CN108948381B - 一种用于去除水中银离子的壳聚糖基水凝胶及其制备方法 - Google Patents

一种用于去除水中银离子的壳聚糖基水凝胶及其制备方法 Download PDF

Info

Publication number
CN108948381B
CN108948381B CN201810817221.6A CN201810817221A CN108948381B CN 108948381 B CN108948381 B CN 108948381B CN 201810817221 A CN201810817221 A CN 201810817221A CN 108948381 B CN108948381 B CN 108948381B
Authority
CN
China
Prior art keywords
chitosan
based hydrogel
hydrogel
silver ions
water
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.)
Active
Application number
CN201810817221.6A
Other languages
English (en)
Other versions
CN108948381A (zh
Inventor
马肃
王超
金璐怡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alibaba Biological New Materials Changzhou Co Ltd
Original Assignee
Alibaba Biological New Materials Changzhou Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Alibaba Biological New Materials Changzhou Co Ltd filed Critical Alibaba Biological New Materials Changzhou Co Ltd
Priority to CN201810817221.6A priority Critical patent/CN108948381B/zh
Publication of CN108948381A publication Critical patent/CN108948381A/zh
Application granted granted Critical
Publication of CN108948381B publication Critical patent/CN108948381B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • 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
    • B01J13/0052—Preparation of gels
    • B01J13/0065—Preparation of gels containing an organic phase
    • 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
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

本发明属于新型功能材料领域，公开了一种用于去除水中银离子的壳聚糖基水凝胶的制备方法。制备方法步骤为：将对羧基苯甲醛和二羟乙基硫醚溶解在THF中，然后在20℃以及氮气保护下反应一段时间，随后再在室温下反应一段时间，然后经过滤、洗涤、沉降、干燥得含硫醚基团酯类化合物DF‑DS，然后将壳聚糖溶解在乙酸中，再在室温下将DF‑DS的水溶液加入到上述溶液中，涡旋，得壳聚糖基水凝胶，该方法在制备水凝胶的过程中，引入了硫醚基团，增加了配位元素硫，且硫醚键易于与银离子形成配位，从而实现了壳聚糖基水凝胶对于水中银离子的吸附。

Description

一种用于去除水中银离子的壳聚糖基水凝胶及其制备方法
技术领域
本发明属于新型功能材料领域，特别涉及一种去除水中银离子的壳聚糖基水凝胶及其制备方法。
背景技术
水凝胶是高度含水的一类软物质，被广泛应用于美容、整形、医疗、医学、污水处理研究等领域，附加值极高，因此，引起了国际上的广泛关注与重视。其中，具有特殊官能团的水凝胶能够利用其官能团与金属络合形成配合物，从而吸附水中的金属离子，达到净化水的目的。
目前，我国关于去除水中金属离子的壳聚糖基水凝胶的专利文献有很多报道，专利CN103804828A提供一种新型高效吸附重金属离子的复合水凝胶及制备方法，是通过未经改性的壳聚糖与PEG和石墨烯形成水凝胶后可去除水中Pb2+，复合水凝胶是由于原料中，聚乙烯醇、壳聚糖和氧化石墨烯含有大量的含O、N官能团对重金属离子具有很强的吸附能力，是水凝胶吸附重金属的主体，该方法是采用物理混合。专利CN106380609A提供了一种抗菌羧甲基壳聚糖水凝胶及其制备方法，利用羧甲基壳聚糖作为制备水凝胶的聚合物部分，在适宜的pH条件下，与作为交联剂部分的过渡金属离子发生离子络合反应，得到抗菌羧甲基壳聚糖水凝胶，该方法是先制备羧甲基壳聚糖然后在与过渡金属离子络合得到壳聚糖水凝胶。以上这些专利报道大都是利用具有螯合作用的官能团，如：N和O原子。
发明内容
在与金属银离子配位时，S原子相对N和O更容易，更具有优势，所以将S引入到水凝胶中，将会对于去除水中银离子具有突出的贡献。因此，本发明提供了一种含有硫醚基团的壳聚糖基水凝胶，并将其用于去除水中的银离子。
本发明提供的壳聚糖基水凝胶的结构如下：
Figure BDA0001740616310000021
本发明还提供了壳聚糖基水凝胶的制备方法，首先合成DF-DS中间产物，然后在制备水凝胶的过程中，引入了硫醚基团，增加了配位元素硫，且硫醚键易于与银离子形成配位，从而实现了壳聚糖基水凝胶对于水中银离子的吸附。
壳聚糖基水凝胶的制备方法，具体步骤如下：
1、含硫醚基团酯类化合物(DF-DS)的合成:
将对羧基苯甲醛，溶解在100mL无水四氢呋喃(THF)中，然后在20℃以及氮气保护下加入二羟乙基硫醚，反应15-20h随后，再在室温下反应5-15h。然后经过过滤、洗涤、沉降、干燥得最终的中间产物DF-DS。
其中，对羧基苯甲醛和二羟乙基硫醚的摩尔为：1-3:1。
2、壳聚糖基水凝胶的制备：
(1)将壳聚糖溶解在质量分数为2.1％的乙酸中配成质量分数为1-5％的壳聚糖溶液；
(2)将DF-DS溶解在蒸馏水中配成质量分数为10-40％的DF-DS溶液；
(3)在室温下将步骤(2)得到的DF-DS溶液加入到步骤(1)得到的壳聚糖溶液中，涡旋1-10min，得壳聚糖基水凝胶。
本发明的壳聚糖基水凝胶用于水中银离子的去除：去除水中银离子的步骤如下：
(1)取0.1-0.5g水凝胶，并向其加入2mL含有100ppm的硝酸银水溶液中；
(2)震荡，参数为：20min，6000rpm，25℃；
(3)利用ICP-AES检测水相中残留银离子浓度，得到壳聚糖基水凝胶对于银离子的吸附率。
制备壳聚糖基水凝胶反应方程式及其吸附水中银离子的原理如下式所示：
Figure BDA0001740616310000031
有益效果：
本发明方法在制备水凝胶的过程中，引入了硫醚基团，增加了配位元素硫，且硫醚键易于与银离子形成配位，从而实现了壳聚糖基水凝胶对于水中银离子的吸附，用于去除水中的银离子，去除率达到70％以上。
具体实施方式
下面结合实施例对本申请作进一步的详细说明，可以理解的是，此处所描述的具体实施例仅仅用于解释本发明，而非对本发明的限定。
实施例1
1.含硫醚基团酯类化合物(DF-DS)的合成
(1)将对羧基苯甲醛(3.00g,20mmol)溶解在100mL无水THF中，然后在20℃以及氮气保护下加入二羟乙基硫醚(1.22g，10mmol)，反应15h随后再在室温下反应6h。然后经过经过滤、洗涤、沉降、干燥得最终的中间产物DF-DS，产率为50.2％。
2.壳聚糖基水凝胶的制备
(1)将壳聚糖溶解在质量分数为2.1％的乙酸中配成质量分数为5％的壳聚糖溶液；然后，将2.0g的DF-DS溶解在3.0g的蒸馏水中配成质量分数为40％的DF-DS溶液；最后，在室温下将上述两溶液混合在一起，涡旋1min左右，得壳聚糖基水凝胶。
3.水中银离子的去除：
水凝胶0.1g，并向其加入300ppm的硝酸银溶液；震荡，参数为：10min，3000rpm，25℃；得到壳聚糖基水凝胶对于银离子的吸附率为59.2％。
实施例2
1.含硫醚基团酯类化合物(DF-DS)的合成
将对羧基苯甲醛(3.75g,25mmol)溶解在100mL无水THF中，然后在20℃以及氮气保护下加入二羟乙基硫醚(1.22g，10mmol)，反应20h随后再在室温下反应13h。然后经过经过滤、洗涤、沉降、干燥得最终的中间产物DF-DS，产率为80.1％。
2.壳聚糖基水凝胶的制备
将壳聚糖溶解在质量分数为2.1％的乙酸中配成质量分数为1％的壳聚糖溶液；然后，将1.0g的DF-DS溶解在9.0g的蒸馏水中配成质量分数为10％的DF-DS溶液；最后，在室温下将上述两溶液混合在一起，涡旋10min左右，得壳聚糖基水凝胶。
3.水中银离子的去除：
水凝胶0.2g，并向其加入100ppm的硝酸银溶液；震荡，参数为：5min，6000rpm，25℃；得到壳聚糖基水凝胶对于银离子的吸附率为71.3％。

Claims (4)

1.一种壳聚糖基水凝胶，其特征在于：所述壳聚糖基水凝胶的结构如下：
Figure FDA0002668421160000011
2.一种如权利要求1所述的壳聚糖基水凝胶的制备方法，其特征在于：所述制备方法步骤如下：
(1)含硫醚基团酯类化合物DF-DS的合成；DF-DS化合物的结构式如下式所示：
Figure FDA0002668421160000012
所述含硫醚基团酯类化合物DF-DS的合成方法为：将对羧基苯甲醛溶解在100mL无水四氢呋喃中，然后在20℃以及氮气保护下加入二羟乙基硫醚，反应15-20h随后再在室温下反应5-15h，然后经过过滤、洗涤、沉降、干燥得DF-DS；
(2)壳聚糖基水凝胶的制备
所述壳聚糖基水凝胶的制备步骤如下：
1)将壳聚糖溶解在质量分数为2.1％的乙酸中配成质量分数为1-5％的壳聚糖溶液；
2)将DF-DS溶解在蒸馏水中配成质量分数为10-40％的DF-DS溶液；
3)在室温下将步骤2)得到的DF-DS溶液加入到步骤1)得到的壳聚糖溶液中，涡旋1-10min，得壳聚糖基水凝胶。
3.根据权利要求2所述的壳聚糖基水凝胶的制备方法，其特征在于：所述对羧基苯甲醛和二羟乙基硫醚的摩尔比为：1-3:1。
4.一种如权利要求1所述的壳聚糖基水凝胶的应用，其特征在于：所述水凝胶用于去除水中银离子，去除水中银离子的方法如下：
(1)取0.1-0.5g水凝胶，并将其加入2mL含有100ppm的硝酸银溶液中；
(2)震荡，参数为：20min，6000rpm，25℃；
(3)利用ICP-AES检测水相中残留银离子浓度，得到壳聚糖基水凝胶对于银离子的吸附率。
CN201810817221.6A 2018-07-24 2018-07-24 一种用于去除水中银离子的壳聚糖基水凝胶及其制备方法 Active CN108948381B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810817221.6A CN108948381B (zh) 2018-07-24 2018-07-24 一种用于去除水中银离子的壳聚糖基水凝胶及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810817221.6A CN108948381B (zh) 2018-07-24 2018-07-24 一种用于去除水中银离子的壳聚糖基水凝胶及其制备方法

Publications (2)

Publication Number Publication Date
CN108948381A CN108948381A (zh) 2018-12-07
CN108948381B true CN108948381B (zh) 2020-10-30

Family

ID=64463693

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810817221.6A Active CN108948381B (zh) 2018-07-24 2018-07-24 一种用于去除水中银离子的壳聚糖基水凝胶及其制备方法

Country Status (1)

Country Link
CN (1) CN108948381B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111617747B (zh) * 2020-05-11 2022-05-31 贵州大学 一种壳聚糖/纳米金属复合水凝胶及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007135114A1 (en) * 2006-05-22 2007-11-29 Universita' Degli Studi Di Trieste Hydrogels of polysaccharide mixtures for tissue engineering and as carriers of active compounds
CN102504312A (zh) * 2011-11-07 2012-06-20 上海同纳环保科技有限公司 双二硫代氨基甲酸基改性壳聚糖珠粒的制备方法
CN104945639A (zh) * 2015-06-17 2015-09-30 华南理工大学 一种含硫改性壳聚糖气凝胶及其制备方法和应用
CN107056965A (zh) * 2017-02-14 2017-08-18 哈尔滨工业大学 一种去除水中二价镉离子的低成本生物吸附剂的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007135114A1 (en) * 2006-05-22 2007-11-29 Universita' Degli Studi Di Trieste Hydrogels of polysaccharide mixtures for tissue engineering and as carriers of active compounds
CN102504312A (zh) * 2011-11-07 2012-06-20 上海同纳环保科技有限公司 双二硫代氨基甲酸基改性壳聚糖珠粒的制备方法
CN104945639A (zh) * 2015-06-17 2015-09-30 华南理工大学 一种含硫改性壳聚糖气凝胶及其制备方法和应用
CN107056965A (zh) * 2017-02-14 2017-08-18 哈尔滨工业大学 一种去除水中二价镉离子的低成本生物吸附剂的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Removal of Cd(II) and Cr(VI) ions by highly cross-linked Thiocarbohydrazide-chitosan gel;Ronghua Li et al.;《International Journal of Biological Macromolecules》;20170703;第104卷;第1072-1081页 *
Sulfur-modified Chitosan Hydrogel as an Adsorbent for Removal of Hg(II) from Effluents;Zhu Xuehuan et al.;《Fibers and Polymers》;20170731;第18卷(第7期);第1229-1234页 *

Also Published As

Publication number Publication date
CN108948381A (zh) 2018-12-07

Similar Documents

Publication Publication Date Title
Dong et al. A novel method for amino starch preparation and its adsorption for Cu (II) and Cr (VI)
Becker et al. Adsorption of nickel (II), zinc (II) and cadmium (II) by new chitosan derivatives
Asere et al. Dialdehyde carboxymethyl cellulose cross-linked chitosan for the recovery of palladium and platinum from aqueous solution
Cui et al. Preparation and application of Aliquat 336 functionalized chitosan adsorbent for the removal of Pb (II)
EP2540746B1 (en) Chitosan derivative, a method for its preparation and its use as an adsorption agent
AU2015349895B2 (en) Preparation of chitosan-based microporous composite material and its applications
AU2014265275A1 (en) Composite materials containing structural polysaccharides and macrocyclic compounds formed from ionic liquid compositions
EP3233783A2 (en) Improved method for the synthesis of ferric oraganic compounds
CN108948381B (zh) 一种用于去除水中银离子的壳聚糖基水凝胶及其制备方法
Pestov et al. Synthesis in a gel and sorption properties of N-2-sulfoethyl chitosan
Lopes et al. Chitosan–cyanuric chloride intermediary as a source to incorporate molecules—Thermodynamic data of copper/biopolymer interactions
US10829592B2 (en) Method for preparing polyaniline complex with antimicrobial activity and heavy metal removal efficiency using conductive poly aniline polymer doped with organic acid and metal ion in defined order
Hong et al. Cellulose-derived polyols as high-capacity adsorbents for rapid boron and organic pollutants removal from water
CN110090615B (zh) 一种高价态金属铁氧体吸附剂的制备方法与应用
KR20180124701A (ko) 희귀 금속 회수용 매트릭스 및 이를 이용한 희귀 금속 회수 방법
Ee et al. Hyperbranched nanocellulose enabling rapid boron removal from aqueous environment
JP3236363B2 (ja) 貴金属イオン捕集剤及びその製法
JP2020019845A (ja) セルロース誘導体、及びこれを含む重金属除去材、並びにこれを用いた重金属除去方法
US8871822B2 (en) Cross-linked polyphosphonate-sulfone composition for removal of metal ions from wastewater
JP5046052B2 (ja) 金属イオンの吸着剤、並びにそれを用いた吸着方法
CN103359789B (zh) 碱式碳酸铋的制备方法
CN103342722A (zh) 碱式没食子酸铋的制备方法
KR102225373B1 (ko) 키틴을 이용한 세슘 흡착용 조성물의 제조방법
EP2670711A1 (en) Cellulose phosphate powder product and process for manufacture thereof, and application to removal of contaminants from aqueous solutions
CN106883409B (zh) 一种聚2-巯基-1，3，4-噻二唑纳米颗粒及其合成方法和用途

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
GR01 Patent grant
GR01 Patent grant