CN106378121A - 一种提高污水降解处理的纳米TiO2光催化剂制备方法 - Google Patents
一种提高污水降解处理的纳米TiO2光催化剂制备方法 Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J35/39—
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- B01J35/40—
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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
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- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
本发明公开了一种提高污水降解处理的纳米TiO2光催化剂制备方法，其特点是以钛源与醇酸共聚物为敖合稳定剂，以碱溶液为水解剂和醇类溶液为反应介质进行水解结晶，合成具有极强可见光响应的纳米二氧化钛复配材料，然后经固液分离和烘干制得具有纯金红石、纯锐钛或金红石与锐钛按一定比例混合晶型的纳米TiO2光催化剂。本发明与现有技术相比具有较强的光催化降解被吸附的有机污染物，吸附、降解效果好，尤其催化剂可再生后重复使用，经济性好，工艺简单，生产成本低，利于工业化规模生产。
Description
技术领域
本发明涉及污水处理剂技术领域，尤其是一种用于提高污水降解处理的纳米TiO2光催化剂制备方法。
背景技术
工业污水中的有机物是环境污染治理的难点和重点，污水处理中一般以化学需氧量COD表示污水中的有机物量，特别是高盐废水、高毒性污水中的有机污染物的去除尤其困难，涉及到精细化工、医药、农药、医药中间体、冶炼、印染等目前重污染的行业和领域，这些领域是目前江河湖海的重污染源头，必须要重点加以治理。
工业污水中有机物的去除常规使用高级氧化法，如铁碳法和芬顿法、生化法等，其中以活性污泥为代表的生化法由于具有处理量大、处理成本低的特点，是目前最常用的方法。但是，如果污水中盐分含量高，或者污水中有机污染物的毒性比较大，则污水的B/C比（即可生化性）就比较差，污水的处理效果就达不到处理要求，很多情况下，细菌容易死亡，造成处理失败。
环境中污染物的吸附处理是常用的处理方法，常规方法使用活性炭材料进行空气以及水中有机污染物的吸附净化处理，也有使用多孔结构的沸石类材料进行污水净化处理的。但这些处理在使用过程中存在一定的局限性，比如活性炭对极性弱的有机物的吸附性能优异，但对极性相对强的有机物，如醇类、低级醚等物质的吸附能力就很弱，一旦这些吸附材料将有机物吸附饱和后，吸附性能就丧失了，且该类材料难以再生，有些物质如活性炭的再生成本相对高，且再生次数很少，因而再生失去实用价值。
纳米二氧化钛问世于80年代后期，是一种半导体材料，当它被合适波长的光照射后，在其表面处于价带低电子受激发跃迁到导带上去，从而分别在导带和价带上产生可移动多高活性光生电子和空穴。导带电子时良好的还原剂，价带空穴是良好的氧化剂，大多数光催化氧化反应便是直接或间接利用空穴的氧化能力。利用光能和二氧化钛材料的光催化氧化能力降解工业废水中的有机污染物，作为一种绿色、节能、环保的治污手段，在环境治理领域具有广阔的前途。但是由于纳米二氧化钛的光催化作用需要中紫外光的照射下才能实现，而自然界中，紫外光的成分不到1%，因而提高纳米二氧化钛对可见光对利用效率对其中污水处理领域的应用具有重要的意义。
专利CN105771950A《一种一维TiO2/SiO2纳米光催化材料的制备方法》提供了一种对TiO2纳米晶体进行表面处理的方法，形成了一种被数个纳米厚度的SiO2纳米包覆的核壳结构，并通过SiO2纳米材料的黏结和支撑锚定在一维有机自组装体。由于表面SiO2纳米材料的保护和固定作用，使得不仅可有效避免二氧化钛纳米晶体的融合和团聚现象，保持较高的比表面积和光催化效率，还可以对有机污染物尤其是阳离子有机污染物表现出强烈的吸附作用，进一步获得较高的光催化降解效果。专利CN105797763A《一种制备碳、氮掺杂二氧化钛的方法》提供了一种具有超快黑暗吸附速度和光催化速度的碳、氮掺杂纳米光催化材料的制备方法，通过碳、氮元素的掺杂，有效地提高了二氧化钛光催化材料对可见光的利用效率。专利CN105771953A《一种钛酸锌/二氧化钛复合纳米材料的制备方法》提供了一种使用钛酸锌复配纳米二氧化钛的材料制备方法，同样这种材料具有较高的光催化活性。专利CN105689015A《一种可见光响应的层状钛酸光催化剂及其过氧化改性方法和应用》公开了一种可见光响应的层状钛酸光催化剂及其过氧化改性方法和应用，其可见光催化活性比商业化的P25要强。
上述专利公开的技术，制备条件苛刻，生产安全难以保证等问题，且产量较低、运行成本较大，难以进行工业化规模化的生产。
发明内容
本发明的目的是针对现有技术的不足而提供的一种提高污水降解处理的纳米TiO2光催化剂制备方法，采用钛源与醇酸聚合物的钛离子水凝胶进行原位水解结晶，合成具有极强可见光响应的纳米二氧化钛复配材料，该纳米材料在外加光源的作用下，可高效地光催化降解被吸附的有机污染物，将其分解成水、二氧化碳和小分子无机盐，并有效吸附污水中的有机物，其吸附能力超过自身重量，具有良好的降解效果，尤其该催化剂经再生后可重复使用，使其重新获得继续吸附并光催化分解水中有机物的能力，经济性好，而且制备工艺简单，生产成本低，利于工业化规模生产。
本发明的目的是这样实现的：一种提高污水降解处理的纳米TiO2光催化剂制备方法，其特点是该纳米TiO2光催化剂的制备按下述步骤进行：
a、将钛源与稳定敖合剂和醇类按10~12：0.5~1.1：2~5摩尔比混合，在0~5℃温度下搅拌1小时为A溶液待用；所述钛源为钛酸四丁酯、四氯化钛或硫酸氧钛中的一种或两种以上的混合；所述稳定敖合剂为接枝共聚物分散剂、聚丙交酯或甲基丙烯酸中的一种或两种以上的混合；所述醇类为甲醇、乙醇、丙醇、异丙醇或特丁醇。
b、在上述A溶液中滴加NaOH、Na2CO3、NaHCO3或氨水中的一种或两种以上混合的碱溶液，搅拌并加热至60~95℃温度后滴加由钼酸盐、FeSO4·7H2O和FeCl3·6H2O按0.1~3.0：0.5~7.5：0.2~6.0摩尔比配置的盐溶液，继续搅拌并加热至90~120℃温度后保温0.5~4小时为B溶液，所述 A溶液与碱溶液和盐溶液的体积摩尔比为50~1200mL：0.05~0.75mol：35 ~65mL。
c、将上述B溶液与C18烯酸、油酸乙酯或聚丙烯酸钠按80~150mL：4.5~7.5mol体积摩尔比混合，充分搅拌后自然冷却至室温，静置分层后除去上清液，沉淀的白色浆料在65~110℃下烘干，制得的产物为金红石矿晶型、锐钛矿晶型或金红石矿和锐钛矿按一定比例混合晶型的纳米TiO2光催化剂。
本发明与现有技术相比具有较强的光催化降解被吸附的有机污染物，将其分解成水、二氧化碳和小分子无机盐，其吸附能力超过自身重量，吸附、降解效果好，吸附量大，尤其可再生重复使用，使其重新获得继续吸附并光催化分解水中有机物的能力，经济性好，而且制备工艺简单，生产成本低，利于工业化规模生产。
下面通过具体的实施方案对本发明作进一步描述。
具体实施方式
实施例1：
a、将10mol硫酸氧钛与0.6mol接枝共聚物分散剂和2.5mol特丁醇混合，在4℃温度下搅拌1小时为A溶液待用。
b、在上述A溶液中滴加50mL浓度为0.07mol/L的NaOH溶液，搅拌并加热至95℃温度后，滴加由0.15mol钼酸盐、2.75molFeSO4·7H2O和1.50molFeCl3·6H2O配制的盐溶液50mL，继续搅拌并加热至105℃温度后保温4小时为B溶液。
c、将5molC18烯酸加入上述制备的B溶液中，充分搅拌后自然冷却至室温，静置分层后除去上清液，沉淀的白色浆料在65℃下烘干，制得的产物为锐钛矿晶型的纳米TiO2光催化剂。
上述产物在氯苯酚废水中，投量为1.0%的条件下，在波长400~500nm的光照下处理2.0h，依据《水质 化学需氧量的测定 重铬酸盐法(GB11914—89)》出水CODCr去除率为93%。
实施例2
a、将75g硫酸氧钛与3.05聚丙交酯和2.55g乙醇混合，在1℃温度下搅拌1小时为A溶液待用。
b、在上述A溶液中滴加50mL浓度为0.05mol/L的NaOH溶液，搅拌并加热至60℃温度后，滴加由0.15mol钼酸盐、F3.50moleSO4·7H2O和6.0molFeCl3·6H2O配制的盐溶液50mL，继续搅拌并加热至90℃温度后保温4小时为B溶液。
c、将5mol聚丙烯酸钠加入上述制备的B溶液中，充分搅拌后自然冷却至室温，静置分层后除去上清液，沉淀的白色浆料在80℃下烘干，、制得的产物为锐钛矿晶型的纳米TiO2光催化剂。
上述产物在农药废水中，投量为1.0%的条件下，在波长450~600nm的光照下处理2.0h，依据《水质 化学需氧量的测定 重铬酸盐法(GB11914—89)》出水CODCr去除率为89%。
实施例3
a、将10mol硫酸氧钛与0.6mol接枝共聚物分散剂和2.5mol特丁醇混合，在4℃温度下搅拌1小时为A溶液待用。
b、在上述A溶液中滴加50mL浓度为0.07mol/L的NaOH溶液，搅拌并加热至80℃温度后，滴加由0.15mol钼酸盐、2.75molFeSO4·7H2O和1.50molFeCl3·6H2O配制的盐溶液50mL，继续搅拌并加热至95℃温度后保温4小时为B溶液。
c、将5molC18烯酸加入上述制备的B溶液中，充分搅拌后自然冷却至室温，静置分层后除去上清液，沉淀的白色浆料在80℃下烘干，、制得的产物为纳米TiO2成品，其粒径为10纳米左右，晶型为纯金红石型。
上述产物在牛仔染料废水中，投量为1.0%的条件下，在波长400~700nm的光照下处理2.0h，依据《水质 化学需氧量的测定 重铬酸盐法(GB11914—89)》出水CODCr去除率为95%。
实施例4
a、将10mol硫酸氧钛与0.6mol接枝共聚物分散剂和2.5mol特丁醇混合，在4℃温度下搅拌1小时为A溶液待用。
b、在上述A溶液中滴加50mL浓度为0.07mol/L的NaOH溶液，搅拌并加热至90℃温度后，滴加由0.15mol钼酸盐、2.75molFeSO4·7H2O和1.50molFeCl3·6H2O配制的盐溶液50mL，继续搅拌并加热至95℃温度后保温3.0小时为B溶液。
c、将5molC18烯酸加入上述制备的B溶液中，充分搅拌后自然冷却至室温，静置分层后除去上清液，沉淀的白色浆料在65℃下烘干，制得的产物为锐钛矿晶型的纳米TiO2光催化剂。
上述产物在酚类混合废水中，投量为1.0%的条件下，在波长400~700nm的光照下处理2.0h，依据《水质 化学需氧量的测定 重铬酸盐法(GB11914—89)》出水CODCr去除率为85%。
实施例5
a、将10mol硫酸氧钛与0.6mol接枝共聚物分散剂和2.5mol特丁醇混合，在4℃温度下搅拌1小时为A溶液待用；
b、在上述A溶液中滴加50mL浓度为0.07mol/L的NaOH溶液，搅拌并加热至90℃温度后，滴加由0.15mol钼酸盐、2.75molFeSO4·7H2O和1.50molFeCl3·6H2O配制的盐溶液50mL，继续搅拌并加热至105℃温度后保温3.5小时为B溶液。
c、将5molC18烯酸加入上述制备的B溶液中，充分搅拌后自然冷却至室温，静置分层后除去上清液，沉淀的白色浆料在100℃下烘干，制得的产物为锐钛矿晶型的纳米TiO2光催化剂。
上述产物在氯苯酚废水中，投量为1.0%的条件下，在波长550~700nm的光照下处理2.0h，依据《水质 化学需氧量的测定 重铬酸盐法(GB11914—89)》出水CODCr去除率为90%。
由上述各实施例可见，通过本发明可以得到纯金红石矿晶型、纯锐钛矿晶型或金红石矿和锐钛矿按一定比例混合的混晶型，并且可以获得从几个纳米到几十纳米范围的粒径，产物分布均匀。所合成的纳米二氧化钛复配材料成品表面被一定比例的羟基、羧基或烃基等有机官能团所修饰，因此在水和醇中具有很好的分散性。本发明制备的纳米二氧化钛复配材料，除具有普通纳米TiO2所具有的抗紫外、杀菌、光催化、光折射等性能。由于结晶产物的分散性好，可以在结晶形成后于均匀稳定液相体系中进行表面再修饰，这样可以形成纯表面修饰产物。由于醇酸聚合物可以使钛离子形成稳定水凝胶，于水凝胶中加入杂化离子后再水解可以得到均匀杂化的纳米TiO2。由于产物表面具有活性官能团（如羟基、羧基），可以根据实际要求进行不同基团的修饰，以满足不同的使用要求和广泛的用途。例如作为抗紫外剂可用于化妆品、纺织、塑料、玻璃等领域；作为杀菌剂可用于农田杀菌，卫浴、陶瓷、塑料、涂料、日化等领域；作为增光剂可用于高级面漆、外墙涂料、日化等领域；此外还可以应用于如红外屏蔽、自洁、防雾、吸附除臭、污染物降解等领域。
以上只是对本发明做进一步说明，并非用以限制本专利，凡为本发明等效实施，均应包含于本专利的权利要求范围之内。
Claims (1)
1.一种提高污水降解处理的纳米TiO2光催化剂制备方法，其特征在于该纳米TiO2光催化剂的制备按下述步骤进行：
a、将钛源与稳定敖合剂和醇类按10~12：0.5~1.1：2~5摩尔比混合，在0~5℃温度下搅拌1小时为A溶液待用；所述钛源为钛酸四丁酯、四氯化钛或硫酸氧钛中的一种或两种以上的混合；所述稳定敖合剂为接枝共聚物分散剂、聚丙交酯或甲基丙烯酸中的一种或两种以上的混合；所述醇类为甲醇、乙醇、丙醇、异丙醇或特丁醇；
b、在上述A溶液中滴加NaOH、Na2CO3、NaHCO3或氨水中的一种或两种以上混合的碱溶液，搅拌并加热至60~95℃温度后滴加由钼酸盐、FeSO4·7H2O和FeCl3·6H2O按0.1~3.0：0.5~7.5：0.2~6.0摩尔比配置的盐溶液，继续搅拌并加热至90~120℃温度后保温0.5~4小时为B溶液，所述 A溶液与碱溶液和盐溶液的体积摩尔比为50~1200mL：0.05~0.75mol：35 ~65mL；
c、将上述B溶液与C18烯酸、油酸乙酯或聚丙烯酸钠按80~150mL：4.5~7.5mol体积摩尔比混合，充分搅拌后自然冷却至室温，静置分层后除去上清液，沉淀的白色浆料在65~110℃下烘干，制得的产物为金红石矿晶型、锐钛矿晶型或金红石矿和锐钛矿按一定比例混合晶型的纳米TiO2光催化剂。
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| CN113134351A (zh) * | 2021-04-22 | 2021-07-20 | 吉林化工学院 | 具有光催化性能的CdMoO4微球催化剂及其制备方法和应用 |
| CN113134351B (zh) * | 2021-04-22 | 2022-06-14 | 吉林化工学院 | 具有光催化性能的CdMoO4微球催化剂及其制备方法和应用 |
| CN115947369A (zh) * | 2023-02-02 | 2023-04-11 | 青岛红星高新材料有限公司 | 一种高比表面积混晶二氧化钛及其制备方法 |
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