CN105883971A - Transformation method of power generating unit condensation water treatment system - Google Patents
Transformation method of power generating unit condensation water treatment system Download PDFInfo
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Abstract
Description
技术领域 technical field
本发明属于电站凝结水处理领域,尤其是涉及一种发电机组凝结水处理系统的改造方法。 The invention belongs to the field of condensed water treatment in power stations, and in particular relates to a modification method for a condensed water treatment system of a generating set.
背景技术 Background technique
目前超临界发电机组的凝结水处理大多采用“前置过滤+高速混床”技术工艺,如图1所示,其中前置过滤采用的是前置过滤器,前置过滤器负责去除凝结水中的悬浮物和腐蚀产物(以铁氧化物为主),高速混床负责去除凝结水中的盐类离子。混床采用体外再生系统,以“高塔法”为主,包括分离塔、阴再生塔、阳再生塔/储存塔,其中阳再生塔/储存塔中会放置一套阴阳混脂,作为备用。 At present, the condensate treatment of supercritical generating units mostly adopts the "pre-filter + high-speed mixed bed" technology, as shown in Figure 1, where the pre-filter uses a pre-filter, and the pre-filter is responsible for removing the condensate Suspended solids and corrosion products (mainly iron oxides), the high-speed mixed bed is responsible for removing salt ions in condensed water. The mixed bed adopts an in vitro regeneration system, mainly based on the "high tower method", including a separation tower, a yin regeneration tower, and a yang regeneration tower/storage tower. A set of yin and yang mixed fat will be placed in the yang regeneration tower/storage tower as a backup.
由于目前超临界及以上参数发电机组采用的给水处理工艺一般为氧化性全挥发处理和还原性全挥发处理,给水pH值一般控制在9.2~9.6范围,凝结水含氨量较大,造成混床周期制水量一般不超过100000m3,运行周期一般在5~7天。在两台600MW机组双机运行(7套树脂)的情况下,混床树脂再生频率约为每周两到三次;而在两台1000MW机组双机运行(9套树脂)的情况下,混床树脂再生频率约为每周四到五次。树脂再生频繁、工作量大,若遇到系统故障,往往导致失效的混床树脂排队等候再生,甚至因无法及时再生树脂而造成无备用混床可用。鉴于以上情况,一些电厂不得不延长已失效混床的运行时间、放任混床由氢型运行状态转入铵型运行状态,此时树脂层中水的pH值上升,OH-离子增多,使树脂的交换反应逆向进行,不仅不吸收氯离子等杂质阴离子,而且原来吸收的部分杂质氯离子,也将被水中的OH-离子所排代,重新回到水中,从而形成氯离子排代峰,与此同时,NH4 +离子开始排代钠离子,使水中出现钠离子排代峰。 Due to the current feedwater treatment process adopted by supercritical and above-parameter generator sets is generally oxidative full-volatility treatment and reductive full-volatility treatment, the pH value of feedwater is generally controlled in the range of 9.2 to 9.6, and the ammonia content in condensed water is relatively large, resulting in mixed beds. Periodic water production generally does not exceed 100,000m 3 , and the operation period is generally 5 to 7 days. In the case of dual operation of two 600MW units (7 sets of resins), the mixed bed resin regeneration frequency is about two to three times a week; while in the case of dual operation of two 1000MW units (9 sets of resins), the mixed bed resin Resin regeneration frequency is approximately four to five times per week. Resin regeneration is frequent and the workload is heavy. In case of system failure, the failed mixed-bed resins are often queued for regeneration, or even no spare mixed-beds are available because the resins cannot be regenerated in time. In view of the above situation, some power plants have to prolong the running time of the failed mixed bed, and allow the mixed bed to change from the hydrogen type operation state to the ammonium type operation state. The exchange reaction of the exchange reaction is carried out in reverse, not only does not absorb impurity anions such as chloride ions, but also part of the impurity chloride ions originally absorbed will be displaced by the OH - ions in the water and return to the water, thereby forming a displacement peak of chloride ions, which is consistent with At the same time, NH 4 + ions begin to displace sodium ions, causing a sodium ion displacement peak to appear in the water.
以上反应可以看成是利用水中NH4OH溶液对混床树脂层中的钠型、氯型失效树脂(RNa、RCl)进行再生的过程,再生反应如下: The above reaction can be regarded as the process of using NH 4 OH solution in water to regenerate the sodium-type and chlorine-type expired resins (RNa, RCl) in the mixed bed resin layer. The regeneration reaction is as follows:
RNa+RCl+NH4OH = RNH4+ROH+Na++ Cl- RNa+RCl+NH 4 OH = RNH 4 +ROH+Na + + Cl -
综上所述,氢型混床失效后,如不及时退出,而是继续运行,并向铵型混床转型,将出现氯离子和钠离子的排代峰,向后释放出大量氯离子和钠离子,会造成热力设备积盐以及腐蚀,而且会降低出水水质。 To sum up, after the failure of the hydrogen-type mixed bed, if it does not exit in time, but continues to operate and transforms to the ammonium-type mixed bed, the displacement peaks of chloride ions and sodium ions will appear, and a large amount of chloride ions and sodium ions will be released backwards. Sodium ions will cause salt accumulation and corrosion of thermal equipment, and will reduce the quality of effluent water.
汤舟虹在《企业技术开发》上公开了600MW机组凝结水精处理系统改造,通过更换前置过滤器启动滤元,更换前置过滤器和高混阀门垫子,更换精处理再生系统阀门,对再生工艺及工艺程序进行优化以及修复及校正进水装置挡板等方法对凝结水精处理系统进行改造,改造后,精处理装置超压、泄漏、出水品质不合格、制水量低问题都得到解决,而且高混出水氢电导明显下降。该改造方法对凝结水精处理系统的水质以及周期制水量的改善不大。 Tang Zhouhong disclosed in "Enterprise Technology Development" the transformation of the condensate polishing system of the 600MW unit, starting the filter element by replacing the pre-filter, replacing the pre-filter and high-mix valve mat, and replacing the valve of the fine treatment regeneration system. The regeneration process and process procedures were optimized, and the baffle plate of the water inlet device was repaired and corrected to transform the condensate fine treatment system. After the transformation, the problems of overpressure, leakage, unqualified effluent quality, and low water production volume of the fine treatment device were all solved. , and the hydrogen conductance of high-mixed water drops significantly. This transformation method has little improvement on the water quality and periodic water production of the condensate polishing system.
对于早期建成的发电厂来说,发电机组凝结水处理系统已建造完成并投入使用,现在若重新设计建设新的发电机组凝结水处理系统成本高,工期长。因此在发电机组凝结水处理系统的基础上进行改造,使其符合现有的工艺条件是十分必要的。 For the power plants built in the early stage, the condensate water treatment system of the generator set has been completed and put into use. Now, if the condensate water treatment system of the new generator set is redesigned, the cost will be high and the construction period will be long. Therefore, it is very necessary to carry out transformation on the basis of the condensate water treatment system of the generating set to make it conform to the existing process conditions.
发明内容 Contents of the invention
有鉴于此,本发明的目的是针对现有技术的不足,提供一种发电机组凝结水处理系统的改造方法,该改造方法简单,成本较低,大大提高了系统的周期制水量和水质。 In view of this, the purpose of the present invention is to provide a modification method for the condensate treatment system of a generating set, which is simple, low in cost, and greatly improves the periodic water production and water quality of the system.
为达到上述目的,本发明采用以下技术方案: To achieve the above object, the present invention adopts the following technical solutions:
一种发电机组凝结水处理系统的改造方法,包括以下步骤: A modification method for a condensate treatment system of a generating set, comprising the following steps:
(1)将前置过滤器替换为前置氢床,所述前置氢床内的阳树脂与高速混床中的阳树脂相同; (1) Replace the pre-filter with a pre-hydrogen bed, and the cation resin in the pre-hydrogen bed is the same as the cation resin in the high-speed mixed bed;
(2)将阳再生塔/贮存塔中的一套备用的阴阳混脂撤除,使阳再生塔/贮存塔保持空塔备用状态; (2) Remove a set of spare yin and yang mixed fat in the yang regeneration tower/storage tower, so that the yang regeneration tower/storage tower remains empty and ready for use;
(3)在前置氢床上安装树脂输送管道,所述树脂输送管道与树脂再生系统的树脂输送管道连接; (3) A resin delivery pipeline is installed on the front hydrogen bed, and the resin delivery pipeline is connected with the resin delivery pipeline of the resin regeneration system;
(4)保留前置过滤器旁的旁路系统,作为前置氢床的旁路系统。 (4) Keep the bypass system next to the pre-filter as the bypass system of the pre-hydrogen bed.
优选的,将2台前置过滤器替换为2-3台前置氢床。 Preferably, 2 pre-filters are replaced with 2-3 pre-hydrogen beds.
优选的,将2台前置过滤器替换为2台各1/2凝结水流量的前置氢床; Preferably, replace the 2 pre-filters with 2 pre-hydrogen beds with 1/2 condensed water flow;
或将2台前置过滤器替换为3台各1/3凝结水流量的前置氢床; Or replace 2 pre-filters with 3 pre-hydrogen beds with 1/3 condensate flow;
或将2台前置过滤器替换为2台各1/2凝结水流量的前置氢床,留1台备用。 Or replace the 2 pre-filters with 2 pre-hydrogen beds with 1/2 condensed water flow each, and keep 1 for backup.
优选的,所述前置氢床运行的流速满足空塔流速为100~120m/h。 Preferably, the operating flow rate of the pre-hydrogen bed satisfies the superficial flow rate of 100-120 m/h.
优选的,所述前置氢床和高速混床中的阳树脂在阳再生塔/贮存塔再生之前,进行空气擦洗,直至阳再生塔/贮存塔排水清澈为止。 Preferably, the cation resin in the pre-hydrogen bed and the high-speed mixed bed is scrubbed with air before the cation regeneration tower/storage tower is regenerated until the drainage of the cation regeneration tower/storage tower is clear.
优选的,所述旁路系统上设置流量调节阀以调节旁路凝结水流量。 Preferably, a flow regulating valve is provided on the bypass system to adjust the flow of condensed water in the bypass.
优选的,所述前置氢床为圆柱形离子交换器或球形离子交换器。 Preferably, the pre-hydrogen bed is a cylindrical ion exchanger or a spherical ion exchanger.
本发明的有益效果是: The beneficial effects of the present invention are:
1、本发明对发电机组凝结水处理系统的改造是在原有的“前置过滤+高速混床”技术工艺基础上进行改造,将前置过滤器撤掉后,替换为前置氢床,并重新布置树脂输送管道和凝结水主管道与前置氢床对接,整体改动小,成本较低,便于施工。 1. The modification of the condensate treatment system of the generating set in the present invention is carried out on the basis of the original "pre-filter + high-speed mixed bed" technical process. After the pre-filter is removed, it is replaced with a pre-hydrogen bed, and Rearrange the resin delivery pipeline and the condensate main pipeline to connect with the pre-hydrogen bed, the overall change is small, the cost is low, and the construction is convenient.
2、将前置过滤器改为前置氢床,不仅保留了除铁功能,更重要的是新增了除氨能力,而且替换为前置氢床后,可保证混床运行在最佳的进水pH值之下,在实际生产中,能够提高混床的制水量4倍以上,且大大降低混床树脂的再生频率,而前置氢床只需要再生阳树脂,操作步骤简单;而且避免了混床出水中产生氯离子、钠离子“排代峰”的风险,提高了混床的除盐能力,切实保证了混床的出水水质,降低了汽轮机等热力设备的腐蚀、积盐、结垢风险。 2. Changing the pre-filter to the pre-hydrogen bed not only retains the iron removal function, but more importantly, adds the ability to remove ammonia, and after replacing it with the pre-hydrogen bed, it can ensure that the mixed bed operates at the best Under the pH value of the feed water, in actual production, the water production capacity of the mixed bed can be increased by more than 4 times, and the regeneration frequency of the mixed bed resin can be greatly reduced, while the pre-hydrogen bed only needs to regenerate the cation resin, and the operation steps are simple; and avoid The risk of chlorine ion and sodium ion "displacement peak" in the effluent of the mixed bed is eliminated, the desalination capacity of the mixed bed is improved, the effluent water quality of the mixed bed is effectively guaranteed, and the corrosion, salt accumulation, and condensation of thermal equipment such as steam turbines are reduced. Dirt risk.
附图说明 Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,下面描述中的附图仅仅是本发明的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。 In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. The accompanying drawings in the following description are only the present invention For the embodiment of the present invention, those of ordinary skill in the art can also obtain other drawings based on these drawings on the premise of not paying creative efforts.
图1为改造前的发电机组凝结水处理系统的结构简图; Figure 1 is a schematic structural diagram of the condensate treatment system of the generating unit before the transformation;
图2为改造后的发电机组凝结水处理系统的结构简图; Figure 2 is a schematic structural diagram of the condensate treatment system of the power unit after transformation;
图3为模拟实验的试验装置图; Fig. 3 is the experimental apparatus diagram of simulation experiment;
图4为模拟实验中比电导率与周期制水量的关系图; Fig. 4 is the relationship diagram between specific conductivity and periodic water production in the simulated experiment;
图5为模拟实验中裸混床出口氯离子含量与比电导率的关系曲线; Fig. 5 is the relational curve of chlorine ion content and specific conductivity in bare mixed bed outlet in simulation experiment;
图6为模拟实验中后置混床出口氯离子含量与比电导率的关系曲线。 Figure 6 is the relationship curve between the chloride ion content at the outlet of the rear mixed bed and the specific conductivity in the simulation experiment.
具体实施方式 detailed description
下面结合附图和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.
对比例 comparative example
图1为改造前的发电机组凝结水处理系统,采用“前置过滤+高速混床”工艺,包括前置过滤器和高速混床,树脂再生系统包括分离塔、阴再生塔和阳再生塔/储存塔,其中阳再生塔同时是树脂储存塔,会放置一套备用的阴阳混脂;前置过滤器旁边会设置旁路系统,即设置旁路阀,当前置过滤器出现问题无法使用时,凝结水直接从旁路系统流过,凝结水泵来水经过前置过滤器后进入高速混床,高速混床中的阴阳树脂经过树脂输送管道输送入树脂再生系统再生。 Figure 1 shows the condensate water treatment system of the generator set before transformation, which adopts the "pre-filter + high-speed mixed bed" process, including pre-filter and high-speed mixed bed, and the resin regeneration system includes separation tower, yin regeneration tower and yang regeneration tower/ The storage tower, in which the yang regeneration tower is also a resin storage tower, will place a set of spare yin and yang mixed fat; a bypass system will be set next to the pre-filter, that is, a bypass valve will be set. When the pre-filter has problems and cannot be used, The condensed water flows directly through the bypass system, and the water from the condensed water pump enters the high-speed mixed bed after passing through the pre-filter. The anion and positive resins in the high-speed mixed bed are sent to the resin regeneration system for regeneration through the resin delivery pipeline.
实施例1 Example 1
图2为改造后的发电机组凝结水处理系统的结构简图,图2相对于图1中的改造方法为: Figure 2 is a schematic structural diagram of the modified condensate treatment system of the generating unit. Compared with Figure 1, the modification method in Figure 2 is as follows:
(1)将前置过滤器撤掉后,替换为前置氢床,前置氢床运行的流速需要满足空塔流速为100~120m/h,其中前置氢床内的阳树脂与高速混床中的阳树脂完全相同,这是因为前置氢床与高速混床共用一套树脂再生系统,前置氢床可以采用圆柱形离子交换器或球形离子交换器; (1) After removing the pre-filter, replace it with a pre-hydrogen bed. The flow rate of the pre-hydrogen bed needs to meet the empty tower flow rate of 100-120m/h, in which the cation resin in the pre-hydrogen bed and the high-speed mixing The cation resin in the bed is exactly the same, because the pre-hydrogen bed and the high-speed mixed bed share a set of resin regeneration system, and the pre-hydrogen bed can use a cylindrical ion exchanger or a spherical ion exchanger;
另外视现场空间条件,可以将2台前置过滤器替换为2-3台前置氢床,其中可以将2台前置过滤器替换为2台各1/2凝结水流量的前置氢床;或将2台前置过滤器替换为3台各1/3凝结水流量的前置氢床;或将2台前置过滤器替换为2台各1/2凝结水流量的前置氢床,留1台备用,本实施例中是将2台前置过滤器替换为2台各1/2凝结水流量的前置氢床。 In addition, depending on the site space conditions, 2 pre-filters can be replaced by 2-3 pre-hydrogen beds, of which 2 pre-filters can be replaced by 2 pre-hydrogen beds with 1/2 condensed water flow ; or replace 2 pre-filters with 3 pre-hydrogen beds with 1/3 condensate flow each; or replace 2 pre-filters with 2 pre-hydrogen beds with 1/2 condensate flow , keep 1 for standby, in this embodiment, replace 2 pre-filters with 2 pre-hydrogen beds with 1/2 flow rate of condensed water.
(2)将阳再生塔/贮存塔中的一套备用的阴阳混脂撤除,使阳再生塔/贮存塔保持空塔备用状态,既可以用于再生前置氢床的阳树脂,也可以用于再生从分离塔底部输送过来的混床阳树脂; (2) Remove a set of spare yin and yang mixed grease in the cation regeneration tower/storage tower, so that the cation regeneration tower/storage tower remains empty and ready for use, which can be used to regenerate the cation resin of the pre-hydrogen bed, or use Used to regenerate the mixed bed cation resin transported from the bottom of the separation tower;
(3)在前置氢床上安装树脂输送管道,如图2所示,在高速混床至树脂再生系统的树脂输送管道靠近前置氢床的位置开三通,接不锈钢管道与前置氢床的树脂输送管道对接,使前置氢床上的树脂输送管道与树脂再生系统的树脂输送管道连接,并安装控制阀门; (3) Install the resin delivery pipeline on the pre-hydrogen bed, as shown in Figure 2, open a three-way connection between the high-speed mixed bed and the resin regeneration system near the pre-hydrogen bed, and connect the stainless steel pipe to the pre-hydrogen bed The resin delivery pipeline is docked, so that the resin delivery pipeline on the pre-hydrogen bed is connected to the resin delivery pipeline of the resin regeneration system, and the control valve is installed;
(4)保留前置过滤器旁的旁路系统,作为前置氢床的旁路系统,而且还可以在旁路系统上设置流量调节阀以调节旁路凝结水流量; (4) The bypass system next to the pre-filter is reserved as the bypass system of the pre-hydrogen bed, and a flow regulating valve can also be set on the bypass system to adjust the bypass condensate flow;
(5)其中前置氢床和高速混床中的阳树脂在阳再生塔/贮存塔再生之前,可以采用罗茨风机进行空气擦洗,直至阳再生塔/贮存塔排水清澈为止。 (5) Before the cation resin in the pre-hydrogen bed and high-speed mixed bed is regenerated in the cation regeneration tower/storage tower, Roots blower can be used for air scrubbing until the drainage of the cation regeneration tower/storage tower is clear.
模拟实验 simulation experiment
以单机600MW机组的凝结水处理系统为模板,模拟高速混床的树脂装填量和高速混床的流量,设计试验装置如图3所示,图3中包括改造前的发电机组凝结水处理系统即“前置过滤器+裸混床”,与图1的结构类似,也包括改造后的发电机组凝结水处理系统即“前置氢床+后置混床”,与图2中的结构类似。其中树脂的装填量为前置氢床装阳树脂4L,裸混床和后置混床分别装填已再生并混合好的阴阳混脂7.5L(阳、阴树脂比例为1:1)。 Taking the condensate treatment system of a single 600MW unit as a template to simulate the resin loading amount and flow rate of the high-speed mixed bed, the designed test device is shown in Figure 3, which includes the condensate treatment system of the power unit before transformation, namely "Pre-filter + naked mixed bed" is similar to the structure in Figure 1, and also includes the modified condensate treatment system of the generating set, namely "pre-hydrogen bed + post-mixed bed", which is similar to the structure in Figure 2. The loading amount of resin is 4L of cation resin in the front hydrogen bed, 7.5L of regenerated and mixed anion and cation mixed resin in the bare mixed bed and post mixed bed (the ratio of cation and anion resin is 1:1).
试验装置安装在某电厂的汽机厂房内,“前置过滤器+裸混床”系统及“前置氢床+后置混床”系统均通过不锈钢内波纹软管及减压阀与凝结水管道上的压力表取样管实现软连接,以凝结水泵来水为进水;试验装置中的所有阀门均使用TP304不锈钢材质,管材、取样阀、流量计等采用无污染的ABS及PVC材质。 The test device was installed in the steam turbine workshop of a power plant. The "pre-filter + bare mixed bed" system and the "pre-hydrogen bed + post-mixed bed" system are all connected through stainless steel inner corrugated hoses, pressure reducing valves and condensate pipes. The pressure gauge sampling pipe on the tester is connected softly, and the water from the condensate pump is used as the water inlet; all valves in the test device are made of TP304 stainless steel, and the pipes, sampling valves, flow meters, etc. are made of non-polluting ABS and PVC materials.
试验装置中的离子交换柱的材质为有机玻璃,顶部设排气门,用于离子交换柱满水排气;离子交换柱上部进水、下部出水,设有集水器,通流面积不小于进水管的通流面积。 The ion exchange column in the test device is made of plexiglass, and the top is equipped with an exhaust valve, which is used to exhaust the ion exchange column when it is full of water; the upper part of the ion exchange column enters the water, and the lower part of the water outlet is equipped with a water collector, and the flow area is not less than The flow area of the inlet pipe.
模拟试验开始后,调节裸混床和前置氢床的进口流量相同,均为0.8m3/h。通过取样门取样检测并记录凝结水入口、裸混床出口、前置氢床出口、后置混床出口的比电导率、累计流量以及Cl-含量等参数;分析混床累计制水量、出水pH、比电导率、Cl-含量变化的相互关系,具体见图4、图5和图6所示。 After the start of the simulation test, the inlet flow rate of the adjusted bare mixed bed and the pre-hydrogen bed are the same, both being 0.8m 3 /h. Sampling through the sampling gate to detect and record parameters such as specific conductivity, cumulative flow, and Cl - content of the condensate inlet, bare mixed bed outlet, pre-hydrogen bed outlet, and post-mixed bed outlet; analyze the cumulative water production volume of the mixed bed and the pH of the effluent , specific conductivity, and Cl - content changes, see Figure 4, Figure 5 and Figure 6 for details.
图4为比电导率与周期制水量的关系图,由图4所示,对于“前置过滤器+裸混床”以及“前置氢床+后置混床”系统系统:试验装置入口处即凝结水入口处的比电导率在3.72~6.07μs/cm之间波动,计算pH值在9.08~9.35之间。裸混床出口的比电导率在制水量达到164.4m3时为0.09μs/cm,当制水量达到172m3时,比电导率达到0.26μs/cm,表面此时裸混床已开始漏氨,进入氢型向铵型的转型阶段。此后,裸混床出口的比电导率快速升高,在制水量达到223m3时,其出口和入口的比电导率基本相等,混床进入铵型运行阶段。 Figure 4 is a relationship diagram between specific conductivity and periodic water production. As shown in Figure 4, for the "pre-filter + bare mixed bed" and "pre-hydrogen bed + post-mixed bed" systems: at the entrance of the test device That is, the specific conductivity at the condensate inlet fluctuates between 3.72 and 6.07 μs/cm, and the calculated pH value is between 9.08 and 9.35. The specific conductivity at the outlet of the bare mixed bed is 0.09μs/cm when the water production volume reaches 164.4m 3 , and when the water production volume reaches 172m 3 , the specific conductivity reaches 0.26μs/cm. It appears that the bare mixed bed has begun to leak ammonia at this time. Enter the transition stage from hydrogen form to ammonium form. After that, the specific conductivity of the outlet of the bare mixed bed increased rapidly. When the water production volume reached 223m 3 , the specific conductivity of the outlet and the inlet were basically equal, and the mixed bed entered the ammonium type operation stage.
对于模拟试验装置中的“前置氢床+后置混床”系统,由于其前置氢床的阳树脂装填量比裸混床的阳树脂装填量多出约6%,因此,其制水量也应略多于裸混床。由图4所示,前置氢床出口比电导率在制水量达到172m3时为0.10μs/cm,当制水量达到183m3时,比电导率达到了0.26μs/cm,此时前置氢床也开始向铵型转型,相比裸混床,其制水量也相对多了约6%(10m3),这与阳树脂的装填量成正比关系。这表明凝结水在混床运行中,由于水汽系统中加了大量氨,占用了阳树脂的大部分交换容量,使得阳树脂过早失效,降低了树脂的利用率。因此决定混床氢型运行的周期长短在于混床阳树脂量的多少。但由于运行机组的凝结水混床及再生设备已经定型,这提示我们采用新的设计思路来提高阳树脂的比例。 For the "pre-hydrogen bed + post-mixed bed" system in the simulation test device, since the cation resin loading of the pre-hydrogen bed is about 6% more than that of the bare mixed bed, the water production capacity It should also be slightly more than a bare mixed bed. As shown in Figure 4, the specific conductivity at the outlet of the pre-hydrogen bed is 0.10 μs/cm when the water production volume reaches 172 m 3 , and when the water production volume reaches 183 m 3 , the specific conductivity reaches 0.26 μs/cm. The bed also began to transform to the ammonium type, and compared with the bare mixed bed, its water production capacity is relatively more by about 6% (10m 3 ), which is proportional to the loading capacity of the cation resin. This shows that the condensed water in the mixed bed operation, due to the addition of a large amount of ammonia in the water vapor system, occupies most of the exchange capacity of the cation resin, which makes the cation resin fail prematurely and reduces the utilization rate of the resin. Therefore, the cycle length of the mixed-bed hydrogen type operation depends on the amount of the mixed-bed cation resin. However, since the condensate mixed bed and regeneration equipment of the operating unit have been finalized, this prompts us to adopt a new design idea to increase the proportion of cation resin.
前置氢床和后置混床串联运行,在前置氢床运行前期,其树脂吸收了凝结水中包括NH4 +离子在内的大部分阳离子,出水只含有少量阴离子杂质,相比裸混床进口,后置混床的进水pH值接近中性,这对混床的除盐反应极为有利: The pre-hydrogen bed and the post-mixed bed operate in series. In the early stage of the operation of the pre-hydrogen bed, its resin absorbs most of the cations in the condensed water, including NH 4 + ions, and the effluent contains only a small amount of anion impurities. Compared with the bare mixed bed At the inlet, the pH value of the influent mixed bed is close to neutral, which is extremely beneficial to the desalination reaction of the mixed bed:
RH+ROH+NaCl = RNa+RCl+H2O RH+ROH+NaCl = RNa+RCl+ H2O
由于混床中阳、阴树脂充分混合,离子交换反应生成的H+和OH-马上结合成离解度极小的H2O分子,消除了反离子作用,离子交换反应进行的十分彻底,出水水质得到良好保障。 Because the positive and negative resins are fully mixed in the mixed bed, the H + and OH - generated by the ion exchange reaction are immediately combined into H 2 O molecules with a very small degree of dissociation, eliminating the effect of counter ions, and the ion exchange reaction is carried out very thoroughly. well protected.
由图4可知,由于前置氢床的存在,使得后置混床在出口比电导率为0.10μs/cm时,其制水量达到了336m3,制水量达到裸混床的2倍以上。 It can be seen from Figure 4 that due to the existence of the pre-hydrogen bed, the post-mixed bed has a water production capacity of 336m 3 when the outlet specific conductivity is 0.10μs/cm, which is more than twice that of the bare mixed bed.
由此可见前置氢床的阳树脂量越多,后置混床的制水量越大。如果失效的前置氢床有备用床可随时替换,则后置混床的周期制水量可以得到极大提高;即使没有备用的前置氢床,只要失效的前置氢床阳树脂能得到便捷快速的再生,后置混床的周期制水量也可以大大提高。而前置氢床失效阳树脂的体外再生过程十分简单,在阳再生塔中可快速完成,无需如混床失效树脂那样必须经过阴阳树脂高塔分离、再生、混脂等复杂操作。这就为大幅提高凝结水混床的周期制水量创造了极为有利的条件。 It can be seen that the more cation resin in the pre-hydrogen bed, the greater the water production capacity of the post-mixed bed. If the failed pre-hydrogen bed has a spare bed that can be replaced at any time, the periodic water production capacity of the post-mixed bed can be greatly improved; even if there is no spare pre-hydrogen bed, as long as the failed pre-hydrogen bed cation resin can be conveniently With rapid regeneration, the periodic water production capacity of the rear mixed bed can also be greatly improved. The in vitro regeneration process of the pre-hydrogen bed spent cation resin is very simple, and can be quickly completed in the cation regeneration tower, without the need for complex operations such as separation, regeneration, and fat mixing of anion and cation resins in high towers like mixed bed spent resins. This creates extremely favorable conditions for greatly increasing the periodic water production capacity of the condensate mixed bed.
图5为裸混床出口氯离子含量与比电导率的关系曲线,图6为后置混床出口氯离子含量与比电导率的关系曲线。图5、图6表明:当混床出口比电导率在0.10μs/cm之下时,混床出口的氯离子含量基本在1μg/L以下波动;当混床出口比电导率超过0.10μs/cm并开始快速升高后,氯离子含量也急剧上升,最后稳定到约5.5μg/L,表明随着混床开始由氢型向铵型转化(出水漏氨),出现了氯离子的“排代峰”,混床在氢型运行阶段吸收的氯离子被大量释放到出水中;这是因为当混床中的阳树脂开始失效后,逐渐失去除氨能力,混床出水开始漏氨,出水pH值和比电导率也逐渐上升。树脂层中水的pH值上升,OH-离子含量增多,使阴树脂的交换反应逆向进行,不仅不再吸收(或吸收不完全),而且原来吸收的氯离子等部分杂质阴离子,也可能被水中的OH-离子所排代,重新回到水中: Figure 5 is the relationship curve between the chlorine ion content at the outlet of the bare mixed bed and the specific conductivity, and Figure 6 is the relationship curve between the chlorine ion content at the outlet of the rear mixed bed and the specific conductivity. Figure 5 and Figure 6 show that: when the specific conductivity of the mixed bed outlet is below 0.10μs/cm, the chloride ion content of the mixed bed outlet basically fluctuates below 1μg/L; when the mixed bed outlet specific conductivity exceeds 0.10μs/cm And began to rise rapidly, the chloride ion content also rose sharply, and finally stabilized to about 5.5μg/L, indicating that as the mixed bed began to transform from hydrogen form to ammonium form (ammonia leakage from the effluent), there was a "displacement of chloride ions". The chlorine ions absorbed by the mixed bed during the hydrogen type operation stage are released into the effluent in large quantities; this is because when the cation resin in the mixed bed begins to fail, it gradually loses its ability to remove ammonia, and the effluent of the mixed bed begins to leak ammonia, and the pH of the effluent The value and specific conductivity also gradually increased. The pH value of water in the resin layer increases, and the content of OH - ions increases, so that the exchange reaction of the anion resin is reversed, not only no longer absorbs (or absorbs incompletely), but also some impurity anions such as chloride ions originally absorbed may also be absorbed by the water. The OH - ions are displaced and return to the water:
ROH+Cl-= RCl+OH-(逆向进行) ROH+Cl - = RCl+OH - (reverse)
以上过程,也可以看做是凝结水中所含NH4OH对树脂层进行再生的过程:对阴树脂,是利用NH4OH离解产生的OH-离子再生阴树脂,使阴树脂已吸收的Cl-被排代出来;对阳树脂,则是NH4 +离子排代Na+,使水中出现Na+排代峰: The above process can also be regarded as the process of regenerating the resin layer by the NH 4 OH contained in the condensed water: for the anion resin, the anion resin is regenerated by using the OH - ions generated by the dissociation of NH 4 OH, so that the Cl - that the anion resin has absorbed is displaced out; for cationic resins, NH 4 + ions displace Na + , so that Na + displacement peaks appear in water:
RNH4+Na+ = RNa+NH4 +(逆向进行) RNH 4 +Na + = RNa+NH 4 + (reverse)
从离子交换反应来看,上述反应的逆向进行实际是凝结水中的NH4OH对阴、阳树脂进行再生,而被排代出来的Na+、Cl-等离子杂质就是再生过程中产生的废液。排代量的多少,与树脂相中杂质离子的含量和氢型运行阶段树脂吸收的杂质离子量有直接关系。经过转型阶段后,混床将彻底进入铵型运行阶段,床层内树脂的离子形态与进水中杂质离子的含量和比例都已达到平衡,表现为出水水质等于进水水质。 From the perspective of ion exchange reaction, the reverse of the above reaction is actually the NH 4 OH in the condensed water regenerates the anion and cation resins, and the displaced Na + , Cl - and other ion impurities are the waste liquid generated during the regeneration process. The amount of displacement is directly related to the content of impurity ions in the resin phase and the amount of impurity ions absorbed by the resin during hydrogen-type operation. After the transformation stage, the mixed bed will completely enter the ammonium type operation stage, and the ion form of the resin in the bed and the content and proportion of impurity ions in the influent have reached a balance, showing that the quality of the effluent water is equal to the quality of the influent water.
上述模拟试验完全证实了混床在从氢型向铵型转型阶段,不仅存在钠离子的排代,而且也存在氯离子的排代。氯离子为腐蚀性阴离子,能够破坏金属表面的保护膜,在发电机组水汽系统中易引发金属点状腐蚀。特别是机组热力系统中的奥氏体钢,更是对氯离子高度敏感,极易在氯离子和应力的共同作用下,发生应力腐蚀开裂。 The above simulation tests have fully confirmed that in the transition stage of the mixed bed from hydrogen to ammonium, there is not only displacement of sodium ions, but also displacement of chloride ions. Chloride ion is a corrosive anion that can destroy the protective film on the metal surface and easily cause metal point corrosion in the water vapor system of the generator set. In particular, the austenitic steel in the thermal system of the unit is highly sensitive to chloride ions, and is prone to stress corrosion cracking under the combined action of chloride ions and stress.
本发明的改造方法将前置过滤器替换为前置氢床,提前消除了混床的除氨负荷,可保证后置混床运行在最佳的进水pH值之下,大幅提高了系统的周期制水量,使混床树脂的再生频率显著下降,彻底消除了混床因树脂来不及再生而被迫转入铵型运行的可能,避免了混床出水中出现氯离子、钠离子“排代峰”的风险,提高了混床的除盐能力,切实保证了混床的出水水质,降低了汽轮机等热力设备的腐蚀、积盐、结垢风险,有利于发电机组的安全、经济、环保、低碳运行。 The transformation method of the present invention replaces the pre-filter with the pre-hydrogen bed, which eliminates the ammonia removal load of the mixed bed in advance, ensures that the post-mixed bed operates under the optimal pH value of the influent, and greatly improves the efficiency of the system. Periodic water production reduces the regeneration frequency of the mixed bed resin significantly, completely eliminates the possibility that the mixed bed is forced to switch to ammonium type operation because the resin is too late to regenerate, and avoids the occurrence of chloride and sodium ion "displacement peaks" in the mixed bed effluent ", which improves the desalination capacity of the mixed bed, effectively guarantees the effluent water quality of the mixed bed, reduces the risk of corrosion, salt accumulation, and scaling of thermal equipment such as steam turbines, and is conducive to the safety, economy, environmental protection, and low cost of power generation units. carbon run.
生产试验 production test
将本发明的发电机组凝结水处理系统改造方法应用于某电厂的2台600MW机组中,在未改造前即采用图1中发电机组凝结水处理系统时,即每台机组配置2台前置过滤器和3台高速混床,总共采用7套树脂,每台混床内有一套,再生间还有一套备用树脂,单台机组运行时,每台混床周期制水量约为10万吨,可运行约7天,再生系统平均每3天再生一套失效树脂;两台机组同时运行时,再生系统平均每1.5天再生一套失效树脂。 Apply the modification method of the generating unit condensate treatment system of the present invention to two 600MW units of a certain power plant, and when the generating unit condensate treatment system in Fig. There are 7 sets of resins in total, including one set in each mixed bed and a set of spare resin in the regeneration room. When a single unit is running, the periodic water production capacity of each mixed bed is about 100,000 tons, which can be After running for about 7 days, the regeneration system regenerates a set of spent resin every 3 days on average; when the two units are running at the same time, the regeneration system regenerates a set of spent resin every 1.5 days on average.
而将图1中的发电机组凝结水处理系统改造成如图2所示,将2台前置过滤器替换为2台前置氢床,即采用2台前置氢床和3台高速混床,将阳再生塔/贮存塔中的备用的阴阳混脂撤除,并在前置氢床上安装树脂输送管道,其中树脂输送管道与树脂再生系统的树脂输送管道连接。改造后,由于前置氢床在运行中已将凝结水中的大部分氨除去,高速混床基本不再承担除氨的任务。每台前置氢床的运行周期约为7天,仅当一台前置氢床失效并退出树脂进行再生时(再生时间不超过6h),需开启旁路系统使含氨的凝结水直接进入高速混床。由此,每台高速混床的周期制水量在理论上可提高约28倍,达到约280万吨;运行周期可长达约196天。但是,为了避免高速混床运行时间过长对树脂产生压实作用,一般控制每台高速混床的运行周期为一个月左右,周期制水量约43万吨,比改造前提高4倍以上。单台机组运行时,再生系统平均每16天再生一套高速混床失效树脂;两台机组同时运行时,再生系统平均每8天再生一套高速混床失效树脂,高速混床树脂的再生频率相当于改造前的约1/5。 However, the condensate water treatment system of the generator set in Fig. 1 is transformed into that shown in Fig. 2, and 2 pre-filters are replaced with 2 pre-hydrogen beds, that is, 2 pre-hydrogen beds and 3 high-speed mixed beds are used. , remove the spare anion and cation mixed fat in the cation regeneration tower/storage tower, and install a resin delivery pipeline on the front hydrogen bed, wherein the resin delivery pipeline is connected with the resin delivery pipeline of the resin regeneration system. After the transformation, since the pre-hydrogen bed has removed most of the ammonia in the condensed water during operation, the high-speed mixed bed basically no longer undertakes the task of removing ammonia. The operating cycle of each pre-hydrogen bed is about 7 days. Only when one pre-hydrogen bed fails and exits the resin for regeneration (regeneration time does not exceed 6 hours), the bypass system needs to be opened to allow the condensed water containing ammonia to enter directly. High speed mixed bed. As a result, the periodic water production capacity of each high-speed mixed bed can theoretically be increased by about 28 times, reaching about 2.8 million tons; the operating cycle can be as long as about 196 days. However, in order to avoid compaction of the resin due to the long running time of the high-speed mixed bed, the operation period of each high-speed mixed bed is generally controlled to be about one month, and the periodic water production is about 430,000 tons, which is more than 4 times higher than before the transformation. When a single unit is running, the regeneration system regenerates a set of high-speed mixed bed failure resin on average every 16 days; when two units are running at the same time, the regeneration system regenerates a set of high-speed mixed bed failure resin on average every 8 days, the regeneration frequency of high-speed mixed bed resin It is equivalent to about 1/5 of that before the transformation.
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,本领域普通技术人员对本发明的技术方案所做的其他修改或者等同替换,只要不脱离本发明技术方案的精神和范围,均应涵盖在本发明的权利要求范围当中。 Finally, it is noted that the above embodiments are only used to illustrate the technical solution of the present invention and not to limit it. Those of ordinary skill in the art may make other modifications or equivalent replacements to the technical solution of the present invention, as long as they do not depart from the spirit and spirit of the technical solution of the present invention. All should be included in the scope of the claims of the present invention.
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Publication number | Priority date | Publication date | Assignee | Title |
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CN113105027A (en) * | 2021-05-10 | 2021-07-13 | 华北电力科学研究院有限责任公司 | A kind of ultra-supercritical direct air cooling unit finishing device and method |
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CN116062834A (en) * | 2022-12-26 | 2023-05-05 | 江苏核电有限公司 | Nuclear power plant fine treatment full bypass operation system and operation maintenance method |
CN115925045A (en) * | 2023-02-01 | 2023-04-07 | 华能太仓发电有限责任公司 | Static cooling water conductivity automatic adjustment control system and method |
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