CN1328971A - 光催化从废水中除去有机物的方法 - Google Patents
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Abstract
本发明涉及一种光催化从废水中除去有机物的方法,其中以颗粒的形式使用光催化剂,该颗粒以热解制得的二氧化钛为基础,并具有以下物化特征数据:平均粒径:10－150μm；BET表面:25－100m2/g；pH值:3－6；紧密堆积密度:100－1200g/l。
Description
本发明涉及光催化从废水中除去有机物的方法。
热解二氧化钛(市售商品名为Degussa TiO2P25)的特征是在光催化领域具有多种可能的应用(R.W.Matthews，S.R.McEvoy，J.Photochem.Photobiol.A：Chem.，64(1992)231-246；R.I.Bickley等人，Journal of SolidState Chemistry，92(1991)，178-190；R.Franke，C.Franke，Chemosphere，第39卷15号(1999)，2651-2659；H.Zen，JETI(1998)，46(10)，66-67)。
其可用作光催化活性高的参比物(V.Loddo等人，Applied Catalysis B：Environmental 20(1999)，29-45)。
本发明提供一种光催化从废水中除去有机物的方法，该方法的特征在于，以颗粒的形式使用光催化剂，该颗粒以热解制得的二氧化钛为基础，并具有以下物化特征数据：
平均粒径： 10—150μm
BET表面： 25—100m2/g
pH值： 3—6
紧密堆积密度：100—1200g/l。
可根据本发明使用的颗粒是如下制备的：将热解制得的二氧化钛分散在水中，喷雾干燥，然后任选地将所得的颗粒在150—1100℃下回火1—8小时。
热解二氧化钛可按照已知的方法通过高温或火焰水解由TiCl4制得(乌尔曼化工词典(Ullmanns Enzyklopaedie der technischen Chemie)，第4版，第21卷，464页(1982))。
在水中用于制备颗粒的分散液可具有3—25重量％的二氧化钛浓度。
可在分散液中添加有机辅助物质，以提高分散液的稳定性，并改善喷雾干燥后的颗粒形态。
例如，可使用以下辅助物质：多元醇、聚醚、氟代烃基的表面活性剂、醇。
喷雾干燥可在200—600℃的温度下进行。在该过程中可使用圆盘式雾化器或喷嘴雾化器。
颗粒的回火可在固定床如箱式炉以及搅动床如转管干燥器中进行。
改变进料以及喷雾和回火过程中的条件，由此可在特定的限制范围内改变颗粒的物化参数，如比表面、粒径分布、紧密堆积密度和pH值。
在成粒时不需要额外的辅助物质。未经喷雾干燥的二氧化钛不具有限定的附聚物尺寸，而与之相比，根据本发明的二氧化钛颗粒具有限定的粒径。
根据本发明的二氧化钛颗粒能够进行无尘处理。由于紧密堆积密度高，在运输时仅需要非常少的包装工作。
根据本发明的方法可在20—40℃的温度下进行。有机物的浓度可为10—150mg/ml。
可用本发明的方法除去的有机物是4—氯苯酚(4—CP)、二氯乙酸(DCA)、三氯乙烯(TCE)、和二氯乙烷(DCE)。
根据本发明的方法具有以下优点：与非颗粒状的二氧化钛P25相比毒性物质更快速分解，而且根据本发明的二氧化钛颗粒可以比非颗粒状的二氧化钛P25更好地与反应混合物分离(更好地沉降)。
以下将参考附图进一步说明本发明，在附图中：
图1是参考物质4—CP的光催化分解—时间曲线。
实施例
对于热解二氧化钛，使用具有以下物化特征数据的二氧化钛P 25。其在一系列题目为“颜料(Pigmente)”的出版物(No.56：“HochdisperseMetalloxide nach dem Aerosilverfahren，第4版，1989年2月，DegussaAG)中是已知的(表1)。
表1
| 二氧化钛P25 | |
| CAS登记号 | 13463—67—7 |
| 相对于水的性质 | 亲水性的 |
| 外观 | 松散的白色粉末 |
| BET表面1，m2/g | 50±15 |
| 主颗粒的平均粒径，nm | 21 |
| 紧密堆积密度2，g/l | 约100 |
| 比重10，g/ml | 约3.7 |
| 离开送料机时的干燥失重3，％(105℃下2小时) | ＜1.5 |
| 点火失重4，7(1000℃下2小时) | ＜2 |
| pH值5(在4％水分散液中) | 3-4 |
| SiO2 8 | ＜0.2 |
| Al2O3 8 | ＜0.3 |
| Fe2O3 8 | ＜0.01 |
| TiO2 8 | ＞99.5 |
| ZrO2 8 | - |
| HfO2 8 | - |
| HCl8，9 | ＜0.3 |
| 过筛存留6(根据Mocker，45μm)，％ | ＜0.05 |
1：根据DIN 66131
2：根据DIN ISO 787/XI，JIS K 5101/18(未过筛)
3：根据DIN ISO 787/II，ASTM D 280，JIS K 5101/21
4：根据DIN 55921，ASTM D 1208，JIS 5101/23
5：根据DIN ISO 787/IX，ASTM D 1207，JIS K 5101/24
6：根据DIN ISO 787/XVIII，JIS K 5101/20
7：相对于在105℃下干燥2小时的物质
8：相对于在1000℃下煅烧2小时的物质
9：HCl含量是点火失重的组分
10：用空气对比的比重瓶测定
为制备二氧化钛，将挥发性的钛化合物通过喷嘴注射入由氢和空气组成的氢氧火焰中。在大多数的情况下，使用四氯化钛。该物质在氢/氧反应过程中形成的水的作用下发生水解，形成二氧化钛和盐酸。离开火焰后，二氧化钛进入所谓的凝聚区，附聚形成二氧化钛的主颗粒和主附聚物。产物在此阶段为气溶胶型，在旋风分离器中与气态的伴随物分离，并随后用湿热空气进行后处理。
二氧化钛的粒径可随反应条件而变化，所述条件例如是火焰温度、氢或氧的比例、四氯化钛的量、在火焰中的停留时间或者凝聚路径的长度。
根据DIN 66 131用氮气测定BET表面。
紧密堆积体积按照ASTM D 4164—88的模型测定。
仪器：Engelsmann制造的冲压式体积计STA V 2003，根据DIN 53194第5.2.b-f部分，测量圆筒250ml，刻度2ml，最大误差范围±0.1g
实施：
将冲压式体积计的计数机构设定在1000次冲压。
称重测量圆筒。
将颗粒填入测量圆筒中最高至250ml刻度。
标注样品的重量(±0.1g)。
将测量圆筒插入冲压式体积计中，然后开动仪器。
冲压结束，1000次冲压后仪器自动关闭。
读取经冲压的堆积体积，精确至1ml。
计算
E：颗粒样品的重量(g)
V：读取的体积(ml)
W：水含量(重量％)(根据实验说明P001测定)
紧密堆积密度＝E×(100—W)/(V×100)
pH值是在4％水分散液中测定，如果是疏水性催化剂载体，则在1：1的水：乙醇中。制备可用于本发明中的颗粒
将热解二氧化钛分散在经过完全脱盐的水中。在此过程中，使用根据转子/定子原理运行的分散单元。喷雾干燥所形成的分散液。通过过滤器或旋风分离器分离最终产品。
在隔焰炉中对喷雾颗粒进行回火。与喷雾干燥有关的数据记录在表2中。
表2：与TiO2 P25水分散液的喷雾干燥有关的数据
| 实施例 | H2O的量(kg) | TiO2P25的量(kg) | 雾化 | 喷雾盘的转速(rpm) | 运行温度(℃) | 废气温度(℃) | 分离 |
| 1 | 10 | 1.5 | 盘 | 35000 | 345 | 100 | 旋风分离器 |
| 2 | 10 | 1.5 | 盘 | 45000 | 370 | 105 | 旋风分离器 |
| 3 | 10 | 1.5 | 盘 | 20000 | 350 | 95 | 旋风分离器 |
| 4 | 10 | 2.5 | 盘 | 15000 | 348 | 100 | 旋风分离器 |
| 5 | 100 | 15 | 2组分喷嘴 | —— | 445 | 130 | 过滤器 |
| 6 | 100 | 15 | 盘 | 10000 | 450 | 105 | 过滤器 |
| 7 | 10 | 2.5 | 盘 | 20000 | 348 | 105 | 旋风分离器 |
| 8 | 10 | 1.5 | 盘 | 15000 | 348 | 105 | 旋风分离器 |
| 9 | 10 | 2.5 | 盘 | 35000 | 300 | 105 | 旋风分离器 |
表3：喷雾干燥产品的物化数据
| 实施例 | BET表面(m2/g) | 紧密堆积密度(g/l) | pH值 | d50值(Cilas)(μm) | 干燥失重(％) | 点火失重(％) |
| 1 | 51 | 641 | 3.9 | 14.6 | 0.9 | 0.9 |
| 2 | 50 | 612 | 3.7 | 10.6 | 0.8 | 1.0 |
| 3 | 52 | 680 | 3.5 | 25.0 | 0.8 | 1.0 |
| 4 | 51 | 710 | 3.7 | 43.6 | 0.8 | 1.2 |
| 5 | 52 | 660 | 4.0 | 17.1 | 0.9 | 0.9 |
| 6 | 53 | 702 | 3.9 | 27.5 | 0.9 | 0.9 |
| 7 | 50 | 708 | 3.5 | 26.7 | 1.1 | 0.6 |
| 8 | 53 | 696 | 3.9 | 30.1 | 1.0 | 0.9 |
| 9 | 49 | 640 | 3.7 | 16.0 | 0.7 | 0.8 |
在任选酸化的水悬浮液中，于紫外照射下在光催化分解氯代烃的过程中测试根据本发明的方法的光催化活性。
通过参考值(零值)，当使用纯的二氧化钛Degussa P25作为光催化剂时，利用在任选酸化的水悬浮液中在紫外照射下氯代烃的光催化速率。用Degussa P25进行实验的持续时间最长为360分钟。
1、测定悬浮液中氯代烃之光催化分解速率的实验方法
为研究氯代烃如4—CP(4—氯苯酚)在纯水或者经酸化的水悬浮液中于紫外照射下光催化分解速率，实验的总运行时间最长为360分钟。
分解反应在搅拌槽反应器中进行。另外，待研究的悬浮液从储存容器倾倒至搅拌槽反应器中，并反方向倾倒，以确保均匀的紫外照射。悬浮液的初始pH值在2—6之间，优选的pH为2—3。搅拌槽反应器中的温度在25—40℃之间，优选在30—35℃之间。给定情况(TiO2 P 25或者颗粒状TiO2)下，光催化活性的二氧化钛的浓度为1g/l。烃的浓度在10—150mg/l之间，优选约为120mg/l。
连续地从储存容器中倾倒至紫外照射单元，并再反方向倒回，另外用冷却水冷却紫外灯系统，由此将温度保持在上述恒定范围内。在分解反应的整个持续时间内，连续地监测氯代烃在紫外照射下的分解进程。以固定间隔测定TOC值(TOC＝总有机碳＝有机键合的碳)，由此可测定TOC/TOC0(TOC0＝悬浮液中有机键合的碳的初始浓度)。TOC/TOC0定义了在具体的取样时间时的TOC百分含量。在TOC/TOC0—时间曲线中，绘制了氯代烃如4—CP(4—氯苯酚)的分解进程。在相同的条件下还用标准品测试了TiO2 P 25的分解速率。记录曲线的总形状。TiO2 P25：
将在酸化的水悬浮液中的120mg/l的4—CP(4—氯苯酚)和1g/l的TiO2P25注入储存容器中，然后再注入搅拌槽反应器中，并根据上述方法进行处理。记录TOC/TOC0—时间曲线。360分钟后，存在40.5％的初始TOC含量。颗粒状的TiO2：
将在酸化的水悬浮液中的120mg/l的4—CP(4—氯苯酚)和1g/l的颗粒状二氧化钛(根据本发明)注入储存容器中，然后再注入搅拌槽反应器中，并根据上述方法进行处理。记录TOC/TOC0—时间曲线。360分钟后，存在35.0％的4—CP(4—氯苯酚)初始TOC含量。
测定的值绘制在图1中。
2、用二氧化钛P25和颗粒状二氧化钛光催化分解4—CP(4—氯苯酚)360分钟后的实验结果
反应器体积：V反应器＝1.7升总体积：V反应器＝3.0升恒定地通入O2辐射器：UVH1022 Z4掺杂铁的高压汞蒸汽灯功率输出：500W(Heraeus)催化剂浓度：1g/l氯代烃的初始浓度：C0＝120mg/l初始pH值：pH0＝2.4
| 催化剂 | 360分钟时存留的TOC/TOC0 | 提高(％) |
| TiO2 P 25 | 40.5 | / |
| 颗粒状的TiO2 | 35.0 | 13.6 |
在纯水或者经酸化的水悬浮液中，于UV照射下使用颗粒状的二氧化钛作为光催化剂进行氯代烃(例如4—CP)的光催化氧化实验。恒定地搅拌悬浮液，并连续地用掺杂铁的高压汞蒸汽灯UVH1022 Z4照射。存在灯的冷却系统，以确保恒定的条件。连续地从储存容器倾倒至反应器中，并按相反方向倒回，以及额外进行冷却，由此也将悬浮液保持在恒定的温度下。
Claims (1)
1、一种光催化从废水中除去有机物的方法，该方法的特征在于，以颗粒的形式使用光催化剂，该颗粒以热解制得的二氧化钛为基础，并具有以下物化特征数据：
平均粒径： 10—150μm
BET表面： 25—100m2/g
pH值： 3—6
紧密堆积密度：100—1200g/l。
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| CN1329313C (zh) * | 2005-10-24 | 2007-08-01 | 东南大学 | 负载纳米二氧化钛的弥散光纤光催化废水处理反应器 |
| US20090053694A1 (en) * | 2005-12-26 | 2009-02-26 | Kriksunov Leo B | Photochemically Amplified Bioassay |
| WO2007085018A2 (en) | 2006-01-20 | 2007-07-26 | Oculus Innovative Sciences, Inc. | Methods of treating or preventing inflammation and hypersensitivity with oxidative reductive potential water solution |
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