WO2017107478A1 - 分子筛膜支撑体的制备方法 - Google Patents

分子筛膜支撑体的制备方法 Download PDF

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WO2017107478A1
WO2017107478A1 PCT/CN2016/091005 CN2016091005W WO2017107478A1 WO 2017107478 A1 WO2017107478 A1 WO 2017107478A1 CN 2016091005 W CN2016091005 W CN 2016091005W WO 2017107478 A1 WO2017107478 A1 WO 2017107478A1
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Prior art keywords
cordierite
molecular sieve
mass
water
sieve membrane
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PCT/CN2016/091005
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English (en)
French (fr)
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孟凡朋
樊震坤
张健
张超
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山东硅元新型材料有限责任公司
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Priority to US15/542,648 priority Critical patent/US10017423B2/en
Publication of WO2017107478A1 publication Critical patent/WO2017107478A1/zh

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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the invention belongs to the technical field of support preparation, and in particular relates to a preparation method of a molecular sieve membrane support.
  • Molecular sieve membrane is a kind of complete dense aluminosilicate film with cubic lattice.
  • the crystal skeleton contains many cavities of the same size, which can pass molecules smaller than the cavity of the cavity, so it can accurately adsorb or separate differently.
  • the size of the molecule It is widely used for separation and purification of organic solvents, as well as separation and purification of gases. For example, the separation and purification of organic acids such as acetic acid and acrylic acid, dehydration of ethanol and propanol, oxygen purification in air, and removal of carbon dioxide by various hydrocarbon product streams. Compared with conventional cryogenic distillation technology, it requires a large amount of energy and equipment investment.
  • molecular sieve membrane for separation and purification instead of cryogenic distillation technology can save a lot of energy and equipment. Since the molecular sieve membrane relies on the cavity of the crystal lattice of the crystal to separate gas or liquid small molecules, the crystal of the molecular sieve membrane should be continuously dense, and defects such as voids and gaps of the crystal thin film may cause the separation efficiency to be greatly reduced.
  • the molecular sieve membrane usually uses a hydrothermal synthesis method in situ and a secondary growth method to grow a molecular sieve membrane on the support.
  • In-situ hydrothermal synthesis refers to the attachment of agglomerated, colloidal, amorphous aluminosilicate materials to a support to provide appropriate supersaturation under hydrothermal synthesis conditions to form crystals at the interface of the support.
  • the core grows into a dense film.
  • the secondary growth method refers to synthesizing the dispersed molecular sieve crystal particles by hydrothermal synthesis, then coating the molecular sieve crystals on the carrier, and then placing them in the molecular sieve synthesis mother liquid to continue hydrothermal synthesis, so that the dispersed molecular sieve crystals continue to grow to form a densified film. .
  • the molecular sieve membrane usually uses a porous support of ⁇ -alumina, stainless steel or mullite having a median pore diameter of about 1 ⁇ m.
  • CN102861516A discloses a method for producing a hollow fiber support of ⁇ -alumina having a pore diameter of 0.9 to 1.3 ⁇ m, which is used as a support for a molecular sieve membrane.
  • CN104987120A discloses a single-tube or multi-channel tubular support having an average pore diameter of from 0.8 to 1.5 microns and a material of alpha alumina and mullite.
  • the main materials of the above two methods are alpha alumina, and the average pore diameter is about 1 micrometer, which is a single layer, and the pore size distribution is difficult to be uniform.
  • the particle size of the crystal nucleus or the seed crystal is nanometer-scale, and it is difficult to uniformly cover the carrier having an average pore diameter of 1 ⁇ m, which is inevitably collapsed or embedded in the pore channel. , resulting in inconsistent or even defective thickness of the molecular sieve membrane.
  • the support of ⁇ -alumina or stainless steel has higher raw material price, higher sintering temperature or harsh sintering atmosphere, and higher manufacturing cost.
  • the coarse particles are added with the cordierite fine powder; or the cordierite coarse particles are added to the fine-grain sintering aid mixed and sintered according to the distribution ratio of the cordierite, and the cordierite porous material is prepared by sintering at a temperature lower than the decomposition of the aggregate cordierite particles.
  • These three methods determine that the pore diameter of the porous material is necessarily large because the sintering aid or the fine particles inevitably block the pores of the cordierite coarse particles, otherwise it is difficult to prepare the cordierite porous material with industrial prospects. For example, Wang Yaoming et al.
  • a sintering aid such as 300 ⁇ m cordierite powder and potassium feldspar to prepare a cordierite support for high-temperature dust removal with a pore size of 128 ⁇ m (Research on Porous Cordierite Ceramic Support Material for High Temperature Flue Gas Purification) 2011 33 (10) 1262-1265).
  • Han Huonian et al. mixed with 25 ⁇ m coarse cordierite powder and 1.5 ⁇ m cordierite fine powder at 1400 ° C to obtain a porous ceramic support.
  • the core of these studies is to use the lower sintering temperature of cordierite fine powder or sintering aid or cordierite to form a fine ceramic powder to bond coarse cordierite particles with higher sintering temperature to avoid decomposition and melting of coarse particles.
  • the pore size of the coarse-grained aggregate is inevitably large, and is usually about 10-150 ⁇ m, which is completely unsupportable as a support for the molecular sieve membrane.
  • fine powder or sintering aids can block the pores, resulting in a decrease in porosity.
  • the cordierite fine powder is used directly, it is difficult to avoid the melt decomposition at the sintering temperature, and only a dense ceramic is obtained. Therefore, it is difficult to prepare a cordierite porous support for a molecular sieve having a pore diameter of about 1 ⁇ m directly using 2-5 ⁇ m cordierite.
  • the object of the present invention is to provide a preparation method of a molecular sieve membrane support body, which overcomes the problem that cordierite can only prepare a large-pore support body of 5 to 100 micrometers or more, and replaces high-priced materials such as alpha alumina and stainless steel, and reduces the support. Cost; at the same time, further coating a layer of zirconia porous film with a thickness of tens of micrometers and a pore size of 0.08-0.4 micrometer as a growth substrate of the molecular sieve membrane on the cordierite layer, the pore diameter is smaller than that of the conventional molecular sieve carrier, and the molecular sieve is eliminated. The possibility of grain sinking in the large pores of the carrier.
  • the preparation method of the molecular sieve membrane support body of the invention has the following steps:
  • the mass ratio of ethanol to water in the step (1) is 0.85-1.15:1; the median diameter of the D50 of the cordierite powder is 2-5 micrometers, and the mass of the cordierite powder is the total mass of ethanol and water. 25-35%.
  • the dispersing agent described in the step (1) is a polyethylene glycol or a PVA-based dispersing agent, the dispersing agent is added in an amount of 2-5% by weight of the cordierite powder; and the polyethylene glycol-based dispersing agent is preferably polyethylene-2.
  • Alcohol 400 or polyethylene glycol 600 polyethylene glycol 400 is preferably added in an amount of 3.5-4% by weight of cordierite powder, and polyethylene glycol 600 is preferably added in an amount of 2.5-3% by weight of cordierite powder;
  • PVA The dispersant is preferably PVA088-20 in an amount of 2-3% by weight of the cordierite powder.
  • the total mass of the orthosilicate, aluminum salt, magnesium salt and strontium salt described in the step (1) is 3-8% of the cordierite powder mass, ethyl orthosilicate, aluminum salt, magnesium salt, strontium
  • the salt has a molar ratio of silicon, aluminum, magnesium and lanthanum of 5-5.2:4:2-2.2:0-3.
  • the aluminum salt described in the step (1) is one or more of its corresponding nitrate, chloride or sulfate, preferably a chlorine salt; the magnesium salt is in its corresponding nitrate, chloride or sulfate One or more of them are preferably a chlorine salt; the phosphonium salt is one or more of its corresponding nitrate, chloride or sulfate, preferably a chloride salt.
  • the heating temperature described in the step (1) is 450 to 650 ° C, and the holding time is 1 to 6 hours.
  • the binder described in the step (2) is methyl cellulose or hydroxypropyl methyl cellulose, and the binder is added in an amount of 4-10% by mass of the cordierite particles; the mass of the water is the mass of the cordierite particles. 20-40%; the humectant is glycerin, and the humectant is added in an amount of 1.5-3.5% of the mass of cordierite particles.
  • the green body described in the step (2) is a single-hole, three-hole or four-hole round tubular green body.
  • the sintering temperature described in the step (2) is 950 to 1150 ° C, and the sintering time is 1-6 hours.
  • the zirconia has a median diameter D50 of 0.25-0.6 ⁇ m, the amount of zirconia added is 10-20% of the mass of water in the coating liquid, and the dispersing agent is a polyethylene glycol dispersing agent.
  • the dispersant is added in an amount of 2-5% by mass of the zirconia;
  • the viscosity modifier is hydroxypropylmethylcellulose, and the viscosity modifier is added in an amount of 0.65-1.5% of the mass of the water in the coating liquid;
  • the mass is 6-12% of the cordierite support mass.
  • the sintering temperature described in the step (3) is 950 to 1150 ° C, and the sintering time is 2-4 hours.
  • the molecular sieve membrane support prepared by the invention wherein the cordierite support layer has a pore diameter of 0.6-1.5 micrometers, a porosity of 33-40%, a support layer thickness of 1-5 mm, and an average pore diameter of the zirconia thin film layer of 0.08-0.4 micrometers.
  • the porosity is 40-55%, and the thickness of the film layer is 3-30 microns.
  • the invention comprises a layer of a cordierite powder coated with a nano-oxide of magnesium, aluminum and silicon and a nano-oxide of a sintering aid, and a cordierite coated with a cordierite component nano-oxide.
  • the fine powder can be sintered at a relatively low temperature to obtain a cordierite porous support having a pore diameter of about 1 ⁇ m.
  • the preparation method of the molecular sieve membrane support body of the invention has the following specific steps:
  • the invention has the following beneficial effects:
  • the present invention is a two-layer composite support, and a zirconia film having a pore diameter of 0.08-0.4 ⁇ m is externally disposed on the main support layer of the cordierite, and the molecular sieve is synthesized and grown on the surface of the film, and the average of the single layer is 1 compared with the prior art.
  • the microporous support body, the base film grown by the support molecular sieve has smaller pore size, more uniformity and higher porosity; the molecular sieve membrane grown on the membrane is relatively more uniform, the growth time is shorter, and there is no defect.
  • the present invention coats a layer of composite sol on a 2-5 micron cordierite fine powder by a sol-gel method, and the composition of the composite sol is composed of cordierite.
  • the sol of rare earth lanthanum is added as a solid sintering aid, and the composite nano-oxide formed by sol pre-sintering can be sintered at a temperature of 950-1150 ° C to synthesize cordierite, which is much lower than the melting temperature of 2-5 micron cordierite.
  • a cordierite support having a pore diameter of 0.6-1.5 ⁇ m and a three-point bending strength of 2000-2700 N is obtained.
  • the rare earth lanthanum further improves the sintering strength of the support, and solves the tens of micron coarse powder which is usually used in cordierite.
  • Micron fine powder, or tens to hundreds of micron coarse powder and other low melting point materials mixed and sintered can only prepare macroporous support of 5 - 100 micron or more, directly sintered with 2-5 micron fine powder, because cordierite melting temperature and The sintering temperature is substantially uniform, and only a dense cordierite support can be obtained in the sintering temperature range, so that it cannot be used for the problem of preparing a support for a molecular sieve membrane.
  • the invention adopts sol-gel encapsulation on cordierite powder as a sintering aid, and does not need to add an independent fine powder as a sintering aid, thereby solving the problem that the fine powder blocks the pores and causes the porosity of the support to decrease.
  • the nano-powder formed by sol-gel makes the sintering temperature only 950-1150 °C, which is lower than the sintering temperature of ⁇ -alumina or other materials, which reduces the sintering cost and the investment cost of the furnace equipment.
  • the cordierite powder used in the invention is low in price, far lower than the ⁇ -alumina, stainless steel, etc. commonly used in the molecular sieve support. material.
  • Example 1 is a scanning electron micrograph of the surface of a zirconia thin film layer prepared in Example 1.
  • the water temperature was raised to 75 ° C, and the molar ratio of 2.2:4:5:0.5 was added to the ratio of magnesium chloride, aluminum chloride, ethyl orthosilicate, and lanthanum nitrate.
  • the total mass of the four was 8% of the cordierite powder, and the mixture was stirred. Make it evenly distributed.
  • the above process maintains the water temperature at 75 °C.
  • the mixed solution after the reaction was transferred to a large vessel under stirring, and after standing and clarifying, the liquid was filtered off with suction, RO water was added and stirred, and the clarification was continued, and the RO water was filtered off with suction.
  • the precipitate was dispersed and packed into a box-shaped container, and the oven was heated at a rate of 1 ° C / minute to 105 ° C for 20 hours. Thereafter, the dried precipitate was charged into a kiln, and heated at a rate of 1 ° C/min to 500 ° C for 2 hours to convert the sol into nanoparticles and firmly sintered on the cordierite powder.
  • the dried green body was placed in a kiln at a rate of 0.5 ° C / min to 1150 ° C and held for 4 hours to obtain a cordierite matrix.
  • the average pore diameter was measured to be 1.5 ⁇ m and the porosity was 33%.
  • the four-hole support body with a diameter of 25 mm has a three-point bending strength of 2550 N.
  • the pore size and porosity of the zirconia film are shown in Figure 1.
  • the average pore diameter is 0.11 ⁇ m
  • the maximum pore diameter is 0.32 ⁇ m
  • the porosity is 48%.
  • the porosity and pore size are greatly optimized compared with the cordierite matrix.
  • Figure 1 uses the Sirion 200 FESEM field emission Scanning electron microscopy, the magnification is 10,000 times. It can be seen from Fig. 1 that the zirconia film has a high porosity and a pore diameter of 0.1-0.4 ⁇ m.
  • the water temperature was raised to 75 ° C, and the molar ratio of 2.2:4:5 was added to magnesium chloride, aluminum chloride and ethyl orthosilicate.
  • the total mass of the three was 8% of cordierite powder, and the mixture was evenly distributed by stirring.
  • the above process maintains the water temperature at 75 °C.
  • the mixed solution after the reaction was transferred to a large vessel under stirring, and after standing and clarifying, the liquid was filtered off with suction, RO water was added and stirred, and the clarification was continued, and the RO water was filtered off with suction.
  • the precipitate was dispersed and packed into a box-shaped container, and the oven was heated at a rate of 1 ° C / minute to 105 ° C for 20 hours. Thereafter, the dried precipitate was charged into a kiln, and heated at a rate of 1 ° C/min to 500 ° C for 2 hours to convert the sol into nanoparticles and firmly sintered on the cordierite powder.
  • the dried green body was placed in a kiln at a rate of 0.5 ° C / min to 1150 ° C and held for 4 hours to obtain a cordierite matrix.
  • the average pore diameter was measured to be 1.5 ⁇ m and the porosity was 33%.
  • the four-hole support body with a diameter of 25 mm has a three-point bending strength of 2050 N. Under the same conditions, without the addition of antimony, the strength of the cordierite support decreased, but it still satisfied the use as a molecular sieve support.
  • the mixture was baked in an oven at 100 ° C for 5 hours to dryness.
  • the mixture was further fed into a kiln, heated to 1150 ° C at a rate of 1 ° C / min, and kept for 2 hours to obtain a cordierite molecular sieve support wrapped with a porous zirconia thin film layer.
  • the zirconia thin film has an average pore diameter of 0.12 ⁇ m, a maximum pore diameter of 0.33 ⁇ m, and a porosity of 47.5%.
  • the porosity and pore diameter have been greatly optimized compared with the cordierite matrix.
  • the above process maintains a water temperature of 70 °C.
  • the mixed solution after the reaction was transferred to a large vessel under stirring, and after standing and clarifying, the liquid was filtered off with suction, RO water was added and stirred, and the clarification was continued, and the RO water was filtered off with suction.
  • the precipitate was dispersed and packed into a box-shaped container, and the oven was heated at a rate of 1 ° C / minute to 105 ° C for 20 hours. Thereafter, the dried precipitate was charged into a kiln, and heated at a rate of 1 ° C/min to 450 ° C for 2 hours to convert the sol into nanoparticles and firmly sintered on the cordierite powder.
  • the green body was placed in an oven, heated to 80 ° C at a rate of 0.5 ° C / min and kept for 10 hours to dry.
  • the dried green body was placed in a kiln at a rate of 0.5 ° C/min to 1050 ° C and held for 2 hours to obtain a cordierite substrate, and the average pore diameter was measured to be 0.8 ⁇ m and the porosity was 29%.
  • the four-hole support body with a diameter of 25 mm has a three-point bending strength of 2450 N.
  • the mixture was baked in an oven at 100 ° C for 5 hours to dryness.
  • the mixture was further fed into a kiln, heated to 1150 ° C at a rate of 1 ° C / min, and kept for 2 hours to obtain a cordierite molecular sieve support wrapped with a porous zirconia thin film layer.
  • the zirconia thin film layer has an average pore diameter of 0.36 ⁇ m, a maximum pore diameter of 0.45 ⁇ m, and a porosity of 44%.
  • the three-point bending strength of the support is 2450N.
  • the water temperature was raised to 65 ° C, and the ratio of molar ratio of 2:4:5.5:0 was added to magnesium chloride, aluminum chloride, ethyl orthosilicate, and lanthanum nitrate.
  • the total mass of the four was 6% of cordierite powder, and the mixture was stirred. Make it evenly distributed.
  • the above process keeps the water temperature at 65 °C. Transfer the mixed solution after the reaction to the stirred state In a large container, after standing and clarifying, the liquid is filtered off, and then RO water is added and stirred. After further clarification, the RO water is filtered off.
  • the precipitate was dispersed and packed into a box-shaped container, and the oven was heated at a rate of 1 ° C / minute to 105 ° C for 20 hours. Thereafter, the dried precipitate was charged into a kiln, and heated at a rate of 1 ° C/min to 450 ° C for 2 hours to convert the sol into nanoparticles and firmly sintered on the cordierite powder.
  • the dried green body was placed in a kiln at a rate of 0.5 ° C / min to 950 ° C and held for 2 hours to obtain a cordierite substrate, and the average pore diameter was measured to be 1.3 ⁇ m and the porosity was 31%.
  • the four-hole support with a diameter of 25 mm has a three-point bending strength of 2,650 N.
  • the zirconium oxide film has an average pore diameter of 0.08 ⁇ m, a maximum pore diameter of 0.15 ⁇ m, and a porosity of 46%.
  • the four-hole support with a diameter of 25 mm has a three-point bending strength of 470 N, and such a low strength cannot be used as a carrier for the molecular sieve membrane.
  • the other green body was sintered to 1350 ° C at the same heating rate for 2 hours, and the four-hole support having a diameter of 23 mm had a three-point bending strength of 2250 N, and the porosity was found to be 5%, and the average pore diameter was 2.9 ⁇ m. Although the strength of the support is sufficient at this sintering temperature, the porosity is too low and the pore diameter is too large to be used as a support for the molecular sieve membrane.
  • Stir well and form a mud material pour the mud into the extruder, open the vacuuming device, and extrude the mud into a single-hole or 4-hole round tube body blank under vacuum.
  • the green body was placed in an oven, heated to 80 ° C at a rate of 0.5 ° C / min and kept for 10 hours to dry.
  • the dried green body was placed in a kiln at a rate of 0.5 ° C/min to 1150 ° C and held for 2 hours to obtain a cordierite substrate, and the average pore diameter was measured to be 1.3 ⁇ m and the porosity was 31%.
  • the four-hole support with a diameter of 25 mm has a three-point bending strength of 230 N, and such a low strength cannot be used as a carrier for the molecular sieve membrane.
  • the other green body was sintered to 1380 ° C at the same heating rate for 2 hours, and the four-hole support having a diameter of 23 mm had a three-point bending strength of 2450 N, and the porosity was 4%, and the average pore diameter was 4.8 ⁇ m. Although the strength of the support is sufficient at this sintering temperature, the porosity is too low and the pore diameter is too large to be used as a support for the molecular sieve membrane.

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Abstract

一种分子筛膜支撑体的制备方法，按堇青石中镁、铝、硅摩尔比，用溶胶－凝胶法制备出镁、铝、硅及烧结助剂镧的纳米复合溶胶包裹粘附在分散好的微米级堇青石粉表面，通过预烧结使溶胶转变成纳米复合氧化物，将此粉体与粘结剂、水等混成泥料，挤出成型并烧结成堇青石支撑体，接着用氧化锆的水分散液在堇青石支撑体外部涂覆一层薄膜并烧结，得到堇青石主支撑层和氧化锆薄膜层复合的分子筛膜支撑体。该方法制备的是双层复合支撑体，支撑体分子筛生长的基层薄膜孔径更小、更均匀，孔隙率更高；使得生长在此薄膜上的分子筛膜相对更均匀、生长时间更短，无缺陷。

Description

分子筛膜支撑体的制备方法 技术领域
本发明属于支撑体制备技术领域，具体涉及一种分子筛膜支撑体的制备方法。
背景技术
分子筛膜是一类具有立方晶格的完整致密的硅铝酸盐薄膜，其晶体骨架中含有许多大小相同的空腔，能够通过直径比空腔孔道小的分子，因此可以精确的吸附或者分离不同大小的分子。其被广泛的用于有机溶剂分离提纯，以及气体的分离提纯上。比如乙酸、丙烯酸等有机酸的分离精制，乙醇、丙醇脱水，空气中氧气提纯，多种烃产物流脱除二氧化碳等。相比常规的低温蒸馏技术需要大量的能量与设备投资经费，采用分子筛膜进行分离提纯替代低温蒸馏技术，可以节约大量的能源与设备经费。由于分子筛膜是依靠其晶体的晶格骨架的空腔来分离气体或液体小分子，因此分子筛膜的晶体应该是连续致密的，晶体薄膜的空洞、间隙等缺陷会导致其分离效率大幅下降。
分子筛膜通常采用原位水热合成法、二次生长法在支撑体上生长出分子筛膜。原位水热合成法是指将凝聚状、胶状、无定型的硅铝酸盐材料附着在载体上，在水热合成条件下，提供适当的过饱和度，使其在载体界面处形成晶核并生长成致密的薄膜。由于作为分子筛支撑体的载体的平均孔径一般在1微米左右，而原位生长法的晶核通常是纳米级，难以避免陷入孔道中导致分子筛膜塌陷产生空洞，因此通常合成时间长或者数次合成来覆盖缺陷。二次生长法是指先通过水热合成分散的分子筛晶体颗粒，然后将分子筛晶体涂覆在载体上，再置于分子筛合成母液中继续水热合成，使分散的分子筛晶体继续生长形成致密化的膜。
目前，分子筛膜通常采用中位孔径在1微米左右的α氧化铝、不锈钢、莫来石材质的多孔支撑体。CN102861516A公开了一种孔径在0.9-1.3微米的α氧化铝材质的中空纤维支撑体的制造方法，用于作为分子筛膜的支撑体。CN104987120A公开了一种单管式或者多通道管状支撑体，平均孔径在0.8-1.5微米，材质为α氧化铝和莫来石。以上两种方法主材料都是α氧化铝，平均孔径基本都在1微米左右，都是单层，孔径分布很难均匀。而不论原位合成法还是二次生长法，其晶核或者晶种的粒径都是纳米级别，难以均匀覆盖在平均孔径在1微米大小的载体上，不可避免有塌陷或者嵌入孔道中的情况，导致分子筛膜厚度不一致甚至产生缺陷。同时，α氧化铝材质或不锈钢材质的支撑体，原料价格较高，烧结温度较高或者烧结气氛较为苛刻，制造成本比较高，在其上制备分子筛膜则进一步推高了制造成本，由于分子筛膜寿命较短，高昂的成本限制了其工业应用。而堇青石作为一种低成本陶瓷材料，由于其 耐热震性、耐腐蚀性好，已有报道将其用于制备多孔陶瓷，但是由于堇青石烧结温度与熔融分解温度相差无几，因此通常采用堇青石粗颗粒加大量烧结助剂；或者堇青石粗颗粒加堇青石细粉；或者堇青石粗颗粒加入按堇青石成分配比的细颗粒烧结助剂混合烧结的方法，在低于骨料堇青石颗粒分解的温度烧结，来制备堇青石多孔材料。这三种方法由于烧结助剂或细颗粒必然堵塞堇青石粗颗粒的孔隙，决定了多孔材料的孔径必然比较大，否则难以制备有工业化前景的堇青石多孔材料。比如王耀明等人用300μm的堇青石粉体加钾长石等烧结助剂制备孔径为128μm的高温除尘用堇青石支撑体(高温烟气净化用多孔堇青石陶瓷支撑体材料的研制硅酸盐学报2011 33(10)1262-1265)。韩火年等用25μm粗堇青石粉和1.5μm的堇青石细粉混合在1400℃烧结得到多孔陶瓷支撑体。这些研究的核心都是利用堇青石细粉或者烧结助剂或者堇青石成分配比的细陶瓷粉体更低的烧结温度来粘结烧结温度更高的堇青石粗颗粒，避免粗颗粒的分解熔融，但这样导致粗颗粒骨料组成的孔径必然是较大的，目前通常在10-150微米左右，完全无法作为分子筛膜的支撑体。同时细粉或者烧结助剂会堵塞孔道，导致孔隙率降低。然而如果直接用堇青石细粉，那在其烧结温度下细粉难以避免熔融分解，只会得到致密的陶瓷。因此，难以直接使用2-5微米堇青石制备出孔径在1微米左右的分子筛用的堇青石多孔支撑体。
发明内容
本发明的目的是提供一种分子筛膜支撑体的制备方法，克服了堇青石只能制备5-100微米以上大孔径支撑体的问题，替代了α氧化铝、不锈钢等高价材料，降低了支撑体成本；同时进一步在堇青石层上额外涂覆烧结一层数十微米厚度、0.08-0.4微米孔径的氧化锆多孔薄膜层作为分子筛膜的生长基底，其孔径比常规分子筛载体更小，杜绝了分子筛晶粒沉陷在载体大孔中的可能性。
本发明所述的分子筛膜支撑体的制备方法，步骤如下：
(1)将乙醇和水加入反应釜，接着加入堇青石粉体搅拌均匀，加入分散剂，再加入正硅酸乙酯、铝盐、镁盐、镧盐，搅拌溶解，得到混合液；将混合液升温至65-80℃，再加入氨水，调节PH＝5-6，反应2-12小时以生成比例与堇青石成分一致的硅、铝、镁及镧的混合溶胶，再调节PH＝8-9反应2-6小时使溶胶老化；然后将混合液倒入容器静置沉淀，用RO水对沉淀进行洗涤，抽滤出液体，将沉淀烘干，接着将烘干的沉淀加热、保温，得到按堇青石成分比例组成的复合纳米氧化物包裹的堇青石颗粒；
(2)将堇青石颗粒、粘结剂、水和保湿剂混合搅拌均匀，形成泥料；将泥料制备成生坯，将生坯烘干，烧结成堇青石支撑体；
(3)将氧化锆加入水中，用硝酸调节PH＝2.5-3，搅拌均匀，再加入分散剂、粘度调节剂，搅拌均匀，得到涂膜液；将涂膜液涂覆到堇青石支撑体的外层，然后将支撑体烘干，烧结得到外层覆盖氧化锆薄膜层的堇青石支撑体。
步骤(1)中所述的乙醇和水的质量比为0.85-1.15:1；堇青石粉体的D50中位粒径在2-5微米，堇青石粉体的质量为乙醇和水总质量的25-35％。
步骤(1)中所述的分散剂为聚乙二醇类或PVA类分散剂，分散剂加入量为堇青石粉体质量的2-5％；聚乙二醇类分散剂优选为聚乙二醇400或聚乙二醇600，聚乙二醇400加入量优选为堇青石粉体质量的3.5-4％，聚乙二醇600加入量优选为堇青石粉体质量的2.5-3％；PVA类分散剂优选为PVA088-20，加入量为堇青石粉体质量的2-3％。
步骤(1)中所述的正硅酸乙酯、铝盐、镁盐和镧盐的总质量为堇青石粉体质量的3-8％，正硅酸乙酯、铝盐、镁盐、镧盐按硅、铝、镁、镧四元素摩尔比为5-5.2:4:2-2.2:0-3。
步骤(1)中所述的铝盐为其相应的硝酸盐、氯盐或硫酸盐中的一种或几种，优选为氯盐；镁盐为其相应的硝酸盐、氯盐或硫酸盐中的一种或几种，优选为氯盐；镧盐为其相应的硝酸盐、氯盐或硫酸盐中的一种或几种，优选为氯盐。
步骤(1)中所述的加热温度为450-650℃，保温时间为1-6小时。
步骤(2)中所述的粘结剂为甲基纤维素或羟丙基甲基纤维素，粘结剂加入量为堇青石颗粒质量的4-10％；水的质量为堇青石颗粒质量的20-40％；保湿剂为甘油，保湿剂加入量为堇青石颗粒质量的1.5-3.5％。
步骤(2)中所述的生坯为单孔、三孔或四孔的圆管状生坯。
步骤(2)中所述的烧结温度为950-1150℃，烧结时间为1-6小时。
步骤(3)中所述的氧化锆的中位粒径D50＝0.25-0.6微米，氧化锆加入量为涂膜液中水的质量的10-20％；分散剂为聚乙二醇类分散剂,分散剂加入量为氧化锆质量的2-5％；粘度调节剂为羟丙基甲基纤维素，粘度调节剂加入量为涂膜液中水的质量的0.65-1.5％；涂膜液的质量为堇青石支撑体质量的6-12％。
步骤(3)中所述的烧结温度为950-1150℃，烧结时间为2-4小时。
本发明制得的分子筛膜支撑体，其中堇青石支撑层孔径为0.6-1.5微米，孔隙率为33-40％，支撑层厚度为1-5mm，氧化锆薄膜层的平均孔径为0.08-0.4微米，孔隙率为40-55％，薄膜层厚度为3-30微米。
本发明在堇青石粉体表面包裹一层和堇青石成分、比例一致的镁、铝、硅的纳米氧化物及烧结助剂镧的纳米氧化物，包裹了堇青石组分纳米氧化物的堇青石细粉可以在较低温度下烧结得到孔径在1微米左右的堇青石多孔支撑体。
本发明所述的分子筛膜支撑体的制备方法，具体步骤如下：
(1)将乙醇和水按0.85-1.15:1质量比加入反应釜，接着加入堇青石粉体搅拌均匀，加入分散剂，再加入正硅酸乙酯、铝盐、镁盐、镧盐，搅拌溶解，得到混合液。将混合液升温至65-80℃，再加入氨水，调节PH＝5-6，反应2-12小时以生成硅、铝、镁、镧的溶胶，再调节PH＝8-9反应2-6小时使溶胶老化。然后将混合液倒入容器静置沉淀，用RO水对沉淀进行洗涤，然后抽滤出液体，将沉淀烘干。接着将烘干的沉淀加热到450-650℃，保温1-6小时，得到复合纳米氧化物包裹的堇青石颗粒。
(2)将该堇青石颗粒和粘结剂、水、保湿剂混合搅拌均匀，形成泥料。将泥料在挤出机中通过模具挤出成单孔、三孔或四孔的圆管状生坯。将生坯烘干水分，接着在950-1150℃条件下保温1-6小时，烧结成堇青石支撑体。
(3)将氧化锆加入水中，用硝酸调节PH＝2.5-3，搅拌均匀。再加入分散剂、粘度调节剂，搅拌均匀，得到涂膜液。将涂膜液浸渍涂覆到堇青石支撑体的外层，然后将支撑体烘干，接着在950-1150℃条件下保温2-4小时，烧结得到外层覆盖氧化锆薄膜层的堇青石支撑体。
本发明与现有技术相比，具有如下有益效果：
1、本发明为双层复合支撑体，堇青石主支撑层外部还有一层孔径为0.08-0.4微米的氧化锆薄膜，分子筛在此薄膜表面合成生长，相比已有技术只有单层的平均1微米孔径的支撑体，本支撑体分子筛生长的基层薄膜孔径更小、更均匀，孔隙率更高；使得生长在此薄膜上的分子筛膜相对更均匀、生长时间更短，无缺陷。
2、本发明在2-5微米的堇青石细粉上，采用溶胶凝胶法包裹一层复合溶胶，该复合溶胶的成分刚好按堇青石成分组成。同时加入稀土镧的溶胶作为固态烧结助剂，溶胶预烧结形成的复合纳米氧化物可在950-1150℃的温度下烧结合成堇青石，该温度远低于2-5微米堇青石的熔融温度，从而得到孔径在0.6-1.5微米，三点抗折强度在2000-2700N的堇青石支撑体，稀土镧进一步提高了支撑体的烧结强度，解决了目前堇青石通常采用的几十微米粗粉加几微米细粉，或者几十到几百微米粗粉加其他低熔点物质混合烧结，只能制备5-100微米以上大孔支撑体，采用2-5微米细粉直接烧结，因为堇青石熔融温度与烧结温度基本一致，在其烧结温度范围内只能得到致密的堇青石支撑体，因而无法用于制备分子筛膜用的支撑体的问题。
3、本发明采用溶胶凝胶包裹在堇青石粉体上作为烧结助剂，无需额外加入独立的细粉作为烧结助剂，解决了细粉堵塞孔道导致支撑体孔隙率下降的问题。同时溶胶-凝胶形成的纳米粉体使得烧结温度仅为950-1150℃，比α氧化铝或其他材质的支撑体烧结温度更低，降低了烧结成本和窑炉设备投资费用。
4、本发明使用的堇青石粉体价格低廉，远低于分子筛支撑体常用的α氧化铝、不锈钢等 材料。
附图说明
图1为实施例1制备的氧化锆薄膜层表面的扫描电镜图。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
(1)在质量比1:1乙醇和RO水的混合溶液中加入中位粒径D50＝5微米的堇青石粉体，加入量为乙醇和水混合溶液质量的35％。搅拌均匀，加入堇青石质量2％的聚乙二醇600，作为分散剂，继续搅拌均匀。将水温升至75℃，按摩尔比2.2:4:5:0.5的比例加入氯化镁、氯化铝、正硅酸乙酯、硝酸镧，四者总质量为堇青石粉体的8％，搅拌使其均匀分布。缓慢喷雾滴加氨水，至溶液PH＝5.5，不断搅拌并反应3小时，生成溶胶。继续滴加氨水至PH＝8.5，不断搅拌5小时使溶胶老化。以上过程保持水温在75℃。在搅拌状态下将反应后的混合溶液转移到大型容器中，静置澄清后抽滤出液体，再加入RO水并搅拌，继续澄清后将RO水抽滤出。沉淀分散装入盒状容器，送烘箱以1℃/分钟的速度升温到105℃烘烤20小时。之后将烘干的沉淀装入窑炉，以1℃/分钟的速度升温到500℃保温2小时，使溶胶转变为纳米粒子并牢固的烧结在堇青石粉体上。
(2)将此包裹着纳米粒子的堇青石粉体倒入捏合机，加入堇青石质量10％的羟丙基甲基纤维素，使二者搅拌均匀。再加入混合均匀的甘油与RO水的混合溶液并搅拌均匀，其中甘油用量为堇青石质量的3.5％，水的质量为堇青石质量的40％。搅拌均匀并形成泥料，将泥料倒入挤出机，开启抽真空装置，在真空状态下将泥料挤出成型为单孔或4孔的圆管体生坯。将生坯放入烘箱，以0.5℃/分钟的速度加温到80℃并保温10小时使其烘干。再将烘干的生坯放入窑炉以0.5℃/分钟的速度升温到1150℃并保温4小时得到堇青石基体。检测其平均孔径为1.5微米，孔隙率为33％。直径25mm的四孔支撑体三点抗折强度为2550N。
(3)将中位粒径D50＝0.35微米的氧化锆倒入水中，其质量为水的质量的20％，搅拌均匀。再加入氧化锆质量的2％的聚乙二醇400，继续搅拌均匀。接着加入水的质量的1％的羟丙基甲基纤维素，搅拌致其完全溶解。之后抽真空消泡。将堇青石基体一端孔道封闭，浸入此氧化锆的分散液中，静置50秒使氧化锆分散液吸附于堇青石基体上，之后取出，再将此吸附了氧化锆分散液的堇青石基体竖立置于100℃烘箱烘烤5小时至干燥。再送入窑炉，以1℃/分钟的速度升温到1150℃，保温2小时，得到包裹着氧化锆多孔薄膜层的堇青石分子筛支撑体。其氧化锆膜层孔径及孔隙率见图1，平均孔径0.11微米，最大孔径0.32微米，孔隙率48％，孔隙率和孔径相比堇青石基体有了大幅度的优化提高。图1采用Sirion 200型FESEM场发射 扫描电镜拍摄，放大倍数为10000倍，从图1中可以看出该氧化锆薄膜的孔隙率高，孔径在0.1-0.4微米之间。
实施例2
(1)在质量比1:1乙醇和RO水的混合溶液中加入中位粒径D50＝5微米的堇青石粉体，加入量为乙醇和水混合溶液质量的35％。搅拌均匀，加入堇青石质量2％的聚乙二醇600，作为分散剂，继续搅拌均匀。将水温升至75℃，按摩尔比2.2:4:5的比例加入氯化镁、氯化铝、正硅酸乙酯，三者总质量为堇青石粉体的8％，搅拌使其均匀分布。缓慢喷雾滴加氨水，至溶液PH＝5.5，不断搅拌并反应3小时，生成溶胶。继续滴加氨水至PH＝8.5，不断搅拌5小时使溶胶老化。以上过程保持水温在75℃。在搅拌状态下将反应后的混合溶液转移到大型容器中，静置澄清后抽滤出液体，再加入RO水并搅拌，继续澄清后将RO水抽滤出。沉淀分散装入盒状容器，送烘箱以1℃/分钟的速度升温到105℃烘烤20小时。之后将烘干的沉淀装入窑炉，以1℃/分钟的速度升温到500℃保温2小时，使溶胶转变为纳米粒子并牢固的烧结在堇青石粉体上。
(2)将此包裹着纳米粒子的堇青石粉体倒入捏合机，加入堇青石质量10％的羟丙基甲基纤维素，使二者搅拌均匀。再加入混合均匀的甘油与RO水的混合溶液并搅拌均匀，其中甘油用量为堇青石质量的3.5％，水的质量为堇青石质量的40％。搅拌均匀并形成泥料，将泥料倒入挤出机，开启抽真空装置，在真空状态下将泥料挤出成型为单孔或4孔的圆管体生坯。将生坯放入烘箱，以0.5℃/分钟的速度加温到80℃并保温10小时使其烘干。再将烘干的生坯放入窑炉以0.5℃/分钟的速度升温到1150℃并保温4小时得到堇青石基体。检测其平均孔径为1.5微米，孔隙率为33％。直径25mm的四孔支撑体三点抗折强度为2050N。同等条件下，未加入镧元素，堇青石支撑体强度有所下降，但仍满足作为分子筛支撑体的用途。
(3)将中位粒径D50＝0.35微米的氧化锆倒入水中，其质量为水的质量的20％，搅拌均匀。再加入氧化锆质量的2％的聚乙二醇400，继续搅拌均匀。接着加入水的质量的1％的羟丙基甲基纤维素，搅拌致其完全溶解。之后抽真空消泡。将堇青石基体一端孔道封闭，浸入此氧化锆的分散液中，静置50秒使氧化锆分散液吸附于堇青石基体上，之后取出，再将此吸附了氧化锆分散液的堇青石基体竖立置于100℃烘箱烘烤5小时至干燥。再送入窑炉，以1℃/分钟的速度升温到1150℃，保温2小时，得到包裹着氧化锆多孔薄膜层的堇青石分子筛支撑体。氧化锆薄膜层平均孔径0.12微米，最大孔径0.33微米，孔隙率47.5％，孔隙率和孔径相比堇青石基体有了大幅度的优化提高。
实施例3
(1)在质量比1:1乙醇和RO水的混合溶液中加入中位粒径D50＝2微米的堇青石粉体， 加入量为乙醇和水混合溶液质量的25％。搅拌均匀，加入堇青石质量5％的聚乙二醇600，作为分散剂，继续搅拌均匀。将水温升至70℃，按摩尔比2:4:5:1的比例加入氯化镁、氯化铝、正硅酸乙酯、硝酸镧，四者总质量为堇青石粉体的5％，搅拌使其均匀分布。缓慢喷雾滴加氨水，至溶液PH＝5.5，不断搅拌并反应3小时，生成溶胶。继续滴加氨水至PH＝9，不断搅拌5小时使溶胶老化。以上过程保持水温70℃。在搅拌状态下将反应后的混合溶液转移到大型容器中，静置澄清后抽滤出液体，再加入RO水并搅拌，继续澄清后将RO水抽滤出。沉淀分散装入盒状容器，送烘箱以1℃/分钟的速度升温到105℃烘烤20小时。之后将烘干的沉淀装入窑炉，以1℃/分钟的速度升温到450℃保温2小时，使溶胶转变为纳米粒子并牢固的烧结在堇青石粉体上。
(2)将此包裹着纳米粒子的堇青石粉体倒入捏合机，加入堇青石质量4％的羟丙基甲基纤维素，使二者搅拌均匀。再加入混合均匀的甘油与RO水的混合溶液并搅拌均匀，其中甘油用量为堇青石质量的2％，水的质量为堇青石质量的20％。搅拌均匀并形成泥料，将泥料倒入挤出机，开启抽真空装置，在真空状态下将泥料挤出成型为单孔或4孔的圆管体生坯。将生坯放入烘箱，以0.5℃/分钟的速度加温到80℃并保温10小时使其烘干。再将烘干的生坯放入窑炉以0.5℃/分钟的速度升温到1050℃并保温2小时得到堇青石基体，检测其平均孔径为0.8微米，孔隙率为29％。直径25mm的四孔支撑体三点抗折强度为2450N。
(3)将中位粒径D50＝0.6微米的氧化锆倒入水中，其质量为水的质量的10％，搅拌均匀。再加入氧化锆质量的3％的聚乙二醇400，继续搅拌均匀。接着加入水的质量的1％的羟丙基甲基纤维素，搅拌致其完全溶解。之后抽真空消泡。将堇青石基体一端孔道封闭，浸入此氧化锆的分散液中，静置50秒使氧化锆分散液吸附于堇青石基体上，之后取出，再将此吸附了氧化锆分散液的堇青石基体竖立置于100℃烘箱烘烤5小时至干燥。再送入窑炉，以1℃/分钟的速度升温到1150℃，保温2小时，得到包裹着氧化锆多孔薄膜层的堇青石分子筛支撑体。氧化锆薄膜层的平均孔径0.36微米，最大孔径0.45微米，孔隙率44％。支撑体三点抗折强度为2450N。
实施例4
(1)在质量比1:1乙醇和RO水的混合溶液中加入中位粒径D50＝4微米的堇青石粉体，加入量为乙醇和水混合溶液质量的30％。搅拌均匀，加入堇青石质量3％的聚乙二醇600，作为分散剂，继续搅拌均匀。将水温升至65℃，按摩尔比2:4:5.5:0的比例加入氯化镁、氯化铝、正硅酸乙酯、硝酸镧，四者总质量为堇青石粉体的6％，搅拌使其均匀分布。缓慢喷雾滴加氨水，至溶液PH＝5.5，不断搅拌并反应3小时，生成溶胶。继续滴加氨水至PH＝8.5，不断搅拌5小时使溶胶老化。以上过程保持水温在65℃。在搅拌状态下将反应后的混合溶液转移到 大型容器中，静置澄清后抽滤出液体，再加入RO水并搅拌，继续澄清后将RO水抽滤出。沉淀分散装入盒状容器，送烘箱以1℃/分钟的速度升温到105℃烘烤20小时。之后将烘干的沉淀装入窑炉，以1℃/分钟的速度升温到450℃保温2小时，使溶胶转变为纳米粒子并牢固的烧结在堇青石粉体上。
(2)将此包裹着纳米粒子的堇青石粉体倒入捏合机，加入堇青石质量7％的羟丙基甲基纤维素，使二者搅拌均匀。再加入混合均匀的甘油与RO水的混合溶液并搅拌均匀，其中甘油用量为堇青石质量的3％，水的质量为堇青石质量的30％。搅拌均匀并形成泥料，将泥料倒入挤出机，开启抽真空装置，在真空状态下将泥料挤出成型为单孔或4孔的圆管体生坯。将生坯放入烘箱，以0.5℃/分钟的速度加温到80℃并保温10小时使其烘干。再将烘干的生坯放入窑炉以0.5℃/分钟的速度升温到950℃并保温2小时得到堇青石基体，检测其平均孔径为1.3微米，孔隙率为31％。直径25mm的四孔支撑体三点抗折强度为2650N。
(3)将中位粒径D50＝0.25微米的氧化锆倒入水中，其质量为水的质量的15％，搅拌均匀。再加入氧化锆质量的2.5％的聚乙二醇400，继续搅拌均匀。接着加入水的质量的0.65％的羟丙基甲基纤维素，搅拌致其完全溶解。之后抽真空消泡。将堇青石基体一端孔道封闭，浸入此氧化锆的分散液中，静置50秒使氧化锆分散液吸附于堇青石基体上，之后取出，再将此吸附了氧化锆分散液的堇青石基体竖立置于100℃烘箱烘烤5小时至干燥。再送入窑炉，以1℃/分钟的速度升温到1000℃，保温2小时，得到包裹着氧化锆多孔薄膜层的堇青石分子筛支撑体。其氧化锆膜层平均孔径0.08微米，最大孔径0.15微米，孔隙率46％。
对比例1
将中位粒径D50＝5微米的堇青石粉体倒入捏合机，按堇青石中镁、铝、硅摩尔比加入相应的二氧化硅、碳酸镁、氧化铝超细粉，三者的质量之和相当于堇青石粉体质量的15％。接着加入堇青石质量10％的羟丙基甲基纤维素，搅拌均匀。再加入混合均匀的甘油与RO水的混合溶液并搅拌均匀，其中甘油用量为堇青石质量的3.5％，水的质量为堇青石质量的40％。搅拌均匀并形成泥料，将泥料倒入挤出机，开启抽真空装置，在真空状态下将泥料挤出成型为单孔或4孔的圆管体生坯。将生坯放入烘箱，以0.5℃/分钟的速度加温到80℃并保温10小时使其烘干。再将烘干的生坯放入窑炉以0.5℃/分钟的速度升温到1150℃并保温2小时得到堇青石基体，检测其平均孔径为1.1微米，孔隙率为11％。直径25mm的四孔支撑体三点抗折强度为470N，如此低的强度无法作为分子筛膜的载体使用。将另一个生坯以同样升温速度烧结至1350℃，保温2小时，直径23mm的四孔支撑体三点抗折强度为2250N，检测其孔隙率为5％，平均孔径为2.9微米。此烧结温度下虽然支撑体强度足够，但是孔隙率过低，孔径过大，无法作为分子筛膜支撑体使用。
对比例2
将中位粒径D50＝5微米的堇青石粉体倒入捏合机，加入堇青石质量10％的羟丙基甲基纤维素，使二者搅拌均匀。再加入混合均匀的甘油与RO水的混合溶液并搅拌均匀，其中甘油用量为堇青石质量的3.5％，水的质量为堇青石质量的40％。搅拌均匀并形成泥料，将泥料倒入挤出机，开启抽真空装置，在真空状态下将泥料挤出成型为单孔或4孔的圆管体生坯。将生坯放入烘箱，以0.5℃/分钟的速度加温到80℃并保温10小时使其烘干。再将烘干的生坯放入窑炉以0.5℃/分钟的速度升温到1150℃并保温2小时得到堇青石基体，检测其平均孔径为1.3微米，孔隙率为31％。直径25mm的四孔支撑体三点抗折强度为230N，如此低的强度无法作为分子筛膜的载体使用。将另一个生坯以同样升温速度烧结至1380℃，保温2小时，直径23mm的四孔支撑体三点抗折强度为2450N，检测其孔隙率为4％，平均孔径为4.8微米。此烧结温度下虽然支撑体强度足够，但是孔隙率过低，孔径过大，无法作为分子筛膜支撑体使用。
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (10)

  1. 一种分子筛膜支撑体的制备方法，其特征在于步骤如下：
    (1)将乙醇和水加入反应釜，接着加入堇青石粉体搅拌均匀，加入分散剂，再加入正硅酸乙酯、铝盐、镁盐、镧盐，搅拌溶解，得到混合液；将混合液升温至65-80℃，再加入氨水，调节PH＝5-6，反应2-12小时以生成比例与堇青石成分一致的硅、铝、镁及镧的混合溶胶，再调节PH＝8-9反应2-6小时使溶胶老化；然后将混合液倒入容器静置沉淀，用RO水对沉淀进行洗涤，抽滤出液体，将沉淀烘干，接着将烘干的沉淀加热、保温，得到按堇青石成分比例组成的复合纳米氧化物包裹的堇青石颗粒；
    (2)将堇青石颗粒、粘结剂、水和保湿剂混合搅拌均匀，形成泥料；将泥料制备成生坯，将生坯烘干，烧结成堇青石支撑体；
    (3)将氧化锆加入水中，用硝酸调节PH＝2.5-3，搅拌均匀，再加入分散剂、粘度调节剂，搅拌均匀，得到涂膜液；将涂膜液涂覆到堇青石支撑体的外层，然后将支撑体烘干，烧结得到外层覆盖氧化锆薄膜层的堇青石支撑体。
  2. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(1)中所述的乙醇和水的质量比为0.85-1.15:1；堇青石粉体的D50中位粒径在2-5微米，堇青石粉体的质量为乙醇和水总质量的25-35％；分散剂为聚乙二醇类或PVA类分散剂，分散剂加入量为堇青石粉体质量的2-5％。
  3. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(1)中所述的正硅酸乙酯、铝盐、镁盐和镧盐的总质量为堇青石粉体质量的3-8％，正硅酸乙酯、铝盐、镁盐、镧盐按硅、铝、镁、镧四元素摩尔比为5-5.2:4:2-2.2:0-3。
  4. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(1)中所述的铝盐为其相应的硝酸盐、氯盐或硫酸盐中的一种或几种，镁盐为其相应的硝酸盐、氯盐或硫酸盐中的一种或几种，镧盐为其相应的硝酸盐、氯盐或硫酸盐中的一种或几种。
  5. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(1)中所述的加热温度为450-650℃，保温时间为1-6小时。
  6. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(2)中所述的粘结剂为甲基纤维素或羟丙基甲基纤维素，粘结剂加入量为堇青石颗粒质量的4-10％；水的质量为堇青石颗粒质量的20-40％；保湿剂为甘油，保湿剂加入量为堇青石颗粒质量的1.5-3.5％。
  7. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(2)中所述的生坯为单孔、三孔或四孔的圆管状生坯。
  8. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(2)中所述的烧结温度为950-1150℃，烧结时间为1-6小时。
  9. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(3)中所述的氧化锆的中位粒径D50＝0.25-0.6微米，氧化锆加入量为涂膜液中水的质量的10-20％；分散剂为聚乙二醇类分散剂,分散剂加入量为氧化锆质量的2-5％；粘度调节剂为羟丙基甲基纤维素，粘度调节剂加入量为涂膜液中水的质量的0.65-1.5％；涂膜液的质量为堇青石支撑体质量的6-12％。
  10. 根据权利要求1所述的分子筛膜支撑体的制备方法，其特征在于步骤(3)中所述的烧结温度为950-1150℃，烧结时间为2-4小时。
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