技术领域technical field
本发明涉及正渗透技术领域，尤其涉及一种正渗透膜及其制备方法。The invention relates to the technical field of forward osmosis, in particular to a forward osmosis membrane and a preparation method thereof.
背景技术Background technique
目前，人们为了获得足够的淡水供给采取了海水淡化、废水回收等各种水处理方法，但是却以消耗大量能源为代价，因此减小实际能耗与溶液的热力学最小分离能之间的差距一直是研究的热点。其中，正渗透是一种新兴的脱盐和分离技术，它是利用半透膜两端渗透压的不同来实现溶液的自发分离。近年来正渗透已经被应用于很多领域，例如：海水脱盐、污水处理、浓缩垃圾渗滤液等。在水处理领域中，相比于传统技术如微滤、超滤、纳滤、反渗透等膜过程，正渗透过程具有低能耗、低污染趋势、易清洗等优势。然而，正渗透仍然面临着许多问题，其中浓差极化是影响正渗透性能的主要问题之一，浓差极化现象是膜分离过程中普遍存在的，由于半透膜具有截留作用，原料液中未能透过半透膜的部分在膜表面积累或者是由于膜的非均一结构造成的溶质在膜内部的积累而显著的降低了渗透压，从而降低了正渗透的性能。At present, in order to obtain sufficient fresh water supply, people have adopted various water treatment methods such as seawater desalination and waste water recycling, but at the cost of consuming a lot of energy, so reducing the gap between the actual energy consumption and the thermodynamic minimum separation energy of the solution has always been is a research hotspot. Among them, forward osmosis is an emerging desalination and separation technology, which uses the difference in osmotic pressure at both ends of a semipermeable membrane to achieve spontaneous separation of solutions. In recent years, forward osmosis has been applied in many fields, such as: seawater desalination, sewage treatment, concentrated landfill leachate, etc. In the field of water treatment, compared with traditional membrane processes such as microfiltration, ultrafiltration, nanofiltration, and reverse osmosis, the forward osmosis process has the advantages of low energy consumption, low pollution tendency, and easy cleaning. However, forward osmosis still faces many problems, among which concentration polarization is one of the main problems affecting the performance of forward osmosis. The phenomenon of concentration polarization is ubiquitous in the membrane separation process. The part that fails to pass through the semipermeable membrane accumulates on the surface of the membrane or the solute accumulates inside the membrane due to the non-uniform structure of the membrane, which significantly reduces the osmotic pressure, thereby reducing the performance of forward osmosis.
正渗透膜是由活性皮层和多孔支撑层构成，近年来，大量的研究致力于改进膜的支撑层的结构和性能来减少浓差极化现象以提高正渗透膜性能。例如：通过改变铸膜液的溶剂、聚合物的组成和浓度得到具有指状结构的支撑层，或者加入具有亲水性的物质得到亲水性的支撑层。由于亲水的支撑层孔壁表面能被溶液有效润湿，从而促进质量传递减少浓差极化。但是在支撑层亲水性改性中也存在以下几个方面的问题：（1）亲水性的支撑体机械稳定性降低、易在水中溶胀；（2）影响界面聚合反应或改变活性皮层的性质。The forward osmosis membrane is composed of an active skin layer and a porous support layer. In recent years, a lot of research has been devoted to improving the structure and performance of the support layer of the membrane to reduce the concentration polarization phenomenon and improve the performance of the forward osmosis membrane. For example: by changing the solvent of the casting solution, the composition and concentration of the polymer to obtain a support layer with a finger-like structure, or adding a hydrophilic substance to obtain a hydrophilic support layer. Since the surface of the pore wall of the hydrophilic support layer can be effectively wetted by the solution, mass transfer is promoted and concentration polarization is reduced. However, there are also the following problems in the hydrophilic modification of the support layer: (1) The mechanical stability of the hydrophilic support is reduced and it is easy to swell in water; (2) It affects the interfacial polymerization reaction or changes the active skin layer. nature.
因此，现有技术还有待于改进和发展。Therefore, the prior art still needs to be improved and developed.
发明内容Contents of the invention
鉴于上述现有技术的不足，本发明的目的在于提供一种正渗透膜及其制备方法，旨在解决现有支撑层亲水性改性存在亲水性的支撑体机械稳定性降低、易在水中溶胀，影响界面聚合反应或改变活性皮层的性质的问题。In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a forward osmosis membrane and a preparation method thereof, aiming at solving the problem of reduced mechanical stability of the hydrophilic support existing in the hydrophilic modification of the existing support layer, and easy Problems with swelling in water, affecting interfacial polymerization or changing the properties of the active skin.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种正渗透膜的制备方法，其中，包括：A method for preparing a forward osmosis membrane, comprising:
步骤A、分别配置聚砜溶液和聚醚酰亚胺溶液，并分别将所述聚砜溶液和聚醚酰亚胺溶液在60-80℃下搅拌6-7小时；Step A, configuring polysulfone solution and polyetherimide solution respectively, and respectively stirring the polysulfone solution and polyetherimide solution at 60-80°C for 6-7 hours;
步骤B、将聚醚酰亚胺溶液在玻璃板上刮制成聚醚酰亚胺薄膜，然后将聚砜溶液在聚醚酰亚胺薄膜上刮制成聚砜薄膜；Step B, scrape the polyetherimide solution on a glass plate to make a polyetherimide film, then scrape the polysulfone solution on the polyetherimide film to make a polysulfone film;
步骤C、撕去所述聚醚酰亚胺薄膜得到聚砜支撑层，将靠近聚醚酰亚胺薄膜的一面作为所述聚砜支撑层的底部；Step C, tearing off the polyetherimide film to obtain a polysulfone support layer, using the side close to the polyetherimide film as the bottom of the polysulfone support layer;
步骤D、将聚砜支撑层放入二苯甲酮的甲醇溶液中浸泡1.5-2.5小时，取出所述聚砜支撑层放入SMP溶液中，所述聚砜支撑层的底部朝向紫外灯，在紫外灯照射下在所述聚砜支撑层的底部和孔内壁接枝PSMP聚合物；Step D, put the polysulfone support layer into the methanol solution of benzophenone and soak for 1.5-2.5 hours, take out the polysulfone support layer and put it into the SMP solution, the bottom of the polysulfone support layer faces the ultraviolet lamp, Grafting PSMP polymer on the bottom of the polysulfone support layer and the inner wall of the hole under the irradiation of ultraviolet light;
步骤E、分别配置间苯二胺水溶液和均苯三甲酰氯正己烷溶液，将步骤D得到的聚砜支撑层顶部浸泡于间苯二胺水溶液3-10分钟；然后再将得到的聚砜支撑层顶部浸泡于均苯三甲酰氯正己烷溶液1-3分钟。在聚砜支撑层顶部制备得到活性皮层。Step E, configure the m-phenylenediamine aqueous solution and the trimesoyl chloride n-hexane solution respectively, soak the top of the polysulfone support layer obtained in step D in the m-phenylenediamine aqueous solution for 3-10 minutes; then place the obtained polysulfone support layer Soak the top in trimesoyl chloride n-hexane solution for 1-3 minutes. An active skin layer is prepared on top of a polysulfone support layer.
所述的正渗透膜的制备方法，其中，所述步骤A中，所述聚砜溶液由N,N-二甲基乙酰胺、聚乙二醇400和聚砜配置得到。The preparation method of the forward osmosis membrane, wherein, in the step A, the polysulfone solution is prepared from N,N-dimethylacetamide, polyethylene glycol 400 and polysulfone.
所述的正渗透膜的制备方法，其中，所述步骤A中，所述聚醚酰亚胺溶液由N-甲基吡咯烷酮和聚醚酰亚胺配置得到。The preparation method of the forward osmosis membrane, wherein, in the step A, the polyetherimide solution is prepared from N-methylpyrrolidone and polyetherimide.
所述的正渗透膜的制备方法，其中，所述步骤D之前包括步骤：将聚砜薄膜放入甲醇溶液中浸泡1.5-2.5小时。The preparation method of the forward osmosis membrane, wherein, before the step D, there is a step of: soaking the polysulfone membrane in methanol solution for 1.5-2.5 hours.
所述的正渗透膜的制备方法，其中，所述步骤D中，所述二苯甲酮的甲醇溶液中，所述二苯甲酮的浓度为0.1-0.2mol/L。The preparation method of the forward osmosis membrane, wherein, in the step D, the concentration of the benzophenone in the methanol solution of the benzophenone is 0.1-0.2mol/L.
所述的正渗透膜的制备方法，其中，所述步骤D中，所述紫外灯照射的时间为20-40分钟。The preparation method of the forward osmosis membrane, wherein, in the step D, the irradiation time of the ultraviolet lamp is 20-40 minutes.
所述的正渗透膜的制备方法，其中，所述步骤D中，所述紫外灯照射的时间为30分钟。一种正渗透膜，其中，包括聚砜支撑层和复合于所述聚砜支撑层顶部的活性皮层，所述聚砜支撑层的底部和孔内壁接枝有PSMP聚合物；所述正渗透膜采用本发明所述的方法制备得到。The preparation method of the described forward osmosis membrane, wherein, in the step D, the irradiation time of the ultraviolet lamp is 30 minutes. A forward osmosis membrane, wherein, comprising a polysulfone support layer and an active skin layer compounded on the top of the polysulfone support layer, the bottom of the polysulfone support layer and the inner wall of the hole are grafted with PSMP polymer; the forward osmosis membrane Prepared by adopting the method described in the present invention.
所述的正渗透膜，其中，所述聚砜支撑层的孔径为25-35纳米。The forward osmosis membrane, wherein the polysulfone support layer has a pore diameter of 25-35 nanometers.
所述的正渗透膜，其中，所述聚砜支撑层的厚度为80-120微米，所述活性皮层的厚度为5-15纳米。The forward osmosis membrane, wherein, the thickness of the polysulfone support layer is 80-120 microns, and the thickness of the active skin layer is 5-15 nanometers.
有益效果：本发明首次将牺牲层联合铸造制备底部大孔支撑层的方法与紫外辐照接枝亲水性PSMP聚合物改性的方法结合起来综合提升膜的正渗透性能。本发明利用紫外辐照接枝亲水性PSMP聚合物的方法只对多孔支撑层的底部和孔的内壁进行亲水性改性，这样既保持了活性皮层的稳定性，又近一步提高了正渗透膜的透水性能。本发明操作步骤简单易行，效果稳定明显，透水性好，且正渗透的分离选择性有很大提高。Beneficial effect: the present invention combines the method of preparing the macroporous support layer at the bottom by co-casting of the sacrificial layer and the method of ultraviolet radiation grafting hydrophilic PSMP polymer modification for the first time to comprehensively improve the forward osmosis performance of the membrane. In the present invention, the method of grafting hydrophilic PSMP polymer by ultraviolet radiation only carries out hydrophilic modification to the bottom of the porous support layer and the inner wall of the hole, which not only maintains the stability of the active cortex, but also further improves the positive The water permeability of the permeable membrane. The operation steps of the invention are simple and easy, the effect is stable and obvious, the water permeability is good, and the separation selectivity of forward osmosis is greatly improved.
附图说明Description of drawings
图1为实施例中未接枝PSMP的正渗透膜与已接枝PSMP的正渗透膜的SEM图。Fig. 1 is the SEM image of the forward osmosis membrane without grafting PSMP and the forward osmosis membrane with grafted PSMP in the embodiment.
具体实施方式Detailed ways
本发明提供一种正渗透膜及其制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention provides a forward osmosis membrane and a preparation method thereof. In order to make the purpose, technical solution and effect of the present invention clearer and clearer, the present invention will be further described in detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
本发明公开一种正渗透膜的制备方法，其中，包括：The invention discloses a method for preparing a forward osmosis membrane, which includes:
步骤A、分别配置聚砜溶液和聚醚酰亚胺溶液，并分别将所述聚砜溶液和聚醚酰亚胺溶液在60-80℃下搅拌6-7小时；Step A, configuring polysulfone solution and polyetherimide solution respectively, and respectively stirring the polysulfone solution and polyetherimide solution at 60-80°C for 6-7 hours;
步骤B、将聚醚酰亚胺溶液在玻璃板上刮制成聚醚酰亚胺薄膜，然后将聚砜溶液在聚醚酰亚胺薄膜上刮制成聚砜薄膜；Step B, scrape the polyetherimide solution on a glass plate to make a polyetherimide film, then scrape the polysulfone solution on the polyetherimide film to make a polysulfone film;
步骤C、撕去所述聚醚酰亚胺薄膜得到聚砜支撑层，将靠近聚醚酰亚胺薄膜的一面作为所述聚砜支撑层的底部；Step C, tearing off the polyetherimide film to obtain a polysulfone support layer, using the side close to the polyetherimide film as the bottom of the polysulfone support layer;
步骤D、将聚砜支撑层放入二苯甲酮的甲醇溶液中浸泡1.5-2.5小时，取出所述聚砜支撑层放入SMP单体溶液中，所述聚砜支撑层的底部朝向紫外灯，在紫外灯照射下在所述聚砜支撑层的底部和孔内壁接枝PSMP聚合物；Step D, put the polysulfone support layer into the methanol solution of benzophenone and soak for 1.5-2.5 hours, take out the polysulfone support layer and put it into the SMP monomer solution, the bottom of the polysulfone support layer faces the ultraviolet lamp , grafting PSMP polymer on the bottom of the polysulfone support layer and the inner wall of the hole under the irradiation of ultraviolet light;
步骤E、分别配置间苯二胺水溶液和均苯三甲酰氯正己烷溶液，将步骤D得到的聚砜支撑层顶部浸泡于间苯二胺水溶液3-10分钟；然后再将得到的聚砜支撑层顶部浸泡于均苯三甲酰氯正己烷溶液1-3分钟。在聚砜支撑层顶部制备得到活性皮层。Step E, configure the m-phenylenediamine aqueous solution and the trimesoyl chloride n-hexane solution respectively, soak the top of the polysulfone support layer obtained in step D in the m-phenylenediamine aqueous solution for 3-10 minutes; then place the obtained polysulfone support layer Soak the top in trimesoyl chloride n-hexane solution for 1-3 minutes. An active skin layer is prepared on top of a polysulfone support layer.
传统正渗透膜的亲水性改性都是通过增加聚合物中亲水性基团的含量或者与亲水性聚合物共混的方法，这些方法使得支撑层的顶部和底部都具备了亲水性，从而对活性皮层性能有一定的影响，盐的截留性能降低。然而，通过本发明方法可以制备得到顶部疏水底部亲水的大孔支撑层，使得在支撑层顶部制备出性能稳定的活性皮层，这样在不影响对盐截留的情况下提高正渗透膜的水通量。本发明通过紫外接枝的方法将亲水性聚合物接枝到多孔支撑层底部和孔内壁，相对于传统的表面接枝聚合物的方法，紫外接枝的方法步骤简单，接枝时间短，操作简便，接枝结果稳定可控。The hydrophilic modification of traditional forward osmosis membranes is by increasing the content of hydrophilic groups in the polymer or blending with hydrophilic polymers. These methods make the top and bottom of the support layer hydrophilic. Therefore, it has a certain impact on the performance of the active cortex, and the interception performance of salt is reduced. However, a macroporous support layer with a hydrophobic top and a hydrophilic bottom can be prepared by the method of the present invention, so that an active skin layer with stable performance can be prepared on the top of the support layer, so that the water flow of the forward osmosis membrane can be improved without affecting the salt retention. quantity. In the present invention, the hydrophilic polymer is grafted to the bottom of the porous support layer and the inner wall of the hole through the method of ultraviolet grafting. Compared with the traditional method of grafting polymers on the surface, the method of ultraviolet grafting has simple steps and short grafting time. The operation is simple, and the grafting result is stable and controllable.
本发明采用牺牲层联合铸造方法制备得到底部大孔的聚砜支撑层，所述牺牲层联合铸造方法具体包括步骤A-C：The present invention adopts a sacrificial layer co-casting method to prepare a polysulfone support layer with large pores at the bottom, and the sacrificial layer co-casting method specifically includes steps A-C:
所述步骤A具体包括：首先配置两种聚合物溶液。其中聚砜溶液由N,N-二甲基乙酰胺（DMAc）、聚乙二醇400（PEG400）和聚砜（PSf）配置得到；聚醚酰亚胺溶液由N-甲基吡咯烷酮（NMP）和聚醚酰亚胺（PEI）配置得到。分别将两溶液在60℃-80℃水浴搅拌6-7小时直至聚合物完全溶解。The step A specifically includes: first preparing two kinds of polymer solutions. The polysulfone solution is prepared from N,N-dimethylacetamide (DMAc), polyethylene glycol 400 (PEG400) and polysulfone (PSf); the polyetherimide solution is prepared from N-methylpyrrolidone (NMP) and polyetherimide (PEI) configuration. The two solutions were respectively stirred in a 60°C-80°C water bath for 6-7 hours until the polymer was completely dissolved.
所述步骤B具体包括：先将PEI溶液倒在干燥平整的玻璃板上，用100µm的刮刀刮取PEI溶液，制成PEI薄膜；再将PSf溶液倒在PEI薄膜上用300µm的刮刀刮取，制成PSf薄膜。The step B specifically includes: first pour the PEI solution on a dry and flat glass plate, scrape the PEI solution with a 100 μm scraper to make a PEI film; then pour the PSf solution on the PEI film and scrape it with a 300 μm scraper, Made of PSf film.
所述步骤C具体包括：将玻璃板置于纯水中1-2分钟，目的是利用相转化，使得高分子聚合物在界面快速析出，形成极薄的致密层，而在致密层的下面形成了多孔层，形成外密内疏的膜结构。撕去所述PEI薄膜得到PSf支撑层，将靠近PEI薄膜的一面作为PSf支撑层的底部。The step C specifically includes: placing the glass plate in pure water for 1-2 minutes, the purpose is to use the phase inversion to make the high molecular polymer rapidly precipitate at the interface to form an extremely thin dense layer, and form a dense layer under the dense layer. The porous layer is formed to form a membrane structure with dense outside and sparse inside. The PEI film is torn off to obtain the PSf support layer, and the side close to the PEI film is used as the bottom of the PSf support layer.
本发明采用紫外接枝的方法，将亲水性的PSMP聚合物接枝到PSf支撑层的底部和孔内壁。相对于传统的表面接枝聚合物的方法，本发明紫外接枝的方法步骤简单，接枝时间短，操作简便，接枝结果稳定可控。且通过本发明紫外接枝的方法可以制备得到顶部疏水底部亲水的大孔PSf支撑层，使得在PSf支撑层顶部制备出性能稳定的活性皮层，这样在不影响对盐截留的情况下提高正渗透膜的水通量。所述紫外接枝的方法为步骤D：The invention adopts the method of ultraviolet grafting, and the hydrophilic PSMP polymer is grafted to the bottom of the PSf support layer and the inner wall of the hole. Compared with the traditional surface grafting polymer method, the ultraviolet grafting method of the present invention has simple steps, short grafting time, simple and convenient operation, and the grafting result is stable and controllable. Moreover, a macroporous PSf support layer with a hydrophobic top and a hydrophilic bottom can be prepared through the ultraviolet grafting method of the present invention, so that an active skin layer with stable performance can be prepared on the top of the PSf support layer, so that the positive positive effect can be improved without affecting the salt interception. Water flux through a permeable membrane. The method of ultraviolet grafting is step D:
步骤D具体包括：将聚砜支撑层放入甲醇溶液中浸泡1.5-2.5小时（如两小时），使所述聚砜支撑层表面杂质被清除干净。然后从甲醇溶液中取出聚砜支撑层放入0.1-0.2mol/L的二苯甲酮（BP）的甲醇溶液（作为光引发剂，使聚砜支撑层表面活化）中浸泡1.5-2.5小时（如两小时）。最后从二苯甲酮的甲醇溶液中取出聚砜支撑层放入100-200mL的一定浓度的SMP单体溶液中(其中溶剂为体积比V甲醇：V水＝4：1，SMP单体的浓度为0.025-0.15g/mL，如0.05g/mL, 0.1g/mL或0.15g/mL)，置入紫外灯箱中光照20-40分钟（如30分钟）接枝PSMP聚合物，将聚砜支撑层的底部朝上，在顶端放置一片石英玻璃片，减小单体溶剂挥发使单体浓度变化，减少测试误差。Step D specifically includes: soaking the polysulfone support layer in methanol solution for 1.5-2.5 hours (eg, two hours), so that impurities on the surface of the polysulfone support layer are removed. Then take out the polysulfone support layer from the methanol solution and put it into 0.1-0.2mol/L benzophenone (BP) methanol solution (as a photoinitiator to activate the surface of the polysulfone support layer) and soak for 1.5-2.5 hours ( such as two hours). Finally, take out the polysulfone support layer from the methanol solution of benzophenone and put it into a certain concentration of SMP monomer solution of 100-200mL (wherein the solvent is volume ratio V methanol: V water=4:1, the concentration of SMP monomer 0.025-0.15g/mL, such as 0.05g/mL, 0.1g/mL or 0.15g/mL), put it in a UV light box for 20-40 minutes (such as 30 minutes) to graft PSMP polymer, and support polysulfone The bottom of the layer faces up, and a piece of quartz glass is placed on the top to reduce the volatilization of the monomer solvent to change the concentration of the monomer and reduce the test error.
本发明通过界面聚合的方法在聚砜支撑层上制备得到聚酰胺活性皮层，所述界面聚合的方法为步骤E：The present invention prepares the polyamide active skin layer on the polysulfone support layer through the method of interfacial polymerization, and the method of the interfacial polymerization is step E:
步骤E具体包括：配置25mL质量百分比为3wt%的间苯二胺（MPD）水溶液和25mL质量百分比为0.15wt%的均苯三甲酰氯（TMC）正己烷溶液。将步骤D得到的聚砜支撑层放置在夹具上，利用滴管将MPD水溶液滴置于聚砜支撑层的顶部，直至完全覆盖，保持3-10分钟，将多余的MPD水溶液移除；然后再利用滴管将TMC正己烷溶液滴置于聚砜支撑层的顶部，直至完全覆盖，保持1-3分钟，将多余的TMC正己烷溶液移除。通过界面聚合在聚砜支撑层顶部制备得到活性皮层。Step E specifically includes: preparing 25 mL of 3 wt % m-phenylenediamine (MPD) aqueous solution and 25 mL of 0.15 wt % trimesoyl chloride (TMC) n-hexane solution. Place the polysulfone support layer obtained in step D on the fixture, use a dropper to drop the MPD aqueous solution on the top of the polysulfone support layer until it is completely covered, and keep it for 3-10 minutes, and remove the excess MPD aqueous solution; then Use a dropper to drop the TMC n-hexane solution on the top of the polysulfone support layer until it is completely covered, keep it for 1-3 minutes, and remove the excess TMC n-hexane solution. The active skin layer was prepared on top of the polysulfone support layer by interfacial polymerization.
本发明首先采用牺牲层联合铸造方法制备底部大孔的聚砜支撑层，然后采用紫外接枝的方法将亲水性的PSMP聚合物接枝到PSf支撑层的底部和孔内壁，最后采用界面聚合的方法在聚砜支撑层顶部制备活性皮层，得到正渗透膜。本发明制备得到所述正渗透膜后，对所述正渗透膜进行正渗透脱盐测试。The present invention first adopts the sacrificial layer co-casting method to prepare the polysulfone supporting layer with large pores at the bottom, then adopts the method of ultraviolet grafting to graft the hydrophilic PSMP polymer to the bottom of the PSf supporting layer and the inner wall of the hole, and finally adopts interfacial polymerization The method prepared an active skin layer on the top of the polysulfone support layer to obtain a forward osmosis membrane. After the forward osmosis membrane is prepared in the present invention, a forward osmosis desalination test is performed on the forward osmosis membrane.
正渗透脱盐测试：用正渗透装置测量正渗透膜的透水性能和对NaCl的分离选择性。原料液为纯水，汲取液为0.5-4M的NaCl溶液。用电导率仪测量原料液一定时间段的电导率变化，根据电导率与NaCl浓度的函数曲线计算出一定时间段盐的透过量，并测量该段时间内汲取液的体积变化来确定正渗透膜的水通量。Forward osmosis desalination test: use a forward osmosis device to measure the water permeability of the forward osmosis membrane and the separation selectivity to NaCl. The raw material liquid is pure water, and the drawing liquid is 0.5-4M NaCl solution. Use a conductivity meter to measure the conductivity change of the raw material solution for a certain period of time, calculate the permeation amount of salt for a certain period of time according to the function curve of conductivity and NaCl concentration, and measure the volume change of the draw solution during this period to determine the forward osmosis membrane. of water flux.
传统正渗透膜的亲水改性都是通过增加聚合物中亲水性基团的含量或者与亲水性聚合物共混的方法，而本发明是利用紫外辐照接枝亲水性PSMP聚合物的方法只对多孔支撑层的底部和孔的内壁进行亲水性改性，这样既保持了活性皮层的稳定性，又近一步提高了正渗透膜的透水性能。本发明首次将牺牲层联合铸造制备底部大孔支撑层的方法与紫外辐照接枝亲水性PSMP聚合物改性的方法结合起来综合提升膜的正渗透性能。本发明操作步骤简单易行，效果稳定明显，透水性好，且正渗透的分离选择性有很大提高。The hydrophilic modification of the traditional forward osmosis membrane is by increasing the content of the hydrophilic group in the polymer or blending with the hydrophilic polymer, and the present invention uses ultraviolet radiation to graft hydrophilic PSMP polymerization Only the bottom of the porous support layer and the inner wall of the pores are hydrophilically modified by the material method, which not only maintains the stability of the active skin layer, but also further improves the water permeability of the forward osmosis membrane. For the first time, the present invention combines the sacrificial layer co-casting method to prepare the bottom macroporous support layer and the method of ultraviolet radiation grafting hydrophilic PSMP polymer modification to comprehensively improve the forward osmosis performance of the membrane. The operation steps of the invention are simple and easy, the effect is stable and obvious, the water permeability is good, and the separation selectivity of forward osmosis is greatly improved.
本发明还提供一种正渗透膜，其中，包括聚砜支撑层和复合于所述聚砜支撑层顶部的活性皮层，所述聚砜支撑层的底部和孔内壁接枝有PSMP聚合物；所述正渗透膜采用本发明所述的方法制备得到。所述聚砜支撑层的有效孔径约为25-35纳米（如30纳米）。所述聚砜支撑层的厚度约为80-120微米（如100微米），所述活性皮层的厚度约为5-15纳米（如10纳米）。The present invention also provides a forward osmosis membrane, which includes a polysulfone support layer and an active skin layer compounded on the top of the polysulfone support layer, the bottom of the polysulfone support layer and the inner wall of the hole are grafted with PSMP polymer; The forward osmosis membrane is prepared by the method of the present invention. The effective pore diameter of the polysulfone support layer is about 25-35 nanometers (eg, 30 nanometers). The thickness of the polysulfone supporting layer is about 80-120 microns (eg, 100 microns), and the thickness of the active skin layer is about 5-15 nanometers (eg, 10 nanometers).
下面通过实施例对本发明进行详细说明。The present invention will be described in detail below by way of examples.
本实施例正渗透膜的制备方法，包括以下步骤：The preparation method of the forward osmosis membrane of this embodiment comprises the following steps:
1、采用牺牲层联合铸造法制备底部大孔的PSf支撑层：1. The PSf support layer with large holes at the bottom is prepared by the sacrificial layer co-casting method:
首先配置两种聚合物溶液，聚砜溶液：将18g聚砜（PSf）材料溶于74g N,N-二甲基乙酰胺（DMAC）溶液中，加入15g聚乙二醇（PEG400）；聚醚酰亚胺溶液：将17g聚醚酰亚胺（PEI）溶于N-甲基吡咯烷酮（NMP）中。然后两溶液分别置于65℃水浴搅拌7小时，搅拌的转速380r/min。First prepare two polymer solutions, polysulfone solution: dissolve 18g polysulfone (PSf) material in 74g N,N-dimethylacetamide (DMAC) solution, add 15g polyethylene glycol (PEG400); polyether Imide solution: Dissolve 17 g of polyetherimide (PEI) in N-methylpyrrolidone (NMP). Then the two solutions were respectively placed in a 65° C. water bath and stirred for 7 hours at a stirring speed of 380 r/min.
先将PEI溶液倒在干燥平整的玻璃板上，用100µm的刮刀刮取PEI溶液，再将PSf溶液倒在PEI上用300µm的刮刀刮取，最后将玻璃板置于纯水中1分钟，撕去PEI层得到PSf支撑层，将靠近PEI层的一面作为PSf支撑层的底部。所得到的PSf支撑层保存于去离子水中。First pour the PEI solution on a dry and flat glass plate, scrape the PEI solution with a 100µm spatula, then pour the PSf solution on the PEI and scrape it with a 300µm spatula, and finally place the glass plate in pure water for 1 minute, tear it off Remove the PEI layer to obtain the PSf support layer, and use the side close to the PEI layer as the bottom of the PSf support layer. The obtained PSf support layer was kept in deionized water.
2、采用紫外光照接枝PSMP聚合物：2. Using ultraviolet light to graft PSMP polymer:
将PSf支撑层放入甲醇溶液中浸泡两小时，使表面杂质被清除干净。再将PSf支撑层放入0.13mol/L二苯甲酮（BP）的甲醇溶液（光引发剂）中浸泡两小时。最后取出处理好的PSf支撑层放入100mL的0.05g/mL的SMP单体溶液中，置入紫外灯箱中光照半小时接枝PSMP聚合物，PSf支撑层的底部朝向紫外灯，在顶端放置一片石英玻璃片，减小单体溶液中溶剂挥发使单体浓度变化，减少测试误差。Put the PSf support layer into the methanol solution and soak it for two hours to remove the surface impurities. Then put the PSf support layer into 0.13mol/L benzophenone (BP) methanol solution (photoinitiator) and soak for two hours. Finally, take out the treated PSf support layer and put it into 100mL of 0.05g/mL SMP monomer solution, put it into a UV light box for half an hour to irradiate the grafted PSMP polymer, the bottom of the PSf support layer faces the UV lamp, and place a piece of Quartz glass sheet can reduce the volatilization of the solvent in the monomer solution to change the concentration of the monomer and reduce the test error.
3、采用界面聚合的方法制备活性皮层：3. Prepare the active cortex by interfacial polymerization:
配置25mL 2wt%的间苯二胺（MPD）水溶液和25mL 0.1wt%的均苯三甲酰氯（TMC）正己烷溶液。将PSf支撑层放置在夹具上，利用滴管将MPD水溶液滴置于聚砜支撑层的上表面，直至完全覆盖，保持5分钟，将多余的MPD水溶液移除；然后再利用滴管将TMC正己烷溶液滴置于PSf支撑层的上表面，直至完全覆盖，保持2分钟，将多余的TMC正己烷溶液移除。活性皮层制备完成，并将正渗透膜储存于去离子水中。Prepare 25mL 2wt% m-phenylenediamine (MPD) aqueous solution and 25mL 0.1wt% trimesoyl chloride (TMC) n-hexane solution. Place the PSf support layer on the fixture, use a dropper to drop the MPD aqueous solution on the upper surface of the polysulfone support layer until it is completely covered, keep it for 5 minutes, and remove the excess MPD aqueous solution; then use the dropper to place the TMC positively The hexane solution was dropped on the upper surface of the PSf support layer until it was completely covered, and kept for 2 minutes, and the excess TMC n-hexane solution was removed. The active skin layer was prepared, and the forward osmosis membrane was stored in deionized water.
4、正渗透脱盐测试：4. Forward osmosis desalination test:
用正渗透装置测量正渗透膜的透水性能和对NaCl的分离选择性。原料液为纯水，汲取液分别为0.5M、1M、1.5M、2M、4M的NaCl溶液。测量正渗透膜在AL-FS（皮层对着原料液）和AL-DS（皮层对着汲取液）两个模式下的水通量和反向盐通量。反向盐通量是利用电导率仪测量原料液一定时间段的电导率变化，根据电导率与NaCl浓度的函数曲线计算出一定时间段盐的透过量。水通量是通过测量该段时间内汲取液的体积变化来确定正渗透膜的水通量。当0.5M NaCl 为汲取液AL-DS模式下时水通量可高达24L/m2·h，而反向盐通量仅有0.5g左右，表现出卓越的分离选择性。The water permeability and the separation selectivity to NaCl of the forward osmosis membrane were measured with a forward osmosis device. The raw material liquid is pure water, and the drawing liquids are 0.5M, 1M, 1.5M, 2M, 4M NaCl solutions respectively. Measure the water flux and reverse salt flux of the forward osmosis membrane in the two modes of AL-FS (skin layer facing the feed solution) and AL-DS (skin layer facing the draw solution). The reverse salt flux is to use a conductivity meter to measure the conductivity change of the raw material solution for a certain period of time, and calculate the salt penetration in a certain period of time according to the function curve of the conductivity and NaCl concentration. The water flux is determined by measuring the volume change of the draw solution during this period to determine the water flux of the forward osmosis membrane. When 0.5M NaCl is used as the draw solution in AL-DS mode, the water flux can be as high as 24L/m2 ·h, while the reverse salt flux is only about 0.5g, showing excellent separation selectivity.
5、正渗透膜的结构表征：5. Structural characterization of forward osmosis membrane:
如图1所示，图1a为未接枝PSMP的正渗透膜皮层，图1d为未接枝PSMP的正渗透膜中靠近皮层的断面结构；图1b为已接枝PSMP的正渗透膜皮层，图1 e为已接枝PSMP的正渗透膜中靠近皮层的断面结构。从图可以看出，未接枝的正渗透膜皮层相对比较粗糙，已接枝的PSMP正渗透膜的皮层相对更加光滑平整，而更稳定的皮层有助于对NaCl的截留。As shown in Figure 1, Figure 1a is the forward osmosis membrane skin layer without grafting PSMP, Figure 1d is the cross-sectional structure near the skin layer in the forward osmosis membrane without grafting PSMP; Figure 1b is the forward osmosis membrane skin layer grafted PSMP, Figure 1 e is the cross-sectional structure near the cortex in the forward osmosis membrane grafted with PSMP. It can be seen from the figure that the skin layer of the ungrafted forward osmosis membrane is relatively rough, and the skin layer of the grafted PSMP forward osmosis membrane is relatively smoother, and the more stable skin layer helps to intercept NaCl.
综上所述，本发明提供的一种正渗透膜及其制备方法，传统正渗透膜的亲水改性都是通过增加聚合物中亲水性基团的含量或者与亲水性聚合物共混的方法，而本发明是利用紫外辐照接枝亲水性PSMP聚合物的方法只对多孔支撑层的底部和孔的内壁进行亲水性改性，这样既保持了活性皮层的稳定性，又近一步提高了正渗透膜的透水性能。本发明首次将牺牲层联合铸造制备底部大孔支撑层的方法与紫外辐照接枝亲水性PSMP聚合物改性的方法结合起来综合提升膜的正渗透性能。本发明操作步骤简单易行，效果稳定明显，透水性好，且正渗透的分离选择性有很大提高。In summary, the present invention provides a forward osmosis membrane and its preparation method. The hydrophilic modification of the traditional forward osmosis membrane is by increasing the content of hydrophilic groups in the polymer or co-polymerizing with the hydrophilic polymer. mixed method, and the present invention utilizes the method of ultraviolet radiation grafting hydrophilic PSMP polymer to only carry out hydrophilic modification to the bottom of the porous support layer and the inner wall of the hole, so that the stability of the active cortex is maintained, It further improves the water permeability of the forward osmosis membrane. For the first time, the present invention combines the sacrificial layer co-casting method to prepare the bottom macroporous support layer and the method of ultraviolet radiation grafting hydrophilic PSMP polymer modification to comprehensively improve the forward osmosis performance of the membrane. The operation steps of the invention are simple and easy, the effect is stable and obvious, the water permeability is good, and the separation selectivity of forward osmosis is greatly improved.
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。It should be understood that the application of the present invention is not limited to the above examples, and those skilled in the art can make improvements or transformations according to the above descriptions, and all these improvements and transformations should belong to the protection scope of the appended claims of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810160910.4ACN108479395B (en) | 2018-02-27 | 2018-02-27 | A kind of forward osmosis membrane and preparation method thereof |
| PCT/CN2018/124702WO2019165840A1 (en) | 2018-02-27 | 2018-12-28 | Forward osmosis membrane, and preparation method therefor |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810160910.4ACN108479395B (en) | 2018-02-27 | 2018-02-27 | A kind of forward osmosis membrane and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN108479395Atrue CN108479395A (en) | 2018-09-04 |
| CN108479395B CN108479395B (en) | 2020-12-15 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810160910.4AActiveCN108479395B (en) | 2018-02-27 | 2018-02-27 | A kind of forward osmosis membrane and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN108479395B (en) |
| WO (1) | WO2019165840A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718667A (en)* | 2019-01-31 | 2019-05-07 | 深圳大学 | A kind of multi-functional forward osmosis membrane and preparation method thereof |
| WO2019165840A1 (en)* | 2018-02-27 | 2019-09-06 | 深圳大学 | Forward osmosis membrane, and preparation method therefor |
| CN113996182A (en)* | 2021-10-21 | 2022-02-01 | 浙江工业大学 | Method for preparing polyvinyl composite nanofiltration membrane by reverse phase interfacial polymerization |
| CN114797493A (en)* | 2022-04-26 | 2022-07-29 | 西南石油大学 | Temperature-resistant composite separation membrane and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010086852A1 (en)* | 2009-01-29 | 2010-08-05 | Ben-Gurion University Of The Negev Research And Development Authority | A method for modifying composite membranes for liquid separations |
| US20110147308A1 (en)* | 2009-12-21 | 2011-06-23 | Siemens Water Technologies Corp. | Charged Porous Polymeric Membranes and Their Preparation |
| CN105457509A (en)* | 2015-11-27 | 2016-04-06 | 浙江大学 | Polyamide reverse osmosis composite membrane having renewable chlorine resistance and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2010289795B2 (en)* | 2009-08-24 | 2015-09-24 | Oasys Water LLC | Forward osmosis membranes |
| CN108495700A (en)* | 2015-11-24 | 2018-09-04 | Oasys水有限公司 | Supporting layer for forward osmosis membrane |
| CN105617885A (en)* | 2016-03-25 | 2016-06-01 | 北京碧水源膜科技有限公司 | Device and method for continuously preparing forward osmosis composite membrane |
| CN105854630B (en)* | 2016-05-11 | 2019-03-29 | 黑龙江八一农垦大学 | A kind of forward osmosis membrane and preparation method thereof |
| CN108479395B (en)* | 2018-02-27 | 2020-12-15 | 深圳大学 | A kind of forward osmosis membrane and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010086852A1 (en)* | 2009-01-29 | 2010-08-05 | Ben-Gurion University Of The Negev Research And Development Authority | A method for modifying composite membranes for liquid separations |
| US20110147308A1 (en)* | 2009-12-21 | 2011-06-23 | Siemens Water Technologies Corp. | Charged Porous Polymeric Membranes and Their Preparation |
| CN105457509A (en)* | 2015-11-27 | 2016-04-06 | 浙江大学 | Polyamide reverse osmosis composite membrane having renewable chlorine resistance and preparation method thereof |
| Title |
|---|
| GANG CHEN等: "Open porous hydrophilic supported thin-film composite forward osmosis membrane via co-casting for treatment of high-salinity wastewater", 《DESALINATION》* |
| MASAHIDE TANIGUCHI等: "Low fouling synthetic membranes by UV-assisted graft polymerization: monomer selection to mitigate fouling by natural organic matter", 《JOURNAL OF MEMBRANE SCIENCE》* |
| YUN LI等: "Hydrophilicporouspoly(sulfone)membranesmodified byUV-initiated polymerizationforvanadium flow battery application", 《JOURNAL OF MEMBRANE SCIENCE》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019165840A1 (en)* | 2018-02-27 | 2019-09-06 | 深圳大学 | Forward osmosis membrane, and preparation method therefor |
| CN109718667A (en)* | 2019-01-31 | 2019-05-07 | 深圳大学 | A kind of multi-functional forward osmosis membrane and preparation method thereof |
| CN113996182A (en)* | 2021-10-21 | 2022-02-01 | 浙江工业大学 | Method for preparing polyvinyl composite nanofiltration membrane by reverse phase interfacial polymerization |
| CN114797493A (en)* | 2022-04-26 | 2022-07-29 | 西南石油大学 | Temperature-resistant composite separation membrane and preparation method thereof |
| Publication number | Publication date |
|---|---|
| CN108479395B (en) | 2020-12-15 |
| WO2019165840A1 (en) | 2019-09-06 |
| Publication | Publication Date | Title |
|---|---|---|
| CN103977718B (en) | Positive osmosis composite membrane of a kind of high water flux and preparation method thereof | |
| Mansourizadeh et al. | Preparation of blend polyethersulfone/cellulose acetate/polyethylene glycol asymmetric membranes for oil–water separation | |
| Emadzadeh et al. | Synthesis of thin film nanocomposite forward osmosis membrane with enhancement in water flux without sacrificing salt rejection | |
| CN108479395B (en) | A kind of forward osmosis membrane and preparation method thereof | |
| CN103861472B (en) | A kind of preparation method of amino modified graphene oxide compound forward osmosis membrane | |
| CN105056777A (en) | Lignin-crosslinking modified polymer separation membrane and application thereof | |
| CN103816811B (en) | A kind of preparation method of organic forward osmosis membrane | |
| WO2018120476A1 (en) | Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof | |
| CN104474925A (en) | Preparation method of composite high-water-flux polyamide reverse-osmosis membrane | |
| CN107029555A (en) | A kind of solvent resistant NF membrane and preparation method thereof | |
| CN103785301B (en) | A kind of Cellulose acetate forward osmotic membrane material and preparation method thereof | |
| JP2016518982A (en) | Polyamide-based water treatment separation membrane excellent in salt removal rate and permeation flow rate characteristics and method for producing the same | |
| CN113262644A (en) | Novel high-flux positively-charged nanofiltration membrane and preparation method thereof | |
| CN102580561B (en) | Tubular composite nanofiltration membrane | |
| CN107174950A (en) | The positive osmosis composite membrane of high-performance and preparation method that a kind of graphene oxide is modified | |
| CN109224888A (en) | A kind of graphene oxide framework modified polyamide reverse osmose membrane and its application | |
| CN115350603A (en) | Polyvinylidene fluoride-based thin-layer composite nanofiltration membrane and preparation method thereof | |
| CN105582816A (en) | Preparation method of forward osmosis membrane modified with oxidized graphene | |
| Wu et al. | Carboxymethyl chitosan hydrogel network constructed PES ultrafiltration membrane to separate bovine serum albumin from collagen | |
| SG192271A1 (en) | Forward osmosis membrane and method of manufacture | |
| CN116371221B (en) | Polyamide nanofiltration membrane and preparation method and application thereof | |
| CN115253715A (en) | High-desalination composite reverse osmosis membrane with multilayer structure and preparation method thereof | |
| CN118217828A (en) | Preparation method of polysulfone ultrafiltration membrane for reverse osmosis membrane | |
| CN111545083A (en) | A kind of nanofiltration membrane, preparation method and use in fermentation broth concentration | |
| CN109718667A (en) | A kind of multi-functional forward osmosis membrane and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract | Application publication date:20180904 Assignee:Shenzhen Tianqu XingKong Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011755 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250625 Application publication date:20180904 Assignee:Shenzhen Kemai Medical Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011754 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250625 Application publication date:20180904 Assignee:Shenzhen Cleon Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011752 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250625 Application publication date:20180904 Assignee:Shenzhen shunwenjia Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011750 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250625 Application publication date:20180904 Assignee:Shenzhen Shenzhen Zhilian Software Development Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011294 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250624 Application publication date:20180904 Assignee:SHENZHEN MIGOU NETWORK TECHNOLOGY Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011254 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250624 Application publication date:20180904 Assignee:Shenzhen Shunneng Energy Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011766 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250625 | |
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract | Application publication date:20180904 Assignee:Shenzhen Bangqi Technology Innovation Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980012050 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250630 Application publication date:20180904 Assignee:Shenzhen Huarui Wulian Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011909 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Radium Automation Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011907 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Huaqihui Industrial Innovation Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011905 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen jiarunxin Communication Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011903 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Haoyi Software Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011902 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Jingyuan Jiansan Electronics Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011900 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:SHENZHEN CHENDA TECHNOLOGY CO.,LTD. Assignor:SHENZHEN University Contract record no.:X2025980011899 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:SHENZHEN GEAZAN TECHNOLOGY Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011892 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:SHENZHEN ZHONGKE CHUANGXIANG TECHNOLOGY Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011890 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:SHENZHEN FENDA INTELLIGENT TECHNOLOGY Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011887 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Zhiyunqiong Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011882 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Tongxin Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011868 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Zhuoya Automation Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011862 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Xiji Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011751 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250625 Application publication date:20180904 Assignee:RTD SENSORS TECHNOLOGY CO.,LTD. Assignor:SHENZHEN University Contract record no.:X2025980011749 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250625 Application publication date:20180904 Assignee:SHENZHEN BOBEITE TECHNOLOGY DEVELOPMENT Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011748 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Shenzhen Yuanxinxin Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011745 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Shenzhen Guanglan Yuanxin Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011742 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:SHENZHEN YINGLITAISI TECHNOLOGY Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011740 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Kechen Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011736 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Haichuang Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011735 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Huashun Tiancheng Energy Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011733 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Shenzhen Qidihong Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011727 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Yuning Enterprise Management Consulting Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011724 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Xialou Technology (Shenzhen) Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011717 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Shenzhen Hongye New Energy Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011716 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250627 Application publication date:20180904 Assignee:Shenzhen Daiwo Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011714 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Guangdong Zhuoer New Material Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011713 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Shenzhen Zhiqingxin Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011712 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Guangdong zhuozhen Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011710 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Shenzhen Huaqing Construction Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011708 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 Application publication date:20180904 Assignee:Shenzhen Xinyunrui Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011705 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250626 | |
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract | Application publication date:20180904 Assignee:Shenzhen Chaoyong times Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980012441 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250703 Application publication date:20180904 Assignee:Guangdong Jinhui Technology Group Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980012436 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250703 Application publication date:20180904 Assignee:Shenzhen Pengzhi Microelectronics Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980012279 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250702 Application publication date:20180904 Assignee:Shenzhen Xinzhong Concrete Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980012278 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250702 Application publication date:20180904 Assignee:Shenzhen Yueyunqiong Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980012274 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250702 Application publication date:20180904 Assignee:Shenzhen Computing Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011729 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250630 Application publication date:20180904 Assignee:SHENZHEN JINHUI TECHNOLOGY Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980011723 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250630 | |
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract | Application publication date:20180904 Assignee:SHENZHEN MOTONG ELECTRIC CO.,LTD. Assignor:SHENZHEN University Contract record no.:X2025980012626 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250704 | |
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract | Application publication date:20180904 Assignee:Shenzhen Xinxin Weijie Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980012627 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250704 Application publication date:20180904 Assignee:Shenzhen Huiqin Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980013040 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250709 Application publication date:20180904 Assignee:SHENZHEN AZROAD TECHNOLOGY Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980013107 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250709 | |
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract | Application publication date:20180904 Assignee:ADVANCED PLUS GROUP CO.,LTD. Assignor:SHENZHEN University Contract record no.:X2025980013860 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250716 | |
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract | Application publication date:20180904 Assignee:Shenzhen Yuanchuan Intelligent Control Technology Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980014058 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250718 Application publication date:20180904 Assignee:Shenzhen Jiuhe precision automation equipment Co.,Ltd. Assignor:SHENZHEN University Contract record no.:X2025980014061 Denomination of invention:A forward osmosis membrane and its preparation method Granted publication date:20201215 License type:Common License Record date:20250718 |