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CN101100340A - Method and device for producing pharmaceutical water by membrane separation and electrodeionization - Google Patents

Method and device for producing pharmaceutical water by membrane separation and electrodeionization Download PDF

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CN101100340A
CN101100340A CNA2007100585918A CN200710058591A CN101100340A CN 101100340 A CN101100340 A CN 101100340A CN A2007100585918 A CNA2007100585918 A CN A2007100585918A CN 200710058591 A CN200710058591 A CN 200710058591A CN 101100340 A CN101100340 A CN 101100340A
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electrodeionization
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softening
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CN100551848C (en
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王建友
卢会霞
傅学起
付林
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Tianjin Zhongling Water System Technology Co ltd
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Nankai University
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Abstract

一种集膜分离与电去离子生产制药用水的方法与装置,属于纯水制备技术。以城市自来水为原水,依次经低压膜过滤、活性炭吸附、精密过滤、纳滤软化脱盐、电去离子深度软化、电去离子深度除盐、功能荷电膜过滤等水处理工艺,有效去除水中的各种无机离子、有机污染物以及细菌病毒等微生物,得到制药用纯水、超纯水。与现有技术相比,该制水工艺的原水利用率得到有效提高,制水成本则明显降低。整个制水系统避免了化学再生型的软化与去离子手段,不消耗任何酸碱,不排放环境危害性污染物,能够适应更宽广范围的原水条件,在高效可靠、高水利用率、连续化、环境友好的前提下生产制药用纯水、超纯水。

Figure 200710058591

The invention discloses a method and device for producing pharmaceutical water through membrane separation and electrodeionization, belonging to pure water preparation technology. Taking urban tap water as raw water, it undergoes water treatment processes such as low-pressure membrane filtration, activated carbon adsorption, precision filtration, nanofiltration softening and desalination, deep softening of electrodeionization, deep deionization of electrodeionization, and functional charged membrane filtration to effectively remove pollutants in the water. Various inorganic ions, organic pollutants, bacteria, viruses and other microorganisms can be used to obtain pure water and ultrapure water for pharmaceutical use. Compared with the prior art, the raw water utilization rate of the water production process is effectively improved, and the water production cost is obviously reduced. The whole water production system avoids chemical regeneration softening and deionization methods, does not consume any acid and alkali, does not discharge environmentally harmful pollutants, and can adapt to a wider range of raw water conditions. , Production of pure water and ultrapure water for pharmaceutical use under the premise of environmental friendliness.

Figure 200710058591

Description

集膜分离与电去离子生产制药用水的方法与装置Method and device for producing pharmaceutical water by membrane separation and electrodeionization

技术领域technical field

本发明涉及一种集膜分离与电去离子生产制药用水的方法与装置,属于纯水制备技术。The invention relates to a method and a device for producing pharmaceutical water through membrane collection separation and electrodeionization, belonging to pure water preparation technology.

背景技术Background technique

制取药用水的现有工艺中,具有代表性的有以下三类:一是以离子交换技术为核心的工艺,二是以电渗析、反渗透等膜技术与离子交换相结合的工艺,三是以两级反渗透为核心的工艺。前两种主要用于纯化水(精制水)的生产,第三种工艺除可生产纯化水外,在一些国家也被允许用来生产注射用水。随着膜分离技术的不断发展与成熟,膜技术已经成为纯水制备的最通用和最经济的手段,在纯水制造的各个阶段不断以膜技术代替传统的水处理工艺,是现代纯水技术的发展趋势。Among the existing processes for preparing medicinal water, there are three representative types: one is the process with ion exchange technology as the core, and the other is the process of combining electrodialysis, reverse osmosis and other membrane technologies with ion exchange. The third is the process with two-stage reverse osmosis as the core. The first two are mainly used for the production of purified water (purified water). The third process is not only able to produce purified water, but also allowed to produce water for injection in some countries. With the continuous development and maturity of membrane separation technology, membrane technology has become the most versatile and economical means of pure water production. In all stages of pure water production, membrane technology is continuously used to replace traditional water treatment processes. It is a modern pure water technology. development trend.

由于任何一种膜分离技术都与传统分离技术一样,都存在各自特定的技术边界和经济边界,都只在一些特定的分离对象和工况条件下才体现出自身的显著优势,因此对于医药用水的制备等复杂的分离问题,需要采用膜技术与传统工艺,以及不同的膜技术之间优化组合,构成高效的集成膜过程,以充分发挥各分离技术的优势,实现最佳的工艺搭配和最低的经济投资,使过程最优化。Since any kind of membrane separation technology, like traditional separation technology, has its own specific technical boundaries and economic boundaries, and only shows its own significant advantages under some specific separation objects and working conditions, so for medical water Complicated separation problems such as the preparation of membranes require the use of membrane technology and traditional processes, as well as the optimal combination of different membrane technologies to form an efficient integrated membrane process, so as to give full play to the advantages of each separation technology and achieve the best process matching and the lowest Economical investment to optimize the process.

发明专利ZL99111578.3提供了一种制药用水的生产工艺及设备,集超滤、反渗透、电去离子、荷电微孔滤膜四种膜分离技术为一体,原水先后经超滤预处理、反渗透初级脱盐、电去离子(EDI)深度脱盐及荷电微孔滤膜终端过滤的流程而得到制药用水。该设计工艺的主要不足有以下两点:Invention patent ZL99111578.3 provides a production process and equipment for pharmaceutical water, which integrates four membrane separation technologies: ultrafiltration, reverse osmosis, electrodeionization, and charged microporous membrane. Raw water is pretreated by ultrafiltration, Reverse osmosis primary desalination, electrodeionization (EDI) deep desalination and charged microporous membrane terminal filtration process to obtain pharmaceutical water. The main deficiency of this design process has the following two points:

(1)采取反渗透为电去离子的前处理,成本高,水利用率偏低。尤其对小规模的制水系统而言,原水浪费较高。(1) Reverse osmosis is used as the pretreatment of electrodeionization, which has high cost and low water utilization rate. Especially for small-scale water production systems, the waste of raw water is high.

对于医药用纯水,一般并不要求非常高的无机离子去除率,其产品水的电导率一般达到1μS/cm即可,如美国药典规定的指标即为1.3μS/cm。由于通常的一级反渗透技术不能直接获得电导率1μS/cm左右的纯水,因此必须和离子交换或者电去离子技术相结合,这种组合可以容易地获得电导率0.1μS/cm以下的高纯水。然而,采用反渗透技术为离子交换或者电去离子技术的前处理,需要采用高压反渗透泵,运行压力较高,电能消耗和制水系统投资成本偏高,不利于该技术的推广应用;但更关键的问题在于,采用反渗透工艺使得水利用率往往过低。产水量数升至数十升/小时的实验室规模反渗透膜,其标准水利用率一般为15%,产水量数百升至数吨/小时的大型反渗透膜,单支膜的标准水利用率则更仅为8%。即使采取多支膜串联的方法,水利用率也不超过60%。这都导致了水资源的较大浪费。For pure water for medical use, a very high inorganic ion removal rate is generally not required, and the conductivity of the product water generally reaches 1 μS/cm, such as the index specified by the United States Pharmacopoeia is 1.3 μS/cm. Since the usual one-stage reverse osmosis technology cannot directly obtain pure water with a conductivity of about 1 μS/cm, it must be combined with ion exchange or electrodeionization technology. This combination can easily obtain high-purity water with a conductivity of less than 0.1 μS/cm . However, the use of reverse osmosis technology as the pretreatment of ion exchange or electrodeionization technology requires the use of high-pressure reverse osmosis pumps, high operating pressure, high power consumption and water system investment costs, which are not conducive to the popularization and application of this technology; but The more critical problem is that the use of reverse osmosis technology makes water utilization often too low. The standard water utilization rate of laboratory-scale reverse osmosis membranes with a water production rate ranging from several liters to tens of liters per hour is generally 15%. The utilization rate is only 8%. Even if the method of connecting multiple membranes in series is adopted, the water utilization rate does not exceed 60%. This has all resulted in a greater waste of water resources.

(2)以荷电微孔滤膜为终端过滤手段,制水系统运行不可靠,产品水质不安全。(2) With the charged microporous membrane as the terminal filtration method, the operation of the water production system is unreliable, and the product water quality is unsafe.

这种特殊的微孔滤膜在制作过程中以使用特定的荷电剂的方法使得膜的表面具有一定量的正电荷。由于水中的细菌、病毒、细菌内毒素带有负电荷,所以可以被吸附到荷正电微孔滤膜的表面而被截留,该膜的孔径最高可达1.6μm。然而这种微孔滤膜的使用同样又带来以下三个危险。一是吸附饱和具有不可预测性。由于不能实时确切地掌握膜表面的有效正电荷以及所处理的水溶液中细菌、病毒的含量,因此容易发生吸附饱和时膜仍在被使用的情况。此时,荷电膜表面已经不具备有效的正电荷;二是由于荷电膜的膜孔径比普通微孔滤膜要大2-8倍,因此当系统操作压力较大,水流速度较高时,静电引力很可能不足以捕获细菌和病毒,从而导致泄漏;三是荷正电微孔滤膜只适宜在弱酸性介质中使用。当处理溶液的pH为中性至碱性而大于膜的等电点时,荷电基团的电性就会发生改变从而使膜呈负电性。此时荷电膜不仅丧失靠静电引力分离杂质的能力,而且膜上所吸附的杂质还会被洗脱下来,反而使产品水杂质含量增高。电去离子(EDI)组件产水的典型pH值为中性,一定条件下pH值会接近7.5。在这种条件下,将荷电微孔滤膜用作终端过滤具有较大的不安全性。This special microporous filter membrane has a certain amount of positive charge on the surface of the membrane by using a specific charging agent during the production process. Because bacteria, viruses, and bacterial endotoxins in water are negatively charged, they can be adsorbed to the surface of a positively charged microporous membrane to be retained. The pore size of the membrane can reach up to 1.6 μm. However, the use of this microporous membrane also brings the following three dangers. One is that adsorption saturation is unpredictable. Since the effective positive charge on the surface of the membrane and the content of bacteria and viruses in the treated aqueous solution cannot be accurately grasped in real time, it is easy for the membrane to still be used when the adsorption is saturated. At this time, the surface of the charged membrane no longer has effective positive charges; secondly, because the membrane pore size of the charged membrane is 2-8 times larger than that of ordinary microporous membranes, when the system operating pressure is high and the water flow rate is high , electrostatic attraction may not be enough to capture bacteria and viruses, resulting in leakage; third, positively charged microporous membranes are only suitable for use in weakly acidic media. When the pH of the treatment solution is neutral to alkaline and greater than the isoelectric point of the membrane, the electrical properties of the charged groups change and the membrane becomes negatively charged. At this time, the charged membrane not only loses the ability to separate impurities by electrostatic attraction, but also the impurities adsorbed on the membrane will be eluted, which will increase the impurity content of the product water instead. The typical pH of the product water from an electrodeionization (EDI) module is neutral, with pH values approaching 7.5 under certain conditions. Under such conditions, it is unsafe to use charged microporous membranes as terminal filters.

此外,对杂质的吸附去除对于荷电膜而言相当于吸附污染。这使得必须在吸附饱和,即膜被污染后立即更换新膜,因此与制水系统中前三个工序不同的是,终端过滤工序不能长时间稳定运行,从而限制了系统的自动化、集成化程度,对生产效率带来了不利影响。In addition, the adsorption removal of impurities is equivalent to adsorption pollution for charged membranes. This makes it necessary to replace the new membrane immediately after the adsorption is saturated, that is, the membrane is polluted. Therefore, unlike the first three processes in the water production system, the terminal filtration process cannot run stably for a long time, which limits the degree of automation and integration of the system. , which adversely affects production efficiency.

发明内容Contents of the invention

本发明的目的是针对现有水处理工艺的不足,提供一种新型高效的全膜法集成膜过程超纯水生产工艺,有效去除水中的各种无机离子和有机污染物,在环境友好、高效、可靠、连续化的前提下生产药用水、超纯水,显著提高水资源利用率、降低制水系统的运行成本。The purpose of the present invention is to address the shortcomings of the existing water treatment process, to provide a new type of high-efficiency full-membrane integrated membrane process ultrapure water production process, which can effectively remove various inorganic ions and organic pollutants in the water, and is environmentally friendly and efficient. Production of medicinal water and ultra-pure water under the premise of high reliability, reliability and continuity can significantly improve the utilization rate of water resources and reduce the operating cost of the water system.

本发明的目的是通过下述技术方案加以实现的:The purpose of the present invention is achieved through the following technical solutions:

一种集膜分离与电去离子生产制药用水的方法,其特征在于包括以下水处理过程。A method for producing pharmaceutical water by collecting membrane separation and electrodeionization is characterized in that it includes the following water treatment process.

1、原水的低压膜过滤预处理过程1. Low-pressure membrane filtration pretreatment process of raw water

以符合国家标准GB5749-2006的城市自来水为原水,以0.1-0.4MPa的操作压力,将原水经过膜孔径为0.001--0.1μm的有机高分子超滤膜,或无机陶瓷超滤膜,或膜孔径为0.1-0.22μm的有机高分子微滤膜,或无机陶瓷微滤膜,进行截留、去除原水中的微粒、胶体、色素、铁锈、细菌等杂质的过滤预处理,所截留的杂质通过预处理过程的浓缩水排出,透过液则为净化水。Use urban tap water that conforms to the national standard GB5749-2006 as raw water, and pass the raw water through an organic polymer ultrafiltration membrane with a membrane pore size of 0.001--0.1μm, or an inorganic ceramic ultrafiltration membrane, or a membrane with an operating pressure of 0.1-0.4MPa Organic polymer microfiltration membranes with a pore size of 0.1-0.22 μm, or inorganic ceramic microfiltration membranes, perform filtration pretreatment to intercept and remove particles, colloids, pigments, rust, bacteria and other impurities in raw water, and the retained impurities pass through the pretreatment The concentrated water in the treatment process is discharged, and the permeate is purified water.

对于本发明,当原水水质较差,如浊度、色度较高时,则在低压膜过滤单元之前设置石英砂滤器,即将原水首先经过具有自动冲洗功能的石英砂滤器组件,其中装填有过滤介质为0.4-1.0mm的石英砂,然后再进入低压膜过滤组件,从而能有效减轻低压膜滤器的通量衰减情况。For the present invention, when the raw water quality is poor, such as turbidity and chromaticity are high, a quartz sand filter is set before the low-pressure membrane filter unit, that is, the raw water first passes through a quartz sand filter assembly with automatic flushing function, which is filled with filter The medium is quartz sand of 0.4-1.0mm, and then enters the low-pressure membrane filter assembly, which can effectively reduce the flux attenuation of the low-pressure membrane filter.

2、预处理水的软化除盐过程2. Softening and desalination process of pretreated water

将经过上述步骤1预处理的水,首先经过颗粒大小为20-80目渗银颗粒活性炭或纤维活性炭吸附过滤,去除水中余氯、细菌、微生物,以及过滤介质为0.2-5μm的精密过滤器,去除0.2μm以上的颗粒物后,再以0.5-0.7MPa的操作压力,通过膜孔径为1-3nm的有机高分子纳滤膜,进行脱除包括水中二价及以上高价离子、分子量大于200的有机物、以及细菌、病毒、细菌内毒素等杂质的处理,得到纳滤软化水。The water pretreated in the above step 1 is firstly filtered through adsorption and filtration of silver-infiltrated granular activated carbon or fiber activated carbon with a particle size of 20-80 mesh to remove residual chlorine, bacteria, microorganisms, and a precision filter with a filter medium of 0.2-5 μm. After removing the particles above 0.2μm, the operating pressure of 0.5-0.7MPa passes through the organic polymer nanofiltration membrane with a membrane pore size of 1-3nm to remove organic substances including divalent and above high-valent ions and molecular weight greater than 200 in water , and the treatment of impurities such as bacteria, viruses, and bacterial endotoxins to obtain nanofiltration softened water.

对于本发明中的活性炭吸附过滤工艺,当系统产水量较小时,则使用渗银颗粒活性炭。渗银活性炭使得不仅对水中有机污染物有吸附作用,同时还具有杀菌功能,可保证活性炭在使用一定时间之后,不会出现因具有杀菌作用的余氯不存在而滋长细菌、以及亚硝酸盐含量增高的问题;而系统产水量较大,如超过10m3/h时,则使用纤维活性炭。纤维活性炭具有较颗粒活性炭更发达的微孔结构、巨大的表面积以及众多的官能团,吸附容量与吸附速度大大超过其它活性炭。同时,纤维活性炭具有较好的强度和形状,在水流冲击中不会产生装填松动和过分密实的现象,运行中不会产生沟流和床层显著沉降,再生时也更容易脱附,因而更适宜在大流量处理系统中使用。For the activated carbon adsorption and filtration process in the present invention, when the water output of the system is small, silver-infiltrated granular activated carbon is used. Silver-infiltrated activated carbon not only has adsorption effect on organic pollutants in water, but also has bactericidal function, which can ensure that after a certain period of use of activated carbon, bacteria will not grow due to the absence of bactericidal residual chlorine and nitrite content The problem of increased height; and the system has a large water production rate, such as more than 10m 3 /h, then use fiber activated carbon. Fiber activated carbon has a more developed microporous structure than granular activated carbon, a huge surface area and numerous functional groups, and its adsorption capacity and adsorption speed are much higher than other activated carbons. At the same time, fiber activated carbon has good strength and shape, and will not cause loose packing and over-compacting in the impact of water flow, and will not cause channeling and significant bed settlement during operation, and it is easier to desorb during regeneration, so it is more efficient. Suitable for use in large flow processing systems.

对于本发明,可使用的纳滤膜种类有醋酸纤维素-三醋酸纤维素(CA-CTA)膜、芳香聚酰胺复合膜和磺化聚醚砜膜等。For the present invention, the types of nanofiltration membranes that can be used include cellulose acetate-triacetate cellulose (CA-CTA) membranes, aromatic polyamide composite membranes, and sulfonated polyethersulfone membranes.

3、软化除盐水的深度软化过程3. Deep softening process of softening desalinated water

将经步骤2软化除盐的水,通过在淡水室中填充大孔强酸强碱性阴阳混床树脂,且其中阳树脂所占体积比例为0.7-1.0,阴树脂所占体积比例为0-0.3的深度软化电去离子(EDI)膜堆,在工作膜对电压为0.5-5V的操作条件下,去除软化除盐水中残余的Ca2+、Mg2+等二价和高价离子,以及部分其他一价离子,得到初级纯水。The water softened and desalinated in step 2 is filled with macroporous strong acid and strong basic anion and yang mixed bed resin in the fresh water chamber, and the volume ratio of the cation resin is 0.7-1.0, and the volume ratio of the anion resin is 0-0.3 The deep softening electrodeionization (EDI) membrane stack, under the operating condition of the working membrane pair voltage of 0.5-5V, removes divalent and high-valent ions such as Ca 2+ and Mg 2+ remaining in the softened desalinated water, as well as some other Monovalent ions, get primary pure water.

4、深度软化水的深度除盐过程4. Deep desalination process of deeply softened water

将经步骤3深度软化得到的初级纯水,通过在淡水室中填充均匀混床树脂,且其中阴:阳树脂比例为6∶4-2∶1的深度除盐电去离子(EDI)膜堆,在工作膜对电压为8-12V的条件下,进一步脱除水中残余的其他各种带电离子和杂质,得到电阻率16-18MΩ·cm的高电阻率深度除盐水。The primary pure water obtained through deep softening in step 3 is filled with uniform mixed bed resin in the fresh water chamber, and the deep desalination electrodeionization (EDI) membrane stack in which the anion: anion resin ratio is 6:4-2:1 , under the condition that the voltage of the working membrane is 8-12V, other various charged ions and impurities remaining in the water are further removed, and a high-resistivity deep desalinated water with a resistivity of 16-18MΩ·cm is obtained.

5、深度除盐水的荷电膜过滤过程5. Charged membrane filtration process of deep desalinated water

将经步骤4深度除盐的水,经以N,O-羧甲基壳聚糖为复合材料,聚醚砜微孔膜为基膜,经二次复合而得到的,在高分子骨架上既有弱酸性的-COOH基团,又有弱碱性的-NH2基团的功能羧甲基壳聚糖/聚醚砜(CM-CS/PES)复合超滤膜,或只进行一次复合而得到的CM-CS/PES荷电微滤膜,去除水中可能产生的颗粒物和滋生细菌,最终得到不含任何杂质的制药用水、超纯水。The water desalinated in depth in step 4 is obtained through secondary compounding with N, O-carboxymethyl chitosan as the composite material and polyethersulfone microporous membrane as the base membrane. Functional carboxymethyl chitosan/polyethersulfone (CM-CS/PES) composite ultrafiltration membrane with weakly acidic -COOH group and weakly basic -NH2 group, or only once compounded The obtained CM-CS/PES charged microfiltration membrane removes possible particles and bacteria in the water, and finally obtains pharmaceutical water and ultrapure water without any impurities.

实现上述方法所采用的装置,包括预处理单元中的低压膜过滤器、纳滤软化除盐装置、深度软化电去离子装置、深度除盐电去离子装置和荷电膜过滤装置。所述的深度软化电去离子装置结构主要包括膜堆、膜堆支撑装置、电极装置、夹紧装置四部分。夹紧装置由两块夹紧板和拉紧螺栓与螺母组成;在两张夹紧板内侧分别是正、负电极室与电极隔板组成的正、负电极装置;在正负电极之间是由相互粘连的矩形中空支撑边框板构成的膜堆支撑装置;在中空支撑边框板的中空腔体内是膜堆,膜堆的基本单元为膜对,每个膜对依次由阳离子交换膜、浓水室隔板、阴离子交换膜、淡水室隔板各一张组成,并在淡水室隔板中填充有离子交换树脂,其特征在于:在淡水室中填充的阴阳混床树脂,其类型为大孔型强酸强碱性离子交换树脂,其中阳树脂所占体积比例为0.7-1.0;淡水室隔板厚度为3-8mm且树脂粒径为0.4-0.9mm,平均工作膜对电压为1-5V。The devices used to realize the above method include a low-pressure membrane filter in the pretreatment unit, a nanofiltration softening and desalination device, a deep softening electrodeionization device, a deep desalination electrodeionization device and a charged membrane filtration device. The structure of the deep softening electrodeionization device mainly includes four parts: a membrane stack, a membrane stack supporting device, an electrode device, and a clamping device. The clamping device is composed of two clamping plates, tension bolts and nuts; inside the two clamping plates are positive and negative electrode devices composed of positive and negative electrode chambers and electrode separators; between the positive and negative electrodes is a The membrane stack support device is composed of rectangular hollow supporting frame plates that are adhered to each other; in the hollow cavity of the hollow supporting frame plate is a membrane stack, and the basic unit of the membrane stack is a membrane pair, each membrane pair is sequentially composed of a cation exchange membrane, a concentrated water chamber The separator, the anion exchange membrane, and the separator of the fresh water chamber are each composed of one piece, and the separator of the fresh water chamber is filled with ion exchange resin. Strong acid and strong base ion exchange resin, in which the volume ratio of cationic resin is 0.7-1.0; the thickness of the fresh water chamber partition is 3-8mm and the resin particle size is 0.4-0.9mm, and the average working membrane voltage is 1-5V.

本发明的各个膜分离水处理单元集成为一个整体,产生如下效果:Each membrane separation water treatment unit of the present invention is integrated into a whole to produce the following effects:

(1)避免了化学再生型的软化与去离子手段,不消耗任何酸碱,整个工艺不排放任何环境危害性污染物;(1) It avoids the softening and deionization means of chemical regeneration, does not consume any acid and alkali, and does not discharge any environmentally harmful pollutants in the whole process;

(2)与“两级反渗透”、“反渗透/电去离子”及“反渗透/离子交换”等其他技术相比,以“纳滤/电去离子/电去离子”为核心的制水工艺,水利用率有显著提高,系统投资则相应降低;(2) Compared with other technologies such as "two-stage reverse osmosis", "reverse osmosis/electrodeionization" and "reverse osmosis/ion exchange", the production centered on "nanofiltration/electrodeionization/electrodeionization" Water technology, the water utilization rate has been significantly improved, and the system investment has been reduced accordingly;

(3)每一组成部分都可实现长期连续运行,系统易于集成和自动化,不需设计备用系统,运行维护费用低;(3) Each component can realize long-term continuous operation, the system is easy to integrate and automate, no need to design a backup system, and the operation and maintenance costs are low;

(4)终端荷电膜过滤更为高效可靠,不会产生吸附和污染饱和。(4) Terminal charged membrane filtration is more efficient and reliable, without adsorption and pollution saturation.

显然,本发明所述的膜集成技术纯水生产工艺,其适用对象并不局限于制药用水。对于电子、电力、生物等其他工业部门和实验室研究领域的纯水制备,也是适用的。Apparently, the pure water production process of the membrane integration technology described in the present invention is not limited to pharmaceutical water. It is also applicable to the preparation of pure water in other industrial sectors and laboratory research fields such as electronics, electric power, and biology.

附图说明Description of drawings

图1为本发明所提供的集膜分离与电去离子生产制药用水的艺流程框图;Fig. 1 is the block diagram of the technological process of producing pharmaceutical water by membrane separation and electrodeionization provided by the present invention;

图2为实现发明的深度软化电去离子装置内部结构示意图,图3为实现本发明的深度除盐电去离子装置内部结构示意图,图中:Fig. 2 is a schematic diagram of the internal structure of the deep softening electrodeionization device for realizing the invention, and Fig. 3 is a schematic diagram of the internal structure of the deep desalination electrodeionization device for realizing the present invention, in the figure:

1-正电极;2-正极室;3-淡化室;4-浓缩室;5-负极室;6-负电极;7-阴树脂;8-阳树脂;9-膜对;1-Positive electrode; 2-Positive electrode chamber; 3-Desalination chamber; 4-Concentration chamber; 5-Negative electrode chamber; 6-Negative electrode; 7-Anion resin;

图4为本发明所提供的一种实施例装置的具体流程结构图,图中:Fig. 4 is the specific flow chart of a kind of embodiment device provided by the present invention, in the figure:

10-原水;11-截止阀;12-增压泵;13-电磁阀;14-压力表;15-超滤膜组件;16-超滤净化水;17-超滤浓缩水;18-活性炭吸附滤器;19-精密过滤器;20-纳滤高压泵;21-纳滤膜组件;22-纳滤软化水;23-纳滤浓缩水;24-深度软化电去离子组件;25-深度软化电去离子电极水;26-深度软化电去离子产品水;27-深度软化电去离子浓缩水;28-单向阀;29-深度除盐电去离子组件;30-深度除盐电去离子电极水;31-深度除盐电去离子产品水;32-深度除盐电去离子浓缩水;33-荷电膜过滤组件;34-荷电膜浓缩水;35-在线电阻率仪;36-超纯产品水;37-装置总排放水;10-raw water; 11-stop valve; 12-booster pump; 13-solenoid valve; 14-pressure gauge; 15-ultrafiltration membrane module; 16-ultrafiltration purified water; 17-ultrafiltration concentrated water; 18-activated carbon adsorption Filter; 19-precision filter; 20-nanofiltration high-pressure pump; 21-nanofiltration membrane module; 22-nanofiltration softened water; 23-nanofiltration concentrated water; Deionized electrode water; 26-deeply softened electrodeionized product water; 27-deeply softened electrodeionized concentrated water; 28-one-way valve; 29-deeply deionized electrodeion components; 30-deeply deionized electrode Water; 31-Deep deionization product water; 32-Deep deionization concentrated water; 33-Charged membrane filter module; 34-Charged membrane concentrated water; 35-Online resistivity meter; 36-Ultra Pure product water; 37-the total discharge water of the device;

具体实施方式Detailed ways

下面结合附图及实施例对本发明作进一步描述。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

图4所提供的实施例中,采用城市自来水为原水,先后经过超滤与渗银颗粒活性炭、精密过滤联合工艺净化,下游的软化除盐单元采取一级纳滤膜分离组件,深度软化及除盐单元采用两级电去离子组件,终端过滤为抗污染荷电超滤膜组件。其中,超滤为两支HYDRAcap40-LD组件并联,单支稳定产水量1.2m3/h,共产水2.4m3/h;纳滤采用三支HL4040FF组件串联,产水量1.8m3/h;深度软化电去离子装置采用的淡水室隔板规格为200*400*3mm,膜对数为40,其软化产品水、浓缩水和电极水流量分别为1.5m3/h、0.25m3/h和0.05m3/h;深度除盐电去离子装置的膜对数为36,其淡化产品水、浓缩水和电极水流量分别为1.3m3/h、0.15m3/h和0.05m3/h;终端荷电膜过滤组件的产品水和浓缩水流量分别为1.2m3/h和0.1m3/h。整个系统正常运行时的水利用率为71%。In the example provided in Figure 4, city tap water is used as raw water, which is purified by ultrafiltration, silver-infiltrated granular activated carbon, and precision filtration. The salt unit adopts two-stage electrodeionization components, and the terminal filter is an anti-pollution charged ultrafiltration membrane component. Among them, ultrafiltration is two HYDRAcap40-LD modules connected in parallel, with a single stable water production of 1.2m 3 /h and a total water production of 2.4m 3 /h; nanofiltration uses three HL4040FF modules in series, with a water production of 1.8m 3 /h; depth The size of the fresh water chamber partition used in the softening electrodeionization device is 200*400*3mm, and the number of membrane pairs is 40. The flow rates of softened product water, concentrated water and electrode water are 1.5m 3 /h, 0.25m 3 /h and 0.05m 3 /h; the membrane logarithm of the deep desalination electrodeionization device is 36, and the flow rates of desalinated product water, concentrated water and electrode water are 1.3m 3 /h, 0.15m 3 /h and 0.05m 3 /h respectively ; The product water and concentrated water flows of the terminal charged membrane filtration module are 1.2m 3 /h and 0.1m 3 /h respectively. The water utilization rate of the whole system during normal operation is 71%.

左超滤器前设置有增压泵12和压力表14。若原水10的水压较高,超滤组件将直接工作;若原水水压较低,增压泵将自动启动;若水源供应不足,原水水压过低,则超滤泵将自动停止工作,系统电源自动切断以保护制水系统的安全性。A booster pump 12 and a pressure gauge 14 are arranged before the left ultrafilter. If the water pressure of the raw water 10 is high, the ultrafiltration unit will work directly; if the raw water pressure is low, the booster pump will automatically start; if the water supply is insufficient and the raw water pressure is too low, the ultrafiltration pump will automatically stop working. The system power is automatically cut off to protect the safety of the water system.

预处理中的两支超滤膜组件15,还可以通过5个电磁阀13之间的相互配合,在PLC程序控制下实现自动相互反冲洗,即在反冲洗的前半个周期,利用其中一个组件的净化水对另一个组件实施反冲洗,冲洗时间可事先设定;在后半个周期,则反之;全部反冲洗完成,则除超滤产水电磁阀以外的4个电磁阀均打开,对两支超滤组件进行正冲洗,冲洗时间也可事先设定。全部冲洗完成,两支超滤组件的浓缩水排放电磁阀关闭,产水电磁阀打开,进入正常制水工序。超滤浓缩水17直接排放,超滤净化水16经活性炭吸附滤器18和精密过滤器19进入纳滤单元。The two ultrafiltration membrane modules 15 in the pretreatment can also realize automatic mutual backwashing under the control of the PLC program through the mutual cooperation between the five solenoid valves 13, that is, in the first half cycle of backwashing, one of the components is used The purified water backwashes another component, and the flushing time can be set in advance; in the second half cycle, the opposite is true; when all backwashing is completed, all four solenoid valves except the ultrafiltration water solenoid valve are opened, and the The two ultrafiltration components perform positive flushing, and the flushing time can also be set in advance. After all flushing is completed, the concentrated water discharge solenoid valves of the two ultrafiltration components are closed, and the produced water solenoid valves are opened to enter the normal water production process. The ultrafiltration concentrated water 17 is directly discharged, and the ultrafiltration purified water 16 enters the nanofiltration unit through the activated carbon adsorption filter 18 and the precision filter 19 .

纳滤组件前设有动力泵20和耐震压力表14。3支纳滤膜组件以1-1-1方式串联排列,即将上一支组件的浓缩水作为下一支组件的进水。纳滤浓缩水23排放。在精密过滤器19和纳滤泵29之间设置低压保护开关LP。当上游发生故障或原水供应故障时,低压开关LP将自动感应并切断纳滤泵和系统电源,保护制水系统;在最后一支纳滤膜组件和浓缩水排放截止阀11、电磁阀14之间管路上则设置高压开关HP。当因浓水排放阀误操作或意外故障不能打开,导致管路中压力骤然升高时,高压开关HP将同样自动切断纳滤泵和系统电源,保护装置免受损坏。A power pump 20 and a shock-resistant pressure gauge 14 are arranged in front of the nanofiltration module. Three nanofiltration membrane modules are arranged in series in a 1-1-1 manner, and the concentrated water of the previous module is used as the water inlet of the next module. Nanofiltration concentrated water 23 is discharged. A low pressure protection switch LP is provided between the precision filter 19 and the nanofiltration pump 29 . When the upstream fails or the raw water supply fails, the low pressure switch LP will automatically sense and cut off the power supply of the nanofiltration pump and the system to protect the water system; A high pressure switch HP is set on the inter-pipeline. When the concentrated water discharge valve cannot be opened due to misoperation or accidental failure, resulting in a sudden increase in the pressure in the pipeline, the high pressure switch HP will also automatically cut off the power supply of the nanofiltration pump and the system to protect the device from damage.

在纳滤泵启动初期,浓水排放电磁阀14打开,对纳滤系统进行正冲洗。到冲洗时间完成时,电磁阀关闭,纳滤系统的排放水量由截止阀11手工调整。At the initial stage of starting the nanofiltration pump, the concentrated water discharge solenoid valve 14 is opened to positively flush the nanofiltration system. When the flushing time is completed, the electromagnetic valve is closed, and the discharge water volume of the nanofiltration system is manually adjusted by the shut-off valve 11.

纳滤软化水22一分为三,进入下游的深度软化电去离子组件24,后者的电极水25排放;浓缩水27通过单向阀28回收至活性炭滤器18之前,实际为纳滤的进水;深度软化电去离子的产品水26则再次分为三股水流,进入深度除盐电去离子组件29。该组件的电极水30也直接排放,浓缩水32同样通过一个单向阀28回收至活性炭滤器18之前。深度除盐电去离子组件的产品水31进入下游荷电膜终端过滤组件33,最终不含任何杂质的超纯产品水36,其电阻率通过一个在线电阻率仪35实时监测。荷电膜过滤组件33的浓缩水34亦通过一个单向阀28回收至活性炭滤器18之前,。The nanofiltration demineralized water 22 is divided into three parts, and enters the downstream deep softening electrodeionization module 24, and the electrode water 25 of the latter is discharged; the concentrated water 27 is recycled to the activated carbon filter 18 through the check valve 28, and is actually a nanofiltration process. water; the deeply softened electrodeionized product water 26 is divided into three streams again and enters the deep desalination electrodeionization component 29 . The electrode water 30 of this assembly is also discharged directly, and the concentrated water 32 is also recovered before the activated carbon filter 18 through a one-way valve 28 . The product water 31 of the deep desalination electrodeionization module enters the downstream charged membrane terminal filter module 33, and finally ultra-pure product water 36 without any impurities, whose resistivity is monitored by an online resistivity meter 35 in real time. The concentrated water 34 of the charged membrane filter module 33 is also recycled to before the activated carbon filter 18 through a one-way valve 28 .

超滤、纳滤和两级电去离子的电极水的全部排放水,最终收集、混合为一体,由装置的总排放水口37排放。All the discharge water of the electrode water of ultrafiltration, nanofiltration and two-stage electrodeionization is finally collected and mixed into one, and discharged from the general discharge water port 37 of the device.

该具体实施例中,具备自反冲洗、自动排污功能的超滤膜过滤预处理除去了原水中的颗粒、微粒、胶体、铁锈、色素等,保证产水的污染指数可降至3以下,此外同时去除掉了可能导致下游的活性炭很快达到吸附饱和的有机物、微生物等杂质,从而为其提供了有效保护。活性炭主要用于在纳滤之前除去对下游膜工艺有害的余氯,同时进一步降低有机物的含量。虽然活性炭不具备自动排污功能,但由于具备有效的前置超滤膜过滤,其使用周期得到了大大延长。超滤膜过滤和活性炭的联合预处理为纳滤膜提供了可靠的进水条件,减轻了纳滤膜被污染的可能性。In this specific embodiment, the ultrafiltration membrane filtration pretreatment with self-backwashing and automatic sewage discharge functions removes particles, particles, colloids, rust, pigments, etc. in the raw water, ensuring that the pollution index of the produced water can be reduced to below 3. In addition At the same time, impurities such as organic matter and microorganisms that may cause the downstream activated carbon to quickly reach adsorption saturation are removed, thereby providing effective protection for it. Activated carbon is mainly used to remove residual chlorine that is harmful to downstream membrane processes before nanofiltration, while further reducing the content of organic matter. Although activated carbon does not have the function of automatic sewage discharge, its service life has been greatly extended due to the effective pre-ultrafiltration membrane filtration. The combined pretreatment of ultrafiltration membrane filtration and activated carbon provides reliable water inlet conditions for nanofiltration membranes and reduces the possibility of nanofiltration membranes being polluted.

系统中的一级纳滤膜软化除盐,其总脱盐率为60%,对不利于下游的电去离子组件的钙镁硬度离子及其他高价离子的脱除率则达到93.6%,同时还可去除分子量200以上的有机物以及微量的滋生细菌,为下游电去离子单元提供了最佳的保护。由于纳滤膜的操作压力为0.5-0.7MPa,显著低于反渗透膜的操作压力,因此与相同产水量的反渗透装置相比,纳滤系统所用高压泵的成本和电能消耗也相应得到降低。更主要的是,该一级纳滤系统的浓水排放量为0.6m3/h,水利用率为75%。若采用一级反渗透工艺,则水利用率最高仅为50%。可见,本发明提供的水处理新工艺水资源利用效率得到显著提高。The first-stage nanofiltration membrane in the system softens and removes salt, with a total desalination rate of 60%, and a removal rate of 93.6% for calcium, magnesium, hardness ions and other high-priced ions that are not conducive to downstream electrodeionization components. It removes organic matter with a molecular weight above 200 and a small amount of bacterial growth, providing the best protection for the downstream electrodeionization unit. Since the operating pressure of the nanofiltration membrane is 0.5-0.7MPa, which is significantly lower than that of the reverse osmosis membrane, the cost and power consumption of the high-pressure pump used in the nanofiltration system are correspondingly reduced compared with the reverse osmosis device with the same water production capacity. . More importantly, the concentrated water discharge of the primary nanofiltration system is 0.6m 3 /h, and the water utilization rate is 75%. If the first-stage reverse osmosis process is adopted, the highest water utilization rate is only 50%. It can be seen that the water resource utilization efficiency of the new water treatment process provided by the present invention is significantly improved.

纳滤软化水经特种电去离子深度软化单元进一步除硬脱盐,其残余硬度离子去除率高于99%,总脱盐率高于92%,出水中Ca2+和Mg2+总含量仅为0.01mg·L-1。该电去离子深度软化装置中,在膜堆的淡水室中填充的树脂以阳离子交换树脂为主,少量掺杂阴离子交换树脂,其中阳树脂所占体积分数为0.85,工作膜对电压为2V,即总膜堆电压为80V。在淡水室中填充的树脂为具有窄粒径分布的D072大孔强酸性和D296大孔强碱性树脂,所用树脂粒径为0.4-0.9mm。采用这种粒径分布窄的树脂,较0.3-1.2mm标准粒径分布的树脂有更低的水流阻力和流体力学特性,除盐过程可快速达到稳态。The nanofiltration softened water is further hardened and desalinated by the special electrodeionization deep softening unit, the residual hardness ion removal rate is higher than 99%, the total desalination rate is higher than 92%, and the total content of Ca 2+ and Mg 2+ in the effluent is only 0.01 mg·L -1 . In this electrodeionization deep softening device, the resin filled in the fresh water chamber of the membrane stack is mainly cation exchange resin, and a small amount of anion exchange resin is doped, wherein the volume fraction of cation resin is 0.85, and the working membrane pair voltage is 2V. That is, the total membrane stack voltage is 80V. The resins filled in the fresh water chamber are D072 macroporous strongly acidic and D296 macroporous strongly basic resins with narrow particle size distribution, and the used resin particle size is 0.4-0.9mm. Using this kind of resin with a narrow particle size distribution has lower water flow resistance and hydrodynamic properties than resins with a standard particle size distribution of 0.3-1.2mm, and the desalination process can quickly reach a steady state.

电去离子深度软化单元的浓缩水回收到上游纳滤膜过滤单元的进水,因此该单元仅有极少量的电极水排放,水利用率达到97.2%。与传统的阳离子交换树脂软化技术相比,电去离子深度软化彻底避免了使用化学药剂对树脂的周期性再生,不产生任何环境危害性废液,又使过程持续运行,显著提高了生产效率和产水水质。The concentrated water of the electrodeionization deep softening unit is recycled to the inlet water of the upstream nanofiltration membrane filtration unit, so the unit only discharges a very small amount of electrode water, and the water utilization rate reaches 97.2%. Compared with the traditional cation exchange resin softening technology, the deep softening of electrodeionization completely avoids the periodic regeneration of the resin with chemicals, does not produce any environmentally harmful waste liquid, and keeps the process running continuously, significantly improving production efficiency and Produced water quality.

电去离子深度软化单元的淡化水由于硬度离子含量极低,保证了下游电去离子深度除盐单元不会产生结垢危险,而其并不很低的电导率则使得电去离子深度除盐单元能保持适宜的的工作电流,从而确保出水水质达到超纯水水平。深度除盐电去离子单元在各淡水室中填充的树脂为凝胶型001×7、201×7混床树脂,二者的体积比为1∶2。装置的工作膜对电压为10V,即总膜堆电压为360V,其产水电阻率达到超过了17.5MΩ·cm。Due to the extremely low content of hardness ions in the desalinated water of the electrodeionization deep softening unit, it ensures that the downstream electrodeionization deep desalination unit will not cause scaling risks, and its not very low conductivity makes the electrodeionization deep desalination The unit can maintain an appropriate working current to ensure that the quality of the effluent water reaches the level of ultra-pure water. The resins filled in each fresh water chamber of the deep desalination electrodeionization unit are gel-type 001×7 and 201×7 mixed-bed resins, and the volume ratio of the two is 1:2. The working membrane pair voltage of the device is 10V, that is, the total membrane stack voltage is 360V, and the resistivity of the produced water exceeds 17.5MΩ·cm.

与上游电去离子深度软化单元相似,电去离子深度除盐单元的浓缩水亦回收至纳滤膜过滤的进水,排放的电极水则仅为50升/小时,因此水利用率达到96.7%。该实施例中独特的两级电去离子串联工艺实现了在不消耗任何酸碱的条件下连续制取超纯水,不排放污染性废水,消除了环境污染。Similar to the upstream electrodeionization deep softening unit, the concentrated water of the electrodeionization deep desalination unit is also recycled to the influent water filtered by the nanofiltration membrane, and the discharged electrode water is only 50 liters per hour, so the water utilization rate reaches 96.7% . The unique two-stage electrodeionization series process in this embodiment realizes the continuous production of ultrapure water without consuming any acid and alkali, does not discharge polluting waste water, and eliminates environmental pollution.

实施例中的终端荷电膜过滤单元,所采用的荷电膜为CM-CS/PES复合超滤膜,其高分子骨架上既有弱酸性的-COOH基团,又有弱碱性的-NH2基团,因此同时带有数量众多而位置固定的正负电荷,但其流动电位呈负值。含有细菌和细菌内毒素的水通过这种荷电膜进行过滤时,这些杂质就因为强烈的静电排斥作用而不能达到膜的表面,从而不能透过膜而是从浓缩水中被排出。因此,该功能荷电膜具有非常优异的抗污染性能,不存在吸附/污染饱和的问题,因此确保了对细菌、细菌内毒素等微生物的绝对截留,从而可以连续、长期使用,也保证了整个制水系统的长期、稳定、连续运行。In the terminal charged membrane filtration unit in the embodiment, the charged membrane used is a CM-CS/PES composite ultrafiltration membrane, and its polymer skeleton has both weakly acidic -COOH groups and weakly basic - The NH2 group therefore has a large number of positive and negative charges with fixed positions at the same time, but its streaming potential is negative. When water containing bacteria and bacterial endotoxins is filtered through this charged membrane, these impurities cannot reach the surface of the membrane due to strong electrostatic repulsion, so they cannot pass through the membrane but are discharged from the concentrated water. Therefore, the functional charged membrane has very excellent anti-pollution performance, and there is no problem of adsorption/pollution saturation, so it ensures the absolute interception of microorganisms such as bacteria and bacterial endotoxins, so that it can be used continuously and for a long time, and also ensures the entire Long-term, stable and continuous operation of the water system.

由于终端的荷电膜处理对象中杂质含量已经极低,其浓缩水所占比例很小,且与上游两级电去离子装置的浓缩水一样,回收至纳滤膜的进水,因此该单元实际无任何废水排放,水利用率为100%。Since the impurity content of the charged membrane treatment object at the terminal is already extremely low, the concentrated water accounts for a very small proportion, and it is the same as the concentrated water of the upstream two-stage electrodeionization device, which is recycled to the feed water of the nanofiltration membrane, so the unit There is actually no waste water discharge, and the water utilization rate is 100%.

下表给出了图4所示实施例中各工艺阶段的产水量和典型水质参数。The following table shows the water yield and typical water quality parameters of each process stage in the embodiment shown in Fig. 4 .

  产水量m3/hWater production m 3 /h     电导率μS/cm Conductivity μS/cm  Ca2+、Mg2+总含量mg·L-1 Ca 2+ , Mg 2+ total content mg·L -1     电阻率MΩ·cm Resistivity MΩ cm   超滤净化水 Ultrafiltration water purification   2.4 2.4     466 466  18.7 18.7     -- --   纳滤软化水 Nanofiltration softened water   1.8 1.8     190 190  1.2 1.2     -- --   深度软化水 Deeply softened water   1.5 1.5     14 14  0.010 0.010     -- --   深度除盐水 Deeply demineralized water   1.3 1.3     0.056 0.056  -- --     17.78 17.78   超纯产品水   Ultra pure product water   1.2 1.2     0.056 0.056  -- --     17.71 17.71

从水质分析数据可见,深度软化电去离子过程对纳滤软化水残余的Ca2+、Mg2+离子去除率超过99%,总脱盐率超过92%,对下游深度除盐电去离子过程制备高电阻率纯水起到了关键作用。It can be seen from the water quality analysis data that the deep softening and electrodeionization process can remove more than 99% of Ca 2+ and Mg 2+ ions in nanofiltration softened water, and the total desalination rate is more than 92%. High-resistivity pure water plays a key role.

Claims (4)

1、一种集膜分离与电去离子生产制药用水的方法,其特征在于以城市自来水为原水,依次经过以下的水处理过程而得到制药用水、超纯水:1. A method for producing pharmaceutical water by membrane separation and electrodeionization, characterized in that city tap water is used as raw water, and the following water treatment processes are followed successively to obtain pharmaceutical water and ultrapure water: (1)采用膜孔径为0.001-0.1μm的有机高分子超滤膜,或无机陶瓷超滤膜,或膜孔径为0.1-0.22μm的有机高分子微滤膜,或无机陶瓷微滤膜的低压膜过滤组件,在0.1-0.4MPa的压力下对原水进行膜过滤净化预处理;(1) Use organic polymer ultrafiltration membranes with a membrane pore size of 0.001-0.1 μm, or inorganic ceramic ultrafiltration membranes, or organic polymer microfiltration membranes with a membrane pore size of 0.1-0.22 μm, or the low pressure of inorganic ceramic microfiltration membranes Membrane filtration module, under the pressure of 0.1-0.4MPa, the raw water is pretreated by membrane filtration and purification; (2)采用颗粒大小为20-80目的渗银颗粒活性炭或纤维活性炭吸附组件对经步骤(1)预处理所得的水进行吸附过滤,然后用过滤介质为0.2-5μm的精密过滤器进行过滤,再在0.5-0.7MPa的操作压力下用膜孔径为1-3nm的纳滤膜分离工艺对经上述处理的水进行软化除盐;(2) adopt particle size to be 20-80 purpose silver-infiltrated granular activated carbon or fiber activated carbon adsorption assembly to carry out adsorption filtration to the water obtained through the pretreatment of step (1), then filter with the precision filter that filter medium is 0.2-5 μm, Then, under the operating pressure of 0.5-0.7MPa, the nanofiltration membrane separation process with a membrane pore size of 1-3nm is used to soften and desalinate the above-mentioned treated water; (3)采用电去离子深度软化工艺,在工作膜对电压为0.5-5V的操作条件下对经步骤(2)所得的纳滤软化水进行深度软化和进一步除盐;(3) Using the electrodeionization deep softening process, the nanofiltration demineralized water obtained in step (2) is deeply softened and further desalted under the operating condition that the working membrane voltage is 0.5-5V; (4)采用电去离子深度除盐工艺,在工作膜对电压为6-12V的操作条件下对经步骤(3)所得的深度软化水进行深度除盐;(4) Using the electrodeionization deep desalination process, under the operating condition that the working membrane voltage is 6-12V, the deep demineralized water obtained in step (3) is deeply demineralized; (5)采用荷电滤膜组件对经步骤(4)所得的深度除盐水进行终端过滤。(5) Perform terminal filtration on the deeply desalted water obtained in step (4) by using a charged membrane filter module. 2、根据权利要求1所述的集膜分离与电去离子生产制药用水的方法,其特征还在于步骤(5)中所述的荷电滤膜组件所采用的荷电膜,是以聚醚砜微孔膜为基膜,以N,O-羧甲基壳聚糖为复合材料,经一次或二次复合而制得的羧甲基壳聚糖/聚醚砜(CM-CS/PES)复合膜。2. The method for producing pharmaceutical water by membrane separation and electrodeionization according to claim 1, further characterized in that the charged membrane used in the charged membrane module described in step (5) is made of polyether Carboxymethyl chitosan/polyether sulfone (CM-CS/PES) made of sulfone microporous membrane as the base membrane and N,O-carboxymethyl chitosan as the composite material after one or two composites Composite film. 3、一种集膜分离与电去离子生产制药用水的装置,包括低压膜过滤器、纳滤软化除盐装置、深度软化电去离子装置、深度除盐电去离子装置和荷电膜过滤装置,其特征在于,所述的深度软化电去离子装置的膜堆各淡水室中填充的树脂为大孔强酸强碱性树脂,且其粒径为0.4-0.9mm,同时阳树脂在总树脂体积中所占比例为70-100%。3. A device for producing pharmaceutical water with membrane separation and electrodeionization, including a low-pressure membrane filter, nanofiltration softening and desalination device, deep softening and electrodeionization device, deep desalination and electrodeionization device, and a charged membrane filtration device , it is characterized in that, the resin filled in each fresh water chamber of the membrane stack of the deep softening electrodeionization device is a macroporous strong acid and strong basic resin, and its particle size is 0.4-0.9mm, while the cationic resin is in the total resin volume The proportion in the middle is 70-100%. 4、根据权利要求2所述的集膜分离与电去离子生产制药用水的装置,其特征还在于,深度软化电去离子装置、深度除盐电去离子装置和荷电膜过滤装置的浓缩水均通过一个单向阀而回收至纳滤膜软化装置的上游,作为纳滤装置的进水。4. The device for producing pharmaceutical water by membrane separation and electrodeionization according to claim 2, further characterized in that the concentrated water of the deep softening electrodeionization device, the deep desalination electrodeionization device and the charged membrane filtration device All are recycled to the upstream of the nanofiltration membrane softening device through a one-way valve, as the inlet water of the nanofiltration device.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557293A (en) * 2011-12-15 2012-07-11 中国人民解放军军事医学科学院卫生装备研究所 Portable emergent pharmaceutical water preparation process and device
WO2014089796A1 (en) * 2012-12-13 2014-06-19 General Electric Company Method for treating high concentration wastewater such as ro brine
CN109160663A (en) * 2018-10-16 2019-01-08 江苏环保产业技术研究院股份公司 A kind of dye industry waste water from dyestuff sub-prime with high salt recycles technique and device
CN114031159A (en) * 2021-12-15 2022-02-11 安徽尚蓝环保科技有限公司 A water treatment system based on enhanced electrodeionization EDI module

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557293A (en) * 2011-12-15 2012-07-11 中国人民解放军军事医学科学院卫生装备研究所 Portable emergent pharmaceutical water preparation process and device
WO2014089796A1 (en) * 2012-12-13 2014-06-19 General Electric Company Method for treating high concentration wastewater such as ro brine
CN109160663A (en) * 2018-10-16 2019-01-08 江苏环保产业技术研究院股份公司 A kind of dye industry waste water from dyestuff sub-prime with high salt recycles technique and device
CN114031159A (en) * 2021-12-15 2022-02-11 安徽尚蓝环保科技有限公司 A water treatment system based on enhanced electrodeionization EDI module

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