CN114477653B - A method and system for treating wastewater in a molecular sieve production process - Google Patents
A method and system for treating wastewater in a molecular sieve production process Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 76
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002351 wastewater Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 44
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- 239000007788 liquid Substances 0.000 claims description 18
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims description 14
- FOWDOWQYRZXQDP-UHFFFAOYSA-N adamantan-2-ol Chemical compound C1C(C2)CC3CC1C(O)C2C3 FOWDOWQYRZXQDP-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000005842 biochemical reaction Methods 0.000 claims description 5
- 229940052761 dopaminergic adamantane derivative Drugs 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 claims description 3
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- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
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- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/26—Synthetic macromolecular compounds
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Abstract
Description
技术领域technical field
本发明涉及废水处理领域，具体涉及一种分子筛生产过程废水处理方法及系统。The invention relates to the field of wastewater treatment, in particular to a method and system for treating wastewater in a molecular sieve production process.
背景技术Background technique
柴油发动机凭借其优势在运输行业的应用越来越普遍，然而，柴油发动机排出的尾气中含有的氮氧化物（NOx）严重污染环境，危害人体健康。选择性催化还原技术（SCR）是目前被广泛应用的脱硝技术，研发稳定高效的催化剂是采用该技术的核心。Due to its advantages, diesel engines are more and more widely used in the transportation industry. However, the nitrogen oxides (NO x ) contained in the exhaust exhaust from diesel engines seriously pollute the environment and endanger human health. Selective Catalytic Reduction (SCR) is currently a widely used denitrification technology, and the development of stable and efficient catalysts is the core of this technology.
SSZ-13分子筛催化剂逐渐受到人们的关注。目前，水热合成法成为工业上合成SSZ-13分子筛的主流技术，一般以水、硅源、碱源、有机模板剂等为原料，在一定温度和压力下合成分子筛。分子筛在合成过程中产生的废水成分复杂，具有高pH、高COD、高氨氮、高固含量等特点，处理难度极大。SSZ-13 molecular sieve catalysts have gradually attracted people's attention. At present, the hydrothermal synthesis method has become the mainstream technology for industrially synthesizing SSZ-13 molecular sieves. Generally, water, silicon sources, alkali sources, organic templates, etc. are used as raw materials to synthesize molecular sieves at a certain temperature and pressure. The wastewater generated during the synthesis of molecular sieves has complex components and features such as high pH, high COD, high ammonia nitrogen, and high solid content, making it extremely difficult to treat.
目前，现有专利中有关分子筛废水的处理方法多为物化处理和生化处理相结合的方法。CN106554124B公开了一种分子筛催化剂生产过程中产生废水的处理方法：采用石灰法降低分子筛废水悬浮物浓度，之后将其和生活污水按1:(10～50)的比例混合然后进行生化处理。在生化处理阶段需要添加多种微生物生长促进剂，来防止微生物失活，该方法运行不稳定。At present, most of the treatment methods related to molecular sieve wastewater in the existing patents are a combination of physical and chemical treatment and biochemical treatment. CN106554124B discloses a treatment method for wastewater generated during the production of molecular sieve catalysts: the lime method is used to reduce the concentration of suspended matter in molecular sieve wastewater, and then it is mixed with domestic sewage at a ratio of 1: (10-50) and then subjected to biochemical treatment. In the biochemical treatment stage, a variety of microbial growth promoters need to be added to prevent microbial inactivation, and this method is unstable.
CN103771646A公开了一种钛硅分子筛生产废水的处理方法：将废水pH调至碱性，然后进行蒸发，将冷凝液进行生化处理。在SSZ-13分子筛废水中含有1-金刚烷醇、2-金刚烷醇、金刚烷类化合物，其升华特性使得废水在蒸发过程中的有机物进入冷凝液，导致蒸发冷凝液COD含量高达400～1500mg/L。由于1-金刚烷醇、2-金刚烷醇、金刚烷类化合可生化性极差，现有技术路线并不能有效处理该废水。因此，开发经济高效的SSZ-13分子筛生产过程废水处理方法具有重要意义。CN103771646A discloses a method for treating waste water produced by titanium-silicon molecular sieves: the pH of the waste water is adjusted to be alkaline, then evaporated, and the condensate is subjected to biochemical treatment. The SSZ-13 molecular sieve wastewater contains 1-adamantanol, 2-adamantanol, and adamantane compounds. Their sublimation characteristics make the organic matter in the wastewater enter the condensate during the evaporation process, resulting in a high COD content of 400-1500mg in the evaporation condensate. /L. Due to the extremely poor biodegradability of 1-adamantanol, 2-adamantanol, and adamantanes, the existing technical routes cannot effectively treat the wastewater. Therefore, it is of great significance to develop a cost-effective method for the wastewater treatment of SSZ-13 molecular sieve production process.
发明内容Contents of the invention
本发明的目的为了克服现有的分子筛废水生化处理、蒸发过程中存在的缺点，提供一种分子筛生产过程废水处理方法及系统，能够实现分子筛生产过程废水的有效处理，降低蒸发冷凝液中COD含量、提高可生化性。The purpose of the present invention is to overcome the existing shortcomings in the biochemical treatment and evaporation process of molecular sieve wastewater, and provide a method and system for treating wastewater in the molecular sieve production process, which can realize the effective treatment of wastewater in the molecular sieve production process and reduce the COD content in the evaporation condensate , Improve biodegradability.
为实现上述目的，本发明采用的技术方案如下：To achieve the above object, the technical scheme adopted in the present invention is as follows:
一种分子筛生产过程废水处理方法，包括如下步骤：A method for treating wastewater in a molecular sieve production process, comprising the steps of:
将分子筛生产过程中产生的废水pH值调至4.0～7.0，然后过滤，将过滤后的滤液进行蒸发处理，得到蒸发冷凝液，将蒸发冷凝液经吸附剂进行吸附去除有机物。Adjust the pH value of the waste water produced in the molecular sieve production process to 4.0-7.0, then filter, and evaporate the filtered filtrate to obtain an evaporation condensate, which is adsorbed by an adsorbent to remove organic matter.
进一步的，所述分子筛为具有CHA结构的分子筛。Further, the molecular sieve is a molecular sieve with a CHA structure.
所述分子筛为含Fe、Cu、Mn、Ce、Ti、Zn与Na中至少一种金属元素的SSZ-13分子筛或H-SSZ-13。The molecular sieve is SSZ-13 molecular sieve or H-SSZ-13 containing at least one metal element of Fe, Cu, Mn, Ce, Ti, Zn and Na.
进一步的，所述分子筛生产过程中产生的废水pH＞7.0；所述分子筛生产过程中产生的废水含有金刚烷类衍生物。Further, the pH of the wastewater generated during the molecular sieve production process is >7.0; the wastewater generated during the molecular sieve production process contains adamantane derivatives.
进一步的，金刚烷类衍生物包括1-金刚烷醇、2-金刚烷醇以及金刚烷胺。Further, the adamantane derivatives include 1-adamantanol, 2-adamantanol and amantadine.
进一步的，将蒸发冷凝液经吸附剂进行吸附去除有机物后，进行生化处理。Further, after the evaporative condensate is adsorbed by an adsorbent to remove organic matter, biochemical treatment is performed.
进一步的，采用盐酸、硫酸、硝酸与磷酸中的一种或多种，将分子筛生产过程中产生的废水pH值调至4.0～7.0。Further, one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid is used to adjust the pH value of the wastewater generated in the molecular sieve production process to 4.0-7.0.
进一步的，吸附剂为超高联交吸附树脂、活性炭、膨润土或分子筛，吸附的温度为5～55℃。Further, the adsorbent is ultra-highly cross-linked adsorption resin, activated carbon, bentonite or molecular sieve, and the adsorption temperature is 5-55°C.
一种如上所述方法采用的分子筛生产过程废水处理系统，包括分子筛废水储罐、调酸装置、固液分离装置、蒸发浓缩装置、吸附/脱附装置与分离装置；A molecular sieve production process wastewater treatment system adopted by the above method, comprising a molecular sieve wastewater storage tank, an acid adjustment device, a solid-liquid separation device, an evaporation concentration device, an adsorption/desorption device and a separation device;
其中，分子筛废水储罐与调酸装置入口相连，调酸装置出口与固液分离装置相连，固液分离装置与蒸发浓缩装置相连，蒸发浓缩装置与吸附/脱附装置相连，吸附/脱附装置的第一出口与分离装置相连。Among them, the molecular sieve wastewater storage tank is connected to the inlet of the acid adjustment device, the outlet of the acid adjustment device is connected to the solid-liquid separation device, the solid-liquid separation device is connected to the evaporation concentration device, the evaporation concentration device is connected to the adsorption/desorption device, and the adsorption/desorption device The first outlet is connected to the separation device.
进一步的，吸附/脱附装置的第二出口与生化反应装置相连。Further, the second outlet of the adsorption/desorption device is connected with the biochemical reaction device.
与现有技术相比，本发明具有以下有益效益：先将分子筛生产过程中产生的废水调酸去除悬浮物、硅溶胶等，再利用蒸发去除水中无机盐及大部分COD，再利用吸附法除去冷凝液中难降解有机物，实现废水达标排放，或者进入生化处理，实现废水处理。通过吸附法除去蒸发冷凝液中难降解有机物，达到直排标准或者提高可生化性，解决了蒸发冷凝液中COD含量高、可生化性差的问题，开发了一种经济高效的SSZ-13分子筛生产过程废水处理方法，工艺安全可靠，处理效果好；同时可以回收废水中的有机物，实现其资源化利用。Compared with the prior art, the present invention has the following beneficial effects: firstly adjust the acidity of the wastewater produced in the molecular sieve production process to remove suspended solids, silica sol, etc., then use evaporation to remove inorganic salts and most of COD in water, and then use adsorption to remove The refractory organic matter in the condensate can be discharged up to the standard, or enter the biochemical treatment to realize the wastewater treatment. Removal of refractory organic matter in evaporative condensate by adsorption method, reaching the standard of direct discharge or improving biodegradability, solving the problem of high COD content and poor biodegradability in evaporative condensate, and developing an economical and efficient SSZ-13 molecular sieve production The process wastewater treatment method has a safe and reliable process and a good treatment effect; at the same time, the organic matter in the wastewater can be recovered to realize its resource utilization.
附图说明Description of drawings
图1为分子筛废水处理技术路线。Figure 1 shows the technical route of molecular sieve wastewater treatment.
图2为分子筛废水处理系统结构示意图。Fig. 2 is a schematic structural diagram of a molecular sieve wastewater treatment system.
图中，1-分子筛废水储罐，2-酸储罐，3-第一物料泵，4-酸输送泵，5-调酸装置，6-第二物料泵，7-固液分离装置，8-第三物料泵，9-蒸发浓缩装置，10-第四物料泵，11-吸附/脱附装置，12-吸附出水储罐，13-第五物料泵，14-生化反应装置，15-分离装置，16-有机物回收罐。In the figure, 1-molecular sieve wastewater storage tank, 2-acid storage tank, 3-first material pump, 4-acid delivery pump, 5-acid adjustment device, 6-second material pump, 7-solid-liquid separation device, 8 -The third material pump, 9-evaporation and concentration device, 10-the fourth material pump, 11-adsorption/desorption device, 12-adsorption water storage tank, 13-fifth material pump, 14-biochemical reaction device, 15-separation Device, 16-organic matter recovery tank.
具体实施方式Detailed ways
下面结合附图对本发明进行详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings.
本发明针对的具有CHA结构的SSZ-13分子筛生产过程废水处理。The present invention aims at the wastewater treatment in the production process of SSZ-13 molecular sieve with CHA structure.
参见图2，本发明的分子筛生产过程废水处理系统，包括：分子筛废水储罐1、酸储罐2、第一物料泵3、酸输送泵4、调酸装置5、第二物料泵6、固液分离装置7、第三物料泵8、蒸发浓缩装置9、第四物料泵10、吸附/脱附装置11、吸附出水储罐12、第五物料泵13、生化反应装置14、分离装置15以及有机物回收罐16。Referring to Fig. 2, the molecular sieve production process wastewater treatment system of the present invention comprises: molecular sieve wastewater storage tank 1,
其中，分子筛废水储罐1与第一物料泵3相连，第一物料泵3与调酸装置5入口相连，Wherein, the molecular sieve wastewater storage tank 1 is connected to the
酸储罐2与酸输送泵4相连，酸输送泵4与调酸装置5入口相连，调酸装置5出口与第二物料泵6相连，第二物料泵6与固液分离装置7相连，固液分离装置7与第三物料泵8相连，第三物料泵8与蒸发浓缩装置9相连，蒸发浓缩装置9与第四物料泵10相连，第四物料泵10与吸附/脱附装置11相连，吸附/脱附装置11的第一出口与分离装置15相连，分离装置15与有机物回收罐相连。The
吸附/脱附装置11的第二出口与吸附出水储罐12相连，吸附出水储罐12与第五物料泵13相连，第五物料泵13与生化反应装置14相连。The second outlet of the adsorption/
参见图1，本发明公开了一种分子筛生产过程废水处理方法，包括如下步骤：Referring to Fig. 1, the present invention discloses a kind of molecular sieve production process wastewater treatment method, comprises the following steps:
步骤1，分子筛生产过程中产生的废水，通过加酸将pH值调至4.0～7.0；其中，所述的分子筛为具有CHA结构的分子筛，特别是含Fe、Cu、Mn、Ce、Ti、Zn与Na等其中至少一种金属元素的SSZ-13分子筛或H-SSZ-13。Step 1, the pH value of the wastewater generated during the production of molecular sieves is adjusted to 4.0-7.0 by adding acid; wherein, the molecular sieves are molecular sieves with a CHA structure, especially containing Fe, Cu, Mn, Ce, Ti, Zn SSZ-13 molecular sieve or H-SSZ-13 with at least one metal element such as Na.
所述的废水为分子筛生产过程中产生的pH＞7.0的合成母液、洗涤水及综合废水，组分中至少包含金刚烷类衍生物。金刚烷类衍生物为1-金刚烷醇、2-金刚烷醇与金刚烷胺中的一种。The waste water is synthetic mother liquor, washing water and comprehensive waste water with pH>7.0 generated during the molecular sieve production process, and the components at least include adamantane derivatives. The adamantane derivative is one of 1-adamantanol, 2-adamantanol and amantadine.
所述的酸为盐酸、硫酸、硝酸与磷酸中的一种或多种。The acid is one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
步骤2，将步骤1得到的废水过滤，滤液经过蒸发处理，得到蒸发冷凝液，将蒸发冷凝液中的有机物利用吸附剂在一定温度下在吸附/脱附装置11中进行吸附去除，从吸附/脱附装置11中排出的滤液直接达标排放或进生化系统进行处理；
其中，所述的蒸发冷凝液中有机物为1-金刚烷醇、2-金刚烷醇与金刚烷化合物中的至少一种。Wherein, the organic matter in the evaporation condensate is at least one of 1-adamantanol, 2-adamantanol and adamantane compounds.
所述蒸发处理是采用单效或多效蒸发器进行处理。The evaporation treatment is carried out by using a single-effect or multi-effect evaporator.
所述步骤2中，所述的吸附剂为超高联交吸附树脂、活性炭、膨润土或分子筛等，吸附温度为5～55℃。In the
本发明采用吸附法，利用流体与多孔固体物质接触时，流体中的一种或多种组分扩散到多孔物质外表面和微孔内表面，并通过分子间的范德华力或多种作用力而被吸附在吸附剂上。若吸附剂对流体中某一组分的吸附具有选择性，那么该组分就会被吸附富集在吸附剂上从而实现与流体中其它组分的分离。吸附剂由于具有可调节的孔结构和表面化学结构，因而可通过筛分作用以及分子间的作用力强弱的不同，实现废水中有机物的分离。吸附法处理效果好、操作简单、方便管理、工艺简单，处理装置安装维护简便、材料更换简单易行。The present invention adopts the adsorption method. When the fluid contacts the porous solid substance, one or more components in the fluid diffuse to the outer surface of the porous substance and the inner surface of the micropore, and are separated by van der Waals force or various forces between molecules. adsorbed on the adsorbent. If the adsorbent is selective for the adsorption of a certain component in the fluid, then the component will be adsorbed and enriched on the adsorbent to achieve separation from other components in the fluid. Due to the adjustable pore structure and surface chemical structure of the adsorbent, the separation of organic matter in wastewater can be realized through the sieving effect and the difference in the strength of the intermolecular force. The adsorption method has good treatment effects, simple operation, convenient management, simple process, easy installation and maintenance of treatment devices, and simple and easy material replacement.
步骤3，对步骤2中吸附/脱附装置11中的吸附剂进行再生，同时对吸附剂再生过程中产生的有机物进行回收。
所述步骤3中，所述的再生方式为溶剂法、热法中的一种。In the
下面为具体实施例。The following are specific examples.
实施例1Example 1
对Cu-SSZ-13分子筛废水进行处理：Treatment of Cu-SSZ-13 molecular sieve wastewater:
首先用HNO3将pH值调到5.6，然后通过固液分离得到滤液。将上述滤液采用三效蒸发进行处理，得到的冷凝液pH为6.9，其中冷凝液中含有1-金刚烷醇和2-金刚烷醇等化合物，COD为1224mg/L。冷凝液经过吸附/脱附装置（树脂型号为ASD-100型吸附树脂，吸附温度为20℃）进行吸附，吸附出水COD为189mg/L。将吸附出水采用水解酸化6h后进行CASS池工艺处理6h。处理后的出水COD<50mg/L，达到排放标准。对吸附/脱附装置11内失活后的树脂进行溶剂法再生后循环利用。The pH value was first adjusted to 5.6 with HNO3 , and then the filtrate was obtained by solid-liquid separation. The above filtrate was treated by three-effect evaporation, and the obtained condensate had a pH of 6.9, and the condensate contained compounds such as 1-adamantanol and 2-adamantanol, and the COD was 1224mg/L. The condensate is adsorbed by an adsorption/desorption device (the resin model is ASD-100 adsorption resin, and the adsorption temperature is 20°C), and the COD of the adsorbed water is 189mg/L. The adsorbed water is hydrolyzed and acidified for 6 hours, and then treated by CASS pool process for 6 hours. The treated effluent COD<50mg/L meets the discharge standard. The deactivated resin in the adsorption/
实施例2Example 2
对Fe-SSZ-13分子筛废水进行处理：Treatment of Fe-SSZ-13 molecular sieve wastewater:
首先用H3PO4将pH值调到4.8，然后通过固液分离得到滤液。将分离所得滤液采用三效蒸发进行处理，得到的冷凝液pH为7.0，其中冷凝液中含有1-金刚烷醇和2-金刚烷醇等化合物，COD为457mg/L。冷凝液经过吸附/脱附装置11（树脂型号为JDA-015吸附树脂，吸附温度为55℃）进行吸附，吸附出水COD为41mg/L。处理后的出水COD<50mg/L，达到排放标准。Firstly, the pH value was adjusted to 4.8 with H 3 PO 4 , and then the filtrate was obtained by solid-liquid separation. The separated filtrate was treated by three-effect evaporation, and the obtained condensate had a pH of 7.0, and the condensate contained compounds such as 1-adamantanol and 2-adamantanol, and the COD was 457 mg/L. The condensate is adsorbed through the adsorption/desorption device 11 (the resin model is JDA-015 adsorption resin, and the adsorption temperature is 55°C), and the COD of the adsorbed water is 41mg/L. The treated effluent COD<50mg/L meets the discharge standard.
对吸附/脱附装置11内失活后的树脂进行溶剂法再生后循环利用。The deactivated resin in the adsorption/
实施例3Example 3
对Fe-Cu-SSZ-13分子筛废水进行处理：Treatment of Fe-Cu-SSZ-13 molecular sieve wastewater:
首先用HNO3将pH值调到6.2，然后通过固液分离得到滤液。将上述分离所得滤液采用三效蒸发进行蒸发，得到的冷凝液pH为6.5，其中含有1-金刚烷醇和2-金刚烷醇等化合物，COD为1050mg/L。将冷凝液经过活性炭吸附装置11（吸附温度为25℃）进行吸附，吸附出水COD为320mg/L。将吸附出水采用水解酸化6h，然后进行CASS池工艺处理6h。处理后的出水COD<50mg/L，达到排放标准。The pH value was first adjusted to 6.2 with HNO3 , and then the filtrate was obtained by solid-liquid separation. The filtrate obtained from the above separation was evaporated by three-effect evaporation, and the obtained condensate had a pH of 6.5, contained compounds such as 1-adamantanol and 2-adamantanol, and had a COD of 1050 mg/L. The condensate is adsorbed by the activated carbon adsorption device 11 (adsorption temperature is 25° C.), and the COD of the adsorbed water is 320 mg/L. The adsorbed water is hydrolyzed and acidified for 6 hours, and then treated by CASS pool process for 6 hours. The treated effluent COD<50mg/L meets the discharge standard.
对吸附/脱附装置11内失活后的活性炭进行热法再生后循环利用。The deactivated activated carbon in the adsorption/
实施例4Example 4
对Cu-SSZ-13分子筛废水进行处理：Treatment of Cu-SSZ-13 molecular sieve wastewater:
首先用H2SO4将pH值调到5.8，然后通过固液分离得到滤液。将分离所得滤液采用三效蒸发进行处理，得到的冷凝液pH为6.8，其中冷凝液中含有1-金刚烷醇和2-金刚烷醇等化合物，COD为1100mg/L，将冷凝液经过树脂附装置（树脂型号为ASD-100型吸附树脂，吸附温度为45℃）进行吸附，吸附出水COD为115mg/L，将吸附出水采用水解酸化+CASS池工艺处理，处理后的出水COD<50mg/L，达到排放标准。The pH value was first adjusted to 5.8 with H 2 SO 4 , and then the filtrate was obtained by solid-liquid separation. The separated filtrate is treated by three-effect evaporation, and the obtained condensate has a pH of 6.8, and the condensate contains compounds such as 1-adamantanol and 2-adamantanol, and the COD is 1100 mg/L. The condensate is passed through the resin attachment device (The resin model is ASD-100 adsorption resin, and the adsorption temperature is 45°C) for adsorption. The COD of the adsorbed effluent is 115mg/L. The adsorbed effluent is treated by hydrolytic acidification + CASS pool process. The treated effluent COD<50mg/L, meet emission standards.
对吸附/脱附装置11内失活后的树脂进行溶剂法再生后循环利用。The deactivated resin in the adsorption/
实施例5Example 5
对Fe-SSZ-13分子筛废水进行处理：Treatment of Fe-SSZ-13 molecular sieve wastewater:
首先用盐酸将pH值调到4.5，然后通过固液分离得到滤液。将分离所得滤液采用三效蒸发进行蒸发，得到的冷凝液pH为7.0，其中冷凝液中含有1-金刚烷醇和2-金刚烷醇等化合物物，COD为435mg/L，将冷凝液经过树脂吸附装置（树脂采用ASD-100型吸附树脂，吸附温度为35℃）进行吸附，吸附出水COD为40mg/L。处理后的出水COD<50mg/L，达到排放标准。Firstly, the pH value was adjusted to 4.5 with hydrochloric acid, and then the filtrate was obtained by solid-liquid separation. The separated filtrate was evaporated by three-effect evaporation, and the pH of the obtained condensate was 7.0. The condensate contained 1-adamantanol and 2-adamantanol and other compounds, and the COD was 435mg/L. The condensate was adsorbed by resin The device (resin adopts ASD-100 type adsorption resin, and the adsorption temperature is 35°C) is used for adsorption, and the COD of the adsorbed water is 40mg/L. The treated effluent COD<50mg/L meets the discharge standard.
对吸附/脱附装置11内失活后的树脂进行溶剂法再生后循环利用。The deactivated resin in the adsorption/
实施例6Example 6
对Ti-Cu-SSZ-13分子筛废水进行处理：Treatment of Ti-Cu-SSZ-13 molecular sieve wastewater:
首先用H2SO4将pH值调到6.5，然后通过固液分离得到滤液。将分离所得滤液采用三效蒸发进行处理，得到的冷凝液pH为6.8，其中冷凝液中含有1-金刚烷醇与2-金刚烷醇等化合物，COD为1200mg/L，将冷凝液经过树脂吸附装置（树脂采用ASD-100型吸附树脂，吸附温度为5℃）进行吸附，吸附出水COD为125mg/L，将吸附出水采用水解酸化6h+CASS池工艺处理6h，处理后的出水COD<50mg/L，达到排放标准。The pH value was first adjusted to 6.5 with H 2 SO 4 , and then the filtrate was obtained by solid-liquid separation. The separated filtrate was treated by three-effect evaporation, and the pH of the obtained condensate was 6.8. The condensate contained 1-adamantanol and 2-adamantanol and other compounds, and the COD was 1200mg/L. The condensate was adsorbed by resin The device (resin adopts ASD-100 type adsorption resin, the adsorption temperature is 5°C) is used for adsorption, and the COD of the adsorbed effluent is 125mg/L. The adsorbed effluent is treated with hydrolytic acidification for 6h+CASS pool process for 6h, and the treated effluent COD<50mg/L L, meet emission standards.
对吸附/脱附装置11内失活后的树脂进行溶剂法再生后循环利用。The deactivated resin in the adsorption/
实施例7Example 7
对H-SSZ-13分子筛废水进行处理：Treatment of H-SSZ-13 molecular sieve wastewater:
首先用盐酸将pH值调到7，然后通过固液分离得到滤液。将分离所得滤液采用三效蒸发进行处理，得到的冷凝液pH为6.8，其中冷凝液中含有1-金刚烷醇与2-金刚烷醇等化合物，COD为1000mg/L，将冷凝液经过膨润土吸附装置（膨润土，吸附温度为25℃）进行吸附，吸附出水COD为265mg/L，将吸附出水采用水解酸化6h+CASS池工艺处理6h，处理后的出水COD<50mg/L，达到排放标准。Firstly, the pH value was adjusted to 7 with hydrochloric acid, and then the filtrate was obtained by solid-liquid separation. The separated filtrate was treated by three-effect evaporation, and the pH of the obtained condensate was 6.8. The condensate contained compounds such as 1-adamantanol and 2-adamantanol, and the COD was 1000 mg/L. The condensate was absorbed by bentonite The device (bentonite, adsorption temperature is 25°C) is used for adsorption, and the COD of the adsorption effluent is 265mg/L. The adsorption effluent is treated by hydrolytic acidification for 6h+CASS pool process for 6h, and the treated effluent COD<50mg/L, reaching the discharge standard.
对吸附/脱附装置11内失活后的膨润土进行热法再生后循环利用。The bentonite deactivated in the adsorption/
实施例8Example 8
对Mn-SSZ-13分子筛废水进行处理：Treatment of Mn-SSZ-13 molecular sieve wastewater:
首先用HNO3将pH值调到6，然后通过固液分离得到滤液。将分离所得滤液采用三效蒸发进行处理，得到的冷凝液pH为6.8，其中冷凝液中含有1-金刚烷醇、2-金刚烷醇等化合物，COD为1100mg/L，将冷凝液经过大孔分子筛吸附装置（大孔分子筛，吸附温度为35℃）进行吸附，吸附出水COD为205mg/L，将吸附出水采用水解酸化6h+CASS池工艺处理6h，处理后的出水COD<50mg/L，达到排放标准。The pH value was first adjusted to 6 with HNO3 , and then the filtrate was obtained by solid-liquid separation. The separated filtrate is treated by three-effect evaporation, and the obtained condensate has a pH of 6.8. The condensate contains 1-adamantanol, 2-adamantanol and other compounds, and the COD is 1100mg/L. The condensate is passed through the macropore Molecular sieve adsorption device (large-pore molecular sieve, adsorption temperature is 35°C) for adsorption, the COD of the adsorbed water is 205mg/L, and the adsorbed water is treated with hydrolytic acidification for 6h+CASS pool process for 6h, and the treated effluent COD<50mg/L, reaching Emission Standards.
对吸附/脱附装置11内失活后的大孔分子筛进行热法再生后循环利用。The deactivated macroporous molecular sieve in the adsorption/
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