WO2022068110A1 - Ceramic filter membrane with membrane thickness in gradient distribution, and preparation method therefor - Google Patents
Ceramic filter membrane with membrane thickness in gradient distribution, and preparation method therefor Download PDFInfo
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- WO2022068110A1 WO2022068110A1 PCT/CN2020/140326 CN2020140326W WO2022068110A1 WO 2022068110 A1 WO2022068110 A1 WO 2022068110A1 CN 2020140326 W CN2020140326 W CN 2020140326W WO 2022068110 A1 WO2022068110 A1 WO 2022068110A1
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- 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
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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
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- 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
- B01D69/10—Supported membranes; Membrane supports
Definitions
- the invention belongs to the technical field of membrane separation materials, in particular to a ceramic filter membrane with a gradient distribution of membrane thickness and a preparation method thereof.
- Ceramic membranes usually have a three-layer structure (porous support layer, transition layer and separation layer) with asymmetric distribution, and their pore size specifications range from 0.8nm to 1 ⁇ m. .
- the support of the ceramic membrane is usually produced by extrusion molding, grouting molding, gel injection molding, etc., while the preparation of the transition film layer and the filter film layer is usually performed by dip coating method, spraying method, tape casting method, sol conventional preparation methods such as gel method.
- the porosity and thickness of the ceramic membrane layer prepared by the above conventional method are relatively uniform.
- the ceramic membrane usually adopts the method of cross-flow filtration, and the liquid feed liquid in the membrane filtration process can be divided into feed liquid, concentrated liquid and permeate liquid.
- the pressure of the feed liquid at the inlet of the membrane feed liquid is greater than the pressure of the concentrated liquid at the position of the membrane feed liquid, resulting in the flow rate and pollution speed at the inlet position of the membrane feed liquid being much greater than that at the outlet position of the membrane feed liquid, and along the length of the membrane tube, from the feed port Towards the discharge port, the infiltration pressure gradually decreases, the infiltration flow decreases gradually, and the pollution rate decreases gradually. This results in uneven discharge of the membrane tube, low membrane filtration efficiency at the back end of the membrane tube, and serious pollution at the front end.
- CN 101182233A discloses a kind of sizing material configured with a solvent such as ammonium polyacrylate and ceramic powder, and the film thickness is controlled by a scraper by means of tape casting.
- a solvent such as ammonium polyacrylate and ceramic powder
- the film thickness is controlled by a scraper by means of tape casting.
- This method is complicated in process and difficult to operate.
- the solvent used to prepare the slurry also has certain toxicity, pollutes the environment, and is affected by the dispersibility and fluidity of the high-solid content ceramic slurry itself, so the film thickness control cannot be very precise.
- CN 101182233A discloses a kind of ceramic membrane with pore gradient distribution along the film thickness direction prepared by light curing rapid prototyping combined with gel film injection molding, but this method is complicated in process, high in preparation cost, and the prepared ceramic membrane does not It cannot solve the problems of high inlet pressure, low outlet pressure, uneven membrane flux and membrane fouling, and low membrane effective utilization in cross-flow filtration.
- the purpose of the present invention is to overcome the defects of the prior art and provide a ceramic filter membrane with a gradient distribution of membrane thickness.
- Another object of the present invention is to provide a method for preparing the above-mentioned ceramic filter membrane with a gradient distribution of film thickness.
- a ceramic filtration membrane with film thickness gradient distribution whose pure water flux under 0.1MPa pressure is 2100-3200LMH, comprises a ceramic membrane support body and a ceramic membrane layer arranged on the surface of the ceramic membrane support body, and the ceramic membrane layer is The thickness gradually decreases from the feed end to the discharge end, and the thickness gradually decreases from 35-55 ⁇ m to 8-25 ⁇ m, the porosity of the ceramic membrane layer is 32-40%, and the pore diameter is 80-300 nm.
- the preparation method of the above-mentioned film thickness gradient distribution ceramic filter membrane comprises the following steps:
- step (3) sintering the material obtained in step (2) to obtain the ceramic filter membrane with gradient distribution of membrane thickness.
- the pore diameter D50 of the ceramic membrane support body is 1-8 ⁇ m.
- the melting point of the paraffin in the paraffin film layer is 60-115°C.
- the temperature of the hot air of the hot air blasting device is 45-85°C.
- the injection pressure of the hot air blasting device is 1.8-2.2 MPa.
- the moving speed of the hot air blasting device is 0.008-0.012m/s.
- the sintering temperature is 1100-1700°C.
- the sintering time is 2-6h.
- the present invention solves the problems of high inlet pressure, low outlet pressure, uneven membrane flux and membrane fouling, and low membrane effective utilization in cross-flow filtration.
- the preparation method of the present invention can deposit a ceramic membrane layer with a thickness gradient distribution along the membrane length direction on the ceramic membrane support body.
- the preparation method of the present invention has the advantages of simple process and equipment, easy automatic control, high production efficiency, non-toxic auxiliary agent, safety and reliability.
- the preparation method of the present invention can directly form the separation membrane layer on the ceramic membrane support without the transition membrane layer in the traditional process, further improving the production efficiency and greatly reducing the production cost.
- the moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 3m 3 /h to 15m 3 /h at a constant speed within 120s to obtain a ceramic film layer, which was then sintered at 1375°C 2.5h, thus finally preparing a ceramic filtration membrane with a membrane porosity of 38% and a membrane pore size of 200nm.
- the thickness of the membrane along the length of the membrane is gradually reduced from 55 ⁇ m to 15 ⁇ m.
- Gradient distribution ceramic filtration membrane, Its pure water flux is 2300LMH under 0.1MPa pressure.
- the moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 6m 3 /h to 12m 3 /h at a constant speed within 120s to obtain a ceramic film layer, which was then sintered at 1650°C 6h, so as to finally prepare a ceramic filtration membrane with a membrane porosity of 32% and a membrane pore size of 300 nm, and the membrane thickness along the length of the membrane (the direction from the feed end to the discharge end) is gradually reduced from 50 ⁇ m to 25 ⁇ m.
- the pure water flux is 2800LMH under 0.1MPa pressure.
- the moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow rate was controlled to increase from 3m 3 /h to 8m 3 /h within 120s to obtain a ceramic film layer, which was then sintered at 1120°C 1h, so as to finally prepare a ceramic filtration membrane with a membrane porosity of 40% and a membrane pore size of 80 nm, and the membrane thickness along the membrane length direction (the direction from the feed end to the discharge end) is gradually reduced from 35 ⁇ m to 8 ⁇ m.
- the pure water flux is 2100LMH under 0.1MPa pressure.
- the moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 3m 3 /h to 15m 3 /h at a constant speed within 120s to obtain a ceramic film layer, which was then sintered at 1375°C 2.5h, the film layer fell off seriously.
- the moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 3m 3 /h to 15m 3 /h at a constant speed within 120s to obtain a ceramic film layer, which was then sintered at 1375°C 2.5h, the strength of the film layer is low, the bonding is loose, and some parts fall off.
- the moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 2m 3 /h to 15m 3 /h uniformly within 120s to obtain a ceramic film layer, which was then sintered at 1375°C 2.5h, so as to finally prepare a ceramic membrane with a membrane porosity of 38%, a membrane pore size of 200nm, and a ceramic membrane with a gradient distribution along the length of the membrane (the direction from the feed end to the discharge end), the thickness of which is gradually reduced from 55 ⁇ m to 5 ⁇ m.
- the membrane layer is thinner and the strength is lower, and the pure water flux is 3200LMH under 0.1MPa pressure.
- the moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 3m3 /h to 16m3/h at a constant speed within 120s to obtain a ceramic film layer, and then sintered at 1375°C for 2.5 h, to finally prepare a ceramic membrane with a membrane porosity of 38%, a membrane pore size of 200 nm, and a ceramic membrane with a gradient distribution along the length of the membrane (the direction from the feed end to the discharge end), the thickness of which is gradually reduced from 62 ⁇ m to 15 ⁇ m.
- the layer is too thick, the membrane resistance is large, the sintering strength is low, and the pure water flux is 1900LMH under 0.1MPa pressure.
- the position with the large thickness of the ceramic membrane layer is used as the feed end, the filtration resistance is large, and the position with the small thickness of the ceramic membrane layer is used as the discharge end, and the filtration resistance is small, so as to solve the problem that the pressure of the feed port is large and the discharge port in the cross-flow filtration.
- the paraffin film layer becomes soft due to the blowing of hot air, and the ceramic powder of the film layer can be embedded in the paraffin film layer by the kinetic energy given by the sandblasting equipment and the heat energy carried by itself, and tightly packed.
- the paraffin film layer can also use its own viscosity to firmly adhere the embedded ceramic particles, and at the same time fix the injection pressure and moving speed of the sandblasting equipment.
- the amount of sandblasting of the ceramic particles is used to deposit a ceramic membrane layer with a thickness gradient along the length of the membrane on the ceramic membrane support.
- the invention discloses a ceramic filtration membrane with film thickness gradient distribution and a preparation method thereof.
- the pure water flux under the pressure of 0.1 MPa is 2100-2800 LMH, which comprises a ceramic membrane support body and a ceramic membrane arranged on the surface of the ceramic membrane support body.
- Membrane layer the thickness of the ceramic membrane layer gradually decreases along the direction from the feed end to the discharge end, and the thickness gradually decreases from 35-55 ⁇ m to 8-25 ⁇ m, the porosity of the ceramic membrane layer is 32-40%,
- the pore size is 80-300nm.
- the position with large thickness of the ceramic membrane layer is used as the feed end, the filtration resistance is large, and the position with the small thickness of the ceramic membrane layer is used as the discharge end, and the filtration resistance is small, so as to solve the problem that the pressure of the feed port is large and the discharge port in cross-flow filtration.
- the problems of low pressure, uneven membrane flux and membrane fouling, and low membrane effective utilization rate have industrial practicability.
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Abstract
Description
本发明属于膜分离材料技术领域，具体涉及一种膜厚梯度分布陶瓷过滤膜及其制备方法。The invention belongs to the technical field of membrane separation materials, in particular to a ceramic filter membrane with a gradient distribution of membrane thickness and a preparation method thereof.
膜技术和膜应用在科技创新和国民经济发展中的重要性已经越来越明显，膜与膜过程目前已经受到世界各国的高度重视。相较于传统聚合物分离膜材料，陶瓷膜具有化学稳定性好，能耐酸、耐碱、耐有机溶剂；机械强度大，可反向冲洗；抗微生物能力强；耐高温；孔径分布窄、分离效率高等优点，在食品工业、生物工程、环境工程、化学工业、石油化工、冶金工业等领域得到了广泛的应用。The importance of membrane technology and membrane application in scientific and technological innovation and national economic development has become more and more obvious. Membrane and membrane process have been highly valued by countries all over the world. Compared with traditional polymer separation membrane materials, ceramic membrane has good chemical stability, acid resistance, alkali resistance, organic solvent resistance; high mechanical strength, can be reverse flushed; strong antimicrobial ability; high temperature resistance; narrow pore size distribution, separation The advantages of high efficiency have been widely used in food industry, biological engineering, environmental engineering, chemical industry, petrochemical industry, metallurgical industry and other fields.
商品化的陶瓷膜通常具有三层结构(多孔支撑层、过渡层及分离层)，呈非对称分布，其孔径规格为0.8nm-1μm不等，过滤精度涵盖微滤、超滤、纳滤级别。陶瓷膜的支撑体通常采用挤出成型、注浆成型、凝胶注膜成型等方式生产，而过渡膜层和过滤膜层的制备通常采用浸渍涂膜法、喷涂法、流延成型法、溶胶凝胶法等常规制备方法。通过上述常规方法制备的陶瓷膜层，其孔隙率和膜层厚度相对均一。但在实际应用过程中，陶瓷膜通常采用错流过滤的方式，膜过滤过程中的液体料液可以分为进料液、浓缩液和渗透液。膜料液进口位置的进料液压力大于膜出口位置的浓缩液压力，导致膜料液进口位置的流量和污染速度远大于膜料液出口位置，及沿着膜管长度方向，由进料口向出料口，渗透压力逐渐降低，渗透流量逐渐减小，污染速度逐渐降低。这就导致膜管出料不均，膜管后端膜过滤效率低，前端严重污染的问题。Commercial ceramic membranes usually have a three-layer structure (porous support layer, transition layer and separation layer) with asymmetric distribution, and their pore size specifications range from 0.8nm to 1μm. . The support of the ceramic membrane is usually produced by extrusion molding, grouting molding, gel injection molding, etc., while the preparation of the transition film layer and the filter film layer is usually performed by dip coating method, spraying method, tape casting method, sol conventional preparation methods such as gel method. The porosity and thickness of the ceramic membrane layer prepared by the above conventional method are relatively uniform. However, in the actual application process, the ceramic membrane usually adopts the method of cross-flow filtration, and the liquid feed liquid in the membrane filtration process can be divided into feed liquid, concentrated liquid and permeate liquid. The pressure of the feed liquid at the inlet of the membrane feed liquid is greater than the pressure of the concentrated liquid at the position of the membrane feed liquid, resulting in the flow rate and pollution speed at the inlet position of the membrane feed liquid being much greater than that at the outlet position of the membrane feed liquid, and along the length of the membrane tube, from the feed port Towards the discharge port, the infiltration pressure gradually decreases, the infiltration flow decreases gradually, and the pollution rate decreases gradually. This results in uneven discharge of the membrane tube, low membrane filtration efficiency at the back end of the membrane tube, and serious pollution at the front end.
CN 101182233A公开了一种采用聚丙烯酸铵等溶剂与陶瓷粉配置成胶料，采用流延成型的方式，通过刮刀控制膜层厚度，经低温冷冻后原位成型为膜厚梯度分布的陶瓷膜。但此方法工艺复杂，操作难度大，配置浆料的溶剂也有一定的毒性，污染环境，且受高固含量陶瓷浆料自身分散性和流动性的影响，膜厚控制并不能非常精确。CN 101182233A公开了一种利用光固化快速成型结合凝胶注膜成型制备一种沿着膜厚度方向呈孔梯度分布的陶瓷膜，但此方法工艺复杂，制备成本高，且其制备的陶瓷膜并不能解决错流过滤中进料口压力大，出料口压力小，膜通量和膜污染不均，膜有效利用率低的问题。CN 101182233A discloses a kind of sizing material configured with a solvent such as ammonium polyacrylate and ceramic powder, and the film thickness is controlled by a scraper by means of tape casting. However, this method is complicated in process and difficult to operate. The solvent used to prepare the slurry also has certain toxicity, pollutes the environment, and is affected by the dispersibility and fluidity of the high-solid content ceramic slurry itself, so the film thickness control cannot be very precise. CN 101182233A discloses a kind of ceramic membrane with pore gradient distribution along the film thickness direction prepared by light curing rapid prototyping combined with gel film injection molding, but this method is complicated in process, high in preparation cost, and the prepared ceramic membrane does not It cannot solve the problems of high inlet pressure, low outlet pressure, uneven membrane flux and membrane fouling, and low membrane effective utilization in cross-flow filtration.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于克服现有技术缺陷，提供一种膜厚梯度分布陶瓷过滤膜。The purpose of the present invention is to overcome the defects of the prior art and provide a ceramic filter membrane with a gradient distribution of membrane thickness.
本发明的另一目的在于提供上述膜厚梯度分布陶瓷过滤膜的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned ceramic filter membrane with a gradient distribution of film thickness.
本发明的技术方案如下：The technical scheme of the present invention is as follows:
一种膜厚梯度分布陶瓷过滤膜，其在0.1MPa压力下的纯水通量为2100-3200LMH，包括陶瓷膜支撑体和设于该陶瓷膜支撑体表面的陶瓷膜层，该陶瓷膜层的厚度沿进料端至出料端的方向逐渐减小，且该厚度从35-55μm逐渐减小至8-25μm，该陶瓷膜层的孔隙率为32-40％，孔径为80-300nm。A ceramic filtration membrane with film thickness gradient distribution, whose pure water flux under 0.1MPa pressure is 2100-3200LMH, comprises a ceramic membrane support body and a ceramic membrane layer arranged on the surface of the ceramic membrane support body, and the ceramic membrane layer is The thickness gradually decreases from the feed end to the discharge end, and the thickness gradually decreases from 35-55 μm to 8-25 μm, the porosity of the ceramic membrane layer is 32-40%, and the pore diameter is 80-300 nm.
上述膜厚梯度分布陶瓷过滤膜的制备方法，包括如下步骤：The preparation method of the above-mentioned film thickness gradient distribution ceramic filter membrane comprises the following steps:
(1)在所述陶瓷膜支撑体上涂覆一厚度为40-70μm的石蜡膜层，并自然冷却；(1) Coating a paraffin film layer with a thickness of 40-70 μm on the ceramic membrane support, and cooling it naturally;
(2)将用于制备所述陶瓷膜层的陶瓷粉末颗粒加热至80-100℃，然后采用热风喷砂装置将其喷射于上述石蜡膜层，其中热风喷砂装置在固定喷射压力和移动速度的条件下，喷砂流量沿陶瓷膜支撑体的一端至另一端的方向在120s内从3-6m 3/h匀速增加至8-15m 3/h； (2) Heating the ceramic powder particles for preparing the ceramic film layer to 80-100° C., and then spraying them on the above-mentioned paraffin film layer using a hot-air sandblasting device, wherein the hot-air sandblasting device has a fixed spray pressure and moving speed. Under the same conditions, the sandblasting flow rate increases from 3-6m 3 /h to 8-15m 3 /h at a constant speed in 120s along the direction from one end to the other end of the ceramic membrane support;
(3)将步骤(2)所得的物料进行烧结，即得所述膜厚梯度分布陶瓷过滤膜。(3) sintering the material obtained in step (2) to obtain the ceramic filter membrane with gradient distribution of membrane thickness.
在本发明的一个优选实施方案中，所述陶瓷膜支撑体的孔径D50＝1-8μm。In a preferred embodiment of the present invention, the pore diameter D50 of the ceramic membrane support body is 1-8 μm.
在本发明的一个优选实施方案中，所述陶瓷膜层由D50＝0.3-0.8μm的陶瓷粉末颗粒制成。In a preferred embodiment of the present invention, the ceramic membrane layer is made of ceramic powder particles with D50=0.3-0.8 μm.
在本发明的一个优选实施方案中，所述石蜡膜层中的石蜡的熔点为60-115℃。In a preferred embodiment of the present invention, the melting point of the paraffin in the paraffin film layer is 60-115°C.
进一步优选的，所述热风喷砂装置的热风的温度为45-85℃。Further preferably, the temperature of the hot air of the hot air blasting device is 45-85°C.
在本发明的一个优选实施方案中，所述热风喷砂装置的喷射压力为1.8-2.2MPa。In a preferred embodiment of the present invention, the injection pressure of the hot air blasting device is 1.8-2.2 MPa.
在本发明的一个优选实施方案中，所述热风喷砂装置的移动速度为0.008-0.012m/s。In a preferred embodiment of the present invention, the moving speed of the hot air blasting device is 0.008-0.012m/s.
在本发明的一个优选实施方案中，所述烧结的温度为1100-1700℃。In a preferred embodiment of the present invention, the sintering temperature is 1100-1700°C.
进一步优选的，所述烧结的时间为2-6h。Further preferably, the sintering time is 2-6h.
本发明的有益效果是：The beneficial effects of the present invention are:
1、本发明解决错流过滤中进料口压力大，出料口压力小，膜通量和膜污染不均，膜有效利用率低的问题。1. The present invention solves the problems of high inlet pressure, low outlet pressure, uneven membrane flux and membrane fouling, and low membrane effective utilization in cross-flow filtration.
2、本发明的制备方法能够在陶瓷膜支撑体上沉积出沿着膜长度方向厚度梯度分布的陶瓷膜层。2. The preparation method of the present invention can deposit a ceramic membrane layer with a thickness gradient distribution along the membrane length direction on the ceramic membrane support body.
3、本发明的制备方法工艺和设备简单，易自动化控制，生产效率高，无毒性助剂，安全可靠。3. The preparation method of the present invention has the advantages of simple process and equipment, easy automatic control, high production efficiency, non-toxic auxiliary agent, safety and reliability.
4、本发明的制备方法可以在陶瓷膜支撑体上直接成型分离膜层，无需传统工艺中的过渡膜层，进一步提高了生产效率，大幅度降低了生产成本。4. The preparation method of the present invention can directly form the separation membrane layer on the ceramic membrane support without the transition membrane layer in the traditional process, further improving the production efficiency and greatly reducing the production cost.
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。The technical solutions of the present invention will be further illustrated and described below through specific embodiments.
实施例1Example 1
在孔径D50＝3μm的氧化铝陶瓷膜支撑体上采用流延成型法涂覆一层45μm的石蜡(熔点，90℃)膜层并自然冷却，然后将制备膜层的氧化铝陶瓷粉末颗粒(D50＝0.6μm)加热至65℃，并采用热风(60℃)喷砂装置，将其喷射于石蜡膜层。固定喷砂设备的移动速度(0.01m/s)和喷射压力(2Mpa)，控制喷砂流量在120s内由3m 3/h匀速增加至15m 3/h，获得陶瓷膜层，然后于1375℃烧结2.5h，从而最终制备出膜孔隙率38％，膜孔径200nm，沿着膜长度方向(进料端至出料端的方向)膜厚度由55μm逐渐减薄至15μm的膜厚梯度分布陶瓷过滤膜，其在0.1MPa压力下纯水通量为2300LMH。 A 45 μm paraffin (melting point, 90°C) film layer was coated on an alumina ceramic membrane support with a pore diameter of D50 = 3 μm by tape casting and cooled naturally. Then the alumina ceramic powder particles (D50 = 0.6 μm) to be heated to 65° C., and sprayed on the paraffin film layer using a hot air (60° C.) sandblasting device. The moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 3m 3 /h to 15m 3 /h at a constant speed within 120s to obtain a ceramic film layer, which was then sintered at 1375°C 2.5h, thus finally preparing a ceramic filtration membrane with a membrane porosity of 38% and a membrane pore size of 200nm. The thickness of the membrane along the length of the membrane (the direction from the feed end to the discharge end) is gradually reduced from 55 μm to 15 μm. Gradient distribution ceramic filtration membrane, Its pure water flux is 2300LMH under 0.1MPa pressure.
实施例2Example 2
在孔径为D50＝8μm的氧化铝陶瓷膜支撑体上采用流延成型法涂覆一层70μm的石蜡(熔点，115℃)膜层并自然冷却，然后将制备膜层的氧化铝陶瓷粉末颗粒(D50＝0.8μm)加热至90℃，并采用热风(85℃)喷砂装置，将其喷射于石蜡膜层。固定喷砂设备的移动速度(0.01m/s)和喷射压力(2Mpa)，控制喷砂流量在120s内由6m 3/h匀速增加至12m 3/h，获得陶瓷膜层，然后于1650℃烧结6h，从而最终制备出膜孔隙率32％，膜孔径300nm，沿着膜长度方向(进料端至出料端的方向)膜厚度由50μm逐渐减薄至25μm的膜厚梯度分布陶瓷过滤膜，其在0.1MPa压力下纯水通 量为2800LMH。 A 70 μm paraffin (melting point, 115°C) film layer was coated on an alumina ceramic membrane support with a pore size of D50 = 8 μm by tape casting and cooled naturally, and then the alumina ceramic powder particles ( D50=0.8 μm) was heated to 90° C., and sprayed on the paraffin film layer using a hot air (85° C.) sandblasting device. The moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 6m 3 /h to 12m 3 /h at a constant speed within 120s to obtain a ceramic film layer, which was then sintered at 1650°C 6h, so as to finally prepare a ceramic filtration membrane with a membrane porosity of 32% and a membrane pore size of 300 nm, and the membrane thickness along the length of the membrane (the direction from the feed end to the discharge end) is gradually reduced from 50 μm to 25 μm. The pure water flux is 2800LMH under 0.1MPa pressure.
实施例3Example 3
在孔径为D50＝1μm的氧化铝陶瓷膜支撑体上采用流延成型法涂覆一层40μm的石蜡(熔点，60℃)膜层并自然冷却，然后将制备膜层的氧化铝陶瓷粉末颗粒(D50＝0.3μm)加热至45℃，并采用热风(45℃)喷砂装置，将其喷射于石蜡膜层。固定喷砂设备的移动速度(0.01m/s)和喷射压力(2Mpa)，控制喷砂流量在120s内由3m 3/h匀速增加至8m 3/h，获得陶瓷膜层，然后于1120℃烧结1h，从而最终制备出膜孔隙率40％，膜孔径80nm，沿着膜长度方向(进料端至出料端的方向)膜厚度由35μm逐渐减薄至8μm的膜厚梯度分布陶瓷过滤膜，其在0.1MPa压力下纯水通量为2100LMH。 A 40 μm paraffin (melting point, 60°C) film layer was coated on an alumina ceramic membrane support with a pore size of D50 = 1 μm by tape casting and cooled naturally, and then the alumina ceramic powder particles ( D50=0.3 μm) was heated to 45°C, and was sprayed on the paraffin film layer using a hot air (45°C) sandblasting device. The moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow rate was controlled to increase from 3m 3 /h to 8m 3 /h within 120s to obtain a ceramic film layer, which was then sintered at 1120°C 1h, so as to finally prepare a ceramic filtration membrane with a membrane porosity of 40% and a membrane pore size of 80 nm, and the membrane thickness along the membrane length direction (the direction from the feed end to the discharge end) is gradually reduced from 35 μm to 8 μm. The pure water flux is 2100LMH under 0.1MPa pressure.
对比例1Comparative Example 1
在孔径D50＝3μm的氧化铝陶瓷膜支撑体上采用流延成型法涂覆一层80μm的石蜡(熔点，90℃)膜层并自然冷却，然后将制备膜层的氧化铝陶瓷粉末颗粒(D50＝0.6μm)加热至65℃，并采用热风(60℃)喷砂装置，将其喷射于石蜡膜层。固定喷砂设备的移动速度(0.01m/s)和喷射压力(2Mpa)，控制喷砂流量在120s内由3m 3/h匀速增加至15m 3/h，获得陶瓷膜层，然后于1375℃烧结2.5h，膜层脱落严重。 A layer of 80 μm paraffin (melting point, 90° C.) film was coated on an alumina ceramic membrane support with a pore diameter of D50 = 3 μm by tape casting and cooled naturally, and then the alumina ceramic powder particles (D50 = 0.6 μm) to be heated to 65° C., and sprayed on the paraffin film layer using a hot air (60° C.) sandblasting device. The moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 3m 3 /h to 15m 3 /h at a constant speed within 120s to obtain a ceramic film layer, which was then sintered at 1375°C 2.5h, the film layer fell off seriously.
对比例2Comparative Example 2
在孔径D50＝3μm的氧化铝陶瓷膜支撑体上采用流延成型法涂覆一层30μm的石蜡(熔点，90℃)膜层并自然冷却，然后将制备膜层的氧化铝陶瓷粉末颗粒(D50＝0.6μm)加热至65℃，并采用热风(60℃)喷砂装置，将其喷射于石蜡膜层。固定喷砂设备的移动速度(0.01m/s)和喷射压力(2Mpa)，控制喷砂流量在120s内由3m 3/h匀速增加至15m 3/h，获得陶瓷膜层，然后于1375℃烧结2.5h，膜层强度低，结合疏松，部分位置脱落。 A layer of 30 μm paraffin (melting point, 90°C) film was coated on an alumina ceramic membrane support with a pore diameter of D50 = 3 μm by tape casting and cooled naturally. Then the alumina ceramic powder particles (D50 = 0.6 μm) to be heated to 65° C., and sprayed on the paraffin film layer using a hot air (60° C.) sandblasting device. The moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 3m 3 /h to 15m 3 /h at a constant speed within 120s to obtain a ceramic film layer, which was then sintered at 1375°C 2.5h, the strength of the film layer is low, the bonding is loose, and some parts fall off.
对比例3Comparative Example 3
在孔径D50＝3μm的氧化铝陶瓷膜支撑体上采用流延成型法涂覆一层45μm的石蜡(熔点，90℃)膜层并自然冷却，然后将制备膜层的氧化铝陶瓷粉末颗粒(D50＝0.6μm)加热至65℃，并采用热风(60℃)喷砂装置，将其喷射于石蜡膜层。固定喷砂设备的移动速度(0.01m/s)和喷射压力(2Mpa)，控制喷砂流量在120s内由2m 3/h匀速增加至15m 3/h，获得陶瓷膜层，然后于1375℃烧结2.5h，从而最终制备出膜孔隙率38％，膜孔径200nm，沿着膜长度方向(进料端至出料端的方向)膜厚度由55μm逐渐减薄至5μm的梯度分布的陶瓷膜，其末端膜层较薄，强度较低，在0.1MPa压力下纯水通量为3200LMH。 A 45 μm paraffin (melting point, 90°C) film layer was coated on an alumina ceramic membrane support with a pore diameter of D50 = 3 μm by tape casting and cooled naturally, and then the alumina ceramic powder particles (D50 = 0.6 μm) to be heated to 65° C., and sprayed on the paraffin film layer using a hot air (60° C.) sandblasting device. The moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 2m 3 /h to 15m 3 /h uniformly within 120s to obtain a ceramic film layer, which was then sintered at 1375°C 2.5h, so as to finally prepare a ceramic membrane with a membrane porosity of 38%, a membrane pore size of 200nm, and a ceramic membrane with a gradient distribution along the length of the membrane (the direction from the feed end to the discharge end), the thickness of which is gradually reduced from 55 μm to 5 μm. The membrane layer is thinner and the strength is lower, and the pure water flux is 3200LMH under 0.1MPa pressure.
对比例4Comparative Example 4
在孔径D50＝3μm的氧化铝陶瓷膜支撑体上采用流延成型法涂覆一层45μm的石蜡(熔点，90℃)膜层并自然冷却，然后将制备膜层的氧化铝陶瓷粉末颗粒(D50＝0.6μm)加热至65℃，并采用热风(60℃)喷砂装置，将其喷射于石蜡膜层。固定喷砂设备的移动速度(0.01m/s)和喷射压力(2Mpa)，控制喷砂流量在120s内由3m3/h匀速增加至16m 3/h，获得陶瓷膜层，然后于1375℃烧结2.5h，从而最终制备出膜孔隙率38％，膜孔径200nm，沿着膜长度方向(进料端至出料端的方向)膜厚度由62μm逐渐减薄至15μm的梯度分布的陶瓷膜，其末端膜层太厚，膜阻力大，烧结强度较低，在0.1MPa压力下纯水通量为1900LMH。 A 45 μm paraffin (melting point, 90°C) film layer was coated on an alumina ceramic membrane support with a pore diameter of D50 = 3 μm by tape casting and cooled naturally. Then the alumina ceramic powder particles (D50 = 0.6 μm) to be heated to 65° C., and sprayed on the paraffin film layer using a hot air (60° C.) sandblasting device. The moving speed (0.01m/s) and injection pressure (2Mpa) of the sandblasting equipment were fixed, and the sandblasting flow was controlled to increase from 3m3 /h to 16m3/h at a constant speed within 120s to obtain a ceramic film layer, and then sintered at 1375℃ for 2.5 h, to finally prepare a ceramic membrane with a membrane porosity of 38%, a membrane pore size of 200 nm, and a ceramic membrane with a gradient distribution along the length of the membrane (the direction from the feed end to the discharge end), the thickness of which is gradually reduced from 62 μm to 15 μm. The layer is too thick, the membrane resistance is large, the sintering strength is low, and the pure water flux is 1900LMH under 0.1MPa pressure.
各实施例和对比例所制得的产品的对比如下表所示：The comparison of the prepared products of each embodiment and comparative example is shown in the following table:
本发明将陶瓷膜层厚度大的位置作为进料端，过滤阻力大，陶瓷膜层厚度小的位置作为出料端，过滤阻力小，从而解决错流过滤中进料口压力大，出料口压力小，膜通量和膜污染不均，膜有效利用率低的问题。In the invention, the position with the large thickness of the ceramic membrane layer is used as the feed end, the filtration resistance is large, and the position with the small thickness of the ceramic membrane layer is used as the discharge end, and the filtration resistance is small, so as to solve the problem that the pressure of the feed port is large and the discharge port in the cross-flow filtration. Low pressure, uneven membrane flux and membrane fouling, and low membrane effective utilization.
本发明的制备方法中，由于热风的吹扫，石蜡膜层变软，而膜层陶瓷粉末可以利用喷砂设备赋予的动能和自身携带的热能嵌入石蜡膜层中，并紧密堆积。石蜡膜层也能利用自身的粘性将嵌入的陶瓷颗粒牢固黏附，同时固定喷砂设备的喷射压力和移动速度，通过控制在对应所要喷涂的膜面的喷砂流量，以控制在此膜面段陶瓷颗粒的喷砂量，从而在陶瓷膜支撑体上沉积出沿着膜长度方向厚度梯度分布的陶瓷膜层。In the preparation method of the present invention, the paraffin film layer becomes soft due to the blowing of hot air, and the ceramic powder of the film layer can be embedded in the paraffin film layer by the kinetic energy given by the sandblasting equipment and the heat energy carried by itself, and tightly packed. The paraffin film layer can also use its own viscosity to firmly adhere the embedded ceramic particles, and at the same time fix the injection pressure and moving speed of the sandblasting equipment. The amount of sandblasting of the ceramic particles is used to deposit a ceramic membrane layer with a thickness gradient along the length of the membrane on the ceramic membrane support.
以上所述，仅为本发明的较佳实施例而已，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。The above are only the preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly, that is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the description should still be covered by the present invention. In the range.
本发明公开了一种膜厚梯度分布陶瓷过滤膜及其制备方法，其在0.1MPa压力下的纯水通量为2100-2800LMH，包括陶瓷膜支撑体和设于该陶瓷膜支撑体表面的陶瓷膜层，该陶瓷膜层的厚度沿进料端至出料端的方向逐渐减小，且该厚度从35-55μm逐渐减小至8-25μm，该陶瓷膜层的孔隙率为32-40％，孔径为80-300nm。本发明将陶瓷膜层厚度大的位置作为进料端，过滤阻力大，陶瓷膜层厚度小的位置作为出料端， 过滤阻力小，从而解决错流过滤中进料口压力大，出料口压力小，膜通量和膜污染不均，膜有效利用率低的问题,具有工业实用性。The invention discloses a ceramic filtration membrane with film thickness gradient distribution and a preparation method thereof. The pure water flux under the pressure of 0.1 MPa is 2100-2800 LMH, which comprises a ceramic membrane support body and a ceramic membrane arranged on the surface of the ceramic membrane support body. Membrane layer, the thickness of the ceramic membrane layer gradually decreases along the direction from the feed end to the discharge end, and the thickness gradually decreases from 35-55 μm to 8-25 μm, the porosity of the ceramic membrane layer is 32-40%, The pore size is 80-300nm. In the invention, the position with large thickness of the ceramic membrane layer is used as the feed end, the filtration resistance is large, and the position with the small thickness of the ceramic membrane layer is used as the discharge end, and the filtration resistance is small, so as to solve the problem that the pressure of the feed port is large and the discharge port in cross-flow filtration. The problems of low pressure, uneven membrane flux and membrane fouling, and low membrane effective utilization rate have industrial practicability.
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