the outer surface of the sintered metal catalyst separation membrane precursor prepared in comparative example 1.
Detailed Description
The present invention will be further described in detail with reference to examples, but the scope of the present invention is not limited to the examples. It is to be understood by persons of ordinary skill in the art that the following detailed description is illustrative and not restrictive, and should not be taken as limiting the scope of the present disclosure.
In the specification, unless specified otherwise, the percentages refer to mass percentages and the temperature is in degrees centigrade (DEG C).
The invention provides a preparation method of a metal hollow fiber catalytic membrane reactor, which comprises the following steps: the metal powder casting solution preparation step, the temporary outer skin layer casting solution preparation step, the metal hollow fiber catalytic membrane reactor precursor preparation step, and the firing step are described in this order.
[ Metal powder casting solution preparation Process ]
In the preparation process of the metal powder casting solution, after the organic polymer is dissolved in the organic solvent, the metal powder is added and stirred uniformly to obtain the metal powder casting solution.
Preferably, the metal powder is added in portions after the organic polymer is dissolved in the organic solvent. The aforementioned agitation may be, for example, mechanical agitation.
The composition of the metal powder casting solution may be, for example, 5 to 10% by weight of an organic polymer, 12 to 65% by weight of an organic solvent, and 30 to 80% by weight of a metal powder.
The organic polymer may be at least one selected from the group consisting of polysulfone, polyethersulfone, polyacrylonitrile, and polyetherimide.
The organic solvent may be at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylamide, N-dimethylacetamide and dimethylsulfoxide.
The metal powder is at least one selected from nickel powder, iron powder, copper powder, silver powder, zinc powder, vanadium powder, niobium powder, and alloy powders thereof;
The particle size of the metal powder may be, for example, in the range of 0.2 to 5. Mu.m.
[ Preparation Process of temporary outer skin layer casting solution ]
In the preparation process of the temporary outer skin layer casting solution, after the organic polymer is dissolved in the organic solvent, the regulator is added to obtain the temporary outer skin layer casting solution.
Preferably, the modulator is added in portions after the organic polymer is dissolved in the organic solvent.
The organic polymer may be at least one selected from the group consisting of polysulfone, polyethersulfone, polyacrylonitrile, and polyetherimide. The organic polymer used in the temporary outer skin layer casting solution preparation step may be the same as or different from the organic polymer used in the metal powder casting solution preparation step described above, and is preferably the same.
The organic solvent may be at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylamide, N-dimethylacetamide and dimethylsulfoxide. The organic solvent used in the temporary outer skin layer casting solution preparation step may be the same as or different from the organic solvent used in the metal powder casting solution preparation step, and is preferably the same.
The mass ratio of the regulating agent in the temporary outer skin layer casting solution is, for example, in the range of 2% -40%. The regulator is at least one selected from the group consisting of water, ethanol, polyvinylpyrrolidone, ammonium polymethacrylate, polymethyl methacrylate and phosphate.
[ Procedure for preparing precursor of Metal hollow fiber catalytic Membrane reactor ]
In the preparation process of the metal hollow fiber catalytic membrane reactor precursor, after the prepared metal powder casting solution and the temporary outer surface layer casting solution are subjected to vacuum degassing, the metal powder casting solution, the temporary outer surface layer casting solution and the inner coagulating solution are extruded into the outer coagulating solution through a double-layer spinneret by using a high-pressure injection pump, and under the coagulating action of the inner coagulating solution and the outer coagulating solution, the metal powder casting solution and the temporary outer surface layer casting solution are respectively solidified to form the metal hollow fiber catalytic membrane reactor precursor. The precursor of the metal hollow fiber catalytic membrane reactor comprises a metal powder layer and a temporary outer skin layer, wherein the temporary outer skin layer is coated outside the metal powder layer.
The vacuum degassing is performed under conditions of, for example, atmospheric pressure of 0.01 to 0.1 MPa. By setting the atmospheric pressure of vacuum degassing to 0.1 MPa or less, the gas in the metal powder casting solution and the temporary outer skin layer casting solution can be sufficiently removed, and the presence of the gas does not adversely affect the structure of the subsequent metal powder layer, such as defects. The atmospheric pressure for vacuum degassing is set to 0.01 or more in view of the working efficiency and cost.
The thickness of the obtained metal powder layer can be adjusted by adjusting the extrusion speed of the metal powder casting solution. For example, the higher the extrusion speed of the metal powder casting solution, the thicker the metal powder layer obtained. The extrusion speed of the metal powder casting solution may be, for example, 1 to 15mL/min.
The faster the extrusion rate of the temporary skin layer casting solution, the thicker the temporary skin layer obtained, and the density and pore size of the open finger pore channels on the outer surface of the exposed metal powder layer are correspondingly increased after the external organic layer is removed by the sintering procedure. Therefore, the thickness of the obtained temporary outer skin can be adjusted through the extrusion speed of the temporary outer skin casting solution, so that the density and the pore diameter of the pore canal outside the obtained metal hollow fiber catalytic membrane reactor can be further adjusted. The extrusion speed of the temporary outer skin layer casting solution is, for example, 1-15 mL/min.
In some embodiments, the flow rate of the internal coagulation liquid may be, for example, 1 to 20ml/min. The internal coagulation liquid is a mixture of a solvent and a non-solvent. In some embodiments, the solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide. In some embodiments, the non-solvent is at least one selected from the group consisting of water, ethanol, propanol, and ethylene glycol.
In some embodiments, the mass fraction of the non-solvent in the internal coagulation liquid may be, for example, 20-80%.
In some embodiments, the temperature of the external coagulation liquid is, for example, 20 to 80 ℃.
The external coagulation liquid is a mixture of a solvent and a non-solvent. In some embodiments, the solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide. In some embodiments, the non-solvent is at least one selected from the group consisting of water, ethanol, propanol, and ethylene glycol.
In some embodiments, the mass ratio of the non-solvent in the external coagulation liquid may be, for example, 20 to 100%.
By adjusting the composition of the inner and outer coagulation liquids, the microstructure of the precursor can be regulated. Thereby achieving the purpose of adjusting the size and depth of the exposed pore canal structure. For example, as the non-solvent content in the internal coagulation liquid increases, the phase inversion speed in the precursor increases, so that the prepared metal catalytic separation membrane has a thicker compact separation layer, can be better applied to a production scene with larger internal and external pressure difference of the membrane, but the hydrogen flux decreases.
Fig. 1 shows a schematic diagram of a double layer spinneret used in one embodiment. As shown in fig. 1, the double-layer spinneret has passages for passing a metal powder casting solution 1, a temporary outer skin layer casting solution 2, and an inner coagulation solution 3, respectively. The outer coagulation liquid level is outside the double layer spinneret, not shown in fig. 1. The metal powder casting solution 1, the temporary outer surface layer casting solution 2 and the inner coagulating solution 3 flow out from the double-layer spinneret into the outer coagulating solution, and the metal powder casting solution and the temporary outer surface layer casting solution are respectively solidified under the solidification action of the inner coagulating solution and the outer coagulating solution to form the metal hollow fiber catalytic membrane reactor precursor, and the structure of the precursor is shown in figure 2. The precursor of the metal hollow fiber catalytic membrane reactor shown in fig. 2 comprises a metal powder layer 4 and a temporary outer surface layer 5, wherein the temporary outer surface layer 4 is coated outside the metal powder layer 5, and the metal powder layer 4 comprises an internal solidification liquid 6. After the metal hollow fiber catalytic membrane reactor precursor is formed, it is cut into desired lengths. Thereby, the internal coagulation liquid 6 is also removed.
[ Roasting step ]
In the roasting step, the precursor of the metal hollow fiber catalytic membrane reactor is roasted in an oxidizing atmosphere, so that organic matters in the temporary outer surface layer and the metal powder layer are removed, part of metal in the metal powder layer is oxidized, and then the oxidized metal is reduced by roasting in a reducing atmosphere, so that the metal catalytic separation membrane is obtained.
In the baking under the oxidizing atmosphere, the oxidizing atmosphere may be, for example, air or a mixed gas of air and N 2, and is not particularly limited. In some embodiments, the flow rate of the oxidizing atmosphere is, for example, in the range of 10 to 300 mL/min. And heating to 300-800 ℃ in the roasting under the oxidizing atmosphere.
In the calcination in the oxidizing atmosphere, the calcination time may be, for example, 2 to 10 hours.
By performing firing under an oxidizing atmosphere, the aforementioned temporary outer skin layer is oxidized by the oxidizing atmosphere and removed, thereby exposing the metal powder layer coated therewith. Further, by baking in an oxidizing atmosphere, the organic substances in the metal powder layer are also removed by sintering.
In the baking under an oxidizing atmosphere, a part of the metal in the metal powder layer is oxidized. Therefore, after the completion of the baking in the oxidizing atmosphere, the atmosphere is replaced with a reducing atmosphere to reduce the oxidized metal. In some embodiments, the reducing atmosphere may be, for example, a mixture of H 2 -Ar or H 2-N2, and the volume fraction of H 2 in the mixture may be, for example, 2-80%.
In some embodiments, in the calcination in the reducing atmosphere, the flow rate of the reducing atmosphere may be, for example, in a range of 10 to 300 ml/min.
In some embodiments, the temperature rising rate may be, for example, 1 to 20 ℃/min in the calcination under the reducing atmosphere.
In some embodiments, in the roasting under the reducing atmosphere, the temperature of the roasting may be, for example, 1100 to 1400 ℃.
In some embodiments, in the roasting under the reducing atmosphere, the time of the roasting may be, for example, 2 to 10 hours.
On the other hand, the invention also provides a metal hollow fiber catalytic membrane reactor, which is prepared by the preparation method of the metal hollow fiber catalytic membrane reactor.
In yet another aspect, the invention also provides the use of the metal hollow fiber catalytic membrane reactor described above for reforming hydrogen.
Examples
Example 1
10G of polysulfone was weighed, dissolved in 40g of N, N-dimethylacetamide solvent (NMP) with stirring, then 100g of nickel alloy powder with a particle size of 1.5 μm was added, and stirring was continued for 72 hours to obtain a uniform and stable metal powder casting solution. The weight ratio of each component in the casting film liquid is metal powder: and (2) polymer: solvent = 1:0.1:0.4. 20g of polysulfone was weighed, stirred and dissolved in 80g of N, N-dimethylacetamide solvent (NMP), then 6g of polyvinylpyrrolidone was added in portions, and stirring was continued for 24 hours, to obtain a uniform and stable temporary outer skin layer casting solution.
The prepared metal powder casting solution and the temporary outer skin layer casting solution are respectively transferred into a metal syringe, and then placed in a vacuum box of 0.002 MPa for degassing for 1 hour. The metal powder casting solution, the temporary outer skin layer casting solution and the inner coagulation solution (i.e., the inner core solution) with the mass percentage of 80% NMP-20% H 2 O are extruded into deionized water with the temperature of 25 ℃ serving as the outer coagulation solution through a double-layer spinneret (shown in figure 1) at the speeds of 5mL/min, 2.5mL/min and 7mL/min respectively by a high-pressure injection pump.
Cutting the obtained metal hollow fiber catalytic membrane reactor precursor into a length of about 60cm after the metal powder casting solution and the temporary outer surface layer casting solution are solidified, straightening at room temperature and naturally drying for 24 hours, and finally putting the metal hollow fiber catalytic membrane reactor precursor into an atmosphere furnace (air) for sintering. Heating to 600 deg.c at 3 deg.c/min for 2 hr to eliminate organic matter from the temporary outer surface layer and the metal powder layer. Then, mixed gas containing 50% of H 2-N2 is introduced, and the mixture is heated to 1300 ℃ at the same heating rate, and sintered for 3 hours at high temperature. And finally naturally cooling to room temperature to obtain the metal hollow fiber catalytic membrane reactor.
FIG. 3 shows an electron micrograph of the resulting metal hollow fiber catalytic membrane reactor, wherein A of FIG. 3 is a photograph of a cross section of the precursor; FIG. 3B is a photograph of a cross section of a metal hollow fiber catalytic membrane reactor; FIG. 3C is a photograph of the exterior surface of a metal hollow fiber catalytic membrane reactor; fig. 3D is an enlarged view of fig. 2C. As can be seen from FIG. 3, the obtained metal hollow fiber catalytic membrane reactor has an asymmetric composite tube wall structure, an outer layer is a porous supporting layer of 80 mu m, and an inner layer is a dense separating layer of 10 mu m.
The prepared metal hollow fiber catalytic membrane reactor is used for hydrogen separation test, specifically, 50vol% of H 2/Ar is introduced outside the metal hollow fiber catalytic membrane reactor, N 2 is used as purge gas, the H 2 content in the purge gas is measured on a gas chromatograph, and the temperature is regulated to be measured at different temperatures, so that the hydrogen permeation quantity at different temperatures is obtained, and the result is shown in fig. 4. As can be seen from FIG. 4, the hydrogen permeation amount increases with the increase of the temperature, and at 900 ℃, the hydrogen permeation amount can reach 4.13mL/min.
Example 2
A metal powder casting solution and a temporary outer skin layer casting solution were prepared in the same manner as in example 1.
Then the metal powder casting solution, the temporary outer surface layer casting solution and the inner coagulating solution (namely the inner core solution) of 60 percent of NMP-40 percent of H 2 O by mass percent are extruded into deionized water with the temperature of 25 ℃ serving as the outer coagulating solution through a double-layer spinneret at the speeds of 6mL/min, 2.5mL/min and 8mL/min respectively by a high-pressure injection pump.
And cutting the obtained precursor of the metal hollow fiber catalytic membrane reactor into a length of about 60cm after the metal powder casting solution and the temporary outer surface layer casting solution are solidified, airing at room temperature, and sintering in the same way as in the example 1 to obtain the metal hollow fiber catalytic membrane reactor.
The hydrogen permeation amount was measured at 900℃under the same test conditions as in example 1, and it was found that 2.97mL/min was reached.
Example 3
A metal powder casting solution and a temporary outer skin layer casting solution were prepared in the same manner as in example 1, and 80% NMP-20% H 2 O by mass percentage of the metal casting solution, the temporary outer skin layer casting solution and the inner coagulation solution (i.e., the inner core solution) were extruded from the double layer spinneret into deionized water having a temperature of 25℃as the outer coagulation solution at a rate of 4mL/min, 4mL/min and 7mL/min, respectively, by a high pressure injection pump.
And cutting the obtained precursor of the metal hollow fiber catalytic membrane reactor into a length of about 60cm after the metal powder casting solution and the temporary outer surface layer casting solution are solidified, airing at room temperature, and sintering in the same way as in the example 1 to obtain the metal hollow fiber catalytic membrane reactor. FIG. 5 shows an electron micrograph of the metal hollow fiber catalytic membrane reactor precursor prepared in example 3 and the metal hollow fiber catalytic membrane reactor, wherein A of FIG. 5 is a photograph of a cross section of the precursor; FIG. 5B is a photograph of a cross section of a metal hollow fiber catalytic membrane reactor; FIG. 5C is a photograph of the exterior surface of a metal hollow fiber catalytic membrane reactor; d of fig. 5 is an enlarged view of C of fig. 5.
Further, methane steam reforming experiments at different temperatures were performed on the prepared metal hollow fiber catalytic membrane reactor under the conditions that CH 4, 15mL/min water vapor and 15mL/min He as diluent gas were fed outside the membrane and 60mL/min N 2 was used as purge gas in the membrane, the methane conversion results at different temperatures are shown in FIG. 6, and the hydrogen permeation results at different temperatures are shown in FIG. 7. As can be seen from fig. 6, the methane conversion is 70.90% at 900 ℃. As can be seen from FIG. 7, the flow rate of hydrogen gas separated at 900℃was 3.74mL/min.
Comparative example 1
A metal powder casting solution was prepared in the same manner as in example 1, 90wt% NMP-ethanol was used instead of the temporary outer skin layer casting solution in example 1, and the metal powder casting solution, 90wt% NMP-ethanol and H 2 O as an inner coagulation solution (i.e., an inner core solution) were extruded into deionized water as an outer coagulation solution at a temperature of 25℃through a double layer spinneret as shown in FIG. 1 at a rate of 8mL/min, 2.5mL/min and 8mL/min, respectively, by a high pressure injection pump, and the air gap was controlled to 80cm. After spinning, a 60cm hollow fiber precursor was cut, dried at room temperature, and sintered in the same manner as in example 1 to obtain a metal catalytic separation membrane.
Fig. 8 shows SEM pictures of the outer surface of the metal catalytic separation membrane obtained as described above, and it can be seen that the density of pores formed on the membrane surface by the method of comparative example 1 is small and uneven, and finger-shaped pores inside a part of the membrane body are not exposed.
It should be apparent that the foregoing examples of the present disclosure are merely illustrative of the present disclosure and not limiting of the embodiments of the present disclosure, and that various other changes and modifications may be made by one of ordinary skill in the art based on the foregoing description, and it is not intended to be exhaustive of all embodiments, and all obvious changes and modifications that come within the scope of the present disclosure are intended to be embraced by the technical solution of the present disclosure.
Claims (9)
1. A preparation method of a metal hollow fiber catalytic membrane reactor comprises the following steps:
preparing a metal powder casting solution: dissolving an organic polymer in an organic solvent, adding metal powder, and uniformly stirring to obtain a metal powder casting solution;
Preparing a temporary outer skin layer casting solution: after dissolving an organic polymer in an organic solvent, adding a regulating agent to obtain a temporary outer skin layer casting solution;
The preparation process of the precursor of the metal hollow fiber catalytic membrane reactor comprises the following steps: the metal powder casting film liquid and the temporary outer surface layer casting film liquid are respectively subjected to vacuum degassing, the metal powder casting film liquid, the temporary outer surface layer casting film liquid and the inner solidification liquid are extruded into the outer solidification liquid through a double-layer spinneret by using a high-pressure injection pump, and under the action of the inner solidification liquid and the outer solidification liquid, the metal powder casting film liquid and the temporary outer surface layer casting film liquid are respectively solidified and formed into a metal powder layer and a temporary outer surface layer, the temporary outer surface layer is coated on the outer surface of the metal powder layer, and a precursor of the metal hollow fiber catalytic film reactor is obtained after natural drying;
And (3) roasting: and roasting the precursor of the metal hollow fiber catalytic membrane reactor in an oxidizing atmosphere to remove the temporary outer surface layer and the organic matters in the metal powder layer, oxidizing part of metal in the metal powder layer, and roasting in a reducing atmosphere to reduce the oxidized metal to obtain the metal hollow fiber catalytic membrane reactor.
2. The method for producing a metal hollow fiber catalytic membrane reactor as claimed in claim 1, wherein,
The internal coagulation liquid is a mixture of a solvent and a non-solvent, wherein the solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the non-solvent is at least one selected from the group consisting of water, ethanol, propanol and ethylene glycol;
The mass fraction of the non-solvent in the internal coagulation liquid is 20-80%.
3. The method for producing a metal hollow fiber catalytic membrane reactor as claimed in claim 1, wherein,
The temperature of the external solidification liquid is 20-80 ℃;
The external coagulation liquid is a mixture of a solvent and a non-solvent, wherein the solvent is at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the non-solvent is at least one selected from the group consisting of water, ethanol, propanol and ethylene glycol;
the mass ratio of the non-solvent in the external coagulation liquid is 20-100%.
4. The method for producing a metal hollow fiber catalytic membrane reactor according to claim 1, wherein the metal powder casting solution preparation step satisfies at least one of the following conditions:
in the metal powder film casting liquid, the weight percentage of the organic polymer is 5-10%, the weight percentage of the organic solvent is 12-65%, and the weight percentage of the metal powder is 30-80%;
the organic polymer is at least one selected from the group consisting of polysulfone, polyethersulfone, polyacrylonitrile and polyetherimide;
The organic solvent is at least one selected from N-methylpyrrolidone, N-dimethylamide, N-dimethylacetamide and dimethyl sulfoxide;
the metal powder is at least one selected from nickel powder, iron powder, copper powder, silver powder, zinc powder, vanadium powder and niobium powder and alloy powder thereof;
The particle size of the metal powder is 0.1-5 mu m.
5. The method for producing a metal hollow fiber catalytic membrane reactor according to claim 1, wherein the temporary outer skin layer casting solution preparation process satisfies at least one of the following conditions:
The mass ratio of the regulating agent in the temporary outer skin layer casting solution is 2% -40%;
the regulator is at least one selected from the group consisting of water, ethanol, polyvinylpyrrolidone, ammonium polymethacrylate, polymethyl methacrylate and phosphate.
6. The method for producing a metal hollow fiber catalytic membrane reactor according to claim 1, wherein the metal hollow fiber catalytic membrane reactor precursor production process satisfies at least one of the following conditions:
The vacuum degassing is carried out under the condition of atmospheric pressure of 0.01-0.1 MPa;
the extrusion speed of the metal powder casting film liquid is 1-15 mL/min;
the extrusion speed of the temporary outer skin layer casting solution is 1-15 mL/min;
the flow rate of the internal coagulation liquid is 1-20 mL/min.
7. The method for producing a metal hollow fiber catalytic membrane reactor according to claim 1, wherein the firing step satisfies at least one of the following conditions:
the oxidizing atmosphere is air;
heating to 300-800 ℃ in the roasting under the oxidizing atmosphere;
the roasting time in the roasting under the oxidizing atmosphere is 2-10 h;
In the roasting under the reducing atmosphere, the reducing atmosphere is H 2 -Ar or H 2-N2 mixed gas, and the volume fraction of H 2 in the mixed gas is 2-80%;
The roasting temperature in the roasting under the reducing atmosphere is 1100-1400 ℃;
and the roasting time in the roasting under the reducing atmosphere is 2-10 h.
8. A metal hollow fiber catalytic membrane reactor prepared by the method for preparing a metal hollow fiber catalytic membrane reactor according to any one of claims 1 to 7.
9. Use of the metal hollow fiber catalytic membrane reactor of claim 8 for reforming hydrogen production.
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| CN102228803A (en) * | 2011-04-19 | 2011-11-02 | 蒋兰英 | Method for preparing hollow fiber composite membrane |
| KR20130042131A (en) * | 2011-10-18 | 2013-04-26 | 웅진케미칼 주식회사 | Manufacturing method of metallic hollow fiber having porosity |
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