WO2014198179A1 - Chemical decalcification based recycling device and method for advanced treatment of papermaking wastewater - Google Patents

Abstract

A chemical decalcification based recycling device for advanced treatment of papermaking wastewater, comprising a chemical decalcification system, a filtration system, an electrolysis system, a membrane separation system and a desalination system. The chemical decalcification system is provided with a dosing system, and the membrane separation system is an ultrafiltration system or an MBR system. Also disclosed is a chemical decalcification based recycling method for advanced treatment of papermaking wastewater, comprising the sequential steps of chemical decalcification, filtration, electrolysis, membrane separation (ultrafiltration or MBR) and desalination. 70%-85% of wastewater is regenerated and recycled using the present method.

Description

基于化学脱钙的造纸深度处理废水回用装置及方法  Papermaking advanced treatment wastewater recycling device and method based on chemical decalcification 技术领域Technical field

本发明涉及一种造纸深度处理废水的处理装置及方法，特别是涉及一种基于化学脱钙技术、电化学技术和膜技术的造纸深度处理废水的回用装置及方法。 The invention relates to a processing device and a method for treating waste water of papermaking, in particular to a recycling device and a method for treating waste water of papermaking based on chemical decalcification technology, electrochemical technology and membrane technology.

背景技术Background technique

制浆造纸废水是指化学法制浆产生的蒸煮废液（又称黑液、红液），洗浆漂白过程中产生的中段水及抄纸工序中产生的白水。一般每生产1t硫酸盐浆就有1t有机物和400kg碱类、硫化物溶解于黑液中；生产1t亚硫酸盐浆约有900kg有机物和200kg氧化物（钙、镁等）与硫化物溶于红液中。废液排入江河中不仅严重污染水源，而且造成大量的资源浪费。造纸业是传统的用水大户，也是造成水污染的重要污染源之一。目前，我国造纸工业废水排放量及COD排放量均居我国各类工业排放量的首位，造纸工业对水环境的污染最为严重，它不但是我国造纸工业污染防治的首要问题，也是全国工业废水进行达标处理和节水的首要问题。据统计，我国县及县以上造纸及纸制品工业废水排放量占全国工业总排放量的18.6%，其中处理排放达标量占造纸工业废水总排放量的49.3%，排放废水中COD约占全国工业COD总排放量的44.0%。因此，如何消除造纸废水污染并使废液中的宝贵资源得到利用是一项具有重大社会意义和经济价值的工作，应当十分重视。随着经济的发展，我国日益面临淡水资源短缺、原料匮乏的问题，而另一方面，水污染也越来越严重。近年来，经多方不懈努力，造纸工业水污染防治已经取得了一定的成绩，虽然纸及纸板产量逐年增加，但是排放废水中的COD却逐年降低。但是，目前造纸行业约占排放总量50%的废水尚未进行达标处理，造纸废水处理后再循环利用的更是少之又少，因此，造纸废水污染防治和循环使用任务还相当繁重。Pulp and papermaking wastewater refers to the cooking waste liquid (also known as black liquor, red liquor) produced by chemical pulping, the middle water produced during the washing and bleaching process, and the white water produced in the papermaking process. Generally, for every 1 t of kraft slurry, 1 t of organic matter and 400 kg of alkali and sulfide are dissolved in black liquor; 1 t of sulfite pulp is produced with about 900 kg of organic matter and 200 kg of oxide (calcium, magnesium, etc.) and sulfide are dissolved in red. In the liquid. The discharge of waste liquid into rivers not only seriously pollutes the water source, but also causes a large amount of waste of resources. The paper industry is a traditional water user and one of the important sources of water pollution. At present, China's paper industry wastewater discharge and COD emissions rank first in all types of industrial emissions in China. The paper industry has the most serious pollution to the water environment. It is not only the primary problem of pollution prevention and control in China's paper industry, but also the national industrial wastewater. The primary problem of compliance and water conservation. According to statistics, China's county and county paper and paper products industrial wastewater discharge accounted for 18.6% of the country's total industrial emissions, of which treatment discharge standards accounted for 49.3% of the total discharge of paper industry wastewater, COD emissions from wastewater accounted for national industry 44.0% of total COD emissions. Therefore, how to eliminate the pollution of papermaking wastewater and make use of valuable resources in waste liquid is a work of great social and economic value, which should be taken seriously. With the development of the economy, China is increasingly facing the shortage of fresh water resources and the shortage of raw materials. On the other hand, water pollution is becoming more and more serious. In recent years, through the unremitting efforts of many parties, the paper industry has achieved certain results in water pollution prevention and control. Although the output of paper and paperboard has increased year by year, the COD in wastewater discharge has been decreasing year by year. However, at present, the wastewater industry accounts for about 50% of the total discharge of wastewater, and the recycling of papermaking wastewater is rare. Therefore, the prevention and recycling of papermaking wastewater is quite arduous.

造纸废水成分复杂，可生化性差，属于较难处理的工业废水，其来源和特点是：Papermaking wastewater has complex composition and poor biodegradability. It is a difficult industrial wastewater. Its sources and characteristics are:

1、蒸煮工段废液1. Cooking section waste liquid

即碱法制浆产生的黑液和酸法制浆产生的红液。绝大部分造纸厂采用碱法制浆而产生黑液。黑液中所含污染物占到了造纸工业污染排放总量的90%以上，且具有高浓度和难降解的特性，它的治理一直是一大难题。黑液中的主要成分有3种，即木质素、聚戊糖和总碱。木质素是一类无毒的天然高分子物质，作为化工原料具有广泛的用途，聚戊糖可用作牲畜饲料。That is, the black liquor produced by alkaline pulping and the red liquor produced by acid pulping. Most paper mills use alkaline pulping to produce black liquor. The pollutants contained in the black liquor account for more than 90% of the total pollution discharge of the paper industry, and have high concentration and refractory characteristics. Its treatment has always been a major problem. There are three main components in the black liquor, namely lignin, polypentose and total alkali. Lignin is a kind of non-toxic natural high-molecular substance. It has a wide range of uses as a chemical raw material, and polypentose can be used as livestock feed.

2、中段水2, middle water

制浆中段废水是指经黑液提取后的蒸煮浆料在筛选、洗涤、漂白等过程中排出的废水，颜色呈深黄色，占造纸工业污染排放总量的8%～9%，吨浆COD负荷310kg左右。中段水浓度高于生活污水，BOD和COD的比值在0.20到0.35之间，可生化性较差，有机物难以生物降解且处理难度大。中段水中的有机物主要是木质素、纤维素、有机酸等，以可溶性COD为主。其中，对环境污染最严重的是漂白过程中产生的含氯废水，例如氯化漂白废水、次氯酸盐漂白废水等。次氯酸盐漂白废水主要含三氯甲烷，还含有40多种其他有机氯化物，其中以各种氯代酚为最多，如二氯代酚、三氯代酚等。此外，漂白废液中含有毒性极强的致癌物质二恶英，对生态环境和人体健康造成了严重威胁。The mid-stage pulping wastewater refers to the wastewater discharged from the cooking slurry after black liquor extraction in the process of screening, washing and bleaching. The color is dark yellow, accounting for 8% to 9% of the total pollution discharge of the paper industry. The load is about 310kg. The water concentration in the middle section is higher than that in domestic sewage. The ratio of BOD to COD is between 0.20 and 0.35. The biodegradability is poor, the organic matter is difficult to biodegrade and the treatment is difficult. The organic matter in the middle water is mainly lignin, cellulose, organic acid, etc., mainly soluble COD. Among them, the most serious environmental pollution is the chlorine-containing wastewater generated during the bleaching process, such as chlorinated bleaching wastewater and hypochlorite bleaching wastewater. Hypochlorite bleaching wastewater mainly contains chloroform and contains more than 40 kinds of other organic chlorides, among which various chlorophenols are the most, such as dichlorophenol and trichlorophenol. In addition, the bleaching waste liquid contains toxic dioxins, which are extremely toxic, posing a serious threat to the ecological environment and human health.

3、白水3, white water

白水即抄纸工段废水，它来源于造纸车间纸张抄造过程。白水主要含有细小纤维、填料、涂料和溶解了的木材成分，以及添加的胶料、湿强剂、防腐剂等，以不溶性COD为主，可生化性较低，其加入的防腐剂有一定的毒性。白水水量较大，但其所含的有机污染负荷远远低于蒸煮黑液和中段废水。现在几乎所有的造纸厂造纸车间都采用了部分或全封闭***以降低造纸耗水量，节约动力消耗，提高白水回用率，减少多余白水排放。White water is the papermaking section wastewater, which comes from the papermaking process in the papermaking workshop. White water mainly contains fine fibers, fillers, coatings and dissolved wood components, as well as added rubber compounds, wet strength agents, preservatives, etc., which are mainly insoluble COD, have low biodegradability, and have a certain preservative added. toxicity. White water has a large amount of water, but its organic pollution load is much lower than that of cooking black liquor and middle-stage wastewater. Almost all paper mill paper mills now use partial or fully enclosed systems to reduce paper consumption, save power, increase white water reuse, and reduce excess white water emissions.

目前，用于造纸废水处理的方法主要有：物理过滤法、混凝沉淀法、吸附法、高级氧化法、气浮法、加酸吸收法、催化氧化法、生化法等，每种方法都具有各自的优缺点。由于单一的处理方法很难达到效果，在实际运用中，通常是根据要处理废水的实际情况，将几种方法结合使用，典型的生产工艺是将造纸废水经过过滤等物理处理，然后经过絮凝沉淀后再经生化处理后达标排放。At present, the methods used for papermaking wastewater treatment mainly include: physical filtration method, coagulation sedimentation method, adsorption method, advanced oxidation method, air floatation method, acid absorption method, catalytic oxidation method, biochemical method, etc., each method has Their respective advantages and disadvantages. Since the single treatment method is difficult to achieve the effect, in practical application, several methods are usually combined according to the actual situation of the wastewater to be treated. The typical production process is to physically treat the papermaking wastewater through filtration and then flocculation and sedimentation. After the biochemical treatment, the standard is discharged.

中国专利CN101708927A公开一种投资小、工艺简单、污染物去除率高、运行费用低廉的氧化降解+絮凝沉淀+砂滤的造纸废水深度处理方法。经该方法处理后COD＜70mg/L，BOD5＜20mg/L，SS＜30mg/L。Chinese patent CN101708927A discloses an advanced treatment method for papermaking wastewater with small investment, simple process, high pollutant removal rate and low operating cost, oxidative degradation + flocculation sedimentation + sand filtration. After treatment by this method, the COD was <70 mg/L, the BOD5 was <20 mg/L, and the SS was <30 mg/L.

中国专利CN1420091公开一种造纸废水的生态处理和资源化循环利用方法，它是利用生态工程技术，造纸综合废水在沉淀池内进行BOD₅∶COD_Cr的比值调整，然后进入串联厌氧塘和兼性塘消化，排水在调节池内进行COD_Cr∶N∶P比值调整后，通过输配水***布入多组并联的地表径流湿地，出水优于造纸工业水污染物排放的一级标准，可经好氧塘储留、补充调节池所需清水，回流到地表径流湿地进行深度再处理。该方法克服了造纸废水营养结构不平衡、可生化性差的缺点，可稳定有效地实现造纸废水的生态处理和资源化循环利用。Chinese patent CN1420091 discloses an ecological treatment and resource recycling method for papermaking wastewater. It uses ecological engineering technology to adjust the ratio of BOD _{5 :} COD _Cr in the sedimentation tank, and then enters the series anaerobic pond and facultative After digesting the pond and draining the COD _Cr: N:P ratio in the regulating tank, multiple sets of parallel surface runoff wetlands are arranged through the water distribution system. The effluent is superior to the first-class standard for water pollutant discharge in the paper industry. The oxygen ponds are reserved and replenished with fresh water required for the adjustment tank, and returned to the surface runoff wetland for further reprocessing. The method overcomes the disadvantages of unbalanced nutrient structure and poor biodegradability of papermaking wastewater, and can realize the ecological treatment and resource recycling of papermaking wastewater stably and effectively.

中国专利CN101337752公开一种造纸废水深度处理工艺，该工艺包括以下步骤：将经二级生化处理后的造纸废水引入微曝气铁还原床，在微曝气铁还原床中装填铁屑，造纸废水在微曝气铁还原床中进行还原反应；将步骤①处理后的出水引入混凝池中，在混凝池中加入混凝剂和助凝剂，促使水中的颗粒凝聚；将步骤②处理后的出水引入沉淀池中进行泥水分离；将沉淀池的出水引入过滤池中进行过滤，过滤后的出水经杀菌消毒后，引入回用水管网；将沉淀池中的污泥以及过滤池中的反冲洗排污水引入污泥浓缩池，经脱水后外运处置；同时，脱水滤液和污泥浓缩池中的溢流液引入混凝池中进行再处理。该发明工艺简单、脱色效果好而且成本低廉。Chinese patent CN101337752 discloses an advanced treatment process for papermaking wastewater, which comprises the steps of introducing a second-stage biochemically treated papermaking wastewater into a micro-aerated iron reduction bed, and charging iron scraps and papermaking wastewater in a micro-aerated iron reduction bed. The reduction reaction is carried out in the micro-aerated iron reduction bed; the effluent treated in step 1 is introduced into the coagulation tank, and a coagulant and a coagulant are added to the coagulation tank to promote particle agglomeration in the water; after the step 2 is treated The effluent is introduced into the sedimentation tank to separate the muddy water; the effluent from the sedimentation tank is introduced into the filter tank for filtration, and the filtered effluent is sterilized and disinfected, and then introduced into the reuse water pipe network; the sludge in the sedimentation tank and the reverse in the filter tank The flushing sewage is introduced into the sludge concentration tank, and is transported by dewatering and then disposed of; and the overflow liquid in the dewatering filtrate and the sludge concentration tank is introduced into the coagulation tank for further treatment. The invention has simple process, good decolorization effect and low cost.

以上方法对造纸废水的处理都取得比较好的效果，但是都存在处理深度不够，生产的中水还含有较多的污染物，只能适合一些对用水质量要求不高的生产工艺，使其的用途用量都受到限制。要使造纸废水再生，满足不同生产工艺的用水要求，特别是高质量用水的要求，必须对其进行深度净化处理，如将生化所得的废水经过进一步净化再经过膜过滤处理，得到纯水。中国专利201010567041.0、201020635352.1介绍了造纸深度处理废水采用膜过滤进行再生循环利用的方法，但是在实施过程中，发现造纸废水中钙离子含量高达150～400mg/L，产生大量结垢，对废水的再生造成严重的困难。The above methods have achieved good results in the treatment of papermaking wastewater, but there are insufficient treatment depths, and the produced water also contains more pollutants, which can only be suitable for some production processes that require less water quality. The amount of use is limited. In order to regenerate the papermaking wastewater and meet the water requirements of different production processes, especially the requirements of high quality water, it must be deeply purified. For example, the biochemical wastewater is further purified and then subjected to membrane filtration to obtain pure water. China Patent 201010567041.0, 201020635352.1 introduced the method of membrane filtration for recycling and recycling of papermaking advanced treatment wastewater, but in the process of implementation, it was found that the calcium ion content in papermaking wastewater is as high as 150-400mg/L, resulting in a large amount of scale and regeneration of wastewater. Caused serious difficulties.

技术问题technical problem

本发明的目的在于针对现有的造纸废水处理方法中所存在的成本较高、效能较低、处理后的废水多为排放、没有深度处理循环利用、浪费水资源等问题，提供一种基于化学脱钙技术、电化学技术与膜技术相结合，成本较低，效能较高，使之达到循环利用的造纸深度处理废水的回用装置及方法。 The object of the present invention is to provide a chemical-based chemistry based on the problems of high cost, low efficiency, mostly treated wastewater, no deep treatment and recycling, and waste of water resources in the existing papermaking wastewater treatment method. The decalcification technology, the electrochemical technology and the membrane technology are combined, the cost is low, and the efficiency is high, so that the recycled papermaking advanced treatment wastewater recycling device and method are realized.

技术解决方案Technical solution

本发明所述基于化学脱钙的造纸深度处理废水回用装置设有化学脱钙***、过滤***、电解***、膜分离***、脱盐***。The chemical decalcification-based papermaking advanced treatment wastewater recycling device of the present invention is provided with a chemical decalcification system, a filtration system, an electrolysis system, a membrane separation system, and a desalination system.

化学脱钙***用于脱除造纸深度处理废水中的钙镁、降低水的硬度，化学脱钙***包括一级脱钙反应池、截止阀、二级脱钙反应池和沉淀池，一级脱钙反应池与截止阀的进口联接，截止阀的出口接二级脱钙反应池的进口，二级脱钙反应池的出口与截止阀的进口联接，截止阀的出口与沉淀池的进口联接，沉淀池的出口接过滤***的进口。The chemical decalcification system is used to remove calcium and magnesium from the advanced wastewater treatment and reduce the hardness of the water. The chemical decalcification system includes a primary decalcification reaction tank, a shut-off valve, a secondary decalcification reaction tank and a sedimentation tank. The calcium reaction tank is connected with the inlet of the shut-off valve, the outlet of the shut-off valve is connected to the inlet of the secondary decalcification reaction tank, the outlet of the secondary decalcification reaction tank is connected with the inlet of the shut-off valve, and the outlet of the shut-off valve is connected with the inlet of the sedimentation tank. The outlet of the sedimentation tank is connected to the inlet of the filtration system.

所述化学脱钙***中的一级脱钙反应池和二级脱钙反应池还配有加药***，加药***设有加药罐和加药泵，加药罐出口接加药泵的进口，加药泵的出口接一级脱钙反应池或二级脱钙反应池的进口。The primary decalcification reaction tank and the secondary decalcification reaction tank in the chemical decalcification system are further provided with a dosing system, and the dosing system is provided with a dosing tank and a dosing pump, and the dosing tank outlet is connected with the dosing pump. Import, the outlet of the dosing pump is connected to the inlet of the first decalcification reaction tank or the secondary decalcification reaction tank.

过滤***用于将化学脱钙后的废水进行过滤分离，过滤***包括截止阀、供水泵、过滤器、反冲洗泵和清洗液罐，截止阀的进口接化学脱钙***的出口，供水泵的进口接截止阀的出口，供水泵的出口接过滤器的进口，过滤器的出口一路与电解***联接，另一路依次经反洗泵接清洗液罐。The filtering system is used for filtering and separating the chemically decalcified wastewater, and the filtering system comprises a shut-off valve, a water supply pump, a filter, a backwashing pump and a cleaning liquid tank, and the inlet of the shut-off valve is connected to the outlet of the chemical decalcification system, and the water supply pump The inlet of the inlet is connected to the outlet of the shut-off valve, the outlet of the water supply pump is connected to the inlet of the filter, the outlet of the filter is connected to the electrolysis system, and the other is connected to the cleaning liquid tank by the backwashing pump.

所述过滤***中的过滤是多介质过滤、纤维滤芯、砂滤、活性砂滤、滤布滤池中的一种。The filtration in the filtration system is one of a multi-media filtration, a fiber filter, a sand filter, an active sand filter, and a filter cloth filter.

电解***用于对过滤分离后的出水进行电解处理，电解***设有截止阀、供水泵和电解机，截止阀的进口外接过滤***出口，供水泵的进口接截止阀的出口，供水泵的出口接电解机的进口，电解机的出口与膜分离***的进口联接。The electrolysis system is used for electrolytic treatment of the effluent after filtration and separation. The electrolysis system is provided with a shut-off valve, a water supply pump and an electrolysis machine. The inlet of the shut-off valve is connected to the outlet of the filter system, the inlet of the water supply pump is connected to the outlet of the shut-off valve, and the outlet of the water supply pump The inlet of the electrolysis machine is connected to the inlet of the membrane separation system.

所述电解***中电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性电极中的一种，所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。The electrolysis machine in the electrolysis system is provided with a power source and an electrolytic cell, and the electrodes in the electrolysis cell are graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inert electrode. In one embodiment, the surface layer of the nano catalytic inert electrode is coated with a metal oxide inert catalytic coating having a crystal grain of 10 to 35 nm, and the substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.

膜分离***通过膜的分离作用对废水中的颗粒和大分子胶体、微生物进行快速去除，得到造纸净化废水。The membrane separation system rapidly removes particles, macromolecular colloids and microorganisms in the wastewater through the separation of the membrane to obtain papermaking purification wastewater.

所述膜分离***可以为超滤和MBR中的一种。The membrane separation system may be one of ultrafiltration and MBR.

所述超滤***设有截止阀、供水泵、超滤膜***、反冲洗泵、透析水贮罐和阀门，截止阀的进口接电解机的出口，截止阀的出口接供水泵的进口，供水泵的出口接超滤膜***的出口、超滤膜***的透析水出口一路接透析水贮罐，另一路经反冲洗泵接透析水贮罐，超滤膜***的浓缩水则经管道和阀门回流至电解***中循环利用；所述超滤***截留分子量为1000～100000MWCO，工作条件为：常温～45℃，超滤***为浸没式超滤、柱式超滤、管式超滤、卷式超滤或板式超滤的一种，浸没式超滤的工作压力为-1～-50kPa，柱式超滤、管式超滤、卷式超滤和板式超滤的工作压力为3～300kPa。The ultrafiltration system is provided with a shut-off valve, a water supply pump, an ultrafiltration membrane system, a backwashing pump, a dialysis water storage tank and a valve, an inlet of the shut-off valve is connected to an outlet of the electrolysis machine, and an outlet of the shut-off valve is connected to an inlet of the water supply pump for supply The outlet of the water pump is connected to the outlet of the ultrafiltration membrane system, the dialysis water outlet of the ultrafiltration membrane system is connected to the dialysis water storage tank, and the other is connected to the dialysis water storage tank by the backwashing pump, and the concentrated water of the ultrafiltration membrane system is passed through the pipeline and the valve. Returning to the electrolysis system for recycling; the ultrafiltration system has a molecular weight cutoff of 1000-100,000 MWCO, working conditions are: normal temperature to 45 ° C, and the ultrafiltration system is submerged ultrafiltration, column ultrafiltration, tubular ultrafiltration, and coil type. One type of ultrafiltration or plate ultrafiltration, the working pressure of immersion ultrafiltration is -1 to -50 kPa, and the working pressure of column ultrafiltration, tubular ultrafiltration, coil ultrafiltration and plate ultrafiltration is 3 to 300 kPa.

所述MBR***设有截止阀、MBR反应池、MBR膜组件、鼓风机、曝气器、排污泵、出水泵、初级再生水贮罐，电解***所得净化污水通过进水管经截止阀接MBR反应池的进口，MBR膜组件浸没在MBR反应池内，通过鼓风机及分布的曝气器对其进行曝气，MBR反应池的出口接出水泵的进口，产生的滤液（水）收集到初级再生水贮罐用于进一步经过脱盐***脱盐得供生产上循环利用的高纯再生水，少量污泥经过排污泵抽吸排放；所述MBR***的膜组件选自聚偏氟乙烯中空纤维膜、聚丙烯中空纤维膜、聚砜中空纤维膜、聚醚砜中空纤维膜、聚丙烯腈中空纤维膜和聚氯乙烯中空纤维膜中的一种；所述MBR***的MBR膜组件的膜孔径为0.10～0.2μm，工作压力为-1～-50kPa，工作温度为5～45℃。The MBR system is provided with a shut-off valve, an MBR reaction tank, an MBR membrane module, a blower, an aerator, a sewage pump, a water discharge pump, a primary reclaimed water storage tank, and the purified sewage obtained by the electrolysis system is connected to the MBR reaction tank through a water inlet pipe through a shut-off valve. Imported, the MBR membrane module is immersed in the MBR reaction tank, aerated by a blower and a distributed aerator, the outlet of the MBR reaction tank is taken out of the inlet of the water pump, and the produced filtrate (water) is collected into the primary reclaimed water storage tank for use. Further, the desalted system is desalted to obtain high-purity reclaimed water for recycling in production, and a small amount of sludge is pumped and discharged through a sewage pump; the membrane module of the MBR system is selected from a polyvinylidene fluoride hollow fiber membrane, a polypropylene hollow fiber membrane, and a poly One of a sulfone hollow fiber membrane, a polyethersulfone hollow fiber membrane, a polyacrylonitrile hollow fiber membrane, and a polyvinyl chloride hollow fiber membrane; the MBR membrane module of the MBR system has a membrane pore diameter of 0.10 to 0.2 μm, and the working pressure is -1 ~ -50kPa, working temperature is 5 ~ 45 °C.

所述超滤***或MBR***还包括化学清洗***，化学清洗***用于清洗超滤或MBR***的膜组件，化学清洗***设有清洗液罐、化学清洗泵和截止阀，清洗液罐的出口接化学清洗泵的进口，化学清洗泵的出口经截止阀接超滤膜或MBR***。The ultrafiltration system or the MBR system further comprises a chemical cleaning system for cleaning the membrane module of the ultrafiltration or MBR system, the chemical cleaning system is provided with a cleaning liquid tank, a chemical cleaning pump and a shut-off valve, and an outlet of the cleaning liquid tank Connect the inlet of the chemical cleaning pump, and the outlet of the chemical cleaning pump is connected to the ultrafiltration membrane or MBR system through the shut-off valve.

脱盐***将膜分离***所得透析水经经脱盐***分离得透析水和浓缩水，透析水进入贮罐得再生水，浓缩水回流至电解***，多余部分排放。所述脱盐***设有截止阀、供水泵、脱盐装置、再生水贮罐、截止阀，截止阀的进口接膜分离***的出口，截止阀的出口接供水泵的进口、供水泵的出口接脱盐装置的进口、脱盐装置的透析水出口依次接截止阀和再生水贮罐，脱盐装置的浓缩水出口经截止阀流至电解***。The desalination system separates the dialysis water obtained by the membrane separation system into dialysis water and concentrated water through a desalting system, and the dialysis water enters the storage tank to obtain reclaimed water, and the concentrated water is returned to the electrolysis system, and the excess portion is discharged. The desalination system is provided with a shut-off valve, a water supply pump, a desalination device, a reclaimed water storage tank, a shut-off valve, an outlet of the shut-off valve inlet membrane separation system, an outlet of the shut-off valve is connected to the inlet of the water supply pump, and the outlet of the water supply pump is connected to the desalination device. The dialysis water outlet of the inlet and desalination device is connected to the shut-off valve and the reclaimed water storage tank in turn, and the concentrated water outlet of the desalination device flows through the shut-off valve to the electrolysis system.

所述脱盐***是纳滤、反渗透、正渗透、电渗析、电容吸附、离子交换或填充电渗析（EDI）的一种。The desalination system is one of nanofiltration, reverse osmosis, forward osmosis, electrodialysis, capacitive adsorption, ion exchange or filled electrodialysis (EDI).

所述纳滤中的纳滤膜组件为管式膜组件、卷式膜组件或平板膜组件的一种，工作压力为6～45bar，工作温度为20～45℃，最佳温度为35～40℃。The nanofiltration membrane module in the nanofiltration is a tubular membrane module, a coil membrane module or a flat membrane module, and the working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimal temperature is 35 to 40. °C.

所述反渗透的反渗透膜组件为卷式膜组件，膜材料为有机膜中醋酸纤维膜或复合膜，膜材料的截留分子量为50～200MWCO，进压可为6.0～45.0bar，出压可为4.5～33.5bar。The reverse osmosis reverse osmosis membrane module is a roll membrane module, and the membrane material is an acetate membrane or a composite membrane in an organic membrane. The membrane material has a molecular weight cutoff of 50-200 MWCO, and the inlet pressure can be 6.0-45.0 bar, and the pressure can be It is 4.5 to 33.5 bar.

所述的正渗透的膜组件为板框式膜组件、卷式膜组件、管式膜组件和包式膜组件中的一种。The forward osmosis membrane module is one of a plate and frame membrane module, a roll membrane module, a tubular membrane module, and a bag membrane module.

所述的电渗析的工作条件是操作电压压力0.5～3.0㎏/cm²，操作电压50～250V，电流强度1～3A。The working conditions of the electrodialysis are an operating voltage of 0.5 to 3.0 kg/cm ² , an operating voltage of 50 to 250 V, and a current intensity of 1 to 3 A.

所述的电容吸附的工作条件是直流电压为110V/m~2×10⁶V/m。The working condition of the capacitor adsorption is that the DC voltage is 110V/m~2×10 ⁶ V/m.

所述的离子交换使用的离子交换剂分为无机离子交换剂和有机离子交换剂两大类，无机离子交换剂有天然沸石和合成沸石等，有机交换树脂为强酸阳离子交换树脂、弱酸阳离子交换树脂、强碱阴离子交换树脂、弱碱阴离子交换树脂、螯合树脂和有机吸附树脂等中的一种。The ion exchanger used in the ion exchange is divided into two types: an inorganic ion exchanger and an organic ion exchanger. The inorganic ion exchanger has a natural zeolite and a synthetic zeolite, and the organic exchange resin is a strong acid cation exchange resin and a weak acid cation exchange resin. One of a strong base anion exchange resin, a weak base anion exchange resin, a chelating resin, and an organic adsorption resin.

所述的填充电渗析（EDI）是一种将电渗析与离子交换有机结合在一起的膜分离脱盐工艺，填充电渗析装置进水要求为电阻率为0.025～0.5MΩ·cm。The filled electrodialysis (EDI) is a membrane separation and desalination process in which electrodialysis and ion exchange are organically combined, and the water injecting electrodialysis device requires a resistivity of 0.025 to 0.5 MΩ·cm.

本发明所述基于化学脱钙的造纸深度处理废水回用方法包括以下步骤：The chemical decalcification-based papermaking advanced treatment wastewater reuse method of the present invention comprises the following steps:

（1）化学脱钙 (1) Chemical decalcification

造纸生化处理后的二沉池出水（即造纸深度处理废水）经管道流入一级脱钙反应池，通过加药装置在搅拌下先加入适量石灰饱和溶液调pH值至8.5～9.5，脱除假性硬度（碳酸氢盐）后，流入二级脱钙反应池，加入100~600mg/L的Na₂CO₃，使碳酸根与钙镁离子反应生成碳酸盐沉淀，然后加入2~10mg/L的FeSO₄，再加入Na₂CO₃反调pH值至8～9，最后加入1~3mg/L的聚苯烯酰胺（PAM），反应完全后进入沉淀池，进行沉淀分离，从而脱除造纸深度处理废水中的钙镁、将废水的硬度降低到30~80mg/L，防止后续设备、设施因为Ca²⁺、Mg²⁺浓度过高而结垢；沉淀物（即污泥）经过泵和管道送入污泥池中，最后在污泥脱水装置中进行过滤分离，并回收碳酸钙，废水则进入下一步骤过滤；The effluent from the secondary sedimentation tank after the biochemical treatment of papermaking (ie, the papermaking advanced treatment wastewater) flows into the first-stage decalcification reaction tank through the pipeline, and the pH is adjusted to 8.5-9.5 by adding a proper amount of lime saturated solution under stirring by the dosing device to remove the false After the hardness (bicarbonate), it flows into the secondary decalcification reaction tank, and 100~600mg/L of Na ₂ CO _{3 is} added to react the carbonate with calcium and magnesium ions to form a carbonate precipitate, and then add 2~10mg/L. FeSO ₄ , then add Na ₂ CO _{3 to} adjust the pH to 8-9, and finally add 1~3mg/L polyphenylene amide (PAM). After the reaction is complete, enter the sedimentation tank and carry out sedimentation separation to remove the papermaking depth. Treat calcium and magnesium in wastewater, reduce the hardness of wastewater to 30~80mg/L, prevent subsequent equipment and facilities from scaling due to excessive concentration of Ca ²⁺ and Mg ²⁺ ; sediment (ie sludge) passes through pumps and pipelines It is sent to the sludge tank, and finally filtered and separated in the sludge dewatering device, and the calcium carbonate is recovered, and the wastewater is filtered into the next step;

（2）过滤(2) Filtering

将化学脱钙后的废水泵入过滤***进行过滤分离，进一步除去水中的SS和胶体；The chemically decalcified wastewater is pumped into a filtration system for filtration separation to further remove SS and colloid in water;

（3）电解(3) Electrolysis

将过滤后的废水泵入电解机电解，以降解有机大分子，脱除色度，提高废水的可生化性，电解机的相邻两电极间的电压为2～12V，电流密度为10～320mA/cm²；The filtered wastewater is pumped into the electrolysis machine to decompose organic macromolecules, remove the chroma and improve the biodegradability of the wastewater. The voltage between the adjacent electrodes of the electrolysis machine is 2-12V, and the current density is 10~320mA. /cm ² ;

（4）膜分离 (4) Membrane separation

经过电解后的废水进入膜分离***，通过膜分离作用去除废水中的颗粒、大分子胶体化合物和微生物，得到透析水和浓缩水，透析水进入脱盐处理***，浓缩水经管道回流至步骤（3）的电解机中循环利用；The electrolyzed wastewater enters the membrane separation system, and the particles, macromolecular colloidal compounds and microorganisms in the wastewater are removed by membrane separation to obtain dialysis water and concentrated water, and the dialysis water enters the desalination treatment system, and the concentrated water is refluxed through the pipeline to the step (3) Recycling in the electrolysis machine;

（5）脱盐(5) Desalting

膜分离所得透析水用泵泵入脱盐***，经脱盐***过滤分离得透析水和浓缩水，透析水进入贮罐得再生水；浓缩水一部分回流到电解***，多余部分排放。The dialysis water obtained by membrane separation is pumped into the desalting system, and the dialysis water and concentrated water are separated by filtration through the desalination system, and the dialysis water enters the storage tank to obtain reclaimed water; a part of the concentrated water is returned to the electrolysis system, and the excess is discharged.

步骤（2）过滤所述的过滤***是多介质过滤、纤维滤芯、砂滤、活性砂滤、滤布滤池中的一种。Step (2) Filtration The filtration system is one of a multi-media filtration, a fiber filter, a sand filter, an active sand filter, and a filter cloth filter.

步骤（3）电解所述电解机设有电源和电解槽，所述电解槽内的电极材料为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性材料中的一种；所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。Step (3) Electrolysis The electrolysis machine is provided with a power source and an electrolytic cell, and the electrode materials in the electrolytic cell are graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy and nano catalytic inertia. One of the materials; the surface layer of the nano catalytic inert electrode is coated with a metal oxide inert catalytic coating having a crystal grain of 10 to 35 nm, and the substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.

步骤（4）所述膜分离***为超滤或MBR中的一种。所述超滤截留分子量为1000～50000MWCO，工作条件为：常温～45℃，浸没式超滤的工作压力为-1～-50kPa，超滤为浸没式超滤、柱式超滤、管式超滤、卷式超滤或板式超滤的一种，柱式超滤、管式超滤、卷式超滤和板式超滤的工作压力为3～300kPa。所述MBR***的膜组件选自聚偏氟乙烯中空纤维膜、聚丙烯中空纤维膜、聚砜中空纤维膜、聚醚砜中空纤维膜、聚丙烯腈中空纤维膜和聚氯乙烯中空纤维膜中的一种；所述MBR***的MBR膜组件的膜孔径为0.10～0.2μm，工作压力为-1～-50kPa，工作温度为5～45℃。The membrane separation system of the step (4) is one of ultrafiltration or MBR. The ultrafiltration molecular weight cutoff is 1000-50,000 MWCO, the working conditions are: normal temperature ~ 45 ° C, the working pressure of immersion ultrafiltration is -1 ~ -50 kPa, ultrafiltration is submerged ultrafiltration, column ultrafiltration, tubular super One type of filtration, roll ultrafiltration or plate ultrafiltration, column ultrafiltration, tubular ultrafiltration, roll ultrafiltration and plate ultrafiltration have a working pressure of 3 to 300 kPa. The membrane module of the MBR system is selected from the group consisting of a polyvinylidene fluoride hollow fiber membrane, a polypropylene hollow fiber membrane, a polysulfone hollow fiber membrane, a polyethersulfone hollow fiber membrane, a polyacrylonitrile hollow fiber membrane, and a polyvinyl chloride hollow fiber membrane. The MBR membrane module of the MBR system has a membrane pore size of 0.10 to 0.2 μm, a working pressure of -1 to -50 kPa, and an operating temperature of 5 to 45 °C.

步骤（5）所述脱盐***是纳滤、反渗透、正渗透、电渗析、电容吸附、离子交换或填充电渗析（EDI）的一种。所述的纳滤***的膜组件为管式膜组件、卷式膜组件或平板膜组件的一种，工作压力为6～45bar，工作温度为20～45℃，最佳温度为35～40℃。所述反渗透膜***采用截留分子量可为50～200MWCO的反渗透膜，膜组件为管式膜组件或卷式膜组件，进压可为6.0～35.0bar，出压可为4.5～33.5bar。所述的正渗透的膜组件为板框式膜组件、卷式膜组件、管式膜组件和包式膜组件中的一种。所述的电渗析的工作条件是操作电压压力0.5～3.0㎏/cm² The desalination system of step (5) is one of nanofiltration, reverse osmosis, forward osmosis, electrodialysis, capacitive adsorption, ion exchange or filled electrodialysis (EDI). The membrane module of the nanofiltration system is a tubular membrane module, a membrane membrane module or a flat membrane module, and the working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimal temperature is 35 to 40 ° C. . The reverse osmosis membrane system adopts a reverse osmosis membrane with a molecular weight cutoff of 50-200 MWCO, and the membrane module is a tubular membrane module or a membrane membrane module, the inlet pressure can be 6.0-35.0 bar, and the outlet pressure can be 4.5-33.5 bar. The forward osmosis membrane module is one of a plate and frame membrane module, a roll membrane module, a tubular membrane module, and a bag membrane module. The working condition of the electrodialysis is an operating voltage pressure of 0.5 to 3.0 kg/cm ²

，操作电压50～250V，电流强度1～3A。所述的电容吸附的工作条件是直流电压为110V/m～2×10⁶V/m。所述的离子交换使用的离子交换剂分为无机离子交换剂和有机离子交换剂两大类，无机离子交换剂有天然沸石和合成沸石等，有机交换树脂为强酸阳离子交换树脂、弱酸阳离子交换树脂、强碱阴离子交换树脂、弱碱阴离子交换树脂、螯合树脂和有机吸附树脂等中的一种。所述的填充电渗析（EDI）是一种将电渗析与离子交换有机结合在一起的膜分离脱盐工艺，填充电渗析装置进水要求为电阻率为0.025～0.5MΩ·cm。The operating voltage is 50-250V, and the current intensity is 1~3A. The operating condition of the capacitor adsorption is that the DC voltage is 110V/m to 2×10 ⁶ V/m. The ion exchanger used in the ion exchange is divided into two types: an inorganic ion exchanger and an organic ion exchanger. The inorganic ion exchanger has a natural zeolite and a synthetic zeolite, and the organic exchange resin is a strong acid cation exchange resin and a weak acid cation exchange resin. One of a strong base anion exchange resin, a weak base anion exchange resin, a chelating resin, and an organic adsorption resin. The filled electrodialysis (EDI) is a membrane separation and desalination process in which electrodialysis and ion exchange are organically combined, and the water injecting electrodialysis device requires a resistivity of 0.025 to 0.5 MΩ·cm.

有益效果Beneficial effect

本发明既克服了单用膜过滤分离处理或吸附处理成本过高的缺陷，又克服了常规的造纸废水方法的处理效果不理想，排放的废水污染环境等缺陷，将现有的造纸深度处理废水净化及回收循环利用。与现有技术比较，具有以下突出优点：The invention not only overcomes the defects of excessive filtration filtration treatment or adsorption treatment, but also overcomes the defects of the conventional papermaking wastewater treatment method, the waste water pollution environment and the like, and the existing papermaking advanced treatment wastewater. Purification and recycling. Compared with the prior art, it has the following outstanding advantages:

（1）造纸深度处理废水经过处理，70%～85%可以再生循环利用，既减少废水排放，避免废水对环境污染，又减少水资源浪费，还可以使再生的循环水成本低于自来水价格，经济合理，产生较好的经济效益。(1) After the treatment of wastewater treatment, 70%-85% can be recycled and reused, which not only reduces wastewater discharge, avoids environmental pollution of wastewater, but also reduces water waste, and can also make the cost of recycled recycled water lower than the price of tap water. Economically reasonable, resulting in better economic returns.

（2）通过化学脱钙***的一级脱钙反应脱除假性硬度（碳酸氢盐）后，再经过二级脱钙反应池使碳酸根与钙镁离子反应生成碳酸盐沉淀，然后与FeSO₄和聚苯烯酰胺（PAM）等助凝剂互相絮凝，聚集成粗大的矾花颗粒，在沉淀池中沉降下来，最终有效脱除造纸深度处理废水中的高浓度钙、镁离子，降低水的硬度，防止设备结垢，保证后续工艺顺利、稳定运行。(2) After removing the pseudo hardness (bicarbonate) by the primary decalcification reaction of the chemical decalcification system, the carbonate is precipitated by reacting the carbonate with the calcium and magnesium ions through a secondary decalcification reaction tank, and then The coagulant such as FeSO ₄ and polyphenylene amide (PAM) flocculates with each other, aggregates into coarse squid granules, and settles in the sedimentation tank, finally effectively removing high concentration of calcium and magnesium ions in the papermaking advanced treatment wastewater and reducing The hardness of the water prevents the equipment from scaling and ensures smooth and stable operation of the subsequent process.

（3）通过纳米催化电解进一步降低COD，一是可以使废水的回用率提高，既减少废水排放，避免废水对环境污染，又减少水资源浪费；二是能杀灭废水中的细菌等微生物，根除后续纳滤膜和反渗透膜的生物污染，大幅度减少纳滤膜和反渗透膜的清洗次数，降低膜清洁再生成本，提高膜的使用效率，延长膜的使用寿命，减少膜更换成本。(3) Further reduce COD by nano-catalytic electrolysis. First, it can improve the reuse rate of wastewater, reduce wastewater discharge, avoid wastewater pollution to the environment, and reduce water waste. Second, it can kill bacteria and other microorganisms in wastewater. Eliminate the biological contamination of the subsequent nanofiltration membrane and reverse osmosis membrane, greatly reduce the cleaning times of the nanofiltration membrane and the reverse osmosis membrane, reduce the membrane cleaning regeneration cost, improve the membrane use efficiency, prolong the membrane service life, and reduce the membrane replacement cost. .

（4）经过膜分离***处理后，使废水中的颗粒和大分子胶体化合物进一步去除，为后续的工艺创造良好的水质条件，同时通过MBR***中微生物的氧化分解作用将进一步分解水中污染物质，利用膜的高效截留效果，使SS、色度、污染物等指标得到有效去除。(4) After treatment by the membrane separation system, the particles and macromolecular colloidal compounds in the wastewater are further removed, thereby creating good water quality conditions for the subsequent process, and further decomposing the pollutants in the water through the oxidative decomposition of microorganisms in the MBR system. Using the high-efficiency retention effect of the membrane, indicators such as SS, chromaticity, and pollutants are effectively removed.

（5）大幅度降低吨纸的水消耗指标和废水排放指标，提高企业经济技术指标。(5) Substantially reduce water consumption indicators and wastewater discharge indicators of tons of paper, and improve economic and technical indicators of enterprises.

本发明所称造纸深度处理废水是指造纸废水经过传统的过滤、絮凝处理后二沉池出水，即达到三级以上排放标准的废水。The invention relates to the papermaking advanced treatment wastewater, which refers to the wastewater from the secondary sedimentation tank after the traditional filtration and flocculation treatment of the papermaking wastewater, that is, the wastewater that meets the discharge standard of the third grade or above.

附图说明DRAWINGS

图1为本发明基于化学脱钙的造纸深度处理废水回用装置膜分离采用超滤***的结构示意图；1 is a schematic view showing the structure of an ultrafiltration system for membrane separation of a papermaking advanced treatment wastewater reuse device based on chemical decalcification;

图2为本发明基于化学脱钙的造纸深度处理废水回用装置膜分离采用MBR***的结构示意图；2 is a schematic structural view of a membrane separation using a chemical decalcification method for a papermaking advanced treatment wastewater reuse device according to the present invention;

图3本发明加药***的结构示意图。Figure 3 is a schematic view showing the structure of the dosing system of the present invention.

本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION

本发明是在对现有造纸深度处理废水的成份、性质和现有处理方案进行深入***的对比研究之后完成的对造纸深度处理后废水的净化和回用装置的设计，它由化学脱钙***、过滤***、电解***、膜分离***和脱盐***组成。The invention is a design of a purification and reuse device for wastewater after deep treatment of papermaking, which is completed after in-depth systematic comparison research on the composition, properties and existing treatment schemes of the existing papermaking advanced treatment wastewater, which is composed of a chemical decalcification system. , filtration system, electrolysis system, membrane separation system and desalination system.

下面实施例将结合附图对本发明作进一步的说明。The invention will be further illustrated by the following examples in conjunction with the drawings.

参见图1、图2、图3，本发明所述基于化学脱钙的造纸深度处理废水回用装置包括：Referring to FIG. 1 , FIG. 2 and FIG. 3 , the chemical decalcification-based papermaking advanced treatment wastewater recycling device of the present invention comprises:

化学脱钙***：化学脱钙***用于脱除造纸深度处理废水中的钙镁、降低水的硬度，化学脱钙***设有一级脱钙反应池11、截止阀12、二级脱钙反应池13、截止阀14、沉淀池15，一级脱钙反应池11与截止阀12的进口联接，截止阀12的出口接二级脱钙反应池13的进口，二级脱钙反应池13的出口与截止阀14的进口联接，截止阀14的出口与沉淀池15的进口联接，沉淀池15的出口接过滤***的进口。Chemical decalcification system: The chemical decalcification system is used to remove calcium and magnesium from the advanced wastewater treatment and reduce the hardness of water. The chemical decalcification system has a primary decalcification reaction tank 11, a shut-off valve 12, and a secondary decalcification reaction tank. 13. The shut-off valve 14 and the sedimentation tank 15, the primary decalcification reaction tank 11 is connected to the inlet of the shut-off valve 12, the outlet of the shut-off valve 12 is connected to the inlet of the secondary decalcification reaction tank 13, and the outlet of the secondary decalcification reaction tank 13 Coupled with the inlet of the shut-off valve 14, the outlet of the shut-off valve 14 is coupled to the inlet of the settling tank 15, and the outlet of the settling tank 15 is connected to the inlet of the filtration system.

加药***：参照图3，加药***用于对废水投加脱钙剂和混凝剂，加药***设有石灰加药罐16、加药泵161、Na₂CO₃加药罐17、加药泵171、FeSO₄加药罐18、加药泵181、PAM加药罐19、加药泵191；石灰加药罐16的出口接加药泵161的进口，加药泵161的出口接一级脱钙反应池11的进口；Na₂CO₃加药罐17的出口接加药泵171的进口，加药泵171的出口接二级脱钙反应池13的进口；FeSO₄加药罐18的出口接加药泵181的进口，加药泵181的出口接二级脱钙反应池13的进口；PAM加药罐19的出口接加药泵191的进口，加药泵191的出口接二级脱钙反应池13的进口。Dosing system: Referring to Figure 3, the dosing system is used for adding decalcifying agent and coagulant to the wastewater, and the dosing system is provided with a lime dosing tank 16, a dosing pump 161, a Na ₂ CO ₃ dosing tank 17, The dosing pump 171, the FeSO ₄ dosing tank 18, the dosing pump 181, the PAM dosing tank 19, the dosing pump 191; the outlet of the lime dosing tank 16 is connected to the inlet of the dosing pump 161, and the outlet of the dosing pump 161 is connected The inlet of the primary decalcification reaction tank 11; the outlet of the Na ₂ CO ₃ dosing tank 17 is connected to the inlet of the dosing pump 171, the outlet of the dosing pump 171 is connected to the inlet of the secondary decalcification reaction tank 13; and the FeSO ₄ dosing tank The outlet of 18 is connected to the inlet of the dosing pump 181, the outlet of the dosing pump 181 is connected to the inlet of the secondary decalcification reaction tank 13; the outlet of the PAM dosing tank 19 is connected to the inlet of the dosing pump 191, and the outlet of the dosing pump 191 is connected The inlet of the secondary decalcification reaction tank 13.

过滤***：过滤***用于将化学脱钙后的废水进行过滤分离，过滤***设有截止阀21、供水泵22、过滤器23、截止阀24、反冲洗泵25和清洗液罐26；截止阀21的进口接化学脱钙***的出口，供水泵22的进口接截止阀21的出口，供水泵22的出口接过滤器23的进口，过滤器23的出口一路与电解***联接，另一路依次经反洗泵25接清洗液罐26。Filtration system: the filtration system is used for filtering and separating the chemically decalcified wastewater. The filtration system is provided with a shut-off valve 21, a water supply pump 22, a filter 23, a shut-off valve 24, a backwash pump 25 and a cleaning liquid tank 26; The inlet of 21 is connected to the outlet of the chemical decalcification system, the inlet of the water supply pump 22 is connected to the outlet of the shut-off valve 21, the outlet of the water supply pump 22 is connected to the inlet of the filter 23, the outlet of the filter 23 is connected to the electrolysis system, and the other is sequentially The backwash pump 25 is connected to the wash tank 26.

电解***：电解***用于对过滤分离后的出水进行电解处理，电解***设有截止阀31、供水泵32和电解机33；截止阀31的进口外接过滤***排出口，供水泵32的进口接截止阀31的出口，供水泵32的出口接电解机33的进口，电解机33的出口与膜分离***的进口联接。Electrolysis system: The electrolysis system is used for electrolytic treatment of the effluent after filtration and separation. The electrolysis system is provided with a shut-off valve 31, a water supply pump 32 and an electrolysis machine 33; the inlet of the shut-off valve 31 is externally connected to the discharge port of the filter system, and the inlet of the water supply pump 32 is connected. At the outlet of the shutoff valve 31, the outlet of the water supply pump 32 is connected to the inlet of the electrolysis machine 33, and the outlet of the electrolysis machine 33 is coupled to the inlet of the membrane separation system.

膜分离***：膜分离***用于通过膜的分离作用对废水中的颗粒和大分子胶体、微生物进行快速去除，得到造纸净化废水。膜分离***可以为超滤和MBR中的一种。Membrane Separation System: Membrane separation system is used to rapidly remove particles, macromolecular colloids and microorganisms in wastewater by separation of membranes to obtain papermaking purification wastewater. The membrane separation system can be one of ultrafiltration and MBR.

参照图1，超滤***设有截止阀41、供水泵42、超滤膜***43、反冲洗泵44、截止阀45、透析水贮罐46和阀门47，截止阀41的进口接电解机33的出口，截止阀41的出口接供水泵42的进口，供水泵42的出口接超滤膜***43的出口，超滤膜***43的透析水出口依次经反冲洗泵44、截止阀45接透析水贮罐46，超滤膜***43的浓缩水则经阀门47回流至电解***中重复利用。Referring to Fig. 1, the ultrafiltration system is provided with a shutoff valve 41, a water supply pump 42, an ultrafiltration membrane system 43, a backwash pump 44, a shutoff valve 45, a dialysis water storage tank 46, and a valve 47, and an inlet electrolysis machine 33 of the shutoff valve 41. The outlet of the shut-off valve 41 is connected to the inlet of the water supply pump 42, the outlet of the water supply pump 42 is connected to the outlet of the ultrafiltration membrane system 43, and the dialysis water outlet of the ultrafiltration membrane system 43 is sequentially dialyzed by the backwash pump 44 and the shut-off valve 45. The water storage tank 46, the concentrated water of the ultrafiltration membrane system 43 is returned to the electrolysis system via valve 47 for reuse.

参照图2，MBR***,设有截止阀41、MBR膜组件42、鼓风机43、曝气器44、MBR反应池45、排污泵46、出水泵47和初级再生水贮罐48。截止阀41的进口接电解机33的出口，截止阀41的出口依次经过MBR反应池45、出水泵47进入初级再生水贮罐48。Referring to Fig. 2, the MBR system is provided with a shutoff valve 41, an MBR membrane module 42, a blower 43, an aerator 44, an MBR reaction tank 45, a sewage pump 46, an outlet pump 47, and a primary reclaimed water storage tank 48. The inlet of the shutoff valve 41 is connected to the outlet of the electrolysis machine 33, and the outlet of the shutoff valve 41 sequentially passes through the MBR reaction tank 45 and the outlet water pump 47 to enter the primary reclaimed water storage tank 48.

超滤或MBR化学清洗***：化学清洗***用于清洗超滤或MBR***，化学清洗***设有清洗液罐51、化学清洗泵52和截止阀53，清洗液罐51的出口接化学清洗泵52的进口，化学清洗泵52的出口经截止阀53接超滤或MBR***。Ultrafiltration or MBR chemical cleaning system: The chemical cleaning system is used to clean the ultrafiltration or MBR system. The chemical cleaning system is provided with a cleaning liquid tank 51, a chemical cleaning pump 52 and a shut-off valve 53, and the outlet of the cleaning liquid tank 51 is connected to the chemical cleaning pump 52. The inlet of the chemical cleaning pump 52 is connected to the ultrafiltration or MBR system via a shut-off valve 53.

脱盐***：脱盐***将膜分离***所得透析水用泵泵入脱盐***，经脱盐***分离得透析水和浓缩水，透析水进入贮罐得再生水；浓缩水一部分回流到电解***，多余部分排放。所述脱盐***可以是是纳滤、反渗透、正渗透、电渗析、电容吸附、离子交换或填充电渗析（EDI）的一种。Desalination system: The desalination system pumps the dialysis water obtained by the membrane separation system into the desalination system, and separates the dialysis water and the concentrated water through the desalination system. The dialysis water enters the storage tank to obtain the reclaimed water; a part of the concentrated water is returned to the electrolysis system, and the excess is discharged. The desalination system may be one of nanofiltration, reverse osmosis, forward osmosis, electrodialysis, capacitive adsorption, ion exchange or filled electrodialysis (EDI).

脱盐***设有截止阀61、供水泵62、脱盐装置63、截止阀64、再生水贮罐65、截止阀66。截止阀61的进口接膜分离***透析水贮罐的出口，截止阀61的出口依次经供水泵62、脱盐装置63，脱盐装置63的透析水出口经截止阀64接再生水贮罐65的进口，脱盐装置63的回流浓缩水出口经截止阀66回流至电解***。The desalination system is provided with a shutoff valve 61, a water supply pump 62, a desalination device 63, a shutoff valve 64, a reclaimed water storage tank 65, and a shutoff valve 66. The inlet of the shutoff valve 61 is connected to the outlet of the dialysis water storage tank, and the outlet of the shutoff valve 61 is sequentially passed through the water supply pump 62 and the desalination device 63. The dialysis water outlet of the desalination device 63 is connected to the inlet of the reclaimed water storage tank 65 via the shutoff valve 64. The reflux concentrated water outlet of the desalination device 63 is returned to the electrolysis system via a shutoff valve 66.

本发明的实施方式Embodiments of the invention

以下结合图1、图2和图3给出基于化学脱钙的造纸深度处理废水回用装置的具体实施例。A specific embodiment of a chemical decalcification-based papermaking advanced treatment wastewater reuse apparatus is given below in conjunction with Figs. 1, 2 and 3.

实施例1Example 1

800吨/日造纸深度处理废水的回用方法。Recycling method for 800 tons/day papermaking advanced treatment wastewater.

所述的造纸深度处理废水水质指标经测定如表1所示。The water quality index of the papermaking advanced treatment wastewater is determined as shown in Table 1.

表1造纸深度处理废水的水质指标Table 1 Water quality indicators of papermaking advanced treatment wastewater

序号Serial number	项目project	单位unit	测定值measured value	序号Serial number	项目project	单位unit	测定值measured value
11	CODCr COD Cr	mg/LMg/L	150150	44	色度Chroma		100100
22	SSSS	mg/LMg/L	120120	55	CaCa	mg/LMg/L	400400
33	电导率Conductivity	µS/cmμS/cm	16001600	66	硬度hardness	mmol/LMmmol/L	9.99.9

（1）化学脱钙(1) Chemical decalcification

造纸生化处理后二沉池出水（即造纸深度处理废水）经管道流入一级脱钙反应池11，通过加药装置在搅拌下先加入适量石灰饱和溶液调pH值至8.5，脱除假性硬度（碳酸氢盐）后，流入二级脱钙反应池13，加入600mg/L的Na₂CO₃，使碳酸根与钙镁离子反应生成碳酸盐沉淀，然后加入5mg/L的FeSO₄，再加入Na₂CO₃反调pH值至8.5，最后加入1mg/L的聚苯烯酰胺（PAM），反应完全后进入沉淀池15，进行沉淀分离，从而脱除造纸深度处理废水中的钙镁、降低水的硬度，防止后续设备、设施因为Ca²⁺浓度过高而结垢；沉淀物（即污泥）经过泵和管道送入污泥池中，最后在污泥脱水装置中进行过滤分离，并回收碳酸钙，废水则进入下一步骤过滤；After the biochemical treatment of the paper, the effluent from the secondary settling tank (ie, the papermaking advanced treatment wastewater) flows into the primary decalcification reaction tank 11 through the pipeline, and the pH is adjusted to 8.5 by adding a proper amount of lime saturated solution under stirring by the dosing device to remove the pseudo hardness. After (bicarbonate), it flows into the secondary decalcification reaction tank 13, and 600 mg/L of Na ₂ CO _{3 is} added to react the carbonate with the calcium and magnesium ions to form a carbonate precipitate, and then 5 mg/L of FeSO _{4 is added} , and then Adding Na ₂ CO _{3 to} adjust the pH to 8.5, and finally adding 1 mg/L of polyphenylene amide (PAM), after the reaction is completed, it enters the sedimentation tank 15 and is subjected to precipitation separation, thereby removing calcium and magnesium in the papermaking advanced treatment wastewater and reducing The hardness of the water prevents the subsequent equipment and facilities from scaling due to excessive Ca ²⁺ concentration; the sediment (ie sludge) is sent to the sludge tank through the pump and pipeline, and finally filtered and separated in the sludge dewatering device, and The calcium carbonate is recovered, and the wastewater is filtered into the next step;

（2）过滤(2) Filtering

将化学脱钙后的废水泵入过滤***进行过滤分离，进一步除去水中的SS和胶体；The chemically decalcified wastewater is pumped into a filtration system for filtration separation to further remove SS and colloid in water;

上述过滤为多介质过滤。过滤可以是多介质过滤、纤维滤芯、砂滤、活性砂滤、滤布滤池中的一种。The above filtration is multi-media filtration. The filtration may be one of a multi-media filtration, a fiber filter, a sand filter, an active sand filter, and a filter cloth filter.

（3）电解(3) Electrolysis

将过滤后的废水泵入电解机33电解，以降解有机大分子，脱除色度，提高废水的可生化性，电解机33的相邻两电极间的电压为2V，电流密度为200mA/cm²；The filtered wastewater is pumped into the electrolysis machine 33 for electrolysis to degrade the organic macromolecules, remove the chromaticity, and improve the biodegradability of the wastewater. The voltage between the adjacent electrodes of the electrolysis machine 33 is 2V, and the current density is 200 mA/cm. ² ;

（4）膜分离(4) Membrane separation

经过电解后的废水进入膜分离***，通过膜分离作用去除废水中的颗粒、大分子胶体化合物和微生物，得到透析水和浓缩水，透析水进入脱盐处理***，浓缩水经管道回流至步骤（3）的电解机33中循环利用；The electrolyzed wastewater enters the membrane separation system, and the particles, macromolecular colloidal compounds and microorganisms in the wastewater are removed by membrane separation to obtain dialysis water and concentrated water, and the dialysis water enters the desalination treatment system, and the concentrated water is refluxed through the pipeline to the step (3) Recycling in the electrolysis machine 33;

所述膜分离***为MBR***。MBR***的膜组件选自聚偏氟乙烯中空纤维膜、聚丙烯中空纤维膜、聚砜中空纤维膜、聚醚砜中空纤维膜、聚丙烯腈中空纤维膜和聚氯乙烯中空纤维膜中的一种；MBR膜组件的膜孔径为0.10～0.2μm，工作压力为-1～-50kPa，工作温度为5～45℃。The membrane separation system is an MBR system. The membrane module of the MBR system is selected from the group consisting of a polyvinylidene fluoride hollow fiber membrane, a polypropylene hollow fiber membrane, a polysulfone hollow fiber membrane, a polyethersulfone hollow fiber membrane, a polyacrylonitrile hollow fiber membrane, and a polyvinyl chloride hollow fiber membrane. The membrane pore size of the MBR membrane module is 0.10-0.2 μm, the working pressure is -1 to -50 kPa, and the working temperature is 5 to 45 °C.

（5）脱盐*** (5) Desalination system

膜分离所得透析水用泵泵入脱盐***，经脱盐***过滤分离得透析水和浓缩水，透析水进入贮罐得再生水；浓缩水一部分回流到电解***，多余部分排放。The dialysis water obtained by membrane separation is pumped into the desalting system, and the dialysis water and concentrated water are separated by filtration through the desalination system, and the dialysis water enters the storage tank to obtain reclaimed water; a part of the concentrated water is returned to the electrolysis system, and the excess is discharged.

所述脱盐***为反渗透***。反渗透膜***采用截留分子量可为50～200MWCO的反渗透膜，膜组件为管式膜组件或卷式膜组件，进压可为6.0～35.0bar，出压可为4.5～33.5bar。The desalination system is a reverse osmosis system. The reverse osmosis membrane system adopts a reverse osmosis membrane having a molecular weight cutoff of 50 to 200 MWCO, and the membrane module is a tubular membrane module or a membrane module, the inlet pressure can be 6.0 to 35.0 bar, and the pressure can be 4.5 to 33.5 bar.

再生水水质指标经测定如表2所示。The water quality indicators of reclaimed water were determined as shown in Table 2.

表2再生水的水质指标Table 2 Water quality indicators of reclaimed water

序号Serial number	项目project	单位unit	测定值measured value	序号Serial number	项目project	单位unit	测定值measured value
11	CODCr COD Cr	mg/LMg/L	88	44	色度Chroma		88
22	SSSS	mg/LMg/L	≤1≤1	55	CaCa	mg/LMg/L	4545
33	电导率Conductivity	µS/cmμS/cm	8080	66	硬度hardness	mmol/LMmmol/L	1.11.1

实施例2Example 2

5000吨/日造纸深度处理废水的回用方法。Recycling method for 5000 tons/day papermaking advanced treatment wastewater.

所述的造纸深度处理废水水质指标经测定如表3所示。The water quality index of the papermaking advanced treatment wastewater is determined as shown in Table 3.

表3造纸深度处理废水的水质指标Table 3 Water quality indicators of papermaking advanced treatment wastewater

序号Serial number	项目project	单位unit	测定值measured value	序号Serial number	项目project	单位unit	测定值measured value
11	CODCr COD Cr	mg/LMg/L	100100	44	色度Chroma		150150
22	SSSS	mg/LMg/L	120120	55	CaCa	mg/LMg/L	150150
33	电导率Conductivity	µS/cmμS/cm	18001800	66	硬度hardness	mmol/LMmmol/L	44

（1）化学脱钙(1) Chemical decalcification

造纸生化处理后二沉池出水（即造纸深度处理废水）经管道流入一级脱钙反应池11，通过加药装置在搅拌下先加入适量石灰饱和溶液调pH值至9，脱除假性硬度（碳酸氢盐）后，流入二级脱钙反应池13，加入100mg/L的Na₂CO₃，使碳酸根与钙镁离子反应生成碳酸盐沉淀，然后加入2mg/L的FeSO₄，再加入Na₂CO₃反调pH值至8，最后加入3mg/L的聚苯烯酰胺（PAM），反应完全后进入沉淀池15，进行沉淀分离，从而脱除造纸深度处理废水中的钙镁、降低水的硬度，防止后续设备、设施因为Ca²⁺浓度过高而结垢；沉淀物（即污泥）经过泵和管道送入污泥池中，最后在污泥脱水装置中进行过滤分离，并回收碳酸钙，废水则进入下一步骤过滤；After the biochemical treatment of the paper, the effluent from the secondary settling tank (ie, the papermaking advanced treatment wastewater) flows into the first-stage decalcification reaction tank 11 through the pipeline, and the pH is adjusted to 9 by adding a proper amount of lime saturated solution under stirring by the dosing device to remove the pseudo hardness. After (bicarbonate), it flows into the secondary decalcification reaction tank 13, and 100 mg/L of Na ₂ CO _{3 is} added to react the carbonate with the calcium and magnesium ions to form a carbonate precipitate, and then 2 mg/L of FeSO _{4 is added} , and then Adding Na ₂ CO _{3 to} adjust the pH to 8 and finally adding 3 mg/L of polyphenylene amide (PAM). After the reaction is completed, it enters the sedimentation tank 15 and is subjected to precipitation separation, thereby removing calcium and magnesium in the papermaking advanced treatment wastewater and reducing The hardness of the water prevents the subsequent equipment and facilities from scaling due to excessive Ca ²⁺ concentration; the sediment (ie sludge) is sent to the sludge tank through the pump and pipeline, and finally filtered and separated in the sludge dewatering device, and The calcium carbonate is recovered, and the wastewater is filtered into the next step;

（2）过滤(2) Filtering

将化学脱钙后的废水泵入过滤***进行过滤分离，进一步除去水中的SS和胶体；The chemically decalcified wastewater is pumped into a filtration system for filtration separation to further remove SS and colloid in water;

上述过滤为多介质过滤。过滤可以是多介质过滤、纤维滤芯、砂滤、活性砂滤、滤布滤池中的一种。The above filtration is multi-media filtration. The filtration may be one of a multi-media filtration, a fiber filter, a sand filter, an active sand filter, and a filter cloth filter.

（3）电解(3) Electrolysis

将过滤后的废水泵入电解机33电解，以降解有机大分子，脱除色度，提高废水的可生化性，电解机33的相邻两电极间的电压为12V，电流密度为10mA/cm²；The filtered wastewater is pumped into the electrolysis machine 33 for electrolysis to degrade the organic macromolecules, remove the chromaticity, and improve the biodegradability of the wastewater. The voltage between the adjacent electrodes of the electrolysis machine 33 is 12V, and the current density is 10 mA/cm. ² ;

（4）膜分离(4) Membrane separation

经过电解后的废水进入膜分离***，通过膜分离作用去除废水中的颗粒、大分子胶体化合物和微生物，得到透析水和浓缩水，透析水进入脱盐处理***，浓缩水经管道回流至步骤（3）的电解机33中循环利用；The electrolyzed wastewater enters the membrane separation system, and the particles, macromolecular colloidal compounds and microorganisms in the wastewater are removed by membrane separation to obtain dialysis water and concentrated water, and the dialysis water enters the desalination treatment system, and the concentrated water is refluxed through the pipeline to the step (3) Recycling in the electrolysis machine 33;

所述膜分离***为超滤***，超滤为浸没式超滤，工作条件为：常温～45℃，工作压力为-1～-50kPa；超滤可以是浸没式超滤、柱式超滤、管式超滤、卷式超滤或板式超滤的一种。The membrane separation system is an ultrafiltration system, and the ultrafiltration is an immersion ultrafiltration. The working conditions are: normal temperature ~ 45 ° C, working pressure is -1 ~ -50 kPa; ultrafiltration can be immersion ultrafiltration, column ultrafiltration, A type of tubular ultrafiltration, coil ultrafiltration or plate ultrafiltration.

（5）脱盐***(5) Desalination system

膜分离所得透析水经用泵泵入脱盐***，经脱盐***过滤分离得透析水和浓缩水，透析水进入贮罐得再生水；浓缩水一部分回流到电解***，多余部分排放。The dialysis water obtained by membrane separation is pumped into the desalination system, and the dialysis water and concentrated water are separated by filtration through a desalting system, and the dialysis water enters the storage tank to obtain reclaimed water; a part of the concentrated water is returned to the electrolysis system, and the excess is discharged.

所述脱盐***为反渗透***。反渗透膜***采用截留分子量可为50～200MWCO的反渗透膜，膜组件为管式膜组件或卷式膜组件，进压可为6.0～35.0bar，出压可为4.5～33.5bar。The desalination system is a reverse osmosis system. The reverse osmosis membrane system adopts a reverse osmosis membrane having a molecular weight cutoff of 50 to 200 MWCO, and the membrane module is a tubular membrane module or a membrane module, the inlet pressure can be 6.0 to 35.0 bar, and the pressure can be 4.5 to 33.5 bar.

再生水水质指标经测定如表4所示。The reclaimed water quality indicators were determined as shown in Table 4.

表4再生水的水质指标Table 4 Water quality indicators of reclaimed water

序号Serial number	项目project	单位unit	测定值measured value	序号Serial number	项目project	单位unit	测定值measured value
11	CODCr COD Cr	mg/LMg/L	1010	44	色度Chroma		55
22	SSSS	mg/LMg/L	≤1≤1	55	CaCa	mg/LMg/L	3030
33	电导率Conductivity	µS/cmμS/cm	100100	66	硬度hardness	mmol/LMmmol/L	0.750.75

实施例3Example 3

20000吨/日造纸深度处理废水的回用方法。Reuse method of 20000 ton / day papermaking advanced treatment wastewater.

所述的造纸深度处理废水水质指标经测定如表5所示。The water quality index of the papermaking advanced treatment wastewater is determined as shown in Table 5.

表5造纸深度处理废水的水质指标Table 5 Water quality indicators of papermaking advanced treatment wastewater

序号Serial number	项目project	单位unit	测定值measured value	序号Serial number	项目project	单位unit	测定值measured value
11	CODCr COD Cr	mg/LMg/L	150150	44	色度Chroma		120120
22	SSSS	mg/LMg/L	8080	55	CaCa	mg/LMg/L	200200
33	电导率Conductivity	µS/cmμS/cm	12001200	66	硬度hardness	mmol/LMmmol/L	55

（1）化学脱钙(1) Chemical decalcification

造纸生化处理后二沉池出水（即造纸深度处理废水）经管道流入一级脱钙反应池11，通过加药装置在搅拌下先加入适量石灰饱和溶液调pH值至9.5，脱除假性硬度（碳酸氢盐）后，流入二级脱钙反应池13，加入350mg/L的Na₂CO₃，使碳酸根与钙镁离子反应生成碳酸盐沉淀，然后加入10mg/L的FeSO₄，再加入Na₂CO₃反调pH值至9，最后加入2mg/L的聚苯烯酰胺（PAM），反应完全后进入沉淀池15，进行沉淀分离，从而脱除造纸深度处理废水中的钙镁、降低水的硬度，防止后续设备、设施因为Ca²⁺浓度过高而结垢；沉淀物（即污泥）经过泵和管道送入污泥池中，最后在污泥脱水装置中进行过滤分离，并回收碳酸钙，废水则进入下一步骤过滤；After the biochemical treatment of the paper, the effluent from the secondary settling tank (ie, the papermaking advanced treatment wastewater) flows into the primary decalcification reaction tank 11 through the pipeline, and the appropriate amount of lime saturated solution is first added to the 9.5 by the dosing device to remove the pseudo hardness. After (bicarbonate), it flows into the secondary decalcification reaction tank 13, and 350 mg/L of Na ₂ CO _{3 is} added to react the carbonate with the calcium and magnesium ions to form a carbonate precipitate, and then 10 mg/L of FeSO _{4 is added} , and then Adding Na ₂ CO _{3 to} adjust the pH to 9 and finally adding 2 mg/L of polyphenylene amide (PAM). After the reaction is completed, it enters the sedimentation tank 15 and is subjected to precipitation separation, thereby removing calcium and magnesium in the papermaking advanced treatment wastewater and reducing The hardness of the water prevents the subsequent equipment and facilities from scaling due to excessive Ca ²⁺ concentration; the sediment (ie sludge) is sent to the sludge tank through the pump and pipeline, and finally filtered and separated in the sludge dewatering device, and The calcium carbonate is recovered, and the wastewater is filtered into the next step;

（2）过滤(2) Filtering

将化学脱钙后的废水泵入过滤***进行过滤分离，进一步除去水中的SS和胶体；The chemically decalcified wastewater is pumped into a filtration system for filtration separation to further remove SS and colloid in water;

上述过滤为活性砂滤。过滤可以是多介质过滤、纤维滤芯、砂滤、活性砂滤、滤布滤池中的一种。The above filtration is active sand filtration. The filtration may be one of a multi-media filtration, a fiber filter, a sand filter, an active sand filter, and a filter cloth filter.

（3）电解(3) Electrolysis

将过滤后的废水泵入电解机33电解，以降解有机大分子，脱除色度，提高废水的可生化性，电解机33的相邻两电极间的电压为2V，电流密度为320mA/cm²；The filtered wastewater is pumped into the electrolysis machine 33 for electrolysis to degrade the organic macromolecules, remove the chromaticity, and improve the biodegradability of the wastewater. The voltage between the adjacent electrodes of the electrolysis machine 33 is 2V, and the current density is 320 mA/cm. ² ;

（4）膜分离(4) Membrane separation

经过电解后的废水进入膜分离***，通过膜分离作用去除废水中的颗粒、大分子胶体化合物和微生物，得到透析水和浓缩水，透析水进入脱盐处理***，浓缩水经管道回流至步骤（3）的电解机33中循环利用；The electrolyzed wastewater enters the membrane separation system, and the particles, macromolecular colloidal compounds and microorganisms in the wastewater are removed by membrane separation to obtain dialysis water and concentrated water, and the dialysis water enters the desalination treatment system, and the concentrated water is refluxed through the pipeline to the step (3) Recycling in the electrolysis machine 33;

所述膜分离***为MBR***。MBR***的膜组件选自聚偏氟乙烯中空纤维膜、聚丙烯中空纤维膜、聚砜中空纤维膜、聚醚砜中空纤维膜、聚丙烯腈中空纤维膜和聚氯乙烯中空纤维膜中的一种；MBR膜组件的膜孔径为0.10～0.2μm，工作压力为-1～-50kPa，工作温度为5～45℃。The membrane separation system is an MBR system. The membrane module of the MBR system is selected from the group consisting of a polyvinylidene fluoride hollow fiber membrane, a polypropylene hollow fiber membrane, a polysulfone hollow fiber membrane, a polyethersulfone hollow fiber membrane, a polyacrylonitrile hollow fiber membrane, and a polyvinyl chloride hollow fiber membrane. The membrane pore size of the MBR membrane module is 0.10-0.2 μm, the working pressure is -1 to -50 kPa, and the working temperature is 5 to 45 °C.

（5）脱盐***(5) Desalination system

膜分离所得透析水用泵泵入脱盐***，经脱盐***过滤分离得透析水和浓缩水，透析水进入贮罐得再生水；浓缩水一部分回流到电解***，多余部分排放。The dialysis water obtained by membrane separation is pumped into the desalting system, and the dialysis water and concentrated water are separated by filtration through the desalination system, and the dialysis water enters the storage tank to obtain reclaimed water; a part of the concentrated water is returned to the electrolysis system, and the excess is discharged.

所述脱盐***为纳滤***。所述的纳滤***的膜组件为管式膜组件、卷式膜组件或平板膜组件的一种，工作压力为6～45bar，工作温度为20～45℃，最佳温度为35～40℃。The desalination system is a nanofiltration system. The membrane module of the nanofiltration system is a tubular membrane module, a membrane membrane module or a flat membrane module, and the working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimal temperature is 35 to 40 ° C. .

再生水水质指标经测定如表6所示。The water quality indicators of the reclaimed water were measured as shown in Table 6.

表6再生水的水质指标Table 6 Water quality indicators of reclaimed water

序号Serial number	项目project	单位unit	测定值measured value	序号Serial number	项目project	单位unit	测定值measured value
11	CODCr COD Cr	mg/LMg/L	88	44	色度Chroma		66
22	SSSS	mg/LMg/L	≤1≤1	55	CaCa	mg/LMg/L	6060
33	电导率Conductivity	µS/cmμS/cm	6060	66	硬度hardness	mmol/LMmmol/L	1.51.5

工业实用性Industrial applicability

造纸深度处理废水经过处理，70%～85%可以再生循环利用，既减少废水排放，避免废水对环境污染，又减少水资源浪费，还可以使再生的循环水成本低于自来水价格，经济合理，产生较好的经济效益，具备良好的工业实用性。 After the papermaking treatment wastewater is treated, 70%-85% can be recycled and reused, which not only reduces wastewater discharge, avoids environmental pollution of wastewater, but also reduces water waste. It can also make the cost of recycled recycled water lower than the price of tap water, and the economy is reasonable. Produce better economic benefits and have good industrial applicability.

Claims (30)

1. 基于化学脱钙的造纸深度处理废水回用装置，其特征在于：包括化学脱钙***、过滤***、电解***、膜分离***和脱盐***； A papermaking advanced treatment wastewater reuse device based on chemical decalcification, comprising: a chemical decalcification system, a filtration system, an electrolysis system, a membrane separation system and a desalination system;

   所述化学脱钙***包括一级脱钙反应池、截止阀、二级脱钙反应池和沉淀池，一级脱钙反应池与截止阀的进口联接，截止阀的出口接二级脱钙反应池的进口，二级脱钙反应池的出口与截止阀的进口联接，截止阀的出口与沉淀池的进口联接，沉淀池的出口接过滤***的进口；The chemical decalcification system comprises a primary decalcification reaction tank, a shut-off valve, a secondary decalcification reaction tank and a sedimentation tank, the primary decalcification reaction tank is connected with the inlet of the shut-off valve, and the outlet of the shut-off valve is connected to the secondary decalcification reaction. The inlet of the tank, the outlet of the secondary decalcification reaction tank is connected with the inlet of the shut-off valve, the outlet of the shut-off valve is connected with the inlet of the sedimentation tank, and the outlet of the sedimentation tank is connected to the inlet of the filtration system;

   所述化学脱钙***中的一级脱钙反应池和二级脱钙反应池还配有加药***，加药***设有加药罐和加药泵，加药罐出口接加药泵的进口，加药泵的出口接一级脱钙反应池或二级脱钙反应池；The primary decalcification reaction tank and the secondary decalcification reaction tank in the chemical decalcification system are further provided with a dosing system, and the dosing system is provided with a dosing tank and a dosing pump, and the dosing tank outlet is connected with the dosing pump. Import, the outlet of the dosing pump is connected to the first decalcification reaction tank or the secondary decalcification reaction tank;

   所述过滤***包括截止阀、供水泵、过滤器、反冲洗泵和清洗液罐，截止阀的进口接化学脱钙***的出口，供水泵的进口接截止阀的出口，供水泵的出口接过滤器的进口，过滤器的出口一路与电解***联接，另一路依次经反洗泵接清洗液罐；The filtering system comprises a shut-off valve, a water supply pump, a filter, a backwashing pump and a cleaning liquid tank, the inlet of the shut-off valve is connected to the outlet of the chemical decalcification system, the inlet of the water supply pump is connected to the outlet of the shut-off valve, and the outlet of the water supply pump is connected to the filter. The inlet of the filter, the outlet of the filter is connected to the electrolysis system, and the other is connected to the cleaning liquid tank by the backwashing pump;

   所述电解***包括截止阀、供水泵和电解机，截止阀的进口外接过滤***出口，供水泵的进口接截止阀的出口，供水泵的出口接电解机的进口，电解机的出口与膜分离***的进口联接；The electrolysis system comprises a shut-off valve, a water supply pump and an electrolysis machine, the inlet of the shut-off valve is connected to the outlet of the filter system, the inlet of the water supply pump is connected to the outlet of the shut-off valve, the outlet of the water supply pump is connected to the inlet of the electrolysis machine, and the outlet of the electrolysis machine is separated from the membrane. Import connection of the system;

   所述膜分离***为超滤***和MBR***中的一种，所述超滤***包括截止阀、供水泵、超滤膜***、反冲洗泵、透析水贮罐和阀门，截止阀的进口接电解机的出口，截止阀的出口接供水泵的进口，供水泵的出口接超滤膜***的进口，超滤膜***的透析水出口一路接透析水贮罐，另一路经反冲洗泵接透析水贮罐，超滤膜***的浓缩水则经管道和阀门回流至电解***中循环利用；所述MBR***包括截止阀、MBR反应池、MBR膜组件、鼓风机、曝气器、排污泵、出水泵、初级再生水贮罐，电解***所得净化污水通过进水管经截止阀接MBR反应池的进口，MBR膜组件浸没在MBR反应池内，通过鼓风机及分布的曝气器对其进行曝气，MBR反应池的出口接出水泵的进口，产生的滤液收集到初级再生水贮罐用于进一步经过脱盐处理***得供生产上循环利用的高纯再生水，少量污泥经过排污泵抽吸排放；The membrane separation system is one of an ultrafiltration system including a shut-off valve, a water supply pump, an ultrafiltration membrane system, a backwash pump, a dialysis water storage tank, and a valve, and an inlet port of the shut-off valve. The outlet of the electrolysis machine, the outlet of the shut-off valve is connected to the inlet of the water supply pump, the outlet of the water supply pump is connected to the inlet of the ultrafiltration membrane system, the dialysis water outlet of the ultrafiltration membrane system is connected to the dialysis water storage tank, and the other is connected by the backwash pump. The water storage tank and the concentrated water of the ultrafiltration membrane system are recycled to the electrolysis system through the pipeline and the valve for recycling; the MBR system includes a shut-off valve, an MBR reaction tank, an MBR membrane module, a blower, an aerator, a sewage pump, and an outlet. The pump, the primary reclaimed water storage tank, the purified sewage obtained by the electrolysis system is connected to the inlet of the MBR reaction tank through the inlet pipe through the shut-off valve, and the MBR membrane module is immersed in the MBR reaction tank, and is aerated by the blower and the distributed aerator, and the MBR reaction is performed. The outlet of the tank is taken out of the inlet of the water pump, and the produced filtrate is collected into the primary reclaimed water storage tank for further high-purity reclaimed water for recycling in the desalination treatment system, and a small amount of sludge. Over-discharge sewage suction pump;

   所述超滤***或MBR***还包括化学清洗***，化学清洗***用于清洗超滤或MBR***的膜组件，化学清洗***设有清洗液罐、化学清洗泵和截止阀，清洗液罐的出口接化学清洗泵的进口，化学清洗泵的出口经截止阀接超滤膜或MBR***；The ultrafiltration system or the MBR system further comprises a chemical cleaning system for cleaning the membrane module of the ultrafiltration or MBR system, the chemical cleaning system is provided with a cleaning liquid tank, a chemical cleaning pump and a shut-off valve, and an outlet of the cleaning liquid tank Connect the inlet of the chemical cleaning pump, and the outlet of the chemical cleaning pump is connected to the ultrafiltration membrane or MBR system through the shut-off valve;

   所述脱盐***设有截止阀、供水泵、脱盐装置和再生水贮罐，截止阀的进口接膜分离***的出口，截止阀的出口经供水泵进入脱盐装置，脱盐装置的透析水出口接再生水贮罐的进口，脱盐装置的浓缩水出口经截止阀回流至电解***。The desalination system is provided with a shut-off valve, a water supply pump, a desalination device and a reclaimed water storage tank. The inlet of the shut-off valve is connected to the outlet of the membrane separation system, the outlet of the shut-off valve enters the desalination device via the water supply pump, and the dialysis water outlet of the desalination device is connected to the reclaimed water storage. The inlet of the tank, the concentrated water outlet of the desalination device is returned to the electrolysis system via a shut-off valve.
2. 根据权利要求1所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述过滤***为多介质过滤、纤维滤芯、砂滤、活性砂滤、滤布滤池***中的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 1, wherein the filtration system is in a multi-media filtration, a fiber filter, a sand filter, an active sand filter, and a filter cloth filter system. One.
3. 如权利要求1所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述电解***中电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性电极中的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 1, wherein the electrolysis machine in the electrolysis system is provided with a power source and an electrolysis cell, and the electrodes in the electrolysis cell are graphite, titanium, One of iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloys, and nano catalytically inert electrodes.
4. 如权利要求4所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 4, wherein the surface layer of the nano catalytic inert electrode is coated with a metal oxide inert catalytic coating having a crystal grain size of 10 to 35 nm. The substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.
5. 根据权利要求1所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述超滤***的截留分子量为1000～100000MWCO，工作条件为：常温～45℃，超滤***为浸没式超滤、柱式超滤、管式超滤、卷式超滤或板式超滤中的一种，浸没式超滤的工作压力为-1～-50kPa，而柱式超滤、管式超滤、卷式超滤和板式超滤的工作压力为3～300kPa。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 1, wherein the ultrafiltration system has a molecular weight cutoff of 1000 to 100,000 MWCO, and the working condition is: normal temperature to 45 ° C, and the ultrafiltration system is One of immersion ultrafiltration, column ultrafiltration, tubular ultrafiltration, coil ultrafiltration or plate ultrafiltration, immersion ultrafiltration working pressure is -1 ~ -50kPa, and column ultrafiltration, tubular The working pressure of ultrafiltration, roll ultrafiltration and plate ultrafiltration is 3 to 300 kPa.
6. 根据权利要求1所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述MBR***的膜组件选自聚偏氟乙烯中空纤维膜、聚丙烯中空纤维膜、聚砜中空纤维膜、聚醚砜中空纤维膜、聚丙烯腈中空纤维膜和聚氯乙烯中空纤维膜中的一种，所述MBR***的MBR膜组件的膜孔径为0.10～0.2μm，工作压力为-1～-50kPa，工作温度为5～45℃。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 1, wherein the membrane component of the MBR system is selected from the group consisting of a polyvinylidene fluoride hollow fiber membrane, a polypropylene hollow fiber membrane, and a polysulfone hollow. One of a fiber membrane, a polyethersulfone hollow fiber membrane, a polyacrylonitrile hollow fiber membrane, and a polyvinyl chloride hollow fiber membrane. The MBR membrane module of the MBR system has a membrane pore diameter of 0.10 to 0.2 μm and a working pressure of -1. ~-50kPa, working temperature is 5 ~ 45 °C.
7. 根据权利要求1所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述脱盐***为纳滤、反渗透、正渗透、电渗析、电容吸附、离子交换或填充电渗析（EDI）中的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 1, wherein the desalination system is nanofiltration, reverse osmosis, forward osmosis, electrodialysis, capacitance adsorption, ion exchange or filled electrodialysis. One of (EDI).
8. 根据权利要求7所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述纳滤***中的纳滤膜组件为管式膜组件、卷式膜组件或平板膜组件的一种，工作压力为6～45bar，工作温度为20～45℃，最佳温度为35～40℃。The chemical decalcification-based papermaking advanced treatment wastewater recycling apparatus according to claim 7, wherein the nanofiltration membrane module in the nanofiltration system is a tubular membrane module, a wound membrane module or a flat membrane module. One type, the working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimum temperature is 35 to 40 ° C.
9. 根据权利要求7所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述反渗透***中的反渗透膜组件为卷式膜组件，膜材料为有机膜中醋酸纤维膜或复合膜，膜材料的截留分子量为50～200MWCO，进压可为6.0～45.0bar，出压可为4.5～33.5bar。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 7, wherein the reverse osmosis membrane module in the reverse osmosis system is a wound membrane module, and the membrane material is an acetate membrane in an organic membrane. Or a composite membrane, the membrane material has a molecular weight cutoff of 50 to 200 MWCO, a feed pressure of 6.0 to 45.0 bar, and a pressure of 4.5 to 33.5 bar.
10. 根据权利要求7所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述的正渗透的膜组件为板框式膜组件、卷式膜组件、管式膜组件和包式膜组件中的一种。The chemical decalcification-based papermaking advanced treatment wastewater recycling apparatus according to claim 7, wherein the forward osmosis membrane module is a plate and frame membrane module, a wound membrane module, a tubular membrane module and a package. One of the membrane modules.
11. 根据权利要求7所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述的电渗析的工作条件是操作电压压力0.5～3.0㎏/cm²，操作电压50～250V，电流强度1～3A。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 7, wherein the working condition of the electrodialysis is an operating voltage of 0.5 to 3.0 kg/cm ² and an operating voltage of 50 to 250 V. The current intensity is 1 to 3A.
12. 根据权利要求7所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述的电容吸附的工作条件是直流电压为110V/m～2×10⁶V/m。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 7, wherein the capacitive adsorption operating condition is a direct current voltage of 110 V/m to 2 x 10 ⁶ V/m.
13. 根据权利要求7所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：所述的离子交换使用的离子交换剂分为无机离子交换剂和有机离子交换剂两大类，无机离子交换剂包括天然沸石和合成沸石，有机交换树脂为强酸阳离子交换树脂、弱酸阳离子交换树脂、强碱阴离子交换树脂、弱碱阴离子交换树脂、螯合树脂和有机吸附树脂中的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse device according to claim 7, wherein the ion exchange agent used for the ion exchange is divided into two categories: an inorganic ion exchanger and an organic ion exchanger. The ion exchanger includes natural zeolite and synthetic zeolite, and the organic exchange resin is one of a strong acid cation exchange resin, a weak acid cation exchange resin, a strong base anion exchange resin, a weak base anion exchange resin, a chelating resin, and an organic adsorption resin.
14. 根据权利要求7所述的基于化学脱钙的造纸深度处理废水回用装置，其特征在于：填充电渗析装置进水要求为电阻率为0.025～0.5MΩ·cm。The chemical decalcification-based papermaking advanced treatment wastewater recycling apparatus according to claim 7, wherein the filling electrodialysis unit is required to have a specific resistance of 0.025 to 0.5 M?cm.
15. 基于化学脱钙的造纸深度处理废水回用方法，它包括以下步骤：A method for recycling wastewater based on chemical decalcification, which comprises the following steps:

    （1）化学脱钙(1) Chemical decalcification

    造纸生化处理后的二沉池出水（即造纸深度处理废水）经管道流入一级脱钙反应池，通过加药装置在搅拌下先加入适量石灰饱和溶液调pH值至8.5～9.5，脱除假性硬度（碳酸氢盐）后，流入二级脱钙反应池，加入100~600mg/L的Na₂CO₃，使碳酸根与钙镁离子反应生成碳酸盐沉淀，然后加入2~10mg/L的FeSO₄，再加入Na₂CO₃反调pH值至8～9，最后加入1~3mg/L的聚苯烯酰胺（PAM），反应完全后进入沉淀池进行沉淀分离，从而脱除造纸深度处理废水中的钙镁、将废水的硬度降低到30~80mg/L，沉淀物（即污泥）经过泵和管道送入污泥池中，最后在污泥脱水装置中进行过滤分离，并回收碳酸钙，废水则进入下一步骤过滤；The effluent from the secondary sedimentation tank after the biochemical treatment of papermaking (ie, the papermaking advanced treatment wastewater) flows into the first-stage decalcification reaction tank through the pipeline, and the pH is adjusted to 8.5-9.5 by adding a proper amount of lime saturated solution under stirring by the dosing device to remove the false After the hardness (bicarbonate), it flows into the secondary decalcification reaction tank, and 100~600mg/L of Na ₂ CO _{3 is} added to react the carbonate with calcium and magnesium ions to form a carbonate precipitate, and then add 2~10mg/L. FeSO ₄ , then add Na ₂ CO _{3 to} adjust the pH value to 8 ~ 9, and finally add 1 ~ 3mg / L of polyphenylene amide (PAM), after the reaction is complete, enter the sedimentation tank for precipitation separation, thereby removing the papermaking depth treatment Calcium and magnesium in the wastewater, the hardness of the wastewater is reduced to 30~80mg/L, and the sediment (ie sludge) is sent to the sludge tank through the pump and pipeline, and finally filtered and separated in the sludge dewatering device, and the carbonic acid is recovered. Calcium, wastewater will be filtered in the next step;

    （2）过滤(2) Filtering

    将化学脱钙后的废水泵入过滤***进行过滤分离，进一步除去水中的SS和胶体；The chemically decalcified wastewater is pumped into a filtration system for filtration separation to further remove SS and colloid in water;

    （3）电解(3) Electrolysis

    将过滤后的废水泵入电解机电解，以降解有机大分子，脱除色度，提高废水的可生化性，电解机的相邻两电极间的电压为2～12V，电流密度为10～320mA/cm²；The filtered wastewater is pumped into the electrolysis machine to decompose organic macromolecules, remove the chroma and improve the biodegradability of the wastewater. The voltage between the adjacent electrodes of the electrolysis machine is 2-12V, and the current density is 10~320mA. /cm ² ;

    （4）膜分离(4) Membrane separation

    经过电解后的废水进入膜分离***，通过膜分离作用去除废水中的颗粒、大分子胶体化合物和微生物，得到透析水和浓缩水，透析水进入脱盐处理***，浓缩水经管道回流至步骤（3）的电解机中循环利用；The electrolyzed wastewater enters the membrane separation system, and the particles, macromolecular colloidal compounds and microorganisms in the wastewater are removed by membrane separation to obtain dialysis water and concentrated water, and the dialysis water enters the desalination treatment system, and the concentrated water is refluxed through the pipeline to the step (3) Recycling in the electrolysis machine;

    （5）脱盐(5) Desalting

    膜分离所得透析水经保安过滤后用泵泵入脱盐***，经脱盐***过滤分离得透析水和浓缩水，透析水进入贮罐得再生水；浓缩水一部分回流到电解***，多余部分排放。The dialysis water obtained by membrane separation is filtered by the security and pumped into the desalination system, and the dialysis water and the concentrated water are separated by filtration through the desalination system, and the dialysis water enters the storage tank to obtain the reclaimed water; a part of the concentrated water is returned to the electrolysis system, and the excess is discharged.
16. 如权利要求15所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：步骤（2）过滤所述的过滤***为多介质过滤、纤维滤芯、砂滤、活性砂滤、滤布滤池中的一种。The method for recycling chemical wastewater based on chemical decalcification according to claim 15, wherein the filtering system is multi-media filtration, fiber filter, sand filtration, active sand filtration, filtration in step (2). One of the cloth filters.
17. 如权利要求15所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：步骤（3）电解所述电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金纳米和催化惰性电极中的一种。The method for recycling chemical wastewater based on chemical decalcification according to claim 15, wherein: (3) electrolyzing the electrolysis machine is provided with a power source and an electrolytic cell, and the electrode in the electrolytic cell is graphite. One of titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, alloy nano and catalytically inert electrodes.
18. 如权利要求17所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 17, wherein the surface layer of the nano catalytic inert electrode is coated with a metal oxide inert catalytic coating having a crystal grain size of 10 to 35 nm. The substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.
19. 根据权利要求15所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：步骤（4）所述膜分离***为超滤或MBR的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 15, wherein the membrane separation system of the step (4) is one of ultrafiltration or MBR.
20. 如权利要求19所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述超滤截留分子量为1000～50000MWCO，工作条件为常温～45℃，超滤为浸没式超滤、柱式超滤、管式超滤、卷式超滤或板式超滤的一种，其中，浸没式超滤的工作压力为-1～-50kPa，柱式超滤、管式超滤、卷式超滤和板式超滤的工作压力为3～300kPa。The method for recycling chemical wastewater based on chemical decalcification according to claim 19, wherein the ultrafiltration molecular weight cutoff is 1000 to 50000 MWCO, the working condition is normal temperature to 45 ° C, and the ultrafiltration is immersion ultrafiltration. , column ultrafiltration, tubular ultrafiltration, coil ultrafiltration or plate ultrafiltration, wherein the submerged ultrafiltration working pressure is -1 ~ -50kPa, column ultrafiltration, tubular ultrafiltration, volume The working pressure of the ultrafiltration and plate ultrafiltration is 3 to 300 kPa.
21. 如权利要求19所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述MBR的膜组件选自聚偏氟乙烯中空纤维膜、聚丙烯中空纤维膜、聚砜中空纤维膜、聚醚砜中空纤维膜、聚丙烯腈中空纤维膜和聚氯乙烯中空纤维膜中的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 19, wherein the membrane component of the MBR is selected from the group consisting of a polyvinylidene fluoride hollow fiber membrane, a polypropylene hollow fiber membrane, and a polysulfone hollow fiber. One of a membrane, a polyethersulfone hollow fiber membrane, a polyacrylonitrile hollow fiber membrane, and a polyvinyl chloride hollow fiber membrane.
22. 如权利要求19或21所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述MBR膜组件的膜孔径为0.10～0.2μm，工作压力为-1～-50kPa，工作温度为5～45℃。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 19 or 21, wherein the MBR membrane module has a membrane pore diameter of 0.10 to 0.2 μm and a working pressure of -1 to -50 kPa. The temperature is 5 to 45 °C.
23. 根据权利要求15所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：步骤（5）所述脱盐***是纳滤、反渗透、正渗透、电渗析、电容吸附、离子交换或填充电渗析（EDI）的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 15, wherein the desalination system of the step (5) is nanofiltration, reverse osmosis, forward osmosis, electrodialysis, capacitance adsorption, ion exchange. Or a type of electrodialysis (EDI) filled.
24. 根据权利要求23所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述纳滤***的膜组件为管式膜组件、卷式膜组件或平板膜组件的一种，工作压力为6～45bar，工作温度为20～45℃，最佳温度为35～40℃。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 23, wherein the membrane module of the nanofiltration system is a tubular membrane module, a wound membrane module or a flat membrane module. The working pressure is 6 to 45 bar, the working temperature is 20 to 45 ° C, and the optimum temperature is 35 to 40 ° C.
25. 根据权利要求23所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述反渗透采用截留分子量可为50～200MWCO的反渗透膜，膜组件为管式膜组件或卷式膜组件，进压为6.0～35.0bar，出压为4.5～33.5bar。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 23, wherein the reverse osmosis membrane adopts a reverse osmosis membrane having a molecular weight cutoff of 50 to 200 MWCO, and the membrane module is a tubular membrane module or a coil. The membrane module has a pressure of 6.0 to 35.0 bar and an outlet pressure of 4.5 to 33.5 bar.
26. 根据权利要求23所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述的正渗透的膜组件为板框式膜组件、卷式膜组件、管式膜组件和包式膜组件中的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 23, wherein the forward osmosis membrane module is a plate and frame membrane module, a wound membrane module, a tubular membrane module and a package. One of the membrane modules.
27. 根据权利要求23所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述的电渗析的工作条件是操作电压压力0.5～3.0㎏/㎝²，操作电压50～250V，电流强度1～3A。The method for recycling chemical wastewater based on chemical decalcification according to claim 23, wherein the working condition of the electrodialysis is an operating voltage of 0.5 to 3.0 kg/cm ² and an operating voltage of 50 to 250 V. The current intensity is 1 to 3A.
28. 根据权利要求23所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述的电容吸附的工作条件是直流电压为110V/m~2×10⁶V/m。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 23, wherein the capacitor adsorption working condition is a DC voltage of 110 V/m to 2 x 10 ⁶ V/m.
29. 根据权利要求23所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述的离子交换使用的离子交换剂分为无机离子交换剂和有机离子交换剂两大类，无机离子交换剂包括天然沸石和合成沸石，有机交换树脂为强酸阳离子交换树脂、弱酸阳离子交换树脂、强碱阴离子交换树脂、弱碱阴离子交换树脂、螯合树脂和有机吸附树脂中的一种。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 23, wherein the ion exchange agent used for the ion exchange is divided into two categories: an inorganic ion exchanger and an organic ion exchanger, and the inorganic The ion exchanger includes natural zeolite and synthetic zeolite, and the organic exchange resin is one of a strong acid cation exchange resin, a weak acid cation exchange resin, a strong base anion exchange resin, a weak base anion exchange resin, a chelating resin, and an organic adsorption resin.
30. 根据权利要求23所述的基于化学脱钙的造纸深度处理废水回用方法，其特征在于：所述的填充电渗析（EDI）是一种将电渗析与离子交换有机结合在一起的膜分离脱盐工艺，填充电渗析装置进水要求为电阻率为0.025～0.5MΩ·cm。The chemical decalcification-based papermaking advanced treatment wastewater reuse method according to claim 23, wherein the charged electrodialysis (EDI) is a membrane separation and desalting that combines electrodialysis and ion exchange organically. The process, filling electrodialysis unit requires water to have a resistivity of 0.025 to 0.5 MΩ·cm.