CN101555053B - A composite coagulant and treatment method that can be used to treat rare earth high-concentration ammonia nitrogen wastewater and recover industrial-grade ammonium chloride - Google Patents

A composite coagulant and treatment method that can be used to treat rare earth high-concentration ammonia nitrogen wastewater and recover industrial-grade ammonium chloride Download PDF

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CN101555053B
CN101555053B CN2008100273450A CN200810027345A CN101555053B CN 101555053 B CN101555053 B CN 101555053B CN 2008100273450 A CN2008100273450 A CN 2008100273450A CN 200810027345 A CN200810027345 A CN 200810027345A CN 101555053 B CN101555053 B CN 101555053B
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ammonia nitrogen
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黄海明
肖贤明
晏波
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Guangzhou Institute of Geochemistry of CAS
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Abstract

本发明提供一种可用于处理稀土高浓度氨氮废水回收工业级氯化铵的复合混凝剂及处理方法,属于化工环保和资源回收技术领域。复合混凝剂为草酸铵、硫酸铵、重金属沉淀剂DTCR及聚丙烯酰胺(PAM)的混合液。使用复合混凝剂处理废水的处理方法为:废水首先经隔油池和气浮室去除废水中的油类物质,再进入pH调节沉淀池调节pH为7.5~8.5,然后进入混凝沉淀池,加入复合混凝剂,经混凝沉淀后的废水进入pH调节池调节pH为2.5~4,经调节pH后的废水再进入活性炭滤塔吸附过滤后在负压条件下蒸发浓缩。本发明中使用的复合混凝剂处理方法简单,费用低,效果好。本发明中的处理方法工艺流程短,处理简单易行,不仅解决了高浓度氨氮废水污染的问题,同时也回收了有价值物质。

Figure 200810027345

The invention provides a composite coagulant and a treatment method which can be used for treating rare earth high-concentration ammonia nitrogen wastewater to recover industrial-grade ammonium chloride and a treatment method, belonging to the technical fields of chemical environmental protection and resource recovery. The composite coagulant is a mixture of ammonium oxalate, ammonium sulfate, heavy metal precipitant DTCR and polyacrylamide (PAM). The treatment method of using composite coagulant to treat wastewater is as follows: the wastewater first passes through the grease trap and the air flotation chamber to remove the oily substances in the wastewater, then enters the pH adjustment sedimentation tank to adjust the pH to 7.5-8.5, and then enters the coagulation sedimentation tank, adding Composite coagulant, the wastewater after coagulation and precipitation enters the pH adjustment tank to adjust the pH to 2.5-4, and the wastewater after pH adjustment enters the activated carbon filter tower for adsorption and filtration, and then evaporates and concentrates under negative pressure conditions. The composite coagulant used in the invention has simple processing method, low cost and good effect. The treatment method in the invention has short process flow, simple and easy treatment, not only solves the problem of high-concentration ammonia nitrogen wastewater pollution, but also recovers valuable substances.

Figure 200810027345

Description

一种可用于处理稀土高浓度氨氮废水回收工业级氯化铵的复合混凝剂及处理方法 A composite coagulant and treatment method that can be used to treat rare earth high-concentration ammonia nitrogen wastewater and recover industrial-grade ammonium chloride

技术领域technical field

本发明涉及一种可用于处理稀土高浓度氨氮废水回收工业级氯化铵的混凝剂及处理方法,属于化工环保和资源回收技术领域。The invention relates to a coagulant and a treatment method that can be used for treating rare earth high-concentration ammonia nitrogen wastewater to recover industrial-grade ammonium chloride, and belongs to the technical fields of chemical environmental protection and resource recovery.

背景技术Background technique

稀土湿法冶炼采用萃取工艺进行各组分分离,该工艺需有大量碱液参与反应,考虑到生产成本问题,目前绝大部分企业都采用氨水进行皂化,所产生的废水若不经处理直接排放将给所排入的水体带来极其严重的氨氮污染。高浓度的氨氮废水是稀土冶炼企业处理的重点和难点,目前针对该类废水的处理工艺较多,在国内外现阶段可用来处理氨氮废水的成熟及处于研究开发阶段的技术和方法主要有:蒸发结晶法、反渗透脱盐、电渗析、土壤灌溉;空气吹脱(或蒸汽吹脱)、化学沉淀法、折点氯化、乳液膜吸附分离法、吸附、离子交换法、高级催化氧化法、超重力脱氮法、生化处理法等十多种,但能真正用于工业应用的却只有寥寥数种。Rare earth wet smelting adopts extraction process to separate components. This process requires a large amount of lye to participate in the reaction. Considering the production cost, most enterprises currently use ammonia water for saponification. If the waste water generated is not treated, it will be discharged directly. It will bring extremely serious ammonia nitrogen pollution to the discharged water. High-concentration ammonia-nitrogen wastewater is the focus and difficulty in the treatment of rare earth smelting enterprises. At present, there are many treatment processes for this type of wastewater. The mature technologies and methods that can be used to treat ammonia-nitrogen wastewater at home and abroad at this stage and are in the research and development stage mainly include: Evaporation and crystallization, reverse osmosis desalination, electrodialysis, soil irrigation; air stripping (or steam stripping), chemical precipitation, breakpoint chlorination, emulsion membrane adsorption separation, adsorption, ion exchange, advanced catalytic oxidation, There are more than ten kinds of high-gravity denitrification methods, biochemical treatment methods, etc., but only a few of them can be really used in industrial applications.

由于稀土冶炼中不同工艺段排放的废水性质差异大,氨氮浓度有高有低。根据废水氨氮浓度,可分为三种不同浓度废水:大于10000mg/L的高浓度氨氮废水(稀土皂废水、碳铵沉淀母液)、500-10000mg/L的中等浓度氨氮废水和小于500mg/L的低浓度氨氮废水。对于大于10000mg/L高浓度的氨氮废水采用蒸发结晶法是最为经济可行的,蒸发结晶法在国内外水处理及化工行业已被大量应用,技术成熟可靠。Due to the large difference in the nature of wastewater discharged from different process stages in rare earth smelting, the concentration of ammonia nitrogen varies from high to low. According to the concentration of ammonia nitrogen in wastewater, it can be divided into three different concentrations of wastewater: high concentration ammonia nitrogen wastewater greater than 10000mg/L (rare earth soap wastewater, ammonium bicarbonate precipitation mother liquor), medium concentration ammonia nitrogen wastewater of 500-10000mg/L and less than 500mg/L Low concentration ammonia nitrogen wastewater. For ammonia nitrogen wastewater with a high concentration of more than 10000mg/L, it is most economically feasible to use the evaporation crystallization method. The evaporation crystallization method has been widely used in water treatment and chemical industries at home and abroad, and the technology is mature and reliable.

采用蒸发结晶法回收铵盐(氯化铵),可抵消设备运行费用,但由于废水中油类及萃取剂、重金属等其他杂质含量多,采用传统的加氢氧化钠作为沉淀剂去除重金属后蒸发结晶,虽然能去除大部分重金属,但同时也引入了钠,降低了产品纯度,严重影响了回收铵盐产品的质量和销售,若采用氨水中和由于pH值最多只能调节到9~10,对重金属等杂质去除效果差,回收的产品最好只能做到农用级别,而在市面上销售的农用级氯化铵价格仅为工业级一半,因此如何在预处理过程中降低废水中杂质,使经蒸发结晶后能回收到工业级氯化铵将是极具经济效益的处理方法。Recovering ammonium salt (ammonium chloride) by evaporation and crystallization can offset equipment operating costs, but due to the high content of oils, extractants, heavy metals and other impurities in wastewater, traditional sodium hydroxide is used as a precipitant to remove heavy metals and evaporate to crystallize , although most of the heavy metals can be removed, sodium is also introduced at the same time, which reduces the product purity and seriously affects the quality and sales of recovered ammonium salt products. The removal effect of heavy metals and other impurities is poor, and the recovered products should only be agricultural grade, and the price of agricultural grade ammonium chloride sold on the market is only half of the industrial grade, so how to reduce impurities in wastewater during pretreatment, so that It will be a very economical treatment method to recover industrial grade ammonium chloride after evaporation and crystallization.

发明内容Contents of the invention

本发明的一个目的是提供一种可去除稀土高浓度氨氮废水中重金属等杂质的复合混凝剂。An object of the present invention is to provide a composite coagulant capable of removing impurities such as heavy metals in rare earth high-concentration ammonia nitrogen wastewater.

本发明的另一个目的是提供一种使用该复合混凝剂处理稀土高浓度氨氮废水回收工业级氯化铵的处理方法,既达到了处理废水的目的又回收了有价值的资源。Another object of the present invention is to provide a treatment method for using the composite coagulant to treat rare earth high-concentration ammonia nitrogen wastewater and recover industrial-grade ammonium chloride, which not only achieves the purpose of treating wastewater but also recovers valuable resources.

本发明的目的采用以下技术方案予以实现:复合混凝剂为草酸铵、硫酸铵、重金属沉淀剂DTCR及聚丙烯酰胺(PAM)的混合液。按四种药剂重量配比即:草酸铵∶硫酸铵∶DTCR∶PAM=0.6~3∶0.4~1.5∶1∶0.01~0.03称取药剂溶于水中,然后混合搅拌均匀,配制成四种药剂总质量浓度为3.5%~10%的混合液。稀土高浓度氨氮废水中含有较多的油类及萃取剂、重金属元素及钙离子,使用该复合混凝剂处理废水,草酸铵提供草酸根离子沉淀废水中的钙离子,硫酸铵提供硫酸根离子以去除废水中的钡离子,DTCR与重金属离子强力螯合,生成不溶物,能形成良好的絮凝,以致沉降快速,达到去除重金属离子的目的,聚丙烯酰胺在被吸附的粒子间形成“桥联”,生成较大的絮团,有利于微粒下沉并能有效的吸附有机物。The object of the present invention is achieved by the following technical solutions: the composite coagulant is a mixed solution of ammonium oxalate, ammonium sulfate, heavy metal precipitant DTCR and polyacrylamide (PAM). According to the weight ratio of the four kinds of medicines: ammonium oxalate: ammonium sulfate: DTCR: PAM=0.6~3:0.4~1.5:1:0.01~0.03 Weigh the medicines and dissolve them in water, then mix and stir them evenly, and prepare the four kinds of medicines. A mixed solution with a mass concentration of 3.5% to 10%. Rare earth high-concentration ammonia nitrogen wastewater contains more oils, extractants, heavy metal elements and calcium ions. This composite coagulant is used to treat wastewater. Ammonium oxalate provides oxalate ions to precipitate calcium ions in wastewater, and ammonium sulfate provides sulfate ions. To remove barium ions in wastewater, DTCR strongly chelates heavy metal ions to form insoluble matter, which can form good flocculation, resulting in rapid sedimentation, and achieve the purpose of removing heavy metal ions. Polyacrylamide forms a "bridge" between the adsorbed particles ", to generate larger flocs, which is conducive to the sinking of particles and can effectively adsorb organic matter.

为使在处理废水时不带入其他杂质,本发明中的复合混凝剂中的重金属沉淀剂DTCR为:螯合基-NH-CSSNH4型式。In order not to bring in other impurities when treating wastewater, the heavy metal precipitant DTCR in the composite coagulant of the present invention is: chelating group-NH-CSSNH 4 type.

使用复合混凝剂处理废水回收工业级氯化铵的处理方法及步骤如下:The treatment method and steps of using composite coagulant to treat waste water and recover industrial grade ammonium chloride are as follows:

a、稀土高浓度氨氮废水首先进入隔油池,使稀土废水中的浮油及分散油中颗粒较大的油滴上升到表面,通过刮油机刮油以达到去除浮油的目的,然后废水进入气浮室,通过气浮去除废水中的乳化油以及疏水性细微固体悬浮物。a. The rare earth high-concentration ammonia nitrogen wastewater first enters the grease trap, so that the slick oil in the rare earth wastewater and the larger oil droplets in the dispersed oil rise to the surface, and the oil is scraped by the oil scraper to achieve the purpose of removing the slick oil, and then the wastewater Enter the air flotation chamber, and remove the emulsified oil and hydrophobic fine suspended solids in the wastewater by air flotation.

b、经除油后的废水进入pH调节沉淀池,然后向废水中加入浓度为25%~30%的浓氨水调节pH为7.5~8.5,再向每m3废水中加入1~2g PAM搅拌反应10~15min,静置35~50min,产生的污泥经池底的排泥管排出,上清液及污泥滤液进入混凝沉淀池。b. The degreased waste water enters the pH adjustment sedimentation tank, then adds concentrated ammonia water with a concentration of 25% to 30% to the waste water to adjust the pH to 7.5 to 8.5, and then adds 1 to 2g of PAM to each m3 of waste water to stir the reaction 10-15 minutes, stand still for 35-50 minutes, the generated sludge is discharged through the sludge discharge pipe at the bottom of the tank, and the supernatant and sludge filtrate enter the coagulation sedimentation tank.

c、往混凝沉淀池中按每m3废水中加入3~15L复合混凝剂,快速搅拌5~10min,然后慢速搅拌10~15min后静置30~40min,产生的污泥经池底的排泥管排出,上清液及污泥滤液进入pH调节池,然后向废水中加入质量浓度为30%~38%的浓盐酸调节pH为2.5~4。c. Add 3-15L compound coagulant to the coagulation-sedimentation tank per m3 of wastewater, stir rapidly for 5-10min, then stir slowly for 10-15min and then let it stand for 30-40min. The generated sludge passes through the bottom of the pool The supernatant and sludge filtrate enter the pH adjustment tank, and then add concentrated hydrochloric acid with a mass concentration of 30% to 38% to the wastewater to adjust the pH to 2.5 to 4.

d、经调节pH后的废水再进入活性炭滤塔,控制滤速为3~5m/h,吸附及过滤废水中残余的重金属及微量油类物质,经活性炭处理后的废水再进入蒸发结晶塔在负压条件下蒸发浓缩。d. After adjusting the pH, the wastewater enters the activated carbon filter tower, and the filtration rate is controlled to be 3-5m/h to absorb and filter the residual heavy metals and trace oils in the wastewater. After the activated carbon treatment, the wastewater enters the evaporation and crystallization tower. Concentrate by evaporation under negative pressure.

本发明的有益效果:Beneficial effects of the present invention:

a、本发明中使用的复合混凝剂处理方法简单,费用低,能做到多种重金属离子共存的情况下经一次处理后,使废水中的各种重金属离子及钙离子达到极微量,即使对与重金属络合的盐(如NH3)也能充分发挥作用,并具有絮凝体粗大、沉淀快、脱水快、后处理容易、污泥量少且稳定无毒、不给废水带入其他杂质、没有二次公害等特点。a, the composite coagulant treatment method used in the present invention is simple, and cost is low, and after a treatment under the situation that multiple heavy metal ions can coexist, make various heavy metal ions and calcium ions in the wastewater reach a very small amount, even if It can also fully exert its effect on salts complexed with heavy metals (such as NH 3 ), and has the characteristics of coarse flocs, fast sedimentation, fast dehydration, easy post-treatment, less sludge, stable and non-toxic, and does not bring other impurities into wastewater , No secondary pollution and other characteristics.

b、本发明中的处理方法工艺流程短,处理简单易行,经该方法处理后的废水最后经蒸发结晶回收的氯化铵可达到工业级合格产品,以较小的成本获得极大的经济利润,不仅解决了高浓度氨氮废水污染的问题,同时也回收了有价值物质,实现了较高的经济效益和环境效益。b, the process flow of the treatment method in the present invention is short, and the treatment is simple and easy. The ammonium chloride recovered by evaporation and crystallization of the waste water treated by the method can reach industrial-grade qualified products, and obtain great economic benefits at a relatively low cost. The profit not only solves the problem of high-concentration ammonia nitrogen wastewater pollution, but also recovers valuable substances, achieving high economic and environmental benefits.

附图说明Description of drawings

图1是使用本发明中的复合混凝剂处理稀土高浓度氨氮废水回收工业级氯化铵的处理方法的流程示意图。Fig. 1 is a schematic flow chart of a treatment method for recovering industrial-grade ammonium chloride from rare-earth high-concentration ammonia-nitrogen wastewater using a composite coagulant of the present invention.

具体实施方式Detailed ways

下面结合实施例进一步详细说明本发明的技术方案,本发明的保护范围不局限于下述的具体实施方式。The technical solutions of the present invention will be further described in detail below in conjunction with the examples, and the scope of protection of the present invention is not limited to the following specific embodiments.

复合混凝剂实施例如下:Examples of composite coagulants are as follows:

实施例1Example 1

分别称取600g克草酸铵、200g硫酸铵、200g重金属沉淀剂DTCR和3g PAM,然后依次溶于13L水中,不断搅拌混合均匀后配制总质量浓度为7.1%的复合混凝剂。Weigh 600g of ammonium oxalate, 200g of ammonium sulfate, 200g of heavy metal precipitant DTCR and 3g of PAM respectively, and then dissolve them in 13L of water in turn, stir and mix evenly to prepare a composite coagulant with a total mass concentration of 7.1%.

实施例2Example 2

分别称取450g克草酸铵、150g硫酸铵、200g重金属沉淀剂DTCR和2g PAM,然后依次溶于13L水中,不断搅拌混合均匀后配制总质量浓度为5.8%的复合混凝剂。Weigh 450g of ammonium oxalate, 150g of ammonium sulfate, 200g of heavy metal precipitant DTCR and 2g of PAM, and then dissolve them in 13L of water in turn, stir and mix evenly to prepare a composite coagulant with a total mass concentration of 5.8%.

使用复合混凝剂处理稀土高浓度氨氮废水回收工业级氯化铵的处理方法的实施例如下:The embodiment of the treatment method of using composite coagulant to process rare earth high concentration ammonia nitrogen wastewater to reclaim industrial grade ammonium chloride is as follows:

对上述两个应用实例制得的复合混凝剂编号,依次为1号复合混凝剂、2号复合混凝剂,对污水进行处理。废水取自某稀土冶炼厂中的稀土皂废水和碳铵沉淀母液,其水质特点如下:The numbers of the composite coagulants prepared in the above two application examples are sequentially No. 1 composite coagulant and No. 2 composite coagulant for treating sewage. The wastewater is taken from rare earth soap wastewater and ammonium bicarbonate precipitation mother liquor in a rare earth smelter, and its water quality characteristics are as follows:

表1稀土皂废水水质(pH=0.47,[Cl-]=96800mg/L,单位为mg/L)Table 1 Water quality of rare earth soap wastewater (pH=0.47, [Cl - ]=96800mg/L, unit is mg/L)

 NH4 + NH4 +   油类oil   Ca2+ Ca 2+   Na+ Na +   Al3+ Al 3+   Mn2+ Mn 2+   Cu2+ Cu 2+   Zn2+ Zn 2+   Pb2+ Pb 2+   Ba2+ Ba 2+   Cr3+ Cr 3+   Ni2+ Ni 2+  4805048050   1580.51580.5   200200   4242   56.356.3   24 twenty four   3.73.7   1717   67.867.8   242242   1.61.6   2.12.1

表2碳铵沉淀母液水质(pH=6.47,[Cl-]=27730mg/L,单位为mg/L)Table 2 Water Quality of Ammonium Bicarbonate Precipitation Mother Liquor (pH=6.47, [Cl - ]=27730mg/L, unit is mg/L)

 NH4 + NH4 +   油类oil   Ca2+ Ca 2+   Na+ Na +   Al3+ Al 3+   Mn2+ Mn 2+   Cu2+ Cu 2+   Zn2+ Zn 2+   Pb2+ Pb 2+   Ba2+ Ba 2+   Cr3+ Cr 3+   Ni2+ Ni 2+  1315213152   80.580.5   0.30.3   18.618.6   16.316.3   0.50.5   2.72.7   3636   0.180.18   0.90.9   2.12.1   2 2

实施例3Example 3

a、取1m3稀土皂废水首先进入斜板隔油池,废水停留时间为2.5h,使稀土废水中的浮油及分散油中颗粒较大的油滴上升到表面,刮掉上层浮油,然后废水进入射流式气浮室,通过气浮去废水中的乳化油以及疏水性细微固体悬浮物,该步处理后油类及萃取剂含量为80mg/L。a. Take 1m 3 rare earth soap wastewater and enter it into the slanted plate grease trap first, the wastewater residence time is 2.5h, make the slick oil in the rare earth wastewater and the oil droplets with larger particles in the dispersed oil rise to the surface, scrape off the upper layer of slick oil, Then the wastewater enters the jet-type air flotation chamber, and the emulsified oil and hydrophobic fine solid suspended matter in the wastewater are removed by air flotation. After this step, the content of oil and extractant is 80mg/L.

b、经除油后的废水进入pH调节沉淀池,然后向废水中加入16L浓度为30%的浓氨水调节pH为8,再向废水中加入1.5g PAM搅拌反应15min,静置40min,产生的污泥经池底的排泥管排出,上清液及污泥滤液进入混凝沉淀池。B, the waste water after degreasing enters the pH adjustment sedimentation tank, then adding 16L concentration to the waste water is the strong ammonia water of 30% to adjust the pH to be 8, then adds 1.5g PAM to the waste water and stirs the reaction for 15min, and leaves standstill for 40min, the produced The sludge is discharged through the sludge discharge pipe at the bottom of the tank, and the supernatant and sludge filtrate enter the coagulation sedimentation tank.

c、往混凝沉淀池中加入13L 1号复合混凝剂,快速搅拌10min,然后慢速搅拌15min后静置40min,产生的污泥经池底的排泥管排出,上清液及污泥滤液进入pH调节池,然后向废水中加入7L质量浓度为35%的浓盐酸调节pH为3。c. Add 13L No. 1 composite coagulant to the coagulation sedimentation tank, stir rapidly for 10 minutes, then stir slowly for 15 minutes and then let it stand for 40 minutes. The generated sludge is discharged through the sludge discharge pipe at the bottom of the tank, and the supernatant and sludge The filtrate enters the pH adjustment tank, and then 7L of concentrated hydrochloric acid with a mass concentration of 35% is added to the waste water to adjust the pH to 3.

d、经调节pH后的废水再进入活性炭滤塔,控制滤速为3m/h,吸附及过滤废水中残余的重金属及微量油类物质,经活性炭处理后的废水再进入蒸发结晶塔在负压条件下蒸发浓缩。所得蒸馏水氨氮浓度为13.5mg/L,所得氯化铵量为150kg,品质见表3。d. After adjusting the pH, the wastewater enters the activated carbon filter tower, and the filtration rate is controlled to 3m/h to absorb and filter the residual heavy metals and trace oils in the wastewater. After the activated carbon treatment, the wastewater enters the evaporation crystallization tower under negative pressure. Concentrated by evaporation. The ammonia nitrogen concentration of the obtained distilled water is 13.5 mg/L, and the amount of ammonium chloride obtained is 150 kg, and the quality is shown in Table 3.

表3所得氯化铵分析数据表Table 3 gained ammonium chloride analysis data table

 工业级氯化铵指标名称Industrial grade ammonium chloride index name   一等品 First grade   合格品Qualified product   所得氯化铵The resulting ammonium chloride  氯化铵(NH4Cl)含量(以干基计),%,≥Ammonium chloride (NH 4 Cl) content (on a dry basis), %, ≥   99.399.3   99.099.0   99.199.1  水分,%,≤Moisture,%, ≤   0.70.7   1.01.0   --  灼烧残渣,%,≤Residue on ignition, %, ≤   0.40.4   0.40.4   0.380.38  铁(Fe)含量,%,≤Iron (Fe) content, %, ≤   0.0010.001   0.0030.003   0.00250.0025  重金属(以Pb计)含量,%,≤Heavy metal (calculated as Pb) content, %, ≤   0.00050.0005   0.0010.001   0.00080.0008  硫酸盐(以SO4)含量,%,≤Sulfate (as SO 4 ) content, %, ≤   0.020.02   --   0.010.01  pH值(200g/L溶液,温度25℃)pH value (200g/L solution, temperature 25°C)   4.0~5.84.0~5.8   4.0~5.84.0~5.8   4.94.9

实施例4Example 4

a、按稀土皂废水和碳铵沉淀母液的实际废水量(4∶1)配制1m3混合废水首先进入斜板隔油池,废水停留时间为2.5h,使废水中的浮油及分散油中颗粒较大的油滴上升到表面,刮掉上层浮油,然后废水进入射流式气浮室,通过气浮去废水中的乳化油以及疏水性细微固体悬浮物,该步处理后油类及萃取剂含量为73mg/L。a. According to the actual amount of wastewater (4:1) of rare earth soap wastewater and ammonium bicarbonate precipitation mother liquor, 1m3 mixed wastewater is first entered into the inclined plate grease trap, and the residence time of wastewater is 2.5h, so that the slick oil and dispersed oil in the wastewater The oil droplets with larger particles rise to the surface, scrape off the upper oil slick, and then the wastewater enters the jet-type air flotation chamber, and the emulsified oil and hydrophobic fine solid suspended matter in the wastewater are removed by air flotation. After this step, the oil and extracted The dose content is 73mg/L.

b、经除油后的废水进入pH调节沉淀池,然后向废水中加入13L浓度为30%的浓氨水调节pH为8.05,再向废水中加入1.5g PAM搅拌反应15min,静置40min,产生的污泥经池底的排泥管排出,上清液及污泥滤液进入混凝沉淀池。B, the waste water after degreasing enters the pH adjustment sedimentation tank, then adding 13L concentration to the waste water is the strong ammonia water of 30% to adjust the pH to be 8.05, then adds 1.5g PAM to the waste water and stirs the reaction for 15min, and leaves standstill for 40min, the produced The sludge is discharged through the sludge discharge pipe at the bottom of the tank, and the supernatant and sludge filtrate enter the coagulation sedimentation tank.

c、往混凝沉淀池中加入13L 2号复合混凝剂,快速搅拌10min,然后慢速搅拌15min后静置40min,产生的污泥经池底的排泥管排出,上清液及污泥滤液进入pH调节池,然后向废水中加入5.7L质量浓度为35%的浓盐酸调节pH为3.1。c. Add 13L No. 2 compound coagulant to the coagulation sedimentation tank, stir rapidly for 10 minutes, then stir slowly for 15 minutes and then let it stand for 40 minutes. The generated sludge is discharged through the sludge discharge pipe at the bottom of the tank, and the supernatant and sludge The filtrate enters the pH adjustment tank, and then 5.7 L of concentrated hydrochloric acid with a mass concentration of 35% is added to the waste water to adjust the pH to 3.1.

d、经调节pH后的废水再进入活性炭滤塔,控制滤速为3m/h,吸附及过滤废水中残余的重金属及微量油类物质,经活性炭处理后的废水再进入蒸发结晶塔在负压条件下蒸发浓缩。所得蒸馏水氨氮浓度为10.5mg/L,所得氯化铵量为135kg,品质见表4。d. After adjusting the pH, the wastewater enters the activated carbon filter tower, and the filtration rate is controlled to 3m/h to absorb and filter the residual heavy metals and trace oils in the wastewater. After the activated carbon treatment, the wastewater enters the evaporation crystallization tower under negative pressure. Concentrated by evaporation. The ammonia nitrogen concentration of the obtained distilled water is 10.5 mg/L, and the amount of ammonium chloride obtained is 135 kg, and the quality is shown in Table 4.

表4所得氯化铵分析数据表Table 4 gained ammonium chloride analysis data table

 工业级氯化铵指标名称Industrial grade ammonium chloride index name   一等品 First grade   合格品Qualified product   所得氯化铵The resulting ammonium chloride  氯化铵(NH4Cl)含量(以干基计),%,≥Ammonium chloride (NH 4 Cl) content (on a dry basis), %, ≥   99.399.3   99.099.0   99.299.2  水分,%,≤Moisture,%, ≤   0.70.7   1.01.0   --  灼烧残渣,%,≤Residue on ignition, %, ≤   0.40.4   0.40.4   0.350.35

 铁(Fe)含量,%,≤Iron (Fe) content, %, ≤   0.0010.001   0.0030.003   0.00150.0015  重金属(以Pb计)含量,%,≤Heavy metal (calculated as Pb) content, %, ≤   0.00050.0005   0.0010.001   0.00080.0008  硫酸盐(以SO4)含量,%,≤Sulfate (as SO 4 ) content, %, ≤   0.020.02   --   0.020.02  pH值(200g/L溶液,温度25℃)pH value (200g/L solution, temperature 25°C)   4.0~5.84.0~5.8   4.0~5.84.0~5.8   4.34.3

Claims (3)

1. one kind is used to handle the compound coagulant that rare-earth highly concentrated ammonia nitrogen waste water reclaims industrial grade ammonium chloride, it is characterized in that: this compound coagulant is the mixed solution of ammonium oxalate, ammonium sulfate, heavy metal precipitator DTCR and polyacrylamide (PAM), by four kinds of medicament weight proportions promptly: it is soluble in water that ammonium oxalate: ammonium sulfate: DTCR: PAM=0.6~3: 0.4~1.5: 1: 0.01~0.03 takes by weighing medicament, mixing and stirring then is mixed with four kinds of medicament total mass concentrations and is 3.5%~10% mixed solution.
2. one kind is used the described compound coagulant of claim 1 to handle the treatment process that rare-earth highly concentrated ammonia nitrogen waste water reclaims industrial grade ammonium chloride, it is characterized in that:
A, rare-earth highly concentrated ammonia nitrogen waste water at first enter oil trap, make that the bigger oil droplet of particle rises to the surface in oil slick in the RE waste water and the dispersed oil, by the Oil scraper frizing to reach the purpose of removing oil slick, waste water enters gas-floating chamber then, by oil in water emulsion and the trickle suspended solid of hydrophobicity in the air supporting removal waste water;
B, the waste water after oil removing enter the pH regulator settling tank, and adding concentration then and be 25%~30% strong aqua in waste water, to regulate pH be 7.5~8.5, again to every m 3Add 1~2g PAM stirring reaction, 10~15min in the waste water, leave standstill 35~50min, the shore pipe of the mud of generation at the bottom of the pond discharged, and supernatant liquor and mud filtrate enter coagulative precipitation tank;
C, in the coagulative precipitation tank by every m 3Add 3~15L compound coagulant in the waste water, stir 5~10min fast, leave standstill 30~40min after stirring 10~15min at a slow speed then, the shore pipe of the mud that produces at the bottom of the pond discharged, supernatant liquor and mud filtrate enter the pH regulator pond, and adding mass concentration then and be 30%~38% concentrated hydrochloric acid in waste water, to regulate pH be 2.5~4;
D, the waste water after regulating pH enter active carbon filter tower again, and the control filtering velocity is 3~5m/h, and heavy metal and the micro-oily substance of remnants enter evaporating and crystallizing tower evaporation concentration under condition of negative pressure again through the waste water after the activated carbon treatment in absorption and the filtered wastewater.
3. according to claim 1 being used to handled the compound coagulant that rare-earth highly concentrated ammonia nitrogen waste water reclaims industrial grade ammonium chloride, and it is characterized in that: the heavy metal precipitator DTCR in the compound coagulant is: chelate group-NH-CSSNH 4Pattern.
CN2008100273450A 2008-04-11 2008-04-11 A composite coagulant and treatment method that can be used to treat rare earth high-concentration ammonia nitrogen wastewater and recover industrial-grade ammonium chloride Expired - Fee Related CN101555053B (en)

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