CN112108106A - 一种焙烧态钙镁铝基LDHs的制备方法及其除磷应用 - Google Patents
一种焙烧态钙镁铝基LDHs的制备方法及其除磷应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 35
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- 238000004448 titration Methods 0.000 claims abstract description 21
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 150000001768 cations Chemical class 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
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- 239000011777 magnesium Substances 0.000 claims description 5
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- 239000000203 mixture Substances 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 abstract description 50
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 50
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 49
- 238000001179 sorption measurement Methods 0.000 abstract description 27
- 239000003463 adsorbent Substances 0.000 abstract description 13
- 239000002351 wastewater Substances 0.000 abstract description 8
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- 229910019142 PO4 Inorganic materials 0.000 description 5
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- 150000004692 metal hydroxides Chemical class 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
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- 150000001450 anions Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 229960001545 hydrotalcite Drugs 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J20/041—Oxides or hydroxides
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种焙烧态钙镁铝基LDHs的制备方法及其除磷应用,包括如下步骤:(a)按照二价金属阳离子与三价金属阳离子钙镁铝一定摩尔比配置混合金属盐溶液,沉淀剂采用NaOH溶液;(b)将混合金属盐溶液与NaOH溶液共同滴加到盛有NaCl溶液的烧杯中,在设定一定温度范围内恒温搅拌,控制混合金属盐溶液的滴定速度,至混合金属盐溶液滴定完毕后停止滴定,继续恒温搅拌;(c)在一定温度下水浴晶化一段时间,然后用蒸馏水离心洗涤材料至上清液中无Cl‑检出,鼓风干燥,研磨后在一定温度条件下焙烧,得到焙烧态钙镁铝基LDHs。制备方法相对简单,吸附剂磷吸附量巨大,并且具有良好的吸附动力学性能,可应用于工农业含磷废水的处理以及生态环境保护中的磷的应急污染处理。
Description
技术领域
本发明属于水处理材料制备与应用领域,具体涉及一种焙烧态钙镁铝基层状双羟基复合金属氢氧化物(LDHs)吸附剂的制备及其对含磷废水的处理应用。
背景技术
磷在农业和工业中应用广泛,但磷的过度使用带来了许多问题,导致水体富营养化现象,严重恶化水体水质,破坏水生生态系统的稳定。因此废水在排入环境之前必须经过处理,以减小对生态环境的干扰。目前,常采用化学、生物和物理吸附方法去除废水中的磷。化学法是去除高浓度磷酸盐的最初和有效的方法,但沉淀不仅产生的污泥量大、而且含水率高,后续脱水困难、污泥处理成本较高。生物法通常除磷过程慢、周期长,运行操作受环境温度、原水水体水质等诸多因素的影响,稳定性较差。吸附法除磷是利用适当的吸附材料,通过一系列的离子交换、表面沉淀、静电吸引、配合络合等物理化学反应使废水中的磷转移到吸附材料上。具有工艺简单、除磷效率高、成本低、操作灵活、可循环等优点,发展前景广阔。而磷作为多数富营养化水体的主要限制元素,控制水体中的磷浓度对防止水体富营养化起着重要作用,因此寻找一种高效的除磷方法迫在眉睫。层状双羟基复合金属氢氧化物(LDHs)是水滑石和类水滑石的统称,是由两种或两种以上的金属氢氧化物构成的带正电荷的层板与层间阴离子有序组装成的一种层状阴离子型黏土材料,其作为一种有效的吸附剂受到了广泛的关注。层状双羟基复合金属氢氧化物(LDHs)具有层间离子交换性、带永久正电荷的性质,其焙烧后产物具有巨大的比表面积又能在一定的环境中恢复成原来的层状结构,所以是一种优良的吸附除磷材料,被广泛的应用于去除水中的磷酸根。
发明内容
有鉴于此,本发明提供了一种焙烧态钙镁铝基LDHs的制备方法及其除磷应用,采用恒定pH双滴定共沉淀法制备钙镁铝基LDHs。
为了解决上述技术问题,本发明通过以下技术方案来实现:本发明提供一种焙烧态钙镁铝基LDHs的制备方法,包括以下步骤:
(a)按照二价金属阳离子(Ca2+、Mg2+)与三价金属阳离子(Al3+)钙镁铝摩尔比5:1:2配置混合金属盐溶液,其中,其中钙镁铝金属阳离子分别采用无水CaCl2、MgCl2·6H2O、Al(NO)3·9H2O配置,沉淀剂采用1mol/L的NaOH溶液;
(b)将250mL混合金属盐溶液与NaOH溶液共同滴加到盛有200mL、0.5mol/L的NaCl溶液的烧杯中,在设定温度35℃-75℃范围内恒温搅拌,控制搅拌速率(从初始的700r/min上升至1000r/min)使溶液充分混合,混合金属盐溶液的滴定速度约为1滴/秒(每分钟约4ml),控制NaOH溶液的滴定速度维持共沉淀反应pH为9-13范围内,至混合金属盐溶液滴定完毕后停止滴定,继续恒温搅拌30min;
(c)然后于70℃下水浴晶化24h,用蒸馏水离心洗涤材料至上清液中无Cl-检出(AgNO3滴定无沉淀),110℃下鼓风干燥24h,研磨后在300℃-800℃范围内的条件下焙烧4h,得到焙烧态钙镁铝基LDHs。
本发明同时还提供了上述焙烧态钙镁铝基LDHs的制备方法制备的焙烧态钙镁铝基LDHs在除磷中的应用。
与现有技术相比,本发明技术方案带来的有益效果如下:
本发明制备的焙烧态钙镁铝基层状双羟基复合金属氢氧化物(LDHs)对磷酸根具有很好的吸附效果,将该吸附剂用于处理含磷污废水,能够很好地解决含磷废水对环境的污染问题,具有显著的社会价值和研究价值。
上述说明仅是本发明技术方案的概述,为了能够更清楚了解本发明的技术手段,而可依照说明书的内容予以实施,并且为了让本发明的上述和其他目的、特征和优点能够更明显易懂,以下结合优选实施例,并配合附图,详细说明如下。
附图说明
为了更清楚地说明本发明实施例的技术方案,附图用来提供对本发明技术方案的进一步理解,并且构成说明书的一部分,与本申请的实施例一起用于解释本发明的技术方案,并不构成对本发明技术方案的限制。下面将对实施例的附图作简单地介绍。
图1是本发明制备流程图;
图2是本发明制备装置示意图;附图说明:1-铁架台,2-梨形分液漏斗,3-烧杯,4-磁砖子,5-pH计,6-恒温磁力搅拌器。
图3是对比例1所制备材料的XRD图谱;由图中可以看出曲线b、c、d的XRD图谱基线低平,基本无杂峰,低2θ区对应的(002)晶面的衍射峰峰型尖锐,对称性较高,说明制得的材料较纯,结晶度高,表明共沉淀反应温度为45℃、55℃和65℃时样品已结晶成完整的单斜对称的层状结构,规整度较高。
图4是对比例1中所制备材料的除磷结果。
图5是对比例2所制备材料的XRD图谱;由图中可以看出当共沉淀反应pH为10的时候,产物中出现了水铝钙石的衍射峰,并且峰型尖锐,对称性好,基线低平,产物的结晶性能较好,产物为纯水铝钙石矿物相。
图6是对比例2中所制备材料的除磷结果。
图7是对比例3所制备材料的XRD图谱;由图中可以看出曲线d、e、f在2θ为11.3左右出现了水铝钙石(002)晶面对应的特征衍射峰,焙烧温度升高到600℃后,由于其结构记忆效应,焙烧后材料在空气中吸收水分导致部分恢复了层状结构。
图8是对比例3中所制备材料的除磷结果。
图9是测试例1中所制备材料的除磷结果。
图10是测试例2中所制备材料的除磷结果。
图11是测试例3中所制备材料的除磷结果。
图12是实施例1制得的焙烧态钙镁铝基LDHs吸附剂的电子显微镜图,由图中可以看出该材料呈片层状堆叠结构。
图13是实施例1制得的焙烧态钙镁铝基LDHs吸附剂的准二级动力学拟合结果,拟合相关系数R2=0.993,很好的描述对磷的吸附过程,说明对磷酸根的吸附主要为化学吸附,即对磷酸根的吸附主要是共享或交换电子进而形成了价力。
图14是实施例1制得的焙烧态钙镁铝基LDHs吸附剂的Langmuir模型拟合结果,拟合相关系数R2>0.99,随着吸附反应温度由15℃上升到35℃,Langmuir模型拟合的饱和吸附量由130.79mg/g增加到161.66mg/g,说明升高温度有利于CCMA-0.83-600对磷的吸附。
具体实施方式
下面结合附图详细说明本发明的具体实施方式,其作为本说明书的一部分,通过实施例来说明本发明的原理,本发明的其他方面、特征及其优点通过该详细说明将会变得一目了然。在所参照的附图中,不同的图中相同或相似的部件使用相同的附图标号来表示。
本发明实施例提供的焙烧态钙镁铝基LDHs的制备方法,采用恒定pH双滴定共沉淀法制备钙镁铝基LDHs。具体过程如图1、图2所示,包括以下步骤:
(a)按照二价金属阳离子(Ca2+和Mg2+)与三价金属阳离子(Al3+)钙镁铝摩尔比5:1:2配置混合金属盐溶液,其中钙镁铝金属阳离子分别采用无水CaCl2、MgCl2·6H2O、Al(NO)3·9H2O配置,沉淀剂采用1mol/L的NaOH溶液;
(b)将250mL混合金属盐溶液与NaOH溶液共同滴加到盛有200mL、0.5mol/L的NaCl溶液的烧杯中,在设定温度35℃-75℃范围内恒温搅拌,控制搅拌速率(从初始的700r/min上升至1000r/min)使溶液充分混合,混合金属盐溶液的滴定速度约为1滴/秒(每分钟约4ml),控制NaOH溶液的滴定速度维持共沉淀反应pH为9-13范围内,至混合金属盐溶液滴定完毕后停止滴定,继续恒温搅拌30min;
(c)然后于70℃下水浴晶化24h,用蒸馏水离心洗涤材料至上清液中无Cl-检出(AgNO3滴定无沉淀),110℃下鼓风干燥24h,研磨后在300℃-800℃范围条件下焙烧4h,得到焙烧态钙镁铝基LDHs。
实施例1
焙烧态钙镁铝基LDHs吸附剂,按以下步骤进行制备:
(a)按照二价金属阳离子(Ca2+和Mg2+)与三价金属阳离子(Al3+)钙镁铝摩尔比5:1:2配置混合金属盐溶液,其中钙镁铝金属阳离子分别采用无水CaCl2、MgCl2·6H2O、Al(NO)3·9H2O配置,沉淀剂采用1mol/L的NaOH溶液;
(b)将250mL混合金属盐溶液与NaOH溶液共同滴加到盛有200mL、0.5mol/L的NaCl溶液的烧杯中,在设定温度65℃条件下恒温搅拌,控制搅拌速率(从初始的700r/min上升至1000r/min)使溶液充分混合,混合金属盐溶液的滴定速度约为1滴/秒(每分钟约4ml),控制NaOH溶液的滴定速度维持共沉淀反应pH为10,至混合金属盐溶液滴定完毕后停止滴定,继续恒温搅拌30min;
(c)然后于70℃下水浴晶化24h,用蒸馏水离心洗涤材料至上清液中无Cl-检出(AgNO3滴定无沉淀),110℃下鼓风干燥24h,研磨后在600℃条件下焙烧4h,得到焙烧态钙镁铝基LDHs。
将0.08g的焙烧态钙镁铝基LDHs投加到250ml锥形瓶中放置100ml初始浓度为100mg/L的磷溶液里面,设置摇床在25℃、200r/min条件下振荡反应24h,此时磷吸附量为124.53mg/g,磷去除率为99.62%,既能保持较高的吸附量,又能保证高的去除率,此时出水磷浓度为0.38mg/L,满足污水综合排放标准(GB8978-1996)中的一级A排放标准(≤0.5mg/L)。
对比例1
对比例1的材料制备方法及除磷实验与实施例1步骤完全相同,不同之处在于:将焙烧温度设定为400℃,分别测定共沉淀反应温度为35℃、45℃、55℃、65℃、75℃条件下制备材料的结构,XRD图谱结果见图3;对比实施例1除磷实验,将投加量变为0.1g,平衡吸附量结果见图4。
对比例2
对比例2的材料制备方法及除磷实验与实施例1步骤完全相同,不同之处在于:将焙烧温度设定为400℃,分别测定在共沉淀反应pH为9、10、11、12、13的条件下制备材料的结构,XRD图谱结果见图5;对比实施例1除磷实验,将投加量变为0.1g,平衡吸附量结果见图6。
对比例3
对比例3的材料制备方法及除磷实验与实施例1步骤完全相同,不同之处在于:分别测定在焙烧温度300℃、400℃、500℃、600℃、700℃、800℃的条件下制备材料的结构,XRD图谱结果见图7;对比实施例1除磷实验,将投加量变为0.1g,平衡吸附量结果见图8。
测试例1
测试例1的材料制备方法及除磷实验与实施例1步骤完全相同,不同之处在于:将分别投加0.01g、0.02g、0.04g、0.06g、0.08g、0.10g进行除磷实验,平衡吸附量结果见图9。当投加量为0.08g,此时的磷吸附量为124.53mg/g,磷去除率为99.62%。
测试例2
测试例2的材料制备方法及除磷实验与实施例1步骤完全相同,不同之处在于:将初始溶液pH设定为2-12范围进行除磷实验,平衡吸附量结果见图10。焙烧态钙镁铝基LDHs在pH为3-8的范围内始终保持着很高的磷吸附量,在初始pH为4的条件下,磷吸附量最高为124.59mg/g,并且对溶液的pH有一定的调控作用。
测试例3
测试例3的材料制备方法及除磷实验与实施例1步骤完全相同,不同之处在于:配置的磷溶液中加入CO3 2-、SO4 2-、NO3-、Cl-四种水体中常见阴离子,共存离子浓度分别为20mg/L、50mg/L、100mg/L、200mg/L的模拟水样进行除磷实验,平衡吸附量结果见图11。当溶液中存在竞争离子时,焙烧态钙镁铝基LDHs的磷吸附量均出现不同程度的降低,当溶液中存在同一种竞争离子时,竞争离子的抑制作用随着其浓度的增加而增强。当竞争离子浓度相同时,不同阴离子对焙烧态钙镁铝基LDHs吸磷能力的抑制顺序为CO3 2->SO4 2->NO3->Cl-。
综上所述,本方法制备的焙烧态钙镁铝基LDHs吸附剂是一种高效的除磷材料。制备方法相对简单,吸附剂磷吸附量巨大,并且具有良好的吸附动力学性能,可应用于工农业含磷废水的深度处理以及生态环境保护中的磷的应急污染处理。
以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和变动,这些改进和变动也视为本发明的保护范围。
Claims (2)
1.一种焙烧态钙镁铝基LDHs的制备方法,其特征在于,包括以下步骤:
(a)按照二价金属阳离子Ca2+、Mg2+与三价金属阳离子Al3+摩尔比5:1:2配置混合金属盐溶液,其中,其中钙镁铝金属阳离子分别采用无水CaCl2、MgCl2·6H2O、Al(NO)3·9H2O配置,沉淀剂采用1mol/L的NaOH溶液;
(b)将250mL混合金属盐溶液与NaOH溶液共同滴加到盛有200mL、0.5mol/L的NaCl溶液的烧杯中,在设定温度35℃-75℃范围内恒温搅拌,控制搅拌速率使溶液充分混合,混合金属盐溶液的滴定速度约为1滴/秒,控制NaOH溶液的滴定速度维持共沉淀反应pH为9-13范围内,至混合金属盐溶液滴定完毕后停止滴定,继续恒温搅拌30min;
(c)然后于70℃下水浴晶化24h,用蒸馏水离心洗涤材料至上清液中无Cl-检出,110℃下鼓风干燥24h,研磨后在300℃-800℃范围条件下焙烧4h,得到焙烧态钙镁铝基LDHs。
2.一种如权利要求1所述的焙烧态钙镁铝基LDHs的制备方法制备的焙烧态钙镁铝基LDHs在除磷中的应用。
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