CN101318106A - Plate shaped ceramic film composed of multiple hollow fiber ceramic films by parallel connection and preparation thereof - Google Patents
Plate shaped ceramic film composed of multiple hollow fiber ceramic films by parallel connection and preparation thereof Download PDFInfo
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- CN101318106A CN101318106A CNA2008101233427A CN200810123342A CN101318106A CN 101318106 A CN101318106 A CN 101318106A CN A2008101233427 A CNA2008101233427 A CN A2008101233427A CN 200810123342 A CN200810123342 A CN 200810123342A CN 101318106 A CN101318106 A CN 101318106A
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Abstract
The invention discloses a tabular hollow fiber ceramic membrane element formed by connecting a plurality of hollow fiber ceramic membranes in parallel and a preparation method thereof. The invention is characterized in that a plurality of hollow fiber ceramic membrane green bodies, one end of which is open and the other end of which is closed or both ends of which are open are sintered at the temperature ranging from 900 to 1600 DEG C for 5 to 20 hours in a state of mutual close contact by aligning both ends and driving single layer to stand side by side; or the tabular hollow fiber ceramic membrane green bodies, which are prepared by a single layered parallel connection of hollow fiber ceramic membranes using extrusion, are sintered at a high temperature ranging from 900 and 1600 DEG C for 5 to 20 hours after being dried. Compared with a single fiber hollow ceramic membrane element, the mechanical strength of the tabular hollow fiber ceramic membrane element is significantly enhanced, thus being beneficial to preparing large-size membrane elements, enhancing the reliability and the service life of the ceramic membrane; moreover, owing to the decrease of the assembly dispersity, the packing density of the membrane components is further enhanced far from being lowered. The tabular hollow fiber ceramic membrane element can be used for manufacturing gas or liquid separation and purification device or high temperature heat exchanger.
Description
Technical field
The invention belongs to the hollow fiber ceramic membrane technical field, be specifically related to ceramic membrane isolation technics and ceramic membrane heat exchanger technology, particularly a kind of tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes and preparation method thereof.
Background technology
Introduce according to " american chemical IEEE magazine " (AIChE Journal, 51 (7) (2005) 1991-2000), the structure of present ceramic membrane mainly contains plate, three kinds of cast and doughnuts.For the ceramic membrane that high temperature uses, there is the problem of membrane module sealing difficulty in existing plate ceramic membrane; The tubular ceramic film can move on to low-temperature space with the sealing station of membrane module, solved the problem of ceramic film component sealing difficulty, but because the tubular ceramic film is thicker, the permeation flux of film is low, and the effective film area (loading density that is called membrane module) in the membrane module unit volume is lower; It is higher that the membrane module of hollow fiber ceramic membrane element is loaded density.
Chinese patent publication number CN101108310A (number of patent application: 200710025876.1) " a kind of hollow fiber ceramic membrane element and the assembly thereof " of Pi Luing, some hollow fiber ceramic membranes are assembled the hollow fiber ceramic membrane bundle, adopt the encapsulation of ceramic sealing material high temperature by the membrane module two ends of hollow fiber ceramic membrane bundle assembling, solved the problem that the membrane module that adopts the organic bond encapsulation can not use under harsh conditions such as high temperature, strong acid, highly basic.This membrane module that constitutes by some hollow fiber ceramic membrane simple set bunchys and two ends fixing seal, also exist following deficiency: one, single hollow fiber ceramic membrane element, because its mechanical strength is lower, factory length is restricted, and is not suitable for making large scale and membrane area membrane module capacious; They are two years old, because the length of single hollow fiber ceramic membrane element is very big, crooked randomly easily and distortion in the actual fabrication process, Zu Zhuan membrane module thus, wherein the curve form of every hollow fiber ceramic membrane and degree have nothing in common with each other, when at high temperature using and being reduced in the process of room temperature the thermal expansion of each root hollow fiber ceramic membrane, contraction and thermal stress state difference in temperature, easily cause the damaged and fracture of part hollow fiber ceramic membrane, reduced the service life of membrane module; The 3rd, when the actual assembled membrane module, realize the strict refractory ceramics sealing of the every hollow fiber ceramic membrane in hollow fiber ceramic membrane tube bank two ends, very high to the requirement of Sealing Technology, so yield rate is low, the manufacturing cost height.
Summary of the invention
The present invention proposes a kind of tabular hollow fiber ceramic membrane element that is connected and composed side by side by many hollow fiber ceramic membranes and preparation method thereof, when the membrane module that keeps hollow fiber ceramic membrane is loaded the high advantage of density, significantly improve the mechanical strength of ceramic membrane element, thereby improve the fabrication yield of ceramic membrane, help manufacturing large scale, the high ceramic film component of loading density, high membrane area capacity, high reliability.
The tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes of the present invention, by 0.5～3.0 millimeter of internal diameter, 1～5 millimeter of external diameter, 0.1～1 millimeter of wall thickness, long 50～2000 millimeters hollow fiber ceramic membrane constitutes, it is characterized in that: connect and compose long 50～2000 millimeters side by side by many hollow fiber ceramic membrane individual layers, wide 10～200 millimeters whole tabular hollow fiber ceramic membrane element, the minimum range between the wherein adjacent hollow fiber ceramic membrane inwall is more than or equal to the wall thickness of corresponding hollow fiber ceramic membrane, less than two times of hollow fiber ceramic membrane wall thickness; On the thickness direction of tabular hollow fiber ceramic membrane element, the minimum size for connection between adjacent hollow fiber ceramic membrane is 10～50% of an adjacent hollow fiber ceramic membrane external diameter.
The preparation method of the tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes of the present invention, it is characterized in that earlier taking by weighing 70～80% ceramic membrane material powder, 0.4～0.6% polyether sulfone forming agent, 20～30% N-methyl pyrrolidone (NMP) organic solvent and 0.03～0.05% polyvinylpyrrolidone (PVP) surfactant by mass ratio, ball milling mixes made the ceramic powder slurry in 24～48 hours; Adopt phase inversion that the ceramic powder pulp preparation is become the ceramic membrane green compact then, be prepared into tabular hollow fiber ceramic membrane element in 5～20 hours with 900～1600 ℃ of sintering at last;
Described employing phase inversion becomes the ceramic membrane green compact with the ceramic powder pulp preparation, one of following dual mode of optional usefulness carries out: first kind of mode is to adopt the required hollow fiber ceramic membrane single tube green compact of phase inversion extrusion molding earlier, then many measure-alike hollow fiber ceramic membrane single tube green compact individual layers are listed on the plane bottom plate, and both sides from many hollow fiber ceramic membrane single tube green compact arranged side by side, edge and column direction inwardly impose the even extruding force of 0.05～0.5N/cm, under the condition of mutual extrusion contact between each hollow fiber ceramic membrane single tube green compact arranged side by side, with 900～1600 ℃ of sintering 5～20 hours, sintering connected and composed the whole tabular hollow fiber ceramic membrane element that is connected and composed side by side by many hollow fiber ceramic membranes; Or, the second way is adopt earlier the direct extrusion molding of phase inversion to serve as reasons whole tabular hollow fiber ceramic membrane element green compact that many hollow fiber ceramic membranes connect and compose side by side, then with 900～1600 ℃ of sintering 5～20 hours, sintering forms the whole tabular hollow fiber ceramic membrane element that is connected and composed side by side by many hollow fiber ceramic membranes.
When adopting above-mentioned first kind of mode to prepare, the mould that the wet base of extrusion molding hollow fiber ceramic membrane single tube uses by two coaxial in, outer tube constitutes, the internal diameter of mould outer tube is corresponding to the external diameter of each hollow fiber ceramic membrane in the tabular hollow fiber ceramic membrane element that will prepare, the external diameter of pipe is corresponding to the internal diameter of each hollow fiber ceramic membrane in the tabular hollow fiber ceramic membrane element that will prepare in the mould, 1/2nd wall thickness corresponding to each hollow fiber ceramic membrane in the tabular hollow fiber ceramic membrane element that will prepare of the difference of the external diameter of the interior pipe of mould and the internal diameter of outer tube; During extrusion molding, the ceramic powder slurry is extruded the circular ring type slit between the mould inner and outer pipe under the promotion of the pressure of 0.02～1MPa, is shaped to the wet base of cannulated fiber ceramics film; Wet base when mould is extruded at hollow fiber ceramic membrane, the employed curing agent water of phase inversion enters in the pipe of the hollow fiber ceramic membrane of extruding from the interior pipe of the mould flow with 2～20 milliliters of per minutes, and the wet base of just having extruded from mould of film pipe immerses in the curing agent tank immediately; Under 20～50 ℃ of conditions, the organic solvent while in the wet base tube wall of hollow fiber ceramic membrane exchanges with the water of the inside and outside both sides of tube wall, exchanges 24～48 hours caudacoria pipes and solidifies, and is dry under 10～50 ℃ of atmospheric environments then; Dried hollow fiber ceramic membrane green compact are cut into the hollow fiber ceramic membrane single tube green compact of Len req; With some measure-alike hollow fiber ceramic membrane single tube green compact justify aligns, individual layer solid matter on plane bottom plate, and from the both sides of many hollow fiber ceramic membrane single tube green compact arranged side by side, along and column direction inwardly impose the even extruding force of 0.05～0.5N/cm, under the condition that is tight extruding contact between each hollow fiber ceramic membrane single tube green compact arranged side by side, with 900～1600 ℃ of sintering 5～20 hours.
When adopting the second way recited above to prepare, adopt the extrusion molding mould of the wet base of whole tabular hollow fiber ceramic membrane element, this mould is constituted by epimorph and pectination core rod; Described pectination core rod is: on total straight tube of one one end sealing, from 5～10 millimeters of distance blind ends, on same straight line, equidistantly distribute the arm of several equal lengths successively, the external diameter of this arm is corresponding to the internal diameter of each hollow fiber ceramic membrane of the tabular hollow fiber ceramic membrane element that will prepare, distance between adjacent external diameter of pipe is corresponding to the minimum range between the adjacent hollow fiber ceramic membrane inwall in the tabular hollow fiber ceramic membrane element that will prepare, the radical of arm is corresponding to the quantity of the hollow fiber ceramic membrane that is comprised in the tabular hollow fiber ceramic membrane element that will prepare, and a length of tube is 10～20 millimeters; Total straight tube is connected with each arm, and the non-blind end of total straight tube is as the input port of the used curing agent water of phase inversion; Described epimorph is: on thick 5～10 millimeters flat board, the equidistant equal and interconnective through hole of a plurality of internal diameters that offers on same straight line, the quantity in hole equates with the quantity of core rod arm, centre distance on the centre distance of adjacent holes and the core rod between the adjacent arm equates, the internal diameter in hole and core rod prop up 1/2nd wall thickness corresponding to the hollow fiber ceramic membrane of the tabular hollow fiber ceramic membrane element that will prepare of the difference of external diameter of pipe; The circle in two holes of adjacent connection intersect and the chord length of the public string determined corresponding to the tabular hollow fiber ceramic membrane element that will prepare in the minimum size for connection between adjacent hollow fiber ceramic membrane on the thickness direction; When the epimorph of assembling extrusion molding mould and core rod, the epimorph porous plate is as the jar end of ceramic slurry batch can, and each arm of core rod is coaxial with corresponding each hole of epimorph, inserts each corresponding hole vertically from top to bottom; Total straight tube of core rod is being fixed in the ceramic slurry batch can at distance jar 5～10 millimeters places of inner surface, the end, inner surface on the inner surface and at the bottom of being parallel to jar at the bottom of being positioned at jar; The lower end of each arm of core rod is concordant with the lower surface at the bottom of the ceramic slurry batch can jar; During extrusion molding, ceramic powder slurry in the slurry tank is being extruded and moulding from the slit between epimorph and the core rod arm under the promotion of 0.02～1MPa pressure, meanwhile, curing agent water enters in the pipe of each hollow fiber ceramic membrane with the flow of 2～20 milliliters of per minutes, and the wet base of just extruding from mould is immersed in the curing agent tank immediately; Under 20～50 ℃ of conditions, curing agent water from the inside and outside both sides of the wet base of ceramic membrane simultaneously with wet base film in organic solvent exchange, exchange 24～48 hours and makes the wet base curing of film; Dry under 10～50 ℃ of atmospheric environments then; Dried ceramic membrane green compact are cut into Len req, then with 900～1600 ℃ of high temperature sinterings 5～20 hours.
Described hollow fiber ceramic membrane is dense ceramic membrane or porous ceramic film; Can be both ends open, or the hollow fiber ceramic membrane of an end opening, other end sealing.
The described tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes, preparing used ceramic powder material is: when preparation is used for the ceramic of compact membrane component of gas separation, select the ion-electron hybrid conductive material of corresponding gas for use, wherein, be used to prepare the material that fine and close oxygen separates ceramic membrane element and comprise La
0.75Sr
0.25MnO
3, SrCo
0.8Fe
0.2O
3, Ba
0.5Sr
0.5Co
0.8Fe
0.5O
3, volume ratio accounts for 40～60% Zr
0.82Y
0.18O
2With La
0.75Sr
0.25MnO
3Two-phase composite oxygen ion-electronics hybrid conductive material or volume ratio account for 40～60% Ce
0.8Sm
0.2O
2With Ba
0.5Sr
0.5Co
0.8Fe
0.5O
3Two-phase composite oxygen ion-electronics hybrid conductive material; Be used to prepare the heterogeneous compound hydrogen ion of material selection-electronics hybrid conductive material Ni-Ba (Zr that fine and close hydrogen separates ceramic membrane element
0.1Ce
0.7Y
0.2) O
3When the preparation heat exchanger was used the porous ceramics membrane component with ceramic of compact membrane component or preparation screening, the material of selecting for use comprised Al
2O
3, Zr
0.82Y
0.18O
2Or MgAl
2O
4
Because the sintering retractable property difference of different ceramic materials, the solid content of slurry difference of using when also wetting base owing to identical ceramic material as if the extrusion-formation of ceramic film, the sintering retractable property of the curing of the wet base of ceramic membrane, dry contraction and dried is also with difference.Therefore, when adopting one of above-mentioned dual mode preparation ceramic membrane green compact, should be according to the physical dimension of the tabular hollow fiber ceramic membrane element that will prepare, reserve the wet base of corresponding ceramic membrane in curing, dry run, and the contraction change amount of dried each size in sintering process, carrying out wet base extrusion die physical dimension design of ceramic membrane and dried, to block length definite; Or according to the amount of contraction result from the wet base of ceramic membrane to sinter molding that preliminary experiment obtains, carrying out wet base extrusion die physical dimension design of ceramic membrane and dried, to block length definite.
Compared with prior art, the present invention compares with single hollow fiber ceramic membrane element owing to the tabular hollow fiber ceramic membrane element that many hollow fiber ceramic membranes is connected and composed side by side an integral body, and mechanical strength significantly improves.Because the raising of ceramic membrane element mechanical strength, manufacturing dimension, the especially length dimension of single-piece ceramic membrane element be can increase greatly, large scale, ceramic film component that the membrane area capacity is high helped making, and the reliability and the service life of improving ceramic film component, be more suitable for commercial Application.This is one of outstanding advantage of the tabular hollow fiber ceramic membrane element that is connected and composed side by side by many hollow fiber ceramic membranes of the present invention.
Tabular hollow fiber ceramic membrane of the present invention has wide industrial and uses: by the tabular fine and close hollow fiber ceramic membrane element of difference in functionality ceramic material, can be used for making the separating film module or the chemical industry membrane reactor of all gases; By the tabular fine and close hollow fiber ceramic membrane element of chemical inertness ceramic material, can be used as and make refractory ceramics film heat exchanger; Tabular porous hollow fiber ceramic membrane element can be used for assembling various sub-sieves and purification membrane module.
The tabular hollow fiber ceramic membrane element that connects and composes integral body by many hollow fiber ceramic membranes side by side of the present invention, compare with the hollow fiber ceramic membrane element that respective numbers is discrete, on the surface owing to the part membrane area has been lost in the connection of adjacent hollow fiber ceramic membrane, but in actual the use is with some ceramic membrane element component film assemblies, because the needs that membrane module sealing and associative operation medium transport, between each ceramic membrane element, to reserve certain distance, therefore, compare with employing tabular hollow fiber ceramic membrane element assembling film assembly of the present invention, adopt discrete single hollow fiber ceramic membrane element assembling film assembly, because arranging of ceramic membrane element disperses relatively, the quantity of the discrete hollow fiber ceramic membrane element that the membrane module of same size can be installed reduces relatively.Therefore, with regard to the loading density of membrane module, adopt tabular hollow fiber ceramic membrane element assembling film assembly of the present invention, can not cause the filling density of membrane module to descend because of the connection and the loss of part membrane area of hollow fiber ceramic membrane, on the contrary, often can further improve filling density, especially assemble large-sized commercial Application membrane module.
Tabular hollow fiber ceramic membrane element of the present invention, the physical dimension of each hollow fiber ceramic membrane is chosen as 0.1～1 millimeter of wall thickness, 0.5～3.0 millimeter of internal diameter, 1～5 millimeter of external diameter and grows 50～2000 millimeters, mainly be to consider from intensity and preparation yield rate, when the wall thickness of doughnut ceramic membrane is selected by the lower limit of its scope, the interior external diameter of hollow fiber ceramic membrane and length is the lower limit of its scope of corresponding selection also, otherwise, select by the upper limit; And will this tabular hollow fiber ceramic membrane element be chosen as 50～2000 millimeters of length and 10～200 millimeters scopes of width mainly also is to consider from the intensity of membrane component and preparation complexity or fabrication yield, the size of each hollow fiber ceramic membrane in tabular hollow fiber ceramic membrane element (wall thickness, interior external diameter and length) is chosen as the following of size range and prescribes a time limit, the length of tabular hollow fiber ceramic membrane element and width dimensions be the lower limit of its scope of corresponding selection also, otherwise the length and width of tabular hollow fiber ceramic membrane element is selected by the upper limit of its size range; The tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes of the present invention, the size for connection arranged side by side of adjacent hollow fiber ceramic membrane wherein, that is: the minimum range between the adjacent hollow fiber ceramic membrane inwall, more than or equal to the wall thickness of corresponding hollow fiber ceramic membrane, less than two times of hollow fiber ceramic membrane wall thickness, and, on the thickness direction of tabular hollow fiber ceramic membrane element, the minimum size for connection between adjacent hollow fiber ceramic membrane is 10～50% of a corresponding hollow fiber ceramic membrane external diameter; This size for connection selects one to be to consider the compression strength of general brittle ceramic materials much larger than its tensile strength, and the 2nd, consider under the enough condition of bonding strength, reduce the area of the effective film that loses because of the connection of adjacent hollow fiber ceramic membrane as far as possible.
Description of drawings
Fig. 1 is a tabular hollow fiber ceramic membrane element of the present invention perpendicular to the cross section structure schematic diagram on the hollow fiber ceramic membrane central axis direction.
Fig. 2 is the structural representation of the tabular hollow fiber ceramic membrane element of an end opening of the present invention, other end sealing.
Fig. 3 is the structural representation of the tabular hollow fiber ceramic membrane element of both ends open of the present invention.
Fig. 4 is the vertical section structure schematic diagram of the wet base extrusion die of the whole tabular hollow fiber ceramic membrane that is connected and composed side by side by some hollow fiber ceramic membranes of the present invention.
Fig. 5 is the cross section structure schematic diagram of the wet base extrusion die of the whole tabular hollow fiber ceramic membrane that is connected and composed side by side by some hollow fiber ceramic membranes of the present invention.
The specific embodiment
Embodiment 1: adopt phase inversion to prepare an end opening, end sealed L SM-YSZ hollow fiber ceramic membrane single tube green compact, then with the hollow fiber ceramic membrane green compact individual layer solid matter arranged side by side of 30 dryings, and between adjacent hollow fiber ceramic membrane green compact, apply certain extruding force, under this state,, make the tabular fine and close doughnut oxygen permeable ceramic film element that connects and composes side by side by 30 hollow fiber ceramic membranes with high temperature sintering.
The concrete steps of present embodiment are as follows:
1, presses La
0.7Sr
0.3MnO
3(LSM) and Zr
0.82Y
0.18O
2(YSZ) mass ratio is 70: 100, takes by weighing average grain diameter and be the YSZ that 0.6 micron LSM powder and average grain diameter are 0.3 micron, is that medium mixes LSM and YSZ ball milling 24 hours with ethanol, and ethanol medium is removed in evaporation then, obtains the LSM/YSZ mixed powder.
2, take by weighing 70% LSM/YSZ mixed powder, 0.5% polyether sulfone (PESf) forming agent (or claiming flocculating agent), 30% N-methyl pyrrolidone (NMP) organic solvent and 0.04% polyvinylpyrrolidone (PVP) surfactant by mass ratio, the ball milling mixing was prepared into slurry in 48 hours, and slurry was carried out vacuum outgas 1～2 hour.
3, utilize the slurry of above-mentioned preparation to adopt phase inversion to prepare the LSM/YSZ hollow fiber ceramic membrane green compact of end sealing, an end opening.So-called phase inversion prepares the hollow fiber ceramic membrane green compact, be meant earlier ceramic powder, the high molecular polymer forming agent, the organic solvent of solubilized high molecular polymer forming agent and an amount of surfactant, evenly be mixed with into the ceramic powder slurry, adopt the slurry extruding technology ceramic powder slurry to be made the wet base of ceramic membrane then, use again and the immiscible curing agent of high molecular polymer forming agent, water for example, organic solvent in the wet base of exchange ceramic membrane, owing to the high molecular polymer forming agent in the wet base of ceramic membrane is insoluble to curing agent water become " stiff ", stiff polymer molecule forms has certain rigidity and flexible three-dimensional network, and powder granule fixed, thereby realize the curing of the wet base of pottery.Why being called phase inversion, is because this technology has been utilized the ternary phase diagrams equilibrium principle of organic solvent, curing agent and high molecular polymer.The bibliographical information of " membrane science magazine " (Journal ofMembrane Science 193 (2001) 249-260) that correlation technique can be published referring to Dutch Elsevier company.
The mould that the wet base extrusion molding of present embodiment hollow fiber ceramic membrane is used is: 1.6 millimeters of the external diameters of interior pipe, 1 millimeter of the internal diameter of interior pipe, the internal diameter of outer tube are 2.6 millimeters.The extrusion pressure that when extruding ceramic size is applied is 0.1MPa, and the flow of interior pipe curing agent water is 6 ml/min, and temperature is 25 ℃, and wet base film submergence in 25 ℃ of water changed and solidified in 24 hours mutually.In order to prepare the hollow fiber ceramic membrane of end sealing, an end opening, present embodiment adopts the extruding sealing technology, promptly in the extrusion of the wet base of hollow fiber ceramic membrane, the wet firm extrusion die of base of hollow fiber ceramic membrane and uncured before, every interval 110 centimetre lengths, use anchor clamps squeeze film pipe axisymmetrically from outside to inside, form the endoporus close segments that is about 5 millimeters; Treat to soak among the wet base film Guan Zaishui finished in 24 hours change mutually and solidify after, in the centre position of film pipe orifice close segments and the centre position of two endoporus close segments, the film pipe is blocked also drying at room temperature; The LSM/YSZ hollow fiber ceramic membrane green compact of dried end sealing, an end opening are of a size of: 2.35 millimeters of external diameters, 0.33 millimeter of wall thickness, 52 centimetres of length, wet base film pipe is in curing, dry run, radial shrinkage ratio is about 8.5%, axial shrinkage rate about 5%.
4, with 30 end sealings by step 3 preparation, the dried, hollow fiber ceramics film green compact of one end opening, openend and openend alignment, blind end aligns with blind end, individual layer closely is listed on the plane bottom plate, the both sides of 30 hollow fiber ceramic membrane green compact arranged side by side add that two cross sections are square straight ceramic cleat, cleat, the length of clamping plate is more than or equal to the length of hollow fiber ceramic membrane green compact, and wherein the clamping plate of a side are fixed, another is surveyed movably clamping plate and surveys outward, be provided with some equally distributed application of force push rods, one end of push rod withstands clamping plate, the other end links to each other with the spring of adjustable in pressure, regulates the extruding force of clamping plate to 30 hollow fiber ceramic membrane green compact arranged side by side by the compression elasticity of regulating every push rod spring.The average extruding force that applies in the present embodiment is 0.2N/cm.Between each hollow fiber ceramic membrane green compact arranged side by side, be in contact with one another under the condition that extruding force is 0.2N/cm, 1350 ℃ of sintering 10 hours, obtain by the tabular fine and close LSM/YSZ hollow fiber ceramic membrane element that connects and composes side by side behind 30 hollow fiber ceramic membrane sintering, its length L is that 40 centimetres, wide W are 5 centimetres, the outer diameter D of wherein each hollow fiber ceramic membrane is 1.8 millimeters, wall thickness δ is 0.16 millimeter, inner diameter d is 1.48 millimeters, radially sintering shrinkage corresponding to green compact is about 23%, and axial sintering shrinkage is about 21%; On the thickness direction of tabular hollow fiber ceramic membrane element, the minimum size for connection H between adjacent hollow fiber ceramic membrane is 0.2 millimeter, and the minimum range between the adjacent hollow fiber ceramic membrane inwall is 0.31 millimeter apart from S.About 573 square centimeters of the effective film area of every tabular fine and close LSM/YSZ hollow fiber ceramic membrane element, the feature number note is done: 40-5-1.8-573-U, that is: length-wide-thick-membrane area-type, the tabular hollow fiber ceramic membrane element of " U " expression " end sealing, an end opening ".
Accompanying drawing 1 is a tabular hollow fiber ceramic membrane element of the present invention perpendicular to the cross section structure schematic diagram on the hollow fiber ceramic membrane central axis direction, and the upper right side among Fig. 1 is the enlarged drawing of two adjacent hollow fiber ceramic membrane cross section structure sizes wherein.Accompanying drawing 2 has provided the structural representation of the tabular hollow fiber ceramic membrane element of the end opening for preparing in the present embodiment, other end sealing.
Experimental result shows, when adopting phase inversion to prepare the solid content of the powdery pulp that LSM/YSZ hollow fiber ceramic membrane green compact use when too low, for example 60%, the curing of wet base at this moment, the dry contraction can be much larger than 8～9%, reach about 12%, the green sintering shrinkage factor can reach 24～25%.In the preparation process of ceramic component, big contraction distortion is with the fabrication yield of appreciable impact ceramic membrane.Improve the extrusion molding solid content of slurry, can reduce the sintering shrinkage of curing, drying shrinkage and the green compact of wet base.But solid content of slurry is too high, for example greater than 80%, with the flowability and the extrusion molding of appreciable impact slurry.Therefore, the present invention's slurry range of solid content that will adopt phase inversion to prepare the ceramic membrane green compact is chosen as 70～80%.
5, utilize the tabular fine and close LSM/YSZ hollow fiber ceramic membrane element 40-5-1.8-573-U of above-mentioned preparation, adopt bell-jar metal shell assembling oxygen (air) separating film module, the wall thickness of bell-jar metal shell is 10 millimeters, its hypomere is a cylinder, the top is isodiametric spherical crown, the height of cylindrical section is 41 centimetres, 200 millimeters of internal diameters; Bell-jar metal shell membrane module is divided into oxygen flow chamber, pure oxygen collecting chamber and between oxygen flow chamber and pure oxygen collecting chamber and with the mounting seat of the tabular hollow fiber ceramic membrane element of both seal isolation, the pure oxygen collecting chamber be positioned at mounting seat below; Tabular fine and close LSM/YSZ hollow fiber ceramic membrane element 40-5-1.8-573-U openend is installed on base downwards, each hollow fiber ceramic membrane pipe of ceramic membrane element is communicated with the pure oxygen collecting chamber, spacing between parallel each tabular hollow fiber ceramic membrane element that is installed on base is 0.5 millimeter, distance between tabular hollow fiber ceramic membrane element and the metal shell inwall is 5 millimeters, and promptly the tabular hollow fiber ceramic membrane element installation circular diameter of actual installation base is 190 millimeters; Adopt the refractory ceramics sealing-in between tabular hollow fiber ceramic membrane element and the mounting seat, the base plate of tabular hollow fiber ceramic membrane element is installed and the sealing-in total length is 5 millimeters, the effective film space wastage about 1% of the tabular fine and close LSM/YSZ hollow fiber ceramic membrane element 40-5-1.8-573-U of corresponding single-piece; The membrane module of present embodiment, the filling volume of ceramic membrane are 12560 cubic centimetres of (π r
2L=π * 10
2* 40); By above-mentioned design and installation, can load 214 tabular fine and close LSM/YSZ hollow fiber ceramic membrane elements of 40-5-1.8-573-U, total effective film area is 121396 square centimeters (573 * 214 * 0.99), the filling density of corresponding membrane module is 966 (m
2/ m
3).
6,900～1000 ℃ high pressure preheated air is imported the oxygen flow chamber from the spherical crown top of membrane module shell, oxygen sees through tabular fine and close LSM/YSZ hollow fiber ceramic membrane, and enter the pure oxygen collecting chamber by the interior hole path of ceramic membrane, from the outlet output of pure oxygen collecting chamber, the oxygen deprivation hot-air is from being located at the exhaust outlet output of oxygen flow chamber cylindrical metal shell hypomere then.
It is that 1.8 millimeters, inner diameter d are that 1.48 millimeters, wall thickness δ are 0.16 millimeter hollow fiber ceramic membrane element that discrete outer diameter D is used in contrast, and the film gross area of 30 hollow fiber ceramic membrane elements is 616 square centimeters.Calculate thus as can be known, the tabular hollow fiber ceramic membrane element 40-5-1.8-573-U that present embodiment connects and composes after by 30 hollow fiber ceramic membrane sintering side by side connects the membrane area that loses side by side and accounts for 6.8% because of sintering makes between the hollow fiber ceramic membrane.If adopting length L is that 40 centimetres, outer diameter D are that 1.8 millimeters, wall thickness δ are 0.16 millimeter end sealing, the discrete hollow fiber ceramic membrane element assembling film assembly of an end opening, the spacing distance of arranging between the membrane component is similarly 0.5 millimeter, the quantity that then designs installable discrete hollow fiber ceramic membrane element is 5206, the membrane area that calculates single hollow fiber ceramic membrane is 20.3 square centimeters (deduction installation, loss of seal 1%), and the filling density of membrane module only is 841 (m
2/ m
3), be lower than 966 (m of present embodiment
2/ m
3) filling density.
Should be noted that, for ceramic membrane element base plate being installed is circular membrane module, adopt the 40-5-1.8-573-U ceramic membrane element assembling film assembly of present embodiment, the erection space (corresponding with the cross section of single-piece film) that desired specific dimensions is installed owing to the single-piece ceramic membrane element is bigger, the residual area that is not enough to install again a 21-5-1.8-480-U ceramic membrane on the base plate is bigger, but the ratio that these unavailable erection spaces are shared, to reduce along with the relative increase of circular mounting base plate size, in other words, the filling density of membrane module will further improve along with the relative increase of circular mounting base plate size.
Should emphasize that in addition any is, because the mechanical strength of single hollow fiber ceramic membrane element is low, actual fabrication joint length L is that 40 centimetres, outer diameter D are that 1.8 millimeters, wall thickness δ are 0.16 millimeter end sealing, the discrete hollow fiber ceramic membrane element of an end opening, quite difficult technically, or yield rate is very low; In addition, compare with adopting tabular hollow fiber ceramic membrane element of the present invention, adopt discrete hollow fiber ceramic membrane element assembling film assembly that the complex structure of base plate is installed, the sealing difficulty of membrane module is big, is unfavorable for suitability for industrialized production.
The tabular hollow fiber ceramic membrane element 40-5-1.8-573-U that connects and composes by many hollow fiber ceramic membrane sintering arranged side by side of present embodiment preparation, minimum size for connection H between its adjacent hollow fiber ceramic membrane inner hole wall on the thickness direction of tabular hollow fiber ceramic membrane element is 0.2 millimeter, be about 11% of hollow fiber ceramic membrane external diameter, corresponding membrane area loses about 7%; If the plate shaped ceramic element of preparation broad, for example W=10 centimetre, at this moment the absolute value of H should be big slightly, and with the horizontal bend resistance intensity of raising plate shaped ceramic element, but H is big more, and the space wastage of corresponding effective film is just big more.
Embodiment 2: the tabular fine and close doughnut oxygen permeable ceramic film element that preparation is connected and composed side by side by the fine and close LSM-YSZ hollow fiber ceramic membrane of 30 both ends opens
The structural representation of the tabular fine and close LSM/YSZ hollow fiber ceramic membrane element of the both ends open that Fig. 3 will prepare for present embodiment.
Adopt the concrete steps of phase inversion and sintering preparation as follows:
The preparation method of LSM-YSZ mixed powder and slurry is substantially the same manner as Example 1, the LSM-YSZ solid content of slurry of different just present embodiment preparation is about 80%, and promptly the batching of slurry is: 80% LSM-YSZ powder, 0.5% polyether sulfone forming agent, 20% N-methyl pyrrolidone organic solvent and 0.04% polyvinylpyrrolidone surfactant.
The LSM-YSZ slurry is adopted the basic identical of step 3 among the extruding of LSM-YSZ hollow fiber ceramic membrane green compact, curing process parameter that phase inversion prepares both ends open and the embodiment 1, and the hollow fiber ceramic membrane green compact of different is present embodiment do not carry out extruding sealing; In addition, because the extruded ceramic solid content of slurry of present embodiment is 80%, the flowability of slurry is poorer slightly than embodiment's 1 (slurry solid content 70%), and therefore, the extrusion pressure of present embodiment is 0.3MPa.
It is 1000 millimeters that dried LSM-YSZ hollow fiber ceramic membrane green compact are cut into length L.The external diameter of the LSM-YSZ hollow fiber ceramic membrane dried of both ends open is about 0.35 millimeter of 2.4 millimeter, wall thickness in the present embodiment.30 LSM-YSZ hollow fiber ceramic membrane green compact justify aligns are listed on the plane bottom plate, closely contact between the adjacent single tube, impose the extruding force (application of force method is identical with embodiment 1) of 0.3N/cm from the both sides of doughnut arranged side by side, 1350 ℃ of sintering 10 hours, obtaining length L is 82 centimetres, wide W is 5.3 centimetres a tabular fine and close LSM/YSZ hollow fiber ceramic membrane element, wherein the outer diameter D of each fine and close LSM/YSZ hollow fiber ceramic membrane is 1.82 millimeters, wall thickness δ is 0.163 millimeter, sintering size for connection H between adjacent fine and close LSM-YSZ hollow fiber ceramic membrane is 0.25 millimeter, and the minimum range between the adjacent hollow fiber ceramic membrane inwall is 0.31 millimeter apart from S; The effective film area of the tabular fine and close LSM/YSZ hollow fiber ceramic membrane element of single-piece is 1358 square centimeters, and the feature number note is done: 82-5-1.82-1358-T, tabular densification of " T " expression " both ends open " or porous hollow fiber ceramic membrane element.
In the present embodiment wet base film pipe solidify, the radial shrinkage ratio of dry run is about 7.5%, is lower than 8.5% of embodiment 1; The sintering shrinkage of dry LSM/YSZ hollow-fibre membrane green compact is about 22%, and is same less than 23% of embodiment 1.The universal law that obtains according to experiment is: phase inversion prepares the slurry of extruding of ceramic membrane green compact use, its solid content height, and corresponding wet base solidifies, drying, and the shrinkage factor of green sintering process is relatively low; Otherwise the shrinkage factor of correlated process is relatively large.
Utilize the tabular fine and close LSM/YSZ hollow fiber ceramic membrane element 82-5-1.8-1358-T assembling cylindrical metal shell membrane module of above-mentioned preparation: at first some 82-5-1.8-1358-T ceramic membrane elements are installed on diameter and are between two round metal dish-type mounting flanges of 300 millimeters, the periphery of round metal dish-type mounting flange stays the blank of 5 millimeters width, all the other areas are installed the 82-5-1.8-1358-T ceramic membrane element by 0.5 millimeter vertical arrangement of spacing, the ceramic membrane element two ends are concordant with the outerplanar of rosette mount pad, and with epoxide-resin glue sealing, constitute " the film core " of membrane module; Be placed on internal diameter then and be in 300 millimeters the membrane module metal shell; The rosette at film core two ends, the wherein mounting flange fixed seal connection of the rosette of an end and metal shell one end, the lateral surface and the collection chamber of rosette are tightly connected; Between the adpting flange of the rosette seat of the film core other end and the other end of membrane module metal shell, adopt silicone rubber seal to be that envelope is close to be flexible coupling, the another side and the gas distributing chamber of rosette are tightly connected; The gas distributing chamber of membrane module and collection chamber are respectively equipped with air inlet and gas outlet; Membrane module is placed low, middle high syllogic temperature field, two ends, or be used for air oxygen separation system pure oxygen, or be used as the membrane reactor of methane portion oxidation;
When separating the preparation pure oxygen as air oxygen, the air inlet sealing of membrane module distribution end, high temperature compressed or atmospheric air is imported from the metal shell of membrane module, and oxygen permeates by entering interior pipe behind the fine and close LSM/YSZ hollow fiber ceramic membrane of flat board, enter collection chamber by interior pipe, export by the gas outlet again;
During as the methane portion oxidation membrane reactor, air oxygen is still imported from the metal shell of membrane module, infiltration is by arriving interior pipe behind the dull and stereotyped fine and close LSM/YSZ hollow fiber ceramic membrane, methane reaction gas is by the air inlet input of membrane module distribution, in entering each dull and stereotyped fine and close LSM/YSZ hollow fiber ceramic membrane, gas distributing chamber manages, the oxygen that enters interior pipe with infiltration reacts, and the methane portion oxidation product gas is from the collection chamber gas outlet output of the membrane module other end.
Embodiment 3: preparation is by many Ni-Ba (Zr
0.1Ce
0.7Y
0.2) O
3-d(below be abbreviated as Ni-BZCY7) parallel tabular fine and close hollow fiber ceramic membrane element that connects and composes side by side of hollow fiber ceramic membrane is used to assemble the hydrogen permeation membrane assembly.
1, taking by weighing average grain diameter is 5 microns metal Ni powder 60 gram, and BZCY7 powder 60 grams that average grain diameter is 1 micron are that the medium ball milling mixed in 24 hours with ethanol, evaporate away ethanol, drying then.
2, take by weighing 75% Ni/BZCY7 mixed powder, 25% N-methyl pyrrolidone (NMP) organic solvent, 0.05% polyvinylpyrrolidone (PVP) forming agent and 0.4% polyether sulfone (PESf) surfactant by mass ratio, ball milling was mixed with form slurry in 48 hours, to slurry vacuum outgas 1～2 hour.
3, the slurry after the above-mentioned vacuum outgas is adopted phase inversion prepare the Ni-BZCY7 hollow fiber ceramic membrane green compact of end sealing, an end opening, related preparation technology and step are identical with step 3 among the embodiment 1.The Ni-BZCY7 hollow fiber ceramic membrane green compact of dried end sealing, an end opening are of a size of: 2.35 millimeters of external diameters, 0.33 millimeter of wall thickness, 52 centimetres of length.
4, the doughnut Ni-BZCY7 ceramic membrane green compact that 20 steps 3 are prepared, openend and openend alignment, blind end align with blind end and are listed on the plane bottom plate, closely contact between the adjacent single tube, impose the extruding force (application of force method is identical with embodiment 1) of 0.08N/cm from the both sides of doughnut arranged side by side, sintering is 5 hours under 1400 ℃, reducing atmosphere, obtain long L and be 40 centimetres, wide W and be 3.5 centimetres tabular fine and close Ni-BZCY7 hollow fiber ceramic membrane element, its structure as shown in Figure 2, cross section structure is as shown in Figure 1; Hollow fiber ceramic membrane outer diameter D wherein is 1.8 millimeters, and wall thickness δ is 0.16 millimeter, and the sintering size for connection H of adjacent hollow fiber ceramic membrane is 0.25 millimeter, and the minimum range between the adjacent hollow fiber ceramic membrane inwall is 0.3 millimeter apart from S; The membrane area of the tabular fine and close Ni-BZCY7 hollow fiber ceramic membrane element of single-piece is 410 square centimeters, and the feature number note is done: 40-3.5-1.8-410-U.
5, utilize the tabular fine and close Ni-BZCY7 hollow fiber ceramic membrane element of 40-3.5-1.8-410-U of present embodiment step 4 preparation, be assembled into bell-jar membrane module with embodiment 1 same size, can assemble 324 tabular fine and close Ni-BZCY7 hollow fiber ceramic membrane elements of 40-3.5-1.8-410-U, the filling density of corresponding membrane module is 1047 (m
2/ m
3).Estimated as embodiment 1, along with plate shaped ceramic component size (mainly being width W) with respect to the reducing of circular mounting base plate size, adopt the membrane module of tabular hollow fiber ceramic membrane element assembling of the present invention, it is loaded density and can further increase.
6, with about 800 ℃ H that contains
2, H
2O mist (as water-gas) is from the input of membrane module shell spherical crown top, and tabular fine and close Ni-BZCY7 hollow fiber ceramic membrane is passed through in the hydrogen infiltration, and enters pure hydrogen collecting chamber, and from delivery outlet output, remaining high temperature contains H then
2, H
2O mist (as water-gas) is from being located at the exhaust outlet output of cylindrical section metal shell hypomere.
Embodiment 4: adopt the preparation of phase inversion and sintering by many porous Al
2O
3The parallel tabular hollow fiber ceramic membrane element of porous that connects and composes side by side of hollow fiber ceramic membrane.Concrete steps are as follows:
1, takes by weighing 75% Al by mass ratio
2O
3+ graphite mixed powder (wherein the mass ratio of the spherical graphite pore creating material of the about 4 μ m of particle diameter is 10%), 25% N-methyl pyrrolidone (NMP), 0.03～0.05% polyvinylpyrrolidone (PVP) and 0.4～0.6% polyether sulfone (PESf), ball milling was mixed with form slurry in 48 hours, and vacuum outgas 1～2 hour.
2, utilize the slurry of above-mentioned preparation, adopt phase inversion and sintering to prepare the porous Al of an end closure, an end opening
2O
3The hollow fiber ceramic membrane green compact, step 3 is similar among processing step and the embodiment 1.The extrusion die of the wet base of present embodiment doughnut, interior external diameter of pipe is 4.3 millimeters, and the internal diameter of outer tube is 5.5 millimeters, and the flow of interior pipe curing agent water is 12ml/min, and extrusion pressure is 0.08MPa; Dried Al
2O
3The outer diameter D of hollow fiber ceramic membrane green compact is that 5 millimeters, wall thickness δ are 0.5 millimeter, and the length L that is cut into is 2000 millimeters.
3, with the Al of 50 above-mentioned preparations
2O
3The hollow fiber ceramic membrane green compact, openend aligns with openend, blind end aligns with blind end, parallelly be listed on the plane bottom plate, closely contact between the adjacent single tube, impose the extruding force (application of force method is identical with embodiment 1) of 0.4N/cm from the both sides of doughnut arranged side by side, 1600 ℃ of sintering 10 hours, obtain length L and be 165 centimetres, wide W and be 20 centimetres tabular porous Al
2O
3Hollow fiber ceramic membrane element, wherein each porous Al
2O
3The outer diameter D of hollow fiber ceramic membrane is 4.1 millimeters, and wall thickness δ is 0.38 millimeter, and the sintering size for connection H between the adjacent hollow fiber ceramic membrane is 1 millimeter, and the minimum range between the adjacent hollow fiber ceramic membrane inwall is 0.75 millimeter apart from S; The porosity of film is 50～56%, and the most probable aperture is 1.5 microns, and 95% pore-size distribution is at 1～1.8 micrometer range; The tabular porous Al of single-piece
2O
3The effective film area of hollow fiber ceramic membrane element is 7064 square centimeters, and the feature number note is done: 165-20-4.1-7060-U-P, " U " still represent the tabular hollow fiber ceramic membrane of " end sealing, an end opening ", and " P " is expressed as perforated membrane.
4, adopt the tabular porous Al of above-mentioned preparation
2O
3Hollow fiber ceramic membrane element 165-20-4.1-7060-U-P is assembled into bell-jar high-temperature smoke purification separation ceramic film component, and the structure of membrane module and embodiment's 1 is similar; The cylinder segment length of membrane module metal bell jar shell is 165 centimetres, internal diameter is 500 millimeters, 165-20-4.1-7060-U-P between the spacing of arranging be 0.5 millimeter, refractory ceramics sealing-in between 165-20-4.1-7060-U-P and the mounting seat is installed and sealing-in length is 10 millimeters.
When 5, membrane module moves, contain the spherical crown top input of the high-temperature smoke of solid particle from bell-jar membrane module metal shell, pure high-temperature gas (containing the micronic dust of small quantities of particles less than membrane aperture) sees through porous ceramic film, and big dust particle is sized to be held back.
The porous Al of present embodiment preparation
2O
3Hollow fiber ceramic membrane element and membrane module, except that can be used for the high-temperature smoke purified treatment, the isolation of purified that also can be used for various liquid mediums is handled.
Embodiment 5: the whole tabular hollow fiber ceramic membrane green compact that adopt phase inversion one-shot forming preparation to be connected and composed side by side by 40 hollow fiber ceramic membranes, high temperature sintering prepares the tabular compact YSZ hollow fiber ceramic membrane element of both ends open then.The extrusion molding mould of the tabular hollow fiber ceramic membrane element of present embodiment green compact, structure is shown in accompanying drawing 4 and accompanying drawing 5.Concrete preparation process is as follows:
1, take by weighing 80% YSZ, 20% N-methyl pyrrolidone (NMP), 0.05% polyvinylpyrrolidone (PVP) and 0.5% polyether sulfone (PESf) by mass ratio, ball milling was mixed with form slurry in 48 hours, and vacuum outgas 1～2 hour.
2, the tabular YSZ hollow fiber ceramic membrane green compact that the YSZ slurry of preparation adopted phase inversion extrusion molding preparation connect and compose side by side by the YSZ hollow-fibre membrane of 40 both ends opens.The extrusion die that present embodiment uses, its structure is: total straight tube of pectination core rod is 1 millimeter of 8 millimeters of internal diameters, wall thickness, the about 200 millimeters stainless steel tube of length of end sealing, from 5 millimeters of distance blind ends, total straight tube is provided with 40 equal lengths, equidistant, stainless steel arm that straight line distributes, the length of each arm is 15 millimeters, 3.5 millimeters of external diameters, 2.5 millimeters of internal diameters, and the center distance between the adjacent arm is 4.5 millimeters; Epimorph is the oval corrosion resistant plate of 6 millimeters of thickness, long axis of ellipse is that 210 millimeters, minor axis are 150 millimeters, interlude at transverse, it is 5.1 millimeters hole that straight line equidistantly distributes 40 diameters, the spacing in hole is 4.5 millimeters, the straight line distribution length in 40 holes is 180.6 millimeters, corresponding to the width (4.5 * 39+5.1) of extruding tabular wet base; As making oval slurry tank at the bottom of the jar, the tank body of slurry tank adopts the corrosion resistant plate of 2 millimeters of thickness with this ellipse orifice plate (being the epimorph porous plate), high about 250 millimeters of tank body; With the core rod of mould and epimorph (being oval orifice plate) when assembling, each arm of core rod is axial along each hole of epimorph, down insert each corresponding hole from last (being in the slurry tank), and coaxial with corresponding hole, and the lower end of each arm is concordant with the lower surface at the bottom of the slurry tank jar; Total straight tube of core rod is fixed in the pipe, and is parallel to the inner bottom surface and distance jar 9 millimeters at the end (16-6) of slurry tank; The openend of the total straight tube of core rod passes the tank skin of slurry tank outside jar, is connected with the water pipe that is used as curing agent; During extrusion molding, the ceramic powder slurry in the slurry tank is imposed the pressure of 0.2MPa, force slurry to be extruded and moulding by the slit between epimorph and the core rod arm; When mould was extruded, curing agent water entered each arm from total straight tube of core rod at wet base, and the flow of the average curing agent water in 40 each arms is 12 milliliters of per minutes, and the wet base of just extruding from mould is immersed in the curing agent tank immediately; Under 25 ℃ of conditions, curing agent water exchanges 48 hours from the inside and outside both sides of the wet base of ceramic membrane and the organic solvent in the wet base film, and the wet base of film is solidified; With the wet base after solidifying under room temperature and atmospheric environment dry 10 days, the ceramic membrane green compact with drying were cut into 220 centimeter length then, wide about 17.5 centimetres of green compact (the wet base of the pottery of present embodiment solidifies, the radial shrinkage ratios about 7% of dry run).
3, with 220 centimetres of the length of step 2 preparation, wide about 17.5 centimetres tabular hollow fiber ceramic membrane green compact that connect and compose side by side by 40 hollow fiber ceramic membranes, with 1500 ℃ of sintering 10 hours, obtain the YSZ hollow fiber ceramic membrane element of tabular densification, its length L is 180 centimetres (axially sintering shrinkages about 18%), and width W is 13.5 centimetres (radially sintering shrinkage about 23%); The outer diameter D of each hollow-fibre membrane is about 3.62 millimeters in the tabular compact YSZ hollow fiber ceramic membrane element, wall thickness δ is about 0.57 millimeter, the intermembranous sintering size for connection H of adjacent fine and close doughnut is 1.6 millimeters (are equivalent to hollow-fibre membrane diameter 44%), and the minimum range between the adjacent hollow fiber ceramic membrane inwall is 0.71 millimeter apart from S; The tabular compact YSZ hollow fiber ceramic membrane element of present embodiment is with respect to 40 discrete hollow fibre membrane components, because the connection arranged side by side of hollow fiber ceramic membrane wherein causes the loss about 26% of membrane area; The effective surface area of this tabular compact YSZ hollow fiber ceramic membrane element is 5042 square centimeters, and the feature number note is done: 180-14-4-5042-T.The cross section structure of 180-14-4-5042-T as shown in Figure 1, configuration is as shown in Figure 3.
4, utilize the tabular compact YSZ hollow fiber ceramic membrane element 180-14-4-5042-T of above-mentioned preparation, be assembled into cylindric membrane module.The internal diameter of membrane module metal shell is 410 millimeters, and two ends are provided with the installation base plate and the mounting flange of 180-14-4-5042-T ceramic membrane element, and wherein an end is the metal mounting flange, seals with epoxide-resin glue between 180-14-4-5042-T and the metal peace flange; The other end is ceramic mounting flange, adopts the refractory ceramics sealing-in between 180-14-4-5042-T and the ceramic mounting flange; The diameter that the ceramic membrane element of metal and ceramic mounting flange is installed disc is 400 millimeters, the nearest spacing of 180-14-4-5042-T ceramic membrane element and membrane module metal shell inwall is designed to 5 millimeters, and the installation interval distance of adjacent 180-14-4-5042-T is 0.5 millimeter; To place in the membrane module metal shell by being assembled in the film core that ceramic membrane element constituted between two mounting seat flanges; Wherein refractory ceramics sealing-in mounting flange is that ceramic seal is fixedlyed connected with metal shell, and the outside and collection chamber are tightly connected, and collection chamber is surveyed outward and connected the medium output channel; Epoxide-resin glue sealing mounting flange is flexible coupling by the silicone rubber seal sealing with metal shell, and design has water-cooling system, and the epoxide-resin glue sealing mounting flange outside and gas distributing chamber are tightly connected, and the outside of gas distributing chamber is provided with the medium input channel; In addition, the two ends of membrane module metal shell, in the inboard input port that also is provided with high-temperature medium of ceramic membrane mounting flange near the ceramic membrane mounting flange, the delivery outlet of high-temperature medium after the inboard of metal mounting flange also is provided with heat exchange near the metal mounting flange; When the refractory ceramics film heat exchanger that constitutes is operated like this, the cold medium that heats enters the internal channel of tabular compact YSZ hollow fiber ceramic membrane from the gas distributing chamber of epoxide-resin glue sealing mounting flange end, the high temperature heat-carrying agent is entered in the ceramic membrane high-temperature heat exchanger by the outer high-temperature medium input port of membrane module metal, the high temperature heat-carrying agent heats tabular compact YSZ hollow fiber ceramic membrane and lowers the temperature, and the medium of ceramic membrane internal channel obtains energy and is heated from the ceramic membrane inwall; The medium of the ceramic membrane internal channel behind the heat temperature raising enters the collection chamber of refractory ceramics sealing-in mounting flange one end, and from the medium output channel output that is connected with collection chamber, the heat-carrying agent of cooling flows out from the high-temperature medium delivery outlet.
Claims (8)
1, a kind of tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes, by 0.5～3.0 millimeter of internal diameter, 1～5 millimeter of external diameter, 0.1～1 millimeter of wall thickness, long 50～2000 millimeters hollow fiber ceramic membrane constitutes, it is characterized in that: connect and compose long 50～2000 millimeters side by side by many hollow fiber ceramic membrane individual layers, wide 10～200 millimeters whole tabular hollow fiber ceramic membrane element, the minimum range between the wherein adjacent hollow fiber ceramic membrane inwall is more than or equal to the wall thickness of corresponding hollow fiber ceramic membrane, less than two times of hollow fiber ceramic membrane wall thickness; On the thickness direction of tabular hollow fiber ceramic membrane element, the minimum size for connection between adjacent hollow fiber ceramic membrane is 10～50% of an adjacent hollow fiber ceramic membrane external diameter.
2, a kind of preparation method of the described tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes of claim 1, it is characterized in that earlier taking by weighing 70～80% ceramic membrane material powder, 0.4～0.6% polyether sulfone, 20～30% N-methyl pyrrolidone and 0.03～0.05% polyvinylpyrrolidone by mass ratio, ball milling mixes made the ceramic powder slurry in 24～48 hours; Adopt the phase inversion extrusion molding to prepare the needed hollow fiber ceramic membrane single tube of tabular hollow fiber ceramic membrane element green compact then: the mould that the wet base of extrusion molding hollow fiber ceramic membrane single tube uses is in coaxial by two, outer tube constitutes, the internal diameter of mould outer tube is corresponding to the external diameter of each hollow fiber ceramic membrane in the tabular hollow fiber ceramic membrane element that will prepare, the external diameter of pipe is corresponding to the internal diameter of each hollow fiber ceramic membrane in the tabular hollow fiber ceramic membrane element that will prepare in the mould, 1/2nd wall thickness corresponding to each hollow fiber ceramic membrane in the tabular hollow fiber ceramic membrane element that will prepare of the difference of the external diameter of the interior pipe of mould and the internal diameter of outer tube; During extrusion molding, the ceramic powder slurry is extruded and is shaped to the wet base of cannulated fiber ceramics film the circular ring type slit between the mould inner and outer pipe under the promotion of the pressure of 0.02～1MPa; Wet base when mould is extruded at hollow fiber ceramic membrane, the employed curing agent water of phase inversion enters in the pipe of the hollow fiber ceramic membrane of extruding from the interior pipe of the mould flow with 2～20 milliliters of per minutes, and the wet base of just having extruded from mould of film pipe immerses in the curing agent tank immediately; Under 20～50 ℃ of conditions, the organic solvent while in the wet base tube wall of hollow fiber ceramic membrane exchanges with the water of the inside and outside both sides of tube wall, exchanges 24～48 hours caudacoria pipes and solidifies, and is dry under 10～50 ℃ of atmospheric environments then; Dried hollow fiber ceramic membrane green compact are cut into the hollow fiber ceramic membrane single tube green compact of Len req; Then with some measure-alike hollow fiber ceramic membrane single tube green compact justify aligns, individual layer solid matter on plane bottom plate, and from the both sides of many hollow fiber ceramic membrane single tube green compact arranged side by side, along and column direction inwardly impose the even extruding force of 0.05～0.5N/cm, under the condition that is tight extruding contact between each hollow fiber ceramic membrane single tube green compact arranged side by side, with 900～1600 ℃ of sintering 5～20 hours, promptly obtain whole tabular hollow fiber ceramic membrane element.
3, the another kind of preparation method of the described tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes of claim 1, it is characterized in that earlier taking by weighing 70～80% ceramic membrane material powder, 0.4～0.6% polyether sulfone, 20～30% N-methyl pyrrolidone and 0.03～0.05% polyvinylpyrrolidone by mass ratio, ball milling mixes made the ceramic powder slurry in 24～48 hours; Adopt the phase inversion extrusion molding to serve as reasons then the wet base of whole tabular hollow fiber ceramic membrane element that many hollow fiber ceramic membranes connect and compose side by side; The extrusion molding mould of the wet base of the tabular hollow fiber ceramic membrane element of this integral body is for to be constituted by epimorph and pectination core rod; Described pectination core rod is: on total straight tube of one one end sealing, from 5～10 millimeters of distance blind ends, on same straight line, equidistantly distribute the arm of several equal lengths successively, the external diameter of this arm is corresponding to the internal diameter of each hollow fiber ceramic membrane of the tabular hollow fiber ceramic membrane element that will prepare, distance between adjacent external diameter of pipe is corresponding to the minimum range between the adjacent hollow fiber ceramic membrane inwall in the tabular hollow fiber ceramic membrane element that will prepare, the radical of arm is corresponding to the quantity of the hollow fiber ceramic membrane that is comprised in the tabular hollow fiber ceramic membrane element that will prepare, propping up length of tube is 10～20 millimeters, total straight tube is connected with each arm, and the non-blind end of total straight tube is as the input port of the used curing agent water of phase inversion; Described epimorph is: on thick 5～10 millimeters flat board, the equidistant equal and interconnective through hole of a plurality of internal diameters that offers on same straight line, the quantity in hole equates with the quantity of core rod arm, centre distance on the centre distance of adjacent holes and the core rod between the adjacent arm equates that the internal diameter in hole and core rod prop up 1/2nd wall thickness corresponding to the hollow fiber ceramic membrane in the tabular hollow fiber ceramic membrane element that will prepare of the difference of external diameter of pipe; The circle in two holes of adjacent connection intersect and the chord length of the public string determined corresponding to the tabular hollow fiber ceramic membrane element that will prepare in the minimum size for connection between adjacent hollow fiber ceramic membrane on the thickness direction; When the epimorph of assembling extrusion molding mould and core rod, the epimorph porous plate is as the jar end of ceramic slurry batch can, and each arm of core rod is coaxial with corresponding each hole of epimorph, inserts each corresponding hole vertically from top to bottom; Total straight tube of core rod is fixed in the ceramic slurry batch can, at the bottom of being parallel to jar inner surface and be positioned at jar at the bottom of on the inner surface 5～10 millimeters; The lower end of each arm of core rod is concordant with the lower surface at the bottom of the ceramic slurry batch can jar; During extrusion molding, ceramic powder slurry in the slurry tank is under the promotion of 0.02～1MPa pressure, extrude and moulding from the slit between epimorph and the core rod arm, meanwhile, curing agent water enters in the pipe of each hollow fiber ceramic membrane with the flow of 2～20 milliliters of per minutes, and the wet base of just extruding from mould is immersed in the curing agent tank immediately; Under 20～50 ℃ of conditions, curing agent water from the inside and outside both sides of the wet base of ceramic membrane simultaneously with wet base film in organic solvent exchange, exchange 24～48 hours and makes the wet base curing of film; Dry under 10～50 ℃ of atmospheric environments again; Dried ceramic membrane green compact are cut into Len req,, promptly obtain tabular hollow fiber ceramic membrane element with 900～1600 ℃ of high temperature sinterings 5～20 hours.
4, the tabular hollow fiber ceramic membrane element that is connected and composed side by side by many hollow fiber ceramic membranes according to claim 1 or as claim 2 or 3 described preparation methods is characterised in that described hollow fiber ceramic membrane is dense ceramic membrane or porous ceramic film.
5, the tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes according to claim 1 or as claim 2 or 3 described preparation methods, be characterised in that described hollow fiber ceramic membrane is a both ends open, or the hollow fiber ceramic membrane of an end opening, other end sealing.
6, the tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes according to claim 1 or as claim 2 or 3 described preparation methods, be characterised in that when preparation be fine and close oxygen when separating ceramic membrane element, the material of selecting for use comprises La
0.75Sr
0.25MnO
3, SrCo
0.8Fe
0.2O
3, Ba
0.5Sr
0.5Co
0.8Fe
0.5O
3, volume ratio accounts for 40～60% Zr
0.82Y
0.18O
2With La
0.75Sr
0.25MnO
3Two-phase composite oxygen ion-electronics hybrid conductive material or volume ratio account for 40～60% Ce
0.8Sm
0.2O
2With Ba
0.5Sr
0.5Co
0.8Fe
0.5O
3Two-phase composite oxygen ion-electronics hybrid conductive material.
7, the tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes according to claim 1 or as claim 2 or the described preparation method of claim 3, be characterised in that the material of selecting for use is heterogeneous compound hydrogen ion-electronics hybrid conductive material Ni-Ba (Zr when preparation is used for fine and close hydrogen and separates ceramic membrane element
0.1Ce
0.7Y
0.2) O
3
8, the tabular hollow fiber ceramic membrane element that connects and composes side by side by many hollow fiber ceramic membranes according to claim 1 or as claim 2 or the described preparation method of claim 3, be characterised in that the material of selecting for use comprises Al when the preparation heat exchanger is used the porous ceramics membrane component with ceramic of compact membrane component or preparation screening
2O
3, Zr
0.82Y
0.18O
2Or MgAl
2O
4
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| CN109534818A (en) * | 2017-09-22 | 2019-03-29 | 萍乡市普天高科实业有限公司 | Porous ceramics film preparation mold and method |
| CN111013403A (en) * | 2019-11-15 | 2020-04-17 | 河北工业大学 | Preparation method of hollow flat ceramic membrane |
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2008
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| CN102198372A (en) * | 2010-03-25 | 2011-09-28 | 吕晓龙 | Separating membrane and preparation method thereof |
| CN102515817A (en) * | 2011-11-16 | 2012-06-27 | 伍协 | Hollow fiber ceramic membrane and preparation method thereof |
| CN106334452A (en) * | 2016-08-26 | 2017-01-18 | 杭州太仆汽车科技有限公司 | Filter membrane component and preparation method thereof |
| CN109534818A (en) * | 2017-09-22 | 2019-03-29 | 萍乡市普天高科实业有限公司 | Porous ceramics film preparation mold and method |
| CN111013403A (en) * | 2019-11-15 | 2020-04-17 | 河北工业大学 | Preparation method of hollow flat ceramic membrane |
| CN111013408A (en) * | 2019-11-15 | 2020-04-17 | 河北工业大学 | Preparation method of integrated hollow flat plate separation membrane |
| CN111013403B (en) * | 2019-11-15 | 2021-04-23 | 河北工业大学 | Preparation method of hollow flat ceramic membrane |
| CN113200708A (en) * | 2021-05-12 | 2021-08-03 | 四川凯歌微纳科技有限公司 | End-capping method for tubular ceramic membrane |
| CN113426306A (en) * | 2021-06-25 | 2021-09-24 | 深圳通微纳米科技有限公司 | Double-layer hollow ceramic membrane and production process thereof |
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