WO2023103119A1 - 一种危险废物填埋场渗滤液的处理方法 - Google Patents

一种危险废物填埋场渗滤液的处理方法 Download PDF

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WO2023103119A1
WO2023103119A1 PCT/CN2021/142247 CN2021142247W WO2023103119A1 WO 2023103119 A1 WO2023103119 A1 WO 2023103119A1 CN 2021142247 W CN2021142247 W CN 2021142247W WO 2023103119 A1 WO2023103119 A1 WO 2023103119A1
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liquid
waste
leachate
mixed
waste liquid
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English (en)
French (fr)
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吴文彪
徐文彬
徐梦兰
覃伟宁
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东江环保股份有限公司
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Priority to US18/014,118 priority Critical patent/US20240092663A1/en
Publication of WO2023103119A1 publication Critical patent/WO2023103119A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F2001/5218—Crystallization
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/44—Time
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

Definitions

  • the invention relates to the technical field of water treatment, more specifically, it relates to a treatment method for leachate of hazardous waste landfill.
  • Hazardous wastes buried in hazardous waste landfills generally include wastes with high soluble salt content, such as incineration fly ash, evaporated salt mud, etc. After these hazardous wastes are stabilized and solidified, the soluble salt content will have a certain degree However, it is inevitable that some of them will be dissolved in the leachate of the landfill.
  • the leachate is mainly a mixed solution of calcium chloride, sodium chloride and potassium chloride, and contains a small amount of bromide, sulfate and nitrate.
  • the main components of its leachate are calcium chloride 10.33% (wt), sodium chloride 6.00% (wt), potassium chloride 4.96% (wt), and a small amount of Other components, such as bromide 6560mg/L, sulfate 519mg/L, nitrate 310mg/L, heavy metal 50mg/L in Pb, etc., the pH value of the leachate is 10.78, and the density is 1.15g/cm-1.
  • Evaporating under acidic conditions can reduce the content of ammonia nitrogen in distilled water and reduce the formation of scaling, but due to the high content of bromine in the system, hydrogen bromide will seriously corrode the evaporator under high temperature conditions, even titanium If the material evaporator is used, the tubes will be corroded and penetrated in two or three months.
  • the present invention provides a treatment method for the leachate of hazardous waste landfills, which can not only realize the recycling of sodium chloride and potassium chloride in the leachate, but also effectively avoid the impact of hydrogen bromide on the leachate. Evaporator corrosion.
  • a kind of processing method of leachate of hazardous waste landfill comprises the following steps;
  • Step 1 adding sodium carbonate required to completely remove the calcium ion content in the leachate, reacting for 30 minutes, filtering to obtain calcium carbonate slag and the first waste liquid;
  • Step 2 adding hydrochloric acid to the first waste liquid, adjusting its pH value to obtain the first mixed liquid;
  • Step 3 After heating the first mixed liquid to 80°C, a certain amount of chlorine gas is introduced into the first mixed liquid, and air is simultaneously introduced into the first mixed liquid. After the stripping reaction, the second waste liquid and the first mixed liquid are obtained. gas;
  • Step 4 passing the first mixed gas into the alkali liquid absorption tower to obtain an absorption liquid, and sending the absorption liquid into a bromine recovery device to recover bromine;
  • Step 5 heating the second waste liquid to 100°C, evaporating and crystallizing to obtain evaporative condensed water and concentrated liquid;
  • Step 6 centrifuging the concentrated solution to obtain sodium chloride wet salt and centrifuged solution
  • Step 7 pumping the centrifugal separation liquid into a cooling crystallization tank, and after the temperature of the centrifugal separation liquid is cooled to 40° C., centrifuging to obtain potassium chloride wet salt and final mother liquor;
  • Step 8 returning the final mother liquor to the first waste liquor or the second waste liquor for recycling.
  • the pH value of the first mixed solution is 4.0-6.0.
  • the chlorine gas can be produced by chemical reaction or electrolysis of sodium chloride solution.
  • CaCl in the leachate and the slightly excessive sodium carbonate added can be converted into NaCl, that is, the original
  • the CaCl 2 -NaCl-KCl-H 2 O quaternary system in water is reduced to the NaCl-KCl-H 2 O ternary system, which greatly reduces the difficulty of subsequent salt separation treatment.
  • the bromide ion in the leachate is removed in advance through the debromination tower, which avoids the corrosion of the subsequent hydrogen bromide to the evaporator equipment, and also eliminates the influence of the bromide on the subsequent salt separation and the purity of the salt product .
  • Fig. 1 is a schematic flow chart of the present invention.
  • first and second are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features.
  • the features defined as “first” and “second” may explicitly or implicitly include at least one of these features.
  • “plurality” means at least two, unless otherwise specifically defined.
  • the first feature may be in direct contact with the first feature or the first and second feature may be in direct contact with the second feature through an intermediary. touch.
  • “above”, “above” and “above” the first feature on the second feature may mean that the first feature is directly above or obliquely above the second feature, or simply means that the first feature is higher in level than the second feature.
  • “Below”, “beneath” and “beneath” the first feature may mean that the first feature is directly below or obliquely below the second feature, or simply means that the first feature is less horizontally than the second feature.
  • a kind of processing method of leachate of hazardous waste landfill comprises the following steps;
  • Step 1 adding sodium carbonate to the leachate to obtain calcium carbonate slag and the first waste liquid;
  • reaction time of sodium carbonate and leachate is 30min;
  • calcium carbonate slag can be used as a neutralizing agent to neutralize waste acid.
  • Step 2 adding hydrochloric acid to the first waste liquid, adjusting its pH value to obtain the first mixed liquid;
  • the pH value of the first mixed solution is 4.0-6.0, preferably, the pH value is 5.0;
  • Step 3 After heating the first mixed liquid to 80°C, a certain amount of chlorine gas is introduced into the first mixed liquid, and air is simultaneously introduced into the first mixed liquid. After the stripping reaction, the second waste liquid is mixed with the first gas;
  • the chlorine gas used above can be directly derived from a chlorine gas bottle, or can be obtained by electrolysis or chemical reaction;
  • the electrolytic method for preparing chlorine gas is preferably ion membrane electrolysis sodium chloride solution, and the sodium chloride here can be produced by using this process to obtain The sodium chloride product;
  • Chemical reaction prepares chlorine preferably reacts with hydrochloric acid and calcium hypochlorite or sodium hypochlorite;
  • Step 4 the first mixed gas is passed into the lye absorption tower to obtain the absorption liquid, specifically, the lye is 5% sodium hydroxide solution; the absorption liquid is sent to the bromine recovery device for bromine recovery Recycle;
  • Step 5 heating the second waste liquid to 100°C to make it evaporating and crystallizing for about 45 minutes to obtain evaporative condensed water and concentrated liquid;
  • the above evaporation and crystallization time needs to be changed according to the change of sodium chloride and potassium chloride content in the feed liquid;
  • Step 6 centrifuging and filtering the concentrated solution to obtain sodium chloride wet salt and centrifuged solution
  • the sodium chloride can be used as a raw material for producing chlorine by electrolysis
  • Step 7 pump the centrifugal separation liquid into the cooling crystallization tank, the temperature of the centrifugal separation cooling crystallization is 30-50°C, the preferred temperature is 40°C, when the temperature of the centrifugal separation liquid is cooled, the centrifugal separation obtains Potassium chloride wet salt and final mother liquor;
  • Step 8 returning the final mother liquor to the first waste liquor or the second waste liquor for secondary treatment.
  • the above-mentioned treatment method for the leachate of the hazardous waste landfill is to remove calcium by adding a theoretical amount of sodium carbonate solid to the leachate of the hazardous waste landfill, and convert the calcium chloride therein into calcium carbonate and sodium chloride.
  • the content of heavy metals in terms of Pb can also be reduced from about 50 mg/L to below 5 mg/L;
  • the filtrate after decalcification is first adjusted to a pH value of 4.0-6.0 with hydrochloric acid to avoid the reaction of chlorine gas and excess sodium carbonate, and then the It is heated to above 80°C, a certain amount of chlorine gas is introduced into it, and air is simultaneously introduced into it, and the bromine generated by the reaction is blown out of the leachate system by means of high-temperature blow-off, which can reduce the content of bromide ions from 6560mg/L To below 70mg/L, the bromine content in subsequent sodium chloride and potassium chloride products will be greatly reduced; the leachate after bromine removal will continue to be heated to 100
  • the main components of the hazardous waste landfill leachate in this embodiment are calcium chloride 10.33% (wt), sodium chloride 6.00% (wt), potassium chloride 4.96% (wt), bromide 6560mg/L, heavy metal 50mg/L as Pb, density 1.15g/cm 3 .
  • the specific processing method is as follows:
  • the concentrated solution is centrifugally separated and filtered to obtain a sodium chloride wet salt product and a filtrate;
  • the final mother liquor is returned to the second waste liquor to continue the same subsequent step treatment, and the mother liquor is circulated 17 times.
  • the main components of the hazardous waste landfill leachate in this embodiment are calcium chloride 10.33% (wt), sodium chloride 6.00% (wt), potassium chloride 4.96% (wt), bromide 6560mg/L, heavy metal 50mg/L as Pb, density 1.15g/cm 3 .
  • the specific processing method is as follows:
  • the concentrated solution is centrifugally separated and filtered to obtain a sodium chloride wet salt product and a filtrate;
  • the leachate from the hazardous waste landfill was not subjected to debromination treatment, and the bromide content in the final sodium chloride product was as high as 0.54%, and the bromide content in the potassium chloride product was as high as 1.47%.
  • increase debromination step the content of the bromide in the sodium chloride and potassium chloride product is all lower than 0.002%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Mechanical Engineering (AREA)
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Abstract

一种危险废物填埋场渗滤液的处理方法，将碳酸钠加入渗滤液中，得到碳酸钙渣与第一废液；将盐酸加入第一废液中，得到第一混合液；将第一混合液加热后，向第一混合液中通入定量氯气，并同步通入空气，得到第二废液与第一混合气；将第一混合气通入碱液吸收塔；将第二废液加热,得到蒸发冷凝水与浓缩液；将浓缩液离心分离，得到氯化钠湿盐与离心分离液；将离心分离液泵入冷却结晶罐中，离心分离得到氯化钾湿盐与最终母液；将最终母液返回至第一废液或第二废液中循环使用。该方法大幅降低后续分盐处理的难度，避免了后续溴化氢对蒸发器设备的腐蚀，实现了氯化钠和氯化钾的资源化回收。

Description

一种危险废物填埋场渗滤液的处理方法 技术领域
本发明涉及水处理的技术领域，更具体地说，它涉及一种危险废物填埋场渗滤液的处理方法。
背景技术
危险废物填埋场填埋的危险废物一般都包括可溶性盐含量高的废物，如焚烧飞灰、蒸发盐泥等，这些危险废物经稳定化和固化处理后，其中的可溶性盐含量会有一定程度的降低，但难免也会有部分溶解到填埋场的渗滤液中。一般来说，该渗滤液主要为氯化钙、氯化钠和氯化钾的混合溶液，并含少量的溴化物、硫酸盐和硝酸盐。以深圳市某危险废物填埋场为例，其渗滤液的主要成分分别为氯化钙10.33％(wt)、氯化钠6.00％(wt)、氯化钾4.96％(wt)，同时含有少量其它成分，如溴化物6560mg/L、硫酸盐519mg/L、硝酸盐310mg/L、重金属以Pb计50mg/L等，渗滤液的pH值10.78，密度1.15g/cm-1。
目前国内外均没有该类废液的处理研究报告，基本都采用常规的“物化+蒸发+生化”的工艺来处理，蒸发得到的盐泥返回填埋场填埋。然而，该类废液由于氯化钙含量较高，直接碱性条件下蒸发不仅易造成蒸发器的结垢，而且由于氯化钙的溶解度较大，直接蒸发处理(如MVR蒸发)，实际上很难析出固体，采用三效蒸发倒是能析出，但析出的固体是一种混合盐，需要另行处置，浪费了大量的有价资源；同时，碱性条件下蒸发，蒸馏水中的氨氮较高，不利于后续的生化处理。酸性条件下蒸发的话，虽然可以降低蒸馏水中的氨氮含量，并降低结垢的生成，但由于体系中的溴含量较高，溴化氢在高温条件下对蒸发器的腐蚀非常严重，即便是钛材蒸发器，两三个月也会把其列管腐蚀穿透。
发明内容
针对现有技术存在的不足，本发明提供一种危险废物填埋场渗滤液的处 理方法，不仅可以实现渗滤液中氯化钠、氯化钾的资源化回收，而且可以有效避免溴化氢对蒸发器的腐蚀。
本发明的上述技术目的是通过以下技术方案得以实现的：一种危险废物填埋场渗滤液的处理方法，包括以下步骤；
步骤1，在渗滤液中加入可以完全去除其中钙离子含量所需的碳酸钠，反应30min后，过滤得到碳酸钙渣与第一废液；
步骤2，将盐酸加入所述第一废液中，调节其pH值，得到第一混合液；
步骤3，将所述第一混合液加热至80℃后，向所述第一混合液中通入定量氯气，并同步通入空气，经过吹脱反应后，得到第二废液与第一混合气；
步骤4，将所述第一混合气通入碱液吸收塔，得到吸收液，将所述吸收液送入溴素回收装置对溴素进行回收；
步骤5，将所述第二废液加热至100℃后,使其蒸发结晶，得到蒸发冷凝水与浓缩液；
步骤6，将所述浓缩液离心分离，得到氯化钠湿盐与离心分离液；
步骤7，将所述离心分离液泵入冷却结晶罐中，当所述离心分离液温度冷却至40℃后，离心分离得到氯化钾湿盐与最终母液；
步骤8，将所述最终母液返回至所述第一废液或所述第二废液中循环使用。
在其中一个实施例中，所述第一混合液的pH值为4.0-6.0。
在其中一个实施例中，所述氯气可通过化学反应或电解氯化钠溶液制得。
上述一种危险废物填埋场渗滤液的处理方法，具有以下有益效果：
其一，本发明中，经预处理除钙，并调除钙后滤液pH值至酸性，可将渗滤液中的CaCl 2及加入的稍过量的碳酸钠均转化为NaCl，也即可将原水中CaCl 2-NaCl-KCl-H 2O四元体系降为NaCl-KCl-H 2O三元体系，大幅降低后续分 盐处理的难度。
其二，本发明中，渗滤液中的溴离子经脱溴塔提前去除，避免了后续溴化氢对蒸发器设备的腐蚀，同时也消除了溴化物对后续分盐及分盐产品纯度的影响。
其三，本发明中，经蒸发结晶和冷却结晶处理，实现了氯化钠和氯化钾的资源化回收。
附图说明
图1是本发明的流程示意图。
具体实施方式
下面结合附图和实施例，对本发明进行详细描述。
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中，“多个”的含义是至少两个，除非另有明确具体的限定。
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接或彼此可通讯； 可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系，除非另有明确的限定。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。
在本发明中，除非另有明确的规定和限定，第一特征在第二特征“上”或“下”可以是第一和第二特征直接接触，或第一和第二特征通过中间媒介间接接触。而且，第一特征在第二特征“之上”、“上方”和“上面”可是第一特征在第二特征正上方或斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”可以是第一特征在第二特征正下方或斜下方，或仅仅表示第一特征水平高度小于第二特征。
一种危险废物填埋场渗滤液的处理方法,如图1所示，包括以下步骤；
步骤1，将碳酸钠加入渗滤液中，得到碳酸钙渣与第一废液；
在渗滤液中加入可以完全去除其中钙离子含量的碳酸钠 1，碳酸钠与所述渗滤液充分反应后，压滤，得到碳酸钙渣与第一废液；
具体地，碳酸钠与渗滤液的反应时间为30min；
具体地，碳酸钙渣可作为中和剂用于中和废酸。
步骤2，将盐酸加入所述第一废液中，调节其pH值，得到第一混合液；
具体地，所述第一混合液的pH值为4.0-6.0，优选地，pH值为5.0；
步骤3，将所述第一混合液加热到80℃后，向所述第一混合液中通入定量氯气，并同步通入空气，经过吹脱反应后，得到第二废液与第一混合气；
具体地，上述使用的氯气可直接来源于氯气瓶，也可通过电解或化学反应制得；电解方法制备氯气优选离子膜电解氯化钠溶液，并且此处的氯化钠可使用本工艺生产得到的氯化钠产品；化学反应制备氯气优选盐酸与次氯酸钙或次氯酸钠反应；
步骤4，将所述第一混合气通入碱液吸收塔，得到吸收液，具体地，碱液为5％的氢氧化钠溶液；将所述吸收液送入溴素回收装置对溴素进行回收；
步骤5，将所述第二废液加热到100℃,使其蒸发结晶，蒸发结晶约45min,得到蒸发冷凝水与浓缩液；
具体地，上述蒸发结晶时间需根据料液中氯化钠和氯化钾含量的变化而变化；
将所述冷凝水生化处理达标后排放；
步骤6，将所述浓缩液离心分离后过滤，得到氯化钠湿盐与离心分离液；
具体地，所述氯化钠可作为电解制备氯气的原料；
步骤7，将所述离心分离液泵入冷却结晶罐中，所述离心分离冷却结晶的温度为30-50℃，优选的温度为40℃，当所述离心分离液温度冷却后，离心分离得到氯化钾湿盐与最终母液；
步骤8，将所述最终母液返回至所述第一废液或所述第二废液中循环使用进行二次处理。
上述危险废物填埋场渗滤液的处理方法，通过向危险废物填埋场渗滤液中加入理论量的碳酸钠固体来除钙，将其中的氯化钙转化为碳酸钙和氯化钠，该过程中，还可将重金属以Pb计的含量由50mg/L左右降至5mg/L以下；除钙后的滤液先用盐酸调节pH值至4.0-6.0，避免氯气与过量的碳酸钠反应，而后将其加热至80℃以上，向其中通入定量的氯气，并同步通入空气，通过高温吹脱的办法将反应生成的溴素吹脱出渗滤液体系，可将溴离子的含量从6560mg/L降至70mg/L以下，大幅降低后续氯化钠、氯化钾产品中的溴含量；除溴后的渗滤液继续加热至100℃，通过蒸发结晶分离得到氯化钠产品，再通过冷却结晶分离得到氯化钾产品，最终的母液返回前面继续蒸发，以提高总盐的回收率。母液经17次循环后，总盐的回收率可达到95％以上，并且不 会影响氯化钠和氯化钾产品的品质。
实施例1
本实施例的危险废物填埋场渗滤液的主要成分分别为氯化钙10.33％(wt)、氯化钠6.00％(wt)、氯化钾4.96％(wt)、溴化物6560mg/L、重金属以Pb计50mg/L、密度1.15g/cm 3。具体处理方法如下：
在1L危险废物填埋场渗滤液中加入114g无水碳酸钠固体，反应30min后过滤，得到碳酸钙渣和第一废液；
向第一废液中滴加浓盐酸，调节pH值为5后，得到第一混合液，将第一混合液加热至80℃后，通入约3g的氯气(由17.1g浓度为36％的浓盐酸与6g次氯酸钙固体定量反应制得)，并同步用气泵通入空气，吹脱反应过程中生成的溴素，吹脱完成后，得到第二废液和第一混合气，第一混合气用5％的氢氧化钠溶液吸收；
加热第二废液至100℃，蒸发结晶约45min，停止加热，得到蒸发冷凝水和浓缩液；
将浓缩液离心分离过滤，得到氯化钠湿盐产品及滤液；
将滤液自然冷却至40℃后，过滤得到氯化钾湿盐产品和最终母液；
将最终母液返回至第二废液中继续进行相同的后续步骤处理，母液循环17次。
在本实施例中，危险废物填埋场渗滤液经脱溴处理后，第二废液中溴化物的浓度降为68.2mg/L，送检母液循环第1、5、9、13、17次时得到的氯化钠和氯化钾产品，其各项指标分别如表1和表2所示。由表1可以发现母液循环17次，得到的氯化钠产品均能达到《GB/T 5462-2015工业盐》中工业干盐二级品的要求，得到的氯化钾产品也均能达到《GB/T 7118-2008工业用氯化钾》二级品的要求，并且国标中未作要求的溴化物的含量也均低于 0.013％。
表1氯化钠产品理化指标
Figure PCTCN2021142247-appb-000001
表2氯化钾产品理化指标
Figure PCTCN2021142247-appb-000002
Figure PCTCN2021142247-appb-000003
实施例2
本实施例的危险废物填埋场渗滤液的主要成分分别为氯化钙10.33％(wt)、氯化钠6.00％(wt)、氯化钾4.96％(wt)、溴化物6560mg/L、重金属以Pb计50mg/L、密度1.15g/cm 3。具体处理方法如下：
在1L危险废物填埋场渗滤液中加入114g无水碳酸钠固体，反应30min，过滤，得到碳酸钙渣和第一废液；
向第一废液中加入浓盐酸，调节其pH值为5后，加热至100℃以上，蒸发结晶约45min，停止加热，得到蒸发冷凝水和浓缩液；
将浓缩液离心分离过滤，得到氯化钠湿盐产品及滤液；
将滤液自然冷却至40℃后，过滤得到氯化钾湿盐产品和最终母液。
在本实施例中，危险废物填埋场渗滤液未进行脱溴处理，最终得到的氯化钠产品中的溴化物含量高达0.54％，氯化钾产品中的溴化物含量高达1.47％。而上述实施例1中在其它条件均相同的情况下，增加脱溴步骤，氯化钠和氯化钾产品中的溴化物的含量均低于0.002％。
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例为申请人真实试验结果加以论证。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (3)

  1. 一种危险废物填埋场渗滤液的处理方法，其特征在于：包括以下步骤；
    步骤1，在渗滤液中加入可以完全去除其中钙离子含量所需的碳酸钠，反应30min后，过滤得到碳酸钙渣与第一废液；
    步骤2，将盐酸加入所述第一废液中，调节其pH值，得到第一混合液；
    步骤3，将所述第一混合液加热至80℃后，向所述第一混合液中通入定量氯气，并同步通入空气，经过吹脱反应后，得到第二废液与第一混合气；
    步骤4，将所述第一混合气通入碱液吸收塔，得到吸收液，将所述吸收液送入溴素回收装置对溴素进行回收；
    步骤5，将所述第二废液加热至100℃后,使其蒸发结晶，得到蒸发冷凝水与浓缩液；
    步骤6，将所述浓缩液离心分离，得到氯化钠湿盐与离心分离液；
    步骤7，将所述离心分离液泵入冷却结晶罐中，当所述离心分离液温度冷却至40℃后，离心分离得到氯化钾湿盐与最终母液；
    步骤8，将所述最终母液返回至所述第一废液或所述第二废液中循环使用。
  2. 根据权利要求1所述的一种危险废物填埋场渗滤液的处理方法，其特征在于：所述第一混合液的pH值为4.0-6.0。
  3. 根据权利要求1所述的一种危险废物填埋场渗滤液的处理方法，其特征在于：所述氯气可通过化学反应或电解氯化钠溶液制得。
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