CN114797814A - 一种改性天然木质材料的制备方法及其在污水处理中的应用 - Google Patents
一种改性天然木质材料的制备方法及其在污水处理中的应用 Download PDFInfo
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- CN114797814A CN114797814A CN202210247986.7A CN202210247986A CN114797814A CN 114797814 A CN114797814 A CN 114797814A CN 202210247986 A CN202210247986 A CN 202210247986A CN 114797814 A CN114797814 A CN 114797814A
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- modified natural
- natural wood
- wood material
- wood
- lignin
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Abstract
本发明属于污水处理领域,涉及一种改性天然木质材料的制备方法及其在污水处理中的应用。所述改性天然木质材料的制备方法包括如下步骤:S1.将木材放入木质素脱除溶液中,加热反应后,将所述木材洗涤、浸渍、冷冻干燥处理,得到脱除木质素木材;S2.将TiO2与NaBH4共混,进行低热还原处理,然后清洗、烘干,得到还原黑钛;S3.将所述还原黑钛超声分散于溶剂中,然后滴涂至所述脱除木质素木材上,烘干,得到所述改性天然木质材料。本发明制备的改性天然木质材料具有高效的消毒灭菌性能,且具备去除生物风险性组分的能力,对污水消毒灭菌技术的发展具有重要意义。
Description
技术领域
本发明属于污水处理领域,涉及一种改性天然木质材料的制备方法及其在污水处理中的 应用。
背景技术
除传统氮磷、重金属、有机污染物外,大肠菌群、消毒副产物(DBPs)、抗生素抗性基因(ARGs)等具有一定生物风险性的新型污染物也应当给予足够的重视。
水环境中的微生物污染问题因其存在可诱发疾病发生的风险,因而对控制传染病传播具 有重要意义。绝大多数微生物以自然流动的方式存在于水环境中,主要来自于土壤冲刷,一 般对人类无致病作用;而还有一部分水环境微生物来自于垃圾、人畜粪便、以及皮革或食品 工业废水,其中包含一些风险性病原微生物,易导致腹泻、伤寒、痢疾等疾病,严重危害人 体健康。此外,为了预防及治疗人类与动物由细菌感染所引起的传染病,抗生素在医疗与农 业领域也获得广泛应用;但是相关研究表明,抗生素不会被人体或动物体完全吸收,摄入后 超过50%的抗生素以原结构、超过40%的抗生素以其衍生物形式随人畜***物排除体外,随 废水进入市政排水管网,而传统污水处理厂处理工艺并不能有效去除污水中抗生素,仍有大 量抗生素排入自然水体,从而影响微生物群落结构以及水环境生态功能;还需要指出的是, 自2010年后,人类并未发现新的抗生素,这或许也是由于环境微生物因抗生素的大量使用、 排放,而产生一定抗药性所致。基于此,消毒处理在污水处理中至关重要,在灭活病原微生 物、减少水介质传染疾病的传播发挥着重要作用。
传统消毒工艺主要包括加氯消毒、紫外消毒、臭氧消毒等。尽管加氯消毒技术成熟、设 备故障率低、运行成本低,然而加氯消毒容易与水中残留有机物发生取代反应生成三卤甲烷 等卤代DBPs,且氯残留也容易对水环境生态***造成一定不利影响;紫外消毒不会改变水体 物化性质,且单位时间内辐照剂量越大,消毒效果越好,但是其主要缺陷也在于无持续消毒 效果;臭氧消毒尽管具备一定优点,如可对污水高效脱色、脱臭,对强抗药性微生物也具有 良好的杀灭效果,同时可降低消毒过程中卤代DBPs生成量,但是由于其稳定性较差,难以 贮存运输,需现场制备使用,使得其设备投资大、电耗投入运行成本高,操作管理复杂。需 要指出的是,以上这些消毒工艺对水环境中一般微生物能够起到一定的杀灭作用,但对ARGs 等生物风险性组分的去除并不高效,且高能耗、高物料投加量,使得传统消毒过程容易造成 二次环境污染,增加污水处理压力。基于上述问题,本发明旨在研发更加低成本、低能耗、 低环境影响的污水消毒工艺,克服现行技术的成本与环境压力,为保障水环境生态安全提供 有效的技术支持。
太阳能作为自然界储量最为丰富的可再生能源之一,其本身组成即含有一定量紫外光波 段,可用于消毒杀菌,且太阳能光谱其他波段所包含的能量也能够被用于光热杀菌,但是当 其作用于整体污水消毒时,因大量热扩散及损失,能量转换利用率低;近年来,光热界面是 一种能高效的将太阳能能量集中在气液界面处,形成热值集中界面,蒸发生产洁净淡水的新 型太阳能利用模式;同时,通过改性材料的修饰,能够在辐照界面诱导产生光热效应与光激 发含氧自由基生成过程,耦合后能够有效地利用于消毒杀菌领域。但当前所使用的这类材料 普遍为碳基纳米材料、半导体基材料、等离激元金属基材料等,存在成本高、用量大、制备 复杂、易二次环境污染等问题,且应用于实际水环境中时多为粉末投加,难以回收,因其纳 米尺寸效应,也容易造成环境毒性积累。
因此,亟需开发一种价廉易得、环境影响小、可持续利用、同时可自支撑使用的新型光 热材料,利用界面光热效应、光激发含氧自由基共同作用与自支撑材料的诱导富集效应,实 现污水高效消毒,以及生物风险性组分的去除。
发明内容
为解决上述现有技术问题,本发明公开了一种廉价、安全、绿色、高效、可持续的改性 天然木质材料及其制备方法,并将其应用于消毒灭菌中,为水体中生物风险性组分的去除提 供了新方法、新思路。
本发明的一个目的在于,提供一种改性天然木质材料的制备方法,所述改性天然木质材 料的制备方法包括以下步骤:
S1.将木材放入木质素脱除溶液中,加热反应后,将所述木材洗涤、浸渍、冷冻干燥处 理,得到脱除木质素木材;
将TiO2与NaBH4共混,进行低热还原处理,然后清洗、烘干,得到还原黑钛;
S2.将所述还原黑钛超声分散于溶剂中,然后涂覆于所述脱除木质素木材上,烘干,得 到所述改性天然木质材料;
其中,
所述天然木质材料为美洲轻木;
所述还原黑钛的带隙为2.10-2.20eV。
本发明中的还原黑钛为由P25型TiO2经低热化学还原法制备所得,相较于P25型TiO2原晶型中金红石相和锐钛矿相占比为约为2:8,用高热还原法制备的还原黑钛中金红石相和锐 钛矿相为混合相,而本发明制备的还原黑钛在经还原处理后,晶型完全转变为金红石相,金 红石相的TiO2内部晶型结构更为牢固,性能也更为稳定,从而能够在可见光太阳能谱段内提 高对太阳光能的有效吸收及利用。
进一步地,步骤S1中,所述木质素脱除溶液的制备方法,包括如下步骤:将乙酸盐溶解 于水中,调节pH值,然后加入亚氯酸盐,搅拌溶解,得到所述木质素脱除溶液。
进一步地,所述乙酸盐与亚氯酸盐的摩尔比为(2.5-3):1。
进一步地,所述pH值为4.4-4.8。
进一步地,步骤S1中,所述加热反应的温度为100-120℃,时间为8-10h。
进一步地,步骤S1中,所述TiO2与NaBH4的摩尔比为(1-1.5):1。
进一步地,步骤S1中,所述TiO2与NaBH4共混的方法为球磨混合。
进一步地,步骤S1中,所述低热还原处理在惰性气体氛围下进行,温度为300-350℃, 时间为1-1.5h。
进一步地,步骤S2中,所述超声分散的时间为20-40min。
本发明的另一个目的在于,提供上述改性天然木质材料在污水处理中的应用。
本发明的有益效果如下:
1.本发明中选用的天然木材为美洲轻木,廉价易得,节约了成本,且能够自然降解,避 免了对环境产生二次污染;并且美洲轻木具有丰富的吸附孔结构,经木质素脱除处理后暴露 其纤维素基高化学活性表面,能够负载作为光热修饰组分的还原黑钛,利用太阳能诱导的光 热效应及光激发含氧自由基,对污水中微生物进行高效杀灭;同时利用其特征吸附孔结构, 诱导ARGs等生物风险性组分富集在改性材料中,达到去除效果,保障水环境生态安全,对 水体消毒灭菌技术的发展具有重要意义。
2.本发明利用NaBH4中-1价态H的强还原性对TiO2进行还原制备还原黑钛,在较低温 度下即可进行充分反应,制备条件容易实现、能耗低;并且NaBH4对TiO2的还原更加彻底,能将TiO2主要晶型由锐钛矿相转变为金红石相;同时,NaBH4的强还原性也能使P25 TiO2形成更多还原缺陷位,从而降低所得还原黑钛的带隙宽度,进一步提高了改性天然木质材料的光热性能;相较于传统TiO2材料而言,还原黑钛能够显著提升对可见光的吸收响应特性,可高效利用吸收光子能量诱导产生电子空穴对,促进光催化过程,同时在改性复合材料内部 产生一定量热效应,两种效应可高效协同地用于污水消毒。
附图说明
图1示出了实施例1中对P25 TiO2和步骤S1制备的还原黑钛进行XRD检测结果图。
图2示出了实施例1中对P25 TiO2和步骤S1制备的还原黑钛的紫外-可见漫反射光谱图。
图3示出了测试例1中一般微生物生长结果图;
其中,
图3(a)为生活污水中一般微生物生长测试结果图(空白样1);
图3(b)为实施例1制备的改性天然木质材料对一般微生物灭杀性能测试结果图;
图3(c)为对比例1制备的改性天然木质材料对一般微生物灭杀性能测试结果图;
图3(d)为对比例2制备的改性天然木质材料对一般微生物灭杀性能测试结果图。
图4示出了测试例2中大肠杆菌生长结果图;
其中,
图4(a)为生活污水中大肠杆菌生长测试结果图(空白样2);
图4(b)为实施例1制备的改性天然木质材料对大肠杆菌进行灭杀性能测试结果图;
图4(c)为对比例1制备的改性天然木质材料对大肠杆菌进行灭杀性能测试结果图;
图4(d)为对比例2制备的改性天然木质材料对大肠杆菌进行灭杀性能测试结果图。
图5示出了测试例2中对改性天然木质材料产生的含氧自由基进行检测结果图;
其中,
图5(a)示出了1自然光强辐照1h条件下改性天然木质材料产生的含氧自由基的磁场强度 -信号强度曲线;
图5(b)示出了无辐照条件下改性天然木质材料产生的含氧自由基的磁场强度-信号强度曲 线。
图6示出了测试例3中对样品中ARGs生物风险性组分测试结果图;
其中,
图6(a)示出了生活污水中生物风险性组分含量测试结果图(空白样3);
图6(b)示出了实施例1制备的改性天然木质材料对ARGs生物风险性组分富集分离效果 测试结果图;
图6(c)示出了对比例1制备的改性天然木质材料对ARGs生物风险性组分富集分离效果 测试结果图;
图6(d)示出了对比例2制备的改性天然木质材料对ARGs生物风险性组分富集分离效果 测试结果图。
具体实施方式
为了更清楚地说明本发明的技术方案,列举如下实施例,但本发明并不局限于此。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法;下述实施例中所用的试 剂、材料等,如无特殊说明,均可从商业途径得到。
本发明实施例中的木材为美洲轻木,采购自当地木材零售市场,尺寸为30mm×30mm ×5mm(长×宽×高)。
本发明实施例中的TiO2为商用P25 TiO2。
本发明实施例中的木质素脱除溶液的制备方法为:将0.2mol乙酸钠溶解于150mL去离 子水中,滴加冰乙酸调节pH值至4.6,然后加入去离子水至300mL,然后加入0.07mol亚氯酸钠,搅拌溶解,得到木质素脱除溶液。
本发明测试例中的LB-琼脂固体培养基的成分如下:每升LB-琼脂培养基内含蛋白胨 10.0g、酵母膏粉5.0g、氯化钠5.0g、葡萄糖1.0g、琼脂15.0g,最终调节pH值为7.0。
本发明测试例中的EMB-琼脂固体培养基的成分如下:每升EMB-琼脂培养基内含蛋白胨 10.0g、乳糖10.0g、磷酸二氢钾2.0g、琼脂15.0g、伊红0.4g、美蓝0.065g,最终调节pH值 为7.1。
本发明测试例中的电子顺磁共振仪牌号为Bruker A300。
本发明测试例中的宏基因组-抗生素抗性基因测试方法如下:首先对原始样品进行微生物 总DNA提取,之后对DNA样品进行检测,总量及纯度等符合要求后进行后续实验,否则应 根据具体原因进行DNA重新提取或对现有DNA进行纯化;质检合格的DNA样品加入破碎 缓冲液中,采用超声破碎仪进行随机打断,将打断后的短片段DNA用于构建文库,而后进行文库质检,对质检合格的文库采用Illumina HiSeq 2500高通量测序平台进行PE150测序, 测序所得原始图像数据文件经碱基识别分析转化为原始测序序列。获得原始样品宏基因组测 序数据后,对原始数据进行质量控制,对需测序数据质量进行评估并对低质量数据进行去除, 以保证后续分离结果可信度。对经质控处理后的各样品进行宏基因组组装,将各样品单独组 装与样品间混合组装后的开放阅读框合并,进行基因聚类及去冗余处理,每个聚类取最长的 序列为代表性序列,得到非冗余的基因目录(gene catalogue);针对具有抗药性的样品进行 抗性基因注释,利用CARD(The Comprehensive AntibioticResistance Database)耐药基因数 据库,可标注不同环境来源的细菌抗药性基因,获得各类抗性机制作用基因注释及相应的抗 性机制基因数目。
实施例1
一种改性天然木质材料的制备方法,包括如下步骤:
S1.将木材放入木质素脱除溶液中,100℃油浴中反应8h后,用去离子水洗涤所述木材 3次,然后将所述木材放入去离子水中浸渍12h,然后在-20℃预冻24h后,冷冻干燥12h, 得到脱除木质素木材;
将摩尔比为1.25:1的TiO2与NaBH4低速球磨混合后,放入刚玉坩埚,氩气氛围下以10℃/min速率升温至350℃,反应1h后冷却至室温,然后用去离子水和无水乙醇分别清洗3次,烘箱中60℃烘干,得到还原黑钛;
S2.将0.5g所述还原黑钛放入于5mL无水乙醇中,超声分散30min,然后分3次滴涂修饰至所述脱除木质素木材上,烘箱中60℃烘干,得到所述改性天然木质材料。
图1示出了对P25 TiO2和步骤S1制备的还原黑钛进行XRD检测结果图,可以看出,本 发明制备的还原黑钛主要晶型由P25 TiO2中的锐钛矿相全部转变为金红石相。
图2示出了对P25 TiO2和步骤S1制备的还原黑钛的紫外-可见漫反射光谱图,根据曲线 在横坐标上的截距可计算得出,P25 TiO2的带隙约为3.21eV,本发明制备的还原黑钛带隙约 为2.15eV。
实施例2
一种改性天然木质材料的制备方法,包括如下步骤:
S1.将木材放入木质素脱除溶液中,110℃油浴中反应9h后,用去离子水洗涤所述木材 3次,然后将所述木材放入去离子水中浸渍12h,然后在-20℃预冻24h后,冷冻干燥12h, 得到脱除木质素木材;
将摩尔比为1.2:1的TiO2与NaBH4低速球磨混合后,放入刚玉坩埚,氩气氛围下以10℃/min速率升温至340℃,反应1.2h后冷却至室温,然后用去离子水和无水乙醇分别清洗3次,烘箱中60℃烘干,得到还原黑钛;
S2.将0.5g所述还原黑钛放入于5mL无水乙醇中,超声分散20min,然后分3次滴涂修饰至所述脱除木质素木材上,烘箱中60℃烘干,得到所述改性天然木质材料。
实施例3
一种改性天然木质材料的制备方法,包括如下步骤:
S1.将木材放入木质素脱除溶液中,120℃油浴中反应10h后,用去离子水洗涤所述木材 3次,然后将所述木材放入去离子水中浸渍12h,然后在-20℃预冻24h后,冷冻干燥12h, 得到脱除木质素木材;
将摩尔比为1.5:1的TiO2与NaBH4低速球磨混合后,放入刚玉坩埚,氩气氛围下以10℃/min速率升温至330℃,反应1.5h后冷却至室温,然后用去离子水和无水乙醇分别清洗3次,烘箱中60℃烘干,得到还原黑钛;
S2.将0.5g所述还原黑钛放入于5mL无水乙醇中,超声分散40min,然后分3次滴涂修饰至所述脱除木质素木材上,烘箱中60℃烘干,得到所述改性天然木质材料。
对比例1
本对比例与实施例1的区别在于:步骤S1中,还原黑钛使用真空高热法制备,具体步骤 如下:将1g TiO2放入5mL无水乙醇中,超声分散30min,然后用无水乙醇与去离子水对TiO2分散液进行抽滤清洗,将滤饼在烘箱中60℃烘干,然后将所得TiO2放入刚玉坩埚,在 真空条件下,以5℃/min速率升温至800℃,反应5h后冷却至室温,降温至200℃时恢复至 常压,用去离子水和无水乙醇清洗后,烘箱中60℃烘干,得到还原黑钛;其余制备方法与实 施例1相同。
对比例2
本对比例与实施例1的区别在于:步骤S1中,还原黑钛使用高热还原法制备,具体步骤 如下:将1g TiO2超声清洗、烘干后,放入刚玉坩埚中,氩气氛围下以10℃/min速率升温至 800℃,反应2h后冷却至室温,得到还原黑钛;其余制备方法与实施例1相同。
测试例1
生活污水中一般微生物生长测试:
取10μL生活污水,无菌条件下,均匀涂布至LB-琼脂固体培养基上,然后置于培养箱 中37℃恒温培养48h,观察培养基表面微生物生长情况。
改性天然木质材料对一般微生物灭杀性能测试:
分别取50mL生活污水置于蒸发容器中,将实施例1和对比例1-2制备的改性天然木质 材料分别置于蒸发容器上表面,将上述容器置于透明球形玻璃罩所搭建冷凝装置中,在1个 自然光模拟辐照下处理连续12h,无菌条件下收集冷凝玻璃罩中凝结水相,将所述水相均匀 涂布至LB-琼脂固体培养基上,然后置于培养箱中37℃恒温培养48h,观察培养基表面微生 物生长情况。
测试结果:
图3(a)为生活污水中一般微生物生长测试结果图(空白样1),可以看出,菌落数量极多, 微生物生长迅速;
图3(b)为实施例1制备的改性天然木质材料对一般微生物灭杀性能测试结果图,无肉眼 可见的菌群,说明本发明的改性天然木质材料对微生物的灭杀性能良好;
图3(c)为对比例1制备的改性天然木质材料对一般微生物灭杀性能测试结果图,可以看 出,对比例1制备的改性天然木质材料未能有效灭杀微生物,培养基表面仍有一定量菌落生 长;
图3(d)为对比例2制备的改性天然木质材料对一般微生物灭杀性能测试结果图,可以看 出,培养基表面仍存在一定量菌落,说明完全转变为金红石相的还原黑钛相比金红石相混合 锐钛矿相的还原黑钛具有更强的光热性能,能促进光催化过程,从而产生更高热值,对微生 物的灭杀性能更强。
测试例2
生活污水中大肠杆菌生长测试:
取10μL生活污水,无菌条件下,均匀涂布至EMB-琼脂固体培养基上,然后置于培养箱 中37℃恒温培养48h,观察培养基表面大肠杆菌生长情况。
改性天然木质材料对大肠杆菌灭杀性能测试:
分别取50mL生活污水置于蒸发容器中,将实施例1和对比例1-2制备的改性天然木质 材料分别置于蒸发容器上表面,将上述容器置于透明球形玻璃罩所搭建冷凝装置中,在1个 自然光模拟辐照下处理连续12h,无菌条件下收集冷凝玻璃罩中凝结水相,将所述水相均匀 涂布至EMB-琼脂固体培养基上,然后置于培养箱中37℃恒温培养48h,观察培养基表面大 肠杆菌生长情况。然后使用电子顺磁共振仪在可见光模拟光源激发和无辐照条件下对实施例 1制备的改性天然木质材料中的含氧自由基数量进行检测。
测试结果:
图4(a)为生活污水中大肠杆菌生长测试结果图(空白样2),可以看出,培养基表面有大 量呈金属光泽的大肠杆菌菌群;
图4(b)为实施例1制备的改性天然木质材料对大肠杆菌进行灭杀性能测试结果图,无肉 眼可见的菌群,说明本发明的改性天然木质材料对大肠杆菌的灭杀性能良好;
图4(c)为对比例1制备的改性天然木质材料对大肠杆菌进行灭杀性能测试结果图,可以 看出,对比例1制备的改性天然木质材料对大肠杆菌菌群未能实现有效的选择性杀灭;
图4(d)为对比例2制备的改性天然木质材料对大肠杆菌进行灭杀性能测试结果图,可以 看出,对比例2制备的改性天然木质材料对大肠杆菌菌群未能实现有效的选择性杀灭。
含氧自由基数量检测结果如表1和图5所示:
表1含氧自由基数量检测结果
图5示出了对改性天然木质材料进行含氧自由基数量检测结果图,图5(a)示出了1自然 光强辐照1h条件下改性天然木质材料产生自由基的磁场强度-信号强度曲线,可以看出改性 天然木质材料利用表面修饰还原黑钛组分,能够在可见光激发下产生单线态氧、羟基自由基、 超氧自由基等含氧自由基,可高效用于生活污水微生物杀菌消毒;图5(b)示出了无辐照条件 下改性天然木质材料产生自由基的磁场强度-信号强度曲线,可以看出,即使在有还原黑钛组 分修饰的情况下,改性天然木质材料在无辐照条件下仍无法产生含氧自由基,说明可见光激 发对含氧自由基的产生也是至关重要的。
测试例3
生活污水中生物风险性组分含量测试:
取50mL生活污水作为样品,对所述样品进行宏基因组-抗生素抗性基因测试。
改性天然木质材料对生物风险性组分富集分离效果测试:
分别取50mL生活污水作为样品,在1个自然光强下分别使用实施例1和对比例1-2制 备的改性天然木质材料处理15h,然后对所述改性天然木质材料进行宏基因组-抗生素抗性基 因测试。
测试结果如表2和图6所示:
表2宏基因组-抗生素抗性基因测试结果
根据表2可以得出,本发明制备的改性天然木质材料对污水中的ARGs成分具有高效的 富集分离能力。其中,实施例1中“抗生素靶向改变”基因的数量高于空白样中的数量,是 因为空白样中的抗性基因数量本身即较低,而实施例1在处理过程中经过不断富集,导致富 集部分基因数量超过空白样中的对应数值;实施例1中“对抗生素渗透性降低”基因的数量 低于对比例,可能是抗性基因测序样品不均匀所致,而实施例1对其他种类抗性基因的富集 效果均明显高于对比例,因此仍然可以得出本发明具有高效分离生物风险性组分的能力。
图6(a)示出了生活污水中生物风险性组分含量测试结果图(空白样3),可以看出,生活 污水中含有大量抗生素抗性基因等生物风险性组分;
图6(b)示出了实施例1制备的改性天然木质材料对生物风险性组分富集分离效果测试结 果图,可以看出,本发明的改性天然木质材料与未经处理的生活污水中的抗生素抗性基因组 成及数量相似,说明生活污水中的抗生素抗性基因被富集转移至改性天然木质材料中,本发 明的改性天然木质材料对抗生素抗性基因等生物风险性组分具有高效的去除能力;
图6(c)和图6(d)示出了对比例1和对比例2制备的改性天然木质材料对生物风险性组分 富集分离效果测试结果图,可以看出,对比例1和对比例2制备的改性天然木质材料对生活 污水中生物风险性组分也能够利用光热效应进行富集分离,但效果有所下降,明显弱于实施 例1制备的改性天然木质材料。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离 本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一 点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求 而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括 在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一 个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明 书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解 的其他实施方式。
Claims (10)
1.一种改性天然木质材料的制备方法,其特征在于,所述改性天然木质材料的制备方法包括以下步骤:
S1.将木材放入木质素脱除溶液中,加热反应后,将所述木材洗涤、浸渍、冷冻干燥处理,得到脱除木质素木材;
将TiO2与NaBH4共混,进行低热还原处理,然后清洗、烘干,得到还原黑钛;
S2.将所述还原黑钛超声分散于溶剂中,然后涂覆于所述脱除木质素木材上,烘干,得到所述改性天然木质材料;
其中,
所述天然木质材料为美洲轻木;
所述还原黑钛的带隙为2.10-2.20eV。
2.根据权利要求1所述改性天然木质材料的制备方法,其特征在于,步骤S1中,所述木质素脱除溶液的制备方法,包括如下步骤:将乙酸盐溶解于水中,调节pH值,然后加入亚氯酸盐。
3.根据权利要求2所述改性天然木质材料的制备方法,其特征在于,所述乙酸盐与亚氯酸盐的摩尔比为(2.5-3):1。
4.根据权利要求2所述改性天然木质材料的制备方法,其特征在于,所述pH值为4.4-4.8。
5.根据权利要求1所述改性天然木质材料的制备方法,其特征在于,步骤S1中,所述加热反应的温度为100-120℃,时间为8-10h。
6.根据权利要求1所述改性天然木质材料的制备方法,其特征在于,步骤S1中,所述TiO2与NaBH4的摩尔比为(1-1.5):1。
7.根据权利要求1所述改性天然木质材料的制备方法,其特征在于,步骤S1中,所述TiO2与NaBH4共混的方法为球磨混合。
8.根据权利要求1所述改性天然木质材料的制备方法,其特征在于,步骤S1中,所述低热还原处理在惰性气体氛围下进行,温度为300-350℃,时间为1-1.5h。
9.根据权利要求1所述改性天然木质材料的制备方法,其特征在于,步骤S2中,所述超声分散的时间为20-40min。
10.权利要求1-9任一项所述改性天然木质材料在污水处理中的应用。
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