CN111921486A - 纳米碳酸钙及其制备方法和应用 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 13
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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Abstract
本发明提供的纳米碳酸钙及其制备方法和应用,将8g废弃鸡蛋壳与50mL3mol L‑1的盐酸溶液充分反应至没有气泡冒出后;将反应后的溶液与0.1mol L‑1的碳酸钠溶液按照不同的体积比进行反应,在30℃条件下磁力搅拌0.5h,用UP水洗涤沉淀物3次,离心;在55℃烘箱内烘干至恒重,最终得到碳酸钙纳米材料。本发明是以废弃鸡蛋壳为钙源运用共沉淀法合成花生壳形貌的碳酸钙纳米材料,碳酸钙材料短时间内对VB吸附效果较好,该吸附基本符合等温吸附Langmuir模型。吸附过程遵循准二级动力学模型,可以再生并循环使用。该吸附剂具有去除水溶液中VB的潜力。
Description
技术领域
本发明属于废水处理技术领域,具体涉及一种纳米碳酸钙及其制备方法和应用。
背景技术
随着工业的发展,有机染料被广泛应用于纺织、皮革、造纸、油墨、橡胶和塑料等工业生产中,所产生的大量染料废水最终被排放到环境水体中。由于染料废水中具有成分复杂、毒性强、色度深、难降解的有机物,对环境造成较严重的危害。因此,染料废水处理成为解决环境的一大难题。目前,染料废水的处理方法主要有:吸附法、光催化降解、混凝法等,其中吸附法具有去除效率高、处理工艺简单、无二次污染等优点,是一种很有前途的处理低浓度染料废水的方法。常用的吸附剂如活性炭、金属氧化物、生物质材料等常存在一些缺点,如成本高、吸附能力低、合成步骤多、不能再生和回收等。因此,有必要开发一种低成本、易合成、高吸附量、可再生的吸附材料。
碳酸钙(CaCO3)是自然界最丰富的生物材料之一,广泛用于橡胶、塑料、纸张、牙膏、药物等工业的填料。普通碳酸钙作为填料仅起到增容、降低成本的作用,而纳米碳酸钙由于其特殊的尺寸使其产生特殊的性质,如表面效应、量子尺寸效应、宏观量子隧道效应等,使得纳米碳酸钙在磁性、催化性、力学性能等方面显示较优越的性能,在橡胶、塑料、高级油墨和涂料中领域中具有更广阔的应用前景。但以废弃鸡蛋壳为碳源,采用共沉淀法合成具有花生壳形貌的纳米碳酸钙,并将其作为一种高效吸附剂的研究则尚未见报道。
发明内容
针对上述技术问题,本发明提供一种纳米碳酸钙及其制备方法和应用。
具体的技术方案为:
纳米碳酸钙,由以下原料按照以下的物质比例制备,包括以下步骤:
将8g废弃鸡蛋壳与50mL3mol L-1的盐酸溶液充分反应至没有气泡冒出后;
将反应后的溶液与0.1mol L-1的碳酸钠溶液按照不同的体积比进行反应,在30℃条件下磁力搅拌0.5h,用UP水洗涤沉淀物3次,离心;
在55℃烘箱内烘干至恒重,最终得到碳酸钙纳米材料。
本发明的纳米碳酸钙的应用,作为含有维多利亚蓝B(VB)染料的废水处理吸附剂。
本发明提供的纳米碳酸钙及其制备方法和应用,是以废弃鸡蛋壳为钙源运用共沉淀法合成花生壳形貌的碳酸钙纳米材料,研究了在不同条件下碳酸钙纳米材料对有机染料VB的吸附性能,利用吸附热力学和吸附动力学讨论了其吸附行为,碳酸钙材料短时间内对VB吸附效果较好,该吸附基本符合等温吸附Langmuir模型。吸附过程遵循准二级动力学模型。在不显著降低该吸附剂的吸附性能的前提下,其可以再生并循环使用。因此,该吸附剂具有去除水溶液中VB的潜力。
附图说明
图1a为实施例的氯化钙和碳酸钠体积比对碳酸钙材料吸附效果影响;
图1b为实施例的反应温度对碳酸钙材料吸附效果的影响;
图1c为实施例的反应时间对碳酸钙材料吸附效果的影响;
图2a为实施例的CaCO3材料的SEM图像之一;
图2b为实施例的CaCO3材料的SEM图像之二;
图2c为实施例的CaCO3材料的SEM图像之三;
图2d为实施例的CaCO3材料的SEM图像之四;
图3a为实施例所合成的碳酸钙材料的XRD谱图;
图3b为实施例所合成的碳酸钙材料的FT-IR谱图;
图4a为实施例的方解石型碳酸钙的典型XPS全谱;
图4b为实施例的方解石型碳酸钙Ca 2pXPS的谱图;
图4c为实施例的方解石型碳酸钙C1sXPS谱图
图4d为实施例的方解石型碳酸钙O1s XPS谱图
图5a为染料初始浓度对碳酸钙材料吸附性能的影响;
图5b为吸附时间对碳酸钙材料吸附性能的影响
图5c为温度对碳酸钙材料吸附性能的影响;
图5d为pH值对碳酸钙材料吸附性能的影响;
图6a为准一级速率方程拟合曲线;
图6b为准二级速率方程拟合曲线;
图6c为颗粒内扩散方程拟合曲线;
图7a为对Langmuir吸附等温模型的实验数据拟合结果;
图7b为对Freundlich吸附等温模型的实验数据拟合结果;
图7c为对Temkin吸附等温模型的实验数据拟合结果;
图8a为热力学线性拟合;
图8b为吸附剂的循环使用指标。
具体实施方式
结合实施例说明本发明的具体技术方案。
1主要仪器和试剂
U-3010紫外可见分光光度计(日本日立);傅里叶红外光谱仪WQF-510A(北分瑞利分析仪器有限责任公司);高速台式离心机TGL-10C(上海安亭科学仪器厂);DF-101S集热式恒温加热磁力搅拌器(上海兴创科学仪器设备有限公司);TGL-10C高速台式离心机(上海安亭科学仪器厂)。
废弃鸡蛋壳;无水碳酸钠(Na2CO3)、盐酸等分析纯(AR)化学试剂均购自四川省成都市科龙化工试剂厂;维多利亚蓝B(VB,生化试剂)购自天津市光复精细化工研究所。实验用水均为超纯水(UP)(R≈18.25MΩ)。
2实验方法
2.1材料的合成
将8g废弃鸡蛋壳与50mL3mol L-1的盐酸溶液充分反应至没有气泡冒出后,将反应后的溶液与0.1mol L-1的碳酸钠溶液按照不同的体积比进行反应,在30℃条件下磁力搅拌0.5h,用UP水洗涤沉淀物3次,离心。在55℃烘箱内烘干至恒重,最终得到碳酸钙纳米材料。
2.2结构表征
利用DX-2700型X射线衍射仪(XRD)对碳酸钙材料的结构进行表征;利用Sigma 300扫描电子显微镜(SEM)表征碳酸钙材料的形貌;运用Escalab 250Xi X射线光电子能谱仪(XPS)确定碳酸钙材料的表面元素的形态和化学行为,运用傅立叶红外光谱(FTIR)对碳酸钙材料的特征基团进行表征。
2.3吸附实验
称取5mg碳酸钙纳米材料,加入适量VB(770mg L-1)溶液中,分别对吸附时间和吸附温度采用单一变量进行吸附脱色。当吸附达到平衡时,离心,测得平衡后溶液的吸光度,并根据吸附前后溶液浓度的变化计算吸附率,并计算吸附量。计算公式如下:
式中,qe(mg g-1)为平衡吸附量,C0和Ce(mg L-1)分别为VB的初始浓度和平衡浓度,V(L)为VB的体积,m(g)为碳酸钙材料的质量。
3结果与讨论
3.1碳酸钙材料的合成
利用共沉淀法合成了碳酸钙纳米材料,分别考察了材料比、反应温度和反应时间的影响。如图1a随着氯化钙和碳酸钠体积比增加,所得碳酸钙材料对VB的吸附效果先增加后减少。当体积比为10:25时,吸附量达到最大,故最佳材料比选择10:25。如图1b,随着水浴温度的升高,所得碳酸钙材料对VB的吸附量先增加后减少。当水浴温度达到30℃时,其对应的吸附量最大,之后随着温度升高,吸附量则下降,故最佳反应温度为30℃。图1c为反应时间对碳酸钙材料的影响。当反应时间达到30min时,所制得的碳酸钙材料对VB染料的吸附量最大,且随反应时间的增加,吸附量反而下降。故最佳制碳酸钙材料的时间为30min。
3.2碳酸钙材料的表征
3.2.1 SEM图像
图2a到图2d为CaCO3材料的SEM图像。CaCO3材料是由六面体颗粒组装成的表面粗糙的空心小球,继而空心小球堆积成具有花生壳状的不规则形貌的CaCO3材料。与常规吸附材料相比,具有球形形貌的吸附剂在质量扩散和传输方面具有更大的优势,此外,由于所合成的碳酸钙材料表面粗糙,可提供较多的吸附活性位点,有利于碳酸钙材料与吸附质充分接触,提高了碳酸钙的吸附能力。
3.2.2 X射线衍射(XRD)分析
图3a为所合成的碳酸钙材料的XRD谱图。碳酸钙材料分别在29.4°、31.4°、39.4°、43.1°、47.1°、48.5°出现几个较强的特征衍射峰,分别对应碳酸钙的(104)(006)(113)(202)(024)(116)晶面,其衍射峰的位置、强度和晶面指数均与方解石的XRD标准谱图(01-071-3699)相一致。这说明所合成的碳酸钙材料为具有典型的斜方六面体结构的方解石晶体,且图中没有其它杂峰存在,证明产物的纯度特别的高。
3.2.3傅立叶变换红外光谱(FT-IR)分析
利用FT-IR分析研究所合成的碳酸钙材料的分子的结构和化学键。如图3b,在1461,1078,875,746和712cm-1处有明显的吸收峰,为方解石型碳酸钙材料的特征峰,尤其是712cm-1处的吸收峰为方解石的特征峰。由此,进一步证明了所合成的碳酸钙材料为方解石晶相,与XRD分析结果基本吻合。
3.2.4 X射线光电子能谱(XPS)分析
为了确定所合成的碳酸钙材料的化学组成,采用XPS分析技术对碳酸钙材料表面元素的组成和结合状态进行测定。图4a为方解石型碳酸钙的典型XPS全谱,含有Ca、C和O元素。Ca 2pXPS的拟合谱图在347.18和350.68eV处有两个峰(图4b),分别归属于Ca 2p3/2和Ca2p1/2,说明有CaCO3存在。C1s谱(图4c)分别在285.38、287.68和289.68eV处有三个拟合峰,分别属于O-C=O、O-C-O和CO3基团。O1s XPS谱图(图4d)在531.58eV处有一个峰,为Ca-O键。
3.3吸附性能
3.3.1 VB初始浓度的影响
固定吸附剂用量、染料初始浓度和吸附时间,分别考察了碳酸钙材料对刚果红(CR1)、甲基橙(MO)、甲酚红(CR2)、结晶紫(CV)、罗丹明B(RhB)和VB的吸附性能,并与商用活性碳(CAC)对VB的吸附比较,结果表明,碳酸钙材料对VB有选择性吸附(图5a内插图)。为了实现碳酸钙材料对VB的最佳吸附,VB的起始浓度是最大限度地增强VB与碳酸钙吸附位点相互作用的重要因素。随着VB初始浓度增大,吸附量随之增大,当VB初始浓度为840mg L-1时,基本达到吸附平衡(图5a)。这可能是由于VB与吸附剂碳酸钙之间的VB浓度梯度增加所致。此外,在VB初始浓度较高时,吸附剂的吸附活性位点已饱和,VB从本体溶液向吸附剂表面的扩散减小。
3.3.2吸附时间的影响
图5b为吸附时间对碳酸钙材料对VB吸附能力的影响。随着吸附时间的增加,VB吸附量随之增大。当吸附时间达到60min后,吸附达平衡。碳酸钙材料对VB的吸附量在前60min内迅速增加,吸附初期的快速吸附可能是由于碳酸钙材料表面未覆盖及其活性位点有剩余。
3.3.3温度的影响
考察不同温度对碳酸钙材料吸附VB的影响(图5c),结果表明,在25℃~35℃范围内,碳酸钙对VB的吸附量随着温度的升高而增加,这可能是由于在高温条件下,溶剂粘度较低,VB的平均动能较高,增强了VB与碳酸钙活性位点之间的键合作用。而在35℃过后,吸附量随着温度升高而降低,这是由于吸附过程中存在物理吸附。本文选择在35℃下进行后续实验。
3.3.4 pH的影响
在吸附过程中,pH值是影响吸附剂的表面电荷、染料的结构和离子化程度的重要参数。考察了不同pH值下碳酸钙材料对VB的吸附效果的影响,如图5d,在pH值2-6范围内,随着pH值的增大,吸附量随之增大,在pH6时吸附效果达到最好。在较低的pH值条件下,碳酸钙材料与酸发生了反应导致吸附材料减少,所以吸附量较少。并且阳离子染料VB与H+在碳酸钙活性位点上竞争吸附,从而导致吸附量较低。在碱性环境中,随着碱性的增加,材料的吸附量减小,这是由于在碱性条件下,染料的颜色发生了变化。
3.4吸附动力学
为了解释吸附过程中固液之间的传质过程和所涉及的化学反应,利用准一级方程、准二级方程等吸附动力学模型进行研究。
准一级线性方程:
ln(qe-qt)=lnqe-k1t (1)
式中,qe(mgg-1)表示最大吸附量,qt(mgg-1)表示吸附平衡时的吸附量,k1(min-1)是准一级吸附方程的速率常数,t(min-1)是吸附时间。
准二级线性方程:
式中,k2(g mg-1min-1)是准二级吸附方程的速率常数。
颗粒内扩散方程:
qt=kit1/2+c(3)
式中,ki(mg g-1min-1/2)为颗粒内扩散速率常数,c(mgg-1)是表示边界层厚度的常数。
准一级速率方程和准二级速率方程拟合曲线如图6a和图6b,动力学参数qe、k1、k2和相关系数R2由线性回归方程得到,并列于表1。在不同浓度下,准一级动力学模型的R2小于准二级动力学模型的R2(R2≥0.99),且准二级动力学模型拟合得到的平衡吸附量与实验测得的平衡吸附量基本吻合,说明准二级动力学模型更适合用来描述碳酸钙材料对VB的吸附行为。图6c和表2分别为颗粒内扩散方程拟合曲线和相应参数。根据颗粒内扩散方程,qt对t1/2的曲线应是条直线,且若这些直线经过原点,则颗粒内扩散是唯一的速控步。如图6c,这些曲线在整个时间范围内均不是线性的,而是可以被分成多线性曲线,说明吸附过程涉及多个阶段。即所合成的碳酸钙材料吸附VB涉及两个过程,且颗粒内扩散不是决速步。
表1
注:C0是染料初始浓度,qe(exp)实验测定的最大吸附量,qe(cal),1是准一级动力学方程拟合出的平衡吸附量,qe(cal),2是准二级动力学方程拟合出的平衡吸附量。
表2
3.5吸附等温线和热力学研究
吸附等温线表明吸附过程达到平衡时吸附质在固相和液相间的分布情况。本文主要利用Langmuir、Freundlich和Temkin三个吸附等温模型,对碳酸钙材料吸附VB染料进行数据分析,其等温方程如下:
Temkin:qe=Alnce+B (6)
式中,Ce(mg L-1)为溶液中VB的平衡浓度,qe为平衡吸附量(mgg-1),KL为Langmuir吸附常数(Lmg-1),qm(mgg-1)为单层吸附的最大吸附量。Kf[mg g-1(mg L-1)-1/n]和n为Freundlich等温常数,分别描述多层吸附能力和强度。A和B是Temkin方程常数。
对Langmuir、Freundlich和Temkin三个吸附等温模型的实验数据进行拟合,拟合结果和相关参数如图7a到图7c和表3。由三个等温吸附模型的线性相关系数R2比较,可以得出Langmuir等温吸附理论更适合吸附过程。这说明碳酸钙材料对VB吸附受单层覆盖的限制,且表面相对均匀。并且在25-35℃范围内随着温度升高,qm随之增大,说明在此温度范围内该吸附过程为吸热过程,且为化学吸附。
表3
碳酸钙材料吸附VB的热力学行为可以通过吉布斯自由能变(ΔG)、焓变(ΔH)、熵变(ΔS)等热力学参数来评价。这些参数可由下列方程式计算:
ΔG=-RTlnKC (8)
式中,KC为热力学平衡常数(Lg-1),R为通用气体常数(8.314J mol-1K-1),T为温度(K)。KC根据式(7)计算,ΔG由式(8)计算,而ΔH和ΔS可以分别根据KC对1/T关系图的斜率和截距得到的。
热力学线性拟合如图8a,ΔG、ΔH和ΔS值如表4所示。在25、30和35℃下,ΔG值分别为-19.71、-26.82和-28.71kJ mol-1,说明吸附过程的可行性和自发性。并且ΔG值随温度升高而减小,说明VB吸附过程的自发性和可行性呈增加的趋势。ΔH值为129.8kJ mol-1,表明碳酸钙材料吸附VB是吸热过程。此外,由于ΔH值介于20-400kJ mol-1,说明碳酸钙吸附VB为化学吸附。ΔS值为515.4J mol-1K-1,说明吸附过程中固液界面的自由度增加。
表4
3.6可再生性
吸附剂的循环使用是降低材料成本的一个重要经济方面。如图8b,开始时,碳酸钙材料对VB的去除率是92.3%,循环5次后,碳酸钙材料对VB的去除率为88.5%,与初次吸附的去除率相比较,降低了3.8%,说明所合成的碳酸钙纳米材料具有一定的再生能力,具有从水溶液中去除VB的潜力。
4结论
以废鸡蛋壳为钙源采用共沉淀法合成了具有花生壳形貌的碳酸钙纳米材料。所合成的碳酸钙材料对VB染料有较好的吸附性能。在35℃时,碳酸钙材料吸附VB 60min达平衡,且其平衡吸附量可高达1387mgg-1。碳酸钙材料对VB的吸附过程遵循准二级动力学模型和Langmuir等温模型。由热力学参数可知,碳酸钙材料吸附VB的过程为吸热、熵增、自发的,并且该吸附过程为主要为化学吸附。吸附-解吸实验表明所合成的碳酸钙对VB可以再生使用,有望成为一种去除水溶液中VB的高效吸附剂。
Claims (3)
1.纳米碳酸钙的制备方法,其特征在于,由以下原料按照以下的物质比例制备,包括以下步骤:
将8g废弃鸡蛋壳与50mL3mol L-1的盐酸溶液充分反应至没有气泡冒出后;
将反应后的溶液与0.1mol L-1的碳酸钠溶液按照不同的体积比进行反应,在30℃条件下磁力搅拌0.5h,用UP水洗涤沉淀物3次,离心;
在55℃烘箱内烘干至恒重,最终得到碳酸钙纳米材料。
2.纳米碳酸钙,其特征在于,由权利要求1所述的制备方法制备所得。
3.根据权利要求2所述的纳米碳酸钙的应用,其特征在于,作为含有维多利亚蓝B染料的废水处理吸附剂。
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