CN116790042B - 一种复合水凝胶、制备方法及其应用 - Google Patents
一种复合水凝胶、制备方法及其应用 Download PDFInfo
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- CN116790042B CN116790042B CN202310762686.7A CN202310762686A CN116790042B CN 116790042 B CN116790042 B CN 116790042B CN 202310762686 A CN202310762686 A CN 202310762686A CN 116790042 B CN116790042 B CN 116790042B
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- composite hydrogel
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- yellow water
- composite
- crude polysaccharide
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- 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
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- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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- 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
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明属于水凝胶环保技术领域,公开了一种复合水凝胶、制备方法及其应用,所述复合水凝胶的组分包括羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子;所述羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子的质量比为1:10‑20:2‑6。本发明的制备方法简单,原料易得,价格低廉;通过羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子的配比,发挥协同作用,在染料的循环吸附中,吸附量产生的损耗小,能够提升对染料的处理能力,满足生产要求。
Description
技术领域
本发明属于水凝胶环保技术领域,具体涉及一种复合水凝胶、制备方法及其应用。
背景技术
近年来,天然高分子(多糖、蛋白质等)代替传统的石油基化合物制备功能高分子材料受到研究人员的广泛关注。随着人们对天然多糖资源的开发不断深入,以天然多糖,如纤维素、淀粉、壳聚糖以及海藻酸盐等原料制备的水凝胶在废水处理领域被广泛的研究。但是纤维素、淀粉、壳聚糖由于其自身的局限性,包括溶解性低、机械性能差、吸附性能低等,通常不作为吸附剂单独使用。羧甲基化是最简单也是最普遍的多糖结构改性方法,对纤维素、淀粉、壳聚糖进行羧甲基化改性有利于提高其理化性质,包括水溶性和粗糙度增加、结构更加蓬松等。
水凝胶因其独特的三维网状结构、较高的吸附量、较好的吸附速率、良好的可再生性在金属离子吸附领域引起了人们的广泛关注,水凝胶及其复合水凝胶的应用越来越广泛。羧甲基纤维素、羧甲基壳聚糖等也已经在吸附型水凝胶领域广泛应用。中国专利CN106589414A公开了一种水性ATRP聚合法的复合磁性微球水凝胶及其制备方法,采用ATRP聚合法引发单体聚合、交联,聚合物链可在聚合反应中处于松弛状态,聚合反应生成分子量分布窄、且分子量、交联密度可控的高分子水凝胶,且水凝胶组成一致、均匀;磁性微球比表面积较大,其纳米四氧化三铁的磁性多金属离子具有特殊的吸附作用;多糖/阴离子型多糖,例如羧甲基壳聚糖也可与金属离子紧密结合,不容易发生脱吸附行为。中国专利CN107876001A公开了一种改性镁砂重金属脱除剂及其制备方法,由电石炉尾气粉尘、海藻酸钠、壳聚糖、镁砂、正硅酸乙酯、四氧化三铁粉末等原料制成,该发明采用工业废料电石炉尾气粉尘与多糖混合浸渍包覆改性镁砂,利用粉尘密度小、粒度细以及多糖黏度较大的特点提高了与改性镁砂结合的稳定性,同时克服了单独使用多糖包覆造成机械强度差的缺陷,利用改性镁砂提升对重金属的吸附种类和吸附强度,具有制备简单、原料易得,且对环境友好,不造成二次污染等特点,重金属脱除效果优秀,适用于各类型的重金属污染治理使用。但是上述复合磁性微球水凝胶的循环吸附性能效果较差,不能达到行业生产标准,且制备过程复杂,所用原料多。
现有技术中尚未有一种在染料循环吸附中吸附量的损耗小,且能够提升对染料的处理能力的复合水凝胶。
发明内容
为了解决上述技术问题,本发明提供了一种复合水凝胶、制备方法及其应用,通过羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子的协同作用,提高复合水凝胶的孔隙率和循环吸附性能,对染料的处理能力强。
为了实现上述目的,本发明采用以下技术方案:
一方面,本发明提供了一种复合水凝胶,所述复合水凝胶的组分包括羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子。
优选地,所述羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子的质量比为1:10-20:2-6。
优选地,所述羧甲基化黄水粗多糖的制备方法包括将黄水粗多糖碱化和醚化后制得。
优选地,所述黄水粗多糖是从酿酒黄水中提取的一种多糖;所述提取的方法包括将酿酒黄水进行离心、超滤、醇沉、脱蛋白、水洗、透析和冻干,得到所述的黄水粗多糖。
具体地,所述酿酒黄水是传统固态法白酒酿造过程中产生的液体副产物。
优选地,所述离心的条件为:离心力7000-9000g,时间为15-20min;所述冻干的条件为:温度为-40~-60℃、时间为20-40h。
优选地,所述酿酒黄水中酒的香型包括清香型、酱香型、浓香型、馥郁香型、芝麻香型、米香型、凤香型中的一种或多种。
优选地,所述碱化的方法包括先将碱溶解于异丙醇溶液,再加入黄水粗多糖溶液;所述醚化的方法包括先将一氯乙酸溶解于异丙醇溶液,再加入黄水粗多糖溶液和溶解于异丙醇的碱溶液。
优选地,所述异丙醇的浓度为70%-90%(v/v);所述的碱为氢氧化钠。
优选地,所述黄水粗多糖在进行碱化和醚化之前需要先溶解于70%-90%(v/v)的异丙醇溶液。
优选地,所述碱化的条件包括:反应时间1h-3h,反应温度35℃-55℃;所述醚化的条件包括:反应时间5h-7h,反应温度35℃-55℃。
优选地,所述磁性纳米粒子的制备方法包括:在Fe2+和Fe3+混合溶液中加入碱搅拌,之后进行磁分离、水洗、透析和干燥,得到所述的磁性纳米粒子。
优选地,所述Fe2+的浓度为0.5-0.7mol/L;所述Fe3+的浓度为0.05-0.2mol/L。
本发明还提供了一种上述的复合水凝胶的制备方法,包括以下步骤:
S1、将羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子搅拌混合,静置得到无泡复合溶液;
S2、将所述的无泡复合溶液通过钙离子诱导交联,得到所述的复合水凝胶。
优选地,步骤S1所述的搅拌的条件包括:温度25℃-45℃,时间3h-6h;步骤S1所述静置的时间为4h-8h。
优选地,步骤S2所述钙离子的浓度为0.1mol/L-0.5mol/L;步骤S2所述交联的时间为12h-24h。
另一方面,本发明提供了一种上述的复合水凝胶或上述的复合水凝胶的制备方法制备得到的复合水凝胶在制备染料吸附剂中的应用。
优选地,所述染料为亚甲基蓝染料。
优选地,所述复合水凝胶作为染料吸附剂中的工作温度为20℃-70℃;
优选地,所述工作温度为20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃或65℃。
本发明还提供了一种染料吸附剂,包括上述的复合水凝胶或上述复合水凝胶的制备方法制备得到的复合水凝胶。
本发明的有益效果为:
本发明的制备方法简单,原料易得,价格低廉;本发明通过添加羧甲基化黄水粗多糖能提高复合水凝胶的孔隙率和吸附性能;本发明制得的复合水凝胶通过羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子的配比,发挥协同作用,在4次循环吸附中,吸附量产生的损耗小,能够提升对染料的处理能力,吸附稳定性强。
附图说明
图1为实施例1中的McHSP的宏观形貌图;
图2为实施例1中的羧甲基化黄水粗多糖与单糖标准品的高效液相图;
图3为实施例1中McHSP和cHSP的红外光谱图;
图4为实施例1中的复合水凝胶的红外光谱图;
图5为实施例1复合水凝胶SA-FFO-McHSP和对比例2的复合水凝胶SA-FFO-MCS的热重曲线图;
图6为实施例1中的SA-FFO和SA-FFO-McHSP的磁化曲线图;
图7为循环吸附性能图。
具体实施方式
以下实施例的说明只是用于帮助理解本发明的方法及其核心思想。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,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。对所公开的实施例的下述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例中,而是可以应用于符合与本文所公开的原理和新颖特点相一致的更宽的范围。虽然在本发明的实施或测试中可以使用与本发明中所述相似或等价的任何方法和材料,本文在此处列举优选的方法和材料。
除非另外定义,本文中使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同意义。
需要说明的是:
本发明中,cHSP表示黄水粗多糖、SA表示海藻酸钠、McHSP表示羧甲基化黄水粗多糖、FFO表示磁性纳米粒子、SA-FFO表示由海藻酸钠和磁性纳米粒子组成的复合水凝胶、MCS表示羧甲基壳聚糖、SA-FFO-McHSP表示本发明实施例1-3的复合水凝胶、SA-FFO-MCS表示由海藻酸钠、磁性纳米粒子、羧甲基壳聚糖组成的复合水凝胶、MB表示亚甲基蓝染料。
单糖标品(甘露糖,核糖,鼠李糖,葡萄糖醛酸,半乳糖醛酸,N-乙酰氨基葡萄糖,葡萄糖,N-乙酰氨基半乳糖,半乳糖,木糖,阿拉伯糖,岩藻糖),均为色谱级,购于Sigma公司
主要仪器与设备如表1所示:
表1主要仪器与设备信息
实施例1一种复合水凝胶
由以下步骤制得:
S1、黄水粗多糖的制备:取酿酒黄水(由宜宾五粮液股份有限公司提供)分装于50mL的离心管并于9000rpm下离心15min,除去不溶物,收集滤液。将滤液进行超滤,收集大于3000Da的部分。在4℃下用80%乙醇醇沉24h,离心取沉淀。用无水乙醇和丙酮依次洗涤沉淀3次,以此除去脂质和色素,随后用Sevag试剂(氯仿/正丁醇=4:1,v/v)脱蛋白4次,每次在旋涡混匀仪上振摇3min。将获得的沉淀用蒸馏水洗涤4次后加少量蒸馏水复溶,在4℃下透析72h,每12h更换一次水,以除去小分子物质。透析结束后溶液在-45℃下经真空冷冻仪干燥32h后得到cHSP。
S2、羧甲基化黄水粗多糖的制备:将0.2032g的cHSP溶于9mL的蒸馏水中,然后在450rpm的搅拌下缓慢滴加34mL的异丙醇,随后升温至35℃,继续搅拌30分钟。将15mL溶有2.22g的NaOH的85%(v/v)异丙醇溶液缓慢滴入cHSP-异丙醇混合溶液中。在45℃碱化2h后,往碱化液缓慢滴入15mL溶有7.0g一氯乙酸的85%(v/v)异丙醇溶液,同时再滴加15mL溶有2.22g NaOH的85%(v/v)异丙醇溶液。在45℃醚化6h后,用盐酸-醇溶液(盐酸:无水乙醇=3:7)调至中性,醇洗浓缩,透析后在-54℃下真空干燥即得McHSP样品。
S3、磁性纳米粒子的制备:往150mL的三孔烧瓶中加入50mL浓度为0.5mol/L的Fe2+和50mL浓度为0.05mol/L的Fe3+,25℃在N2氛围下剧烈搅拌1h。20mL浓度为10M的NaOH溶液缓慢滴加到Fe3+和Fe2+混合溶液中,分别在25℃和90℃各搅拌1h。待反应液冷却至室温,用磁倾析法收集磁性纳米颗粒,并用蒸馏水洗涤数次后透析至中性,在-54℃下真空冷冻干燥,得到Fe3O4磁性纳米颗粒样品。
S4、复合水凝胶的制备:取1.0g的SA在35℃下溶解于60mL蒸馏水,依次加入0.2g的Fe3O4磁性纳米颗粒样品和0.05g的McHSP样品,继续搅拌4h后得到复合溶液。将此复合溶液转移到烧杯中,静置6h以除气泡。将复合液滴入200mL浓度为0.1mol/L的CaCl2溶液中,经12h固化交联后得到复合水凝胶。用蒸馏水把复合水凝胶洗涤数次,去除水凝胶表面残留的Ca2+离子,在-50℃下干燥,得到复合水凝胶样品SA-FFO-McHSP。
实施例2一种复合水凝胶
由以下步骤制得:
S1、黄水粗多糖的制备同实施例1。
S2、羧甲基化黄水粗多糖的制备:将0.2032g的cHSP溶于9mL的蒸馏水中,然后在450rpm的搅拌下缓慢滴加34mL的异丙醇,随后升温至35℃,继续搅拌30分钟。将15mL溶有2.22g的NaOH的85%(v/v)异丙醇溶液缓慢滴入cHSP-异丙醇混合溶液中。在35℃碱化3h后,往碱化液缓慢滴入15mL溶有7.0g一氯乙酸的85%(v/v)异丙醇溶液,同时再滴加15mL溶有2.22g NaOH的85%(v/v)异丙醇溶液。在35℃醚化7h后,用盐酸-醇溶液(盐酸:无水乙醇=3:7)调至中性,醇洗浓缩,透析后在-54℃下真空干燥即得McHSP样品。
S3、磁性纳米粒子的制备:往150mL的三孔烧瓶中加入50mL浓度为0.6mol/L的Fe2+和50mL浓度为0.1mol/L的Fe3+,25℃在N2氛围下剧烈搅拌1h。20mL浓度为10M的NaOH溶液缓慢滴加到Fe3+和Fe2+混合溶液中,分别在25℃和90℃各搅拌1h。待反应液冷却至室温,用磁倾析法收集磁性纳米颗粒,并用蒸馏水洗涤数次后透析至中性,在-54℃下真空冷冻干燥,得到Fe3O4磁性纳米颗粒样品。
S4、复合水凝胶的制备:取0.75g的SA在45℃下溶解于60mL蒸馏水,依次加入0.3g的Fe3O4磁性纳米颗粒样品和0.05g的McHSP样品,继续搅拌6h后得到复合溶液。将此复合溶液转移到烧杯中,静置6h以除气泡。将复合液滴入200mL浓度为0.3mol/L的CaCl2溶液中,经18h固化交联后得到复合水凝胶。用蒸馏水把复合水凝胶洗涤数次,去除水凝胶表面残留的Ca2+离子,在-50℃下干燥,得到复合水凝胶样品SA-FFO-McHSP。
实施例3一种复合水凝胶
由以下步骤制得:
S1、黄水粗多糖的制备同实施例1。
S2、羧甲基化黄水粗多糖的制备:将0.2032g的cHSP溶于9mL的蒸馏水中,然后在450rpm的搅拌下缓慢滴加34mL的异丙醇,随后升温至35℃,继续搅拌30分钟。将15mL溶有2.22g的NaOH的85%(v/v)异丙醇溶液缓慢滴入cHSP-异丙醇混合溶液中。在55℃碱化1h后,往碱化液缓慢滴入15mL溶有7.0g一氯乙酸的85%(v/v)异丙醇溶液,同时再滴加15mL溶有2.22g NaOH的85%(v/v)异丙醇溶液。在55℃醚化5h后,用盐酸-醇溶液(盐酸:无水乙醇=3:7)调至中性,醇洗浓缩,透析后在-54℃下真空干燥即得McHSP样品。
S3、磁性纳米粒子的制备:往150mL的三孔烧瓶中加入50mL浓度为0.7mol/L的Fe2+和50mL浓度为0.2mol/L的Fe3+,25℃在N2氛围下剧烈搅拌1h。20mL浓度为10M的NaOH溶液缓慢滴加到Fe3+和Fe2+混合溶液中,分别在25℃和90℃各搅拌1h。待反应液冷却至室温,用磁倾析法收集磁性纳米颗粒,并用蒸馏水洗涤数次后透析至中性,在-54℃下真空冷冻干燥,得到Fe3O4磁性纳米颗粒样品。
S4、复合水凝胶的制备:取0.5g的SA在25℃下溶解于60mL蒸馏水,依次加入0.1g的Fe3O4磁性纳米颗粒样品和0.05g的McHSP样品,继续搅拌3h后得到复合溶液。将此复合溶液转移到烧杯中,静置8h以除气泡。将复合液滴入200mL浓度为0.5mol/L的CaCl2溶液中,经24h固化交联后得到复合水凝胶。用蒸馏水把复合水凝胶洗涤数次,去除水凝胶表面残留的Ca2+离子,在-50℃下干燥,得到复合水凝胶样品SA-FFO-McHSP。
对比例1一种复合水凝胶
与实施例1相比,步骤S4中羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子的质量比为1:20:12,其他步骤均与实施例1相同。
对比例2一种复合水凝胶
与实施例1相比,省略步骤S1和S2,并将羧甲基化黄水粗多糖换成羧甲基壳聚糖(MCS,购自陕西龙洲生物科技有限公司,货号LZ-210823002,取代度为1.02),其他步骤均与实施例1相同。
效果例1实施例1复合水凝胶的结构表征
1、McHSP单糖组成分析:精确称取3mg的McHSP样品至10mL的安瓿瓶中,加入3mL2mol/L的三氟乙酸(TFA)后在120℃下密封水解4h,取出后加入甲醇氮吹挥干TFA,加水复溶,取250μL的样品溶液至EP管中,加入250uL 0.6mol/LNaOH和500uL 0.4mol/L1-苯基-3-甲基-5-吡唑啉酮(PMP)-甲醇溶液。在70℃下反应1h后,冷却至室温。用500uL 0.3mol/LHCl中和后,再加入1mL氯仿漩涡1min,在转速为3000rpm下离心10min后取上清,萃取3次得到衍生化后的样品溶液。采用日本Shimadzu公司型号为U3000的高效液相色谱系统,色谱条件:Xtimate C18(4.6mm×200mm,5um)的柱型;流动相为0.05mol/L磷酸二氢钾溶液:乙腈=83:17;1.0mL/min的流速;30℃的柱温;20uL的进样量;检测波长为250nm。以甘露糖,核糖,鼠李糖,葡萄糖醛酸,半乳糖醛酸,N-乙酰-氨基葡萄糖,葡萄糖,N-乙酰-氨基半乳糖,半乳糖,木糖,阿拉伯糖,岩藻糖样品作为对照。
结果如图1和图2所示,图1是McHSP的宏观形貌图,呈白色碎屑状。HPLC出峰结果与单糖标准溶液出峰结果如图2,McHSP水解液的保留时间与单糖标准样品的一致,McHSP单糖组成主要有鼠李糖、葡萄糖和葡萄糖醛酸。在羧甲基化后,多糖的颜色、形状、质地以及单糖组成都发生了变化,是因为在碱化醚化过程中多糖部分色素被去除,并且分子链出现部分降解与重组现象以及引入了羧甲基基团。
2、McHSP取代度分析:采用酸洗法平行测定三组。取20mg的McHSP溶于20mL浓度为0.1M盐酸溶液中。用0.1M的氢氧化钠溶液通过碱式滴定管缓慢滴入McHSP-盐酸混合溶液,期间用多功能pH计监测混合溶液的pH值,记下pH 2.1和pH 4.3时所消耗氢氧化钠的体积,按照A=(Vb-Va)×C÷m计算羧甲基含量A(mol/g),按照DS=0.203A÷(1-0.058A)计算取代度DS;其中,Va和Vb分别是当混合溶液的pH值为2.1和4.3时所消耗氢氧化钠的体积(mL);C是氢氧化钠的浓度(mol/L);m是样品的质量(g);0.058是1毫克当量的-OH转变为-OCH2COOH所净增的分子量。
三次平行试验的结果如表2,McHSP的平均取代度为1.02,这个取代度的水平可以实现对染料的有效吸附。
表2McHSP的取代度
3、化学结构分析
采用红外光谱法分析样品的化学结构,取样品2mg,用ATR模式进行分析测定,波数范围是400-4000cm-1,光谱仪分辨率为4cm-1,信躁比是50000:1,扫描64次。
图3显示,对于McHSP,3423cm-1处的强宽峰属于分子间和分子内羟基形成的多种方式的氢键伸缩振动,2923cm-1处是C-H键伸缩振动引起的。1605cm-1的强吸收峰是C-O键对称与不对称伸缩振动引起的,1420cm-1中等强度的吸收峰与羧基相连的次甲基剪式振动有关,1325cm-1处的吸收峰是C-H非平面摇摆振动引起的。McHSP在1620-1320cm-1出现的吸收峰属于-COO-的特征吸收峰,在1100-1000cm-1的强宽峰是C-O-C醚键不对称伸缩振动的累加,这两处的吸收峰表明cHSP成功被羧甲基化,并且1605cm-1处的吸收峰说明羧甲基基团以钠盐的形式存在。cHSP在848cm-1处有α-吡喃糖特征吸收而McHSP在该处的吸收不明显,这表明改性后的多糖的结构发生了变化。此外,与cHSP相比,McHSP在3500-3000cm-1的吸收峰向低波数发生位移,因为改性后引入的羧基使多糖分子间的氢键相互作用增强。
图4显示,对于实施例1的复合水凝胶,3431cm-1和2920cm-1属于O-H和C-H的伸缩振动峰;1620-1031cm-1处出现羧基特征吸收峰,这是由于海藻酸钠和McHSP中的羧基基团;890cm-1处的吸收峰表明水凝胶的糖苷键类型为β-1,4-糖苷键,这是与海藻酸钠的糖苷键类型一致;565cm-1处的吸收峰属于Fe-O的弯曲振动,这是因为水凝胶中存在Fe3O4纳米颗粒。除此以外,无新的吸收峰出现,这表明复合水凝胶形成的机理仅涉及氢键和静电相互作用。
4、热稳定性分析:
分别称取10mg实施例1和对比例2的复合水凝胶样品,通过热重分析仪测定样品的热重(TG)曲线。测试条件为:在N2氛围下以10℃/min的加热速率从30℃升温至500℃。
图5是复合水凝胶SA-FFO-McHSP和SA-FFO-MCS的TG曲线图,可以看出两种水凝胶都经历两个失重阶段。在200℃之前,随着温度的升高,由于样品中自由水和结合水的蒸发,造成SA-FFO-McHSP和SA-FFO-MCS复合水凝胶分别出现15%和22%的失重,在200℃-400℃出现最大失重,当温度加热到500℃时,SA-FFO-McHSP和SA-FFO-MCS复合水凝胶的残留率分别为53.54%和42.56%,其中SA-FFO-McHSP水凝胶的失重率明显小于SA-FFO-MCS复合水凝胶。SA-FFO-McHSP和SA-FFO-MCS复合水凝胶的初始分解温度分别为239℃和233℃,SA-FFO-McHSP复合水凝胶的初始分解温度大于SA-FFO-MCS复合水凝胶,综上分析表明,添加McHSP比羧甲基壳聚糖(MCS)更有利于提高复合水凝胶的热稳定性。
5、磁性能分析:
在300K下使用振动样品磁强计测量冻干的复合水凝胶的磁化强度,磁场范围选择±18000Oe。
图6是水凝胶SA-FFO和SA-FFO-McHSP的磁化曲线。水凝胶的磁化曲线随着磁场强度从-17000Oe到17000Oe的增加呈S状变化趋势,并且没有出现磁滞现象,这表明Fe3O4在水凝胶中保持良好的顺磁性。另外,SA-FFO和SA-FFO-McHSP水凝胶的磁饱和强度分别为12.5emu/g和10.9emu/g,表明水凝胶的运动行为可以被外加的磁场控制,其在实际应用中能实现快速的分离回收。
效果例2吸附性能研究
称取实施例1-3和对比例1-2复合水凝胶各10±0.5mg,浸入10mL浓度为100mg/L的MB溶液中,待吸附平衡后,吸取0.2mL的MB剩余溶液,经稀释后用酶标仪测定其在固定波长664nm处的吸光值,根据标准曲线法计算MB剩余溶液的浓度,并按照计算平衡吸附量Qe;其中C0和Ce分别是MB溶液的初始浓度和MB溶液的吸附平衡浓度(mg/L);V是MB溶液的体积(L);m是水凝胶的质量(g);Qe是水凝胶对MB的平衡吸附量(mg/g)。接着,将吸附后的水凝胶取出转移到20mL浓度为0.1M的盐酸中进行解吸,每1h更换一次盐酸溶液,经三次更换后完成解吸。随后,水凝胶用蒸馏水多次洗涤,并经打湿滤纸擦拭表面多余的水分后再重新浸入10mL浓度为100mg/L的MB中,开始下一次的吸附实验,吸附-解吸循环总共进行4次,以考察水凝胶的循环吸附性能。
通过4次吸附-解吸循环考察了复合水凝胶对MB的循环吸附性。结果如图7。可以看出,对于MB吸附来说,实施例1-3的复合水凝胶从第1次循环吸附开始,复合水凝胶对MB的吸附量保持稳定,经过4次吸附-解吸循环后,实施例1、实施例2和实施例3的复合水凝胶的吸附量分别占初始吸附量的90%、90%和88%。而对比例1和对比例2的结果显示,经过4次吸附-解吸循环后,MB的吸附量分别为初始吸附量的48.2%和51.3%;SA-FFO在4次吸附-解析循环后,MB吸附量为初始吸附量的49%。结果表明本发明实施例的复合水凝胶具有稳定的循环吸附性。
以上是结合具体实施例对本发明进一步的描述,但这些实施例仅是范例性的,并不对本发明的范围构成任何限制。本领域技术人员应该理解的是,在不偏离本发明的精神和范围下可以对本发明技术方案的细节和形式进行修改或替换,但这些修改和替换均落入本发明的保护范围内。
Claims (9)
1.一种复合水凝胶,其特征在于:所述复合水凝胶的组分包括羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子;所述羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子的质量比为1:10-20:2-6。
2.根据权利要求1所述的复合水凝胶,其特征在于:所述羧甲基化黄水粗多糖的制备方法包括将黄水粗多糖碱化和醚化后制得;所述黄水粗多糖是从酿酒黄水中提取的一种多糖;所述提取的方法包括将酿酒黄水进行离心、超滤、醇沉、脱蛋白、水洗、透析和冻干,得到所述的黄水粗多糖。
3.根据权利要求2所述的复合水凝胶,其特征在于:所述碱化的方法包括先将碱溶解于异丙醇溶液,再加入黄水粗多糖溶液;所述醚化的方法包括先将一氯乙酸溶解于异丙醇溶液,再加入黄水粗多糖溶液和溶解于异丙醇的碱溶液。
4.根据权利要求2所述的复合水凝胶,其特征在于:所述碱化的条件包括:反应时间1h-3h,反应温度35℃-55℃;所述醚化的条件包括:反应时间5h-7h,反应温度35℃-55℃。
5.根据权利要求1所述的复合水凝胶,其特征在于:所述磁性纳米粒子的制备方法包括:在Fe2+和Fe3+混合溶液中加入碱搅拌,之后进行磁分离、水洗、透析和干燥;所述Fe2+的浓度为0.5-0.7mol/L;所述Fe3+的浓度为0.05-0.2mol/L。
6.权利要求1-5任一项所述的复合水凝胶的制备方法,其特征在于:包括以下步骤:
S1、将羧甲基化黄水粗多糖、海藻酸钠和磁性纳米粒子搅拌混合,静置得到无泡复合溶液;
S2、将所述的无泡复合溶液通过钙离子诱导交联,得到所述的复合水凝胶。
7.根据权利要求6所述的制备方法,其特征在于:步骤S1所述搅拌的条件包括:温度25℃-45℃,时间3h-6h;步骤S1所述静置的时间为4h-8h;步骤S2所述钙离子的浓度为0.1mol/L-0.5mol/L;步骤S2所述交联的时间为12h-24h。
8.权利要求1-5任一项所述的复合水凝胶或权利要求6-7任一项所述的复合水凝胶的制备方法制备得到的复合水凝胶在制备染料吸附剂中的应用。
9.一种染料吸附剂,其特征在于:包括权利要求1-5任一项所述的复合水凝胶或权利要求6-7任一项所述的复合水凝胶的制备方法制备得到的复合水凝胶。
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