CN112569805B - Salt ion self-interception seawater desalination method based on continuous filtration method - Google Patents

Salt ion self-interception seawater desalination method based on continuous filtration method Download PDF

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CN112569805B
CN112569805B CN202011164746.8A CN202011164746A CN112569805B CN 112569805 B CN112569805 B CN 112569805B CN 202011164746 A CN202011164746 A CN 202011164746A CN 112569805 B CN112569805 B CN 112569805B
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石国升
陈俊杰
丁洲乐
刘星
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Abstract

本发明公开了一种基于连续过滤方法的盐离子自截留海水淡化方法,将氧化石墨烯薄膜在含盐水溶液中浸润至溶胀状态,正向加压过滤,利用膜压减小膜内盐溶解后形成的水合离子尺寸,截留溶液中盐溶解后形成的水合离子,收集汲取液,重复上述步骤,直至得到符合标准的汲取液。本发明方法在不大于5个大气压过滤压力下,较好实现海水脱盐,与传统超过50个大气反渗透海水淡化技术相比,大大减少了运行过程中能量损耗,不需要特殊高耐压材料,显著降低运行成本,大大降低传统反渗透过程中高压安全隐患,操作容易,运行条件简单,运行环境普适性强,适用于大规模海水、苦咸水淡化和工业高盐废水处理,且在化工、医药、电子行业用水处理方面具有较高潜力。

Figure 202011164746

The invention discloses a salt ion self-retaining sea water desalination method based on a continuous filtration method. The size of the hydrated ions formed, the hydrated ions formed after dissolving the salt in the solution are retained, the extraction solution is collected, and the above steps are repeated until the extraction solution that meets the standard is obtained. The method of the invention can better realize seawater desalination under the filtration pressure of no more than 5 atmospheres. Compared with the traditional reverse osmosis seawater desalination technology with more than 50 atmospheres, the energy loss in the operation process is greatly reduced, and special high-pressure-resistant materials are not required. Significantly reduces operating costs, greatly reduces high-pressure safety hazards in the traditional reverse osmosis process, easy operation, simple operating conditions, and strong operating environment universality, suitable for large-scale seawater, brackish water desalination and industrial high-salt wastewater treatment, and in the chemical industry. , medicine, electronics industry water treatment has high potential.

Figure 202011164746

Description

基于连续过滤方法的盐离子自截留海水淡化方法Salt ion self-retention seawater desalination method based on continuous filtration method

技术领域technical field

本发明涉及海水淡化技术和水处理技术领域,特别是一种基于连续过滤方法的盐离子自截留海水淡化和水处理技术。The invention relates to the technical field of seawater desalination and water treatment, in particular to a seawater desalination and water treatment technology based on a continuous filtration method for self-retention of salt ions.

背景技术Background technique

因人为和自然原因所导致的淡水资源短缺问题一直严重的影响着社会的经济和可持续发展。解决淡水资源短缺问题最理想的途径之一就是海水淡化和劣质水处理技术,即对海水或者工业产生的高盐废水进行脱盐,生产淡水,增加淡水总量,以满足人类日益增长的生活和工农业需求。目前较为成熟的海水或者苦咸水淡化或高盐废水处理技术主要是反渗透法、蒸馏法和电渗析法等,其中反渗透法是目前应用最广泛的海水淡化和苦咸水膜处理技术。The shortage of freshwater resources caused by man-made and natural reasons has been seriously affecting the economic and sustainable development of society. One of the most ideal ways to solve the shortage of freshwater resources is desalination and poor-quality water treatment technology, that is, desalination of seawater or high-salinity wastewater produced by industry, production of fresh water, and increase of the total amount of fresh water to meet the ever-increasing life and work of human beings. agricultural needs. At present, the more mature seawater or brackish water desalination or high-salt wastewater treatment technologies are mainly reverse osmosis, distillation and electrodialysis, among which reverse osmosis is the most widely used seawater desalination and brackish water membrane treatment technology.

但是现有的反渗透技术,在具有产出水质高、设备简单和自动化程度高等优点的同时,普遍存在着以下缺陷:However, while the existing reverse osmosis technology has the advantages of high output water quality, simple equipment and high degree of automation, the following defects generally exist:

1.超高的压力需求伴随着较高的能量消耗,需要压力55bar~68bar,且高压工艺导致其对膜系统组件和运行设备材质要求较高;1. The ultra-high pressure demand is accompanied by high energy consumption, which requires a pressure of 55bar to 68bar, and the high-pressure process leads to higher requirements on the material of membrane system components and operating equipment;

2.超高材料服役强度的工作运行环境,带来了巨大的安全隐患,特别是随着运行时间增长而带来的材料老化和腐蚀等因素;2. The working and operating environment of ultra-high material service strength brings huge potential safety hazards, especially factors such as material aging and corrosion with the increase of operating time;

3.需要繁琐的预处理工艺流程,以维持其长期稳定运作;3. It requires cumbersome pretreatment process to maintain its long-term stable operation;

4.膜的污染严重,定期的化学清洗需要一定的费用(WaterResearch,2014,66:122)。4. The pollution of the membrane is serious, and regular chemical cleaning requires a certain cost (Water Research, 2014, 66: 122).

不仅仅是反渗透技术,传统的海水淡化技术,如:多级闪蒸、多效蒸发和电渗析等,均不同程度的存在着高耗能、高成本和运行环境条件严苛等缺点,这些都转化为了高昂的运行成本,并在一定程度上消耗了部分不可再生资源,造成了环境污染。因此,进一步寻找低耗能、低成本、运行条件简单和绿色环保的海水淡化技术,变得尤为重要,这成为亟待了解决的技术问题。Not only reverse osmosis technology, but traditional seawater desalination technologies, such as multi-stage flash evaporation, multi-effect evaporation and electrodialysis, all have disadvantages such as high energy consumption, high cost and harsh operating conditions to varying degrees. All of them have been transformed into high operating costs, and to a certain extent, some non-renewable resources have been consumed, resulting in environmental pollution. Therefore, it is particularly important to further search for a seawater desalination technology with low energy consumption, low cost, simple operation conditions and environmental protection, which has become an urgent technical problem to be solved.

发明内容SUMMARY OF THE INVENTION

为了解决现有技术问题,本发明的目的在于克服已有技术中海水淡化和高盐废水处理过程中高耗能、高成本和运行条件苛刻等缺陷,提供一种基于连续过滤方法的盐离子自截留海水淡化方法,与传统超过50个大气压的反渗透海水淡化技术相比,可在不大于5个大气压的过滤压力下,较好的实现海水脱盐,不再需要特殊高耐压材料,大大减少了运行过程中能量的损耗。同时,显著降低运行成本,大大降低传统反渗透技术过程中的高压安全隐患,且该方法操作容易,运行条件简单,运行环境普适性强,适用于大规模海水、苦咸水淡化和工业高盐废水处理,且在化工、医药、电子等行业用水处理方面具有较高潜力。In order to solve the problems of the prior art, the object of the present invention is to overcome the defects such as high energy consumption, high cost and harsh operating conditions in the process of seawater desalination and high-salt wastewater treatment in the prior art, and a kind of salt ion self-retention based on continuous filtration method is provided. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, the seawater desalination method can better achieve seawater desalination under the filtration pressure of no more than 5 atmospheres, and no special high-pressure materials are required, which greatly reduces the Loss of energy during operation. At the same time, the operation cost is significantly reduced, and the hidden danger of high pressure in the process of traditional reverse osmosis technology is greatly reduced, and the method is easy to operate, with simple operating conditions and strong operating environment. It is suitable for large-scale seawater, brackish water desalination and industrial high Salt wastewater treatment, and has high potential in water treatment in chemical, pharmaceutical, electronics and other industries.

为达到上述发明创造目的,本发明采用如下技术方案:In order to achieve the above-mentioned purpose of invention and creation, the present invention adopts the following technical solutions:

一种基于连续过滤方法的盐离子自截留海水淡化方法,步骤如下:A salt ion self-retaining seawater desalination method based on a continuous filtration method, the steps are as follows:

采用氧化石墨烯薄膜作为滤膜,所述氧化石墨烯薄膜具有复合材料的片层结构,将氧化石墨烯薄膜在含盐A的水溶液中浸润至溶胀状态,然后对氧化石墨烯薄膜进行正向加压过滤,利用所加压力挤压氧化石墨烯薄膜内的盐A溶解后形成的水合离子,使该水合离子发生变形,从而减小进入氧化石墨烯薄膜内的水合离子尺寸,降低膜内片层之间的距离,从而截留溶液中盐A溶解后形成的尺寸更大的水合离子,收集透过氧化石墨烯薄膜的汲取液;然后将汲取液作为进行下一次过滤处理过程的待处理盐溶液,重复上述步骤,进行连续过滤,直至得到符合标准的汲取液,从而完成含盐水溶液的脱盐过程。A graphene oxide film is used as the filter membrane, and the graphene oxide film has a lamellar structure of a composite material. The graphene oxide film is infiltrated into a swollen state in an aqueous solution containing salt A, and then the graphene oxide film is subjected to positive addition. Pressure filtration, using the applied pressure to squeeze the hydrated ions formed after the dissolution of the salt A in the graphene oxide film, so that the hydrated ions are deformed, thereby reducing the size of the hydrated ions entering the graphene oxide film, reducing the inner lamellae The distance between, thereby the larger hydrated ion formed after the salt A dissolves in the interception solution, collects the drawing liquid that penetrates the graphene oxide film; Then the drawing liquid is used as the salt solution to be treated for carrying out the next filtration process, The above steps are repeated, and continuous filtration is performed until a drawing solution that meets the standard is obtained, thereby completing the desalination process of the salt-containing aqueous solution.

优选地,在所述含盐A的水溶液中,阳离子浓度为0.015~0.6mol/L。Preferably, in the aqueous solution containing the salt A, the cation concentration is 0.015-0.6 mol/L.

优选地,采用孔径不大于0.45μm的水系微孔滤膜作为氧化石墨烯薄膜的支撑基底膜,采用滤膜抽滤法,将氧化石墨烯溶液进行抽滤,将氧化石墨烯沉积截留于作为支撑基底的水系微孔滤膜上,从而制备得到具有复合片层结构的厚度为100-2500nm的氧化石墨烯薄膜。所述氧化石墨烯薄膜应表面平整,没有明显缺陷,较佳的氧化石墨烯薄膜的厚度为100-250μm。Preferably, an aqueous microporous filter membrane with a pore size of not more than 0.45 μm is used as the supporting base membrane of the graphene oxide film, and a filter membrane suction filtration method is used to filter the graphene oxide solution, and the graphene oxide deposition is trapped as a support. A graphene oxide film with a thickness of 100-2500 nm with a composite sheet structure is prepared. The graphene oxide film should have a smooth surface and no obvious defects, and the preferred thickness of the graphene oxide film is 100-250 μm.

优选地,在所述氧化石墨烯薄膜的制备过程中,所述氧化石墨烯溶液的浓度为1~15mg/mL;更佳的氧化石墨烯溶液的浓度为3~5mg/mL。Preferably, in the preparation process of the graphene oxide film, the concentration of the graphene oxide solution is 1-15 mg/mL; a better concentration of the graphene oxide solution is 3-5 mg/mL.

优选地,在所述氧化石墨烯薄膜的制备过程中,所述氧化石墨烯溶液的氧化石墨烯的氧化度为20~55%。更佳的氧化石墨烯溶液的氧化度为30~55%,进一步更佳地氧化石墨烯溶液的氧化度为50~55%。Preferably, in the preparation process of the graphene oxide film, the oxidation degree of graphene oxide in the graphene oxide solution is 20-55%. More preferably, the oxidation degree of the graphene oxide solution is 30-55%, and even more preferably, the oxidation degree of the graphene oxide solution is 50-55%.

优选地,为了保证氧化石墨烯薄膜充分溶胀,以确保达到更好的自截留效果,在所述浸润过程中,控制待处理的含盐A的水溶液温度为15~25℃。更佳地的含盐A的水溶液温度为18~22℃,尤其更佳的含盐A的水溶液温度为20℃。Preferably, in order to ensure that the graphene oxide film is fully swollen to ensure a better self-retention effect, during the infiltration process, the temperature of the aqueous solution containing the salt A to be treated is controlled to be 15-25°C. The more preferable temperature of the aqueous solution containing salt A is 18-22°C, and the especially preferable temperature of the aqueous solution containing salt A is 20°C.

优选地,为了保证氧化石墨烯薄膜溶胀完全,以确保达到更好的自截留效果,在所述浸润过程中,控制浸泡时间为0.2-1h。Preferably, in order to ensure that the graphene oxide film is completely swollen to ensure a better self-interception effect, in the infiltration process, the immersion time is controlled to be 0.2-1 h.

优选地,为了保证过滤脱盐效率达到挤压膜内盐A溶解后形成的水合离子,使该水合离子发生变形的效果,同时减少能耗,在所述加压过滤过程中,对含盐A水溶液所施加的压力为0.05~0.5MPa。Preferably, in order to ensure that the filtration desalination efficiency reaches the hydrated ions formed after the dissolution of the salt A in the extrusion membrane, the hydrated ions are deformed, and the energy consumption is reduced at the same time, during the pressure filtration process, the salt A-containing aqueous solution is The applied pressure is 0.05 to 0.5 MPa.

优选地,所述含盐A的水溶液中的离子包含无机阳离子和无机阴离子中的中的任意一种或任意多种离子。Preferably, the ions in the aqueous solution containing the salt A comprise any one or any plurality of ions among inorganic cations and inorganic anions.

优选地,所述无机阳离子为Mg2+、Zn2+、Ca2+、Li+、K+、Na+、NH4 +中的任意一种或任意多种离子。Preferably, the inorganic cation is any one or any multiple ions of Mg 2+ , Zn 2+ , Ca 2+ , Li + , K + , Na + , and NH 4 + .

优选地,所述无机阴离子为F-、Cl-、Br-、I-、PO4 3-、SO4 2-、CO3 2-、NO3 -中的任意一种或任意多种离子。Preferably, the inorganic anion is any one or any multiple ions of F - , Cl - , Br - , I - , PO 4 3- , SO 4 2- , CO 3 2- , NO 3 - .

优选地,所述含盐A的水溶液中的pH为6~13;较佳的pH为5~8;最佳的pH为7。Preferably, the pH in the aqueous solution containing the salt A is 6-13; the preferred pH is 5-8; the optimum pH is 7.

优选地,所述含盐A水溶液的盐A为含NaCl、KCl、LiCl、MgCl2和CaCl2中的任意一种或任意多种盐。Preferably, the salt A of the salt A-containing aqueous solution is any one or any multiple salts of NaCl, KCl, LiCl, MgCl 2 and CaCl 2 .

优选地,进行重复截留的次数取决于每次加压过滤后汲取液中盐浓度,直至得到的汲取液符合所需的盐浓度标准,从而完成含盐水溶液的脱盐过程。Preferably, the number of times of repeated interception depends on the salt concentration in the drawing solution after each pressure filtration, until the obtained drawing solution meets the required salt concentration standard, thereby completing the desalination process of the saline solution.

本发明与现有技术相比较,具有如下显而易见的突出实质性特点和显著优点:Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:

1.本发明方法在不大于5个大气压的过滤压力下,使用含盐水溶液中盐离子本身提高氧化石墨烯薄膜的截留效果,实现了海水淡化和高盐工业废水的处理;1. the inventive method, under the filtration pressure of no more than 5 atmospheres, uses the salt ion itself in the saline solution to improve the retention effect of the graphene oxide film, and realizes the treatment of seawater desalination and high-salt industrial waste water;

2.与传统超过50个大气压的反渗透海水淡化技术相比,本发明方法大大减少了运行过程中能量的损耗;同时,由于操作压力的显著下降,体系组件材料的选择性更加广泛,不再需要特殊高耐压材料,显著降低了运行成本,大大降低传统反渗透技术过程中的高压安全隐患;2. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, the method of the present invention greatly reduces the energy loss during operation; at the same time, due to the significant drop in the operating pressure, the selectivity of the system component materials is more extensive, no longer necessary. Special high-pressure-resistant materials are required, which significantly reduces operating costs and greatly reduces the hidden dangers of high-pressure safety in the process of traditional reverse osmosis technology;

3.本发明方法操作容易,运行条件简单,运行环境普适性强,适用于大规模海水、苦咸水淡化和工业高盐废水处理,且在化工、医药、电子等行业用水处理方面具有较高潜力,适合推广使用。3. The method of the present invention is easy to operate, has simple operating conditions, and has strong operating environment universality, is suitable for large-scale seawater, brackish water desalination and industrial high-salt wastewater treatment, and has relatively high performance in water treatment in chemical, pharmaceutical, electronic and other industries. High potential, suitable for promotion and use.

附图说明Description of drawings

图1为本发明实施例1中使用浓度0.6mol/L的含NaCl的水溶液被截留至淡水标准每次的截留率情况Fig. 1 is the interception rate situation of each time when the aqueous solution containing NaCl with a concentration of 0.6 mol/L is intercepted to the fresh water standard in Example 1 of the present invention

图2为本发明实施例1中使用浓度0.6mol/L的含NaCl的水溶液被截留至淡水标准每次截留后汲取液浓度情况。Fig. 2 is the concentration situation of drawing liquid after each interception of using the NaCl-containing aqueous solution of concentration 0.6mol/L to be intercepted to the fresh water standard in Example 1 of the present invention.

图3为本发明实施例1中使用浓度0.6mol/L的含NaCl的水溶液每次过滤的水通量情况。Fig. 3 is the water flux of each filtration using an aqueous solution containing NaCl with a concentration of 0.6 mol/L in Example 1 of the present invention.

图4为本发明实施例2中使用浓度0.1mol/L的含KCl的水溶液被截留至较低浓度标准每次截留率情况。Fig. 4 is the interception rate situation of using the KCl-containing aqueous solution with a concentration of 0.1 mol/L in Example 2 of the present invention to be intercepted to a lower concentration standard each time.

图5为本发明实施例2中使用浓度0.1mol/L的含KCl的水溶液被截留至较低浓度标准每次截留后汲取液浓度情况。Fig. 5 is in the embodiment of the present invention 2 using the KCl-containing aqueous solution with a concentration of 0.1 mol/L to be intercepted to a lower concentration standard after each interception of the concentration of the drawn liquid.

图6为本发明实施例2中使用浓度0.1mol/L的含KCl的水溶液每次过滤的水通量情况。FIG. 6 is the water flux of each filtration using an aqueous solution containing KCl with a concentration of 0.1 mol/L in Example 2 of the present invention.

图7为本发明实施例3中使用浓度0.1mol/L的含LiCl的水溶液被截留至较低浓度标准每次截留率情况。FIG. 7 shows the situation of each time the interception rate of using the LiCl-containing aqueous solution with a concentration of 0.1 mol/L is intercepted to a lower concentration standard in Example 3 of the present invention.

图8为本发明实施例3中使用浓度0.1mol/L的含LiCl的水溶液被截留至较低浓度标准每次截留后汲取液浓度情况。FIG. 8 shows the concentration of the extracted solution after each interception of an aqueous solution containing LiCl with a concentration of 0.1 mol/L that is trapped to a lower concentration standard in Example 3 of the present invention.

图9为本发明实施例3中使用浓度0.1mol/L的含LiCl的水溶液每次过滤的水通量情况。FIG. 9 shows the water flux of each filtration using an aqueous solution containing LiCl with a concentration of 0.1 mol/L in Example 3 of the present invention.

图10为本发明实施例4中使用浓度0.1mol/L的含MgCl2的水溶液被截留至较低浓度标准每次截留率情况Fig. 10 is the situation that the aqueous solution containing MgCl 2 with a concentration of 0.1 mol/L is intercepted to a lower concentration standard in Example 4 of the present invention.

图11为本发明实施例4中使用浓度0.1mol/L的含MgCl2的水溶液被截留至较低浓度标准每次截留后汲取液浓度情况。Fig. 11 is the concentration situation of the drawing liquid after each interception of the aqueous solution containing MgCl with a concentration of 0.1 mol/L being trapped to a lower concentration standard in Example 4 of the present invention.

图12为本发明实施例4中使用浓度0.1mol/L的含MgCl2的水溶液每次过滤的水通量情况。Figure 12 shows the water flux of each filtration using an aqueous solution containing MgCl 2 with a concentration of 0.1 mol/L in Example 4 of the present invention.

图13为本发明实施例5中使用浓度0.1mol/L的含CaCl2的水溶液被截留至较低浓度标准每次截留率情况Fig. 13 shows the situation of the interception rate of each time when the aqueous solution containing CaCl 2 with a concentration of 0.1 mol/L is intercepted to a lower concentration standard in Example 5 of the present invention

图14为本发明实施例5中使用浓度0.1mol/L的含CaCl2的水溶液被截留至较低浓度标准每次截留后汲取液浓度情况。FIG. 14 is the concentration situation of the drawn liquid after each interception of the aqueous solution containing CaCl 2 with a concentration of 0.1 mol/L being trapped to a lower concentration standard in Example 5 of the present invention.

图15为本发明实施例5中使用浓度0.1mol/L的含CaCl2的水溶液每次过滤的水通量情况。Figure 15 shows the water flux of each filtration using an aqueous solution containing CaCl 2 with a concentration of 0.1 mol/L in Example 5 of the present invention.

图16为本发明方法采用的连续过滤装置结构示意图。Figure 16 is a schematic structural diagram of the continuous filtering device used in the method of the present invention.

具体实施方式Detailed ways

下面通过实施例的方式进一步说明本发明,但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法,按照常规方法和条件,或按照商品说明书选择。The present invention is further described below by way of examples, but the present invention is not limited to the scope of the described examples. In the following examples, the experimental methods without specific conditions are selected according to conventional methods and conditions, or according to the product description.

以下实施例中,所用的氧化石墨烯溶液购自江苏无锡华鑫检测技术有限公司。使用美国Leeman公司的ICP光谱仪测定汲取液中各离子浓度。In the following examples, the graphene oxide solution used was purchased from Jiangsu Wuxi Huaxin Detection Technology Co., Ltd. The concentration of each ion in the extraction solution was measured using an ICP spectrometer of Leeman Company in the United States.

以下结合具体的实施例子对上述方案做进一步说明,本发明的优选实施例详述如下:The above scheme will be further described below in conjunction with specific embodiments, and preferred embodiments of the present invention are described in detail as follows:

实施例1Example 1

在本实施例中,参见图1、图2和图3,一种基于连续过滤方法的盐离子自截留海水淡化方法,步骤如下:In the present embodiment, referring to Fig. 1, Fig. 2 and Fig. 3, a salt ion self-retaining seawater desalination method based on a continuous filtration method, the steps are as follows:

a.氧化石墨烯薄膜的准备:a. Preparation of graphene oxide films:

采用孔径为0.45μm的水系微孔滤膜作为支撑基底膜,采用滤膜抽滤法,将浓度为5mg/mL的氧化度为55%氧化石墨烯溶液进行抽滤,将氧化石墨烯沉积截留于作为支撑基底的水系微孔滤膜上,从而制备得到具有复合片层结构的厚度为2500nm的氧化石墨烯薄膜,备用;An aqueous microporous membrane with a pore size of 0.45 μm was used as the supporting base membrane, and the membrane suction filtration method was used to filter a graphene oxide solution with a concentration of 5 mg/mL and a degree of oxidation of 55%, and the graphene oxide deposits were trapped in On the water-based microporous filter membrane as a supporting substrate, a graphene oxide film with a thickness of 2500 nm having a composite lamella structure is prepared for use;

b.含盐水溶液的脱盐过程:b. Desalination process of brine solution:

待处理溶液为浓度为0.6mol/L的NaCl溶液,调节NaCl溶液的pH=7,将氧化石墨烯薄膜在NaCl溶液中浸润0.5h,并控制NaCl溶液温度为20℃,使氧化石墨烯薄膜充分溶胀,然后对氧化石墨烯薄膜进行正向加压过滤,在0.1MPa的压力驱动下,挤压氧化石墨烯薄膜内的NaCl溶解后形成的水合离子,使该水合离子发生变形,从而减小进入氧化石墨烯薄膜内的水合离子尺寸,降低膜内片层之间的距离,从而截留溶液中NaCl溶解后形成的尺寸更大的水合离子,收集透过氧化石墨烯薄膜的汲取液并测定其中离子浓度,记录本次过滤的水通量和盐截留率;然后将汲取液作为进行下一次过滤处理过程的待处理盐溶液,重复上述步骤,进行连续过滤,直至汲取液中Na+浓度低于0.017M,从而完成含盐水溶液的脱盐过程。The solution to be treated is a NaCl solution with a concentration of 0.6 mol/L, the pH of the NaCl solution is adjusted to 7, the graphene oxide film is soaked in the NaCl solution for 0.5 h, and the temperature of the NaCl solution is controlled to 20 °C, so that the graphene oxide film is fully Swelling, then the graphene oxide film is subjected to positive pressure filtration, and under the pressure of 0.1MPa, the hydrated ions formed after the dissolution of NaCl in the graphene oxide film is extruded, so that the hydrated ions are deformed, thereby reducing the amount of entering The size of the hydrated ions in the graphene oxide film reduces the distance between the sheets in the film, thereby retaining the larger size hydrated ions formed after the dissolution of NaCl in the solution, collecting the extraction liquid passing through the graphene oxide film and measuring the ions in it Concentration, record the water flux and the salt retention rate of this filtration; then draw the liquid as the salt solution to be treated for carrying out the next filtration process, repeat the above steps, carry out continuous filtration, until the Na concentration in the draw liquid is lower than 0.017 M, thereby completing the desalination process of the brine solution.

实验测试分析:Experimental test analysis:

由图1、图2和图3看出,本实例每次过滤都保持一个相对较高的截留率,且水通量随着加入盐溶液浓度的降低整体呈上升趋势。进行重复截留的次数取决于每次加压过滤后汲取液中盐浓度,直至得到的汲取液符合所需的盐浓度标准,从而完成含盐水溶液的脱盐过程。与传统超过50个大气压的反渗透海水淡化技术相比,本实施例方法在不大于5个大气压的过滤压力下,较好的实现海水脱盐,不再需要特殊高耐压材料,大大减少了运行过程中能量的损耗。显著降低运行成本,大大降低传统反渗透技术过程中的高压安全隐患,且该方法操作容易,运行条件简单,运行环境普适性强。It can be seen from Figure 1, Figure 2 and Figure 3 that this example maintains a relatively high retention rate for each filtration, and the water flux shows an overall upward trend with the decrease in the concentration of the added salt solution. The number of times of repeated interception depends on the salt concentration in the drawing solution after each pressure filtration, until the obtained drawing solution meets the required salt concentration standard, thereby completing the desalination process of the saline solution. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, the method of this embodiment can better achieve seawater desalination under the filtration pressure of no more than 5 atmospheres, and no special high-pressure materials are needed, which greatly reduces the operation time. energy loss in the process. The operation cost is significantly reduced, the hidden danger of high pressure in the process of the traditional reverse osmosis technology is greatly reduced, and the method is easy to operate, the operation conditions are simple, and the operation environment is widely applicable.

实施例2Example 2

本实施例与实施例1基本相同,特别之处在于:This embodiment is basically the same as Embodiment 1, and the special features are:

在本实施例中,参见图4、图5和图6,一种基于连续过滤方法的盐离子自截留海水淡化方法,步骤如下:In this embodiment, referring to Fig. 4, Fig. 5 and Fig. 6, a salt ion self-retaining seawater desalination method based on a continuous filtration method, the steps are as follows:

a.氧化石墨烯薄膜的准备:a. Preparation of graphene oxide films:

采用孔径为0.45μm的水系微孔滤膜作为支撑基底膜,采用滤膜抽滤法,将浓度为5mg/mL的氧化度为55%氧化石墨烯溶液进行抽滤,将氧化石墨烯沉积截留于作为支撑基底的水系微孔滤膜上,从而制备得到具有复合片层结构的厚度为2500nm的氧化石墨烯薄膜,备用;An aqueous microporous membrane with a pore size of 0.45 μm was used as the supporting base membrane, and the membrane suction filtration method was used to filter a graphene oxide solution with a concentration of 5 mg/mL and a degree of oxidation of 55%, and the graphene oxide deposits were trapped in On the water-based microporous filter membrane as a supporting substrate, a graphene oxide film with a thickness of 2500 nm having a composite lamella structure is prepared for use;

b.含盐水溶液的脱盐过程:b. Desalination process of brine solution:

待处理溶液为浓度为0.1mol/L的KCl溶液,调节KCl溶液的pH=7,将氧化石墨烯薄膜在KCl溶液中浸润0.5h,并控制KCl溶液温度为20℃,使氧化石墨烯薄膜充分溶胀,然后对氧化石墨烯薄膜进行正向加压过滤,在0.1MPa的压力驱动下,挤压氧化石墨烯薄膜内的KCl溶解后形成的水合离子,使该水合离子发生变形,从而减小进入氧化石墨烯薄膜内的水合离子尺寸,降低膜内片层之间的距离,从而截留溶液中KCl溶解后形成的尺寸更大的水合离子,收集透过氧化石墨烯薄膜的汲取液并测定其中离子浓度,记录本次过滤的水通量和盐截留率;然后将汲取液作为进行下一次过滤处理过程的待处理盐溶液,重复上述步骤,进行连续过滤,直至汲取液中K+浓度低于0.017M,从而完成含盐水溶液的脱盐过程。The solution to be treated is a KCl solution with a concentration of 0.1 mol/L, the pH of the KCl solution is adjusted to 7, the graphene oxide film is soaked in the KCl solution for 0.5 h, and the temperature of the KCl solution is controlled to be 20 °C, so that the graphene oxide film is fully Swell, and then filter the graphene oxide film under positive pressure. Under the pressure of 0.1MPa, squeeze the hydrated ions formed after the KCl in the graphene oxide film is dissolved, so that the hydrated ions are deformed, thereby reducing the entry of the hydrated ions. The size of the hydrated ions in the graphene oxide film reduces the distance between the sheets in the film, thereby retaining the larger size hydrated ions formed after KCl is dissolved in the solution, collecting the drawing liquid passing through the graphene oxide film and measuring the ions in it Concentration, record the water flux and the salt retention rate of this filtration; then draw the liquid as the salt solution to be treated to carry out the next filtration process, repeat the above steps, carry out continuous filtration, until the K concentration in the draw liquid is lower than 0.017 M, thereby completing the desalination process of the brine solution.

实验测试分析:Experimental test analysis:

由图4、图5和图6看出,本实例K+的截留率在25%附近波动,截留率相对稳定,且水通量随着加入盐溶液浓度的降低整体呈上升趋势。进行重复截留的次数取决于每次加压过滤后汲取液中盐浓度,直至得到的汲取液符合所需的盐浓度标准,从而完成含盐水溶液的脱盐过程。与传统超过50个大气压的反渗透海水淡化技术相比,本实施例方法在不大于5个大气压的过滤压力下,较好的实现海水脱盐,不再需要特殊高耐压材料,大大减少了运行过程中能量的损耗。显著降低运行成本,大大降低传统反渗透技术过程中的高压安全隐患,且该方法操作容易,运行条件简单,运行环境普适性强。It can be seen from Figure 4, Figure 5 and Figure 6 that the retention rate of K + in this example fluctuates around 25%, the retention rate is relatively stable, and the water flux shows an overall upward trend with the decrease of the added salt solution concentration. The number of times of repeated interception depends on the salt concentration in the drawing solution after each pressure filtration, until the obtained drawing solution meets the required salt concentration standard, thereby completing the desalination process of the saline solution. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, the method of this embodiment can better achieve seawater desalination under the filtration pressure of no more than 5 atmospheres, and no special high-pressure materials are needed, which greatly reduces the operation time. energy loss in the process. The operation cost is significantly reduced, the hidden danger of high pressure in the process of the traditional reverse osmosis technology is greatly reduced, and the method is easy to operate, the operation conditions are simple, and the operation environment is widely applicable.

实施例3Example 3

本实施例与前述实施例基本相同,特别之处在于:This embodiment is basically the same as the previous embodiment, and the special features are:

在本实施例中,参见图7、图8和图9,一种基于连续过滤方法的盐离子自截留海水淡化方法,步骤如下:In this embodiment, referring to Fig. 7, Fig. 8 and Fig. 9, a salt ion self-retaining seawater desalination method based on a continuous filtration method, the steps are as follows:

a.氧化石墨烯薄膜的准备:a. Preparation of graphene oxide film:

采用孔径为0.45μm的水系微孔滤膜作为支撑基底膜,采用滤膜抽滤法,将浓度为5mg/mL的氧化度为55%氧化石墨烯溶液进行抽滤,将氧化石墨烯沉积截留于作为支撑基底的水系微孔滤膜上,从而制备得到具有复合片层结构的厚度为2500nm的氧化石墨烯薄膜,备用;An aqueous microporous membrane with a pore size of 0.45 μm was used as the supporting base membrane, and the membrane suction filtration method was used to filter a graphene oxide solution with a concentration of 5 mg/mL and a degree of oxidation of 55%, and the graphene oxide deposits were trapped in On the water-based microporous filter membrane as a supporting substrate, a graphene oxide film with a thickness of 2500 nm having a composite lamella structure is prepared for use;

b.含盐水溶液的脱盐过程:b. Desalination process of brine solution:

待处理溶液为浓度为0.1mol/L的LiCl溶液,调节LiCl溶液的pH=7,将氧化石墨烯薄膜在LiCl溶液中浸润0.5h,并控制LiCl溶液温度为20℃,使氧化石墨烯薄膜充分溶胀,然后对氧化石墨烯薄膜进行正向加压过滤,在0.1MPa的压力驱动下,挤压氧化石墨烯薄膜内的LiCl溶解后形成的水合离子,使该水合离子发生变形,从而减小进入氧化石墨烯薄膜内的水合离子尺寸,降低膜内片层之间的距离,从而截留溶液中LiCl溶解后形成的尺寸更大的水合离子,收集透过氧化石墨烯薄膜的汲取液并测定其中离子浓度,记录本次过滤的水通量和盐截留率;然后将汲取液作为进行下一次过滤处理过程的待处理盐溶液,重复上述步骤,进行连续过滤,直至汲取液中Li+浓度低于0.017M,从而完成含盐水溶液的脱盐过程。The solution to be treated is a LiCl solution with a concentration of 0.1 mol/L, the pH of the LiCl solution is adjusted to 7, the graphene oxide film is soaked in the LiCl solution for 0.5 h, and the temperature of the LiCl solution is controlled to 20 ° C, so that the graphene oxide film is fully Swell, and then filter the graphene oxide film under positive pressure. Under the pressure of 0.1MPa, squeeze the hydrated ions formed after the dissolution of LiCl in the graphene oxide film, so that the hydrated ions are deformed, thereby reducing the amount of entering The size of the hydrated ions in the graphene oxide film reduces the distance between the sheets in the film, thereby retaining the larger size hydrated ions formed after the dissolution of LiCl in the solution, collecting the extraction liquid passing through the graphene oxide film and measuring the ions in it Concentration, record the water flux and salt retention rate of this filtration; then draw the liquid as the to-be - treated salt solution for the next filtration process, repeat the above steps, carry out continuous filtration, until the Li concentration in the drawn liquid is lower than 0.017 M, thereby completing the desalination process of the brine solution.

实验测试分析:Experimental test analysis:

由图7、图8和图9看出,本实例截留率随过滤次数的增加而增加,且水通量随着加入盐溶液浓度的降低整体呈上升趋势。进行重复截留的次数取决于每次加压过滤后汲取液中盐浓度,直至得到的汲取液符合所需的盐浓度标准,从而完成含盐水溶液的脱盐过程。与传统超过50个大气压的反渗透海水淡化技术相比,本实施例方法在不大于5个大气压的过滤压力下,较好的实现海水脱盐,不再需要特殊高耐压材料,大大减少了运行过程中能量的损耗。显著降低运行成本,大大降低传统反渗透技术过程中的高压安全隐患,且该方法操作容易,运行条件简单,运行环境普适性强。It can be seen from Figure 7, Figure 8 and Figure 9 that the retention rate of this example increases with the increase of the number of filtrations, and the water flux shows an overall upward trend with the decrease of the added salt solution concentration. The number of times of repeated interception depends on the salt concentration in the drawing solution after each pressure filtration, until the obtained drawing solution meets the required salt concentration standard, thereby completing the desalination process of the saline solution. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, the method of this embodiment can better achieve seawater desalination under the filtration pressure of no more than 5 atmospheres, and no special high-pressure materials are needed, which greatly reduces the operation time. energy loss in the process. The operation cost is significantly reduced, the hidden danger of high pressure in the process of the traditional reverse osmosis technology is greatly reduced, and the method is easy to operate, the operation conditions are simple, and the operation environment is widely applicable.

实施例4Example 4

本实施例与前述实施例基本相同,特别之处在于:This embodiment is basically the same as the previous embodiment, and the special features are:

在本实施例中,参见图10、图11和图12,一种基于连续过滤方法的盐离子自截留海水淡化方法,步骤如下:In this embodiment, referring to Fig. 10, Fig. 11 and Fig. 12, a salt ion self-retaining seawater desalination method based on a continuous filtration method, the steps are as follows:

a.氧化石墨烯薄膜的准备:a. Preparation of graphene oxide film:

采用孔径为0.45μm的水系微孔滤膜作为支撑基底膜,采用滤膜抽滤法,将浓度为5mg/mL的氧化度为55%氧化石墨烯溶液进行抽滤,将氧化石墨烯沉积截留于作为支撑基底的水系微孔滤膜上,从而制备得到具有复合片层结构的厚度为2500nm的氧化石墨烯薄膜,备用;An aqueous microporous membrane with a pore size of 0.45 μm was used as the supporting base membrane, and the membrane suction filtration method was used to filter a graphene oxide solution with a concentration of 5 mg/mL and a degree of oxidation of 55%, and the graphene oxide deposits were trapped in On the water-based microporous filter membrane as a supporting substrate, a graphene oxide film with a thickness of 2500 nm having a composite lamella structure is prepared for use;

b.含盐水溶液的脱盐过程:b. Desalination process of brine solution:

待处理溶液为浓度为0.1mol/L的MgCl2溶液,调节MgCl2溶液的pH=6,将氧化石墨烯薄膜在MgCl2溶液中浸润0.5h,并控制MgCl2溶液温度为20℃,使氧化石墨烯薄膜充分溶胀,然后对氧化石墨烯薄膜进行正向加压过滤,在0.1MPa的压力驱动下,挤压氧化石墨烯薄膜内的MgCl2溶解后形成的水合离子,使该水合离子发生变形,从而减小进入氧化石墨烯薄膜内的水合离子尺寸,降低膜内片层之间的距离,从而截留溶液中MgCl2溶解后形成的尺寸更大的水合离子,收集透过氧化石墨烯薄膜的汲取液并测定其中离子浓度,记录本次过滤的水通量和盐截留率;然后将汲取液作为进行下一次过滤处理过程的待处理盐溶液,重复上述步骤,进行连续过滤,直至汲取液中Mg2+浓度低于0.017M,从而完成含盐水溶液的脱盐过程。The solution to be treated is a MgCl 2 solution with a concentration of 0.1 mol/L, the pH of the MgCl 2 solution is adjusted to 6, the graphene oxide film is soaked in the MgCl 2 solution for 0.5h, and the temperature of the MgCl 2 solution is controlled to 20 ° C to make the oxidation The graphene film is fully swollen, and then the graphene oxide film is subjected to positive pressure filtration. Under the pressure of 0.1 MPa, the hydrated ions formed after the dissolution of MgCl in the graphene oxide film is extruded to deform the hydrated ions. , thereby reducing the size of the hydrated ions entering the graphene oxide film, reducing the distance between the sheets in the film, thereby intercepting the larger hydrated ions formed after the dissolution of MgCl in the solution, and collecting the hydrated ions that pass through the graphene oxide film. Draw the liquid and measure the ion concentration therein, record the water flux and salt retention rate of this filtration; then use the drawn liquid as the salt solution to be treated for carrying out the next filtration process, repeat the above steps, and carry out continuous filtration until the liquid is drawn. The Mg 2+ concentration is lower than 0.017M, thus completing the desalination process of the brine solution.

实验测试分析:Experimental test analysis:

由图10、图11和图12看出,本实例Mg2+的截留率在25%附近波动,截留率相对稳定,且水通量随着加入盐溶液浓度的降低整体呈上升趋势。进行重复截留的次数取决于每次加压过滤后汲取液中盐浓度,直至得到的汲取液符合所需的盐浓度标准,从而完成含盐水溶液的脱盐过程。与传统超过50个大气压的反渗透海水淡化技术相比,本实施例方法在不大于5个大气压的过滤压力下,较好的实现海水脱盐,不再需要特殊高耐压材料,大大减少了运行过程中能量的损耗。显著降低运行成本,大大降低传统反渗透技术过程中的高压安全隐患,且该方法操作容易,运行条件简单,运行环境普适性强。It can be seen from Figure 10, Figure 11 and Figure 12 that the retention rate of Mg 2+ in this example fluctuated around 25%, the retention rate was relatively stable, and the water flux showed an overall upward trend as the concentration of the added salt solution decreased. The number of times of repeated interception depends on the salt concentration in the drawing solution after each pressure filtration, until the obtained drawing solution meets the required salt concentration standard, thereby completing the desalination process of the saline solution. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, the method of this embodiment can better achieve seawater desalination under the filtration pressure of no more than 5 atmospheres, and no special high-pressure materials are needed, which greatly reduces the operation time. energy loss in the process. The operation cost is significantly reduced, the hidden danger of high pressure in the process of the traditional reverse osmosis technology is greatly reduced, and the method is easy to operate, the operation conditions are simple, and the operation environment is widely applicable.

实施例5Example 5

在本实施例中,参见图13、图14和图15,一种基于连续过滤方法的盐离子自截留海水淡化方法,步骤如下:In this embodiment, referring to Fig. 13, Fig. 14 and Fig. 15, a salt ion self-retaining seawater desalination method based on a continuous filtration method, the steps are as follows:

a.氧化石墨烯薄膜的准备:a. Preparation of graphene oxide film:

采用孔径为0.45μm的水系微孔滤膜作为支撑基底膜,采用滤膜抽滤法,将浓度为5mg/mL的氧化度为55%氧化石墨烯溶液进行抽滤,将氧化石墨烯沉积截留于作为支撑基底的水系微孔滤膜上,从而制备得到具有复合片层结构的厚度为2500nm的氧化石墨烯薄膜,备用;An aqueous microporous membrane with a pore size of 0.45 μm was used as the supporting base membrane, and the membrane suction filtration method was used to filter a graphene oxide solution with a concentration of 5 mg/mL and a degree of oxidation of 55%, and the graphene oxide deposits were trapped in On the water-based microporous filter membrane as a supporting substrate, a graphene oxide film with a thickness of 2500 nm having a composite lamella structure is prepared for use;

b.含盐水溶液的脱盐过程:b. Desalination process of brine solution:

待处理溶液为浓度为0.1mol/L的CaCl2溶液,调节CaCl2溶液的pH=6,将氧化石墨烯薄膜在CaCl2溶液中浸润0.5h,并控制CaCl2溶液温度为20℃,使氧化石墨烯薄膜充分溶胀,然后对氧化石墨烯薄膜进行正向加压过滤,在0.1MPa的压力驱动下,挤压氧化石墨烯薄膜内的CaCl2溶解后形成的水合离子,使该水合离子发生变形,从而减小进入氧化石墨烯薄膜内的水合离子尺寸,降低膜内片层之间的距离,从而截留溶液中CaCl2溶解后形成的尺寸更大的水合离子,收集透过氧化石墨烯薄膜的汲取液并测定其中离子浓度,记录本次过滤的水通量和盐截留率;然后将汲取液作为进行下一次过滤处理过程的待处理盐溶液,重复上述步骤,进行连续过滤,直至汲取液中Ca2+浓度低于0.017M,从而完成含盐水溶液的脱盐过程。The solution to be treated is a CaCl 2 solution with a concentration of 0.1 mol/L, the pH of the CaCl 2 solution is adjusted to 6, the graphene oxide film is soaked in the CaCl 2 solution for 0.5h, and the temperature of the CaCl 2 solution is controlled to be 20 ° C to make the oxidation The graphene film is fully swollen, and then the graphene oxide film is subjected to positive pressure filtration. Under the pressure of 0.1MPa, the hydrated ions formed after the dissolution of CaCl2 in the graphene oxide film is extruded, so that the hydrated ions are deformed. , thereby reducing the size of the hydrated ions entering the graphene oxide film and reducing the distance between the sheets in the film, thereby intercepting the larger hydrated ions formed after the dissolution of CaCl in the solution, and collecting the hydrated ions that pass through the graphene oxide film. Draw the liquid and measure the ion concentration therein, record the water flux and salt retention rate of this filtration; then use the drawn liquid as the salt solution to be treated for carrying out the next filtration process, repeat the above steps, and carry out continuous filtration until the liquid is drawn. The Ca 2+ concentration is lower than 0.017M, thus completing the desalination process of the brine solution.

实验测试分析:Experimental test analysis:

由图13、图14和图15看出,本实例Ca2+的截留率在20%附近波动,截留率较稳定,水通量随着加入盐溶液浓度的降低整体变化不大,处于一个波动的情况。进行重复截留的次数取决于每次加压过滤后汲取液中盐浓度,直至得到的汲取液符合所需的盐浓度标准,从而完成含盐水溶液的脱盐过程。与传统超过50个大气压的反渗透海水淡化技术相比,本实施例方法在不大于5个大气压的过滤压力下,较好的实现海水脱盐,不再需要特殊高耐压材料,大大减少了运行过程中能量的损耗。显著降低运行成本,大大降低传统反渗透技术过程中的高压安全隐患,且该方法操作容易,运行条件简单,运行环境普适性强。It can be seen from Figure 13, Figure 14 and Figure 15 that the retention rate of Ca 2+ in this example fluctuates around 20%, and the retention rate is relatively stable. Case. The number of times of repeated interception depends on the salt concentration in the drawing solution after each pressure filtration, until the obtained drawing solution meets the required salt concentration standard, thereby completing the desalination process of the saline solution. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, the method of this embodiment can better achieve seawater desalination under the filtration pressure of no more than 5 atmospheres, and no special high-pressure materials are needed, which greatly reduces the operation time. energy loss in the process. The operation cost is significantly reduced, the hidden danger of high pressure in the process of the traditional reverse osmosis technology is greatly reduced, and the method is easy to operate, the operation conditions are simple, and the operation environment is widely applicable.

实施例6Example 6

本实施例与前述实施例基本相同,特别之处在于:This embodiment is basically the same as the previous embodiment, and the special features are:

在本实施例中,一种基于连续过滤方法的盐离子自截留海水淡化方法,步骤如下:In the present embodiment, a salt ion self-retaining seawater desalination method based on a continuous filtration method, the steps are as follows:

a.氧化石墨烯薄膜的准备:a. Preparation of graphene oxide film:

采用孔径为0.45μm的水系微孔滤膜作为支撑基底膜,采用滤膜抽滤法,将浓度为3mg/mL的氧化度为30%氧化石墨烯溶液进行抽滤,将氧化石墨烯沉积截留于作为支撑基底的水系微孔滤膜上,从而制备得到具有复合片层结构的厚度为100nm的氧化石墨烯薄膜,备用;An aqueous microporous filter membrane with a pore size of 0.45 μm was used as the supporting base membrane, and the membrane suction filtration method was used to filter a graphene oxide solution with a concentration of 3 mg/mL and a degree of oxidation of 30%, and the graphene oxide deposition was trapped in On the water-based microporous filter membrane as the supporting substrate, a graphene oxide film with a thickness of 100 nm having a composite lamella structure is prepared, for use;

b.含盐水溶液的脱盐过程:b. Desalination process of brine solution:

待处理溶液为浓度为0.1mol/L的NaCl溶液,调节NaCl溶液的pH=6,将氧化石墨烯薄膜在NaCl溶液中浸润1h,并控制NaCl溶液温度为22℃,使氧化石墨烯薄膜充分溶胀,然后对氧化石墨烯薄膜进行正向加压过滤,在0.5MPa的压力驱动下,挤压氧化石墨烯薄膜内的NaCl溶解后形成的水合离子,使该水合离子发生变形,从而减小进入氧化石墨烯薄膜内的水合离子尺寸,降低膜内片层之间的距离,从而截留溶液中NaCl溶解后形成的尺寸更大的水合离子,收集透过氧化石墨烯薄膜的汲取液并测定其中离子浓度,记录本次过滤的水通量和盐截留率;然后将汲取液作为进行下一次过滤处理过程的待处理盐溶液,重复上述步骤,进行连续过滤,直至汲取液中Na+浓度低于0.017M,从而完成含盐水溶液的脱盐过程。The solution to be treated is a NaCl solution with a concentration of 0.1 mol/L, the pH of the NaCl solution is adjusted to 6, the graphene oxide film is immersed in the NaCl solution for 1 h, and the temperature of the NaCl solution is controlled to 22 °C, so that the graphene oxide film is fully swollen Then, the graphene oxide film is subjected to positive pressure filtration. Under the pressure of 0.5MPa, the hydrated ions formed after the dissolution of NaCl in the graphene oxide film is extruded, so that the hydrated ions are deformed, thereby reducing the amount of water entering the oxide film. The size of the hydrated ions in the graphene film reduces the distance between the sheets in the film, thereby retaining the larger hydrated ions formed after the NaCl dissolves in the solution, collects the extraction solution that passes through the graphene oxide film and measures the ion concentration. , record the water flux and the salt retention rate of this filtration; then draw the liquid as the salt solution to be treated for the next filtration process, repeat the above steps, carry out continuous filtration, until the Na concentration in the drawn liquid is lower than 0.017M , so as to complete the desalination process of the brine solution.

实验测试分析:Experimental test analysis:

本实例每次过滤都保持一个相对较高的截留率,且水通量随着加入盐溶液浓度的降低整体呈上升趋势。进行重复截留的次数取决于每次加压过滤后汲取液中盐浓度,直至得到的汲取液符合所需的盐浓度标准,从而完成含盐水溶液的脱盐过程。与传统超过50个大气压的反渗透海水淡化技术相比,本实施例方法在不大于5个大气压的过滤压力下,较好的实现海水脱盐,不再需要特殊高耐压材料,大大减少了运行过程中能量的损耗。显著降低运行成本,大大降低传统反渗透技术过程中的高压安全隐患,且该方法操作容易,运行条件简单,运行环境普适性强。In this example, a relatively high retention rate was maintained for each filtration, and the water flux showed an overall upward trend as the concentration of the added salt solution decreased. The number of times of repeated interception depends on the salt concentration in the drawing solution after each pressure filtration, until the obtained drawing solution meets the required salt concentration standard, thereby completing the desalination process of the saline solution. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, the method of this embodiment can better achieve seawater desalination under the filtration pressure of no more than 5 atmospheres, and no special high-pressure materials are needed, which greatly reduces the operation time. energy loss in the process. The operation cost is significantly reduced, the hidden danger of high pressure in the process of the traditional reverse osmosis technology is greatly reduced, and the method is easy to operate, the operation conditions are simple, and the operation environment is widely applicable.

实施例7Example 7

本实施例与前述实施例基本相同,特别之处在于:This embodiment is basically the same as the previous embodiment, and the special features are:

在本实施例中,参见图11,一种基于连续过滤方法的盐离子自截留海水淡化方法,采用氧化石墨烯薄膜作为滤膜,将氧化石墨烯薄膜分别安装到图11连续过滤装置的每一级过滤装置中,待处理的含盐水体从第一级过滤单元的进水后进入,通过第一级氧化石墨烯薄膜进行过滤,一级汲取液继续进入第二级过滤单元,继续进行过滤。收集每一级过滤单元的透过氧化石墨烯薄膜的汲取液并测定其中离子浓度,记录本次过滤的水通量和盐截留率,进行重复截留的次数或者过滤单元的级数取决于每次加压过滤后汲取液中盐浓度,直至得到的汲取液符合所需的盐浓度标准,从而完成含盐水溶液的脱盐过程。In the present embodiment, referring to FIG. 11 , a salt ion self-retaining seawater desalination method based on a continuous filtration method adopts a graphene oxide film as a filter film, and the graphene oxide film is respectively installed in each of the continuous filtration devices of FIG. 11 . In the first-stage filtration device, the brine-containing water to be treated enters from the water inlet of the first-stage filtration unit, and is filtered through the first-stage graphene oxide film, and the first-stage drawing liquid continues to enter the second-stage filtration unit, and continues to filter. Collect the drawing liquid of each grade of filtration unit through the graphene oxide film and measure the ion concentration, record the water flux and salt rejection rate of this filtration, and the number of times of repeated interception or the number of stages of the filtration unit depends on each time. After the pressure filtration, the salt concentration in the liquid is drawn, until the obtained drawn liquid meets the required salt concentration standard, thereby completing the desalination process of the salt-containing aqueous solution.

本实施例一种基于连续过滤方法的盐离子自截留海水淡化方法,所述氧化石墨烯薄膜具有复合材料的片层结构,将氧化石墨烯薄膜在含盐A的水溶液中浸润至溶胀状态,然后对氧化石墨烯薄膜进行正向加压过滤,利用所加压力挤压氧化石墨烯薄膜内的盐A溶解后形成的水合离子,使该水合离子发生变形,从而减小进入氧化石墨烯薄膜内的水合离子尺寸,降低膜内片层之间的距离,从而截留溶液中盐A溶解后形成的尺寸更大的水合离子,收集透过氧化石墨烯薄膜的汲取液;然后将汲取液作为进行下一次过滤处理过程的待处理盐溶液,重复上述步骤,进行连续过滤,直至得到符合标准的汲取液,从而完成含盐水溶液的脱盐过程。The present embodiment is a salt ion self-retaining seawater desalination method based on a continuous filtration method. The graphene oxide film has a lamellar structure of a composite material. The graphene oxide film is infiltrated in an aqueous solution containing salt A to a swollen state, and then The graphene oxide film is subjected to positive pressure filtration, and the hydrated ions formed after dissolving the salt A in the graphene oxide film are extruded by the applied pressure, so that the hydrated ions are deformed, thereby reducing the amount of water entering the graphene oxide film. The size of the hydrated ions reduces the distance between the sheets in the membrane, thereby retaining the larger hydrated ions formed after dissolving the salt A in the solution, and collecting the drawing solution that penetrates the graphene oxide film; then the drawing solution is used as the next time The salt solution to be treated in the treatment process is filtered, the above steps are repeated, and continuous filtration is performed until a drawing solution that meets the standard is obtained, thereby completing the desalination process of the salt-containing aqueous solution.

本实施例基于连续过滤方法的盐离子自截留海水淡化技术,可在不大于5个大气压的过滤压力下,较好的实现海水脱盐,与传统超过50个大气压的反渗透海水淡化技术相比,大大减少了运行过程中能量的损耗,不需要特殊高耐压材料,显著降低运行成本,大大降低传统反渗透技术过程中的高压安全隐患,且该方法操作容易,运行条件简单,运行环境普适性强,适用于大规模海水、苦咸水淡化和工业高盐废水处理,且在化工、医药、电子等行业用水处理方面具有较高潜力。The salt ion self-retention seawater desalination technology based on the continuous filtration method in this embodiment can better achieve seawater desalination under the filtration pressure of not more than 5 atmospheres. Compared with the traditional reverse osmosis seawater desalination technology with a pressure of more than 50 atmospheres, It greatly reduces the energy loss during operation, does not require special high-pressure-resistant materials, significantly reduces operating costs, and greatly reduces the high-pressure safety hazards in the process of traditional reverse osmosis technology. The method is easy to operate, with simple operating conditions and a universal operating environment. It has strong properties and is suitable for large-scale seawater, brackish water desalination and industrial high-salt wastewater treatment, and has high potential for water treatment in chemical, pharmaceutical, electronic and other industries.

上面对本发明实施例结合附图进行了说明,但本发明不限于上述实施例,还可以根据本发明的发明创造的目的做出多种变化,凡依据本发明技术方案的精神实质和原理下做的改变、修饰、替代、组合或简化,均应为等效的置换方式,只要符合本发明的发明目的,只要不背离本发明的技术原理和发明构思,都属于本发明的保护范围。The embodiments of the present invention have been described above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and various changes can also be made according to the purpose of the invention and creation of the present invention. Changes, modifications, substitutions, combinations or simplifications should be equivalent substitution methods, as long as they meet the purpose of the present invention, as long as they do not deviate from the technical principles and inventive concepts of the present invention, all belong to the protection scope of the present invention.

Claims (8)

1. A salt ion self-interception seawater desalination method based on a continuous filtration method is characterized by comprising the following steps:
the method comprises the steps of taking a graphene oxide film as a filter membrane, wherein the graphene oxide film has a laminated structure made of composite materials, soaking the graphene oxide film in a saline A water solution to a swelling state, then carrying out forward pressure filtration on the graphene oxide film, wherein in the pressure filtration process, the pressure applied to the saline A water solution is 0.05-0.5 MPa, and extruding hydrated ions formed after the saline A in the graphene oxide film is dissolved by utilizing the applied pressure to deform the hydrated ions, so that the size of the hydrated ions entering the graphene oxide film is reduced, the distance between laminated layers in the film is reduced, the hydrated ions with larger size formed after the saline A in the solution is dissolved are intercepted, and a drawing liquid penetrating through the graphene oxide film is collected; and then, taking the drawing liquid as a saline solution to be treated in the next filtering treatment process, repeating the steps, and continuously filtering until the drawing liquid meeting the standard is obtained, thereby completing the desalting process of the saline solution.
2. The method for desalinating seawater by self-interception of salt ions according to claim 1, wherein the concentration of cations in the aqueous solution containing salt A is 0.015-0.6 mol/L.
3. The salt ion self-interception seawater desalination method based on the continuous filtration method as claimed in claim 1, wherein a water system microporous filter membrane with pore size not greater than 0.45 μm is used as a support base membrane of the graphene oxide film, the graphene oxide solution is subjected to suction filtration by a membrane suction filtration method, and the graphene oxide is deposited and intercepted on the water system microporous filter membrane used as the support base membrane, so as to prepare the graphene oxide film with composite lamellar structure and thickness of 100-2500 nm.
4. The salt ion self-interception seawater desalination method based on the continuous filtration method according to claim 3, wherein the concentration of the graphene oxide solution is 1-15 mg/mL in the preparation process of the graphene oxide film;
or in the preparation process of the graphene oxide film, the oxidation degree of graphene oxide in the graphene oxide solution is 20-55%.
5. The method for desalinating the seawater by self-interception of salt ions based on the continuous filtration method according to claim 1, wherein in the infiltration process, the temperature of the aqueous solution containing salt A to be treated is controlled to be 15-25 ℃;
or, in the soaking process, the soaking time is controlled to be 0.2-1 h.
6. The method for desalinating seawater by self-interception of salt ions according to claim 1, wherein said ions in said aqueous solution containing salt a comprise any one or more ions selected from the group consisting of inorganic cations and inorganic anions.
7. The method for desalinating seawater by self-interception of salt ions according to claim 6, wherein said inorganic cation is Mg2+、Zn2+、Ca2+、Li+、K+、Na+、NH4 +Any one or any plurality of ions of (a);
alternatively, the inorganic anion is F-、Cl-、Br-、I-、PO4 3-、SO4 2-、CO3 2-、NO3 -Any one or any plurality of ions of (a);
or the pH value of the salt A-containing aqueous solution is 6-13.
8. The method for desalinating seawater by self-interception of salt ions based on a continuous filtration process according to claim 6, wherein said salt A comprising an aqueous salt A solution is a salt A comprising NaCl, KCl, LiCl, MgCl2And CaCl2Any one or any plurality of salts of (a).
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