CN112473652B - 过氧化氢改性含过渡金属生物炭的制备方法及其应用 - Google Patents
过氧化氢改性含过渡金属生物炭的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种H2O2改性含过渡态金属生物炭的制备方法及应用。以富集有过渡金属的生物炭为原材料,经脱水、热裂解得到过渡金属生物炭样品;将过渡金属生物炭样品置于容器中,经滴加过氧化氢(H2O2)后加盖,盖上留有气孔,放置于恒温振荡箱中振荡12‑24h;将得到的样品经抽滤、水洗、干燥,即可得到过氧化氢改性含过渡金属生物炭产品。富集有锰、铜、铁等过渡态金属的生物炭样品本身无催化性能,通过采用H2O2作为改性剂,可制备得到具有可见光催化活性的锰、铜、铁改性生物炭催化剂,应用于去除水体中的罗丹明B(RhB)和苯酚(Phenol)。
Description
技术领域
针对含锰、铜、铁等重金属污染的土壤或水体,在通过植物修复技术处理后得到的大量生物质材料难以转化再利用等难点,本技术提供了一种简单的过氧化氢改性方法,将上述被金属污染的生物质材料进行资源转化,使其应用于水体中有毒有机污染物的消减与去除。该技术属于资源可持续性利用及污染治理领域。
背景技术
随着矿山开采、矿石冶炼和工业化的高速发展,土壤污染日益加剧,严重的重金属面源污染是当前人类所面临的重要环境问题之一。植物修复技术是目前治理土壤重金属面源污染的绿色、经济、安全的一种新型土壤污染治理技术。其是通过使用植物将土壤中的重金属移出土体,将重金属转移、富集于体内,达到降低土壤中重金属的目的。其中由于锰、铁和铜是植物光合作用和生长过程中必要的元素,因而更容易被植物富集于体内。
但是随着植物修复技术进入田间示范和应用阶段,修复植物的后处理问题亟待解决。大量富含重金属的植物如果不尽快进行妥善处理,其中富集的重金属将会重新进入环境,且由于生物体中的重金属具有更高的活性,会对环境带来更大的危害。然而,运输和储存这些重金属高富集生物质需要占用较大空间,同时,它们也是潜在的生物质能源,不加以利用会造成资源的浪费。因此,修复植物的无害化、资源化是当前环境领域中的研究热点。
生物炭(Biochar, BC)是通过缺氧热解或水热法碳化生物质原料而制备得到的多孔碳质材料。生物炭因其性价比高、可得性广、生态友好等特点,在能源转换和储存、农业生产和环境保护等领域有着广泛的研究和应用前景。但是实践证明,原始生物炭对于污使用染物的吸附能力有限以及用于催化材料时性能较差,为了使生物炭具有更好的吸附性能和催化性能,通常对其进行改性。目前,生物炭表面改性的主要功能基团分为酸碱基团、有机官能团、金属价态改性。其中,使用绿色氧化剂H2O2对生物炭进行氧化改性,从而提升生物炭的吸附性能和催化活性能,是一种非常有效且友好的改性方法。
已有大量报道显示通过在生物炭上负载金属氧化物,能增强生物炭的吸附性能以及对有机污染物的氧化矿化能力,如王风等人将镧负载于羊粪上再进行热解制备生物炭,得到了对磷吸附效果较好的金属镧改性生物炭;邓玉等人将镁负载于玉米芯中再进行热解,制备得到了对水体中磷和氮的有良好的吸附效果的镁改性生物炭;管运涛等人用钨酸铋氮硫共同对生物炭进行了改性,得到了具有良好光催化性能和吸附性能的改性生物炭。
尽管对金属氧化物改性生物炭的报道已有很多,但是对于富集有重金属的生物炭进行改性使其具备去污能力的研究却未见报道。将此类富集有重金属的生物炭材料进行简单的改性,能显著提升其对环境中有机污染物的氧化矿化能力,实现污染物的“以废制废”的绿色循环经济。
发明内容
针对上述技术问题,本发明提供了一种较为简单的改性锰、铜、或铁生物炭方法。采用H2O2改性法制备出H2O2改性锰/铜/铁生物炭。
具体步骤如下进行:
(1)以富集有过渡金属的生物炭为原材料,经脱水、热裂解得到过渡金属生物炭样品;
(2)将过渡金属生物炭样品置于容器中,经滴加H2O2后加盖,盖上留有气孔,放置于恒温振荡箱中振荡12- 24 h;
(3)将步骤(2)得到的样品经抽滤、水洗、干燥,即可得到过氧化氢改性含过渡金属生物炭产品。
步骤(1)中富集有过渡金属的生物炭包括富集有锰、铜、或铁中的一种或多种的生物炭;其中锰含量大于10 mg/g、铜含量大于14 mg/g、铁含量大于9 mg/g。
步骤(1)中热解过程是以15-17℃/min的升温速率升温至300-700℃,热解0.5-2h。
步骤(2)中H2O2的质量浓度为28-30%;质量浓度为28-30%的H2O2的滴加速度为60-75滴/分钟。
步骤(2)中质量浓度为28-30%的H2O2体积(mL)与过渡金属生物炭样品质量(g)之比为45-55:1,优选为50:1。
本发明有一技术方案是将制备得到的过氧化氢改性含过渡金属生物炭在降解有毒有机污染物上的应用。
有毒有机污染物包括但不限于罗丹明B和苯酚。
过氧化氢改性含过渡金属生物炭的添加量为250 mg/L。
H2O2作为一重要的化学药品几乎应用于各工业领域和环保领域。在纺织,造纸等传统的工业上,H2O2通常是用作漂白剂和氧化剂,而近年来H2O2在环保领域的利用又有新的发展。H2O2在环保方面有一个突出的优点,即H2O2参加的反应可产生出纯水和氧气。
本发明的技术方案中,H2O2作为一种具有良好氧化能力的廉价氧化剂,本发明成功地使用H2O2对锰、铜、或铁生物炭进行了改性,使锰、铜、或铁生物炭具备了可见光催化降解污染物的能力。本专利以H2O2作为改性剂成功制备出具有可见光催化降解污染物能力的锰生物炭,并应用于去除罗丹明B(RhB)和有机污染物苯酚(Phenol),结果均显示出H2O2改性锰生物炭对RhB和Phenol的良好去除能力。
本发明原料廉价,来源可靠,绿色安全,制备工艺简便,条件易控,工艺参数可调,有良好的去除污染物能力,H2O2改性锰生物炭的稳定性良好。廉价的H2O2作为改性剂,使原本不具有可见光催化降解污染物能力的锰、铜、或铁生物炭具备了可见光催化降解污染物的能力。拓展了修复植物的资源利用与应用性。经过光催化降解实验发现,H2O2改性锰生物炭能够在可见光条件下降解RhB和Phenol。
本发明的目的是要提供一种简单的改性Mn、Cu或Fe生物炭的制备方法。与未改性的Mn/Cu/Fe生物炭相比,由于未改性的Mn、Cu或Fe生物炭不具有可见光催化能力,因此其对污染物去除效率大多不理想。通过适量的H2O2改性后,铜生物炭材料光照3h可去除68%的罗丹明B(10 mg/L);锰生物炭材料自身拥有了对污染物的去除能力,光照3h可去除98%的罗丹明B(10 mg/L),光照5h可去除52%的Phenol(2mg/L);铁铜生物炭材料光照3h可去除63%的罗丹明B(10 mg/L)。
附图说明
图1为三种不同炭材料在改性过程中滴加H2O2时的图片。
图2为实施例4制备过程中H2O2改性过程所产生气体的气相色谱检测图。
图3为实施例4制备得到的MB-H0和MB-H5的SEM图谱。
图4为实施例4制备得到的MB-H0和MB-H5的XRD图谱。
图5为实施例4制备得到的MB-H0和MB-H5的XPS 图谱。
图6为活性炭、空白生物炭、H2O2改性活性炭和H2O2改性空白生物炭降解RhB的动力学曲线。
图7为实施例1中制备得到的MB-H0和实施例4制备得到的MB-H5锰生物炭对RhB的降解动力学曲线。
图8为实施例6制备得到的CuB-H5对RhB的降解动力学曲线。
图9为实施例7制备得到的FeB-H5对RhB的降解动力学曲线。
图10为实施例4制备得到的MB-H5对Phenol的降解动力学曲线。
具体实施方式
制备了H2O2改性Mn/Cu/Fe生物炭,即直接以H2O2为改性剂制备的Mn、Cu、或Fe生物炭。生物炭的命名(MB-Hx,Mn biochar -H2O2 modified;x代表H2O2使用量ml,0表示未改性;Cu-BC代表未改性铜生物炭,CuB-Hx,代表改性铜生物炭 ;Fe-BC代表未改性铁生物炭,FeB-Hx,代表改性铁生物炭 )。
实施例1
以富集有锰生物炭(Mn,11.3mg/g)、铜生物炭(Cu,14.3mg/g)、铁生物炭(Fe,9.7mg/g)为原材料,分别于60℃烘干24h脱水,在管式炉中于N2气氛下,温度为300℃,热解1h,过100目筛后得到过渡金属生物炭样品,标记为Mn-300℃生物炭样品、Cu-300℃生物炭样品、Fe-300℃生物炭样品。
实施例2
称取Mn-300℃生物炭样品0.1g放置于10ml小玻璃瓶中,60-75D/min滴加初始质量分数为28% 的H2O2 2mL,滴加过程中产生大量带有烧焦气味的白烟,滴加完成后,加盖,盖上留有2-4个气孔,放置于恒温振荡箱中25℃振荡12- 24h;在振荡结束后对锰生物炭材料进行抽滤处理,抽滤时用蒸馏水洗3次,将抽滤好的改性Mn生物炭材料再于恒温干燥箱中60℃烘干12h,即可得到H2O2改性Mn生物炭,命名为MB-H2。
实施例3
称取Mn-300℃生物炭样品0.1g放置于10ml小玻璃瓶中,60-75 D/min滴加初始质量分数为30% 的H2O2 5mL,滴加过程中产生大量带有烧焦气味的白烟,滴加完成后,加盖,盖上留有2-4个气孔,放置于恒温振荡箱中25℃振荡12- 24h;在振荡结束后对锰生物炭材料进行抽滤处理,抽滤时用蒸馏水洗3次,将抽滤好的改性Mn生物炭材料再于恒温干燥箱中60℃烘干12h,即可得到H2O2改性Mn生物炭,命名为MB-H5。
实施例4
称取Cu-300℃生物炭样品0.1g放置于10ml小玻璃瓶中,60-75 D/min滴加初始质量分数为29% 的H2O2 5mL,滴加过程中产生少量烟气,滴加完成后,加盖,盖上留有2-4个气孔,放置于恒温振荡箱中25℃振荡12- 24h;在振荡结束后对锰生物炭材料进行抽滤处理,抽滤时用蒸馏水洗3次,将抽滤好的改性Cu生物炭材料再于恒温干燥箱中60℃烘干12h,即可得到H2O2改性Cu生物炭,命名为CuB-H5。
实施例5
称取Fe-300℃生物炭样品0.1g放置于10ml小玻璃瓶中,60-75 D/min滴加初始质量分数为30% 的H2O2 5mL,滴加过程中产生少量烟气,滴加完成后,加盖,盖上留有2-4个气孔,放置于恒温振荡箱中25℃振荡12- 24h;在振荡结束后对锰生物炭材料进行抽滤处理,抽滤时用蒸馏水洗3次,将抽滤好的改性Fe生物炭材料再于恒温干燥箱中60℃烘干12h,即可得到H2O2改性Fe生物炭,命名为FeB-H5。
实施例6
称取300℃空白生物炭样品0.1g放置于10ml小玻璃瓶中,60-75 D/min滴加初始质量分数为29% 的H2O2 5mL,滴加完成后,加盖,盖上留有2-4个气孔,放置于恒温振荡箱中25℃振荡12- 24h;在振荡结束后对空白生物炭材料进行抽滤处理,抽滤时用蒸馏水洗3次,将抽滤好的改性空白生物炭材料再于恒温干燥箱中60℃烘干12h,即可得到H2O2改性空白生物炭,命名为H2O2 -blank BC。
实施例7
去除实验操作步骤:在70 ml玻璃试管中加入不同40mL降解底物,其初始水浓度分别为RhB=10 mg/L,或Phenol=2mg/L,在上述溶液中加入0.010 g 实施例1-7中得到的样品,在一定反应时间间隔取上清液离心,采用高效液相色谱测定Phenol的浓度Ct。高效液相色谱检测Phenol具体条件:Agilent 1260型高效液相色谱,C18反相色谱柱, 流动相为1:1的甲醇和水,柱温保持在30.00℃,流速 1.00 mL•min-1,进样体积20.00 μL,检测波长λmax=220nm。RhB去除率采用紫外可见分光光度计上测其λmax=554nm的吸光度值At并根据标准曲线计算Ct。
图1显示的是实施例4中Mn-300℃生物炭样品、活性炭(AC)、300℃空白生物炭(blank BC)三种材料在改性过程中滴加H2O2时的图片。从图中可以看出富含锰元素的生物炭在滴加H2O2时有大量的白烟产生,而活性炭和空白生物炭则不产生白烟。这是由于锰生物炭中的过渡态金属锰元素与H2O2发生反应产生的气体。由于活性炭或空白生物炭不含该过渡态金属元素或含量太低,不能与H2O2反应而产生气体,因此看不到有烟气产生。
图2为图1所中所产生气体的气相色谱检测图。在图中可以看出,上述白烟的保留时间与氧气的保留时间一致,表明白烟主要成份为氧气。
图3显示的是MB-H0和MB-H5的SEM图谱。可以看出,在相同放大倍数下, MB-H0催化剂表面有粒状颗粒物存在,MB-H5催化剂表面没有,后者表面更为平滑。
图4显示的是MB-H0和MB-H5的XRD图谱。可以看出,MB-H0样品在2θ=28.3°,40.5°,50.1°,58.6°,66.4°,73.7°处出现了KCl的特征衍射峰(JCPDS No.41-1476),表明MB-H0的主要物质是KCl。除此以外,2θ=36.3°处的衍射峰归属于MnO2,说明未改性的MB-H0样品主要组成为KCl和MnO2。MB-H5样品在2θ=18.8°,21.6°的衍射峰归属于MnO(OH),2θ=24.5°的衍射峰归属于SiO2,说明主要组成为MnO(OH)和SiO2。
图5为MB-H0和MB-H5的XPS 图谱。从图5a、5b可以看出,与改性前MB-H0样品相比,改性过后的MB-H5样品没有K、Cl、Ca元素,却出现Si元素的峰,与XRD的分析结果一致。此外,MB-H0和MB-H5样品的Mn2p图谱 (图5c、5d)显示MB-H0样品中Mn2p为Mn是+2价和+4价的复合价态,而MB-H5样品中Mn的价态为+3价,也与XRD中的分析结果相符。
图6显示的是活性炭(AC)、空白生物炭(blank BC)、H2O2改性活性炭(H2O2-AC)和H2O2改性空白生物炭(H2O2-blank BC)对RhB的降解动力学曲线。可以看出,无论是AC还是blank BC,改性前后都不能够对RhB进行光催化降解。这可能是由于这两种炭材料中没有过渡态金属元素或其含量太低,不具备可见光催化活性,因此不能够进行光催化降解污染物。
图7是改性前后锰生物炭对RhB的降解动力学曲线。可以看出,改性前锰生物炭(MB-H0)本身不具有光催化活性,经过H2O2改性后锰生物炭MB-H2、MB-H4、MB-H5和MB-H6对RhB的降解率分别为74%、79%、98%和86%。结果表明H2O2改性能一定程度上提高锰生物炭的光催化活性,且随着改性过程中H2O2加入量的增加,锰生物炭的光催化降解能力也随之增强。当H2O2的加入量为5 ml时,即添加的H2O2体积(mL)与锰生物炭质量(g)之比为50:1时,制备得到的锰生物炭MB-H5样品,具有最高反应活性,在可见光光反应3小时时对RhB的降解率达到了98%。
图8是改性前后铜物炭对RhB的降解动力学曲线。可见,在光反应3小时后改性铜生物炭(CuB-H5)对RhB的降解率达到了68%,说明改性前的铜生物炭样品不具备光催化活性,经过H2O2改性后具备有可见光催化降解RhB的催化能力。
图9是改性前后铁物炭对RhB的降解动力学曲线。可以看出,在光反应3小时后改性铁生物炭(FeB-H5)对RhB的降解率达到了63%,说明只有经过H2O2改性后铁生物炭(FeB-H5)才具备可见光催化性能。
图10是MB-H5对Phenol的降解动力学曲线。可以看出,MB-H5样品在光反应5小时后对Phenol的去除率为52%,表明经过改性后的锰生物炭对于有机无色小分子污染物也具备显著的可见光催化降解能力。
表1为实施例4、6、7中得到的改性前后生物炭中的锰、铜、铁含量,由表中可以看出,锰生物炭(MB-H0)、铜生物炭(Cu-BC)和铁生物炭(Fe-BC)中锰、铜、铁元素的含量分别是11.3mg/g、14.3mg/g、9.7mg/g。经过H2O2改性后,改性锰生物炭(MB-H5)、改性铜生物炭(CuB-H5)和改性铁生物炭(FeB-H5)中锰、铜、铁元素含量分别为4.4mg/g、5.7mg/g、3.1mg/g。这可能与过渡态金属与H2O2形成了配位物有关,也是其具备光催化活性的根本原因。
表1锰、铜、铁生物炭改性前后生物炭中的锰、铜、铁含量
Mn(mg/g) | Cu(mg/g) | Fe(mg/g) | |
改性前 | 11.3 | 14.3 | 9.7 |
改性后 | 4.4 | 5.7 | 3.1 |
Claims (5)
1.过氧化氢改性含过渡金属生物炭在降解有毒有机污染物上的应用,所述的有毒有机污染物为罗丹明B和苯酚,过氧化氢改性含过渡金属生物炭的制备方法包括如下步骤:
(1)以富集有过渡金属的生物炭为原材料,经脱水、热裂解得到过渡金属生物炭样品;富集有过渡金属的生物炭包括富集有锰、铜、或铁中的一种或多种的生物炭;其中锰含量大于10 mg/g、铜含量大于14 mg/g、铁含量大于9 mg/g;
(2)将过渡金属生物炭样品置于容器中,经滴加过氧化氢后加盖,盖上留有气孔,放置于恒温振荡箱中振荡12- 24h;
(3)将步骤(2)得到的样品经抽滤、水洗、干燥,即可得到过氧化氢改性含过渡金属生物炭产品。
2.根据权利要求1所述的应用,其特征在于,步骤(1)中热解过程是以15-17℃/min的升温速率升温至300-700℃,热解0.5-2h。
3.根据权利要求1所述的应用,其特征在于,步骤(2)中H2O2的质量浓度为28-30%;H2O2的滴加速度为60-75滴/分钟。
4.根据权利要求1所述的应用,其特征在于,步骤(2)中质量浓度为28-30%的H2O2与过渡金属生物炭样品的体积mL-质量g之比为45-55:1。
5.根据权利要求1所述的应用,其特征在于,过氧化氢改性含过渡金属生物炭的添加量为250 mg/L。
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