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CN110252157B - Reinforced metal composite ceramic membrane and preparation method thereof - Google Patents

Reinforced metal composite ceramic membrane and preparation method thereof Download PDF

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Publication number
CN110252157B
CN110252157B CN201910616780.5A CN201910616780A CN110252157B CN 110252157 B CN110252157 B CN 110252157B CN 201910616780 A CN201910616780 A CN 201910616780A CN 110252157 B CN110252157 B CN 110252157B
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ceramic
temperature
powder
alkali metal
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CN110252157A (en
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谢志成
黄德友
曾胜彬
袁年武
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Hunan Zhong Tian Yuan Environmental Engineering Ltd
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Hunan Zhong Tian Yuan Environmental Engineering Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0044—Inorganic membrane manufacture by chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Filtering Materials (AREA)

Abstract

A reinforced metal composite ceramic membrane and a preparation method thereof, wherein the ceramic membrane sequentially comprises a substrate layer, a transition layer and a precision layer; the substrate layer is sintered by simple substance metal or alloy powder; the transition layer is a composite layer sintered by elemental metal or alloy powder and composite or mixed ceramic powder; the precision layer comprises a porous ceramic filter layer sintered by alkali metal oxide doped ceramic powder, and the outside of the precision layer is subjected to ion exchange by molten salt. The method comprises the following steps: (1) adding a forming agent into the elemental metal or alloy powder, mixing, casting and sintering; (2) mixing simple substance metal or alloy powder with composite or mixed ceramic powder, casting and sintering; (3) spraying the alkali metal oxide doped ceramic powder, sintering, ion exchanging, washing with water, and drying. The ceramic membrane has the advantages of high filtration precision, large flux, uniform aperture, high toughness, thermal shock resistance, high mechanical strength and strengthened surface stress. The method is simple, low in cost and suitable for industrial production.

Description

Reinforced metal composite ceramic membrane and preparation method thereof
Technical Field
The invention relates to a ceramic membrane and a preparation method thereof, in particular to a reinforced metal composite ceramic membrane and a preparation method thereof.
Background
The requirements of the filtration and separation industry on the filtration material are that the filtration flow is improved as much as possible, and the filtration resistance of the filter is reduced, so that the production energy consumption is reduced. However, for filters, there is often a contradiction: the filter material gap of the filter element is large, so that high filtering flux can be obtained, but the filtering precision is relatively reduced. The high-precision filter material needs to improve the filtering precision of the filter material to submicron or even nanometer level, and the filtering flux is inevitably reduced.
In the prior art, a nano-grade precision ceramic filter element obtained by sintering a ceramic material is adopted to obtain a high-precision filter element. However, such a filter element has the characteristics of large brittleness, poor thermal shock resistance and low mechanical strength of porous ceramics. Traditional ceramic filter core is very high because the filter fineness of superficial layer, very easily by the colloidal particle in the solution because of the relatively compact cake layer of bridging effect formation, in case form the permanent cake layer of colloidal property, can lead to periodic blowback washing to become invalid, finally arouses that filtration system can't normally filter.
CN102659447A and CN105693276A disclose a method for producing pure silicon carbide ceramic, and the filter element produced by the method belongs to the traditional method for producing ceramic filter elements, and still has the problems of large brittleness, thermal shock resistance and easy breakage of the traditional ceramic filter element.
CN102500245A discloses a preparation method of a metal-based ceramic composite filter membrane, which is to anodically oxidize a porous metal membrane in electrolyte to obtain a transition layer, and then prepare ceramic powder into slurry to be coated on the transition layer to obtain the composite filter element. In fact, the transition layer obtained by oxidation and the subsequent ceramic layer are used as oxide layers, the micro interface of the product after high-temperature sintering belongs to metal and is directly transited to the ceramic coating, and thus the filter element with the structure can directly cause the peeling failure of the ceramic coating due to the inconsistent expansion coefficients of the metal and the ceramic in the variable-temperature environment. The filter element product is a process from high temperature to normal temperature in the sintering process, and the qualified product can hardly be produced in large batch by adopting the method. Therefore, the method does not completely solve the problem of peeling of the metal layer and the ceramic layer under temperature stress.
CN109364583A discloses a Ti-Ti for industrial purification6Si4The preparation method of the external wall light type metal filtering membrane pipe material comprises the step of co-sintering metal titanium powder and metal silicon powder to obtain metal titanium/Ti6Si4A metal ceramic composite filter element. However, this method has a problem that the application range is limited: first, the method is applicable only to metallic titanium and Ti6Si4The compounding of metal compounds is not effective for the compounding of other metal and ceramic powder, and particularly when a filtering system contains fluoride ions and a strong alkaline medium, the filter element is easy to corrode and damage; secondly, raw materials of metal titanium powder and metal silicon powder for producing the filter element are difficult to obtain nano-precision raw materials, and when the filter element with nano-precision needs to be prepared, the method is difficult to solve the problem of high precision; thirdly, the method adopts an isostatic pressing process to prepare the composite filter element, the thickness of the filter element, particularly the precision filter layer, cannot be very thin, and therefore, the product is easy to filterThe amount is small, and the back-blowing effect is poor.
In summary, a metal ceramic composite filter membrane technology is needed to overcome the defects of the traditional ceramic filter core, such as high brittleness, poor thermal shock resistance, low mechanical strength, poor back flushing performance and the like.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a reinforced metal composite ceramic membrane which has the advantages of high filtration precision, large filtration flux, uniform pore diameter, thin thickness, high toughness, good thermal shock resistance, high mechanical strength, easy back flushing cleaning, complete elimination of thermal stress damage and wide application range.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of the reinforced metal composite ceramic membrane, which has simple process and low cost and is suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a reinforced metal composite ceramic membrane sequentially comprises a substrate layer, a transition layer and a precision layer; the substrate layer is formed by sintering elemental metal or alloy powder; the transition layer is a composite layer formed by sintering elemental metal or alloy powder and composite ceramic or mixed ceramic powder; the precision layer comprises a porous ceramic filter layer formed by sintering alkali metal oxide doped ceramic powder, and the outer side of the precision layer is subjected to ion exchange by alkali metal molten salt and/or rare earth molten salt. The metal substrate layer mainly plays a role in improving the mechanical strength and toughness of the filter membrane and preventing the filter element from being broken; the transition layer plays a role in smoothing the bonding stress between the metal substrate layer and the ceramic layer, and the thermal shock resistance of the filter element is improved; the precision layer is a ceramic layer and mainly provides high filtration precision of the filter membrane, and the filtration precision of the precision layer is equal to that of the ceramic filter membrane.
Preferably, the alkali metal element in the alkali metal oxide-doped ceramic powder is not completely the same as or completely different from the alkali metal element in the molten alkali metal salt, and the diameter of the alkali metal element in the molten alkali metal salt is larger than or equal to the diameter of the alkali metal element in the alkali metal oxide-doped ceramic powder. The precise layer is formed by sintering lithium oxide-doped ceramic powder, and the ion exchange is performed on the mixed molten salt of sodium hydroxide and potassium hydroxide as an example: the lithium oxide concentration of the precision layer is relatively high, the lithium oxide concentration in the molten salt is zero, the potassium ion concentration and the sodium ion concentration in the molten salt are very high, under the driving of the concentration difference effect, the lithium ion in the precision layer diffuses to the molten salt, and the potassium ion concentration and the sodium ion concentration in the molten salt diffuse to the precision layer; the lithium ion concentration of the precision layer can be gradually reduced from the inner side to the outer side by controlling the ion exchange time, and the potassium ion and sodium ion concentration in the precision layer is gradually reduced from the outer side to the inner side; because the radius of the sodium ions and the radius of the potassium ions are larger than that of the lithium ions, the surface of the precision layer generates compressive stress relative to the surface of the precision layer before treatment, and the stress changes the original stress state of the precision layer, so that the binding force of the ceramic and the metal layer in the ceramic membrane is effectively adjusted and improved, and the impact resistance of the precision layer in the ceramic membrane is enhanced.
Preferably, the content of the alkali metal element introduced into the alkali metal oxide-doped ceramic powder is gradually decreased from the inside of the precision layer to the outside thereof.
Preferably, the alkali metal molten salt and/or rare earth molten salt introduces an alkali metal and/or rare earth element in an amount gradually decreasing from the outside of the precision layer to the inside of the precision layer, except for the same alkali metal as the alkali metal oxide.
Because the alkali metal of the molten salt and the alkali metal doped in the precision layer are not completely the same or different, the ion concentration is diffused due to the concentration difference in the ion exchange process, so that the ion concentration gradient is formed, and further the surface stress of the ceramic membrane is strengthened. When one of the alkali metals introduced by the molten salt of the alkali metal is the same as one of the alkali metals introduced by the oxide of the alkali metal, the concentration trend of the alkali metal introduced by the oxide of the alkali metal is still gradually reduced from the inside of the precision layer to the outside of the precision layer, and the addition of the same alkali metal in the molten salt is only used for adjusting the ratio of sodium ions to potassium ions in the final precision layer.
Preferably, the molten alkali metal salt is one or more of lithium hydroxide, sodium hydroxide or potassium hydroxide.
Preferably, the rare earth molten salt is one or more of rare earth nitrate, rare earth oxide or rare earth chloride.
More preferably, the molten salt is a mixed molten salt of sodium hydroxide and potassium hydroxide in a mass ratio of 2-4: 1, or a mixed molten salt of sodium hydroxide, potassium hydroxide and a rare earth molten salt in a mass ratio of 10-200: 20-60: 1.
Preferably, the mass ratio of the base layer to the transition layer to the precision layer is 40-90: 30-80: 0.2-20 (more preferably 40-90: 30-80: 0.5-5.0). If the mass of the substrate layer is too large or too thick, the filtration resistance of the filter membrane is increased, and if the mass of the substrate layer is too small or too thin, the strength of the filter membrane is insufficient and the filter membrane is easy to break; if the mass of the transition layer is too large or too thick, the number of layers is too large, so that the production cost is increased, and if the mass of the transition layer is too small or too thin, the number of layers is too small, so that the stress between the metal layer and the ceramic layer is difficult to effectively eliminate; if the mass of the precision layer is too large or too thick, the resistance of the filter membrane is increased, and if the mass of the precision layer is too small or too thin, the sintering defects therein are difficult to completely eliminate.
Preferably, in the transition layer, the mass ratio of the simple substance metal or alloy powder to the composite ceramic or mixed ceramic powder is 95-5: 5-95 (more preferably 60-90: 40-10). The metal filter membrane has the characteristics of high strength, good toughness and the like, but the filtering precision of the filter element is not easy to improve; the ceramic filter element has large brittleness and low thermal shock resistance, and the filter element with nanometer precision can be easily prepared. If the two are combined, the advantages of the two can be effectively exerted, and the defects of the two can be avoided.
Preferably, the thickness ratio of the base layer to the transition layer to the precision layer is 0.5-2.0: 0.1-1.5: 0.01-0.10 (more preferably 0.8-1.8: 0.3-1.3: 0.02-0.08).
Preferably, the transition layer consists of 1-10 layers (more preferably 2-6 layers). If the number of layers of the transition layer is too small, it is difficult to effectively eliminate the bonding stress, and if the number of layers of the transition layer is too large, the production cost is greatly increased.
Preferably, in each layer of the transition layer, the mass ratio of the simple substance metal or the alloy to the composite ceramic or the mixed ceramic is reduced from the base layer to the precision layer by layer. The design principle of the transition layer of the invention is as follows: through multilayer preparation to make metal content as high as possible in the transition layer near metal substrate layer, the transition layer ceramic content that is close to accurate porous ceramic filter layer simultaneously is as high as possible, makes the metal composition and the ceramic composition of filter core all be gradient distribution in both sides, and the proportion change of content is smooth between metal and the pottery, and structural component is more close the bonding stress just lower, thereby effectively reduces the bonding stress of metal substrate layer and accurate ceramic layer.
Preferably, the thickness of each layer in the transition layer is 10 to 1500 μm (more preferably 100 to 1000 μm). If the transition layer is too thick, the production cost may be increased, and if the transition layer is too thin, it may be difficult to effectively eliminate the stress between the metal layer and the ceramic layer.
Preferably, in the precision layer, the alkali metal oxide-doped ceramic powder is a mixture of an alkali metal oxide and a composite ceramic or mixed ceramic powder in a mass ratio of 1:1 to 100 (more preferably 1:2 to 50, and even more preferably 1:3 to 30). If the amount of the alkali metal oxide is too small, the ceramic film may not be sufficiently strengthened, and if the amount of the alkali metal oxide is too large, the strength of the precision layer may be affected.
Preferably, in the precision layer, the thickness of the porous ceramic filter layer is 1-100 μm. If the precision layer is too thick, the resistance of the filter membrane increases, and if the precision layer is too thin, the sintering defects therein are difficult to completely eliminate.
Preferably, the average pore size of the porous ceramic filter layer is 5-100 nm.
Preferably, in the base layer and the transition layer, the elemental metal is elemental iron, elemental nickel, elemental copper, elemental titanium, or the like.
Preferably, in the base layer and the transition layer, the alloy is stainless steel, hastelloy or iron-chromium-aluminum alloy or the like.
Preferably, in the base layer, the average particle size of the elemental metal or alloy powder is 30-800 meshes. If the metal particle size of the base layer is too small, the sintered product has large voids and high flux, but the mechanical strength is too low, and if the metal particle size of the base layer is too large, the sintered product has high strength, but the voids are small and the filtration flux is too low.
Preferably, in the transition layer, the average particle size of the elemental metal or alloy powder is 30-2000 meshes. Since the melting point of the ceramic is higher than that of the metal, in order to match the temperature at which the metal powder and the ceramic powder are sintered together in the transition layer, the ceramic powder needs to be finer, and the corresponding particles of the metal powder need to be coarser.
Preferably, in the transition layer and the precision layer, the composite ceramic is one or more of oxide ceramic, nitride ceramic, carbide ceramic, boride ceramic, silicide ceramic or metal crystal compound. More preferably, the composite oxide ceramic is an alumina/silica composite ceramic, an alumina/zirconia composite ceramic, a zirconia/yttria composite ceramic, or the like.
Preferably, in the transition layer and the precision layer, the mixed ceramic is one or a mixture of several of oxide ceramic, nitride ceramic, carbide ceramic, boride ceramic, silicide ceramic, metal crystal compound and the like. More preferably, the mixed oxide ceramic is an aluminum nitride-silicon nitride mixed ceramic, a zirconia-alumina mixed ceramic, a silica-zirconia mixed ceramic, or the like.
Preferably, in the transition layer and the precision layer, the average particle size of the composite ceramic or mixed ceramic powder is 300-10000 meshes. The porous ceramic filter layer is required to have the highest filtering accuracy, and therefore, the selected ceramic particle size is also finer.
Preferably, in the precision layer, the average particle diameter of the alkali metal oxide is 2000 to 10000 meshes.
Preferably, the precision layer further comprises a ceramic particle modifying layer arranged outside the porous ceramic filter layer. The porous ceramic filter layer sintered by the composite ceramic or the mixed ceramic powder has certain sintering defects, and the gel is soaked in the ceramic particle modification layer formed on the surface of the ceramic layer, so that partial gel is absorbed by local sintering cracks of the porous ceramic filter layer under the capillary action, the sintering defects disappear, and finally the filtering precision of the filter membrane is improved.
Preferably, the mass ratio of the ceramic particle modification layer to the porous ceramic filter layer is 0.04-0.45: 1. The ceramic particle modification layer has the main function of repairing sintering defects generated in the preparation process of the porous ceramic filter layer, if the mass is too large or the thickness is too thick, the filtering flux can be reduced, and if the mass is too small or the thickness is too thin, the effect of eliminating the sintering defects of the ceramic layer is difficult to achieve.
Preferably, the ceramic particle modification layer is composed of 1-4 layers.
Preferably, the thickness of each layer in the ceramic particle modification layer is 1-30 μm.
Preferably, the ceramic particle modification layer is formed by sintering a gel made of composite ceramic or mixed ceramic powder.
Preferably, the composite ceramic or mixed ceramic powder for preparing the gel has an average particle size of 5-100 nm. The ceramic particle modifying layer has the highest filtering precision, so the selected ceramic particle size is also finer.
The technical scheme adopted for further solving the technical problems is as follows: a preparation method of a reinforced metal composite ceramic membrane comprises the following steps:
(1) adding a forming agent into the elemental metal or alloy powder, mixing, heating, casting, and sintering in vacuum to obtain a substrate layer;
(2) mixing simple substance metal or alloy powder with composite ceramic or mixed ceramic powder, heating and casting to the substrate layer obtained in the step (1), and performing vacuum sintering to form a transition layer to obtain an intermediate product;
(3) and (3) spraying alkali metal oxide doped ceramic powder on the transition layer of the intermediate product obtained in the step (2), sintering in vacuum to form a porous ceramic filter layer, placing the outer side of the porous ceramic filter layer in molten alkali metal salt and/or molten rare earth salt for ion exchange, washing with water, and drying to obtain the reinforced metal composite ceramic membrane.
Preferably, in the step (1), the amount of the forming agent is 0.1-20.0% (more preferably 0.5-15.0%) of the mass of the elemental metal or alloy powder. If the amount of the forming agent is too small, the tape casting technology is difficult to be normally applied, and if the amount of the forming agent is too large, the production cost is increased, and the carbon content of the product exceeds the standard. The forming agent can be completely volatilized or decomposed in the sintering process, and the base layer does not contain the forming agent.
Preferably, in the step (1), the forming agent is one or more of polyethylene glycol, polyolefin, paraffin, polyacrylamide, polyurethane, methyl cellulose and the like.
Preferably, in the step (1), the mixing temperature is normal temperature-150 ℃ and the mixing time is 1-3 h. If the mixing time is too short, it is difficult to mix uniformly and, if the mixing time is too long, it wastes equipment resources and energy.
Preferably, in the step (1), the temperature of the heating casting is 60-150 ℃, and the casting speed is 0.5-30 m/min (more preferably 1-15 m/min). The adoption of the tape casting method is more beneficial to the batch preparation of qualified base layer blanks, and the prepared base layer has uniform thickness, thus being easy to realize industrial production. If the casting temperature is too high or the casting speed is too fast, the viscosity of the slurry is low, the casting thickness is not easy to control, and if the casting temperature is too low or the casting speed is too slow, the discharging of the casting equipment is not uniform, and the production efficiency is influenced.
Preferably, in the step (1), the temperature of the vacuum sintering is 1000 to 1500 ℃ (more preferably 1200 to 1400 ℃), and the vacuum degree is 1 × 10-1～1×10-4Pa, the time is 2-8 h. During the vacuum sintering process, bonding between the metal particles occurs, so that the substrate layer has a corresponding mechanical strength. If the temperature of the vacuum sintering is too low or the time is too short, effective sintering is difficult to complete, and if the temperature of the vacuum sintering is too high or the time is too long, the porous metal layer is densified, even the metal substrate layer is completely in a molten state, and finally the steel plate is obtained by sintering.
Preferably, in the step (2), the temperature of the heating casting is 60-150 ℃ (more preferably 80-120 ℃), and the casting speed is 0.5-30 m/min (more preferably 1-15 m/min). The adoption of the tape casting method is more beneficial to the batch preparation of the qualified transition layer, and the prepared transition layer has uniform thickness, thus being easy to realize industrial production. If the casting temperature is too high or the casting speed is too fast, the viscosity of the slurry is low, the casting thickness is not easy to control, and if the casting temperature is too low or the casting speed is too slow, the discharging of the casting equipment is not uniform, and the production efficiency is influenced.
Preferably, in the step (2), the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 × 10-1～1×10-4Pa, for 2-12 h (preferably 2-10 h). The bonding between the metal particles, the bonding between the ceramic particles and the metal powder, and the bonding between the ceramic particles and the ceramic particles occur during the vacuum sintering process, so that the transition layer has corresponding mechanical strength. If the temperature of the vacuum sintering is too low or the time is too short, it is difficult to achieve effective sintering, and if the temperature of the vacuum sintering is too high or the time is too long, the metal particles therein are densified.
Preferably, in the step (2), the operations of powder mixing, heating casting and vacuum sintering are repeated for more than or equal to 1 time to obtain a multi-layer transition layer.
Preferably, in the step (3), the temperature of the vacuum sintering is 1200-1600 ℃ (more preferably 1300-1500 ℃), and the vacuum degree is 1 × 10-1～1×10-4Pa, for 2-14 h (more preferably 8-12 h). During the vacuum sintering process, the ceramic particles are bonded with each other, and a porous ceramic structure is formed. If the temperature of the vacuum sintering is too low, the ceramic layer is difficult to achieve effective sintering, and if the temperature of the vacuum sintering is too high, the metal components in the already formed base layer and transition layer may be densified and even melted.
Preferably, in the step (3), the mass ratio of the molten alkali metal salt and/or the molten rare earth salt to the alkali metal oxide-doped ceramic powder is 1-100: 1 (more preferably 5-50: 1). If the amount of the alkali metal oxide is too small, the ceramic film may not be sufficiently strengthened, and if the amount of the alkali metal oxide is too large, the strength of the precision layer may be affected.
Preferably, in the step (3), the temperature of the ion exchange is 200-800 ℃ (more preferably 400-700 ℃) and the time is 0.5-8.0 h (more preferably 1-5 h). If the temperature of the ion exchange is too low, the ion exchange is difficult to realize, and if the temperature of the ion exchange is too high, the molten salt can corrode the metal substrate layer of the metal composite ceramic membrane; if the time of ion exchange is too short, the ion exchange is insufficient, and the stress intensification degree is insufficient, and if the time of ion exchange is too long, the ion exchange is too sufficient, and even reaches an equilibrium state, and the concentration of alkali metal ions exchanged at each position of the precision layer is uniform, so that it is difficult to realize gradient change of the exchanged ions, and the stress intensification is contradictory.
Preferably, in step (3), before ion exchange, the porous ceramic filter layer is impregnated with a gel made of composite ceramic or mixed ceramic powder and vacuum sintered to form the ceramic particle modifying layer.
Preferably, the dipping temperature is 50-80 ℃ and the time is 0.5-15 min (more preferably 6-12 min). If the temperature for impregnation is too low or the time for impregnation is too short, the gel has a high viscosity and is not easily impregnated uniformly, and if the temperature for impregnation is too high or the time for impregnation is too long, the gel is easily dehydrated in the air and loses stability.
Preferably, the mass fraction of the gel is 1 to 50% (more preferably 5 to 30%). If the mass fraction of the gel is too low, the number of required dipping times increases, and if the mass fraction of the gel is too high, the gel becomes unstable.
Preferably, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, for 2-14 h (more preferably 4-10 h). During vacuum sintering, sintering between ceramic particles occurs due to the gel preferentially impregnated into the defects of the ceramic layer and the gel deposited on the porous ceramic filter layer by the capillary principle. If the temperature of the vacuum sintering is too low, the ceramic gel is difficult to achieve effective sintering, and if the temperature of the vacuum sintering is too high, the metal components in the already formed base layer and transition layer may be densified and even melted.
Preferably, the operations of dipping and vacuum sintering are repeated for more than or equal to 1 time to obtain the multilayer ceramic particle modification layer.
The invention has the following beneficial effects:
(1) the filtering precision of the reinforced metal composite ceramic membrane can reach 1-50 nm, and the filtering flux can reach 500-3000L/h; the aperture is uniform, and the precision and aperture uniformity indexes are far higher than those of a metal filter membrane;
(2) the reinforced metal composite ceramic membrane can control the surface reinforcement degree of the ceramic membrane by changing the type of the exchanged ions and the ion exchange time, thereby controlling the tensile stress, the unstressed state or the tensile stress state of the surface ceramic coating to meet the requirements of different stress occasions;
(3) the reinforced metal composite ceramic membrane has the characteristics of thin thickness and continuous change of metal and ceramic phase components in structural design, so that the reinforced metal composite ceramic membrane has the advantages of high toughness of metal and ceramic phases, good thermal shock resistance, high mechanical strength and easiness in back flushing and cleaning, and can effectively resist damage caused by temperature change when used in a variable-temperature environment;
(4) the reinforced metal composite ceramic membrane can be widely applied to the fields of industrial wastewater, high-temperature corrosive flue gas purification and the like, and can also be applied to various filtering systems with severe temperature changes;
(5) the method has simple process and low cost, and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The mass ratio of aluminum nitride to silicon nitride in the aluminum nitride-silicon nitride mixed ceramic powder used in the embodiment of the invention is 72:27, the mass ratio of alumina to silicon oxide in the alumina/silicon oxide composite ceramic powder is 73:24, and the mass ratio of zirconia to alumina in the zirconia-alumina mixed ceramic powder is 10: 90; the starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.
Example 1 of a reinforced Metal composite ceramic film
The reinforced metal composite ceramic membrane sequentially comprises a 90kg basal layer, a 30kg transition layer and a 0.55kg precision layer;
the base layer is formed by sintering simple substance titanium powder with the average grain diameter of 50 meshes; the thickness of the substrate layer is 1800 mu m;
the transition layer is composed of 1 layer, and is a composite layer formed by sintering simple substance titanium powder with the average grain diameter of 800 meshes and aluminum nitride and silicon nitride mixed ceramic powder with the average grain diameter of 3000 meshes according to the mass ratio of 70: 30; the thickness of the transition layer is 750 mu m;
the precision layer is a porous ceramic filter layer formed by sintering lithium oxide with the average particle size of 2000 meshes and aluminum nitride and silicon nitride mixed ceramic powder mixture with the average particle size of 5000 meshes, wherein the lithium oxide is 0.05kg, and the outside of the precision layer is subjected to ion exchange by mixed molten salt of sodium hydroxide and potassium hydroxide according to the mass ratio of 3: 1; the content of lithium element is gradually reduced from the inside of the precision layer to the outside of the precision layer, and the content of potassium and sodium elements is gradually reduced from the outside of the precision layer to the inside of the precision layer; the thickness of the porous ceramic filter layer is 20 μm; the average pore size of the porous ceramic filter layer is 50 nm.
Example 2 of a reinforced Metal composite ceramic film
The reinforced metal composite ceramic membrane sequentially comprises a 50kg basal layer, a 45kg transition layer and a 2.11kg precision layer;
the base layer is formed by sintering stainless steel 310S powder with the average grain size of 400 meshes; the thickness of the substrate layer is 1200 mu m;
the transition layer consists of 3 layers from the base layer to the precision layer, wherein the 1 st layer is a composite layer sintered by stainless steel 310S powder with the average grain size of 500 meshes and alumina/silicon oxide composite ceramic powder with the average grain size of 5000 meshes in a mass ratio of 90:10, the 2 nd layer is a composite layer sintered by stainless steel 310S powder with the average grain size of 750 meshes and alumina/silicon oxide composite ceramic powder with the average grain size of 5000 meshes in a mass ratio of 50:50, and the 3 rd layer is a composite layer sintered by stainless steel 310S powder with the average grain size of 800 meshes and alumina/silicon oxide composite ceramic powder with the average grain size of 8000 meshes in a mass ratio of 10: 90; each layer of the transition layer is 350 μm thick;
the precision layer comprises a porous ceramic filter layer and a ceramic particle modification layer, wherein the porous ceramic filter layer is formed by sintering a mixture of 0.1kg of lithium oxide with the average particle size of 2000 meshes, 0.01kg of sodium oxide with the average particle size of 3000 meshes and 1.9kg of alumina/silica composite ceramic powder with the average particle size of 10000 meshes, and the ceramic particle modification layer is formed by sintering 0.1kg of gel prepared from alumina/silica composite ceramic powder with the average particle size of 100nm and arranged outside the porous ceramic filter layer; and the outside of the precision layer is subjected to ion exchange by mixed molten salt of sodium hydroxide, potassium hydroxide and lanthanum nitrate in a mass ratio of 150:50: 1; the content of lithium and sodium elements is gradually reduced from the inside of the precision layer to the outside of the precision layer, and the content of potassium and lanthanum elements is gradually reduced from the outside of the precision layer to the inside of the precision layer; the thickness of the porous ceramic filter layer is 45 μm; the average pore size of the porous ceramic filter layer is 10 nm; the ceramic particle modification layer is composed of 1 layer, and the thickness is 25 mu m.
Example 3 of a reinforced Metal composite ceramic film
The reinforced metal composite ceramic membrane sequentially comprises a 40kg basal layer, a 60kg transition layer and a 0.65kg precision layer;
the substrate layer is formed by sintering Hastelloy powder with the average grain size of 300 meshes; the thickness of the substrate layer is 1100 mu m;
the transition layer consists of 2 layers from the base layer to the precision layer, wherein the 1 st layer is a composite layer sintered by Hastelloy powder with the average grain size of 200 meshes and zirconia-alumina mixed ceramic powder with the average grain size of 3000 meshes according to the mass ratio of 70:30, and the 2 nd layer is a composite layer sintered by Hastelloy powder with the average grain size of 800 meshes and zirconia-alumina mixed ceramic powder with the average grain size of 3000 meshes according to the mass ratio of 20: 80; each layer of the transition layer is 650 mu m in thickness;
the precision layer comprises a porous ceramic filter layer and a ceramic particle modification layer, wherein the porous ceramic filter layer is formed by sintering a mixture of 0.15kg of lithium oxide with the average particle size of 4000 meshes and 0.45kg of zirconia-alumina mixed ceramic powder with the average particle size of 10000 meshes, and the ceramic particle modification layer is formed by sintering 0.05kg of gel which is arranged on the outer side of the porous ceramic filter layer and is made of zirconia-alumina mixed ceramic powder with the average particle size of 20 nm; and the outside of the precision layer is subjected to ion exchange by mixed molten salt of sodium hydroxide, potassium hydroxide and lanthanum chloride in a mass ratio of 20:30: 1; the content of lithium element is gradually reduced from the inside of the precision layer to the outside of the precision layer, and the content of sodium, potassium and lanthanum elements is gradually reduced from the outside of the precision layer to the inside of the precision layer; the thickness of the porous ceramic filter layer is 30 μm; the average pore size of the porous ceramic filter layer is 5 nm; the ceramic particle modification layer consists of 2 layers, and the thickness of the ceramic particle modification layer is 5 micrometers and 3 micrometers from inside to outside in sequence.
Preparation method of reinforced metal composite ceramic membrane example 1
(1) Adding 0.45kg of methylcellulose into 90kg of simple substance titanium powder, mixing at normal temperature for 3h, heating at 90 deg.C and 4m/min for tape casting, and heating at 1300 deg.C and 3 × 10-3Vacuum sintering for 6 hours under Pa to obtain a substrate layer;
(2) mixing 21kg of simple substance titanium powder and 9kg of aluminum nitride and silicon nitride mixed ceramic powder, heating and casting the mixture on the substrate layer obtained in the step (1) at 90 ℃ and 4m/min, and heating and casting the mixture at 1400 ℃ and 3 multiplied by 10-3Under Pa, vacuum sintering for 10h to form a transition layer to obtain an intermediate product;
(3) spraying 0.05kg of mixed ceramic powder mixture of lithium oxide and 0.5kg of aluminum nitride and silicon nitride on the transition layer of the intermediate product obtained in the step (2), and carrying out heat treatment at 1400 ℃ and 5X 10-3And (2) sintering for 8 hours in vacuum under Pa to form a porous ceramic filter layer, placing the outer side of the porous ceramic filter layer in mixed molten salt of 3kg of sodium hydroxide and 1kg of potassium hydroxide, performing ion exchange for 2 hours at 550 ℃, washing with water, and drying to obtain the reinforced metal composite ceramic membrane 1.
Through detection, the filtration precision of the reinforced metal composite ceramic membrane 1 obtained in the embodiment of the invention is 50nm, and the filtration flux is 2000L/h; the aperture is uniform, and the precision and aperture uniformity indexes are far higher than those of the metal filter element; and the toughness is high, the mechanical strength is high, and the back flushing cleaning is easy.
Preparation method of reinforced metal composite ceramic membrane example 2
(1) Adding 7.5kg of polypropylene/paraffin (1: 1 by mass) into 50kg of stainless steel 310S powder, mixing at 150 deg.C for 2 hr, heating at 130 deg.C and 5m/min, casting, and heating at 1320 deg.C and 5 × 10-2Vacuum sintering for 3 hours under Pa to obtain a substrate layer;
(2) mixing 13.5kg stainless steel 310S powder and 1.5kg alumina/silica composite ceramic powder, heating and casting at 120 deg.C and 5m/min to the substrate layer obtained in step (1), and heating and casting at 1450 deg.C and 5 × 10-2Under Pa, vacuum sintering for 4h to form a 1 st transition layer;
mixing 7.5kg of stainless steel 310S powder and 7.5kg of alumina/silica composite ceramic powder, heating and casting to the second step at 120 ℃ and 5m/min1 transition layer, 5X 10 at 1450 deg.C-2Under Pa, vacuum sintering for 5h to form a 2 nd transition layer;
mixing 1.5kg stainless steel 310S powder and 13.5kg alumina/silica composite ceramic powder, heating and casting to the 2 nd transition layer at 120 deg.C and 5m/min, and casting at 1450 deg.C and 5 × 10-2Under Pa, vacuum sintering for 6h to form a 3 rd transition layer to obtain an intermediate product;
(3) spraying a mixture of 0.1kg of lithium oxide, 0.01kg of sodium oxide and 1.9kg of alumina/silica composite ceramic powder on the transition layer of the intermediate product obtained in the step (2), and carrying out reaction at 1500 ℃ and 5X 10-2Under Pa, vacuum sintering for 10h to form a porous ceramic filter layer;
soaking 30% gel of alumina/silica composite ceramic powder at 80 deg.C for 6min at 1500 deg.C and 5 × 10-2Under Pa, vacuum sintering for 4h to form a ceramic particle modification layer;
and (3) placing the outer side of the ceramic particle modification layer in mixed molten salt of 15kg of sodium hydroxide, 5kg of potassium hydroxide and 0.1kg of lanthanum nitrate, performing ion exchange for 2 hours at 550 ℃, washing with water, and drying to obtain the reinforced metal composite ceramic membrane 2.
Through detection, the filtration precision of the reinforced metal composite ceramic membrane 2 obtained in the embodiment of the invention is 10nm, and the filtration flux is 800L/h; the aperture is uniform, and the precision and aperture uniformity indexes are far higher than those of the metal filter element; and the toughness is high, the mechanical strength is high, and the back flushing cleaning is easy.
Preparation method of reinforced metal composite ceramic membrane example 3
(1) Adding 0.3kg polyacrylamide into 40kg Hastelloy powder, mixing at room temperature for 1 hr, heating at 80 deg.C and 8m/min for tape casting, and heating at 1400 deg.C and 1 × 10-2Under Pa, vacuum sintering for 2h to obtain a substrate layer;
(2) mixing 21kg of Hastelloy powder and 9kg of zirconia-alumina mixed ceramic powder, heating and casting the mixture on the substrate layer obtained in the step (1) at 80 ℃ and 8m/min, and carrying out casting at 1100 ℃ and 4 multiplied by 10-2Under Pa, vacuum sintering for 4h to form a 1 st transition layer;
mixing 6kg of Hastelloy powder and 24kg of zirconia-alumina mixed ceramic powder, heating and casting to the 1 st transition layer at 80 ℃ and 8m/min, and performing 4 multiplied by 10 casting at 1300 ℃-2Under Pa, vacuum sintering for 8h to form a 2 nd transition layer to obtain an intermediate product;
(3) spraying a ceramic powder mixture of 0.15kg of lithium oxide and 0.45kg of zirconia alumina mixed on the transition layer of the intermediate product obtained in the step (2), and carrying out the step of spraying at 1300 ℃ and 4X 10-2Under Pa, vacuum sintering for 12h to form a porous ceramic filter layer;
soaking gel with 10% mass fraction prepared from zirconia-alumina mixed ceramic powder at 60 deg.C at 1500 deg.C for 12min, and treating at 6 × 10-2Under Pa, vacuum sintering for 8h to form a 1 st ceramic particle modification layer;
soaking gel with mass fraction of 6% prepared from zirconia-alumina mixed ceramic powder at 60 deg.C for 10min at 1400 deg.C and 6 × 10-2Under Pa, vacuum sintering for 5h to form a 2 nd ceramic particle modification layer;
and (3) placing the outer side of the ceramic particle modification layer in mixed molten salt of 10kg of sodium hydroxide, 15kg of potassium hydroxide and 0.5kg of lanthanum chloride, performing ion exchange for 3.5 hours at 600 ℃, washing with water, and drying to obtain the reinforced metal composite ceramic membrane 3.
Through detection, the filtration precision of the reinforced metal composite ceramic membrane 3 obtained in the embodiment of the invention is 5nm, and the filtration flux is 1500L/h; the aperture is uniform, and the precision and aperture uniformity indexes are far higher than those of the metal filter element; and the toughness is high, the mechanical strength is high, and the back flushing cleaning is easy.
Comparative example 1
(1) Adding 0.3kg polyacrylamide into 40kg Hastelloy powder, mixing at room temperature for 1 hr, heating at 80 deg.C and 8m/min for tape casting, and heating at 1400 deg.C and 1 × 10-2Under Pa, vacuum sintering for 2h to obtain a substrate layer;
(2) mixing 21kg of Hastelloy powder and 9kg of zirconia-alumina mixed ceramic powder, heating and casting the mixture on the substrate layer obtained in the step (1) at 80 ℃ and 8m/min, and carrying out casting at 1100 ℃ and 4 multiplied by 10-2Pa is belowVacuum sintering for 4h to form a 1 st transition layer;
mixing 6kg of Hastelloy powder and 24kg of zirconia-alumina mixed ceramic powder, heating and casting to the 1 st transition layer at 80 ℃ and 8m/min, and performing 4 multiplied by 10 casting at 1300 ℃-2Under Pa, vacuum sintering for 8h to form a 2 nd transition layer to obtain an intermediate product;
(3) spraying 0.6kg of zirconia-alumina mixed ceramic powder on the transition layer of the intermediate product obtained in the step (2), and carrying out the step (2) of spraying at 1300 ℃ and 4 multiplied by 10-2Under Pa, vacuum sintering for 12h to form a porous ceramic filter layer;
soaking gel with 10% mass fraction prepared from zirconia-alumina mixed ceramic powder at 60 deg.C at 1500 deg.C for 12min, and treating at 6 × 10-2Under Pa, vacuum sintering for 8h to form a 1 st ceramic particle modification layer;
soaking gel with mass fraction of 6% prepared from zirconia-alumina mixed ceramic powder at 60 deg.C for 10min at 1400 deg.C and 6 × 10-2And (3) sintering for 5 hours in vacuum under Pa to form a 2 nd ceramic particle modification layer, thus obtaining the metal composite ceramic membrane 1.
The impact resistance comparison experiment was performed on the reinforced metal composite ceramic membranes 1-3 of the present invention, commercially available ceramic membranes, and the unreinforced metal composite ceramic membrane 1 of comparative example 1 according to GB4742-B4, the number of each filter membrane sample was 5, and the impact toughness values of different samples were respectively tested, and the results are shown in table 1.
TABLE 1 comparison table of impact toughness of the reinforced metal composite ceramic films 1 to 3 of the present invention and commercially available ceramic films and metal composite ceramic films 1
Figure BDA0002124216340000111
Figure BDA0002124216340000121
As can be seen from Table 1, the impact toughness of the reinforced metal composite ceramic membranes 1-3 of the invention is respectively improved by about 40-140%, 140-270% and 200-370% compared with the commercial ceramic filter element; compared with the metal composite ceramic membrane 1 of the comparative example 1 which is not subjected to ion exchange treatment, the impact toughness of the reinforced metal composite ceramic membrane 3 is improved by about 100-210%, which shows that the impact toughness of the reinforced metal composite ceramic membrane 1-3 is greatly improved after the reinforced metal composite ceramic membrane is reinforced.

Claims (30)

1. A reinforced metal composite ceramic membrane, characterized by: the device sequentially comprises a substrate layer, a transition layer and a precision layer; the substrate layer is formed by sintering elemental metal or alloy powder; the transition layer is a composite layer formed by sintering elemental metal or alloy powder and composite ceramic or mixed ceramic powder; the precision layer comprises a porous ceramic filter layer formed by sintering alkali metal oxide doped ceramic powder, and the outer side of the precision layer is subjected to ion exchange by alkali metal molten salt and/or rare earth molten salt; the mass ratio of the base layer to the transition layer to the precision layer is 40-90: 30-80: 0.5-5.0; in the transition layer, the mass ratio of the simple substance metal or alloy powder to the composite ceramic or mixed ceramic powder is 60-90: 40-10; in the precision layer, the alkali metal oxide doped ceramic powder is a mixture of alkali metal oxide and composite ceramic or mixed ceramic powder in a mass ratio of 1: 3-30; the molten salt is a mixed molten salt of sodium hydroxide and potassium hydroxide in a mass ratio of 2-4: 1, or a mixed molten salt of sodium hydroxide, potassium hydroxide and rare earth in a mass ratio of 10-200: 20-60: 1; the precision layer also comprises a ceramic particle modification layer arranged outside the porous ceramic filter layer; the mass ratio of the ceramic particle modification layer to the porous ceramic filter layer is 0.04-0.45: 1; the ceramic particle modification layer is formed by sintering gel made of composite ceramic or mixed ceramic powder;
the preparation method of the reinforced metal composite ceramic membrane comprises the following steps:
(1) adding a forming agent into the elemental metal or alloy powder, mixing, heating, casting, and sintering in vacuum to obtain a substrate layer;
(2) mixing simple substance metal or alloy powder with composite ceramic or mixed ceramic powder, heating and casting to the substrate layer obtained in the step (1), and performing vacuum sintering to form a transition layer to obtain an intermediate product;
(3) spraying alkali metal oxide doped ceramic powder on the transition layer of the intermediate product obtained in the step (2), sintering in vacuum to form a porous ceramic filter layer, placing the outer side of the porous ceramic filter layer in molten alkali metal salt and/or molten rare earth salt for ion exchange, washing with water, and drying to obtain the reinforced metal composite ceramic membrane; the temperature of the ion exchange is 550-700 ℃, and the time is 2.0-3.5 h;
before ion exchange, soaking gel made of composite ceramic or mixed ceramic powder on the outer side of the porous ceramic filter layer, and vacuum sintering to form a ceramic particle modification layer; the dipping temperature is 50-80 ℃, and the time is 6-12 min; the mass fraction of the gel is 5-30%.
2. The reinforced metal composite ceramic membrane of claim 1, wherein: the alkali metal element in the alkali metal oxide doped ceramic powder is not completely same as or completely different from the alkali metal element in the molten alkali metal salt, and the diameter of the alkali metal element in the molten alkali metal salt is larger than or equal to that of the alkali metal element in the alkali metal oxide doped ceramic powder; the content of alkali metal elements introduced by the alkali metal oxide doped ceramic powder is gradually reduced from the inner side of the precision layer to the outer side of the precision layer; the content of the alkali metal and/or the rare earth element introduced by the molten alkali metal salt and/or the molten rare earth salt is gradually reduced from the outside of the precision layer to the inside of the precision layer, except for the alkali metal which is the same as the alkali metal oxide; the alkali metal molten salt is one or more of lithium hydroxide, sodium hydroxide or potassium hydroxide; the rare earth molten salt is one or more of rare earth nitrate, rare earth oxide or rare earth chloride.
3. A reinforced metal composite ceramic membrane according to claim 1 or 2, wherein: the thickness ratio of the base layer to the transition layer to the precision layer is 0.5-2.0: 0.1-1.5: 0.01-0.10; the transition layer consists of 1-10 layers; in each layer of the transition layer, the mass ratio of the simple substance metal or the alloy to the composite ceramic or the mixed ceramic is reduced from the substrate layer to the precision layer by layer; the thickness of each layer in the transition layer is 10-1500 mu m; in the precision layer, the thickness of the porous ceramic filter layer is 1-100 mu m; the average pore size of the porous ceramic filter layer is 5-100 nm.
4. A reinforced metal composite ceramic membrane according to claim 1 or 2, wherein: in the base layer and the transition layer, the elementary metal is elementary iron, elementary nickel, elementary copper or elementary titanium; the alloy is stainless steel, hastelloy or iron-chromium-aluminum alloy; in the base layer, the average particle size of the simple substance metal or alloy powder is 30-800 meshes; in the transition layer, the average particle size of the simple substance metal or alloy powder is 30-2000 meshes; in the transition layer and the precision layer, the composite ceramic is one or more of oxide ceramic, nitride ceramic, carbide ceramic, boride ceramic, silicide ceramic or metal crystal compound; in the transition layer and the precision layer, the mixed ceramic is one or a mixture of several of oxide ceramic, nitride ceramic, carbide ceramic, boride ceramic, silicide ceramic or metal crystal compound; in the transition layer and the precision layer, the average grain diameter of the composite ceramic or mixed ceramic powder is 300-10000 meshes; in the precision layer, the average particle size of the alkali metal oxide is 2000-10000 meshes.
5. A reinforced metal composite ceramic membrane according to claim 3, wherein: in the base layer and the transition layer, the elementary metal is elementary iron, elementary nickel, elementary copper or elementary titanium; the alloy is stainless steel, hastelloy or iron-chromium-aluminum alloy; in the base layer, the average particle size of the simple substance metal or alloy powder is 30-800 meshes; in the transition layer, the average particle size of the simple substance metal or alloy powder is 30-2000 meshes; in the transition layer and the precision layer, the composite ceramic is one or more of oxide ceramic, nitride ceramic, carbide ceramic, boride ceramic, silicide ceramic or metal crystal compound; in the transition layer and the precision layer, the mixed ceramic is one or a mixture of several of oxide ceramic, nitride ceramic, carbide ceramic, boride ceramic, silicide ceramic or metal crystal compound; in the transition layer and the precision layer, the average grain diameter of the composite ceramic or mixed ceramic powder is 300-10000 meshes; in the precision layer, the average particle size of the alkali metal oxide is 2000-10000 meshes.
6. A reinforced metal composite ceramic membrane according to claim 1 or 2, wherein: the ceramic particle modification layer consists of 1-4 layers; the thickness of each layer in the ceramic particle modification layer is 1-30 mu m; the average particle size of the composite ceramic or mixed ceramic powder for preparing the gel is 5-100 nm.
7. A reinforced metal composite ceramic membrane according to claim 3, wherein: the ceramic particle modification layer consists of 1-4 layers; the thickness of each layer in the ceramic particle modification layer is 1-30 mu m; the average particle size of the composite ceramic or mixed ceramic powder for preparing the gel is 5-100 nm.
8. The reinforced metal composite ceramic membrane of claim 4, wherein: the ceramic particle modification layer consists of 1-4 layers; the thickness of each layer in the ceramic particle modification layer is 1-30 mu m; the average particle size of the composite ceramic or mixed ceramic powder for preparing the gel is 5-100 nm.
9. A reinforced metal composite ceramic membrane according to claim 1 or 2, wherein: in the step (1), the amount of the forming agent is 0.1-20.0% of the mass of the elemental metal or alloy powder; the forming agent is one or more of polyethylene glycol, polyolefin, paraffin, polyacrylamide, polyurethane or methyl cellulose; the mixing temperature is normal temperature-150 ℃, and the mixing time is 1-3 h; the heating casting temperature is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is1×10-1～1×10-4Pa, the time is 2-8 h.
10. A reinforced metal composite ceramic membrane according to claim 3, wherein: in the step (1), the amount of the forming agent is 0.1-20.0% of the mass of the elemental metal or alloy powder; the forming agent is one or more of polyethylene glycol, polyolefin, paraffin, polyacrylamide, polyurethane or methyl cellulose; the mixing temperature is normal temperature-150 ℃, and the mixing time is 1-3 h; the heating casting temperature is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-8 h.
11. The reinforced metal composite ceramic membrane of claim 4, wherein: in the step (1), the amount of the forming agent is 0.1-20.0% of the mass of the elemental metal or alloy powder; the forming agent is one or more of polyethylene glycol, polyolefin, paraffin, polyacrylamide, polyurethane or methyl cellulose; the mixing temperature is normal temperature-150 ℃, and the mixing time is 1-3 h; the heating casting temperature is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-8 h.
12. The reinforced metal composite ceramic membrane of claim 6, wherein: in the step (1), the amount of the forming agent is 0.1-20.0% of the mass of the elemental metal or alloy powder; the forming agent is one or more of polyethylene glycol, polyolefin, paraffin, polyacrylamide, polyurethane or methyl cellulose; the mixing temperature is normal temperature-150 ℃, and the mixing time is 1-3 h; the heating casting temperature is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-8 h.
13. A reinforced metal composite ceramic membrane according to claim 1 or 2, wherein: in the step (2), the temperature of heating and casting is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-12 h; repeating the operations of powder mixing, heating tape casting and vacuum sintering for more than or equal to 1 time to obtain a multi-layer transition layer.
14. A reinforced metal composite ceramic membrane according to claim 3, wherein: in the step (2), the temperature of heating and casting is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-12 h; repeating the operations of powder mixing, heating tape casting and vacuum sintering for more than or equal to 1 time to obtain a multi-layer transition layer.
15. The reinforced metal composite ceramic membrane of claim 4, wherein: in the step (2), the temperature of heating and casting is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-12 h; repeating the operations of powder mixing, heating tape casting and vacuum sintering for more than or equal to 1 time to obtain a multi-layer transition layer.
16. The reinforced metal composite ceramic membrane of claim 6, wherein: in the step (2), the temperature of heating and casting is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-12 h; repeating the operations of powder mixing, heating tape casting and vacuum sintering for more than or equal to 1 time to obtain a multi-layer transition layer.
17. The reinforced metal composite ceramic membrane of claim 9, wherein: in the step (2), the heat castingThe temperature of the casting is 60-150 ℃, and the casting speed is 0.5-30 m/min; the temperature of the vacuum sintering is 1000-1500 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-12 h; repeating the operations of powder mixing, heating tape casting and vacuum sintering for more than or equal to 1 time to obtain a multi-layer transition layer.
18. A reinforced metal composite ceramic membrane according to claim 1 or 2, wherein: in the step (3), when the porous ceramic filter layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-14 h; the mass ratio of the alkali metal molten salt and/or the rare earth molten salt to the alkali metal oxide doped ceramic powder is 1-100: 1.
19. A reinforced metal composite ceramic membrane according to claim 3, wherein: in the step (3), when the porous ceramic filter layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-14 h; the mass ratio of the alkali metal molten salt and/or the rare earth molten salt to the alkali metal oxide doped ceramic powder is 1-100: 1.
20. The reinforced metal composite ceramic membrane of claim 4, wherein: in the step (3), when the porous ceramic filter layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-14 h; the mass ratio of the alkali metal molten salt and/or the rare earth molten salt to the alkali metal oxide doped ceramic powder is 1-100: 1.
21. The reinforced metal composite ceramic membrane of claim 6, wherein: in the step (3), when the porous ceramic filter layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-14 h; the quality of the alkali metal molten salt and/or the rare earth molten salt and the alkali metal oxide doped ceramic powderThe amount ratio is 1-100: 1.
22. The reinforced metal composite ceramic membrane of claim 9, wherein: in the step (3), when the porous ceramic filter layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-14 h; the mass ratio of the alkali metal molten salt and/or the rare earth molten salt to the alkali metal oxide doped ceramic powder is 1-100: 1.
23. The reinforced metal composite ceramic membrane of claim 13, wherein: in the step (3), when the porous ceramic filter layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 multiplied by 10-1～1×10-4Pa, the time is 2-14 h; the mass ratio of the alkali metal molten salt and/or the rare earth molten salt to the alkali metal oxide doped ceramic powder is 1-100: 1.
24. A reinforced metal composite ceramic membrane according to claim 1 or 2, wherein: in the step (3), when the ceramic particle modification layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 × 10-1～1×10-4Pa, the time is 2-14 h; repeating the operations of dipping and vacuum sintering for more than or equal to 1 time to obtain the multilayer ceramic particle modification layer.
25. A reinforced metal composite ceramic membrane according to claim 3, wherein: in the step (3), when the ceramic particle modification layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 × 10-1～1×10-4Pa, the time is 2-14 h; repeating the operations of dipping and vacuum sintering for more than or equal to 1 time to obtain the multilayer ceramic particle modification layer.
26. The reinforced metal composite ceramic membrane of claim 4, wherein: in the step (3), when the ceramic particle modification layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 × 10-1～1×10-4Pa, the time is 2-14 h; repeating the operations of dipping and vacuum sintering for more than or equal to 1 time to obtain the multilayer ceramic particle modification layer.
27. The reinforced metal composite ceramic membrane of claim 6, wherein: in the step (3), when the ceramic particle modification layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 × 10-1～1×10-4Pa, the time is 2-14 h; repeating the operations of dipping and vacuum sintering for more than or equal to 1 time to obtain the multilayer ceramic particle modification layer.
28. The reinforced metal composite ceramic membrane of claim 9, wherein: in the step (3), when the ceramic particle modification layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 × 10-1～1×10-4Pa, the time is 2-14 h; repeating the operations of dipping and vacuum sintering for more than or equal to 1 time to obtain the multilayer ceramic particle modification layer.
29. The reinforced metal composite ceramic membrane of claim 13, wherein: in the step (3), when the ceramic particle modification layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 × 10-1～1×10-4Pa, the time is 2-14 h; repeating the operations of dipping and vacuum sintering for more than or equal to 1 time to obtain the multilayer ceramic particle modification layer.
30. The reinforced metal composite ceramic membrane of claim 18, wherein: in the step (3), when the ceramic particle modification layer is formed, the temperature of the vacuum sintering is 1200-1600 ℃, and the vacuum degree is 1 × 10-1～1×10-4Pa, the time is 2-14 h; repeating the operations of dipping and vacuum sintering for more than or equal to 1 time to obtain the multilayer ceramic particle modification layer.
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