CN109200954A - 一种碳气凝胶的制备方法及其用途 - Google Patents
一种碳气凝胶的制备方法及其用途 Download PDFInfo
- Publication number
- CN109200954A CN109200954A CN201811174963.8A CN201811174963A CN109200954A CN 109200954 A CN109200954 A CN 109200954A CN 201811174963 A CN201811174963 A CN 201811174963A CN 109200954 A CN109200954 A CN 109200954A
- Authority
- CN
- China
- Prior art keywords
- carbon aerogels
- solution
- preparation
- hydrogel
- heavy metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开一种碳气凝胶材料的制备方法其用途。本发明的种碳气凝胶的制备方法是:将海藻酸钠和聚环氧乙烷或聚氧化乙烯(PEO)分别溶于水中,经并充分搅拌使两种溶液完全混合后,在环境温度下在混合溶液中滴加Ca(NO3)2,快速形成海藻酸钙水凝胶块,放置过夜以稳定,并置换出大量的水溶液,再将制备的水凝胶冷冻干燥直至完全没有水分,最后将冷干的块状气凝胶在600℃碳化8小时,得到所述的碳气凝胶。由本发明的方法可制备得到的碳气凝胶材料。这种碳气凝胶材料可用于去除废水中重金属离子。
Description
技术领域
本发明涉及一种功能材料的制备方法及其用途。确切讲本发明涉及一种碳气凝胶的制备方法,以及其用途。
背景技术
碳气凝胶(CA)是一种新型和新兴的吸附材料,它是由三维网络排列的,具有高孔隙率和高表面积的共价键合纳米粒子组成。CA通常以固体形状,粉末和片状形式生产,并以成本有效的方式提供更好的处理效率,以从水中去除重金属离子。然而,对于CA的制造,传统的合成方法涉及碳化低蒸汽压聚合物前体或天然来源都有它们各自的缺点,这些缺点主要与交联反应有关,在高温热解过程中伴随形成焦炭或不受控制地汽化。在某些情况下,更严重的是,直链聚合物在惰性气体下的直接热解将产生不具有多孔特征的碳化产物。另一方面,以这种方式生产的CA具有不受控制的孔径的限制,这是影响其金属离子吸附能力的关键因素之一。
发明内容
本发明提供一种碳气凝胶的制备方法,同时提供用这种方法制备的碳气凝胶和其用途。
本发明的种碳气凝胶的制备方法是:
(1)将海藻酸钠和等于海藻酸钠质量二分之一的聚环氧乙烷或聚氧化乙烯(PEO)分别溶于水中;
(2)然后将所得到的两种溶液混合并充分搅拌;
(3)充分搅拌使两种溶液完全混合后,在环境温度下,将0.1L混合溶液滴加到0.2mmol的30mmol L-1Ca(NO3)2溶液中,快速形成海藻酸钙水凝胶块;
(4)由上一步骤得到水凝胶放置过夜以稳定,并将其浸入丙酮溶液中置换出大量的的水溶液,这里所用丙酮溶液的质量大约为40-160g,室温下置换24h后,去除丙酮和水的混合液;
(5)完成前一步骤后,将制备的水凝胶冷冻干燥直至完全没有水分;
(6)最后将冷干的块状气凝胶在600℃碳化8小时,得到所述的碳气凝胶。
由本发明的方法可制备得到的碳气凝胶材料。这种碳气凝胶材料可用于去除废水中重金属离子。
本发明通过使用含有海藻酸钠(SA)和聚环氧乙烷(PEO)的Ca2+交联聚合物混合物作为前体,然后冷冻干燥然后碳化来制备新型碳气凝胶(CA)材料。其其制备过程中,可以通过酸洗简单地除去Ca2+,从而作为模板在这样的系统中制造大量的微孔。相关的试验结果表明,本发明的经去除Ca2+后的CA能较好的去除废水中重金属离子。
本发明的有益之处是:1、以海藻酸钠和聚环氧乙烯为前驱体,属天然类原料,原料易购。2、制备碳气凝胶的方法相对简单。3、制备的碳气凝具有较好的微孔结构。4、制备的碳气凝胶对于去除水中的重金属离子具有较高的吸附量和去除率。
附图说明
图1是本发明制备碳气凝材料的示意图,图2是本发明制备碳气凝胶交联过程及其去除水中重金属离子的示意图,图3是所本发明制备碳气凝胶材料的SEM图,图4是所制备碳气凝胶材料BET图,图5是本发明的碳气凝胶去除重金属Cr6+的时间曲线图,图6是本发明的碳气凝胶去除重金属Cr6+的浓度曲线图,图7是本发明的碳气凝胶对不同重金属离子的吸附量曲线图。
具体实施方式
以下为本发明的实施例。
一、本发明的碳气凝胶制备
本发明是用Ca2+模板合成碳气凝胶有效去除水中重金属离子,其步骤为:
(1)首先将5g海藻酸钠和2.5g PEO分别溶于500mL超纯水中;
(2)然后用将它们混合在一起搅拌一段时间;
(3)搅拌24小时后,在环境温度下,将0.1L混合溶液滴加到0.2mmol的30mmol L-1Ca(NO3)2溶液中,并在与混合溶液接触时快速形成海藻酸钙水凝胶块;
(4)放置所得水凝胶过夜以稳定,并连续浸入丙酮-水溶液24小时以完成溶剂交换;
(5)之后,将制备的水凝胶冷冻干燥72小时;
(6)最后,块体气凝胶在600℃碳化8小时。
二、本发明制备得到的碳的气凝胶对重金属粒子的吸咐
采用本发明的上述方法获得的碳气凝胶对重金属离子具有较高的吸附量和去除率,并且达到平衡的时间短。
以下为具体的重金属粒子吸咐实施例详细内容。
实施例1:图5显示了碳气凝胶在室温下对Cr(Ⅵ)的吸附动力学。如图6a所示,Cr(Ⅵ)的吸附平衡几乎在200分钟内完成,伴随着两个阶段的动力学行为:初始快速吸附在60分钟内,第二阶段吸附非常低在60-200分钟内。这可能与在初始吸附阶段吸附重金属离子的大量空位介孔接枝活性位点有关。之后,重金属离子必须进一步深入到遇到更大阻力的微孔中,导致吸附速率减慢。结果表明,大部分Cr(Ⅵ)可在200min内去除,其中吸附量qt计算为74.5mg g-1,此后上清液浓度平衡,重金属离子几乎不变,随着接触时间的增加,这表明所有的吸附点已经接近饱和。
实施例2:图6显示了初始金属离子浓度不同时,碳气凝胶上Cr(Ⅵ)的吸附等温线。如图6所示,平衡吸附量取决于平衡时的重金属离子浓度,随着平衡浓度的增加,平衡吸附量逐渐增加,这是因为在较高浓度下,重金属离子的数量相对于吸附位点的可用性相对较高。
实施例3:为了验证钙离子对重金属离子吸附效果的影响,研究重金属离子具有许多不同的基本性质,金属吸附容量的差异可能是由于它们与Ca(NO3)2-海藻酸钠凝胶材料。下面的规则可以考虑作为考虑金属在Ca(NO3)2-海藻酸钠凝胶表面吸附的指导,一方面它的离子半径M2+阳离子,离子半径接近于Ca2+的吸附重金属离子的能力比其他金属高,这个规律可以解释他与Cr6+相比Cd2+,Pb2+和Cu2+更高的能力。另一方面,这可能与金属的电负性有关,这个规则说明电负性较高的金属离子应该更容易吸附。而且,这与溶液的pH值有关,在Cr(Ⅵ)的中性条件下,碳气凝胶对其吸附能力较低,而其他三种金属离子在中性条件下,碳气凝胶对其有较高的吸附量,如图7所示。
Claims (3)
1.一种碳气凝胶的制备方法,其特征在于:
(1)将海藻酸钠和等于海藻酸钠质量二分之一的PEO分别溶于水中;
(2)然后将所得到的两种溶液混合并充分搅拌;
(3)充分搅拌使两种溶液完全混合后,在环境温度下,将0.1L混合溶液滴加到0.2mmol的30mmolL-1Ca(NO3)2溶液中,快速形成海藻酸钙水凝胶块;
(4)由上一步骤得到水凝胶放置过夜以稳定,并将其浸入丙酮溶液中置换出大量的水溶液,这里所用丙酮溶液的质量大约为40-160g,室温下置换24h后,去除丙酮和水的混合液;
(5)完成前一步骤后,将制备的水凝胶冷冻干燥直至完全没有水分;
(6)最后将冷干的块状气凝胶在600℃碳化8小时,得到所述的碳气凝胶。
2.由权利要求1制备得到的碳气凝胶材料。
3.权利要求2所述的碳气凝胶材料在用于去除废水中重金属离子的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811174963.8A CN109200954A (zh) | 2018-10-09 | 2018-10-09 | 一种碳气凝胶的制备方法及其用途 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811174963.8A CN109200954A (zh) | 2018-10-09 | 2018-10-09 | 一种碳气凝胶的制备方法及其用途 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109200954A true CN109200954A (zh) | 2019-01-15 |
Family
ID=64983014
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811174963.8A Pending CN109200954A (zh) | 2018-10-09 | 2018-10-09 | 一种碳气凝胶的制备方法及其用途 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109200954A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112645403A (zh) * | 2020-10-14 | 2021-04-13 | 南昌航空大学 | 一种基于多孔聚合物的地下水重金属处理系统和方法 |
CN112844255A (zh) * | 2020-12-26 | 2021-05-28 | 海南大学 | 一种具有形状记忆性能的智能气凝胶原位复合体系及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101612128A (zh) * | 2009-07-23 | 2009-12-30 | 上海纳米技术及应用国家工程研究中心有限公司 | 海藻酸无机纳米复合凝胶微球及其制备方法 |
KR20130048745A (ko) * | 2013-04-08 | 2013-05-10 | 이재환 | 액상 경화성 조성물 |
CN105905881A (zh) * | 2016-04-12 | 2016-08-31 | 河北省科学院能源研究所 | 一种碳气凝胶及其制备方法 |
CN107115850A (zh) * | 2017-06-14 | 2017-09-01 | 山东省科学院新材料研究所 | 氧化石墨烯‑聚苯胺复合物合成的海藻酸钠凝胶球对水体中铅和镉重金属离子的吸附性去除 |
CN105189839B (zh) * | 2013-04-29 | 2017-12-12 | 韩国生产技术研究院 | 用于制造银纳米纤维的电纺丝溶液组合物 |
-
2018
- 2018-10-09 CN CN201811174963.8A patent/CN109200954A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101612128A (zh) * | 2009-07-23 | 2009-12-30 | 上海纳米技术及应用国家工程研究中心有限公司 | 海藻酸无机纳米复合凝胶微球及其制备方法 |
KR20130048745A (ko) * | 2013-04-08 | 2013-05-10 | 이재환 | 액상 경화성 조성물 |
CN105189839B (zh) * | 2013-04-29 | 2017-12-12 | 韩国生产技术研究院 | 用于制造银纳米纤维的电纺丝溶液组合物 |
CN105905881A (zh) * | 2016-04-12 | 2016-08-31 | 河北省科学院能源研究所 | 一种碳气凝胶及其制备方法 |
CN107115850A (zh) * | 2017-06-14 | 2017-09-01 | 山东省科学院新材料研究所 | 氧化石墨烯‑聚苯胺复合物合成的海藻酸钠凝胶球对水体中铅和镉重金属离子的吸附性去除 |
Non-Patent Citations (1)
Title |
---|
胡志龙: "两种不同多孔材料的制备及其对废水中重金属离子的吸附性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112645403A (zh) * | 2020-10-14 | 2021-04-13 | 南昌航空大学 | 一种基于多孔聚合物的地下水重金属处理系统和方法 |
CN112844255A (zh) * | 2020-12-26 | 2021-05-28 | 海南大学 | 一种具有形状记忆性能的智能气凝胶原位复合体系及其制备方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kasperiski et al. | Production of porous activated carbons from Caesalpinia ferrea seed pod wastes: Highly efficient removal of captopril from aqueous solutions | |
Wu et al. | Comparisons of porous and adsorption properties of carbons activated by steam and KOH | |
Barnie et al. | The influence of pH, co-existing ions, ionic strength, and temperature on the adsorption and reduction of hexavalent chromium by undissolved humic acid | |
Villacañas et al. | Adsorption of simple aromatic compounds on activated carbons | |
El-Sayed | Removal of methylene blue and crystal violet from aqueous solutions by palm kernel fiber | |
Qin et al. | Adsorption of anionic dyes on ammonium-functionalized MCM-41 | |
Srivastava et al. | Adsorptive removal of phenol by bagasse fly ash and activated carbon: equilibrium, kinetics and thermodynamics | |
Krishnan et al. | Removal of mercury (II) from aqueous solutions and chlor-alkali industry effluent by steam activated and sulphurised activated carbons prepared from bagasse pith: kinetics and equilibrium studies | |
Manchón-Vizuete et al. | Adsorption of mercury by carbonaceous adsorbents prepared from rubber of tyre wastes | |
Kennedy et al. | Adsorption of phenol from aqueous solutions using mesoporous carbon prepared by two-stage process | |
Kumar et al. | Adsorption of Victoria blue by carbon/Ba/alginate beads: kinetics, thermodynamics and isotherm studies | |
Vijayaraghavan et al. | Treatment of complex Remazol dye effluent using sawdust-and coal-based activated carbons | |
Liu et al. | Speciation, adsorption and determination of chromium (III) and chromium (VI) on a mesoporous surface imprinted polymer adsorbent by combining inductively coupled plasma atomic emission spectrometry and UV spectrophotometry | |
Hadi et al. | Fabrication of activated carbon from pomegranate husk by dual consecutive chemical activation for 4-chlorophenol adsorption | |
Skwarek et al. | Adsorption of uranium ions on nano-hydroxyapatite and modified by Ca and Ag ions | |
Al-Qodah et al. | Impact of surface modification of green algal biomass by phosphorylation on the removal of copper (II) ions from water | |
Skwarek et al. | Adsorption of uranyl ions at the nano-hydroxyapatite and its modification | |
Nath et al. | Removal of methylene blue from water using okra (Abelmoschus esculentus L.) mucilage modified biochar | |
Velasco et al. | Role of the surface chemistry of the adsorbent on the initialization step of the water sorption process | |
Liu et al. | Efficient static and dynamic removal of Sr (II) from aqueous solution using chitosan ion-imprinted polymer functionalized with dithiocarbamate | |
Moradi | Microwave assisted preparation of sodium dodecyl sulphate (SDS) modified ordered nanoporous carbon and its adsorption for MB dye | |
Liu et al. | Adsorptive removal of humic acid from aqueous solution by micro-and mesoporous covalent triazine-based framework | |
Cotoruelo et al. | Lignin‐based activated carbons as adsorbents for crystal violet removal from aqueous solutions | |
CN109200954A (zh) | 一种碳气凝胶的制备方法及其用途 | |
Kragulj et al. | Adsorption of chlorinated phenols on multiwalled carbon nanotubes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190115 |