目前，杀菌剂是全球使用量第二的农药，而三唑类杀菌剂因其高效、稳定的杀菌活性，在农药市场占有极其重要的地位。粉唑醇是一种新型广谱性三唑类内吸杀菌剂，但其生产废水具有有机物及硫酸盐浓度高、碱性强、含有不可生物降解或对微生物有抑制作用的物质等特点，治理难度大，因此开发先进的原药生产清洁工艺和有效的废水处理技术，已成为粉唑醇制造企业亟须解决的重要课题。

本研究以环氧化反应、缩合反应过程中产生的废水为研究对象，进行了粉唑醇清洁生产工艺研究。一方面，对粉唑醇的生产工艺进行优化，针对性地提出了洗涤废水逆向套用方案,在保证中间体和产品质量稳定、合格的同时，废水总水量能够减少50%。另一方面，采用“甲硫醚萃取回收环氧化物—蒸馏回收甲硫醚—树脂吸附除环氧化物、二氟苯酮—中和—蒸馏回收甲醇、硫酸钾”工艺，对环氧化合成废水进行资源化回收。1吨环氧化合成废水可回收硫酸钾770kg、甲醇143kg、甲硫醚43.5kg以及中间体环氧化物2kg。

实验确定了环氧化合成废水萃取回收环氧化物的工艺条件。首先对动态参数进行了优化：萃取剂使用甲硫醚，相比1:1，温度25℃（常温）。之后通过静态吸附实验，比较TC99、TC150、XAD-4 三种树脂对环氧化物、二氟苯酮的吸附性能， TC150表现最优；在控制动态吸附流速2 BV/h，处理水量15 BV内，环氧化物、二氟苯酮的去除率均高于99%；采用甲醇作脱附剂，控制流速1 BV/h，环氧化物、二氟苯酮的脱除率均为99%，经常压蒸馏回收的硫酸钾，能够达到GB/T20406-2017农业用硫酸钾标准。

实验确定了混合废水的处理工艺，并对工艺的各项参数进行优化，优化后的参数分分别为：铁炭微电解pH为2～4、停留时间3 h、铁炭比为2、膨胀率12%；Fenton氧化的pH为3、停留时间1～1.5 h、30%双氧水与废水的体积比为1:10；UASB水力停留时间为5 d , 容积负荷2.86 kgCOD/(m3·D) ；接触氧化的水力停留时间1.5 d，容积负荷1.96 kgCOD/( m3·D)。实验结果表明“铁炭微电解—Fenton氧化—混凝沉淀”预处理对COD的去除率为82%，“UASB—接触氧化”生化处理对COD的去除率高达95%，可实现企业废水的达标排放。

Fungicides are currently the second most used pesticide in the world, and triazole fungicides play an important role in the pesticide market for their high efficiency and stable bactericidal activity. Flutriafol is a new broad-spectrum triazole systemic bactericide. The production wastewater of flutriafol is strongly alkaline, has high concentration of organic matter and sulfate, and contains substances which are non-biodegradable or have an inhibitory effect on microorganisms. These features greatly increase the difficulty of the wastewater treatment. So the development of cleaner production processes of raw flutriafol and more efficient wastewater treatment technologies has become a major issue for flutriafol manufacturing enterprises.

In this study, the main components and concentration in wastewater produced by the epoxidation reaction and condensation reaction were measured. The production process of flutriafol was then optimized, reducing the water consumption and the amount of wastewater while recycling the source. On the one hand, the reverse application of washing wastewater was proposed for the production process of flutriafol. The collected epoxidized washing wastewater was applied to the first washing of the next batch of epoxidized materials. Similarly, the collected condensed washing wastewater was applied to the first washing of the next batch of condensed materials. Through this method, the quality of intermediates and products are stable and qualified, and the total amount of wastewater could be reduced by 50%. On the other hand, “Extraction and recovery of epoxides using methyl sulfide—Distillation to recovery of methyl sulfide—Adsorption of epoxides and difluorophenone with resin—Neutralization—Distillation to recover methanol and potassium sulfate” process was adopted for the recycling of epoxidized synthetic wastewater. A total of 770 kg potassium sulfate, 143 kg methanol, 43.5 kg methyl sulfide and 2 kg intermediate epoxides can be recovered from one ton of epoxidized wastewater.

Experiments were performed to determine the process conditions for the extraction of epoxides from epoxidized wastewater and the adsorption of epoxides and difluorophenone with resin. Methyl sulfide was used as extractant, temperature was set as 25℃, phase ratio was 1:1. The adsorption performance of TC99, TC150, XAD-4 was compared through the static adsorption experiments, TC150 performed best and was chosen for the following study. When the dynamic adsorption flow rate was 2BV/h and the treated water volume was less than 15BV, the removal rate of epoxide and difluorophenone was over 99%. When methanol was used as the desorbent and the flow rate was below 1BV/h, the removal rate of epoxide and difluorophenone reached 99%. The potassium sulfate recovered through atmospheric distillation could meet the standard for agricultural potassium sulfate in GB/T20406-2017.

The experiment determined the mixed wastewater treatment process of the sewage treatment station of the wastewater treatment station in the raw pesticide production enterprises, and optimized the parameters of the wastewater treatment process. The PH for iron carbon micro-electrolysis is 2~4, the residence time is 3h, the ratio of iron to carbon is 2, the expansion rate is 12%. The PH for Fenton oxidation is 3, the residence time is 1~1.5h, the volume ratio of 30% hydrogen peroxide to wastewater is 1:10. The hydraulic retention time of UASB is 5 days, the volume load is 2.86kg COD/(m3.D). The hydraulic retention time of contact oxidation is 1.5 days, the volume load is 1.96kg COD/(m3.D). “Iron carbon micro-electrolysis—Fenton oxidation—Coagulation precipitation” pretreatment could remove 82% of COD, and “UASB—Contact oxidation process” biochemical treatment could remove 95% of COD, which can make the industry wastewater meet the strict discharge standards.

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