CN114247481B - 一种β-氨基丙腈精制釜残的光催化处理方法 - Google Patents
一种β-氨基丙腈精制釜残的光催化处理方法 Download PDFInfo
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- AGSPXMVUFBBBMO-UHFFFAOYSA-N beta-aminopropionitrile Chemical compound NCCC#N AGSPXMVUFBBBMO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000007670 refining Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 13
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
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- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003446 ligand Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- GJAROXYKDRBDBI-UHFFFAOYSA-J [W+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [W+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJAROXYKDRBDBI-UHFFFAOYSA-J 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开一种β‑氨基丙腈精制釜残的光催化处理方法，包括以下步骤：预稀释的β‑氨基丙腈精制釜残在催化剂、光源和流动的空气作用下发生降解，降解后的废液总含碳量小于50ppm，可实现无害化排放。其中所述催化剂为负载型光催化剂，包括TiO2载体和以配合物形式存在的铁、锌和钨；其中，以TiO2质量为基准，所述各组分的含量如下：铁5‑10wt％，锌1‑5wt％，钨0.5‑2.5wt％，配体10‑50wt％。本发明所使用的光催化处理技术，解决了目前β‑氨基丙腈精制釜残焚烧的高能耗、污染严重的问题，具有操作简单、降解效率高、成本低廉、无二次污染、催化剂可回收等优点。
Description
技术领域
本发明属于光催化技术领域，具体的涉及一种β-氨基丙腈精制釜残的光催化处理方法。
背景技术
β-氨基丙酸在饲料添加剂、医药及食品等领域具有广阔的市场需求，其生产需要一种关键的中间体—β-氨基丙腈。现有的β-氨基丙腈精制环节会产生大量釜残，其主要包括3,3’-亚氨基二丙腈、腈类聚合物、含碳重组分等有机物。现有的工业化处理方式均为焚烧处理，存在能耗高、污染严重等缺点，因此，开发一种更为经济、绿色的处理方式迫在眉睫。
光催化氧化技术，作为一种高级氧化工艺，具有成本低廉、绿色环保等优点。当光催化剂吸收能量后，其会激发产生强氧化活性的空穴和高还原活性的电子。其中高还原性的电子可以还原空气中的O2产生超氧自由基，强氧化性活性的空穴迁移至表面后将水氧化产生羟基自由基。超氧自由基和羟基自由基均具有强氧化性，能够降解有机物，生成二氧化碳和水等。TiO2作为一种典型的光催化剂，性能优良，但也存在禁带宽度较大等缺点。
发明内容
为了解决现有技术中存在的问题，本发明的目的在于提供一种β-氨基丙腈精制釜残的光催化处理方法。本发明中光催化处理技术的使用，解决了目前β-氨基丙腈精制釜残焚烧的高能耗、污染严重的问题，具有操作简单、降解效率高、成本低廉、无二次污染、催化剂可回收等优点。
为了达到上述目的，本发明采用的技术方案如下：
一种β-氨基丙腈精制釜残的光催化处理方法，包括：将预稀释的β-氨基丙腈精制釜残在催化剂、光源和流动的空气作用下发生降解，降解后的废液总含碳量小于50ppm，可实现无害化排放。
本发明所述催化剂为负载型光催化剂，包括TiO2载体和以配合物形式存在的铁、锌和钨。其中，所述催化剂中，以TiO2质量为基准，各组分的含量如下：
铁5-10wt％，优选7-9wt％；
锌1-5wt％，优选2-4wt％；
钨0.5-2.5wt％，优选1.0-1.5wt％；
配体10-50wt％，优选20-40wt％。
本发明所述催化剂可以采用常规方法制备，例如由铁盐、锌盐及钨盐和有机配体为原料合成配合物前驱体，之后与TiO2粉末经超声处理、水热反应合成；
本发明所述的铁盐、锌盐及钨盐选自氯化物、硝酸盐和硫酸盐中的一种或多种；
所述有机配体为羧酸或氮类配体，包括1,3,5-苯三甲酸、1,2,4-苯三甲酸、1,3,5-三(4-羧基苯基)苯、1,10-菲罗琳、2,2'-联吡啶和2,2'-联吡啶-5,5'-二羧酸中的一种或多种；
所述超声处理功率选用30-50KHz，超声时间2-5h；水热反应温度为150-200℃，水热反应时间为8-15h。
本发明所述预稀释的β-氨基丙腈精制釜残为水和β-氨基丙腈精制釜残按照质量比1-3:1稀释得到的稀释废液，其中，通常含有15-50％的有机成分；
所述催化剂的加入量为β-氨基丙腈精制釜残质量的0.01-0.10％，优选0.03-0.08％。
本发明所述光源波长为150-350nm，优选220-300nm；功率为100-300W，优选150-250W。
本发明所述空气流速通过流量计控制，以保持催化剂在整个反应过程中始终处于悬浮状态。
本发明所述光催化反应温度为25-45℃。
本发明的有益效果在于：本发明的光催化处理技术的使用，解决了目前β-氨基丙腈精制釜残焚烧的高能耗、污染严重的问题，具有操作简单、降解效率高、成本低廉、无二次污染、催化剂可回收等优点。
具体实施方式
下面结合具体实施例对本发明作进一步的阐述，需注意的是，本发明的范围包括但不局限于所列举的实施例。
实施例1
称取六水合氯化铁、硝酸锌、硫酸钨、1,3,5-三(4-羧基苯基)苯和TiO2粉末备用，其中铁、锌、钨、配体和TiO2的质量比为7:3:1:30:100。
向带有聚四氟乙烯内衬的反应釜中依次加入六水合氯化铁、硝酸锌、硫酸钨、水、1,3,5-三(4-羧基苯基)苯得到混合溶液，将反应体系密闭后在130℃下反应24h。反应完成后，待体系冷却至室温，用甲醇洗涤三次后于80℃下干燥得到配合物前驱体。将上述配合物前驱体、TiO2粉末和一定量的热水混合形成溶液，将上述溶液使用40KHz超声处理3h后转移至水热反应釜于165℃下反应15h。反应完成后，待体系冷却至室温，离心、洗涤、干燥处理后得到光催化剂。
将β-氨基丙腈精制釜残与水按照质量比1:1稀释后投入反应器中，其中有机物含量为45％，加入占β-氨基丙腈精制釜残0.05％的催化剂，待体系吸附10min后，通入空气、开启光源开始反应，选用光源的波长为250nm，功率为200W。经检测，反应完成后总含碳量为35ppm。
实施例2
称取九水合硝酸铁、硝酸锌、硫酸钨、1,3,5-苯三甲酸和TiO2粉末备用，其中铁、锌、钨、配体和TiO2的质量比为9:2:1:35:100。
向带有聚四氟乙烯内衬的反应釜中依次加入九水合硝酸铁、硝酸锌、硫酸钨、水、1,3,5-苯三甲酸得到混合溶液，将反应体系密闭后在130℃下反应24h。反应完成后，待体系冷却至室温，用甲醇洗涤三次后于80℃下干燥得到配合物前驱体。将上述配合物前驱体、TiO2粉末和一定量的热水混合形成溶液，将上述溶液使用40KHz超声处理3h后转移至水热反应釜于175℃下反应12h。反应完成后，待体系冷却至室温，离心、洗涤、干燥处理后得到光催化剂。
将β-氨基丙腈精制釜残与水按照质量比1:2稀释后投入反应器中，其中有机物含量为30％，加入占β-氨基丙腈精制釜残0.08％的催化剂，待体系吸附10min后，通入空气、开启光源开始反应，选用光源的波长为220nm，功率为300W。经检测，反应完成后总含碳量为45ppm。
实施例3
称取六水合氯化铁、氯化锌、硫酸钨、2,2'-联吡啶-5,5'-二羧酸和TiO2粉末备用，其中铁、锌、钨、配体和TiO2的质量比为8:3:1.5:30:100。
向带有聚四氟乙烯内衬的反应釜中依次加入六水合氯化铁、氯化锌、硫酸钨、水、2,2'-联吡啶-5,5'-二羧酸得到混合溶液，将反应体系密闭后在130℃下反应24h。反应完成后，待体系冷却至室温，用甲醇洗涤三次后于80℃下干燥得到配合物前驱体。将上述配合物前驱体、TiO2粉末和一定量的热水混合形成溶液，将上述溶液使用40KHz超声处理3h后转移至水热反应釜于185℃下反应12h。反应完成后，待体系冷却至室温，离心、洗涤、干燥处理后得到光催化剂。
将β-氨基丙腈精制釜残与水按照质量比1:3稀释后投入反应器中，其中有机物含量为23％，加入占β-氨基丙腈精制釜残0.06％的催化剂，待体系吸附10min后，通入空气、开启光源开始反应，选用光源的波长为250nm，功率为300W。经检测，反应完成后总含碳量为48ppm。
实施例4
将实施例1的降解反应液离心、洗涤、干燥回收光催化剂。将上述光催化剂重复实施例1的废液降解反应。重复5次后，反应效果无下降。
以上具体实施方式，并非对本发明的技术方案作任何形式的限制。凡是依据本发明的技术实质对以上实施例所做的任何简单修改、等同变化与修饰，均落入本发明的保护范围之内。
Claims (8)
1.一种β-氨基丙腈精制釜残的光催化处理方法，包括：预稀释的β-氨基丙腈精制釜残在催化剂、光源和流动的空气作用下发生降解；
其中所述催化剂为负载型光催化剂，包括TiO2载体和以配合物形式存在的铁、锌和钨，所述催化剂中，以TiO2质量为基准，各组分的含量如下：
铁5-10wt%；
锌1-5wt%；
钨0.5-2.5wt%；
有机配体10-50wt%；
所述催化剂由铁盐、锌盐及钨盐和有机配体为原料合成配合物前驱体，之后与TiO2粉末经超声处理、水热反应合成；所述有机配体为1,3,5-苯三甲酸、1,2,4-苯三甲酸、1,3,5-三(4-羧基苯基)苯、1,10-菲罗琳、2,2'-联吡啶和2,2'-联吡啶-5,5'-二羧酸中的一种或多种。
2.根据权利要求1所述的方法，其特征在于，所述催化剂中，以TiO2质量为基准，各组分的含量如下：
铁7-9wt%；
锌2-4wt%；
钨1.0-1.5wt%；
有机配体20-40wt%。
3.根据权利要求1所述的方法，其特征在于，催化剂的加入量为β-氨基丙腈精制釜残质量的0.01-0.10%。
4.根据权利要求1-3任一项所述的方法，其特征在于，所述预稀释的β-氨基丙腈精制釜残为水和β-氨基丙腈精制釜残按照质量比1-3:1稀释得到的稀释废液。
5.根据权利要求1-3任一项所述的方法，其特征在于，所述光源波长为150-350 nm；功率为100-300 W。
6.根据权利要求5所述的方法，其特征在于，所述光源波长为220-300nm；功率为150-250W。
7.根据权利要求1-3任一项所述的方法，其特征在于，流动的空气保持催化剂在整个反应过程中始终处于悬浮状态。
8.根据权利要求1-3任一项所述的方法，其特征在于，光催化反应温度为25-45°C。
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