CN106237983A - 一种有机废水处理剂及其制备方法 - Google Patents
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Abstract
一种有机废水处理剂及其制备方法，由活化分子筛、用以包覆活化分子筛的无机钛盐和用调节反应体系pH值至4~5的碳酸氨反应后脱水、干燥、煅烧而成，无机钛盐按照[Ti]4+与活化分子筛质量比为15~20:100的比例加入，活化分子筛由废弃分子筛粉碎后经硫酸活化后制成。本发明将废弃分子筛进行酸浸活化，使堵塞其孔道的杂质被酸溶解，进而恢复其吸附及离子交换能力，将活化后的分子筛进行纳米二氧化钛负载改性，其目的是赋予活化分子筛一种新的功能，既光催化降解能力，改性后的活化分子筛不但具有吸附、离子交换能力，而且在紫外光照射下，还具有光催化降解能力。
Description
技术领域
本发明涉及到固体废弃物开发利用及环保领域，具体的说是一种有机废水处理剂及其制备方法。
背景技术
分子筛是结晶态的硅酸盐或者硅铝酸盐，由硅氧四面体或铝氧四面体，分子筛因其具有纳米级的微孔结构及较强的吸附性能，在许多领域都有着广泛的应用，微孔分子筛作为吸附分离材料、主要的催化材料和离子交换材料，可应用于石油化工、石油的加工、日用化工以及精细化工领域。但分子筛在使用后就会失活，当前一般失活的分子筛常常被用做筑路的填埋材料使用或者固体废弃物堆积，这造成了巨大的浪费。关于废弃分子筛的研究报道的并不多，但是角度有很多。翟芝明等人研究了废分子筛综合利用问题，该研究是关于废弃分子筛经活化处理后生产脱色剂的工艺的综合性研究，其实验效果明显。初政伟，徐会君等人研究了废弃分子筛制备群蓝颜料问题，该研究是以工业废弃分子筛为原料，加入了活性炭、单质硫、碳酸钠以及二氧化硅，通过高温煅烧方法制备了群蓝颜料。范广能等人研究了废分子筛、废氧化铝的综合利用问题。
发明内容
本发明的目的是提供一种有机废水处理剂及其制备方法，该处理剂是利用废弃分子筛的微孔结构将纳米TiO2进行分散固定，用以提高TiO2催化剂颗粒的使用效率，同时，活化后分子筛的强吸附性可以将水体中有机污染物吸附于其表面，然后，通过光催化作用将其降解为无污染的小分子，最终可分解为CO2和H2O，从根本上将水体中的有机污染物去除。
本发明为实现上述发明目的所提供的技术方案为：一种有机废水处理剂，由活化分子筛、用以包覆活化分子筛的无机钛盐和用调节反应体系pH值至4~5的碳酸氨反应后脱水、干燥、煅烧而成，其中，无机钛盐按照[Ti]4+与活化分子筛质量比为15~20:100的比例加入，所述活化分子筛由废弃分子筛粉碎后经硫酸活化后制成。
所述无机钛盐为四氯化钛、硫酸钛、硫酸氧钛。
所述活化分子筛的制备方法为：首先将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1：5~7的固液比将其与质量浓度为30~50%的硫酸混合反应2~4h，且在反应过程中，不断搅拌并保持反应温度为90~100℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在100~110℃下干燥1~2小时后打散成粉体，即得到活化分子筛。
上述有机废水处理剂的制备方法，首先将废弃分子筛活化后制成粉末，而后利用无机钛盐进行包覆改性后，经脱水、洗涤、烘干、煅烧后制成，所述利用无机钛盐进行包覆改性的具体操作是：将活化后的分子筛粉末与去离子水按照1:15~20的固液比混合制成浆体，并在保持搅拌的条件下，向其中加入无机钛盐水溶液反应30~60分钟，反应结束后，再向其中加入浓度为1~3mol/L的碳酸铵溶液以调节反应体系的pH值为4~5，并继续反应1~2小时后完成包覆改性；
其中，无机钛盐按照[Ti]4+与活化分子筛质量比为15~20:100的比例加入。
所述废弃分子筛活化后制成粉末的操作为：首先将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1: 5~7的固液比将其与质量浓度为30~50%的硫酸混合反应2~4h，且在反应过程中，不断搅拌并保持反应温度为90~100℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在100~110℃下干燥1~2小时后打散成粉体，即得到活化分子筛粉末。
所述包覆改性后的脱水、洗涤、烘干和煅烧操作为：将包覆改性后的反应体系进行脱水、洗涤，洗涤后的滤饼在100~110℃下烘干3~5小时后打散成粉体，而后将该粉体在600~700℃下煅烧3~5小时，自然冷却后即得到产品。
有益效果：分子筛是一种硅铝酸盐，主要由硅铝通过氧桥连接组成空旷的骨架结构，在结构中有很多孔径均匀的孔道和排列整齐、内表面积很大的空穴。此外还含有电价较低而离子半径较大的金属离子和化合态的水。由于水分子在加热后连续地失去，但晶体骨架结构不变，形成了许多大小相同的空腔，空腔又有许多直径相同的微孔相连，比孔道直径小的物质分子吸附在空腔内部，而把比孔道大得分子排斥在外，从而使不同大小形状的分子分开，直到筛分分子的作用，因而称作分子筛，它主要用于各种气体、液体的深度干燥，气体、液体的分离和提纯，催化剂载体等；分子筛长期使用后，其内在孔道会被杂质堵塞，吸附和离子交换能力都会大大减弱，成为废弃分子筛。
本发明将废弃分子筛进行酸浸活化，使堵塞其孔道的杂质被酸溶解，进而恢复其吸附及离子交换能力；将活化后的分子筛进行纳米二氧化钛负载改性，其目的是赋予活化分子筛一种新的功能，既光催化降解能力，改性后的活化分子筛不但具有吸附、离子交换能力，而且在紫外光照射下，还具有光催化降解能力；煅烧的目的一是高温加热使化合态的水失去，以形成大量大小相同的空腔，增加其吸附能力，二是负载在活化分子筛表面的纳米二氧化钛在600℃高温下会实现锐钛矿晶型的转变，进而提高其光催化降解能力。
具体实施方式
下面结合具体实施例对本发明做进一步的阐述。
实施例1
一种有机废水处理剂，由活化分子筛、用以包覆活化分子筛的无机钛盐和用调节反应体系pH值至4的碳酸氨反应后脱水、干燥、煅烧而成，其中，无机钛盐为四氯化钛，其加入量按照[Ti]4+与活化分子筛质量比为15:100的比例加入，所述活化分子筛的制备方法为：首先将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1：5的固液比将其与质量浓度为30%的硫酸混合反应4h，且在反应过程中，不断搅拌并保持反应温度为90℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在100℃下干燥2小时后打散成粉体，即得到活化分子筛。
上述有机废水处理剂的制备方法，首先将废弃分子筛活化后制成粉末，而后利用无机钛盐进行包覆改性后，经脱水、洗涤、烘干、煅烧后制成，具体操作如下：
1）将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1: 5的固液比将其与质量浓度为30%的硫酸混合反应4h，且在反应过程中，不断搅拌并保持反应温度为90℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在100℃下干燥2小时后打散成粉体，即得到活化分子筛粉末；
2）将活化后的分子筛粉末与去离子水按照1:15的固液比混合制成浆体，并在保持搅拌的条件下，向其中加入四氯化钛水溶液反应30分钟，反应结束后，再向其中加入浓度为1mol/L的碳酸铵溶液以调节反应体系的pH值为4，并继续反应1小时后完成包覆改性；其中，四氯化钛按照[Ti]4+与活化分子筛质量比15:100的比例加入；
3）将包覆改性后的反应体系进行脱水、洗涤，洗涤后的滤饼在100℃下烘干5小时后打散成粉体，而后将该粉体在600℃下煅烧5小时，自然冷却后即得到产品。
实施例2
一种有机废水处理剂，由活化分子筛、用以包覆活化分子筛的无机钛盐和用调节反应体系pH值至5的碳酸氨反应后脱水、干燥、煅烧而成，其中，无机钛盐为硫酸钛，其加入量按照[Ti]4+与活化分子筛质量比为20:100的比例加入，所述活化分子筛的制备方法为：首先将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1：7的固液比将其与质量浓度为50%的硫酸混合反应2h，且在反应过程中，不断搅拌并保持反应温度为100℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在110℃下干燥1小时后打散成粉体，即得到活化分子筛。
上述有机废水处理剂的制备方法，首先将废弃分子筛活化后制成粉末，而后利用无机钛盐进行包覆改性后，经脱水、洗涤、烘干、煅烧后制成，具体操作如下：
1）将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1: 7的固液比将其与质量浓度为50%的硫酸混合反应2h，且在反应过程中，不断搅拌并保持反应温度为100℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在110℃下干燥1小时后打散成粉体，即得到活化分子筛粉末；
2）将活化后的分子筛粉末与去离子水按照1: 20的固液比混合制成浆体，并在保持搅拌的条件下，向其中加入硫酸钛水溶液反应60分钟，反应结束后，再向其中加入浓度为3mol/L的碳酸铵溶液以调节反应体系的pH值为5，并继续反应2小时后完成包覆改性；其中，硫酸钛按照[Ti]4+与活化分子筛质量比为20:100的比例加入；
3）将包覆改性后的反应体系进行脱水、洗涤，洗涤后的滤饼在110℃下烘干3小时后打散成粉体，而后将该粉体在700℃下煅烧3小时，自然冷却后即得到产品。
实施例3
一种有机废水处理剂，由活化分子筛、用以包覆活化分子筛的无机钛盐和用调节反应体系pH值至4.5的碳酸氨反应后脱水、干燥、煅烧而成，其中，无机钛盐为硫酸氧钛，其加入量按照[Ti]4+与活化分子筛质量比为17.5:100的比例加入，所述活化分子筛的制备方法为：首先将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1：6的固液比将其与质量浓度为40%的硫酸混合反应3h，且在反应过程中，不断搅拌并保持反应温度为95℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在105℃下干燥1.5小时后打散成粉体，即得到活化分子筛。
上述有机废水处理剂的制备方法，首先将废弃分子筛活化后制成粉末，而后利用无机钛盐进行包覆改性后，经脱水、洗涤、烘干、煅烧后制成，具体操作如下：
1）将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1: 6的固液比将其与质量浓度为40%的硫酸混合反应3h，且在反应过程中，不断搅拌并保持反应温度为95℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在105℃下干燥1.5小时后打散成粉体，即得到活化分子筛粉末；
2）将活化后的分子筛粉末与去离子水按照1:17.5的固液比混合制成浆体，并在保持搅拌的条件下，向其中加入硫酸氧钛水溶液反应45分钟，反应结束后，再向其中加入浓度为2mol/L的碳酸铵溶液以调节反应体系的pH值为4.5，并继续反应1.5小时后完成包覆改性；其中，硫酸氧钛按照[Ti]4+与活化分子筛质量比为17.5:100的比例加入；
3）将包覆改性后的反应体系进行脱水、洗涤，洗涤后的滤饼在105℃下烘干4小时后打散成粉体，而后将该粉体在650℃下煅烧4小时，自然冷却后即得到产品。
分别用实施例1-3制备的产品对学校校园生活废水（校园浴池废水、学生宿舍废水）进行光催化降解法治理，方法如下：
取校园生活废水水样150mL放入烧杯中，然后加入1.5g研制的处理剂，搅拌的同时，放在紫外灯下照射150分钟，停止光照后取上清液测其COD，得到的COD数值与原水COD数值进行对比，得到废水中COD的去除率。COD测定采用国标GB 11914-89化学需氧量的测定--COD标准测定法。
将实施例1-3制备的水处理剂按照前述方法进行光催化废水处理实验，结果发现废水中COD的去除率分别达到95%、96%和93%。
Claims (6)
1.一种有机废水处理剂，其特征在于：由活化分子筛、用以包覆活化分子筛的无机钛盐和用调节反应体系pH值至4~5的碳酸氨反应后脱水、干燥、煅烧而成，其中，无机钛盐按照[Ti]4+与活化分子筛质量比为15~20:100的比例加入，所述活化分子筛由废弃分子筛粉碎后经硫酸活化后制成。
2.根据权利要求1所述的一种有机废水处理剂，其特征在于：所述无机钛盐为四氯化钛、硫酸钛或硫酸氧钛。
3.根据权利要求1所述的一种有机废水处理剂，其特征在于，所述活化分子筛的制备方法为：首先将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1：5~7的固液比将其与质量浓度为30~50%的硫酸混合反应2~4h，且在反应过程中，不断搅拌并保持反应温度为90~100℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在100~110℃下干燥1~2小时后打散成粉体，即得到活化分子筛。
4.根据权利要求1所述的一种有机废水处理剂的制备方法，首先将废弃分子筛活化后制成粉末，而后利用无机钛盐进行包覆改性后，经脱水、洗涤、烘干、煅烧后制成，其特征在于：所述利用无机钛盐进行包覆改性的具体操作是：将活化后的分子筛粉末与去离子水按照1:15~20的固液比混合制成浆体，并在保持搅拌的条件下，向其中加入无机钛盐水溶液反应30~60分钟，反应结束后，再向其中加入浓度为1~3mol/L的碳酸铵溶液以调节反应体系的pH值为4~5，并继续反应1~2小时后完成包覆改性；
其中，无机钛盐按照[Ti]4+与活化分子筛质量比为15~20:100的比例加入。
5.根据权利要求4所述的一种有机废水处理剂的制备方法，其特征在于，所述废弃分子筛活化后制成粉末的操作为：首先将废弃分子筛粉碎至10微米以下制成超细粉体，然后按照1: 5~7的固液比将其与质量浓度为30~50%的硫酸混合反应2~4h，且在反应过程中，不断搅拌并保持反应温度为90~100℃，反应结束后将整个反应体系过滤至无SO4 2-离子，过滤后的滤饼在100~110℃下干燥1~2小时后打散成粉体，即得到活化分子筛粉末。
6.根据权利要求4所述的一种有机废水处理剂的制备方法，其特征在于，所述包覆改性后的脱水、洗涤、烘干和煅烧操作为：将包覆改性后的反应体系进行脱水、洗涤，洗涤后的滤饼在100~110℃下烘干3~5小时后打散成粉体，而后将该粉体在600~700℃下煅烧3~5小时，自然冷却后即得到产品。
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